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Sample records for actinide isotope analysis

  1. Microcalorimeter Q-spectroscopy for rapid isotopic analysis of trace actinide samples

    NASA Astrophysics Data System (ADS)

    Croce, M. P.; Bond, E. M.; Hoover, A. S.; Kunde, G. J.; Mocko, V.; Rabin, M. W.; Weisse-Bernstein, N. R.; Wolfsberg, L. E.; Bennett, D. A.; Hays-Wehle, J.; Schmidt, D. R.; Ullom, J. N.

    2015-06-01

    We are developing superconducting transition-edge sensor (TES) microcalorimeters that are optimized for rapid isotopic analysis of trace actinide samples by Q-spectroscopy. By designing mechanically robust TESs and simplified detector assembly methods, we have developed a detector for Q-spectroscopy of actinides that can be assembled in minutes. We have characterized the effects of each simplification and present the results. Finally, we show results of isotopic analysis of plutonium samples with Q-spectroscopy detectors and compare the results to mass spectrometry.

  2. Isotope ratio analysis of actinides, fission products, and geolocators by high-efficiency multi-collector thermal ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Bürger, S.; Riciputi, L. R.; Bostick, D. A.; Turgeon, S.; McBay, E. H.; Lavelle, M.

    2009-09-01

    A ThermoFisher "Triton" multi-collector thermal ionization mass spectrometer (MC-TIMS) was evaluated for trace and ultra-trace level isotope ratio analysis of actinides (uranium, plutonium, and americium), fission products and geolocators (strontium, cesium, and neodymium). Total efficiencies (atoms loaded to ions detected) of up to 0.5-2% for U, Pu, and Am, and 1-30% for Sr, Cs, and Nd can be reported employing resin bead load techniques onto flat ribbon Re filaments or resin beads loaded into a millimeter-sized cavity drilled into a Re rod. This results in detection limits of <0.1 fg (104 atoms to 105 atoms) for 239-242+244Pu, 233+236U, 241-243Am, 89,90Sr, and 134,135,137Cs, and <=1 pg for natural Nd isotopes (limited by the chemical processing blank) using a secondary electron multiplier (SEM) or multiple-ion counters (MICs). Relative standard deviations (RSD) as small as 0.1% and abundance sensitivities of 1 × 106 or better using a SEM are reported here. Precisions of RSD [approximate]0.01-0.001% using a multi-collector Faraday cup array can be achieved at sub-nanogram concentrations for strontium and neodymium and are suitable to gain crucial geolocation information. The analytical protocols reported herein are of particular value for nuclear forensic and nuclear safeguard applications.

  3. Isotopic biases for actinide-only burnup credit

    SciTech Connect

    Rahimi, M.; Lancaster, D.; Hoeffer, B.; Nichols, M.

    1997-04-01

    The primary purpose of this paper is to present the new methodology for establishing bias and uncertainty associated with isotopic prediction in spent fuel assemblies for burnup credit analysis. The analysis applies to the design of criticality control systems for spent fuel casks. A total of 54 spent fuel samples were modeled and analyzed using the Shielding Analyses Sequence (SAS2H). Multiple regression analysis and a trending test were performed to develop isotopic correction factors for 10 actinide burnup credit isotopes. 5 refs., 1 tab.

  4. Accelerator Mass Spectrometry of Actinides in Ground- and Seawater: An Innovative Method Allowing for the Simultaneous Analysis of U, Np, Pu, Am, and Cm Isotopes below ppq Levels.

    PubMed

    Quinto, Francesca; Golser, Robin; Lagos, Markus; Plaschke, Markus; Schäfer, Thorsten; Steier, Peter; Geckeis, Horst

    2015-06-01

    (236)U, (237)Np, and Pu isotopes and (243)Am were determined in ground- and seawater samples at levels below ppq (fg/g) with a maximum sample size of 250 g. Such high sensitivity was possible by using accelerator mass spectrometry (AMS) at the Vienna Environmental Research Accelerator (VERA) with extreme selectivity and recently improved efficiency and a significantly simplified separation chemistry. The use of nonisotopic tracers was investigated in order to allow for the determination of (237)Np and (243)Am, for which isotopic tracers either are rarely available or suffer from various isobaric mass interferences. In the present study, actinides were concentrated from the sample matrix via iron hydroxide coprecipitation and measured sequentially without previous chemical separation from each other. The analytical method was validated by the analysis of the Reference Material IAEA 443 and was applied to groundwater samples from the Colloid Formation and Migration (CFM) project at the deep underground rock laboratory of the Grimsel Test Site (GTS) and to natural water samples affected solely by global fallout. While the precision of the presented analytical method is somewhat limited by the use of nonisotopic spikes, the sensitivity allows for the determination of ∼10(5) atoms in a sample. This provides, e.g., the capability to study the long-term release and retention of actinide tracers in field experiments as well as the transport of actinides in a variety of environmental systems by tracing contamination from global fallout.

  5. The applicability of MGA method for depleted and natural uranium isotopic analysis in the presence of actinides (232Th, 237Np, 233Pa and 241Am).

    PubMed

    Yücel, Haluk

    2007-11-01

    The multi-group analysis (MGA) method for the determination of uranium isotopic abundances in depleted uranium (DU) and natural uranium (NU) samples is applied in this study. A set of non-destructive gamma-ray measurements of DU and NU samples were performed using a planar Ge detector. The relative abundances of 235U and 238U isotopes were compared with the declared values of the standards. The relative abundance for 235U obtained by MGA for a "clean" DU or NU sample with a content of uranium>1wt% is determined with an accuracy of about +/-5%. However, when several actinides such as 232Th, 237Np, 233Pa and 241Am are present along with uranium isotopes simulating "dirty" DU or NU, it has been observed that MGA method gives erroneous results. The 235U abundance results for the samples were 6-25 times higher than the declared values in the presence of above-mentioned actinides, since MGA is utilized the X-ray and gamma-ray peaks in the 80-130 keV energy region, covering XKalpha and XKbeta regions. After the least-squares fitting of the spectra, it is found that the increases in the intensities of the X-ray and gamma-ray peaks of uranium are remarkably larger in the complex 80-130 keV region. On the other hand, it is observed that the interferences of the actinide peaks are relatively less dominant in the higher gamma-ray region of 130-300 keV. The results imply the need for dirty DU and NU samples that the MGA method should utilize the higher energy gamma-rays (up to 1001 keV of (234m)Pa) combined with lower energies of the spectra, which may be collected in a two detector mode (a planar Ge and a high efficient coaxial Ge).

  6. The applicability of MGA method for depleted and natural uranium isotopic analysis in the presence of actinides (232Th, 237Np, 233Pa and 241Am).

    PubMed

    Yücel, Haluk

    2007-11-01

    The multi-group analysis (MGA) method for the determination of uranium isotopic abundances in depleted uranium (DU) and natural uranium (NU) samples is applied in this study. A set of non-destructive gamma-ray measurements of DU and NU samples were performed using a planar Ge detector. The relative abundances of 235U and 238U isotopes were compared with the declared values of the standards. The relative abundance for 235U obtained by MGA for a "clean" DU or NU sample with a content of uranium>1wt% is determined with an accuracy of about +/-5%. However, when several actinides such as 232Th, 237Np, 233Pa and 241Am are present along with uranium isotopes simulating "dirty" DU or NU, it has been observed that MGA method gives erroneous results. The 235U abundance results for the samples were 6-25 times higher than the declared values in the presence of above-mentioned actinides, since MGA is utilized the X-ray and gamma-ray peaks in the 80-130 keV energy region, covering XKalpha and XKbeta regions. After the least-squares fitting of the spectra, it is found that the increases in the intensities of the X-ray and gamma-ray peaks of uranium are remarkably larger in the complex 80-130 keV region. On the other hand, it is observed that the interferences of the actinide peaks are relatively less dominant in the higher gamma-ray region of 130-300 keV. The results imply the need for dirty DU and NU samples that the MGA method should utilize the higher energy gamma-rays (up to 1001 keV of (234m)Pa) combined with lower energies of the spectra, which may be collected in a two detector mode (a planar Ge and a high efficient coaxial Ge). PMID:17606378

  7. Isotope ratio analysis of actinides, fission products, and geolocators by high-efficiency multi-collector thermal ionization mass spectrometry

    SciTech Connect

    Bürger, Stefan; Riciputi, Lee R; Bostick, Debra A; Turgeon, Steven; McBay, Eddie H; Lavelle, Mark

    2009-01-01

    A ThermoFisher 'Triton' multi-collector thermal ionization mass spectrometer (MC-TIMS) was evaluated for trace and ultra-trace level isotoperatioanalysis of actinides (uranium, plutonium, and americium), fission products and geolocators (strontium, cesium, and neodymium). Total efficiencies (atoms loaded to ions detected) of up to 0.5-2% for U, Pu, and Am, and 1-30% for Sr, Cs, and Nd can be reported employing resin bead load techniques onto flat ribbon Re filaments or resin beads loaded into a millimeter-sized cavity drilled into a Re rod. This results in detection limits of <0.1 fg (10{sup 4} atoms to 10{sup 5} atoms) for {sup 239-242+244}Pu, {sup 233+236}U, {sup 241-243}Am, {sup 89,90}Sr, and {sup 134,135,137}Cs, and {le} 1 pg for natural Nd isotopes (limited by the chemical processing blank) using a secondary electron multiplier (SEM) or multiple-ion counters (MICs). Relative standard deviations (RSD) as small as 0.1% and abundance sensitivities of 1 x 10{sup 6} or better using a SEM are reported here. Precisions of RSD {approx} 0.01-0.001% using a multi-collector Faraday cup array can be achieved at sub-nanogram concentrations for strontium and neodymium and are suitable to gain crucial geolocation information. The analytical protocols reported herein are of particular value for nuclear forensic and nuclear safeguard applications.

  8. High Precision Isotopic Analysis of Actinide Bearing Materials: Performance of a New Generation of Purpose Built Actinide Multi-Collector ICPMS Instruments

    SciTech Connect

    Eiden, Gregory C.; Duffin, Andrew M.; Liezers, Martin; Ward, Jesse D.; Robinson, John W.; Hart, Garret L.; Pratt, Sandra H.; Springer, Kellen WE; Carman, April J.; Duckworth, Douglas C.

    2014-11-14

    Recently, a new class of multi-collector inductively coupled plasma mass spectrometers (MC-ICPMS) has been introduced commercially that includes detector arrays purpose built for actinide measurements. These detector arrays significantly enhance the data quality possible for applications encountered in nuclear forensics. Two such instruments are described in this paper, the NeptunePlusTM, developed by Thermo-Fisher (Bremen, Germany), and the NuPlasma2, developed by Nu Instruments (Wrexham, UK). Research results are presented that have been obtained by the authors using the first commercial NeptunePlusTM. This paper also presents performance characteristics and results for traditional liquid introduction, including a means for ultra-trace detection via electrochemical separation prior to solution nebulization, as well as solid sample introduction with femtosecond-laser ablation. We also discuss the advantages and limitations of the current systems for detection of the transient signals associated with these two methods for introducing sample into the plasma.

  9. Isotopic and criticality validation for actinide-only burnup credit

    SciTech Connect

    Fuentes, E.; Lancaster, D.; Rahimi, M.

    1997-07-01

    The techniques used for actinide-only burnup credit isotopic validation and criticality validation are presented and discussed. Trending analyses have been incorporated into both methodologies, requiring biases and uncertainties to be treated as a function of the trending parameters. The isotopic validation is demonstrated using the SAS2H module of SCALE 4.2, with the 27BURNUPLIB cross section library; correction factors are presented for each of the actinides in the burnup credit methodology. For the criticality validation, the demonstration is performed with the CSAS module of SCALE 4.2 and the 27BURNUPLIB, resulting in a validated upper safety limit.

  10. Method for adding additional isotopes to actinide-only burnup credit

    SciTech Connect

    Lancaster, D.B.; Fuentes, E.; Kang, C.

    1998-01-01

    The Topical Report on Actinide-Only Burnup Credit for Pressurized Water Reactor Spent Nuclear Fuel Packages requires computer code validation to be performed against a benchmark set of chemical assays for isotopic concentration and against a benchmark set of critical experiments for package criticality. Both sets contain all the isotopes included in the methodology. The chemical assays used include the uranium and plutonium isotopes, while the critical experiments were composed of UO{sub 2} or MOX rods, covering the isotopes in the actinide only approach. Since other isotopes are not included in the validation benchmark sets, it would be necessary to justify both the content and worth of any additional isotope for which burnup credit is to be taken (i.e., both the concentration and criticality effect of each particular isotope must be validated). A method is proposed here that can be used for any number of additional isotopes. As does the actinide-only burnup credit methodology, this method makes use of chemical assay data to establish the conservatism in the prediction of each isotope`s concentration. Criticality validation is also performed using a benchmark set of UO{sub 2} and MOX critical experiments, where the additional isotopes are validated using worth experiments to conservatively account for any uncertainty in their cross sections. The remaining requirements (analysis and modeling parameters, loading criteria generation, and physical implementation and controls) are performed exactly as described in the actinide-only burnup credit methodology. This report provides insight into each particular requirement in the new methodology.

  11. The Most Useful Actinide Isotope: Americium-241.

    ERIC Educational Resources Information Center

    Navratil, James D.; And Others

    1990-01-01

    Reviewed is the discovery, nuclear and chemical properties, and uses of an isotope of Americium (Am-241). Production and separation techniques used in industry are emphasized. Processes are illustrated in flow sheets. (CW)

  12. Literature review of United States utilities computer codes for calculating actinide isotope content in irradiated fuel

    SciTech Connect

    Horak, W.C.; Lu, Ming-Shih

    1991-12-01

    This paper reviews the accuracy and precision of methods used by United States electric utilities to determine the actinide isotopic and element content of irradiated fuel. After an extensive literature search, three key code suites were selected for review. Two suites of computer codes, CASMO and ARMP, are used for reactor physics calculations; the ORIGEN code is used for spent fuel calculations. They are also the most widely used codes in the nuclear industry throughout the world. Although none of these codes calculate actinide isotopics as their primary variables intended for safeguards applications, accurate calculation of actinide isotopic content is necessary to fulfill their function.

  13. Isotopic validation for PWR actinide-only burnup credit using Yankee Rowe data

    SciTech Connect

    1997-11-01

    Safety analyses of criticality control systems for transportation packages include an assumption that the spent nuclear fuel (SNF) loaded into the package is fresh or unirradiated. In other words, the spent fuel is assumed to have its original, as-manufactured U-235 isotopic content. The ``fresh fuel`` assumption is very conservative since the potential reactivity of the nuclear fuel is substantially reduced after being irradiated in the reactor core. The concept of taking credit for this reduction in nuclear fuel reactivity due to burnup of the fuel, instead of using the fresh fuel assumption in the criticality safety analysis, is referred to as ``Burnup Credit.`` Burnup credit uses the actual physical composition of the fuel and accounts for the net reduction of fissile material and the buildup of neutron absorbers in the fuel as it is irradiated. Neutron absorbers include actinides and other isotopes generated as a result of the fission process. Using only the change in actinide isotopes in the burnup credit criticality analysis is referred to as ``Actinide-Only Burnup Credit.`` The use of burnup credit in the design of criticality control systems enables more spent fuel to be placed in a package. Increased package capacity results in a reduced number of storage, shipping and disposal containers for a given number of SNF assemblies. Fewer shipments result in a lower risk of accidents associated with the handling and transportation of spent fuel, thus reducing both radiological and nonradiological risk to the public. This paper describes the modeling and the results of comparison between measured and calculated isotopic inventories for a selected number of samples taken from a Yankee Rowe spent fuel assembly.

  14. Systematization of actinides using cluster analysis

    SciTech Connect

    Kopyrin, A.A.; Terent`eva, T.N.; Khramov, N.N.

    1994-11-01

    A representation of the actinides in multidimensional property space is proposed for systematization of these elements using cluster analysis. Literature data for their atomic properties are used. Owing to the wide variation of published ionization potentials, medians are used to estimate them. Vertical dendograms are used for classification on the basis of distances between the actinides in atomic-property space. The properties of actinium and lawrencium are furthest removed from the main group. Thorium and mendelevium exhibit individualized properties. A cluster based on the einsteinium-fermium pair is joined by californium.

  15. Characterization of Tank 48H Samples for Alpha Activity and Actinide Isotopics

    SciTech Connect

    Hobbs, D.T.; Coleman, C.J.; Hay, M.S.

    1995-12-04

    This document reports the total alpha activity and actinide isotopic results for samples taken from Tank 48H prior to the addition of sodium tetraphenylborate and MST in Batch {number_sign}1 of the ITP process. This information used to determine the quantity of MST for Batch {number_sign}1 of the ITP process and the total actinide content in the tank for dose calculations.

  16. The feasibility of electromagnetic actinide isotope separation in the European community

    NASA Astrophysics Data System (ADS)

    van den Berg, Max; Paulsen, Arno; Berthelot, Charles; Babeliowsky, Tom

    1985-06-01

    The production of actinide reference materials in the European Community depends in those cases in which electromagnetically enriched material is required on the supply from the USA Department of Energy/Oak Ridge National Laboratory (DOE/ORNL). A study carried out by the Central Bureau for Nuclear Measurements (CBNM) is based on the needs for actinide reference materials in the European Community (EC) as determined by a separate inquiry in 1977 and examines the conditions for the installation of an electromagnetic separation facility of appropriate size in the EC. From a compilation of all the information about the production, chemical purification and isotopic enrichment of all actinide nuclides needed in the EC those cases have been assessed for which the application of electromagnetic isotope separation is at present unavoided (but feasible with the glovebox technique). Base materials for this separation process are readily available within the EC with the exception of 244Pu. The production of 244Pu was experimentally studied and extrapolated to production scale. The use of this isotope as a spike material in mass spectrometric plutonium determination is shown to be uneconomic. An electromagnetic separator adapted in capacity to EC needs was designed. Special containments and facilities for handling the radioactive actinide elements are proposed. From the cost price of this facility and operational experience of a few EC laboratories the total running costs and the specific product costs for the EC needs are calculated.

  17. Analysis of large soil samples for actinides

    DOEpatents

    Maxwell, III; Sherrod L.

    2009-03-24

    A method of analyzing relatively large soil samples for actinides by employing a separation process that includes cerium fluoride precipitation for removing the soil matrix and precipitates plutonium, americium, and curium with cerium and hydrofluoric acid followed by separating these actinides using chromatography cartridges.

  18. Flammability Analysis For Actinide Oxides Packaged In 9975 Shipping Containers

    SciTech Connect

    Laurinat, James E.; Askew, Neal M.; Hensel, Steve J.

    2013-03-21

    Packaging options are evaluated for compliance with safety requirements for shipment of mixed actinide oxides packaged in a 9975 Primary Containment Vessel (PCV). Radiolytic gas generation rates, PCV internal gas pressures, and shipping windows (times to reach unacceptable gas compositions or pressures after closure of the PCV) are calculated for shipment of a 9975 PCV containing a plastic bottle filled with plutonium and uranium oxides with a selected isotopic composition. G-values for radiolytic hydrogen generation from adsorbed moisture are estimated from the results of gas generation tests for plutonium oxide and uranium oxide doped with curium-244. The radiolytic generation of hydrogen from the plastic bottle is calculated using a geometric model for alpha particle deposition in the bottle wall. The temperature of the PCV during shipment is estimated from the results of finite element heat transfer analyses.

  19. An Approach for Validating Actinide and Fission Product Burnup Credit Criticality Safety Analyses-Isotopic Composition Predictions

    SciTech Connect

    Radulescu, Georgeta; Gauld, Ian C; Ilas, Germina; Wagner, John C

    2011-01-01

    The expanded use of burnup credit in the United States (U.S.) for storage and transport casks, particularly in the acceptance of credit for fission products, has been constrained by the availability of experimental fission product data to support code validation. The U.S. Nuclear Regulatory Commission (NRC) staff has noted that the rationale for restricting the Interim Staff Guidance on burnup credit for storage and transportation casks (ISG-8) to actinide-only is based largely on the lack of clear, definitive experiments that can be used to estimate the bias and uncertainty for computational analyses associated with using burnup credit. To address the issues of burnup credit criticality validation, the NRC initiated a project with the Oak Ridge National Laboratory to (1) develop and establish a technically sound validation approach for commercial spent nuclear fuel (SNF) criticality safety evaluations based on best-available data and methods and (2) apply the approach for representative SNF storage and transport configurations/conditions to demonstrate its usage and applicability, as well as to provide reference bias results. The purpose of this paper is to describe the isotopic composition (depletion) validation approach and resulting observations and recommendations. Validation of the criticality calculations is addressed in a companion paper at this conference. For isotopic composition validation, the approach is to determine burnup-dependent bias and uncertainty in the effective neutron multiplication factor (keff) due to bias and uncertainty in isotopic predictions, via comparisons of isotopic composition predictions (calculated) and measured isotopic compositions from destructive radiochemical assay utilizing as much assay data as is available, and a best-estimate Monte Carlo based method. This paper (1) provides a detailed description of the burnup credit isotopic validation approach and its technical bases, (2) describes the application of the approach for

  20. Neodymium isotope analyses after combined extraction of actinide and lanthanide elements from seawater and deep-sea coral aragonite

    NASA Astrophysics Data System (ADS)

    Struve, Torben; van de Flierdt, Tina; Robinson, Laura F.; Bradtmiller, Louisa I.; Hines, Sophia K.; Adkins, Jess F.; Lambelet, Myriam; Crocket, Kirsty C.; Kreissig, Katharina; Coles, Barry; Auro, Maureen E.

    2016-01-01

    Isotopes of the actinide elements protactinium (Pa), thorium (Th), and uranium (U), and the lanthanide element neodymium (Nd) are often used as complementary tracers of modern and past oceanic processes. The extraction of such elements from low abundance matrices, such as seawater and carbonate, is however labor-intensive and requires significant amounts of sample material. We here present a combined method for the extraction of Pa, Th, and Nd from 5 to 10 L seawater samples, and of U, Th, and Nd from <1 g carbonate samples. Neodymium is collected in the respective wash fractions of Pa-Th and U-Th anion exchange chromatographies. Regardless of the original sample matrix, Nd is extracted during a two-stage ion chromatography, followed by thermal ionization mass spectrometry (TIMS) analysis as NdO+. Using this combined procedure, we obtained results for Nd isotopic compositions on two GEOTRACES consensus samples from Bermuda Atlantic Time Series (BATS), which are within error identical to results for separately sampled and processed dedicated Nd samples (ɛNd = -9.20 ± 0.21 and -13.11 ± 0.21 for 15 and 2000 m water depths, respectively; intercalibration results from 14 laboratories: ɛNd = -9.19 ± 0.57 and -13.14 ± 0.57). Furthermore, Nd isotope results for an in-house coral reference material are identical within analytical uncertainty for dedicated Nd chemistry and after collection of Nd from U-Th anion exchange chromatography. Our procedure does not require major adaptations to independently used ion exchange chromatographies for U-Pa-Th and Nd, and can hence be readily implemented for a wide range of applications.

  1. Fission-product data analysis from actinide samples exposed in the Dounreay Prototype Fast Reactor

    SciTech Connect

    Murphy, B.D.; Dickens, J.K.; Walker, R.L.; Newton, T.D.

    1994-12-31

    Since 1979 a cooperative agreement has been in effect between the United States and the United Kingdom to investigate the irradiation of various actinide species placed in the core of the Dounreay Prototype Fast Reactor (PFR). The irradiated species were isotopes of thorium, protactinium, uranium, neptunium, plutonium, americium, and curium. A set of actinide samples (mg quantities) was exposed to about 490 effective full power days (EFPD) of reactor operations. The fission-product results are reported here. The actinide results will be report elsewhere.

  2. Ultratrace analysis of transuranic actinides by laser-induced fluorescence

    DOEpatents

    Miller, S.M.

    1983-10-31

    Ultratrace quantities of transuranic actinides are detected indirectly by their effect on the fluorescent emissions of a preselected fluorescent species. Transuranic actinides in a sample are coprecipitated with a host lattice material containing at least one preselected fluorescent species. The actinide either quenches or enhances the laser-induced fluorescence of the preselected fluorescent species. The degree of enhancement or quenching is quantitatively related to the concentration of actinide in the sample.

  3. Ultratrace analysis of transuranic actinides by laser-induced fluorescence

    DOEpatents

    Miller, Steven M.

    1988-01-01

    Ultratrace quantities of transuranic actinides are detected indirectly by their effect on the fluorescent emissions of a preselected fluorescent species. Transuranic actinides in a sample are coprecipitated with a host lattice material containing at least one preselected fluorescent species. The actinide either quenches or enhances the laser-induced fluorescence of the preselected fluorescent species. The degree of enhancement or quenching is quantitatively related to the concentration of actinide in the sample.

  4. Meteoritic Sulfur Isotopic Analysis

    NASA Technical Reports Server (NTRS)

    Thiemens, Mark H.

    1996-01-01

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

  5. Heterogeneous sodium fast reactor designed for transmuting minor actinide waste isotopes into plutonium fuel

    NASA Astrophysics Data System (ADS)

    Bays, Samuel Eugene

    2008-10-01

    In the past several years there has been a renewed interest in sodium fast reactor (SFR) technology for the purpose of destroying transuranic waste (TRU) produced by light water reactors (LWR). The utility of SFRs as waste burners is due to the fact that higher neutron energies allow all of the actinides, including the minor actinides (MA), to contribute to fission. It is well understood that many of the design issues of LWR spent nuclear fuel (SNF) disposal in a geologic repository are linked to MAs. Because the probability of fission for essentially all the "non-fissile" MAs is nearly zero at low neutron energies, these isotopes act as a neutron capture sink in most thermal reactor systems. Furthermore, because most of the isotopes produced by these capture reactions are also non-fissile, they too are neutron sinks in most thermal reactor systems. Conversely, with high neutron energies, the MAs can produce neutrons by fast fission. Additionally, capture reactions transmute the MAs into mostly plutonium isotopes, which can fission more readily at any energy. The transmutation of non-fissile into fissile atoms is the premise of the plutonium breeder reactor. In a breeder reactor, not only does the non-fissile "fertile" U-238 atom contribute fast fission neutrons, but also transmutes into fissile Pu-239. The fissile value of the plutonium produced by MA transmutation can only be realized in fast neutron spectra. This is due to the fact that the predominate isotope produced by MA transmutation, Pu-238, is itself not fissile. However, the Pu-238 fission cross section is significantly larger than the original transmutation parent, predominately: Np-237 and Am-241, in the fast energy range. Also, Pu-238's fission cross section and fission-to-capture ratio is almost as high as that of fissile Pu-239 in the fast neutron spectrum. It is also important to note that a neutron absorption in Pu-238, that does not cause fission, will instead produce fissile Pu-239. Given this

  6. Selection of Isotopes and Elements for Fuel Cycle Analysis

    SciTech Connect

    Steven J. Piet

    2009-04-01

    Fuel cycle system analysis simulations examine how the selection among fuel cycle options for reactors, fuel, separation, and waste management impact uranium ore utilization, waste masses and volumes, radiotoxicity, heat to geologic repositories, isotope-dependent proliferation resistance measures, and so forth. Previously, such simulations have tended to track only a few actinide and fission product isotopes, those that have been identified as important to a few criteria from the standpoint of recycled material or waste, taken as a whole. After accounting for such isotopes, the residual mass is often characterized as “fission product other” or “actinide other”. However, detailed assessment of separation and waste management options now require identification of key isotopes and residual mass for Group 1A/2A elements (Rb, Cs, Sr, Ba), inert gases (Kr, Xe), halogens (Br, I), lanthanides, transition metals, transuranic (TRU), uranium, actinide decay products. The paper explains the rationale for a list of 81 isotopes and chemical elements to better support separation and waste management assessment in dynamic system analysis models such as Verifiable Fuel Cycle Simulation (VISION)

  7. Electrochemically-Modulated Separation and Mass Spectrometric Analysis of Actinides in Difficult Matrices

    SciTech Connect

    Duckworth, Douglas C.; Liezers, Martin; Lehn, Scott A.; Douglas, Matthew

    2009-01-01

    Electrochemically-modulated separations (EMS) are a straightforward means of isolating and pre-concentrating elements for on-line mass spectrometric analysis. Elements are accumulated at electrochemical working electrodes and subsequently released into a clean carrier solution for spectroscopic analysis. EMS can employ solely aqueous chemistry and uses electrochemical redox adjustment of oxidation state to “trigger” reversible chelation / complexation. Less tractable elements (e.g., uranium and plutonium), based on redox potentials, can therefore be extracted from difficult matrices following redox adjustment and chelation with electrode chelation sites. Simply put, separation is achieved by a small voltage step that is applied to the target electrode to turn “on” or “off” the specific actinide affinity of an electrode. This separation technology employs both redox and chelation chemistry to effect highly selective accumulation of target actinides, and results in element separation, matrix elimination and analyte preconcentration. Prior studies have developed protocols and preliminary insight into EMS processes for U and Pu. U and Pu are released upon oxidation and reduction, respectively, allowing complete separation due to widely divergent redox potentials. T The coupling of EMS on-line with ICP-MS for elemental and isotopic analysis of uranium and plutonium is presented, with a focus on analytical performance metrics and applicability to safeguards and process monitoring via nondestructive analyses.

  8. APPLICATION OF ABSORPTION SPECTROSCOPY TO ACTINIDE PROCESS ANALYSIS AND MONITORING

    SciTech Connect

    Lascola, R.; Sharma, V.

    2010-06-03

    The characteristic strong colors of aqueous actinide solutions form the basis of analytical techniques for actinides based on absorption spectroscopy. Colorimetric measurements of samples from processing activities have been used for at least half a century. This seemingly mature technology has been recently revitalized by developments in chemometric data analysis. Where reliable measurements could formerly only be obtained under well-defined conditions, modern methods are robust with respect to variations in acidity, concentration of complexants and spectral interferents, and temperature. This paper describes two examples of the use of process absorption spectroscopy for Pu analysis at the Savannah River Site, in Aiken, SC. In one example, custom optical filters allow accurate colorimetric measurements of Pu in a stream with rapid nitric acid variation. The second example demonstrates simultaneous measurement of Pu and U by chemometric treatment of absorption spectra. The paper concludes with a description of the use of these analyzers to supplement existing technologies in nuclear materials monitoring in processing, reprocessing, and storage facilities.

  9. Decay analysis of pre-actinide and trans-actinide nuclei formed using various projectiles on a 197Au target at ECN*=60 MeV

    NASA Astrophysics Data System (ADS)

    Grover, Neha; Kaur, Gurvinder; Sharma, Manoj K.

    2016-01-01

    The collective clusterization approach of the dynamical cluster decay model (DCM) has been applied to study the decay of odd mass nuclei 223Pa*, 215Fr*, 227Np*, and 233Am*, which are formed in heavy-ion-induced reactions. The aim of this study is to investigate the decay pattern and related behavior of these heavy mass nuclei formed in four distinct reactions involving different projectiles (with mass A =18 -36 ) induced on 197Au target nucleus. Further, in order to analyze the role of deformations, the calculations have been done by considering spherical choice of fragmentation as well as with inclusion of quadrupole (β2) deformation. For the heavy mass region, with fission being the dominant decay mode, an attempt has been made to investigate the effect of projectile mass in reference to fission decay patterns of the pre-actinide 215Fr* nucleus and the trans-actinide nuclei 227Np* 223Pa*, 223Am* and formed at common excitation energy, ECN*=60 MeV . Besides this, the shell closure effects and the role of orientation have been explored, which suggest the presence of a noncompound nucleus process such as quasifission (QF) for the odd mass nuclei under consideration. For both the compound nucleus and the noncompound nucleus processes, the results obtained using DCM are found to have nice agreement with experimental observations. The isotopic and isobaric analysis is also worked out so as to have a comprehensive idea about the dynamics involved.

  10. Fission Fragment Yield, Cross Section and Prompt Neutron and Gamma Emission Data from Actinide Isotopes

    NASA Astrophysics Data System (ADS)

    Hambsch, F.-J.; Oberstedt, S.; Al-Adili, A.; Brys, T.; Billnert, R.; Matei, C.; Oberstedt, A.; Salvador-Castiñeira, P.; Tudora, A.; Vidali, M.

    2014-05-01

    Recent experimental investigations on major and minor actinides at the JRC-IRMM are presented. Fission-fragment distributions of isotopes with vibrational resonances in the sub-threshold fission cross section, i. e. 234,238U, have been measured. For 234U, the impact of an increased neutron multiplicity for the heavy fragments with higher incident neutron energies has been studied as observed in experiment and also recently theoretically predicted. The impact is found to be noticeable on post-neutron mass yields, which are the relevant quantities for a-priori waste assessments. The fission cross sections for 240,242Pu at threshold and in the plateau region are being investigated within the ANDES project. The results show some discrepancies to the ENDF/B-VII.1 evaluation mainly for 242Pu around 1 MeV, where the evaluation exhibits a resonance-like structure not observed so clearly in the present work. The requested target accuracy in design studies of innovative reactor concepts like Gen-IV is in the range of a few percent. In order to be able to respond to requests for measurements of prompt neutron and γ-ray emission in fission JRC-IRMM has also invested in setting up a neutron and γ-ray detector array. The neutron array is called SCINTIA and has so far been tested with 252Cf(SF). For γ-ray multiplicity and spectrum measurements of 252Cf(SF) and 235U(nth, f) lanthanum- and cerium-halide detectors were successfully used.

  11. PC/FRAM: A code for the nondestructive measurement of the isotopic composition of actinides for safeguards applications

    SciTech Connect

    Sampson, T.E.; Kelley, T.A.

    1996-12-01

    The Nuclear Safeguards Program at the Los Alamos National Laboratory has developed and fielded techniques for the gamma-ray spectrometry measurement of the isotopic composition of plutonium and other actinides for over 20 years, ever since Parker and Reilly first proposed a practical method for the measurement of the arbitrary sample. Their procedures, incorporating internal (to the measured gamma-ray spectrum) or {open_quotes}intrinsic{close_quotes} self-determination of the relative efficiency function of the sample-detector measurement system, are widely applied today. The PC/FRAM code is the most recent and most highly-developed Los Alamos code developed specifically for the nuclear safeguards applications of this technique. We will describe the measurement principles that allow accurate measurements to be taken on samples of arbitrary size, shape, and measurement geometry- and of arbitrary physical and chemical composition-through the use of known nuclear decay data (half-lives and branching intensities). Subsequently, we will describe the analysis methodology, which is driven by an easily edited parameter file that frees the user from dependence on a dedicated programmer for analyses of special cases. This methodology relies on internal gamma-ray peaks from the spectrum under analysis to self-calibrate the unknown spectrum for energy and peak shape (energy dependence of full width at half maximum (FWHM) and tailing parameters). The program uses these parameters to calculate response functions that are fit to the analysis peaks requested in the parameter file. The structure of the code and its Windows 3.1 user interface allows use with equal ease by the experienced spectroscopist or operator-level personnel in a working facility.

  12. Rapid determination of actinides in seawater samples

    DOE PAGES

    Maxwell, Sherrod L.; Culligan, Brian K.; Hutchison, Jay B.; Utsey, Robin C.; McAlister, Daniel R.

    2014-03-09

    A new rapid method for the determination of actinides in seawater samples has been developed at the Savannah River National Laboratory. The actinides can be measured by alpha spectrometry or inductively-coupled plasma mass spectrometry. The new method employs novel pre-concentration steps to collect the actinide isotopes quickly from 80 L or more of seawater. Actinides are co-precipitated using an iron hydroxide co-precipitation step enhanced with Ti+3 reductant, followed by lanthanum fluoride co-precipitation. Stacked TEVA Resin and TRU Resin cartridges are used to rapidly separate Pu, U, and Np isotopes from seawater samples. TEVA Resin and DGA Resin were used tomore » separate and measure Pu, Am and Cm isotopes in seawater volumes up to 80 L. This robust method is ideal for emergency seawater samples following a radiological incident. It can also be used, however, for the routine analysis of seawater samples for oceanographic studies to enhance efficiency and productivity. In contrast, many current methods to determine actinides in seawater can take 1–2 weeks and provide chemical yields of ~30–60 %. This new sample preparation method can be performed in 4–8 h with tracer yields of ~85–95 %. By employing a rapid, robust sample preparation method with high chemical yields, less seawater is needed to achieve lower or comparable detection limits for actinide isotopes with less time and effort.« less

  13. The Effects of Flux Spectrum Perturbation on Transmutation of Actinides: Optimizing the Production of Transcurium Isotopes

    SciTech Connect

    Hogle, Susan L; Maldonado, G Ivan; Alexander, Charles W

    2012-01-01

    This research presented herein involves the optimization of transcurium production in the High Flux Isotope Reactor at Oak Ridge National Laboratory. Due to the dependence of isotope cross sections on incoming neutron energy, the efficiency with which an isotope is transmuted is highly dependent upon the flux spectrum. There are certain energy bands in which the rate of fission of transcurium production feedstock materials is minimized, relative to the rate of non-fission absorptions. It is proposed that by perturbing the flux spectrum, it is possible to increase the amount of key isotopes, such as 249Bk and 252Cf, that are produced during a transmutation cycle, relative to the consumption of feedstock material. This optimization process is carried out by developing an iterative objective framework involving problem definition, flux spectrum and cross section analysis, simulated transmutation, and analysis of final yields and transmutation parameters. It is shown that it is possible to perturb the local flux spectrum in the transcurium target by perturbing the composition of the target. It is further shown that these perturbations are able to alter the target yields in a non-negligible way. Future work is necessary to develop the optimization framework, and identify the necessary algorithms to update the problem definition based upon progress towards the optimization goals.

  14. Progress toward accurate high spatial resolution actinide analysis by EPMA

    NASA Astrophysics Data System (ADS)

    Jercinovic, M. J.; Allaz, J. M.; Williams, M. L.

    2010-12-01

    High precision, high spatial resolution EPMA of actinides is a significant issue for geochronology, resource geochemistry, and studies involving the nuclear fuel cycle. Particular interest focuses on understanding of the behavior of Th and U in the growth and breakdown reactions relevant to actinide-bearing phases (monazite, zircon, thorite, allanite, etc.), and geochemical fractionation processes involving Th and U in fluid interactions. Unfortunately, the measurement of minor and trace concentrations of U in the presence of major concentrations of Th and/or REEs is particularly problematic, especially in complexly zoned phases with large compositional variation on the micro or nanoscale - spatial resolutions now accessible with modern instruments. Sub-micron, high precision compositional analysis of minor components is feasible in very high Z phases where scattering is limited at lower kV (15kV or less) and where the beam diameter can be kept below 400nm at high current (e.g. 200-500nA). High collection efficiency spectrometers and high performance electron optics in EPMA now allow the use of lower overvoltage through an exceptional range in beam current, facilitating higher spatial resolution quantitative analysis. The U LIII edge at 17.2 kV precludes L-series analysis at low kV (high spatial resolution), requiring careful measurements of the actinide M series. Also, U-La detection (wavelength = 0.9A) requires the use of LiF (220) or (420), not generally available on most instruments. Strong peak overlaps of Th on U make highly accurate interference correction mandatory, with problems compounded by the ThMIV and ThMV absorption edges affecting peak, background, and interference calibration measurements (especially the interference of the Th M line family on UMb). Complex REE bearing phases such as monazite, zircon, and allanite have particularly complex interference issues due to multiple peak and background overlaps from elements present in the activation

  15. Analysis of the Gas Core Actinide Transmutation Reactor (GCATR)

    NASA Technical Reports Server (NTRS)

    Clement, J. D.; Rust, J. H.

    1977-01-01

    Design power plant studies were carried out for two applications of the plasma core reactor: (1) As a breeder reactor, (2) As a reactor able to transmute actinides effectively. In addition to the above applications the reactor produced electrical power with a high efficiency. A reactor subsystem was designed for each of the two applications. For the breeder reactor, neutronics calculations were carried out for a U-233 plasma core with a molten salt breeding blanket. A reactor was designed with a low critical mass (less than a few hundred kilograms U-233) and a breeding ratio of 1.01. The plasma core actinide transmutation reactor was designed to transmute the nuclear waste from conventional LWR's. The spent fuel is reprocessed during which 100% of Np, Am, Cm, and higher actinides are separated from the other components. These actinides are then manufactured as oxides into zirconium clad fuel rods and charged as fuel assemblies in the reflector region of the plasma core actinide transmutation reactor. In the equilibrium cycle, about 7% of the actinides are directly fissioned away, while about 31% are removed by reprocessing.

  16. ACTINIDE REMOVAL PROCESS SAMPLE ANALYSIS, CHEMICAL MODELING, AND FILTRATION EVALUATION

    SciTech Connect

    Martino, C.; Herman, D.; Pike, J.; Peters, T.

    2014-06-05

    Filtration within the Actinide Removal Process (ARP) currently limits the throughput in interim salt processing at the Savannah River Site. In this process, batches of salt solution with Monosodium Titanate (MST) sorbent are concentrated by crossflow filtration. The filtrate is subsequently processed to remove cesium in the Modular Caustic Side Solvent Extraction Unit (MCU) followed by disposal in saltstone grout. The concentrated MST slurry is washed and sent to the Defense Waste Processing Facility (DWPF) for vitrification. During recent ARP processing, there has been a degradation of filter performance manifested as the inability to maintain high filtrate flux throughout a multi-batch cycle. The objectives of this effort were to characterize the feed streams, to determine if solids (in addition to MST) are precipitating and causing the degraded performance of the filters, and to assess the particle size and rheological data to address potential filtration impacts. Equilibrium modelling with OLI Analyzer{sup TM} and OLI ESP{sup TM} was performed to determine chemical components at risk of precipitation and to simulate the ARP process. The performance of ARP filtration was evaluated to review potential causes of the observed filter behavior. Task activities for this study included extensive physical and chemical analysis of samples from the Late Wash Pump Tank (LWPT) and the Late Wash Hold Tank (LWHT) within ARP as well as samples of the tank farm feed from Tank 49H. The samples from the LWPT and LWHT were obtained from several stages of processing of Salt Batch 6D, Cycle 6, Batch 16.

  17. Plutonium Isotopic Gamma-Ray Analysis

    1992-01-08

    The MGA8 (Multiple Group Analysis) program determines the relative abundances of plutonium and other actinide isotopes in different materials. The program analyzes spectra taken of such samples using a 4096-channel germanium (Ge) gamma-ray spectrometer. The code can be run in a one or two detector mode. The first spectrum, which is required and must be taken at a gain of 0.075 Kev/channel with a high resolution planar detector, contains the 0-300 Kev energy region. Themore » second spectrum, which is optional, must be taken at a gain of 0.25 Kev/channel; it becomes important when analyzing high burnup samples (concentration of Pu241 greater than one percent). Isotopic analysis precisions of one percent or better can be obtained, and no calibrations are required. The system also measures the abundances of U235, U238, Np237, and Am241. A special calibration option is available to perform a one-time peak-shape characterization when first using a new detector system.« less

  18. Calculation of the fission-fragment yields of the pre-actinide nuclei by the example of the natPb isotopes

    NASA Astrophysics Data System (ADS)

    Maslyuk, V. T.; Parlag, O. A.; Lendyel, O. I.; Marynets, T. I.; Romanyuk, M. I.; Shevchenko, O. S.; Ranyuk, Ju. Ju.; Dovbnya, A. M.

    2016-11-01

    The calculations of the fission-fragment yields (mass and charge spectra) carried out within the frameworks of the proposed statistical method for the pre-actinide nuclei by the example of natPb (20 isotopes) are presented. The role of neutron shells with N = 50 and N = 82 in realizing the single- and double-humped shape of the fission-fragment yields, respectively, for the neutron-deficit and neutron-excess Pb isotopes has been investigated. An explanation of the experimental results on the natPb fission was performed taking into account transformations to the ensemble of the long- and short-lived nuclear fragments.

  19. Isotope tracer studies of diffusion in silicates and of geological transport processes using actinide elements

    SciTech Connect

    Wasserburg, G.J.

    1992-01-01

    The following are reported: high abundance sensitivity mass spectrometer for U-Th studies; [sup 238]U-[sup 230]Th disequilibrium in recent lavas from Iceland; water-rock interaction from U-Th studies; resonance ionization mass spectrometry of Os and Ti isotopes; and self-diffusion of Mg.

  20. Dynamical approach to isotopic-distribution of fission fragments from actinide nuclei

    NASA Astrophysics Data System (ADS)

    Ishizuka, Chikako; Chiba, Satoshi; Karpov, Alexander V.; Aritomo, Yoshihiro

    2016-06-01

    Measurements of the isotope distribution of fission fragments, often denoted as the primary fission yield (pre-neutron yield) or independent fission yield (post-neutron yield) are still challenging at low excitation energies, so that it is important to investigate it within a theory. Such quantities are vital for applications as well. In this study, fragment distributions from the fission of U isotopes at low excitation energies are studied using a dynamical model. The potential energy surface is derived from the two center shell model including the shell and pairing corrections. In order to calculate the charge distribution of fission fragments, we introduce a new parameter ηZ as the charge asymmetry, in addition to three parameters describing a nuclear shape, z as the distance between two centers of mass, δ as fragment deformation, and ηA as the mass asymmetry. Using this model, we calculated the isotopic distribution of 236U for the n-induced process 235U + n → 236U at low excitation energies. As a result, we found that the current model can well reproduce isotopic fission-fragment distribution which can be compared favorably with major libraries.

  1. Isotopic Analysis and Evolved Gases

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

  2. Isotope Tracer Studies of Diffusion in Sillicates and of Geological Transport Processes Using Actinide Elements

    SciTech Connect

    Wasserburg, Gerald J

    2008-07-31

    The objectives were directed toward understanding the transport of chemical species in nature, with particular emphasis on aqueous transport in solution, in colloids, and on particles. Major improvements in measuring ultra-low concentrations of rare elements were achieved. We focused on two areas of studies: (1) Field, laboratory, and theoretical studies of the transport and deposition of U, Th isotopes and their daughter products in natural systems; and (2) Study of calcium isotope fractionation effects in marine carbonates and in carbonates precipitated in the laboratory, under controlled temperature, pH, and rates of precipitation. A major study of isotopic fractionation of Ca during calcite growth from solution has been completed and published. It was found that the isotopic shifts widely reported in the literature and attributed to biological processes are in fact due to a small equilibrium fractionation factor that is suppressed by supersaturation of the solution. These effects were demonstrated in the laboratory and with consideration of the solution conditions in natural systems, where [Ca{sup 2+}] >> [CO{sub 3}{sup 2-}] + [HCO{sub 3}{sup -}]. The controlling rate is not the diffusion of Ca, as was earlier proposed, but rather the rate of supply of [CO{sub 3}{sup 2-}] ions to the interface. This now opens the issues of isotopic fractionation of many elements to a more physical-chemical approach. The isotopic composition of Ca {Delta}({sup 44}Ca/{sup 40}Ca) in calcite crystals has been determined relative to that in the parent solutions by TIMS using a double spike. Solutions were exposed to an atmosphere of NH{sub 3} and CO{sub 2}, provided by the decomposition of (NH4)2CO3. Alkalinity, pH, and concentrations of CO{sub 3}{sup 2-}, HCO{sub 3}{sup -}, and CO{sub 2} in solution were determined. The procedures permitted us to determine {Delta}({sup 44}Ca/{sup 40}Ca) over a range of pH conditions, with the associated ranges of alkalinity. Two solutions with

  3. Isotope Trace Studies of Diffusion in Silicates and of Geological Transport Processes Using Actinide Elements

    SciTech Connect

    Prof. G. J. Wasserburg

    2001-01-19

    Over the past year we have competed two studies of Os concentration and isotopic composition in rivers from the Himalayan uplift and in hydrothermal fluids from the Juan de Fuca Ridge. Both of these studies have been published. We have completed a study of paleo-climate in Soreq Cave, Israel, and have expanded our studies of the transport of U-Th through riverine and estuarine environments. We are completing two studies of weathering and transport in the vadose in two very different environments--one a tropical regime with a deep laterite profile and the other a northern arboreal forest with only a thin weathering zone. We have begun a new study of U-Th in aquifers with low water velocity.

  4. Consistent Data Assimilation of Actinide Isotopes: 235U and 239Pu

    SciTech Connect

    G. Palmiottti; H. Hiruta; M. Salvatores

    2011-09-01

    In this annual report we illustrate the methodology of the consistent data assimilation that allows to use the information coming from integral experiments for improving the basic nuclear parameters used in cross section evaluation. A series of integral experiments were analyzed using the EMPIRE evaluated files for {sup 235}U, {sup 238}U, and {sup 239}Pu. Inmost cases the results have shown quite large worse results with respect to the corresponding existing evaluations available for ENDF/B-VII. The observed discrepancies between calculated and experimental results were used in conjunction with the computed sensitivity coefficients and covariance matrix for nuclear parameters in a consistent data assimilation. Only the GODIVA and JEZEBEL experimental results were used, in order to exploit information relative to the isotope of interest that are, in this particular case: {sup 235}U and {sup 239}Pu. The results obtained by the consistent data assimilation indicate that with reasonable modifications (mostly within the initial standard deviation) it is possible to eliminate the original large discrepancies on the K{sub eff} of the two critical configurations. However, some residual discrepancy remains for a few fission spectral indices that are, most likely, to be attributed to the detector cross sections.

  5. Rapid determination of actinides in asphalt samples

    DOE PAGES

    Maxwell, Sherrod L.; Culligan, Brian K.; Hutchison, Jay B.

    2014-01-12

    A new rapid method for the determination of actinides in asphalt samples has been developed that can be used in emergency response situations or for routine analysis If a radiological dispersive device (RDD), Improvised Nuclear Device (IND) or a nuclear accident such as the accident at the Fukushima Nuclear Power Plant in March, 2011 occurs, there will be an urgent need for rapid analyses of many different environmental matrices, including asphalt materials, to support dose mitigation and environmental clean up. The new method for the determination of actinides in asphalt utilizes a rapid furnace step to destroy bitumen and organicsmore » present in the asphalt and sodium hydroxide fusion to digest the remaining sample. Sample preconcentration steps are used to collect the actinides and a new stacked TRU Resin + DGA Resin column method is employed to separate the actinide isotopes in the asphalt samples. The TRU Resin plus DGA Resin separation approach, which allows sequential separation of plutonium, uranium, americium and curium isotopes in asphalt samples, can be applied to soil samples as well.« less

  6. Rapid determination of actinides in asphalt samples

    SciTech Connect

    Maxwell, Sherrod L.; Culligan, Brian K.; Hutchison, Jay B.

    2014-01-12

    A new rapid method for the determination of actinides in asphalt samples has been developed that can be used in emergency response situations or for routine analysis If a radiological dispersive device (RDD), Improvised Nuclear Device (IND) or a nuclear accident such as the accident at the Fukushima Nuclear Power Plant in March, 2011 occurs, there will be an urgent need for rapid analyses of many different environmental matrices, including asphalt materials, to support dose mitigation and environmental clean up. The new method for the determination of actinides in asphalt utilizes a rapid furnace step to destroy bitumen and organics present in the asphalt and sodium hydroxide fusion to digest the remaining sample. Sample preconcentration steps are used to collect the actinides and a new stacked TRU Resin + DGA Resin column method is employed to separate the actinide isotopes in the asphalt samples. The TRU Resin plus DGA Resin separation approach, which allows sequential separation of plutonium, uranium, americium and curium isotopes in asphalt samples, can be applied to soil samples as well.

  7. Analysis of hydrogen isotope mixtures

    DOEpatents

    Villa-Aleman, Eliel

    1994-01-01

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

  8. FY2010 Annual Report for the Actinide Isomer Detection Project

    SciTech Connect

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Miller, Erin A.; Hatarik, R.

    2011-01-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for Special Nuclear Materials (SNM). Future work will include a follow-up measurement scheduled for December 2010 at LBNL. Lessons learned from the July 2010 measurements will be incorporated into these new measurements. Analysis of both the July and December experiments will be completed in a few months. A research paper to be submitted to a peer-reviewed journal will be drafted if the conclusions from the measurements warrant publication.

  9. MGA: A gamma-ray spectrum analysis code for determining plutonium isotopic abundances. Volume 3, FORTRAN listing of the GA code

    SciTech Connect

    Gunnink, R

    1991-09-01

    Nondestructive measurements of x-ray and gamma-ray emissions can be used to determine the abundances of various actinides in a sample. Volume 1 of this report describes the methods and algorithms we have developed to determine the relative isotopic abundances of actinides in a sample, by analyzing gamma-ray spectra obtained using germanium detector systems. Volume 2 is a guide to using the MGA (Multiple Group Analysis) computer program we have written to perform plutonium isotopic analyses. This report contains a listing of the FORTRAN instructions of the code.

  10. Managing Inventories of Heavy Actinides

    SciTech Connect

    Wham, Robert M; Patton, Bradley D

    2011-01-01

    The Department of Energy (DOE) has stored a limited inventory of heavy actinides contained in irradiated targets, some partially processed, at the Savannah River Site (SRS) and Oak Ridge National Laboratory (ORNL). The 'heavy actinides' of interest include plutonium, americium, and curium isotopes; specifically 242Pu and 244Pu, 243Am, and 244/246/248Cm. No alternate supplies of these heavy actinides and no other capabilities for producing them are currently available. Some of these heavy actinide materials are important for use as feedstock for producing heavy isotopes and elements needed for research and commercial application. The rare isotope 244Pu is valuable for research, environmental safeguards, and nuclear forensics. Because the production of these heavy actinides was made possible only by the enormous investment of time and money associated with defense production efforts, the remaining inventories of these rare nuclear materials are an important part of the legacy of the Nuclear Weapons Program. Significant unique heavy actinide inventories reside in irradiated Mark-18A and Mark-42 targets at SRS and ORNL, with no plans to separate and store the isotopes for future use. Although the costs of preserving these heavy actinide materials would be considerable, for all practical purposes they are irreplaceable. The effort required to reproduce these heavy actinides today would likely cost billions of dollars and encompass a series of irradiation and chemical separation cycles for at least 50 years; thus, reproduction is virtually impossible. DOE has a limited window of opportunity to recover and preserve these heavy actinides before they are disposed of as waste. A path forward is presented to recover and manage these irreplaceable National Asset materials for future use in research, nuclear forensics, and other potential applications.

  11. Safe actinide disposition in molten salt reactors

    SciTech Connect

    Gat, U.

    1997-03-01

    Safe molten salt reactors (MSR) can readily accommodate the burning of all fissile actinides. Only minor compromises associated with plutonium are required. The MSRs can dispose safely of actinides and long lived isotopes to result in safer and simpler waste. Disposing of actinides in MSRs does increase the source term of a safety optimized MSR. It is concluded that the burning and transmutation of actinides in MSRs can be done in a safe manner. Development is needed for the processing to handle and separate the actinides. Calculations are needed to establish the neutron economy and the fuel management. 9 refs.

  12. Production and measurement of minor actinides in the commercial fuel cycle

    SciTech Connect

    Stanbro, W.D.

    1997-03-01

    The minor actinide elements, particularly neptunium and americium, are produced as a normal byproduct of the operation of thermal power reactors. Because of the existence of long-lived isotopes of these elements, they constitute the major sources of the residual radiation in spent fuel or in wastes resulting from reprocessing. This has led to examinations by some countries of the possibility of separating the minor actinides from waste products. The papers found in this report address the production of minor actinides in common thermal power reactors as well as approaches to measure these materials in various media. The first paper in this volume, {open_quotes}Production of Minor Actinides in the Commercial Fuel Cycle,{close_quotes} uses calculations with the ORIGEN2 reactor and decay code to estimate the amounts of minor actinides in spent fuel and separated plutonium as a function of reactor irradiation and the time after discharge. The second paper, {open_quotes}Destructive Assay of Minor Actinides,{close_quotes} describes a number of promising approaches for the chemical analysis of minor actinides in the various forms in which they are found at reprocessing plants. The next paper, {open_quotes}Hybrid KED/XRF Measurement of Minor Actinides in Reprocessing Plants,{close_quotes} uses the results of a simulation model to examine the possible applications of the hybrid KED/XRF instrument to the determination of minor actinides in some of the solutions found in reprocessing plants. In {open_quotes}Calorimetric Assay of Minor Actinides,{close_quotes} the authors show some possible extensions of this powerful technique beyond the normal plutonium assays to include the minor actinides. Finally, the last paper in this volume, {open_quotes}Environment Measurements of Transuranic Nuclides,{close_quotes} discusses what is known about the levels of the minor actinides in the environment and ways to analyze for these materials in environmental matrices.

  13. Actinides-1981

    SciTech Connect

    Not Available

    1981-09-01

    Abstracts of 134 papers which were presented at the Actinides-1981 conference are presented. Approximately half of these papers deal with electronic structure of the actinides. Others deal with solid state chemistry, nuclear physic, thermodynamic properties, solution chemistry, and applied chemistry.

  14. Calcium isotope analysis by mass spectrometry.

    PubMed

    Boulyga, Sergei F

    2010-01-01

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

  15. Model Analysis of Low-Level Actinide Waste Disposal in Deep Boreholes

    NASA Astrophysics Data System (ADS)

    Glascoe, L. G.; Wolfsberg, A. V.

    2001-12-01

    Deep borehole disposal is considered as a possible mechanism for the safe removal of Greater Than Class C (GTCC) low level actinide waste (Am-241, Pu-239, and Pu-238). Of the three actinides in GTCC waste, only Pu-239 has a half-life greater than 500 years and, thus, will have the longest environmental presence. However, Am-241 and Pu-238 have the potential to create most of the heat associated with GTCC waste disposal in deep boreholes. Therefore, this study considers the nonisothermal release and subsequent migration toward a pumping well of the most persistent radionuclide, Pu-239, from a deep emplacement borehole taking into account the heat created by decay of all three actinides. The Finite-Element Heat- and Mass-Transfer code, FEHM, is employed to simulate three-dimensional, non-isothermal flow and solute transport using particle tracking. Multiple scenarios considering various source emplacement depths, aquifer properties, and hydraulic conditions are evaluated in a sensitivity analysis that seeks to demonstrate competing and offsetting processes affecting the concentration of Pu-239 in the pumped well 100 m down gradient from the borehole source. In general, lower groundwater fluxes, associated with lower gradients and/or lower aquifer permeabilities, lead to less dissolution of the source waste. However, conditions of decreasing groundwater flux also create larger sized capture zones by the pumping well, thus escalating the likelihood of pumping contaminants originating from a source deeper than the pumping well. Retardation by sorption of Pu-239, both in alluvial aquifers and following diffusion from fractures in a tuff aquifer, plays an important role both in delaying radionuclide migration and in reducing the peak aqueous concentration at the pumping well. This work was performed under the auspices of the U.S. Department of Energy by University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48. This work was

  16. Amino acid isotopic analysis in agricultural systems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A relatively new approach to stable isotopic analysis—referred to as compound-specific isotopic analysis (CSIA)—has emerged, centering on the measurement of 15N:14N ratios in amino acids (glutamic acid and phenylalanine). CSIA has recently been used to generate trophic position estimates among anima...

  17. Minor Actinides Recycling in PWRs

    SciTech Connect

    Delpech, M.; Golfier, H.; Vasile, A.; Varaine, F.; Boucher, L.; Greneche, D.

    2006-07-01

    Recycling of minor actinides in current and near future PWR is considered as one of the options of the general waste management strategy. This paper presents the analysis of this option both from the core physics and fuel cycle point of view. A first indicator of the efficiency of different neutron spectra for transmutation purposes is the capture to fission cross sections ratio which is less favourable by a factor between 5 to 10 in PWRs compared to fast reactors. Another indicator presented is the production of high ranking isotopes like Curium, Berkelium or Californium in the thermal or epithermal spectrum conditions of PWR cores by successive neutron captures. The impact of the accumulation of this elements on the fabrication process of such PWR fuels strongly penalizes this option. The main constraint on minor actinides loadings in PWR (or fast reactors) fuels are related to their direct impact (or the impact of their transmutation products) on the reactivity coefficients, the reactivity control means and the core kinetics parameters. The main fuel cycle physical parameters like the neutron source, the alpha decay power, the gamma and neutrons dose rate and the criticality aspects are also affected. Recent neutronic calculations based on a reference core of the Evolutionary Pressurized Reactor (EPR), indicates typical maximum values of 1 % loadings. Different fuel design options for minor actinides transmutation purposes in PWRs are presented: UOX and MOX, homogeneous and heterogeneous assemblies. In this later case, Americium loading is concentrated in specific pins of a standard UOX assembly. Recycling of Neptunium in UOX and MOX fuels was also studied to improve the proliferation resistance of the fuel. The impact on the core physics and penalties on Uranium enrichment were underlined in this case. (authors)

  18. Systematic Analysis of Uranium Isotopes

    SciTech Connect

    Young, Phillip G.; Chadwick, Mark B.; MacFarlane, Robert E.; Madland, David G.; Moeller, Peter; Wilson, William B.; Talou, Patrick; Kawano, Toshihiko

    2005-05-24

    We describe recent nuclear model calculations and evaluations of neutron reactions on the uranium isotopes 232-241U in the keV to 30-MeV energy range. This work makes use of extensive sets of measurements for fission, elastic, inelastic (n,xn) and capture, as well as fission probability data. The 235U(n.f) standard cross section was revised, and the fission cross sections of the uranium isotopes, as well as 237Np and 239Pu, were updated using the revised standard. Nuclear reaction model calculations were performed for the whole suite of uranium isotopes to allow us to take advantage of the systematical properties from isotope-to-isotope, which is especially useful for nuclides where few measurements exist. In addition to improving the neutron cross sections and energy-angle distributions, new prompt fission neutron spectra and prompt/delayed neutron multiplicity evaluations are included for several isotopes. These evaluations are among the pre-ENDF/B-VII evaluations that are currently being considered for the new ENDF file. A companion paper in this Conference by MacFarlane describes critical-assembly integral data testing results for U isotopes.

  19. Systematic Analysis of Uranium Isotopes

    NASA Astrophysics Data System (ADS)

    Young, Phillip G.; Chadwick, Mark B.; MacFarlane, Robert E.; Madland, David G.; Möller, Peter; Wilson, William B.; Talou, Patrick; Kawano, Toshihiko

    2005-05-01

    We describe recent nuclear model calculations and evaluations of neutron reactions on the uranium isotopes 232-241U in the keV to 30-MeV energy range. This work makes use of extensive sets of measurements for fission, elastic, inelastic, (n,xn) and capture, as well as fission probability data. The 235U(n.f) standard cross section was revised, and the fission cross sections of the uranium isotopes, as well as 237Np and 239Pu, were updated using the revised standard. Nuclear reaction model calculations were performed for the whole suite of uranium isotopes to allow us to take advantage of the systematical properties from isotope-to-isotope, which is especially useful for nuclides where few measurements exist. In addition to improving the neutron cross sections and energy-angle distributions, new prompt fission neutron spectra and prompt/delayed neutron multiplicity evaluations are included for several isotopes. These evaluations are among the pre-ENDF/B-VII evaluations that are currently being considered for the new ENDF file. A companion paper in this Conference by MacFarlane describes critical-assembly integral data testing results for U isotopes.

  20. Monte Carlo isotopic inventory analysis for complex nuclear systems

    NASA Astrophysics Data System (ADS)

    Phruksarojanakun, Phiphat

    . Potential applications of MCise include molten salt fueled reactors and liquid breeders in fusion blankets. As an example, the inventory analysis of a liquid actinide fuel in the In-Zinerator, a sub-critical power reactor driven by a fusion source, is examined. The result reassures MCise as a reliable tool for inventory analysis of complex nuclear systems.

  1. Status of nuclear data for actinides

    SciTech Connect

    Guzhovskii, B.Y.; Gorelov, V.P.; Grebennikov, A.N.

    1995-10-01

    Nuclear data required for transmutation problem include many actinide nuclei. In present paper the analysis of neutron fission, capture, (n,2n) and (n,3n) reaction cross sections at energy region from thermal point to 14 MeV was carried out for Th, Pa, U, Np, Pu, Am and Cm isotops using modern evaluated nuclear data libraries and handbooks of recommended nuclear data. Comparison of these data indicates on substantial discrepancies in different versions of files, that connect with quality and completeness of original experimental data.

  2. Identification and Speciation of Actinides in the Environment

    NASA Astrophysics Data System (ADS)

    Degueldre, Claude

    All actinide isotopes are radioactive. Since the middle of the last century, new bactinide and transactinide isotopes have been artificially produced and the use of several of the naturally occurring actinide isotopes has increased. This production is due to the nuclear power industry and the military fabrication and use of nuclear weapons. These activities have created anxiety about the introduction of actinide elements into the environment. Consequently, environmental systems that contain or are exploited for natural actinides, or, are potentially contaminated by anthropogenic actinides, must be investigated. The analytical techniques introduced in this chapter are used, after sampling when required, to identify and quantify the actinide isotopes and to determine the species in which they are present.

  3. Isotope tracer studies of diffusion in silicates and of geological transport processes using actinide elements. Progress report

    SciTech Connect

    Wasserburg, G.J.

    1992-12-31

    The following are reported: high abundance sensitivity mass spectrometer for U-Th studies; {sup 238}U-{sup 230}Th disequilibrium in recent lavas from Iceland; water-rock interaction from U-Th studies; resonance ionization mass spectrometry of Os and Ti isotopes; and self-diffusion of Mg.

  4. Isotope tracer studies of diffusion in silicates and of geological transport processes in aqueous systems using actinide elements

    SciTech Connect

    Wasserburg, G.J.

    1999-02-01

    This research program has moved ahead with success in several areas. The isotopic composition of osmium in seawater and in some rivers was directly determined for the first time. The concentration of osmium was first estimated in both seawater and rivers. A major effort was directed toward the transport of the U,Th series nuclides in a watershed in Sweden. A serious effort was directed at developing a transport model for the U,Th series nuclides in aquifers. A detailed study of {sup 238}U-{sup 230}Th dating of a cave in Israel was carried out collaboratively. The Os-Re fractionation between silicate and sulfide melts were determined in MORB basalts and glasses and the isotopic composition of Os was measured in sulfide samples.

  5. Isoscaling and fission modes in the yields of the Kr and Xe isotopes from photofission of actinides

    NASA Astrophysics Data System (ADS)

    Drnoyan, J.; Zhemenik, V. I.; Mishinsky, G. V.

    2016-05-01

    Yields of Kr and Xe isotopes in photofission of 232Th, 238U, 237Np, 244Pu, 243Am, and 248Cm were tested for isoscaling dependence. Isoscaling for Kr is revealed. For Xe, isoscaling is found to be affected by the STI and STII fission modes governed by the N = 82 and N = 88 neutron shells. The work was performed at the Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research (JINR).

  6. Compound specific isotope analysis of organophosphorus pesticides.

    PubMed

    Wu, Langping; Yao, Jun; Trebse, Polonca; Zhang, Ning; Richnow, Hans H

    2014-09-01

    Compound-specific isotope analysis (CSIA) has been established as a tool to study the environmental fate of a wide range of contaminants. In this study, CSIA was developed to analyse the stable carbon isotope signatures of the widely used organophosphorus pesticides: dichlorvos, omethoate and dimethoate. The linearity of the GC-C-IRMS system was tested for target pesticides and led to an acceptable isotope composition within the uncertainty of the instrument. In order to assess the accuracy of the developed method, the effect of the evaporation procedure on measured carbon isotope composition (δ(13)C) values was studied and showed that concentration by evaporation of solvents had no significant isotope effect. The CSIA was then applied to investigate isotope fractionation of the hydrolysis and photolysis of selected pesticides. The carbon isotope fractionation of tested pesticides was quantified by the Rayleigh model, which revealed a bulk enrichment factor (ε) of -0.2±0.1‰ for hydrolysis of dichlorvos, -1.0±0.1‰ and -3.7±1.1‰ for hydrolysis and photolysis of dimethoate respectively. This study is a first step towards the application of CSIA to trace the transport and degradation of organophosphorus pesticides in the environment.

  7. Analysis on fuel breeding capability of FBR core region based on minor actinide recycling doping

    NASA Astrophysics Data System (ADS)

    Permana, Sidik; Novitrian, Waris, Abdul; Ismail, Suzuki, Mitsutoshi; Saito, Masaki

    2014-09-01

    Nuclear fuel breeding based on the capability of fuel conversion capability can be achieved by convertion rasio of some fertile materials into fissile materials during nuclear reaction processes such as main fissile materials of U-233, U-235, Pu-239 and Pu-241 and for fertile materials of Th-232, U-238, and Pu-240 as well as Pu-238. Minor actinide (MA) loading option which consists of neptunium, americium and curium will gives some additional contribution from converted MA into plutonium such as conversion Np-237 into Pu-238 and it's produced Pu-238 converts to Pu-239 via neutron capture. Increasing composition of Pu-238 can be used to produce fissile material of Pu-239 as additional contribution. Trans-uranium (TRU) fuel (Mixed fuel loading of MOX (U-Pu) and MA composition) and mixed oxide (MOX) fuel compositions are analyzed for comparative analysis in order to show the effect of MA to the plutonium productions in core in term of reactor criticality condition and fuel breeding capability. In the present study, neptunium (Np) nuclide is used as a representative of MAin trans-uranium (TRU) fuel composition as Np-MOX fuel type. It was loaded into the core region gives significant contribution to reduce the excess reactivity in comparing to mixed oxide (MOX) fuel and in the same time it contributes to increase nuclear fuel breeding capability of the reactor. Neptunium fuel loding scheme in FBR core region gives significant production of Pu-238 as fertile material to absorp neutrons for reducing excess reactivity and additional contribution for fuel breeding.

  8. Analysis on fuel breeding capability of FBR core region based on minor actinide recycling doping

    SciTech Connect

    Permana, Sidik; Novitrian,; Waris, Abdul; Ismail; Suzuki, Mitsutoshi; Saito, Masaki

    2014-09-30

    Nuclear fuel breeding based on the capability of fuel conversion capability can be achieved by conversion ratio of some fertile materials into fissile materials during nuclear reaction processes such as main fissile materials of U-233, U-235, Pu-239 and Pu-241 and for fertile materials of Th-232, U-238, and Pu-240 as well as Pu-238. Minor actinide (MA) loading option which consists of neptunium, americium and curium will gives some additional contribution from converted MA into plutonium such as conversion Np-237 into Pu-238 and it's produced Pu-238 converts to Pu-239 via neutron capture. Increasing composition of Pu-238 can be used to produce fissile material of Pu-239 as additional contribution. Trans-uranium (TRU) fuel (Mixed fuel loading of MOX (U-Pu) and MA composition) and mixed oxide (MOX) fuel compositions are analyzed for comparative analysis in order to show the effect of MA to the plutonium productions in core in term of reactor criticality condition and fuel breeding capability. In the present study, neptunium (Np) nuclide is used as a representative of MAin trans-uranium (TRU) fuel composition as Np-MOX fuel type. It was loaded into the core region gives significant contribution to reduce the excess reactivity in comparing to mixed oxide (MOX) fuel and in the same time it contributes to increase nuclear fuel breeding capability of the reactor. Neptunium fuel loading scheme in FBR core region gives significant production of Pu-238 as fertile material to absorp neutrons for reducing excess reactivity and additional contribution for fuel breeding.

  9. Thermal analysis for fuel handling system for sodium cooled reactor considering minor actinide-bearing metal fuel.

    SciTech Connect

    Chikazawa, Y.; Grandy, C.; Nuclear Engineering Division

    2009-03-01

    The Advanced Burner Reactor (ABR) is one of the components of the Global Nuclear Energy Partnership (GNEP) used to close the fuel cycle. ABR is a sodium-cooled fast reactor that is used to consume transuranic elements resulting from the reprocessing of light water reactor spent nuclear fuel. ABR-1000 [1000 MW(thermal)] is a fast reactor concept created at Argonne National Laboratory to be used as a reference concept for various future trade-offs. ABR-1000 meets the GNEP goals although it uses what is considered base sodium fast reactor technology for its systems and components. One of the considerations of any fast reactor plant concept is the ability to perform fuel-handling operations with new and spent fast reactor fuel. The transmutation fuel proposed as the ABR fuel has a very little experience base, and thus, this paper investigates a fuel-handling concept and potential issues of handling fast reactor fuel containing minor actinides. In this study, two thermal analyses supporting a conceptual design study on the ABR-1000 fuel-handling system were carried out. One analysis investigated passive dry spent fuel storage, and the other analysis investigated a fresh fuel shipping cask. Passive dry storage can be made suitable for the ABR-1000 spent fuel storage with sodium-bonded metal fuel. The thermal analysis shows that spent fast reactor fuel with a decay heat of 2 kW or less can be stored passively in a helium atmosphere. The 2-kW value seems to be a reasonable and practical level, and a combination of reasonably-sized in-sodium storage followed by passive dry storage could be a candidate for spent fuel storage for the next-generation sodium-cooled reactor with sodium-bonded metal fuel. Requirements for the shipping casks for minor actinide-bearing fuel with a high decay heat level are also discussed in this paper. The shipping cask for fresh sodium-cooled-reactor fuel should be a dry type to reduce the reaction between residual moisture on fresh fuel and the

  10. Preliminary Calculational Analysis of the Actinide Samples from FP-4 Exposed in the Dounreay Prototype Fast Reactor

    SciTech Connect

    Murphy, B.D.

    1993-01-01

    This report discusses the current status of results from an extensive experiment on the irradiation of selected actinides in a fast reactor. These actinides ranged from thorium to curium. They were irradiated in the core of the Dounreay Prototype Fast Reactor. Rates for depletion, transmutation, and fission-product generation were experimentally measured, and, in turn, were calculated using current cross-section and fission-yield data. Much of the emphasis is on the comparison between experimental and calculated values for both actinide and fission-product concentrations. Some of the discussion touches on the adequacy of current cross-section and fission-yield data. However, the main purposes of the report are (1) to collect in one place the most recent experimental and calculated data, (2) to discuss the comparisons between the experimental and calculated results, (3) to discuss each sample that was irradiated giving details of any adjustments needed or specific problems encountered, and (4) to give a chronology of the analysis as it pertained to the set of samples (referred to as FP-4 samples) that constitutes the most extensively irradiated and final set. The results and trends reported here, together with those discussions touching on current knowledge about cross sections and fission yields, are intended to serve as a starting point for further analysis. In general, these results are encouraging with regard to the adequacy of much of the currently available nuclear data in this region of the periodic table. But there are some cases where adjustments and improvements can be suggested. However, the application of these results in consolidating current cross-section and fission-yield data must await further analysis.

  11. Preliminary calculational analysis of the actinide samples from FP-4 exposed in the Dounreay Prototype Fast Reactor

    SciTech Connect

    Murphy, B.D.; Raman, S.; Newton, T.D.

    1996-12-01

    This report discusses the current status of results from an extensive experiment on the irradiation of selected actinides in a fast reactor. These actinides ranged from thorium to curium. They were irradiated in the core of the Dounreay Prototype Fast Reactor. Rates for depletion, transmutation, and fission-product generation were experimentally measured, and, in turn, were calculated using current cross-section and fission-yield data. Much of the emphasis is on the comparison between experimental and calculated values for both actinide and fission-product concentrations. Some of the discussion touches on the adequacy of current cross-section and fission-yield data. However, the main purposes of the report are: to collect in one place the most recent yield data, to discuss the comparisons between the experimental and calculated results, to discuss each sample that was irradiated giving details of any adjustments needed or specific problems encountered, and to give a chronology of the analysis as it pertained to the set of samples (referred to as FP-4 samples) that constitutes the most extensively irradiated and final set. The results and trends reported here, together with those discussions touching on current knowledge about cross sections and fission yields, are intended to serve as a starting point for further analysis. In general, these results are encouraging with regard to the adequacy of much of the currently available nuclear data in this region of the periodic table. But there are some cases where adjustments and improvements can be suggested. However, the application of these results in consolidating current cross-section and fission-yield data must await further analysis.

  12. Stable isotope and elemental analysis in ants.

    PubMed

    Smith, Chris R; Tillberg, Chadwick V

    2009-07-01

    Over the past 20 yr, the use of stable isotopes to infer feeding ecology and the examination of how energetic and elemental exchanges are affected by and affect life (ecological stoichiometry) have gained momentum. The ecological diversity of ants makes them interesting models to explore dietary ecology and their role in food webs. Moreover, their ecological dominance in most habitats facilitates sampling. The protocol described here will produce samples adequate for submission to most labs that specialize in high-throughput analysis of stable isotopes; one should check with any particular lab for specific submission instructions. Note, however, that this protocol is designed specifically for the quantification of the natural abundance of stable isotopes; it does not cover the preparation of trace samples. PMID:20147207

  13. Conditional flux analysis and stable isotopes

    NASA Astrophysics Data System (ADS)

    Zeeman, M. J.; Knohl, A.; Sturm, P.; Buchmann, N. C.; Thomas, C. K.

    2009-12-01

    We propose to investigate to what extend conditional flux analysis can benefit from the addition of stable isotope information. Stable isotopes have been recognized for their potential as process tracer, and could add an extra dimension to the conditional flux concept, which aims at directly quantifying component fluxes and identifying their sources. Differences in 13C abundance in carbon dioxide can be used to distinguish assimilation or respiration sources, whereas the 18O abundance expresses differences in water exchange, for instance between canopy and soil. Lending to recent advances in measurement technology, stable isotopes can now be measured at high temporal resolutions (10Hz) required for commonly applied micrometeorological methods such as the eddy-covariance technique, or related conditional flux methods. We will present current ideas on how the conditional flux method, as recently proposed and evaluated by Thomas et al. (2008), Scanlon & Sahu (2008), to perform daytime flux partitioning at the ecosystem level, can be refined by stable isotope analysis (13C and 18O) of carbon dioxide as additional dimension for identification of fluxes.

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

    USGS Publications Warehouse

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

    2007-01-01

    Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in "mixed" samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant. ?? 2007 American Chemical Society.

  15. Micro-Analysis of Actinide Minerals for Nuclear Forensics and Treaty Verification

    SciTech Connect

    M. Morey, M. Manard, R. Russo, G. Havrilla

    2012-03-22

    Micro-Raman spectroscopy has been demonstrated to be a viable tool for nondestructive determination of the crystal phase of relevant minerals. Collecting spectra on particles down to 5 microns in size was completed. Some minerals studied were weak scatterers and were better studied with the other techniques. A decent graphical software package should easily be able to compare collected spectra to a spectral library as well as subtract out matrix vibration peaks. Due to the success and unequivocal determination of the most common mineral false positive (zircon), it is clear that Raman has a future for complementary, rapid determination of unknown particulate samples containing actinides.

  16. Novel Separation of Actinides

    SciTech Connect

    Mariella, R

    2011-02-17

    The separation of actinides and other elements of interest for nuclear forensics and threat reduction is currently performed using decades-old chemistries and ion-exchange columns. We propose to determine the technical feasibility of a novel method for separating actinide ions in solution. This method is based upon isotachophoresis (ITP), which has been applied in the purification of pharmaceuticals and other biochemical applications. This technique has the potential to separate inorganic ions more effectively than existing methods, which is key to analyzing very small samples. We will perform a quantitative assessment of the effectiveness of specific isotachophoretic approaches including predicting the physical and chemical properties, such as ion mobility, of inorganic ions under specific solvent conditions using a combination of ab initio calculations and semi-empirical methods. We expect to obtain a thorough understanding of the analytical systems parameters under which ITP is most effective for the separation of inorganic samples, including the influence of the double layer surrounding actinide ions, the Debye length for different ions and ion complexes, and Debye-Hueckel limits. Inorganic separations are key to nuclear forensics for countering terrorism and nuclear proliferation. If found to be feasible and potentially superior to currently used separation approaches, ITP could provide the conceptual basis for an improved means to separate samples of nuclear explosion debris for nuclear forensic analysis, in support of the Laboratory's missions in homeland and national security.

  17. Cyberinfrastructure for isotope analysis and modeling

    NASA Astrophysics Data System (ADS)

    Bowen, Gabriel J.; West, Jason B.; Zhao, Lan; Takahashi, George; Miller, Chris; Zhang, Tonglin

    2012-05-01

    As the quantity and complexity of scientific data expand, accessible interfaces for data manipulation and analysis are needed to support broad and efficient data use. The Isoscapes Modeling, Analysis, and Prediction (IsoMAP; http://isomap.org) Web-based geographical information system (GIS) gateway is an example of such a resource. Recently launched with support from the U.S. National Science Foundation (NSF) Division of Biological Infrastructure, IsoMAP enables analysis and integration of diverse light stable isotope and environmental data by a broad-based user community. It provides an intuitive, spatial interface that streamlines data analysis, modeling, and exploration in research ranging from greenhouse gas biogeochemistry to food science.

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

    PubMed

    Chew, Gina; Walczyk, Thomas

    2013-04-01

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

  19. Actinide abundances in ordinary chondrites

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  20. Analysis of incident-energy dependence of delayed neutron yields in actinides

    SciTech Connect

    Nasir, Mohamad Nasrun bin Mohd Metorima, Kouhei Ohsawa, Takaaki Hashimoto, Kengo

    2015-04-29

    The changes of delayed neutron yields (ν{sub d}) of Actinides have been analyzed for incident energy up to 20MeV using realized data of precursor after prompt neutron emission, from semi-empirical model, and delayed neutron emission probability data (P{sub n}) to carry out a summation method. The evaluated nuclear data of the delayed neutron yields of actinide nuclides are still uncertain at the present and the cause of the energy dependence has not been fully understood. In this study, the fission yields of precursor were calculated considering the change of the fission fragment mass yield based on the superposition of fives Gaussian distribution; and the change of the prompt neutrons number associated with the incident energy dependence. Thus, the incident energy dependent behavior of delayed neutron was analyzed.The total number of delayed neutron is expressed as ν{sub d}=∑Y{sub i} • P{sub ni} in the summation method, where Y{sub i} is the mass yields of precursor i and P{sub ni} is the delayed neutron emission probability of precursor i. The value of Y{sub i} is derived from calculation of post neutron emission mass distribution using 5 Gaussian equations with the consideration of large distribution of the fission fragments. The prompt neutron emission ν{sub p} increases at higher incident-energy but there are two different models; one model says that the fission fragment mass dependence that prompt neutron emission increases uniformly regardless of the fission fragments mass; and the other says that the major increases occur at heavy fission fragments area. In this study, the changes of delayed neutron yields by the two models have been investigated.

  1. Applications of stable isotope analysis in mammalian ecology.

    PubMed

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

    2014-01-01

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

  2. Actinide sulfite tetrahydrate and actinide oxysulfite tetrahydrate

    SciTech Connect

    Baugh, D.; Watt, G.

    1980-07-08

    A compound is prepared that comprises an actinide sulfite tetrahydrate selected from the group consisting of uranium (IV) sulfite tetrahydrate and plutonium (IV) sulfite tetrahydrate. A compound is also prepared that comprises an actinide oxysulfite tetrahydrate selected from the group consisting of uranium (IV) oxysulfite tetrahydrate and plutonium (IV) oxysulfite tetrahydrate

  3. Possibilities of synthesis of unknown isotopes of superheavy nuclei with charge numbers Z > 108 in asymmetric actinide-based complete fusion reactions

    NASA Astrophysics Data System (ADS)

    Hong, Juhee; Adamian, G. G.; Antonenko, N. V.

    2016-10-01

    The possibilities of production of new isotopes of superheavy nuclei with charge numbers Z = 109-114 in various asymmetric hot fusion reactions are studied for the first time. The excitation functions of the formation of these isotopes in the xn evaporation channels are predicted and the optimal conditions for the synthesis are proposed. The products of the suggested reactions can fill a gap of unknown isotopes between the isotopes of the heaviest nuclei obtained in cold and hot complete fusion reactions.

  4. Plutonium and minor actinide utilisation in a pebble-bed high temperature reactor

    SciTech Connect

    Petrov, B. Y.; Kuijper, J. C.; Oppe, J.; De Haas, J. B. M.

    2012-07-01

    This paper contains results of the analysis of the pebble-bed high temperature gas-cooled PUMA reactor loaded with plutonium and minor actinide (Pu/MA) fuel. Starting from knowledge and experience gained in the Euratom FP5 projects HTR-N and HTR-N1, this study aims at demonstrating the potential of high temperature reactors to utilize or transmute Pu/MA fuel. The work has been performed within the Euratom FP6 project PUMA. A number of different fuel types and fuel configurations have been analyzed and compared with respect to incineration performance and safety-related reactor parameters. The results show the excellent plutonium and minor actinide burning capabilities of the high temperature reactor. The largest degree of incineration is attained in the case of an HTR fuelled by pure plutonium fuel as it remains critical at very deep burnup of the discharged pebbles. Addition of minor actinides to the fuel leads to decrease of the achievable discharge burnup and therefore smaller fraction of actinides incinerated during reactor operation. The inert-matrix fuel design improves the transmutation performance of the reactor, while the 'wallpaper' fuel does not have advantage over the standard fuel design in this respect. After 100 years of decay following the fuel discharge, the total amount of actinides remains almost unchanged for all of the fuel types considered. Among the plutonium isotopes, only the amount of Pu-241 is reduced significantly due to its relatively short half-life. (authors)

  5. NEW METHOD FOR DETERMINATION OF ACTINIDES AND STRONTIUM IN ANIMAL TISSUE

    SciTech Connect

    Maxwell, S; Jay Hutchison, J; Don Faison, D

    2007-05-07

    The analysis of actinides in animal tissue samples is very important for environmental monitoring. There is a need to measure actinide isotopes with very low detection limits in animal tissue samples, including fish, deer, hogs, beef and shellfish. A new, rapid actinide separation method has been developed and implemented that allows the measurement of plutonium, neptunium, uranium, americium, curium and strontium isotopes in large animal tissue samples (100-200 g) with high chemical recoveries and effective removal of matrix interferences. This method uses stacked TEVA Resin{reg_sign}, TRU Resin{reg_sign} and DGA-Resin{reg_sign} cartridges from Eichrom Technologies (Darien, IL, USA) that allows the rapid separation of plutonium (Pu), neptunium (Np), uranium (U), americium (Am), and curium (Cm) using a single multi-stage column combined with alpha spectrometry. Sr-90 is collected on Sr Resin{reg_sign} from Eichrom Technologies (Darien, IL, USA). After acid digestion and furnace heating of the animal tissue samples, the actinides and Sr-89/90 are separated using column extraction chromatography. This method has been shown to be effective over a wide range of animal tissue matrices. By using vacuum box cartridge technology with rapid flow rates, sample preparation time is minimized.

  6. Carbon-isotopic analysis of dissolved acetate

    NASA Technical Reports Server (NTRS)

    Gelwicks, J. T.; Hayes, J. M.

    1990-01-01

    Heating of dried, acetate-containing solids together with oxalic acid dihydrate conveniently releases acetic acid for purification by gas chromatography. For determination of the carbon-isotopic composition of total acetate, the acetate-containing zone of the chromatographic effluent can be routed directly to a combustion furnace coupled to a vacuum system allowing recovery, purification, and packaging of CO2 for mass-spectrometric analysis. For analysis of methyl carbon, acetic acid can be cryogenically trapped from the chromatographic effluent, then transferred to a tube containing excess NaOH. The tube is evacuated, sealed, and heated to 500 degrees C to produce methane by pyrolysis of sodium acetate. Subsequent combustion of the methane allows determination of the 13C content at the methyl position in the parent acetate. With typical blanks, the standard deviation of single analyses is less than 0.4% for acetate samples larger than 5 micromoles. A full treatment of uncertainties is outlined.

  7. Compound specific stable isotope analysis vs. bulk stable isotope analysis of agricultural food products

    NASA Astrophysics Data System (ADS)

    Psomiadis, David; Horváth, Balázs; Nehlich, Olaf; Bodiselitsch, Bernd

    2015-04-01

    The bulk analysis of stable isotopes (carbon, nitrogen, sulphur, oxygen and hydrogen) from food staples is a common tool for inferring origin and/or fraud of food products. Many studies have shown that bulk isotope analyses of agricultural products are able to separate large geographical areas of food origin. However, in micro-localities (regions, districts, and small ranges) these general applications fail in precision and discriminative power. The application of compound specific analysis of specific components of food products helps to increase the precision of established models. Compound groups like fatty acids (FAMEs), vitamins or amino acids can help to add further detailed information on physiological pathways and local conditions (micro-climate, soil, water availability) and therefore might add further information for the separation of micro-localities. In this study we are aiming to demonstrate the power and surplus of information of compound specific isotope analysis in comparison to bulk analysis of agricultural products (e.g. olive oil, cereal crops or similar products) and discuss the advantages and disadvantages of such (labor intense) analysis methods. Here we want to identify tools for further detailed analysis of specific compounds with high powers of region separation for better prediction models.

  8. Actinide-ion sensor

    DOEpatents

    Li, Shelly X; Jue, Jan-fong; Herbst, Ronald Scott; Herrmann, Steven Douglas

    2015-01-13

    An apparatus for the real-time, in-situ monitoring of actinide-ion concentrations. A working electrolyte is positioned within the interior of a container. The working electrolyte is separated from a reference electrolyte by a separator. A working electrode is at least partially in contact with the working electrolyte. A reference electrode is at least partially in contact with the reference electrolyte. A voltmeter is electrically connected to the working electrode and the reference electrode. The working electrolyte comprises an actinide-ion of interest. The separator is ionically conductive to the actinide-ion of interest. The separator comprises an actinide, Zr, and Nb. Preferably, the actinide of the separator is Am or Np, more preferably Pu. In one embodiment, the actinide of the separator is the actinide of interest. In another embodiment, the separator further comprises P and O.

  9. The gastrointestinal absorption of the actinide elements.

    PubMed

    Harrison, J D

    1991-03-01

    The greatest uncertainty in dose estimates for the ingestion of long-lived, alpha-emitting isotopes of the actinide elements is in the values used for their fractional absorption from the gastrointestinal tract (f1 values). Recent years have seen a large increase in the available data on actinide absorption. Human data are reviewed here, together with animal data, to illustrate the effect on absorption of chemical form, incorporation into food materials, fasting and other dietary factors, and age at ingestion. The f1 values recommended by the International Commission on Radiological Protection, by an Expert Group of the Nuclear Energy Agency and by the National Radiological Protection Board are discussed.

  10. Wavelength Dispersive X-ray Fluorescence Analysis of Actinides in Dissolved Nuclear Fuels

    SciTech Connect

    O'Hara, David

    2015-10-15

    There is an urgent need for an instrument that can quickly measure the concentration of Plutonium and other Actinides mixed with Uranium in liquids containing dissolved spent fuel rods. Parallax Research, Inc. proposes to develop an x-ray spectrometer capable of measuring U, Np and Pu in dissolved nuclear fuel rod material to less than 10 ppm levels to aid in material process control for these nuclear materials. Due to system noise produced by high radioactivity, previous x-ray spectrometers were not capable of low level measurements but the system Parallax proposed has no direct path for undesired radiation to get to the detector and the detector in the proposed device is well shielded from scatter and has very low dark current. In addition, the proposed spectrometer could measure these three elements simultaneously, also measuring background positions with an energy resolution of roughly 100 eV making it possible to see a small amount of Pu that would be hidden under the tail of the U peak in energy dispersive spectrometers. Another nearly identical spectrometer could be used to target Am and Cm if necessary. The proposed spectrometer needs only a tiny sample of roughly 1 micro-liter (1 mm3) and the measurement can be done with the liquid flowing in a radiation and chemical immune quartz capillary protected by a stainless steel rod making it possible to continuously monitor the liquid or to use a capillary manifold to measure other liquid streams. Unlike other methods such as mass spectroscopy where the sample must be taken to a remote facility and might take days for turn-around, the proposed measurement should take less than an hour. This spectrometer could enable near real-time measurement of U, Pu and Np in dilute dissolved spent nuclear fuel rod streams.

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

    SciTech Connect

    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).

  12. Actinide extraction methods

    DOEpatents

    Peterman, Dean R [Idaho Falls, ID; Klaehn, John R [Idaho Falls, ID; Harrup, Mason K [Idaho Falls, ID; Tillotson, Richard D [Moore, ID; Law, Jack D [Pocatello, ID

    2010-09-21

    Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.

  13. Radionuclide Data Analysis and Evaluation: More Information From Fewer Isotopes

    NASA Astrophysics Data System (ADS)

    Prinke, A.; McIntyre, J.; Cooper, M.; Haas, D.; Lowrey, J.; Miley, H.; Schrom, B.; Suckow, T.

    2013-12-01

    The analysis of the International Monitoring System radionuclide data sets provides daily concentrations for both particulate and radioxenon isotopes. These isotopes can come from many potential sources such as nuclear reactors, nuclear physics experiments, and medical isotope production. These interesting but irrelevant sources have several of the same radio-isotopic signatures from above or underground nuclear explosions and must be ruled out as part of the determination that an event originated as a nuclear explosion. There are several methods under development that aid in this determination and this poster will briefly cover each: radio-isotopic ratios and parent daughter relationships, co-detection of radioxenon and isotopes found on particulates, and past detection history.

  14. Research in actinide chemistry

    SciTech Connect

    Choppin, G.R.

    1993-01-01

    This research studies the behavior of the actinide elements in aqueous solution. The high radioactivity of the transuranium actinides limits the concentrations which can be studied and, consequently, limits the experimental techniques. However, oxidation state analogs (trivalent lanthanides, tetravalent thorium, and hexavalent uranium) do not suffer from these limitations. Behavior of actinides in the environment are a major USDOE concern, whether in connection with long-term releases from a repository, releases from stored defense wastes or accidental releases in reprocessing, etc. Principal goal of our research was expand the thermodynamic data base on complexation of actinides by natural ligands (e.g., OH[sup [minus

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

    EPA Science Inventory

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

  16. Trophic hierarchies revealed via amino acid isotopic analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  17. Isotope ratio determination in boron analysis.

    PubMed

    Sah, R N; Brown, P H

    1998-01-01

    Traditionally, boron (B) isotope ratios have been determined using thermal ionization mass spectrometry (TIMS) and, to some extent, secondary ion mass spectrometry (SIMS). Both TIMS and SIMS use a high-resolution mass analyzer, but differ in analyte ionization methods. TIMS uses electrons from a hot filament, whereas SIMS employs an energetic primary ion beam of Ga+, Cs+, or O- for analyte ionization. TIMS can be used in negative or positive ion modes with high sensitivity and precision of B isotope ratio determination. However, isobaric interferences may be a problem, if the sample is not well purified and/or memory of the previous sample is not removed. Time-consuming sample preparation, analyte (B) purification, and sample determination processes limit the applications of TIMS for routine analyses. SIMS can determine B and its isotope ratio in intact solid samples without destroying them, but has poorer resolution and sensitivity than TIMS, and is difficult to standardize for biological samples. Development of plasma-source mass spectrometry (MS) enabled the determination of B concentration and isotope ratio without requiring sample purification. Commonly used plasma-source MS uses an Ar inductively coupled plasma (ICP) as an ionization device interfaced to a low-resolution quadrupole mass analyzer. The quadrupole ICP-MS is less precise than TIMS and SIMS, but is a popular method for B isotope ratio determination because of its speed and convenience. B determination by ICP-MS suffers no spectroscopic interferences. However, sample matrices, memory effects, and some instrument parameters may affect the accuracy and precision of B isotope ratio determination if adequate precautions are not taken. New generations of plasma-source MS instruments using high-resolution mass analyzers provide better sensitivity and precision than the currently used quadrupole ICP-MS. Because of the convenience and high sample throughput, the high-resolution ICP-MS is expected to be the

  18. Actinide recovery process

    DOEpatents

    Muscatello, Anthony C.; Navratil, James D.; Saba, Mark T.

    1987-07-28

    Process for the removal of plutonium polymer and ionic actinides from aqueous solutions by absorption onto a solid extractant loaded on a solid inert support such as polystyrenedivinylbenzene. The absorbed actinides can then be recovered by incineration, by stripping with organic solvents, or by acid digestion. Preferred solid extractants are trioctylphosphine oxide and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and the like.

  19. Actinide Targets for Neutron Cross Section Measurements

    SciTech Connect

    John D. Baker; Christopher A. McGrath

    2006-10-01

    The Advanced Fuel Cycle Initiative (AFCI) and the Generation IV Reactor Initiative have demonstrated a lack of detailed neutron cross-sections for certain "minor" actinides, those other than the most common (235U, 238U, and 239Pu). For some closed-fuel-cycle reactor designs more than 50% of reactivity will, at some point, be derived from "minor" actinides that currently have poorly known or in some cases not measured (n,?) and (n,f) cross sections. A program of measurements under AFCI has begun to correct this. One of the initial hurdles has been to produce well-characterized, highly isotopically enriched, and chemically pure actinide targets on thin backings. Using a combination of resurrected techniques and new developments, we have made a series of targets including highly enriched 239Pu, 240Pu, and 242Pu. Thus far, we have electrodeposited these actinide targets. In the future, we plan to study reductive distillation to achieve homogeneous, adherent targets on thin metal foils and polymer backings. As we move forward, separated isotopes become scarcer, and safety concerns become greater. The chemical purification and electodeposition techniques will be described.

  20. Use of Stable Isotopes in Forensic Analysis of Microorganisms

    SciTech Connect

    Kreuzer-Martin, Helen W.; Hegg, Eric L.

    2012-01-18

    The use of isotopic signatures for forensic analysis of biological materials is well-established, and the same general principles that apply to interpretation of stable isotope content of C, N, O, and H apply to the analysis of microorganisms. Heterotrophic microorganisms derive their isotopic content from their growth substrates, which are largely plant and animal products, and the water in their culture medium. Thus the isotope signatures of microbes are tied to their growth environment. The C, N, O, and H isotope ratios of spores have been demonstrated to constitute highly discriminating signatures for sample matching. They can rule out specific samples of media and/or water as possible production media, and can predict isotope ratio ranges of the culture media and water used to produce a given sample. These applications have been developed and tested through analyses of approximately 250 samples of Bacillus subtilis spores and over 500 samples of culture media, providing a strong statistical basis for data interpretation. A Bayesian statistical framework for integrating stable isotope data with other types of signatures derived from microorganisms has been able to characterize the culture medium used to produce spores of various Bacillus species, leveraging isotopic differences in different medium types and demonstrating the power of data integration for forensic investigations.

  1. An emergency bioassay method for actinides in urine.

    PubMed

    Dai, Xiongxin; Kramer-Tremblay, Sheila

    2011-08-01

    A rapid bioassay method has been developed for the sequential measurements of actinides in human urine samples. The method involves actinide separation from a urine matrix by co-precipitation with hydrous titanium oxide (HTiO), followed by anion exchange and extraction chromatography column purification, and final counting by alpha spectrometry after cerium fluoride micro-precipitation. The minimal detectable activities for the method were determined to be 20 mBq L(-1) or less for plutonium, uranium, americium and curium isotopes, with an 8-h sample turn-around time. Spike tests showed that this method would meet the requirements for actinide bioassay following a radiation emergency.

  2. Thermodynamic Properties of Actinides and Actinide Compounds

    NASA Astrophysics Data System (ADS)

    Konings, Rudy J. M.; Morss, Lester R.; Fuger, Jean

    The necessity of obtaining accurate thermodynamic quantities for the actinide elements and their compounds was recognized at the outset of the Manhattan Project, when a dedicated team of scientists and engineers initiated the program to exploit nuclear energy for military purposes. Since the end of World War II, both fundamental and applied objectives have motivated a great deal of further study of actinide thermodynamics. This chapter brings together many research papers and critical reviews on this subject. It also seeks to assess, to systematize, and to predict important properties of the actinide elements, ions, and compounds, especially for species in which there is significant interest and for which there is an experimental basis for the prediction.

  3. Actinide partitioning-transmutation program final report. VII. Long-term risk analysis of the geologic repository

    SciTech Connect

    Logan, S.E.; Conarty, R.L.; Ng, H.S.; Rahal, L.J.; Shirley, C.G.

    1980-09-01

    This report supports the overall assessment by Oak Ridge National Laboratory of actinide partitioning and transmutation by providing an analysis of the long-term risks associated with the terminal storage of wastes from a fuel cycle which incorporates partitioning and transmutation (P-T) and wastes from a cycle which does not. The system model and associated computer code, called AMRAW (Assessment Method for Radioactive Waste), are used for the analysis and are applied to the Los Medanos area in southeastern New Mexico. Because a conservative approach is used throughout, calculated results are believed to be consistently higher than reasonable expectations from actual disruptive incidents at the site and therefore are not directly suited for comparison with other analyses of the particular geologic location. The assessment is made with (1) the probabilistic, or risk, mode that uses combinations of reasonable possible release incidents with their probability of occurrence distributed and applied throughout the assessment period, and (2) the consequence mode that forces discrete release events to occur at specific times. An assessment period of 1 million years is used. The principal results are: (1) In all but the expulsive modes, /sup 99/Tc and /sup 129/I completely dominate cumulative effects based on their transport to man through leaching and movement with groundwater, effecting about 33,000 health effects (deaths) over the 1 million years; (2) P-T has only limited effectiveness in reducing long-term risk from a radionuclide waste repository under the conditions studied, and such effectiveness is essentially confined to the extremely unlikely (probability of occurrence 10/sup -12//year) expulsive events; (3) Removal or immobilization of /sup 99/Tc and /sup 129/I might provide benefits sufficiently tangible to warrant special consideration.

  4. Method for preparing actinide nitrides

    DOEpatents

    Bryan, G.H.; Cleveland, J.M.; Heiple, C.R.

    1975-12-01

    Actinide nitrides, and particularly plutonium and uranium nitrides, are prepared by reacting an ammonia solution of an actinide compound with an ammonia solution of a reactant or reductant metal, to form finely divided actinide nitride precipitate which may then be appropriately separated from the solution. The actinide nitride precipitate is particularly suitable for forming nuclear fuels.

  5. Influence of bacteria on lanthanide and actinide transfer from specific soil components (humus, soil minerals and vitrified municipal solid waste incinerator bottom ash) to corn plants: Sr-Nd isotope evidence.

    PubMed

    Aouad, Georges; Stille, Peter; Crovisier, Jean-Louis; Geoffroy, Valérie A; Meyer, Jean-Marie; Lahd-Geagea, Majdi

    2006-11-01

    Experiments have been performed to test the stability of vitrified municipal solid waste (MSW) incinerator bottom ash under the presence of bacteria (Pseudomonas aeruginosa) and plants (corn). The substratum used for the plant growth was a humus-rich soil mixed with vitrified waste. For the first time, information on the stability of waste glasses in the presence of bacteria and plants is given. Results show that inoculated plant samples contained always about two times higher lanthanide and actinide element concentrations. Bacteria support the element transfer since plants growing in inoculated environment developed a smaller root system but have higher trace element concentrations. Compared with the substratum, plants are light rare earth element (LREE) enriched. The vitrified bottom ash has to some extent been corroded by bacteria and plant activities as indicated by the presence of Nd (REE) and Sr from the vitrified waste in the plants. (87)Sr/(86)Sr and (143)Nd/(144)Nd isotope ratios of plants and soil components allow the identification of the corroded soil components and confirm that bacteria accelerate the assimilation of elements from the vitrified bottom ash. These findings are of importance for landfill disposal scenarios, and similar experiments should be performed in order to better constrain the processes of microbially mediated alteration of the MSW glasses in the biosphere.

  6. Isotope analysis in the transmission electron microscope

    NASA Astrophysics Data System (ADS)

    Susi, Toma; Hofer, Christoph; Argentero, Giacomo; Leuthner, Gregor T.; Pennycook, Timothy J.; Mangler, Clemens; Meyer, Jannik C.; Kotakoski, Jani

    2016-10-01

    The Ångström-sized probe of the scanning transmission electron microscope can visualize and collect spectra from single atoms. This can unambiguously resolve the chemical structure of materials, but not their isotopic composition. Here we differentiate between two isotopes of the same element by quantifying how likely the energetic imaging electrons are to eject atoms. First, we measure the displacement probability in graphene grown from either 12C or 13C and describe the process using a quantum mechanical model of lattice vibrations coupled with density functional theory simulations. We then test our spatial resolution in a mixed sample by ejecting individual atoms from nanoscale areas spanning an interface region that is far from atomically sharp, mapping the isotope concentration with a precision better than 20%. Although we use a scanning instrument, our method may be applicable to any atomic resolution transmission electron microscope and to other low-dimensional materials.

  7. Actinide partitioning-transmutation program final report. VI. Short-term risk analysis of reprocessing, refabrication, and transportation: summary

    SciTech Connect

    Fullwood, R.; Jackson, R.

    1980-03-01

    A Partitioning-Transmutation (PT) fuel cycle is being compared to a Reference cycle employing conventional fuel-material recovery methods. The PT cycle uses enhanced recovery methods so that most of the long-lived actinides are recycled to nuclear power plants and transmuted thereby reducing the waste toxicity. This report compares the two fuel cycles on the basis of the short-term radiological and nonradiological risks. The accidental radiological risk to the public is analyzed by estimating the probabilities of sets of accidents; the consequences are calculated using the risk, which is RAC code. Routine radiological risks to the public are estimated from the calculated release amounts, also using the CRAC code. Radiological occupational risks are determined from prior experience, projected standards, and estimates of accident risk. Nonradiological risks are calculated from the number of personnel involved, historical experience, and epidemiological studies. Result of this analysis is that the short-term risk of PT is 2.9 times greater than that of the Reference cycle, primarily due to the larger amount of industry. The nonradiological risk which is about 150 times greater than the radiological risk. If the radiological risk is consdered alone, the ratio of PT to Reference risk is 3, composed as follows: radiological operations affecting the public 5, radiological operations affecting the workers 1.7, and radiological accidents affecting the public 1.4, all in the order of decreasing risk. The absolute risk as estimated for the fuel cycle portions considered in this report is 0.91 fatality/GWe-year for the PT cycle and 0.34 fatality/GWe-year for the reference cycle; this compares with 1.5 for nuclear and 150 for coal. All of the risks assumed here are associated with the production of one billion watts of electricity (GWe) per year.

  8. Actinide partitioning-transmutation program final report. VI. Short-term risk analysis of reprocessing, refabrication, and transportation: appendix

    SciTech Connect

    Fullwood, R.R.; Jackson, R.

    1980-01-01

    The Chemical Technology Division of the Oak Ridge National Laboratory has prepared a set of documents that evaluate a Partitioning-Transmutation (PT) fuel cycle relative to a Reference cycle employing conventional fuel-material recovery methods. The PT cycle uses enhanced recovery methods so that most of the long-lived actinides are recycled to nuclear power plants and transmuted to shorter-lived materials, thereby reducing the waste toxicity. This report compares the two fuel cycles on the basis of the short-term radiological and nonradiological risks they present to the public and to workers. The accidental radiological risk to the public is analyzed by estimating the probabilities of sets of accidents; the consequences are calculated using the CRAC code appropriately modified for the material composition. Routine radiological risks to the public are estimated from the calculated release amounts; the effects are calculated using the CRAC code. Radiological occupational risks are determined from prior experience, projected standards, and estimates of accident risk. Nonradiological risks are calculated from the number of personnel involved, historical experience, and epidemiological studies. The result of this analysis is that the short-term risk of PT is 2.9 times greater than that of the Reference cycle, primarily due to the larger amount of industry. This conclusion is strongly dominated by the nonradiological risk, which is about 150 times greater than the radiological risk. The absolute risk as estimated for the fuel cycle portions considered in this report is 0.91 fatalities/GWe-year for the PT cycle and 0.34 fatalities/GWe-year for the Reference cycle. This should be compared with Inhaber's estimate of 1.5 for nuclear and 150 for coal. All of the risks assumed here are associated with the production of one billion watts of electricity (GWe) per year.

  9. Surrogate Reactions in the Actinide Region

    SciTech Connect

    Burke, J T; Bernstein, L A; Scielzo, N D; Bleuel, D L; Lesher, S R; Escher, J; Ahle, L; Dietrich, F S; Hoffman, R D; Norman, E B; Sheets, S A; Phair, L; Fallon, P; Clark, R M; Gibelin, J; Jewett, C; Lee, I Y; Macchiavelli, A O; McMahan, M A; Moretto, L G; Rodriguez-Vieitez, E; Wiedeking, M; Lyles, B F; Beausang, C W; Allmond, J M; Ai, H; Cizewski, J A; Hatarik, R; O'Malley, P D; Swan, T

    2008-01-30

    Over the past three years we have studied various surrogate reactions (d,p), ({sup 3}He,t), ({alpha},{alpha}{prime}) on several uranium isotopes {sup 234}U, {sup 235}U, {sup 236}U, and {sup 238}U. An overview of the STARS/LIBERACE surrogate research program as it pertains to the actinides is discussed. A summary of results to date will be presented along with a discussion of experimental difficulties encountered in surrogate experiments and future research directions.

  10. PREFACE: Actinides 2009

    NASA Astrophysics Data System (ADS)

    Rao, Linfeng; Tobin, James G.; Shuh, David K.

    2010-07-01

    This volume of IOP Conference Series: Materials Science and Engineering consists of 98 papers that were presented at Actinides 2009, the 8th International Conference on Actinide Science held on 12-17 July 2009 in San Francisco, California, USA. This conference was jointly organized by Lawrence Livermore National Laboratory and Lawrence Berkeley National Laboratory. The Actinides conference series started in Baden-Baden, Germany (1975) and this first conference was followed by meetings at Asilomar, CA, USA (1981), Aix-en-Provence, France (1985), Tashkent, USSR (1989), Santa Fe, NM, USA (1993), Baden-Baden, Germany (1997), Hayama, Japan (2001), and Manchester, UK (2005). The Actinides conference series provides a regular venue for the most recent research results on the chemistry, physics, and technology of the actinides and heaviest elements. Actinides 2009 provided a forum spanning a diverse range of scientific topics, including fundamental materials science, chemistry, physics, environmental science, and nuclear fuels. Of particular importance was a focus on the key roles that basic actinide chemistry and physics research play in advancing the worldwide renaissance of nuclear energy. Editors Linfeng Rao Lawrence Berkeley National Laboratory (lrao@lbl.gov) James G Tobin Lawrence Livermore National Laboratory (tobin1@llnl.gov) David K Shuh Lawrence Berkeley National Laboratory (dkshuh@lbl.gov)

  11. Isotopic abundance in atom trap trace analysis

    DOEpatents

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

    2014-03-18

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

  12. Isotopic ratio correlation for the isotopic composition analysis of plutonium in Am-Pu mixed samples having high americium content.

    PubMed

    Patra, Sabyasachi; Agarwal, Chhavi; Chaudhury, Sanhita; Newton Nathaniel, T; Gathibandhe, M; Goswami, A

    2013-08-01

    Interference of high amount of americium in the plutonium isotopic composition analysis has been studied by simulating gamma-ray spectra for Am-Pu samples over a wide composition range (5-97% (241)Am) for both power and research reactor grade plutonium. An alternate way for isotopic composition analysis has been proposed by correlating the isotopic ratios available in our old database with the experimentally obtained (241)Pu/(239)Pu isotopic ratio. The proposed method has been validated using simulated spectra of known isotopic compositions.

  13. Design of unique pins for irradiation of higher actinides in a fast reactor

    SciTech Connect

    Basmajian, J.A.; Birney, K.R.; Weber, E.T.; Adair, H.L.; Quinby, T.C.; Raman, S.; Butler, J.K.; Bateman, B.C.; Swanson, K.M.

    1982-03-01

    The actinides produced by transmutation reactions in nuclear reactor fuels are a significant factor in nuclear fuel burnup, transportation and reprocessing. Irradiation testing is a primary source of data of this type. A segmented pin design was developed which provides for incorporation of multiple specimens of actinide oxides for irradiation in the UK's Prototype Fast Reactor (PFR) at Dounreay Scotland. Results from irradiation of these pins will extend the basic neutronic and material irradiation behavior data for key actinide isotopes.

  14. Method for isotopic analysis of chlorinated organic compounds

    DOEpatents

    Holt, Ben D.; Sturchio, Neil C.

    1999-01-01

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

  15. Method for isotopic analysis of chlorinated organic compounds

    DOEpatents

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

    1999-08-24

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

  16. Identification of gasoline lead in children's blood using isotopic analysis.

    PubMed

    Tera, O; Schwartzman, D W; Watkins, T R

    1985-01-01

    The isotopic composition and concentrations of lead were measured, using mass spectrometric analysis, in blood drawn from 14 young children who lived in Washington, D.C. The isotopic composition of lead in ambient air, which reflects the changing sources of gasoline lead, was also determined for the period of sampling. Blood lead concentrations ranged from 4.38 to 24.7 micrograms/100 g blood. Based on linear patterns that involved ratios of all four isotopes consistent with two component mixing, we estimate a minimum contribution of recent gasoline lead ranging from 0 to 57% of the blood lead burden.

  17. Actinide abundances in ordinary chondrites

    USGS Publications Warehouse

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

    1990-01-01

    Measurements of 244Pu fission Xe, U, Th, and light REE (LREE) abundances, along with modal petrographic determinations of phosphate abundances, were carried out on equilibrated ordinary chondrites in order to define better the solar system Pu abundance and to determine the degree of variation of actinide and LREE abundances. Our data permit comparison of the directly measured Pu/ U ratio with that determined indirectly as (Pu/Nd) ?? (Nd/U) assuming that Pu behaves chemically as a LREE. Except for Guaren??a, and perhaps H chondrites in general, Pu concentrations are similar to that determined previously for St. Se??verin, although less precise because of higher trapped Xe contents. Trapped 130Xe 136Xe ratios appear to vary from meteorite to meteorite, but, relative to AVCC, all are similar in the sense of having less of the interstellar heavy Xe found in carbonaceous chondrite acid residues. The Pu/U and Pu/Nd ratios are consistent with previous data for St. Se??verin, but both tend to be slightly higher than those inferred from previous data on Angra dos Reis. Although significant variations exist, the distribution of our Th/U ratios, along with other precise isotope dilution data for ordinary chondrites, is rather symmetric about the CI chondrite value; however, actinide/(LREE) ratios are systematically lower than the CI value. Variations in actinide or LREE absolute and relative abundances are interpreted as reflecting differences in the proportions and/or compositions of more primitive components (chondrules and CAI materials?) incorporated into different regions of the ordinary chondrite parent bodies. The observed variations of Th/U, Nd/U, or Ce/U suggest that measurements of Pu/U on any single equilibrated ordinary chondrite specimen, such as St. Se??verin, should statistically be within ??20-30% of the average solar system value, although it is also clear that anomalous samples exist. ?? 1990.

  18. Actinides in the Geosphere

    NASA Astrophysics Data System (ADS)

    Runde, Wolfgang; Neu, Mary P.

    Since the 1950s actinides have been used to benefit industry, science, health, and national security. The largest industrial application, electricity generation from uranium and thorium fuels, is growing worldwide. Thus, more actinides are being mined, produced, used and processed than ever before. The future of nuclear energy hinges on how these increasing amounts of actinides are contained in each stage of the fuel cycle, including disposition. In addition, uranium and plutonium were built up during the Cold War between the United States and the Former Soviet Union for defense purposes and nuclear energy.

  19. Actinide recovery method -- Large soil samples

    SciTech Connect

    Maxwell , S.L. III

    2000-04-25

    There is a need to measure actinides in environmental samples with lower and lower detection limits, requiring larger sample sizes. This analysis is adversely affected by sample-matrix interferences, which make analyzing soil samples above five-grams very difficult. A new Actinide-Recovery Method has been developed by the Savannah River Site Central Laboratory to preconcentrate actinides from large-soil samples. Diphonix Resin (Eichrom Industries), a 1994 R and D 100 winner, is used to preconcentrate the actinides from large soil samples, which are bound powerfully to the resin's diphosphonic acid groups. A rapid microwave-digestion technique is used to remove the actinides from the Diphonix Resin, which effectively eliminates interfering matrix components from the soil matrix. The microwave-digestion technique is more effective and less tedious than catalyzed hydrogen peroxide digestions of the resin or digestion of diphosphonic stripping agents such as HEDPA. After resin digestion, the actinides are recovered in a small volume of nitric acid which can be loaded onto small extraction chromatography columns, such as TEVA Resin, U-TEVA Resin or TRU Resin (Eichrom Industries). Small, selective extraction columns do not generate large volumes of liquid waste and provide consistent tracer recoveries after soil matrix elimination.

  20. Light stable isotope analysis of meteorites by ion microprobe

    NASA Technical Reports Server (NTRS)

    Mcsween, Harry Y., Jr.

    1994-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  2. Dounreay PFR irradiation history for the joint US/UK actinide sample exposures

    SciTech Connect

    Raman, S.; Murphy, B.D.; Nestor, C.W. Jr.

    1995-07-01

    The operating history of the Dounreay Prototype Fast Reactor is presented to the extent that it is relevant to the irradiation of actinide specimens that were subsequently analyzed at Oak Ridge National Laboratory (ORNL). Three fuel pins with actinide samples were irradiated from July 1982 to July 1988 and returned to ORNL for analysis. They contained isotopes of elements from thorium to curium. The times when each of these fuel pins were in the reactor core are described as are the operating power levels and neutron spectra. The appendices give daily power levels of the reactor as well as six-group neutron energy spectra for various times and axial positions in the core.

  3. Use of Information Theory Concepts for Developing Contaminated Site Detection Method: Case for Fission Product and Actinides Accumulation Modeling

    SciTech Connect

    Harbachova, N.V.; Sharavarau, H.A.

    2006-07-01

    Information theory concepts and their fundamental importance for environmental pollution analysis in light of experience of Chernobyl accident in Belarus are discussed. An information and dynamic models of the radionuclide composition formation in the fuel of the Nuclear Power Plant are developed. With the use of code DECA numerical calculation of actinides (58 isotopes are included) and fission products (650 isotopes are included) activities has been carried out and their dependence with the fuel burn-up of the RBMK-type reactor have been investigated. (authors)

  4. Production of heavy actinides in incomplete fusion reactions

    NASA Astrophysics Data System (ADS)

    Antonenko, N. V.; Cherepanov, E. A.; Iljinov, A. S.; Mebel, M. V.

    1994-10-01

    We present preliminary results of calculations by the phenomenological model of the estimated yield of some heavy actinide isotopes. It is assumed that these isotopes are produced as a result of multinucleon transfers followed by neutrons and charged particle emission A.S. Iljinov and E.A. Cherepanov (1980). The yield P(sub Z, N)(E*) of primary excited actinides is found using the model of N.V. Antonenko and R.V. Jolos (1991). Absolute cross-sections for different binary reaction channels are obtained by summing the cross-sections for all subchannels with an appreciable yield according to J. Wilczynski et al. (1980).

  5. Actinide recovery process

    DOEpatents

    Muscatello, A.C.; Navratil, J.D.; Saba, M.T.

    1985-06-13

    Process for the removal of plutonium polymer and ionic actinides from aqueous solutions by absorption onto a solid extractant loaded on a solid inert support such as polystyrene-divinylbenzene. The absorbed actinides can then be recovered by incineration, by stripping with organic solvents, or by acid digestion. Preferred solid extractants are trioctylphosphine oxide and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and the like. 2 tabs.

  6. PRODUCTION OF ACTINIDE METAL

    DOEpatents

    Knighton, J.B.

    1963-11-01

    A process of reducing actinide oxide to the metal with magnesium-zinc alloy in a flux of 5 mole% of magnesium fluoride and 95 mole% of magnesium chloride plus lithium, sodium, potassium, calcium, strontium, or barium chloride is presented. The flux contains at least 14 mole% of magnesium cation at 600-- 900 deg C in air. The formed magnesium-zinc-actinide alloy is separated from the magnesium-oxide-containing flux. (AEC)

  7. Thermochemistry of the actinides

    SciTech Connect

    Kleinschmidt, P.D.

    1993-10-01

    The measurement of equilibria by Knudsen effusion techniques and the enthalpy of formation of the actinide atoms is briefly discussed. Thermochemical data on the sublimation of the actinide fluorides is used to calculate the enthalpies of formation and entropies of the gaseous species. Estimates are made for enthalpies and entropies of the tetrafluorides and trifluorides for those systems where data is not available. The pressure of important species in the tetrafluoride sublimation processes is calculated based on this thermochemical data.

  8. Isotopic analysis of cometary organic matter

    NASA Astrophysics Data System (ADS)

    Kerridge, J. F.

    1991-04-01

    Carbon isotope ratios have been measured for CN in the coma of Comet Halley and for several CHON particles emitted by Halley. Of these, only the CHON-particle data may be reasonably related to organic matter in the cometary nucleus, but the true range of (C-13)/(C-12) values in those particles is quite uncertain. The D/H ratio in H2O in the Halley coma resembles that in Titan/Uranus.

  9. Isotopic analysis of cometary organic matter

    NASA Technical Reports Server (NTRS)

    Kerridge, John F.

    1991-01-01

    Carbon isotope ratios have been measured for CN in the coma of Comet Halley and for several CHON particles emitted by Halley. Of these, only the CHON-particle data may be reasonably related to organic matter in the cometary nucleus, but the true range of (C-13)/(C-12) values in those particles is quite uncertain. The D/H ratio in H2O in the Halley coma resembles that in Titan/Uranus.

  10. Actinide measurements by AMS using fluoride matrices

    NASA Astrophysics Data System (ADS)

    Cornett, R. J.; Kazi, Z. H.; Zhao, X.-L.; Chartrand, M. G.; Charles, R. J.; Kieser, W. E.

    2015-10-01

    Actinides can be measured by alpha spectroscopy (AS), mass spectroscopy or accelerator mass spectrometry (AMS). We tested a simple method to separate Pu and Am isotopes from the sample matrix using a single extraction chromatography column. The actinides in the column eluent were then measured by AS or AMS using a fluoride target matrix. Pu and Am were coprecipitated with NdF3. The strongest AMS beams of Pu and Am were produced when there was a large excess of fluoride donor atoms in the target and the NdF3 precipitates were diluted about 6-8 fold with PbF2. The measured concentrations of 239,240Pu and 241Am agreed with the concentrations in standards of known activity and with two IAEA certified reference materials. Measurements of 239,240Pu and 241Am made at A.E. Lalonde AMS Laboratory agree, within their statistical uncertainty, with independent measurements made using the IsoTrace AMS system. This work demonstrated that fluoride targets can produce reliable beams of actinide anions and that the measurement of actinides using fluorides agree with published values in certified reference materials.

  11. Nonaqueous actinide hydride dissolution and production of actinide $beta$- diketonates

    DOEpatents

    Crisler, L.R.

    1975-11-11

    Actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a hydride of the actinide material in a mixture of carbon tetrachloride and methanol. (auth)

  12. Stable-Isotopic Analysis of Porcine, Bovine, and Ovine Heparins

    PubMed Central

    Jasper, John P.; Zhang, Fuming; Poe, Russell B.; Linhardt, Robert J.

    2014-01-01

    The assessment of provenance of heparin is becoming a major concern for the pharmaceutical industry and its regulatory bodies. Batch-specific [carbon (δ13C), nitrogen (δ15N), oxygen (δ18O), sulfur (δ34S), and hydrogen (δD)] stable-isotopic compositions of five different animal-derived heparins were performed. Measurements readily allowed their differentiation into groups and/or subgroups based on their isotopic provenance. Principle component analysis showed that a bivariate plot of δ13C and δ18O is the best single, bivariate plot that results in the maximum discrimination ability when only two stable isotopes are used to describe the variation in the data set. Stable-isotopic analyses revealed that (i) stable-isotope measurements on these highly-sulfated polysaccharide (MW ~15 kDa) natural products (“biologics”) were feasible; (ii) in bivariate plots, the δ13C versus δ18O plot reveals a well-defined relationship for source differentiation of hogs raised in the US from hogs raised in Europe and China; (iii) the δD versus δ18O plot revealed the most well-defined relationship for source differentiation based on the hydrologic-environmental isotopes of water (D/H and 18O/16O), and (iv) the δ15N versus δ18O and δ34S versus δ18O relationships are both very similar, possibly reflecting the food sources used by the different heparin producers. PMID:25186630

  13. Stable isotopic analysis of porcine, bovine, and ovine heparins.

    PubMed

    Jasper, John P; Zhang, Fuming; Poe, Russell B; Linhardt, Robert J

    2015-02-01

    The assessment of provenance of heparin is becoming a major concern for the pharmaceutical industry and its regulatory bodies. Batch-specific [carbon (δ(13) C), nitrogen (δ(15) N), oxygen (δ(18) O), sulfur (δ(34) S), and hydrogen (δD)] stable isotopic compositions of five different animal-derived heparins were performed. Measurements readily allowed their differentiation into groups and/or subgroups based on their isotopic provenance. Principle component analysis showed that a bivariate plot of δ(13) C and δ(18) O is the best single, bivariate plot that results in the maximum discrimination ability when only two stable isotopes are used to describe the variation in the data set. Stable isotopic analyses revealed that (1) stable isotope measurements on these highly sulfated polysaccharide (molecular weight ∼15 kDa) natural products ("biologics") were feasible; (2) in bivariate plots, the δ(13) C versus δ(18) O plot reveals a well-defined relationship for source differentiation of hogs raised in the United States from hogs raised in Europe and China; (3) the δD versus δ(18) O plot revealed the most well-defined relationship for source differentiation based on the hydrologic environmental isotopes of water (D/H and (18) O/(16) O); and (4) the δ(15) N versus δ(18) O and δ(34) S versus δ(18) O relationships are both very similar, possibly reflecting the food sources used by the different heparin producers. PMID:25186630

  14. Stable isotopic analysis of porcine, bovine, and ovine heparins.

    PubMed

    Jasper, John P; Zhang, Fuming; Poe, Russell B; Linhardt, Robert J

    2015-02-01

    The assessment of provenance of heparin is becoming a major concern for the pharmaceutical industry and its regulatory bodies. Batch-specific [carbon (δ(13) C), nitrogen (δ(15) N), oxygen (δ(18) O), sulfur (δ(34) S), and hydrogen (δD)] stable isotopic compositions of five different animal-derived heparins were performed. Measurements readily allowed their differentiation into groups and/or subgroups based on their isotopic provenance. Principle component analysis showed that a bivariate plot of δ(13) C and δ(18) O is the best single, bivariate plot that results in the maximum discrimination ability when only two stable isotopes are used to describe the variation in the data set. Stable isotopic analyses revealed that (1) stable isotope measurements on these highly sulfated polysaccharide (molecular weight ∼15 kDa) natural products ("biologics") were feasible; (2) in bivariate plots, the δ(13) C versus δ(18) O plot reveals a well-defined relationship for source differentiation of hogs raised in the United States from hogs raised in Europe and China; (3) the δD versus δ(18) O plot revealed the most well-defined relationship for source differentiation based on the hydrologic environmental isotopes of water (D/H and (18) O/(16) O); and (4) the δ(15) N versus δ(18) O and δ(34) S versus δ(18) O relationships are both very similar, possibly reflecting the food sources used by the different heparin producers.

  15. Pitfalls in compound-specific isotope analysis of environmental samples.

    PubMed

    Blessing, Michaela; Jochmann, Maik A; Schmidt, Torsten C

    2008-01-01

    In the last decade compound-specific stable isotope analysis (CSIA) has evolved as a valuable technique in the field of environmental science, especially in contaminated site assessment. Instrumentation and methods exist for highly precise measurements of the isotopic composition of organic contaminants even in a very low concentration range. Nevertheless, the determination of precise and accurate isotope data of environmental samples can be a challenge. Since CSIA is gaining more and more popularity in the assessment of in situ biodegradation of organic contaminants, an increasing number of authorities and environmental consulting offices are interested in the application of the method for contaminated site remediation. Because of this, it is important to demonstrate the problems and limitations associated with compound-specific isotope measurements of environmental samples. In this review, potential pitfalls of the analytical procedure are critically discussed and strategies to avoid possible sources of error are provided. In order to maintain the analytical quality and to ensure the basis for reliable stable isotope data, recommendations on groundwater sampling, and sample preservation and storage are given. Important aspects of sample preparation and preconcentration techniques to improve sensitivity are highlighted. Problems related to chromatographic resolution and matrix interference are discussed that have to be considered in order to achieve accurate gas chromatography/isotope ratio mass spectrometry measurements. As a result, the need for a thorough investigation of compound-specific isotope fractionation effects introduced by any step of the overall analytical method by standards with known isotopic composition is emphasized. Finally, we address some important points that have to be considered when interpreting data from field investigations.

  16. Enantioselective stable isotope analysis (ESIA) of polar Herbicides

    NASA Astrophysics Data System (ADS)

    Maier, Michael; Qiu, Shiran; Elsner, Martin

    2013-04-01

    The complexity of aquatic systems makes it challenging to assess the environmental fate of chiral micropolutants. As an example, chiral herbicides are frequently detected in the environment (Buser and Muller, 1998); however, hydrological data is needed to determine their degradability from concentration measurements. Otherwise declining concentrations cannot unequivocally be attributed to degradation, but could also be caused by dilution effects. In contrast, isotope ratios or enantiomeric ratios are elegant alternatives that are independent of dilution and can even deliver insights into reaction mechanisms. To combine the advantages of both approaches we developed an enatioselective stable isotope analysis (ESIA) method to investigate the fate of the chiral herbicides 4-CPP ((RS)-2-(4-chlorophenoxy)-propionic acid), mecoprop (2-(4-Chloro-2-methylphenoxy)-propionic acid) and dichlorprop (2-(2,4-Dichlorophenoxy)-propionic acid). After testing the applicable concentration range of the method, enantioselective isotope fractionation was investigated by microbial degradation using dichlorprop as a model compound. The method uses enantioselective gas-chromatography (GC) to separate enantiomers. Subsequently samples are combusted online to CO2 and carbon isotope ratios are determined for each enantiomer by isotope-ratio-mass-spectrometry (IRMS). Because the analytes contain a polar carboxyl-group, samples were derivatised prior to GC-IRMS analysis with methanolic BF3 solution. Precise carbon isotope analysis (2σ ≤0.5‰) was achieved with a high sensitivity of ≥ 7 ng C that is needed on column for one analysis. Microbial degradation of the model compound dichlorprop was conducted with Delftia acidovorans MC1 and pronounced enantiomer fractionation, but no isotope fractionation was detected. The absence of isotope fractionation can be explained by two scenarios: either the degrading enzyme has no isotopic preference, or another step in the reaction without an isotopic

  17. Enhanced techniques for the measurement of ultra-low level (pg and fg) actinide analysis by ICP-MS for forensic and geologic applications

    NASA Astrophysics Data System (ADS)

    Pollington, A. D.; Kinman, W.; Hanson, S. K.

    2014-12-01

    and accuracy of actinide isotope measurements and what procedures can be applied to minimize interferences.

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  19. Analysis of proteome dynamics in mice by isotopic labeling.

    PubMed

    Price, John C; Ghaemmaghami, Sina

    2014-01-01

    Recent advances in mass spectrometry and in vivo isotopic labeling have enabled proteome-wide analyses of protein turnover in complex organisms. Here, we describe a protocol for analyzing protein turnover rates in mouse tissues by comprehensive (15)N labeling. The procedure involves the complete isotopic labeling of blue green algae (Spirulina platensis) with (15)N and utilizing it as a source of dietary nitrogen for mice. We outline a detailed protocol for in-house production of (15)N-labeled algae, labeling of mice, and analysis of isotope incorporation kinetics by mass spectrometry. The methodology can be adapted to analyze proteome dynamics in most murine tissues and may be particularly useful in the analysis of proteostatic disruptions in mouse models of disease. PMID:24791984

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

    NASA Technical Reports Server (NTRS)

    Cooper, George

    2004-01-01

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

  1. Hg stable isotope analysis by the double-spike method.

    PubMed

    Mead, Chris; Johnson, Thomas M

    2010-06-01

    Recent publications suggest great potential for analysis of Hg stable isotope abundances to elucidate sources and/or chemical processes that control the environmental impact of mercury. We have developed a new MC-ICP-MS method for analysis of mercury isotope ratios using the double-spike approach, in which a solution containing enriched (196)Hg and (204)Hg is mixed with samples and provides a means to correct for instrumental mass bias and most isotopic fractionation that may occur during sample preparation and introduction into the instrument. Large amounts of isotopic fractionation induced by sample preparation and introduction into the instrument (e.g., by batch reactors) are corrected for. This may greatly enhance various Hg pre-concentration methods by correcting for minor fractionation that may occur during preparation and removing the need to demonstrate 100% recovery. Current precision, when ratios are normalized to the daily average, is 0.06 per thousand, 0.06 per thousand, 0.05 per thousand, and 0.05 per thousand (2sigma) for (202)Hg/(198)Hg, (201)Hg/(198)Hg, (200)Hg/(198)Hg, and (199)Hg/(198)Hg, respectively. This is slightly better than previously published methods. Additionally, this precision was attained despite the presence of large amounts of other Hg isotopes (e.g., 5.0% atom percent (198)Hg) in the spike solution; substantially better precision could be achieved if purer (196)Hg were used.

  2. Nuclear waste actinides as fissile fuel in hybrid blankets

    SciTech Connect

    Sahin, S.; Al-Kusayer, T.A.

    1983-12-01

    The widespread use of the present LWRs produces substantial quantities of nuclear waste materials. Among those, actinide nuclear waste poses a serious problem of stockage because the associated half life times for actinides is measured in terms of geological time periods (several millions of years) so that no waste disposal guarantee over such time intervals can be given, except for space disposal. On the other hand, these nuclear waste actinides are very good fissionable materials for high energetic (D,T) fusion neutrons. It is therefore worthwhile to investigate their quality as potential nuclear fuel in hybrid blankets. The present study investigates the neutronic performance of hybrid blankets containing Np/sup 237/ and Cm/sup 244/ as fissile materials. The isotopic composition of Americium has been adjusted to the spent fuel isotope composition of a LWR. The geometrical design has been made, according to the AYMAN fussion-fission (hybrid) experimental facility, now in the very early phase of planning.

  3. Trophic Hierarchies Illuminated via Amino Acid Isotopic Analysis

    PubMed Central

    Steffan, Shawn A.; Chikaraishi, Yoshito; Horton, David R.; Ohkouchi, Naohiko; Singleton, Merritt E.; Miliczky, Eugene; Hogg, David B.; Jones, Vincent P.

    2013-01-01

    Food web ecologists have long sought to characterize the trophic niches of animals using stable isotopic analysis. However, distilling trophic position from isotopic composition has been difficult, largely because of the variability associated with trophic discrimination factors (inter-trophic isotopic fractionation and routing). We circumvented much of this variability using compound-specific isotopic analysis (CSIA). We examined the 15N signatures of amino acids extracted from organisms reared in pure culture at four discrete trophic levels, across two model communities. We calculated the degree of enrichment at each trophic level and found there was a consistent trophic discrimination factor (~7.6‰). The constancy of the CSIA-derived discrimination factor permitted unprecedented accuracy in the measurement of animal trophic position. Conversely, trophic position estimates generated via bulk-15N analysis significantly underestimated trophic position, particularly among higher-order consumers. We then examined the trophic hierarchy of a free-roaming arthropod community, revealing the highest trophic position (5.07) and longest food chain ever reported using CSIA. High accuracy in trophic position estimation brings trophic function into sharper focus, providing greater resolution to the analysis of food webs. PMID:24086703

  4. Connecting laboratory behavior to field function through stable isotope analysis.

    PubMed

    Glon, Mael G; Larson, Eric R; Pangle, Kevin L

    2016-01-01

    Inherent difficulties of tracking and observing organisms in the field often leave researchers with no choice but to conduct behavioral experiments under laboratory settings. However, results of laboratory experiments do not always translate accurately to natural conditions. A fundamental challenge in ecology is therefore to scale up from small area and short-duration laboratory experiments to large areas and long durations over which ecological processes generally operate. In this study, we propose that stable isotope analysis may be a tool that can link laboratory behavioral observations to past field interactions or function of individual organisms. We conducted laboratory behavioral assays to measure dominance of invasive rusty crayfish, Orconectes rusticus, and used stable isotope analysis to hindcast trophic positions of these crayfish under preceding natural conditions. We hypothesized that more dominant crayfish in our assays would have higher trophic positions if dominance were related to competitive ability or willingness to pursue high-risk, high-reward prey. We did not find a relationship between crayfish dominance and trophic position, and therefore infer that laboratory dominance of crayfish may not necessarily relate to their ecology in the field. However, this is to our knowledge the first attempt to directly relate laboratory behavior to field performance via stable isotope analysis. We encourage future studies to continue to explore a possible link between laboratory and field behavior via stable isotope analysis, and propose several avenues to do so. PMID:27077010

  5. Trophic spectra under the lens of amino acid isotopic analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Recent advances in compound specific isotopic ratio analysis (CSIRA) have allowed researchers to measure trophic fractionation of 15N in specific amino acids, namely glutamic acid and phenylalanine. These amino acids have proven useful in food web studies because of the wide and consistent disparity...

  6. Connecting laboratory behavior to field function through stable isotope analysis

    PubMed Central

    Larson, Eric R.; Pangle, Kevin L.

    2016-01-01

    Inherent difficulties of tracking and observing organisms in the field often leave researchers with no choice but to conduct behavioral experiments under laboratory settings. However, results of laboratory experiments do not always translate accurately to natural conditions. A fundamental challenge in ecology is therefore to scale up from small area and short-duration laboratory experiments to large areas and long durations over which ecological processes generally operate. In this study, we propose that stable isotope analysis may be a tool that can link laboratory behavioral observations to past field interactions or function of individual organisms. We conducted laboratory behavioral assays to measure dominance of invasive rusty crayfish, Orconectes rusticus, and used stable isotope analysis to hindcast trophic positions of these crayfish under preceding natural conditions. We hypothesized that more dominant crayfish in our assays would have higher trophic positions if dominance were related to competitive ability or willingness to pursue high-risk, high-reward prey. We did not find a relationship between crayfish dominance and trophic position, and therefore infer that laboratory dominance of crayfish may not necessarily relate to their ecology in the field. However, this is to our knowledge the first attempt to directly relate laboratory behavior to field performance via stable isotope analysis. We encourage future studies to continue to explore a possible link between laboratory and field behavior via stable isotope analysis, and propose several avenues to do so. PMID:27077010

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

    PubMed

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

    2015-10-01

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

  8. 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.

  9. Stable isotope analysis of breath using the optogalvanic effect

    NASA Astrophysics Data System (ADS)

    Murnick, Daniel E.; Colgan, M. J.; Lie, H. P.; Stoneback, D.

    1996-05-01

    A new technique based on the optogalvanic effect has been developed for the measurement of stable isotope ratios in the carbon dioxide of exhaled breath. Data obtained before and after ingestion of harmless stable isotope labeled compounds, metabolized to carbon dioxide, can be used for sensitive noninvasive diagnostics of various disease conditions. The technique uses the specificity of laser resonance spectroscopy and achieves sensitivity and accuracy typical of sophisticated isotope ratio mass spectrometers. Using fixed frequency carbon dioxide lasers, 13C/12C ratios can be determined with a precision of 2 ppm with 100 second averaging times. Multiple samples can be analyzed simultaneously providing real time continuous calibration. In a first application, analysis of 13C/12C ratios in exhaled human breath after ingestion of 13C labeled urea is being developed as a diagnostic for the bacterium H-pylori, known to be the causative agent for most peptic and duodenal ulcers.

  10. STABLE CARBON ISOTOPE ANALYSIS OF SUBFOSSIL WOOD FROM AUSTRIAN ALPS

    PubMed Central

    KŁUSEK, MARZENA; PAWEŁCZYK, SŁAWOMIRA

    2015-01-01

    The presented studies were carried out in order to check the usefulness of subfossil wood for stable isotope analysis. The aim of research was also to define the optimal method of subfossil samples preparation. Subfossil samples used during the presented studies are a part of the multi-century dendrochronological scale. This chronology originates in an area situated around a small mountain lake — Schwarzersee, in Austria. The obtained results of stable carbon isotope measurements confirmed that the method of α-cellulose extraction by the application of acidic sodium chlorite and sodium hydroxide solutions removes resins and other mobile compounds from wood. Therefore, in the case of the analysed samples, the additional chemical process of extractives removing was found to be unnecessary. Studied wood samples contained an adequate proportion of α-cellulose similar to the values characteristic for the contemporary trees. This proved an adequate wood preservation which is essential for the conduction of isotopic research. PMID:26346297

  11. A method for the rapid radiochemical analysis of uranium and thorium isotopes in impure carbonates.

    PubMed

    Elyahyaoui, A; Zarki, R; Chiadli, A

    2003-01-01

    A simple method combining solvent extraction and electrodeposition procedures is described for the determination of the isotopic composition and content of uranium and thorium in travertine samples. The actinide elements are extracted with diethyl ether from a calcium nitrate solution. The isolation of the elements and the alpha source preparation are performed in two steps after the sample digestion. The acid leaching of samples is performed using both partial and total dissolution methods. High recoveries of both uranium and thorium and good alpha-spectra are obtained with both partial and total dissolution methods. PMID:12485673

  12. Minior Actinide Doppler Coefficient Measurement Assessment

    SciTech Connect

    Nolan E. Hertel; Dwayne Blaylock

    2008-04-10

    The "Minor Actinide Doppler Coefficient Measurement Assessment" was a Department of Energy (DOE) U-NERI funded project intended to assess the viability of using either the FLATTOP or the COMET critical assembly to measure high temperature Doppler coefficients. The goal of the project was to calculate using the MCNP5 code the gram amounts of Np-237, Pu-238, Pu-239, Pu-241, AM-241, AM-242m, Am-243, and CM-244 needed to produce a 1E-5 in reactivity for a change in operating temperature 800C to 1000C. After determining the viability of using the assemblies and calculating the amounts of each actinide an experiment will be designed to verify the calculated results. The calculations and any doncuted experiments are designed to support the Advanced Fuel Cycle Initiative in conducting safety analysis of advanced fast reactor or acceoerator-driven transmutation systems with fuel containing high minor actinide content.

  13. A systematic analysis of the spectra of trivalent actinide chlorides in D sub 3 h site symmetry

    SciTech Connect

    Carnall, W.T. )

    1992-06-15

    The optical spectra of actinide ions in the compound AnCl{sub 3} and doped into single-crystal LaCl{sub 3} were interpreted in terms of transitions within 5{ital f}{sup {ital N}} configurations. Energy-level calculations were carried out using an effective-operator Hamiltonian, the parameters of which were determined by fitting experimental data. Atomic and crystal-field matrices were diagonalized simultaneously assuming an approximate {ital D}{sub 3{ital h}} site symmetry. Spectroscopic data were taken from the literature but in most cases supplemented by unpublished measurements in absorption and in fluorescence. Data for each ion were analyzed independently, then the model parameters were intercompared and in many cases adjusted such that in the final fitting process the principal interactions showed uniform trends in parameter values with increasing atomic number. Consistent with analyses of the spectra of lanthanide ions in both LaCl{sub 3} and LaF{sub 3}, abrupt changes in magnitude of certain crystal-field parameters were found near the center of the 5{ital f}{sup {ital N}} series. This resulted in two groups of parameter values, but with consistent trends for both halves of the series, and generally very good agreement between observed and computed energies. A new energy-level chart based on computed crystal-field level energies for each trivalent actinide ion has been prepared.

  14. Ion Mobility Mass Spectrometry Direct Isotope Abundance Analysis

    SciTech Connect

    Manuel J. Manard, Stephan Weeks, Kevin Kyle

    2010-05-27

    The nuclear forensics community is currently engaged in the analysis of illicit nuclear or radioactive material for the purposes of non-proliferations and attribution. One technique commonly employed for gathering nuclear forensics information is isotope analysis. At present, the state-of-the-art methodology for obtaining isotopic distributions is thermal ionization mass spectrometry (TIMS). Although TIMS is highly accurate at determining isotope distributions, the technique requires an elementally pure sample to perform the measurement. The required radiochemical separations give rise to sample preparation times that can be in excess of one to two weeks. Clearly, the nuclear forensics community is in need of instrumentation and methods that can expedite their decision making process in the event of a radiological release or nuclear detonation. Accordingly, we are developing instrumentation that couples a high resolution IM drift cell to the front end of a MS. The IM cell provides a means of separating ions based upon their collision cross-section and mass-to-charge ratio (m/z). Two analytes with the same m/z, but with different collision cross-sections (shapes) would exit the cell at different times, essentially enabling the cell to function in a similar manner to a gas chromatography (GC) column. Thus, molecular and atomic isobaric interferences can be effectively removed from the ion beam. The mobility selected chemical species could then be introduced to a MS for high-resolution mass analysis to generate isotopic distributions of the target analytes. The outcome would be an IM/MS system capable of accurately measuring isotopic distributions while concurrently eliminating isobaric interferences and laboratory radiochemical sample preparation. The overall objective of this project is developing instrumentation and methods to produce near real-time isotope distributions with a modular mass spectrometric system that performs the required gas-phase chemistry and

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

    USGS Publications Warehouse

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

    2015-01-01

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

  16. Demonstration of compound-specific isotope analysis of hydrogen isotope ratios in chlorinated ethenes.

    PubMed

    Kuder, Tomasz; Philp, Paul

    2013-02-01

    High-temperature pyrolysis conversion of organic analytes to H(2) in hydrogen isotope ratio compound-specific isotope analysis (CSIA) is unsuitable for chlorinated compounds such as trichloroethene (TCE) and cis-1,2-dichloroethene (DCE), due to competition from HCl formation. For this reason, the information potential of hydrogen isotope ratios of chlorinated ethenes remains untapped. We present a demonstration of an alternative approach where chlorinated analytes reacted with chromium metal to form H(2) and minor amounts of HCl. The values of δ(2)H were obtained at satisfactory precision (± 10 to 15 per thousand), however the raw data required daily calibration by TCE and/or DCE standards to correct for analytical bias that varies over time. The chromium reactor has been incorporated into a purge and trap-CSIA method that is suitable for CSIA of aqueous environmental samples. A sample data set was obtained for six specimens of commercial product TCE. The resulting values of δ(2)H were between -184 and +682 ‰, which significantly widened the range of manufactured TCE δ(2)H signatures identified by past work. The implications of this finding to the assessment of TCE contamination are discussed.

  17. Isotope Analysis Reveals Foraging Area Dichotomy for Atlantic Leatherback Turtles

    PubMed Central

    Angulo, Elena; Das, Krishna; Girondot, Marc

    2008-01-01

    Background The leatherback turtle (Dermochelys coriacea) has undergone a dramatic decline over the last 25 years, and this is believed to be primarily the result of mortality associated with fisheries bycatch followed by egg and nesting female harvest. Atlantic leatherback turtles undertake long migrations across ocean basins from subtropical and tropical nesting beaches to productive frontal areas. Migration between two nesting seasons can last 2 or 3 years, a time period termed the remigration interval (RI). Recent satellite transmitter data revealed that Atlantic leatherbacks follow two major dispersion patterns after nesting season, through the North Gulf Stream area or more eastward across the North Equatorial Current. However, information on the whole RI is lacking, precluding the accurate identification of feeding areas where conservation measures may need to be applied. Methodology/Principal Findings Using stable isotopes as dietary tracers we determined the characteristics of feeding grounds of leatherback females nesting in French Guiana. During migration, 3-year RI females differed from 2-year RI females in their isotope values, implying differences in their choice of feeding habitats (offshore vs. more coastal) and foraging latitude (North Atlantic vs. West African coasts, respectively). Egg-yolk and blood isotope values are correlated in nesting females, indicating that egg analysis is a useful tool for assessing isotope values in these turtles, including adults when not available. Conclusions/Significance Our results complement previous data on turtle movements during the first year following the nesting season, integrating the diet consumed during the year before nesting. We suggest that the French Guiana leatherback population segregates into two distinct isotopic groupings, and highlight the urgent need to determine the feeding habitats of the turtle in the Atlantic in order to protect this species from incidental take by commercial fisheries. Our

  18. FY2011 Annual Report for the Actinide Isomer Detection Project

    SciTech Connect

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Tatishvili, Gocha; Hatarik, R.

    2011-10-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for SNM. This project entails isomer identification and characterization and neutron population studies. This document summarizes activities from its third year - completion of the isomer identification characterization experiments and initialization of the neutron population experiments. The population and decay of the isomeric state in 235U remain elusive, although a number of candidate gamma rays have been identified. In the course of the experiments, a number of fission fragment isomers were populated and measured [Ressler 2010]. The decays from these isomers may also provide a suitable signature for the presence of fissile material. Several measurements were conducted throughout this project. This report focuses on the results of an experiment conducted collaboratively by PNNL, LLNL and LBNL in December 2010 at LBNL. The measurement involved measuring the gamma-rays emitted from an HEU target when bombarded with 11 MeV neutrons. This report discussed the analysis and resulting conclusions from those measurements. There was one strong candidate, at 1204 keV, of an isomeric signature of 235U. The half-life of the state is estimated to be 9.3 {mu}s. The measured time dependence fits the decay time structure very well. Other possible explanations for the 1204-keV state were investigated, but they could not explain the gamma ray. Unfortunately, the relatively limited statistics of the measurement limit, and the lack of understanding of some of the systematic of the experiment, limit

  19. A systematic analysis of the spectra of trivalent actinide chlorides in D sub 3h site symmetry

    SciTech Connect

    Carnall, W.T.

    1989-11-01

    The optical spectra of actinide ions in the compound AnCl{sub 3} and doped into single crystal LaCl{sub 3} were interpreted in terms of transitions within 5f{sup N} configurations. Energy-level calculations were carried out using an effective operator Hamiltonian, the parameters of which were determined by fitting experimental data. Atomic and crystal-field matrices were diagonalized simultaneously assuming an approximate D{sub 3h} site symmetry. The spectroscopic data were taken from the literature but in most cases supplemented by unpublished measurements in absorption and in fluorescence. Spectroscopic data for each ion were analyzed independently, then the model parameters were intercompared and in many cases adjusted such that in the final fitting process the principal interactions showed uniform trends in parameter values with increasing atomic number. Consistent with analyses of the spectra of lanthanide ions in both LaCl{sub 3} and LaF{sub 3}, abrupt changes in magnitude of certain crystal-field parameters were found near the center of the 5f{sup N}-series. This resulted in two groups of parameter values, but with consistent trends for both halves of the series, and generally very good agreement between observed and computed energies. A new energy level chart based on computed crystal-field level energies for each trivalent actinide ion has been prepared. in addition, the parameters of the atomic part of each 5f{sup N} Hamiltonian were used to calculate the matrix elements of U{sup ({lambda})} for selected transitions. The values were tabulated to facilitate calculation of intensity-related parameters for 5f{sup N}-transitions using the Judd-Ofelt theory. 44 refs., 10 figs., 3 tabs.

  20. Value of burnup credit beyond actinides

    SciTech Connect

    Lancaster, D.; Fuentes, E.; Kang, Chi

    1997-12-01

    DOE has submitted a topical report to the NRC justifying burnup credit based only on actinide isotopes (U-234, U-235, U-236, U-238, Pu-238, Pu-239, Pu-240, Pu-241, Pu-242, and Am-241). When this topical report is approved, it will allow a great deal of the commercial spent nuclear fuel to be transported in significantly higher capacity casks. A cost savings estimate for shipping fuel in 32 assembly (burnup credit) casks as opposed to 24 assembly (non-burnup credit) casks was previously presented. Since that time, more detailed calculations have been performed using the methodology presented in the Actinide-Only Burnup Credit Topical Report. Loading curves for derated casks have been generated using actinide-only burnup credit and are presented in this paper. The estimates of cost savings due to burnup credit for shipping fuel utilizing 32, 30, 28, and 24 assembly casks where only the 24 assembly cask does not burnup credit have been created and are discussed. 4 refs., 2 figs.

  1. 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.

  2. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

    NASA Astrophysics Data System (ADS)

    Jost, H. J. H.; Stoltmann, T.; Stöbener, N.; Wapelhorst, E.; Mandic, M.; Aepfler, R.; Hinrichs, K. U.; Taubner, H.; Elvert, M.

    2015-12-01

    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.

  3. Compound-specific isotope analysis of benzotriazole and its derivatives.

    PubMed

    Spahr, Stephanie; Huntscha, Sebastian; Bolotin, Jakov; Maier, Michael P; Elsner, Martin; Hollender, Juliane; Hofstetter, Thomas B

    2013-03-01

    Compound-specific isotope analysis (CSIA) is an important tool for the identification of contaminant sources and transformation pathways, but it is rarely applied to emerging aquatic micropollutants owing to a series of instrumental challenges. Using four different benzotriazole corrosion inhibitors and its derivatives as examples, we obtained evidence that formation of organometallic complexes of benzotriazoles with parts of the instrumentation impedes isotope analysis. Therefore, we propose two strategies for accurate [Formula: see text]C and [Formula: see text]N measurements of polar organic micropollutants by gas chromatography isotope ratio mass spectrometry (GC/IRMS). Our first approach avoids metallic components and uses a Ni/Pt reactor for benzotriazole combustion while the second is based on the coupling of online methylation to the established GC/IRMS setup. Method detection limits for on-column injection of benzotriazole, as well as its 1-CH[Formula: see text]-, 4-CH[Formula: see text]-, and 5-CH[Formula: see text]-substituted species were 0.1-0.3 mM and 0.1-1.0 mM for δ(13)C and δ(15)N analysis respectively, corresponding to injected masses of 0.7-1.8 nmol C and 0.4-3.0 nmol N, respectively. The Ni/Pt reactor showed good precision and was very long-lived ([Formula: see text]1000 successful measurements). Coupling isotopic analysis to offline solid-phase extraction enabled benzotriazole-CSIA in tap water, wastewater treatment effluent, activated sludge, and in commercial dishwashing products. A comparison of [Formula: see text]C and [Formula: see text]N values from different benzotriazoles and benzotriazole derivatives, both from commercial standards and in dishwashing detergents, reveals the potential application of the proposed method for source apportionment. PMID:23224662

  4. Automated SIMS Isotopic Analysis Of Small Dust Particles

    NASA Astrophysics Data System (ADS)

    Nittler, L.; Alexander, C.; Gyngard, F.; Morgand, A.; Zinner, E. K.

    2009-12-01

    The isotopic compositions of sub-μm to μm sized dust grains are of increasing interest in cosmochemistry, nuclear forensics and terrestrial aerosol research. Because of its high sensitivity and spatial resolution, Secondary Ion Mass Spectrometry (SIMS) is the tool of choice for measuring isotopes in such small samples. Indeed, SIMS has enabled an entirely new sub-field of astronomy: presolar grains in meteorites. In recent years, the development of the Cameca NanoSIMS ion probe has extended the reach of isotopic measurements to particles as small as 100 nm in diameter, a regime where isotopic precision is strongly limited by the total number of atoms in the sample. Many applications require obtaining isotopic data on large numbers of particles, necessitating the development of automated techniques. One such method is isotopic imaging, wherein images of multiple isotopes are acquired, each containing multiple dispersed particles, and image processing is used to determine isotopic ratios for individual particles. This method is powerful, but relatively inefficient for raster-based imaging on the NanoSIMS. Modern computerized control of instrumentation has allowed for another approach, analogous to commercial automated SEM-EDS particle analysis systems, in which images are used solely to locate particles followed by fully automated grain-by-grain analysis. The first such system was developed on the Carnegie Institution’s Cameca ims-6f, and was used to generate large databases of presolar grains. We have recently developed a similar system for the NanoSIMS, whose high sensitivity allows for smaller grains to be analyzed with less sample consumption than is possible with the 6f system. The 6f and NanoSIMS systems are functionally identical: an image of dispersed grains is obtained with sufficient statistical precision for an algorithm to identify the positions of individual particles, the primary ion beam is deflected to each particle in turn and rastered in a small

  5. 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

  6. Evaluation of Homogeneous Options: Effects of Minor Actinide Exclusion from Single and Double Tier Recycle in Sodium Fast Reactors

    SciTech Connect

    R. M. Ferrer; S. Bays; M. Pope

    2008-03-01

    The Systems Analysis Campaign under the Global Nuclear Energy Partnership (GNEP) has requested the fuel cycle analysis group at the Idaho National Laboratory (INL) to analyze and provide isotopic data for four scenarios in which different strategies for Minor Actinides (MA) management are investigated. A 1000 MWth commercial-scale Sodium Fast Reactor (SFR) design was selected as the baseline in this scenario study. Two transuranic (TRU) conversion ratios, defined as the ratio of the amount of TRU produced over the TRU destroyed in the reactor core, along with different fuel-types were investigated.

  7. 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.

  8. Actinide halide complexes

    SciTech Connect

    Avens, L.R.; Zwick, B.D.; Sattelberger, A.P.; Clark, D.L.; Watkin, J.G.

    1991-02-07

    A compound of the formula MX{sub n}L{sub m} wherein M = Th, Pu, Np,or Am thorium, X = a halide atom, n = 3 or 4, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is 3 or 4 for monodentate ligands or is 2 for bidentate ligands, where n + m = 7 or 8 for monodentate ligands or 5 or 6 for bidentate ligands, a compound of the formula MX{sub n} wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant, are provided.

  9. Analysis of actinides in an ombrotrophic peat core - evidence of post-depositional migration of fallout radionuclides

    NASA Astrophysics Data System (ADS)

    Quinto, Francesca; Hrnecek, Erich; Krachler, Michael; Shotyk, William; Steier, Peter; Winkler, Stephan R.

    2013-04-01

    Plutonium (239Pu, 240Pu, 241Pu, 242Pu) and uranium (236U, 238U) isotopes were analyzed in an ombrotrophic peat core from the Black Forest, Germany, representing the last 80 years of atmospheric deposition. The reliable determination of these isotopes at ultra-trace levels was possible using ultra-clean laboratory procedures and accelerator mass spectrometry. The 240Pu/239Pu isotopic ratios are constant along the core with a mean value of 0.19 ±0.02 (N = 32). This result is consistent with the acknowledged average 240Pu/239Pu isotopic ratio from global fallout in the Northern Hemisphere. The global fallout origin of Pu is confirmed by the corresponding 241Pu/239Pu (0.0012 ±0.0005) and 242Pu/239Pu (0.004 ± 0.001) isotopic ratios. The identification of the Pu isotopic composition characteristic for global fallout in peat layers pre-dating the period of atmospheric atom bomb testing (AD 1956 - AD 1980) is a clear evidence of the migration of Pu downwards the peat profile. The maximum of global fallout derived 236U is detected in correspondence to the age/depth layer of maximum stratospheric fallout (AD 1963). This finding demonstrates that the 236U bomb peak can be successfully used as an independent chronological marker complementing the 210Pb dating of peat cores. The profiles of the global fallout derived 236U and 239Pu are compared with those of 137Cs and 241Am. As typical of ombrothrophic peat, the temporal fallout pattern of 137Cs is poorly retained. Similarly like for Pu, post-depositional migration of 241Am in peat layers preceding the era of atmospheric nuclear tests is observed.

  10. Hanford Isotope Project strategic business analysis Cesium-137 (Cs-137)

    SciTech Connect

    1995-10-01

    The purpose of this business analysis is to address the beneficial reuse of Cesium 137 (Cs-137) in order to utilize a valuable national asset and possibly save millions of tax dollars. Food irradiation is the front runner application along with other uses. This business analysis supports the objectives of the Department of Energy National Isotope Strategy distributed in August 1994 which describes the DOE plans for the production and distribution of isotope products and services. As part of the Department`s mission as stated in that document. ``The Department of Energy will also continue to produce and distribute other radioisotopes and enriched stable isotopes for medical diagnostics and therapeutics, industrial, agricultural, and other useful applications on a businesslike basis. This is consistent with the goals and objectives of the National Performance Review. The Department will endeavor to look at opportunities for private sector to co-fund or invest in new ventures. Also, the Department will seek to divest from ventures that can more profitably or reliably be operated by the private sector.``

  11. A new opportunity: coincident spectroscopy in neutron-deficient actinides

    NASA Astrophysics Data System (ADS)

    Gothe, Oliver; Gates, J. M.; Gregorich, K. E.; Baartman, B.; Fallon, P.; Esker, N. E.; Kwarsick, J.; Machiavelli, A. O.; Mudder, P. R.; Olive, D. T.; Pang, G.; Rissanen, J.; Nitsche, H.

    2014-09-01

    Due to high γ-ray background rates heavy element production facilities are usually not sensitive to the electron capture decay of neutron deficient actinides. We have developed new capabilities at the Berkeley Gas Filled Separator (BGS) that allow us to study these isotopes. The highly selective and efficient separation of compound nucleus evaporation residue products using the BGS couple with a rapid delivery to a low-background detector facility, opens up many new possibilities for nuclear decay and structure studies in the neutron deficient actinides. The decay of these actinides produces vacancies in the K-shell resulting in x-rays uniquely identifying the Z of the decay products. We present the first results of this new methodology in studying the nuclear structure of fermium-254 by observing the gamma rays in coincidence with fermium x-rays. Coincident gamma-decay spectroscopy gives us a new tool to study the nuclear structure of previously inaccessible systems.

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

    NASA Astrophysics Data System (ADS)

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

    2000-10-01

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

  13. Environmental speciation of actinides.

    PubMed

    Maher, Kate; Bargar, John R; Brown, Gordon E

    2013-04-01

    Although minor in abundance in Earth's crust (U, 2-4 ppm; Th, 10-15 ppm) and in seawater (U, 0.003 ppm; Th, 0.0007 ppm), light actinides (Th, Pa, U, Np, Pu, Am, and Cm) are important environmental contaminants associated with anthropogenic activities such as the mining and milling of uranium ores, generation of nuclear energy, and storage of legacy waste resulting from the manufacturing and testing of nuclear weapons. In this review, we discuss the abundance, production, and environmental sources of naturally occurring and some man-made light actinides. As is the case with other environmental contaminants, the solubility, transport properties, bioavailability, and toxicity of actinides are dependent on their speciation (composition, oxidation state, molecular-level structure, and nature of the phase in which the contaminant element or molecule occurs). We review the aqueous speciation of U, Np, and Pu as a function of pH and Eh, their interaction with common inorganic and organic ligands in natural waters, and some of the common U-containing minerals. We also discuss the interaction of U, Np, Pu, and Am solution complexes with common Earth materials, including minerals, colloids, gels, natural organic matter (NOM), and microbial organisms, based on simplified model system studies. These surface interactions can inhibit (e.g., sorption to mineral surfaces, formation of insoluble biominerals) or enhance (e.g., colloid-facilitated transport) the dispersal of light actinides in the biosphere and in some cases (e.g., interaction with dissimilatory metal-reducing bacteria, NOM, or Mn- and Fe-containing minerals) can modify the oxidation states and, consequently, the behavior of redox-sensitive light actinides (U, Np, and Pu). Finally, we review the speciation of U and Pu, their chemical transformations, and cleanup histories at several U.S. Department of Energy field sites that have been used to mill U ores, produce fissile materials for reactors and weapons, and store

  14. Environmental speciation of actinides.

    PubMed

    Maher, Kate; Bargar, John R; Brown, Gordon E

    2013-04-01

    Although minor in abundance in Earth's crust (U, 2-4 ppm; Th, 10-15 ppm) and in seawater (U, 0.003 ppm; Th, 0.0007 ppm), light actinides (Th, Pa, U, Np, Pu, Am, and Cm) are important environmental contaminants associated with anthropogenic activities such as the mining and milling of uranium ores, generation of nuclear energy, and storage of legacy waste resulting from the manufacturing and testing of nuclear weapons. In this review, we discuss the abundance, production, and environmental sources of naturally occurring and some man-made light actinides. As is the case with other environmental contaminants, the solubility, transport properties, bioavailability, and toxicity of actinides are dependent on their speciation (composition, oxidation state, molecular-level structure, and nature of the phase in which the contaminant element or molecule occurs). We review the aqueous speciation of U, Np, and Pu as a function of pH and Eh, their interaction with common inorganic and organic ligands in natural waters, and some of the common U-containing minerals. We also discuss the interaction of U, Np, Pu, and Am solution complexes with common Earth materials, including minerals, colloids, gels, natural organic matter (NOM), and microbial organisms, based on simplified model system studies. These surface interactions can inhibit (e.g., sorption to mineral surfaces, formation of insoluble biominerals) or enhance (e.g., colloid-facilitated transport) the dispersal of light actinides in the biosphere and in some cases (e.g., interaction with dissimilatory metal-reducing bacteria, NOM, or Mn- and Fe-containing minerals) can modify the oxidation states and, consequently, the behavior of redox-sensitive light actinides (U, Np, and Pu). Finally, we review the speciation of U and Pu, their chemical transformations, and cleanup histories at several U.S. Department of Energy field sites that have been used to mill U ores, produce fissile materials for reactors and weapons, and store

  15. Full Range MGA Plutonium Isotopic Analysis using Single Ge Detector

    SciTech Connect

    Buckley, W.M.; Wang, T.F.; Friensehner, A.; Kreek, S.A.; Lanier, R.G.; Parker, W.E.; Ruhter, W.; Twomey, T.; Martinez, D.; Keyser, R.; Sangsingkeow, P.

    2000-06-26

    The Gamma-Ray multi-group analysis code MGA developed at Lawrence Livermore National Laboratory has been widely used in the area of gamma-ray non-destructive plutonium assay. This plutonium isotopic analysis code de-convolutes the complicated, 100-keV x-ray and gamma-ray region to obtain the ratio of Pu isotopes. Calibration of the detector efficiency is not required, but is determined intrinsically from the measured spectra. The code can either analyze low-energy gamma-ray spectrum taken using a high-resolution HPGe detector for energies below 300 keV, or analyze the low-energy spectrum combined with a high-energy spectrum (up to 1 MeV) in the two-detector analysis mode. In the latter case, the use of two detectors has been mandated by the conflicting requirements: excellent resolution at low energies (characteristic of small planar detectors) with good high-energy efficiency (characteristic of coaxial detectors). Usually, a high-energy spectrum taken using a coaxial Ge detector will not provide sufficient energy resolution for 100-keV plutonium isotopic analysis, while the small planar used at low energies has inadequate high-energy efficiency. An optimized-geometry ORTEC HPGe detector has been developed which combines good energy resolution at 100 keV combined with acceptable high-energy ({approx} 1 MeV) efficiency in a single detector. It has been used to gather spectra of both low- and high-energy regions of plutonium spectra simultaneously, for analysis by MGA in the two-detector mode. Five Pu gamma-ray calibration standard sources were used in this study of this special detector.

  16. Characterization of phenols biodegradation by compound specific stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Wei, Xi; Gilevska, Tetyana; Wenzig, Felix; Hans, Richnow; Vogt, Carsten

    2015-04-01

    -cresol degradation and 2.2±0.3‰ for m-cresol degradation, respectively. The carbon isotope fractionation patterns of phenol degradation differed more profoundly. Oxygen-dependent monooxygenation of phenol by A.calcoaceticus as the initial reaction yielded ƐC values of -1.5±0.02‰. In contrast, the anaerobic degradation initiated by ATP-dependent carboxylation performed by Thauera aromatia DSM 6984, produced no detectable fractionation (ƐC 0±0.1‰). D. cetonica showed a slight inverse carbon isotope fractionation (ƐC 0.4±0.1‰). In conclusion, a validated method for compound specific stable isotope analysis was developed for phenolic compounds, and the first data set of carbon enrichment factors upon the biodegradation of phenol and cresols with different activation mechanisms has been obtained in the present study. Carbon isotope fractionation analysis is a potentially powerful tool to monitor phenolic compounds degradation in the environment.

  17. Isotopic analysis for degradation diagnosis of calcite matrix in mortar.

    PubMed

    Dotsika, E; Psomiadis, D; Poutoukis, D; Raco, B; Gamaletsos, P

    2009-12-01

    Mortar that was used in building as well as in conservation and restoration works of wall paintings have been analysed isotopically (delta(13)C and delta(18)O) in order to evaluate the setting environments and secondary processes, to distinguish the structural components used and to determine the exact causes that incurred the degradation phenomena. The material undergoes weathering and decay on a large proportion of its surface and in depth, due to the infiltration of water through the structural blocks. Mineralogical analysis indicated signs of sulphation and dissolution/recrystallisation processes taking place on the material, whereas stable isotopes provided information relative to the origin of the CO(2) and water during calcite formation and degradation processes. Isotopic change of the initial delta(13)C and delta(18)O in carbonate matrix was caused by alteration of the primary source of CO(2) and H(2)O in mortar over time, particularly by recrystallisation of calcite with porewater, evaporated or re-condensed water, and CO(2) from various sources of atmospheric and biogenic origin. Human influence (surface treatment) and biological growth (e.g. fungus) are major exogenic processes which may alter delta(18)O and delta(13)C in lime mortar.

  18. Rapid Separation Methods to Characterize Actinides and Metallic Impurities in Plutonium Scrap Materials at SRS

    SciTech Connect

    Maxwell, S.L. III; Jones, V.D.

    1998-07-01

    The Nuclear Materials Stabilization and Storage Division at SRS plans to stabilize selected plutonium scrap residue materials for long term storage by dissolution processing and plans to stabilize other plutonium vault materials via high-temperature furnace processing. To support these nuclear material stabilization activities, the SRS Analytical Laboratories Department (ALD) will provide characterization of materials required prior to the dissolution or the high-firing of these materials. Lab renovations to install new analytical instrumentation are underway to support these activities that include glove boxes with simulated-process dissolution and high- pressure microwave dissolution capability. Inductively-coupled plasma atomic emission spectrometry (ICP-AES), inductively- coupled mass spectrometry (ICP-MS) and thermal-ionization mass spectrometry (TIMS) will be used to measure actinide isotopics and metallic impurities. New high-speed actinide separation methods have been developed that will be applied to isotopic characterization of nuclear materials by TIMS and ICP-MS to eliminate isobaric interferences between Pu-238 /U- 238 and Pu-241/Am-241. TEVA Resin, UTEVA Resin, and TRU Resin columns will be used with vacuum-assisted flow rates to minimize TIMS and ICP-MS sample turnaround times. For metallic impurity analysis, rapid column removal methods using UTEVA Resin, AGMP-1 anion resin and AG MP-50 cation resin have also been developed to remove plutonium and uranium matrix interferences prior to ICP-AES and ICP- MS measurements.

  19. The Separation and Isotopic Analysis Seawater Cu and Zn

    NASA Astrophysics Data System (ADS)

    Bermin, J.; Vance, D.; Archer, C.; Statham, P. J.

    2004-12-01

    Many transition metals are key micronutrients and their concentration profiles in the oceans often show nutrient-like patterns, with strong surface depletions and deep enrichments1. In addition, their biological usage has been shown to induce isotopic fractionations2 so that the precise and accurate analysis of their isotope systems in seawater has potential applications in tracing metal micronutrient usage in the past ocean. The analytical challenges involved in realising this goal are, however, considerable, given the low concentrations of transition metals in seawater and the requirement to extract small amounts from large samples at low blank and with no artificial isotopic fractionation. Here we present a method for the separation an analysis of Cu and Zn isotopes that is applicable to 0.1-5 L samples of seawater. Trace metals were concentrated from seawater using a Chelex-100 ion-exchange column3 and further purified and separated from each other using a small anion column4,5. All isotopic analyses were performed on a ThermoFinnigan Neptune instrument at the University of Bristol. The main requirements for precise and accurate isotopic analyses are a low contribution from analytical blank and the robust correction for analytical mass discrimination. Our blanks allow the analysis of seawater samples of 50-250 mL for Cu, samples of about 100 mL for Zn in the deep oceans and for Zn-depleted open ocean surface water samples of around 5L. The correction for mass discrimination is most readily considered as two components - that occurring during the chemical separation procedure in response to non-100% yields and that occurring in the mass spectrometer. Correction of all mass discrimination throughout the procedure is most robustly done for Zn and Fe using a double-spike that is added prior to any chemical treatment. This approach has been tested using standard-doped seawater samples that had previously been stripped of their metal contents using the Chelex column

  20. Gas core reactors for actinide transmutation and breeder applications

    NASA Technical Reports Server (NTRS)

    Clement, J. D.; Rust, J. H.

    1978-01-01

    This work consists of design power plant studies for four types of reactor systems: uranium plasma core breeder, uranium plasma core actinide transmuter, UF6 breeder and UF6 actinide transmuter. The plasma core systems can be coupled to MHD generators to obtain high efficiency electrical power generation. A 1074 MWt UF6 breeder reactor was designed with a breeding ratio of 1.002 to guard against diversion of fuel. Using molten salt technology and a superheated steam cycle, an efficiency of 39.2% was obtained for the plant and the U233 inventory in the core and heat exchangers was limited to 105 Kg. It was found that the UF6 reactor can produce high fluxes (10 to the 14th power n/sq cm-sec) necessary for efficient burnup of actinide. However, the buildup of fissile isotopes posed severe heat transfer problems. Therefore, the flux in the actinide region must be decreased with time. Consequently, only beginning-of-life conditions were considered for the power plant design. A 577 MWt UF6 actinide transmutation reactor power plant was designed to operate with 39.3% efficiency and 102 Kg of U233 in the core and heat exchanger for beginning-of-life conditions.

  1. Recovery and chemical purification of actinides at JRC, Karlsruhe

    NASA Astrophysics Data System (ADS)

    Bokelund, H.; Apostolidis, C.; Glatz, J.-P.

    1989-07-01

    The application of actinide elements in research and in technology is many times subject to rather stringent purity requirements; often a nuclear grade quality is specified. The additional possible demand for a high isotopic purity is a special feature in the handling of these elements. The amount of actinide elements contained in or adhering to materials declared as waste should be low for safety reasons and out of economic considerations. The release of transuranium elements to the environment must be kept negligible. For these and for other reasons a keen interest in the separation of actinides from various materials exists, either for a re-use through recycling, or for their safe confinement in waste packages. This paper gives a short review of the separation methods used for recovery and purification of actinide elements over the past years in the European Institute for Transuranium Elements. The methods described here involve procedures based on precipitation, ion exchange or solvent extraction; often used in a combination. The extraction methods were preferably applied in a Chromatographie column mode. The actinide elements purified and/or separated from each other by the above methods include uranium, neptunium, plutonium, americium, curium, and californium. For the various elements the work was undertaken with different aims, ranging from reprocessing and fabrication of nuclear fuels on a kilogramme scale, over the procurement of alpha-free waste, to the preparation of neutron sources of milligramme size.

  2. Enantiomeric and Isotopic Analysis of Sugar Derivatives in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, George; Asiyo, Cynthia; Turk, Kendra; DeVincenzi, Donald (Technical Monitor)

    2002-01-01

    Several classes of organic compounds are found in carbonaceous meteorites including amino acids, carboxylic acids, hydroxy acids, purines, and pyrimidines. Such compounds are thought to have been delivered to the early Earth in asteroids and comets and may have played a role in the origin of life. Likewise, sugar derivatives are critical to all known lifeforms. Recent analyses of the Murchison and Murray carbonaceous meteorites revealed a diverse suite of such derivatives, i.e., sugar alcohols, and sugar acids. This presentation will focus primarily on the analysis of individual sugar acids - their enantiomeric and isotopic composition. Analysis of these compounds may reveal the nature of past (or present) meteoritic sugars themselves. For example, if parent sugars decomposed (by well-known mechanisms) to give the present acids, were their enantiomeric ratios preserved? Combined with other evidence, the enantiomeric composition of such compounds as glyceric acid and (especially) rare acids may help to answer such questions. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) as a group revealed that they were indigenous to the meteorite. Preliminary C-13 analysis of glyceric acid shows that it is also extraterrestrial.

  3. Importance of the (n,gamma) Cm-247 Evaluation on Neutron Emission in Fast Reactor Fuel Cycle Analysis

    SciTech Connect

    Benoit Forget; Mehdi Asgari; Rodolfo M. Ferrer

    2007-11-01

    As part of the GNEP program, it is envisioned to build a fast reactor for the transmutation of minor actinides. The spent nuclear fuel from the current fleet of light water reactors would be recycled, the current baseline is the UREX+1a process, and would act as a feed for the fast reactor. As the fuel is irradiated in a fast reactor a certain quantity of minor actinides would thus build up in the fuel stream creating possible concerns with the neutron emission of these minor actinides for fuel transportation, handling and fabrication. Past neutronic analyses had not tracked minor actinides above Cm-246 in the transmutation chain, because of the small influence on the overall reactor performance and cycle parameters. However, when trying to quantify the neutron emission from the recycled fuel with high minor actinide content, these higher isotopes play an essential role and should be included in the analysis. In this paper, the influence of tracking these minor actinides on the calculated neutron emission is presented. Also presented is the particular influence of choosing a different evaluated cross section data set to represent the minor actinides above Cm-246. The first representation uses the cross-sections provided by MC2-2 for all isotopes, while the second representation uses infinitely diluted ENDF/BVII.0 cross-sections for Cm-247 to Cf-252 and MC2-2 for all other isotopes.

  4. PROCESS OF PRODUCING ACTINIDE METALS

    DOEpatents

    Magel, T.T.

    1959-07-14

    The preparation of actinide metals in workable, coherent form is described. In general, the objects of the invention are achieved by heating a mixture of an oxide and a halide of an actinide metal such as uranium with an alkali metal on alkaline earth metal reducing agent in the presence of iodine.

  5. Actinide Targets for Neutron Cross Section Measurements (C)

    SciTech Connect

    J. D. Baker; C. A. McGrath

    2006-04-01

    The Advanced Fuel Cycle Initiative (AFCI) and the Generation IV Reactor Initiative have demonstrated a lack of detailed neutron cross-sections for certain "minor" actinides, those other than the most common (235U, 238U, and 239Pu). For some closed-fuel-cycle reactor designs more than 50% of reactivity will, at some point, be derived from “minor” actinides that currently have poorly known (n,g) and (n,f) cross sections. A program of measurements under AFCI has begun to correct this. One of the initial hurdles has been to produce well-characterized, highly isotopically enriched, and chemically pure actinide targets on thin backings. Using a combination of resurrected techniques and new developments, we have made a series of targets including highly enriched 240Pu, and 242Pu. Thus far, we have electrodeposited these actinide targets. In the future, we plan to study reductive distillation to achieve homogeneous, adherent targets on thin metal foils and polymer backings. As we move forward, separated isotopes become scarcer, and safety concerns become greater. The chemical purification and electodeposition techniques will be described.

  6. Subterranean Sympatry: An Investigation into Diet Using Stable Isotope Analysis

    PubMed Central

    Robb, Gillian N.; Woodborne, Stephan; Bennett, Nigel C.

    2012-01-01

    In the Western Cape three species of mole-rat occur in sympatry, however, little is known about differences in their dietary preferences. Dietary composition of the three species; the common mole-rat (Cryptomys hottentotus hottentotus), the Cape mole-rat (Georychus capensis) and the Cape dune mole-rat (Bathyergus suillus) were examined using stable isotope analysis. Blood, fur and claw samples were collected from 70 mole-rats, in addition to several potential food items, to assess food selection of the three species under natural conditions. Overall there was a significant difference in the isotopic composition (δ13C and δ15N) between all three species and significant differences in their diet composition. There were also significant differences between tissues in all three species suggesting temporal variation in diet. The small size and colonial lifestyle of C. h. hottentotus allows it to feed almost 100% on bulbs, while the solitary and larger species G. capensis and B. suillus fed to a greater extent on other resources such as grasses and clover. B. suillus, the largest of the species, had the most generalized diet. However, overall all species relied most heavily upon geophytes and consumed the same species suggesting competition for resources could exist. We also showed a high level of individual variation in diet choices. This was most pronounced in B. suillus and G. capensis and less so in C. h. hottentotus. We demonstrate that stable isotope analysis can successfully be applied to examine dietary patterns in subterranean mammals and provide insights into foraging patterns and dietary variation at both the inter and intra population level. PMID:23139795

  7. Extraction Chromatographic Methods in the Sample Preparation Sequence for Thermal Ionization Mass Spectrometric Analysis of Plutonium Isotopes

    SciTech Connect

    Grate, Jay W.; O'Hara, Matthew J.; Farawila, Anne F.; Douglas, Matthew; Haney, Morgan M.; Peterson, Steve L.; Maiti, Tapas C.; Aardahl, Christopher L.

    2011-10-17

    A sample preparation sequence for actinide isotopic analysis by TIMS is described that includes column-based extraction chromatography as the first separation step, followed by anion exchange column separations. The sequence is designed to include a wet ashing step after the extraction chromatography to prevent any leached extractant or oxalic acid eluent reagents from interfering with subsequent separations, source preparation, or TIMS ionization. TEVA-resin and DGA-resin materials, containing extractants that consist only of C, N, O, and H atoms, were investigated for isolation of plutonium. Radiotracer level studies confirmed expected high yields from column-based separation procedures. Femtogram-level studies were carried out with TIMS detection, using multiple isotopic spikes through the separation sequence. Pu recoveries were 87% and 86% for TEVA- and DGA-resins separations respectively. The Pu recoveries from 400 {mu}L anion-exchange column separations were 89% and 93% for trial sequences incorporating TEVA and DGA-resin. Thus, a prior extraction chromatography step in the sequence did not interfere with the subsequent anion exchange separation when a simple wet ash step was carried out in between these column separations. The average measurement efficiency, for Pu, encompassing the chemical separation recoveries and the TIMS ionization efficiency, was 2.73 {+-} 0.77% (2-sigma) for the DGA-resin trials and 2.67 {+-} 0.54% for the TEVA-resin trials, compared to 3.41% and 2.37% (average 2.89%) for two spikes in the experimental set. These compare with an average measurement efficiency of 2.78 {+-} 1.70%, n = 33 from process benchmark analyses using Pu spikes processed through a sequence of oxalate precipitation, wet ash, iron hydroxide precipitation, and anion exchange column separations. We conclude that extraction chromatography can be a viable separation procedure as part of a multistep sequence for TIMS sample preparation.

  8. Actinide halide complexes

    DOEpatents

    Avens, Larry R.; Zwick, Bill D.; Sattelberger, Alfred P.; Clark, David L.; Watkin, John G.

    1992-01-01

    A compound of the formula MX.sub.n L.sub.m wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands, a compound of the formula MX.sub.n wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant, are provided.

  9. Actinide halide complexes

    DOEpatents

    Avens, L.R.; Zwick, B.D.; Sattelberger, A.P.; Clark, D.L.; Watkin, J.G.

    1992-11-24

    A compound is described of the formula MX[sub n]L[sub m] wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands. A compound of the formula MX[sub n] wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds are described including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant.

  10. Actinides AMS at CIRCE in Caserta (Italy)

    NASA Astrophysics Data System (ADS)

    De Cesare, M.; Gialanella, L.; Rogalla, D.; Petraglia, A.; Guan, Y.; De Cesare, N.; D'Onofrio, A.; Quinto, F.; Roca, V.; Sabbarese, C.; Terrasi, F.

    2010-04-01

    The operation of Nuclear Power Plants and atmospheric tests of nuclear weapons performed in the past, together with production, transport and reprocessing of nuclear fuel, lead to the release into the environment of a wide range of radioactive nuclides, such as uranium, plutonium, fission and activation products. These nuclides are present in the environment at ultra trace levels. Their detection requires sensitive techniques like AMS (Accelerator Mass Spectrometry). In order to perform isotopic ratio measurements of the longer-lived actinides, e.g., of 236U relative to the primary 238U and various Pu isotopes relative to 239Pu, an upgrade of the CIRCE accelerator (Center for Isotopic Research on Cultural and Environmental Heritage) in Caserta, Italy, is underway. In this paper we report on the results of simulations aiming to define the best ion optics and to understand the origin of possible measurement background. The design of a high resolution TOF- E (Time of Flight-Energy) detector system is described, which will be used to identify the rare isotopes among interfering background signals.

  11. Reflections on the criticality of special actinide elements

    SciTech Connect

    Clayton, E.D.

    1987-04-01

    During recent years, the list of nuclides known to be capable of supporting a chain reaction has substantially increased. Since the criticality aspects for some of these nuclides differ in important respects from those of the most common fissile nuclides, /sup 235//sub 92/U, and /sup 239//sub 94/Pu, a new term, ''fissible'' was recently proposed in nuclear engineering to help distinguish differences. Activation energies for fission have been calculated for 41 of the actinide isotopes which are grouped according to four types of nuclides, those with even-Z, even-N, odd-Z, odd-N, odd-Z, even-N, and even-Z, odd-N. With the possible exception of /sup 237//sub 92/U, all fissible isotopes listed have even N. The activation energy for fission is less in the case of the even-Z, even-N isotopes, but almost without eception it is the odd-N isotopes that undergo fission with thermal neutrons and which constitute the principal criticality problem. This paper reviews the criticality and fissionability aspects of the fissile and fissible actinide isotopes. The criticality of aqueous mixtures of fissile and fissible isotopes also is briefly discussed, including limits for criticality control.

  12. Flow injection analysis-isotope ratio mass spectrometry for bulk carbon stable isotope analysis of alcoholic beverages.

    PubMed

    Jochmann, Maik A; Steinmann, Dirk; Stephan, Manuel; Schmidt, Torsten C

    2009-11-25

    A new method for bulk carbon isotope ratio determination of water-soluble samples is presented that is based on flow injection analysis-isotope ratio mass spectrometry (FIA-IRMS) using an LC IsoLink interface. Advantages of the method are that (i) only very small amounts of sample are required (2-5 microL of the sample for up to 200 possible injections), (ii) it avoids complex sample preparation procedures such as needed for EA-IRMS analysis (only sample dilution and injection,) and (iii) high throughput due to short analysis times is possible (approximately 15 min for five replicates). The method was first tested and evaluated as a fast screening method with industrially produced ethanol samples, and additionally the applicability was tested by the measurement of 81 alcoholic beverages, for example, whiskey, brandy, vodka, tequila, and others. The minimal sample concentration required for precise and reproducible measurements was around 50 microL L(-1) ethanol/water (1.71 mM carbon). The limit of repeatability was determined to be r=0.49%. FIA-IRMS represents a fast screening method for beverage authenticity control. Due to this, samples can be prescreened as a decisive criterion for more detailed investigations by HPLC-IRMS or multielement GC-IRMS measurements for a verification of adulteration. PMID:19856915

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

    PubMed

    Preston, Tom

    2014-01-01

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

  14. Isotopic Biogeochemistry

    NASA Technical Reports Server (NTRS)

    Hayes, J. M.

    1985-01-01

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

  15. Forensic isotope analysis to refine a hydrologic conceptual model.

    PubMed

    Bassett, R L; Steinwand, Aaron; Jorat, Saeed; Petersen, Christian; Jackson, Randy

    2008-01-01

    Water resources in the arid southwestern United States are frequently the subject of conflict from competing private and public interests. Legal remedies may remove impasses, but the technical analysis of the problem often determines the future success of legal solutions. In Owens Valley, California, the source of water for the Los Angeles Aqueduct (LAA) is flow diverted from the Owens River and its tributaries and ground water from valley aquifers. Future management of ground water delivered to the LAA needs technical support regarding quantity available, interconnection of shallow and confined aquifers, impact on local springs, and rate of recharge. Ground water flow models and ground water composition are tools already in use, but these have large uncertainty for local interpretations. This study conducted targeted sampling of springs and wells to evaluate the hydrologic system to corroborate conceptual and numerical models. The effort included measurement of intrinsic isotopic composition at key locations in the aquifers. The stable isotopic data of boron (delta(11)B), sulfur (delta(34)S), oxygen (delta(18)O), hydrogen (delta D), and tritium ((3)H) supported by basic chemical data provided rules for characterizing the upper and the lower aquifer system, confirmed the interpretation of ground water flow near faults and flow barriers, and detected hydraulic connections between the LAA and the perennial springs at key locations along the unlined reach of the LAA. This study exemplifies the use of forensic isotopic approaches as independent checks on the consistency of interpretations of conceptual models of a ground water system and the numerical hydrologic simulations.

  16. Actinide Burning in CANDU Reactors

    SciTech Connect

    Hyland, B.; Dyck, G.R.

    2007-07-01

    Actinide burning in CANDU reactors has been studied as a method of reducing the actinide content of spent nuclear fuel from light water reactors, and thereby decreasing the associated long term decay heat load. In this work simulations were performed of actinides mixed with natural uranium to form a mixed oxide (MOX) fuel, and also mixed with silicon carbide to form an inert matrix (IMF) fuel. Both of these fuels were taken to a higher burnup than has previously been studied. The total transuranic element destruction calculated was 40% for the MOX fuel and 71% for the IMF. (authors)

  17. 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

  18. Elemental and Isotopic Analysis of Uranium Oxide an NIST Glass Standards by FEMTOSECOND-LA-ICP-MIC-MS

    SciTech Connect

    Ebert, Chris; Zamzow, Daniel S.; McBay, Eddie H.; Bostick, Debra A.; Bajic, Stanley J.; Baldwin, David P.; Houk, R.S.

    2009-06-01

    The objective of this work was to test and demonstrate the analytical figures of merit of a femtosecond-laser ablation (fs-LA) system coupled with an inductively coupled plasma-multi-ion collector-mass spectrometer (ICP-MIC-MS). The mobile fs-LA sampling system was designed and assembled at Ames Laboratory and shipped to Oak Ridge National Laboratory (ORNL), where it was integrated with an ICP-MIC-MS. The test period of the integrated systems was February 2-6, 2009. Spatially-resolved analysis of particulate samples is accomplished by 100-shot laser ablation using a fs-pulsewidth laser and monitoring selected isotopes in the resulting ICP-MS transient signal. The capability of performing high sensitivity, spatially resolved, isotopic analyses with high accuracy and precision and with virtually no sample preparation makes fs-LA-ICP-MIC-MS valuable for the measurement of actinide isotopes at low concentrations in very small samples for nonproliferation purposes. Femtosecond-LA has been shown to generate particles from the sample that are more representative of the bulk composition, thereby minimizing weaknesses encountered in previous work using nanosecond-LA (ns-LA). The improvement of fs- over ns-LA sampling arises from the different mechanisms for transfer of energy into the sample in these two laser pulse-length regimes. The shorter duration fs-LA pulses induce less heating and cause less damage to the sample than the longer ns pulses. This results in better stoichiometric sampling (i.e., a closer correlation between the composition of the ablated particles and that of the original solid sample), which improves accuracy for both intra- and inter-elemental analysis. The primary samples analyzed in this work are (a) solid uranium oxide powdered samples having different {sup 235}U to {sup 238}U concentration ratios, and (b) glass reference materials (NIST 610, 612, 614, and 616). Solid uranium oxide samples containing {sup 235}U in depleted, natural, and enriched

  19. Oxygen isotope corrections for online δ34S analysis

    USGS Publications Warehouse

    Fry, B.; Silva, S.R.; Kendall, C.; Anderson, R.K.

    2002-01-01

    Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the δ34S isotopic composition of plants, animals and soils. We found that the online technology for automated δ34S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO2 produced, and as a result calculated δ34S values were often 1–3‰ too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO2-SiO2 buffering method that minimizes detrimental oxygen isotope variations in SO2.

  20. 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.

  1. Fusion-Fission Burner for Transuranic Actinides

    NASA Astrophysics Data System (ADS)

    Choi, Chan

    2013-10-01

    The 14-MeV DT fusion neutron spectrum from mirror confinement fusion can provide a unique capability to transmute the transuranic isotopes from light water reactors (LWR). The transuranic (TRU) actinides, high-level radioactive wastes, from spent LWR fuel pose serious worldwide problem with long-term decay heat and radiotoxicity. However, ``transmuted'' TRU actinides can not only reduce the inventory of the TRU in the spent fuel repository but also generate additional energy. Typical commercial LWR fuel assemblies for BWR (boiling water reactor) and PWR (pressurized water reactor) measure its assembly lengths with 4.470 m and 4.059 m, respectively, while its corresponding fuel rod lengths are 4.064 m and 3.851 m. Mirror-based fusion reactor has inherently simple geometry for transmutation blanket with steady-state reactor operation. Recent development of gas-dynamic mirror configuration has additional attractive feature with reduced size in central plasma chamber, thus providing a unique capability for incorporating the spent fuel assemblies into transmutation blanket designs. The system parameters for the gas-dynamic mirror-based hybrid burner will be discussed.

  2. Environmental research on actinide elements

    SciTech Connect

    Pinder, J.E. III; Alberts, J.J.; McLeod, K.W.; Schreckhise, R.G.

    1987-08-01

    The papers synthesize the results of research sponsored by DOE's Office of Health and Environmental Research on the behavior of transuranic and actinide elements in the environment. Separate abstracts have been prepared for the 21 individual papers. (ACR)

  3. Isotopic gas analysis through Purcell cavity enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Petrak, B.; Cooper, J.; Konthasinghe, K.; Peiris, M.; Djeu, N.; Hopkins, A. J.; Muller, A.

    2016-02-01

    Purcell enhanced Raman scattering (PERS) by means of a doubly resonant Fabry-Perot microcavity (mode volume ≈ 100 μm3 and finesse ≈ 30 000) has been investigated as a technique for isotopic ratio gas analysis. At the pump frequency, the resonant cavity supports a buildup of circulating power while simultaneously enabling Purcell spontaneous emission rate enhancement at the resonant Stokes frequency. The three most common isotopologues of CO2 gas were quantified, and a signal was obtained from 13C16O2 down to a partial pressure of 2 Torr. Due to its small size and low pump power needed (˜10 mW) PERS lends itself to miniaturization. Furthermore, since the cavity is resonant with the emission frequency, future improvements could allow it to serve as its own spectral analyzer and no separate spectroscopic device would be needed.

  4. The potential for application of ink stable isotope analysis in questioned document examination.

    PubMed

    Chesson, Lesley A; Tipple, Brett J; Barnette, Janet E; Cerling, Thure E; Ehleringer, James R

    2015-01-01

    We investigated a novel application of stable isotope abundance analysis of nitrogen (15N), carbon (13C), hydrogen (2H), and oxygen (18O) to characterize pen ink. We focused on both ballpoint and gel pen inks. We found that the isotope ratios of ink from pens purchased together in a package were similar and within-package stable isotope ratio variability was not significantly larger than the variability of isotope reference materials used during analysis. In contrast, the isotope ratios of ink from pens of the same brand purchased in three states of the continental USA were significantly different from each other and there was isotope ratio variation among pens of the same brand but different, unknown production periods. The stable isotope ratios of inked paper were statistically distinguishable using measured δ15N values. Paper inked with different gel pens was statistically distinguishable using measured δ2H values. The capacity of stable isotope ratios to differentiate among ballpoint inks as well as gel inks shows that stable isotope analysis may be a useful and quantifiable investigative technique for questioned document examination, although current sample size requirements limit its utility. Application of the technique in casework will require the development of micro-scale sampling and analysis methods.

  5. The potential for application of ink stable isotope analysis in questioned document examination.

    PubMed

    Chesson, Lesley A; Tipple, Brett J; Barnette, Janet E; Cerling, Thure E; Ehleringer, James R

    2015-01-01

    We investigated a novel application of stable isotope abundance analysis of nitrogen (15N), carbon (13C), hydrogen (2H), and oxygen (18O) to characterize pen ink. We focused on both ballpoint and gel pen inks. We found that the isotope ratios of ink from pens purchased together in a package were similar and within-package stable isotope ratio variability was not significantly larger than the variability of isotope reference materials used during analysis. In contrast, the isotope ratios of ink from pens of the same brand purchased in three states of the continental USA were significantly different from each other and there was isotope ratio variation among pens of the same brand but different, unknown production periods. The stable isotope ratios of inked paper were statistically distinguishable using measured δ15N values. Paper inked with different gel pens was statistically distinguishable using measured δ2H values. The capacity of stable isotope ratios to differentiate among ballpoint inks as well as gel inks shows that stable isotope analysis may be a useful and quantifiable investigative technique for questioned document examination, although current sample size requirements limit its utility. Application of the technique in casework will require the development of micro-scale sampling and analysis methods. PMID:25577004

  6. Actinide Packaging and Storage Facility (APSF)

    SciTech Connect

    Lavietes, A.D.

    1999-10-01

    The Actinide Packaging and Storage Facility (APSF) was designed to provide long-term storage of radionuclides. Task A.229 defined the requirement for a small, low-power radiation detection capability. This detection system was to be deployed as a component of an autonomously guided vehicle (AGV) located within the storage vault of the facility and necessarily had to exhibit the qualities of low maintenance, long lifetime, and stable performance typically required of unattended monitoring systems. The detection system would interface directly with the on-board computer developed as part of the AGV under a separate task. The overall task for this system would be to provide isotopic identification of the material stored within this facility.

  7. Actinides, accelerators and erosion

    NASA Astrophysics Data System (ADS)

    Tims, S. G.; Fifield, L. K.

    2012-10-01

    Fallout isotopes can be used as artificial tracers of soil erosion and sediment accumulation. The most commonly used isotope to date has been 137Cs. Concentrations of 137Cs are, however, significantly lower in the Southern Hemisphere, and furthermore have now declined to 35% of original values due to radioactive decay. As a consequence the future utility of 137Cs is limited in Australia, with many erosion applications becoming untenable within the next 20 years, and there is a need to replace it with another tracer. Plutonium could fill this role, and has the advantages that there were six times as many atoms of Pu as of 137Cs in fallout, and any loss to decay has been negligible due to the long half-lives of the plutonium isotopes. Uranium-236 is another long-lived fallout isotope with significant potential for exploitation as a tracer of soil and sediment movement. Uranium is expected to be more mobile in soils than plutonium (or caesium), and hence the 236U/Pu ratio will vary with soil depth, and so could provide an independent measure of the amount of soil loss. In this paper we discuss accelerator based ultra-sensitive measurements of plutonium and 236U isotopes and their advantages over 137Cs as tracers of soil erosion and sediment movement.

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  9. Quantitative Analysis by Isotopic Dilution Using Mass Spectroscopy: The Determination of Caffeine by GC-MS.

    ERIC Educational Resources Information Center

    Hill, Devon W.; And Others

    1988-01-01

    Describes a laboratory technique for quantitative analysis of caffeine by an isotopic dilution method for coupled gas chromatography-mass spectroscopy. Discusses caffeine analysis and experimental methodology. Lists sample caffeine concentrations found in common products. (MVL)

  10. A new method for carbon isotopic analysis of protein

    SciTech Connect

    Nelson, D.E. )

    1991-02-01

    The reaction of ninhydrin with amino acids can be used in carbon isotopic studies of protein. The reaction can be applied to extract as carbon dioxide only peptide-bonded carbon in proteinaceous material, thus avoiding most, if not all, contaminants. Test radiocarbon dates on ancient bone indicate that the method provides reliable ages, and stable carbon isotopic data suggest that our understanding of isotopic dietary reconstruction needs detailed examination. The technique should also be useful in biochemical tracing experiments and in global carbon budget studies, and the underlying principle may be applicable to other isotopes and molecules. 28 refs., 1 fig., 1 tab.

  11. Stable isotope analysis of precipitation samples obtained via crowdsourcing reveals the spatiotemporal evolution of Superstorm Sandy.

    PubMed

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

    2014-01-01

    Extra-tropical cyclones, such as 2012 Superstorm Sandy, pose a significant climatic threat to the northeastern United Sates, yet prediction of hydrologic and thermodynamic processes within such systems is complicated by their interaction with mid-latitude water patterns as they move poleward. Fortunately, the evolution of these systems is also recorded in the stable isotope ratios of storm-associated precipitation and water vapor, and isotopic analysis provides constraints on difficult-to-observe cyclone dynamics. During Superstorm Sandy, a unique crowdsourced approach enabled 685 precipitation samples to be obtained for oxygen and hydrogen isotopic analysis, constituting the largest isotopic sampling of a synoptic-scale system to date. Isotopically, these waters span an enormous range of values (> 21‰ for δ(18)O, > 160‰ for δ(2)H) and exhibit strong spatiotemporal structure. Low isotope ratios occurred predominantly in the west and south quadrants of the storm, indicating robust isotopic distillation that tracked the intensity of the storm's warm core. Elevated values of deuterium-excess (> 25‰) were found primarily in the New England region after Sandy made landfall. Isotope mass balance calculations and Lagrangian back-trajectory analysis suggest that these samples reflect the moistening of dry continental air entrained from a mid-latitude trough. These results demonstrate the power of rapid-response isotope monitoring to elucidate the structure and dynamics of water cycling within synoptic-scale systems and improve our understanding of storm evolution, hydroclimatological impacts, and paleo-storm proxies.

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

    PubMed Central

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

    2014-01-01

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

  13. Hanford isotope project strategic business analysis yttrium-90 (Y-90)

    SciTech Connect

    1995-10-01

    The purpose of this analysis is to address the short-term direction for the Hanford yttrium-90 (Y-90) project. Hanford is the sole DOE producer of Y-90, and is the largest repository for its source in this country. The production of Y-90 is part of the DOE Isotope Production and Distribution (IP and D) mission. The Y-90 is ``milked`` from strontium-90 (Sr-90), a byproduct of the previous Hanford missions. The use of Sr-90 to produce Y-90 could help reduce the amount of waste material processed and the related costs incurred by the clean-up mission, while providing medical and economic benefits. The cost of producing Y-90 is being subsidized by DOE-IP and D due to its use for research, and resultant low production level. It is possible that the sales of Y-90 could produce full cost recovery within two to three years, at two curies per week. Preliminary projections place the demand at between 20,000 and 50,000 curies per year within the next ten years, assuming FDA approval of one or more of the current therapies now in clinical trials. This level of production would incentivize private firms to commercialize the operation, and allow the government to recover some of its sunk costs. There are a number of potential barriers to the success of the Y-90 project, outside the control of the Hanford Site. The key issues include: efficacy, Food and Drug Administration (FDA) approval and medical community acceptance. There are at least three other sources for Y-90 available to the US users, but they appear to have limited resources to produce the isotope. Several companies have communicated interest in entering into agreements with Hanford for the processing and distribution of Y-90, including some of the major pharmaceutical firms in this country.

  14. Theoretical investigation on multiple bonds in terminal actinide nitride complexes.

    PubMed

    Wu, Qun-Yan; Wang, Cong-Zhi; Lan, Jian-Hui; Xiao, Cheng-Liang; Wang, Xiang-Ke; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-09-15

    A series of actinide (An) species of L-An-N compounds [An = Pa-Pu, L = [N(CH2CH2NSiPr(i)3)3](3-), Pr(i) = CH(CH3)2] have been investigated using scalar relativistic density functional theory (DFT) without considering spin-orbit coupling effects. The ground state geometric and electronic structures and natural bond orbital (NBO) analysis of actinide compounds were studied systematically in neutral and anionic forms. It was found that with increasing actinide atomic number, the bond length of terminal multiple An-N1 bond decreases, in accordance with the actinide contraction. The Mayer bond order of An-N1 decreases gradually from An = Pa to Pu, which indicates a decrease in bond strength. The terminal multiple bond for L-An-N compounds contains one σ and two π molecular orbitals, and the contributions of the 6d orbital to covalency are larger in magnitude than the 5f orbital based on NBO analysis and topological analysis of electron density. This work may help in understanding of the bonding nature of An-N multiple bonds and elucidating the trends and electronic structure changes across the actinide series. It can also shed light on the construction of novel An-N multiple bonds.

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

    PubMed

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

    2015-01-01

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

  16. Multi element (C, H, O) stable isotope analysis for the authentication of balsamic vinegars.

    PubMed

    Werner, Roland A; Roßmann, Andreas

    2015-01-01

    Balsamic vinegars are important and well-acknowledged products and have become more important all over Europe during the recent past. For their analytical control, stable isotope methods play an important role to check the authenticity of the raw materials applied. For vinegar, but not yet for balsamic vinegar analysis, stable isotope methods using hydrogen, carbon, and oxygen isotope analyses by isotope ratio mass spectrometry and (2)H-NMR have already been introduced as official methods. Nevertheless, the official procedure can be also applied for balsamic vinegars. The evaluation of the stable isotope parameters obtained for the ingredients of balsamic vinegars requires a knowledge and understanding of the natural and industrial processes on which the production of balsamic vinegars is based. Ranges and 'cut-off' values for the multi element stable isotope parameters of balsamic vinegars are described, and a suitable analytical strategy is suggested.

  17. Rapid Column Extraction Method for Actinides and Sr-89/90 in Water Samples

    SciTech Connect

    MAXWELL III, SHERROD L.

    2005-06-15

    The SRS Environmental Laboratory analyzes water samples for environmental monitoring, including river water and ground water samples. A new, faster actinide and strontium 89/90 separation method has been developed and implemented to improve productivity, reduce labor costs and add capacity to this laboratory. This method uses stacked TEVA Resin{reg_sign}, TRU Resin{reg_sign} and Sr-Resin{reg_sign} cartridges from Eichrom Technologies (Darien, IL, USA) that allows the rapid separation of plutonium (Pu), neptunium (Np), uranium (U), americium (Am), curium (Cm) and thorium (Th) using a single multi-stage column combined with alpha spectrometry. By using vacuum box cartridge technology with rapid flow rates, sample preparation time is minimized. The method can be used for routine analysis or as a rapid method for emergency preparedness. Thorium and curium are often analyzed separately due to the interference of the daughter of Th-229 tracer, actinium (Ac)-225, on curium isotopes when measured by alpha spectrometry. This new method also adds a separation step using DGA Resin{reg_sign}, (Diglycolamide Resin, Eichrom Technologies) to remove Ac-225 and allow the separation and analysis of thorium isotopes and curium isotopes at the same time.

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

    EPA Science Inventory

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

  19. Actinide determination and analytical support for characterization of environmental samples

    SciTech Connect

    Rokop, D.J.; Efurd, D.W.; Perrin, R.E.

    1994-03-01

    Clean chemical and Thermal Ionization Mass Spectrometry (TIMS) procedures have been developed to permit the determination of environmental actinide element concentrations and isotopic signatures. The isotopic signatures help identify element origin and separate naturally occurring or background contributions from local anthropogenic sources. Typical sample sizes for processing are 2 liters of water, 1--10 grams of sediment, and 1--20 grams of soil. Measurement limits for Pu, Am, and Np are < 1 {times} 18{sup 8} atoms, and for U are < 2.5 {times} 10{sup 12} atoms. For isotopic signatures, < 5 {times} 10{sup 8} atoms of Pu, Am, and Np are necessary, and 8 {times} 10{sup 12} atoms of U are required. Of potential interest to the IAEA is the incorporation of these techniques into their Safeguards Analytical Laboratory for environmental sampling. Studies made of surface waters, sediments and soils from the Rocky Flats Plant (RFP) in Colorado, US, are used as examples of this methodology. These studies showed that, although plant boundary actinide concentrations approached, on the downstream side, natural or background levels, isotopic signatures characteristic of plant operations were still discernible.

  20. 33rd Actinide Separations Conference

    SciTech Connect

    McDonald, L M; Wilk, P A

    2009-05-04

    Welcome to the 33rd Actinide Separations Conference hosted this year by the Lawrence Livermore National Laboratory. This annual conference is centered on the idea of networking and communication with scientists from throughout the United States, Britain, France and Japan who have expertise in nuclear material processing. This conference forum provides an excellent opportunity for bringing together experts in the fields of chemistry, nuclear and chemical engineering, and actinide processing to present and discuss experiences, research results, testing and application of actinide separation processes. The exchange of information that will take place between you, and other subject matter experts from around the nation and across the international boundaries, is a critical tool to assist in solving both national and international problems associated with the processing of nuclear materials used for both defense and energy purposes, as well as for the safe disposition of excess nuclear material. Granlibakken is a dedicated conference facility and training campus that is set up to provide the venue that supports communication between scientists and engineers attending the 33rd Actinide Separations Conference. We believe that you will find that Granlibakken and the Lake Tahoe views provide an atmosphere that is stimulating for fruitful discussions between participants from both government and private industry. We thank the Lawrence Livermore National Laboratory and the United States Department of Energy for their support of this conference. We especially thank you, the participants and subject matter experts, for your involvement in the 33rd Actinide Separations Conference.

  1. Kinetics of actinide complexation reactions

    SciTech Connect

    Nash, K.L.; Sullivan, J.C.

    1997-09-01

    Though the literature records extensive compilations of the thermodynamics of actinide complexation reactions, the kinetics of complex formation and dissociation reactions of actinide ions in aqueous solutions have not been extensively investigated. In light of the central role played by such reactions in actinide process and environmental chemistry, this situation is somewhat surprising. The authors report herein a summary of what is known about actinide complexation kinetics. The systems include actinide ions in the four principal oxidation states (III, IV, V, and VI) and complex formation and dissociation rates with both simple and complex ligands. Most of the work reported was conducted in acidic media, but a few address reactions in neutral and alkaline solutions. Complex formation reactions tend in general to be rapid, accessible only to rapid-scan and equilibrium perturbation techniques. Complex dissociation reactions exhibit a wider range of rates and are generally more accessible using standard analytical methods. Literature results are described and correlated with the known properties of the individual ions.

  2. MICROBIAL TRANSFORMATIONS OF PLUTONIUM AND OTHER ACTINIDES IN TRANSURANIC AND MIXED WASTES.

    SciTech Connect

    FRANCIS,A.J.

    2003-07-06

    The presence of the actinides Th, U, Np, Pu, and Am in transuranic (TRU) and mixed wastes is a major concern because of their potential for migration from the waste repositories and long-term contamination of the environment. The toxicity of the actinide elements and the long half-lives of their isotopes are the primary causes for concern. In addition to the radionuclides the TRU waste consists a variety of organic materials (cellulose, plastic, rubber, chelating agents) and inorganic compounds (nitrate and sulfate). Significant microbial activity is expected in the waste because of the presence of organic compounds and nitrate, which serve as carbon and nitrogen sources and in the absence of oxygen the microbes can use nitrate and sulfate as alternate electron acceptors. Biodegradation of the TRU waste can result in gas generation and pressurization of containment areas, and waste volume reduction and subsidence in the repository. Although the physical, chemical, and geochemical processes affecting dissolution, precipitation, and mobilization of actinides have been investigated, we have only limited information on the effects of microbial processes. Microbial activity could affect the chemical nature of the actinides by altering the speciation, solubility and sorption properties and thus could increase or decrease the concentrations of actinides in solution. Under appropriate conditions, dissolution or immobilization of actinides is brought about by direct enzymatic or indirect non-enzymatic actions of microorganisms. Dissolution of actinides by microorganisms is brought about by changes in the Eh and pH of the medium, by their production of organic acids, such as citric acid, siderophores and extracellular metabolites. Immobilization or precipitation of actinides is due to changes in the Eh of the environment, enzymatic reductive precipitation (reduction from higher to lower oxidation state), biosorption, bioaccumulation, biotransformation of actinides complexed

  3. Analysis of sequential reactive transformations using stable isotope analysis: a theoretical assessment

    NASA Astrophysics Data System (ADS)

    Thullner, Martin; Jin, Shuang; Stadler, Susanne

    2016-04-01

    Stable isotope methods have been establish as powerful tools for the analysis of reactive transformation in the subsurface with applications ranging from the field of contaminant hydrology to biogeochemical cycling. While the link between single transformations based on stable isotope signatures and their changes is commonly well understood and allows for qualitative and - in case certain requirements are met - also quantitative analysis, the interpretation of sequential reactive transformations, e.g. decay chains, is more complicated. In the latter case isotope signature changes of individual reactive compounds are affected by more than one transformation which challenges the interpretation of these changes. In recent years, some methods have been proposed (e.g. isotope mass balance approaches) which allow at least for a qualitative or semi-quantitative estimation of sequential reactive transformation processes. However, a systematic assessment of the validity of these estimation methods is missing so far and the accuracy of these methods - in general and for specific conditions encountered in the field - is not fully validated. In this presentation we use a combination of mathematical analyses and numerical modeling to test the validity of the proposed estimation methods and to determine the limits of their applicability. Results recommend modifications of existing theoretical estimation approaches and identify sorption processes as potential limitation of their applicability.

  4. Extraction chromatographic methods in the sample preparation sequence for thermal ionization mass spectrometric analysis of plutonium isotopes.

    PubMed

    Grate, Jay W; O'Hara, Matthew J; Farawila, Anne F; Douglas, Matthew; Haney, Morgan M; Petersen, Steven L; Maiti, Tapas C; Aardahl, Christopher L

    2011-12-01

    A sample preparation sequence for actinide isotopic analysis by thermal ionization mass spectrometry (TIMS) is described that includes column-based extraction chromatography as the first separation step, followed by anion-exchange column separations. The sequence is designed to include a wet ashing step after the extraction chromatography to prevent any leached extractant or oxalic acid eluent reagents from interfering with subsequent separations, source preparation, or TIMS ionization. TEVA resin and DGA resin materials, containing extractants that consist only of C, N, O, and H atoms, were investigated for isolation of plutonium. Radiotracer level studies confirmed expected high yields from column-based separation procedures. Femtogram-level studies were carried out with TIMS detection, using multiple monoisotopic spikes applied sequentially throughout the separation sequence. Pu recoveries were 87% and 86% for TEVA and DGA resin separations, respectively. The Pu recoveries from 400 μL anion-exchange column separation sequences were 89% and 93% for trial sequences incorporating TEVA and DGA resin. Thus, a prior extraction chromatography step in the sequence did not interfere with the subsequent anion-exchange separation when a simple wet ash step was carried out in between these column separations. The average measurement efficiency for Pu, encompassing the chemical separation recoveries and the TIMS ionization efficiency, was 2.73% ± 0.77% (2σ) for the DGA resin trials and 2.67% ± 0.54% for the TEVA resin trials, compared to 3.41% and 2.37% (average 2.89%) for two control trials. These compare with an average measurement efficiency of 2.78% ± 1.70%, n = 33 from process benchmark analyses using Pu spikes processed through a sequence of oxalate precipitation, wet ash, iron hydroxide precipitation, and anion-exchange column separations. We conclude that extraction chromatography can be a viable separation procedure as part of a multistep sequence for TIMS

  5. Extraction chromatographic methods in the sample preparation sequence for thermal ionization mass spectrometric analysis of plutonium isotopes.

    PubMed

    Grate, Jay W; O'Hara, Matthew J; Farawila, Anne F; Douglas, Matthew; Haney, Morgan M; Petersen, Steven L; Maiti, Tapas C; Aardahl, Christopher L

    2011-12-01

    A sample preparation sequence for actinide isotopic analysis by thermal ionization mass spectrometry (TIMS) is described that includes column-based extraction chromatography as the first separation step, followed by anion-exchange column separations. The sequence is designed to include a wet ashing step after the extraction chromatography to prevent any leached extractant or oxalic acid eluent reagents from interfering with subsequent separations, source preparation, or TIMS ionization. TEVA resin and DGA resin materials, containing extractants that consist only of C, N, O, and H atoms, were investigated for isolation of plutonium. Radiotracer level studies confirmed expected high yields from column-based separation procedures. Femtogram-level studies were carried out with TIMS detection, using multiple monoisotopic spikes applied sequentially throughout the separation sequence. Pu recoveries were 87% and 86% for TEVA and DGA resin separations, respectively. The Pu recoveries from 400 μL anion-exchange column separation sequences were 89% and 93% for trial sequences incorporating TEVA and DGA resin. Thus, a prior extraction chromatography step in the sequence did not interfere with the subsequent anion-exchange separation when a simple wet ash step was carried out in between these column separations. The average measurement efficiency for Pu, encompassing the chemical separation recoveries and the TIMS ionization efficiency, was 2.73% ± 0.77% (2σ) for the DGA resin trials and 2.67% ± 0.54% for the TEVA resin trials, compared to 3.41% and 2.37% (average 2.89%) for two control trials. These compare with an average measurement efficiency of 2.78% ± 1.70%, n = 33 from process benchmark analyses using Pu spikes processed through a sequence of oxalate precipitation, wet ash, iron hydroxide precipitation, and anion-exchange column separations. We conclude that extraction chromatography can be a viable separation procedure as part of a multistep sequence for TIMS

  6. Actinide-specific sequestering agents and decontamination applications

    SciTech Connect

    Smith, William L.; Raymond, Kenneth N.

    1981-04-07

    With the commercial development of nuclear reactors, the actinides have become very important industrial elements. A major concern of the nuclear industry is the biological hazard associated with nuclear fuels and their wastes. The acute chemical toxicity of tetravalent actinides, as exemplified by Th(IV), is similar to Cr(III) or Al(III). However, the acute toxicity of 239Pu(IV) is similar to strychnine, which is much more toxic than any of the non-radioactive metals such as mercury. Although the more radioactive isotopes of the transuranium elements are more acutely toxic by weight than plutonium, the acute toxicities of 239Pu, 241Am, and 244Cm are nearly identical in radiation dose, ~100 μCi/kg in rodents. Finally and thus, the extreme acute toxicity of 239Pu is attributed to its high specific activity of alpha emission.

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

    USGS Publications Warehouse

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

    1985-01-01

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

  8. In Situ Analysis of Organics and Isotopes at Mars

    NASA Astrophysics Data System (ADS)

    Mahaffy, P. R.; Atreya, S. K.; Brinckerhoff, W. B.; Cabane, M.; Coll, P.; Demick, J.; Harpold, D. N.; Ming, D.; Niemann, H.; Owen, T.; Raulin, F.; Scott, J.; Webster, C.

    2003-05-01

    The recent success of the "follow the water" imperative for Mars exploration is tempered by the fact that more than 2 decades after Viking, much remains unknown about the state of carbon at the planet's surface. Therefore, a key objective for lander missions that follow MER will be a search for the location and nature of organic molecules and other carbon containing species. Reduced or partially oxidized compounds may reveal the nature of ancient or even present biotic or prebiotic processes. Ongoing definition and development of advanced techniques and protocols to "follow the carbon" will be described. For example, an instrument suite presently under development to be proposed for inclusion on the 2009 Mars Science Laboratory consists of an advanced gas chromatograph mass spectrometer (GCMS) with derivatization capability coupled with a laser desorption time-of-flight mass spectrometer (LDMS) and a tunable laser spectrometer (TLS). The suite is designated SAM (for Sample Analysis at Mars) and is designed to carry out analysis of both atmospheric gases and volatiles released from solid phase soils, rock samples, and ices. Volatile organic molecules and their pyrolysis products are analyzed by the GCMS and TLS, and refractory organics and elements by the LDMS. Additional objectives include higher precision measurements than have been obtained, to date, of the abundances and isotope ratios of the noble gases and a range of light elements including H, C, O, and N in both the atmosphere and soil. SAM can also contribute to geochemical objectives with the identification of various minerals through evolved gas analysis (EGA) of stable thermal decomposition products such as H2O, CO2, and oxides of nitrogen and sulfur using the MS and TLS as the detector. Recent EGA studies on Mars analogue materials that illustrate this capability are described. This work is supported by funding from NASA and CNES

  9. Direct analysis of air filter samples for alpha emitting isotopes

    SciTech Connect

    Mohagheghi, A.H.; Ghanbari, F.; Ebara, S.B.; Enghauser, M.E.; Bakhtiar, S.N.

    1997-04-01

    The traditional method for determination of alpha emitting isotopes on air filters has been to process the samples by radiochemical methods. However, this method is too slow for cases of incidents involving radioactive materials where the determination of personnel received dose is urgent. A method is developed to directly analyze the air filters taken from personal and area air monitors. The site knowledge is used in combination with alpha spectral information to identify isotopes. A mathematical function is developed to estimate the activity for each isotope. The strengths and weaknesses of the method are discussed.

  10. Laboratory and field methods for stable isotope analysis in human biology.

    PubMed

    Reitsema, Laurie J

    2015-01-01

    Stable isotope analysis (SIA; carbon, hydrogen, nitrogen, sulfur, and oxygen) of human tissues offers a means for assessing diet among living humans. Stable isotope ratios of broad categories of food and drink food vary systematically, and stable isotope ratios in consumer tissues represent a composite of the isotopic ratios of food and drink consumed during an individual's life. Isotopic evidence for diet is independent of errors in informant recall, and accrues during time periods when researchers are absent. Beyond diet reconstruction, tissue stable isotope ratios are sensitive to excursions from homeostasis, such as starvation and rapid growth. Because of their relationship to diet, geographic location, hydration, and nutritional status, stable isotope signatures in human tissues offer a window into human biocultural adaptations, past and present. This article describes methods for SIA that may be usefully applied in studies of living humans, with emphasis placed on carbon and nitrogen. Some of the ecological, physiological, and evolutionary applications of stable isotope data among living humans are discussed. By incorporating SIA in research, human biologists facilitate a productive dialog with bioarchaeologists, who routinely use stable isotope evidence, mingling different perspectives on human biology and behavior.

  11. Non-lethal sampling of walleye for stable isotope analysis: a comparison of three tissues

    USGS Publications Warehouse

    Chipps, Steven R.; VanDeHey, J.A.; Fincel, M.J.

    2012-01-01

    Stable isotope analysis of fishes is often performed using muscle or organ tissues that require sacrificing animals. Non-lethal sampling provides an alternative for evaluating isotopic composition for species of concern or individuals of exceptional value. Stable isotope values of white muscle (lethal) were compared with those from fins and scales (non-lethal) in walleye, Sander vitreus (Mitchill), from multiple systems, size classes and across a range of isotopic values. Isotopic variability was also compared among populations to determine the potential of non-lethal tissues for diet-variability analyses. Muscle-derived isotope values were enriched compared with fins and depleted relative to scales. A split-sample validation technique and linear regression found that isotopic composition of walleye fins and scales was significantly related to that in muscle tissue for both δ13C and δ15N (r2 = 0.79–0.93). However, isotopic variability was significantly different between tissue types in two of six populations for δ15N and three of six populations for δ13C. Although species and population specific, these findings indicate that isotopic measures obtained from non-lethal tissues are indicative of those obtained from muscle.

  12. Applications, considerations, and sources of uncertainty when using stable isotope analysis in ecotoxicology.

    PubMed

    Jardine, Timothy D; Kidd, Karen A; Fisk, Aaron T

    2006-12-15

    Stable isotope analysis (SIA) has become a powerful tool for ecotoxicologists to study dietary exposure and biomagnification of contaminants in wild animal populations. The use of SIA in ecotoxicology continues to expand and, while much more is known about the mechanisms driving patterns of isotopic ratios in consumers, there remain several considerations or sources of uncertainty that can influence interpretation of data from field studies. We outline current uses of SIA in ecotoxicology, including estimating the importance of dietary sources of carbon and their application in biomagnification studies, and we present six main considerations or sources of uncertainty associated with the approach: (1) unequal diet-tissue stable isotope fractionation among species, (2) variable diet-tissue stable isotope fractionation within a given species, (3) different stable isotope ratios in different tissues of the animal, (4) fluctuating baseline stable isotope ratios across systems, (5) the presence of true omnivores, and (6) movement of animals and nutrients between food webs. Since these considerations or sources of uncertainty are difficult to assess in field studies, we advocate that researchers consider the following in designing ecotoxicological research and interpreting results: assess and utilize variation in stable isotope diet-tissue fractionation among animal groups available in the literature; determine stable isotope ratios in multiple tissues to provide a temporal assessment of feeding; adequately characterize baseline isotope ratios; utilize stomach contents when possible; and assess and integrate life history of study animals in a system.

  13. Sensitivity analysis and quantification of uncertainty for isotopic mixing relationships in carbon cycle research

    NASA Astrophysics Data System (ADS)

    Zobitz, J. M.; Keener, J. P.; Bowling, D. R.

    2004-12-01

    Quantifying and understanding the uncertainty in isotopic mixing relationships is critical to isotopic applications in carbon cycle studies at all spatial and temporal scales. Studies associated with the North American Carbon Program will depend on stable isotope approaches and quantification of isotopic uncertainty. An important application of isotopic mixing relationships is determination of the isotopic content of large-scale respiration (δ 13CR) via an inverse relationship (a Keeling plot) between atmospheric CO2 concentrations ([CO2]) and carbon isotope ratios of CO2 (δ 13C). Alternatively, a linear relationship between [CO2] and the product of [CO2] and δ 13C (a Miller/Tans plot) can also be applied. We used an extensive dataset from the Niwot Ridge Ameriflux Site of [CO2] and δ 13C in forest air to examine contrasting approaches to determine δ 13CR and its uncertainty. These included Keeling plots, Miller/Tans plots, Model I, and Model II regressions Our analysis confirms previous observations that increasing the range of measurements ([CO2] range) reduces the uncertainty associated with δ 13CR. For carbon isotope studies, uncertainty in the isotopic measurements has a greater effect on the uncertainty of δ 13CR than the uncertainty in [CO2]. Reducing the uncertainty of isotopic measurements reduces the uncertainty of δ 13CR even when the [CO2] range of samples is small (< 20 ppm). As a result, improvement in isotope (rather than CO2) measuring capability is needed to substantially reduce uncertainty in δ 13CR. We also find for carbon isotope studies no inherent advantage to using either a Keeling or a Miller/Tans approach to determine δ 13CR.

  14. Actinides and Life's Origins.

    PubMed

    Adam, Zachary

    2007-12-01

    There are growing indications that life began in a radioactive beach environment. A geologic framework for the origin or support of life in a Hadean heavy mineral placer beach has been developed, based on the unique chemical properties of the lower-electronic actinides, which act as nuclear fissile and fertile fuels, radiolytic energy sources, oligomer catalysts, and coordinating ions (along with mineralogically associated lanthanides) for prototypical prebiotic homonuclear and dinuclear metalloenzymes. A four-factor nuclear reactor model was constructed to estimate how much uranium would have been required to initiate a sustainable fission reaction within a placer beach sand 4.3 billion years ago. It was calculated that about 1-8 weight percent of the sand would have to have been uraninite, depending on the weight percent, uranium enrichment, and quantity of neutron poisons present within the remaining placer minerals. Radiolysis experiments were conducted with various solvents with the use of uraniumand thorium-rich minerals (metatorbernite and monazite, respectively) as proxies for radioactive beach sand in contact with different carbon, hydrogen, oxygen, and nitrogen reactants. Radiation bombardment ranged in duration of exposure from 3 weeks to 6 months. Low levels of acetonitrile (estimated to be on the order of parts per billion in concentration) were conclusively identified in 2 setups and tentatively indicated in a 3(rd) by gas chromatography/mass spectrometry. These low levels have been interpreted within the context of a Hadean placer beach prebiotic framework to demonstrate the promise of investigating natural nuclear reactors as power production sites that might have assisted the origins of life on young rocky planets with a sufficiently differentiated crust/mantle structure. Future investigations are recommended to better quantify the complex relationships between energy release, radioactive grain size, fissionability, reactant phase, phosphorus

  15. Actinides and Life's Origins.

    PubMed

    Adam, Zachary

    2007-12-01

    There are growing indications that life began in a radioactive beach environment. A geologic framework for the origin or support of life in a Hadean heavy mineral placer beach has been developed, based on the unique chemical properties of the lower-electronic actinides, which act as nuclear fissile and fertile fuels, radiolytic energy sources, oligomer catalysts, and coordinating ions (along with mineralogically associated lanthanides) for prototypical prebiotic homonuclear and dinuclear metalloenzymes. A four-factor nuclear reactor model was constructed to estimate how much uranium would have been required to initiate a sustainable fission reaction within a placer beach sand 4.3 billion years ago. It was calculated that about 1-8 weight percent of the sand would have to have been uraninite, depending on the weight percent, uranium enrichment, and quantity of neutron poisons present within the remaining placer minerals. Radiolysis experiments were conducted with various solvents with the use of uraniumand thorium-rich minerals (metatorbernite and monazite, respectively) as proxies for radioactive beach sand in contact with different carbon, hydrogen, oxygen, and nitrogen reactants. Radiation bombardment ranged in duration of exposure from 3 weeks to 6 months. Low levels of acetonitrile (estimated to be on the order of parts per billion in concentration) were conclusively identified in 2 setups and tentatively indicated in a 3(rd) by gas chromatography/mass spectrometry. These low levels have been interpreted within the context of a Hadean placer beach prebiotic framework to demonstrate the promise of investigating natural nuclear reactors as power production sites that might have assisted the origins of life on young rocky planets with a sufficiently differentiated crust/mantle structure. Future investigations are recommended to better quantify the complex relationships between energy release, radioactive grain size, fissionability, reactant phase, phosphorus

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

    PubMed

    Weisler, M I; Woodhead, J D

    1995-03-14

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

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

    PubMed

    Weisler, M I; Woodhead, J D

    1995-03-14

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

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

    PubMed Central

    Weisler, M I; Woodhead, J D

    1995-01-01

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

  19. Nuclear waste forms for actinides

    PubMed Central

    Ewing, Rodney C.

    1999-01-01

    The disposition of actinides, most recently 239Pu from dismantled nuclear weapons, requires effective containment of waste generated by the nuclear fuel cycle. Because actinides (e.g., 239Pu and 237Np) are long-lived, they have a major impact on risk assessments of geologic repositories. Thus, demonstrable, long-term chemical and mechanical durability are essential properties of waste forms for the immobilization of actinides. Mineralogic and geologic studies provide excellent candidate phases for immobilization and a unique database that cannot be duplicated by a purely materials science approach. The “mineralogic approach” is illustrated by a discussion of zircon as a phase for the immobilization of excess weapons plutonium. PMID:10097054

  20. 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‰).

  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. Cu isotope fractionation during bornite dissolution: An in situ X-ray diffraction analysis

    SciTech Connect

    Wall, Andrew J.; Mathur, Ryan; Post, Jeffrey E.; Heaney, Peter J.

    2012-10-24

    Low-temperature ore deposits exhibit a large variation in {delta}{sup 65}Cu ({approx}12{per_thousand}), and this range has been attributed, in part, to isotope fractionation during weathering reactions of primary minerals such as chalcocite and chalcopyrite. Here, we examine the fractionation of Cu isotopes during dissolution of another important Cu ore mineral, bornite, using a novel approach that combines time-resolved X-ray diffraction (XRD) and isotope analysis of reaction products. During the initial stages of bornite oxidative dissolution by ferric sulfate (< 5 mol% of total Cu leached), dissolved Cu was enriched in isotopically heavy Cu ({sup 65}Cu) relative to the solid, with an average apparent isotope fractionation ({Delta}{sub aq - min} = {delta}{sup 65}Cu{sub aq} - {delta}{sup 65}Cu{sub min}{sup 0}) of 2.20 {+-} 0.25{per_thousand}. When > 20 mol% Cu was leached from the solid, the difference between the Cu isotope composition of the aqueous and mineral phases approached zero, with {Delta}{sub aq - min}{sup 0} values ranging from - 0.21 {+-} 0.61{per_thousand} to 0.92 {+-} 0.25{per_thousand}. XRD analysis allowed us to correlate changes in the atomic structure of bornite with the apparent isotope fractionation as the dissolution reaction progressed. These data revealed that the greatest degree of apparent fractionation is accompanied by a steep contraction in the unit-cell volume, which we identified as a transition from stoichiometric to non-stoichiometric bornite. We propose that the initially high {Delta}{sub aq - min} values result from isotopically heavy Cu ({sup 65}Cu) concentrating within Cu{sup 2+} during dissolution. The decrease in the apparent isotope fractionation as the reaction progresses occurs from the distillation of isotopically heavy Cu ({sup 65}Cu) during dissolution or kinetic isotope effects associated with the depletion of Cu from the surfaces of bornite particles.

  3. Actinide cation-cation complexes

    SciTech Connect

    Stoyer, N.J.; Seaborg, G.T.

    1994-12-01

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO{sub 2}{sup +}) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO{sub 2}{sup +}; therefore, cation-cation complexes indicate something unique about AnO{sub 2}{sup +} cations compared to actinide cations in general. The first cation-cation complex, NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO{sub 2}{sup +} species, the cation-cation complexes of NpO{sub 2}{sup +} have been studied most extensively while the other actinides have not. The only PuO{sub 2}{sup +} cation-cation complexes that have been studied are with Fe{sup 3+} and Cr{sup 3+} and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, NpO{sub 2}{sup +}{center_dot}Th{sup 4+}, PuO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, and PuO{sub 2}{sup +}{center_dot}Th{sup 4+} at an ionic strength of 6 M using LIPAS are 2.4 {plus_minus} 0.2, 1.8 {plus_minus} 0.9, 2.2 {plus_minus} 1.5, and {approx}0.8 M{sup {minus}1}.

  4. Improved Actinide Neutron Capture Cross Sections Using Accelerator Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Bauder, W.; Pardo, R. C.; Kondev, F. G.; Kondrashev, S.; Nair, C.; Nusair, O.; Palchan, T.; Scott, R.; Seweryniak, D.; Vondrasek, R.; Collon, P.; Paul, M.; Youinou, G.; Salvatores, M.; Palmotti, G.; Berg, J.; Maddock, T.; Imel, G.

    2014-09-01

    The MANTRA (Measurement of Actinide Neutron TRAnsmutations) project will improve energy-integrated neutron capture cross section data across the actinide region. These data are incorporated into nuclear reactor models and are an important piece in understanding Generation IV reactor designs. We will infer the capture cross sections by measuring isotopic ratios from actinide samples, irradiated in the Advanced Test Reactor at INL, with Accelerator Mass Spectrometry (AMS) at ATLAS (ANL). The superior sensitivity of AMS allows us to extract multiple cross sections from a single sample. In order to analyze the large number of samples needed for MANTRA and to meet the goal of extracting multiple cross sections per sample, we have made a number of modifications to the AMS setup at ATLAS. In particular, we are developing a technique to inject solid material into the ECR with laser ablation. With laser ablation, we can better control material injection and potentially increase efficiency in the ECR, thus creating less contamination in the source and reducing cross talk. I will present work on the laser ablation system and preliminary results from our AMS measurements. The MANTRA (Measurement of Actinide Neutron TRAnsmutations) project will improve energy-integrated neutron capture cross section data across the actinide region. These data are incorporated into nuclear reactor models and are an important piece in understanding Generation IV reactor designs. We will infer the capture cross sections by measuring isotopic ratios from actinide samples, irradiated in the Advanced Test Reactor at INL, with Accelerator Mass Spectrometry (AMS) at ATLAS (ANL). The superior sensitivity of AMS allows us to extract multiple cross sections from a single sample. In order to analyze the large number of samples needed for MANTRA and to meet the goal of extracting multiple cross sections per sample, we have made a number of modifications to the AMS setup at ATLAS. In particular, we are

  5. Computer Analysis of Isotope Clusters in Mass Spectrometry

    ERIC Educational Resources Information Center

    Bell, Harold M.

    1974-01-01

    Describes the application of a computer program designed to produce a formula determination simultaneously accounting for both elemental composition and probable isotopic species for a measured ion mass. (SLH)

  6. 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.

  7. Thermodynamics of carbothermic synthesis of actinide mononitrides

    NASA Astrophysics Data System (ADS)

    Ogawa, Toru; Shirasu, Yoshiro; Minato, Kazuo; Serizawa, Hiroyuki

    1997-08-01

    Carbothermic synthesis will be further applied to the fabrication of nitride fuels containing minor actinides (MA) such as neptunium, americium and curium. A thorough understanding of the carbothermic synthesis of UN will be beneficial in the development of the MA-containing fuels. Thermodynamic analysis was carried out for conditions of practical interest in order to better understand the recent fabrication experiences. Two types of solution phases, oxynitride and carbonitride phases, were taken into account. The PuNO ternary isotherm was assessed for the modelling of M(C, N, O). With the understanding of the UN synthesis, the fabrication problems of Am-containing nitrides are discussed.

  8. Actinide Thermodynamics at Elevated Temperatures

    SciTech Connect

    Friese, Judah I.; Rao, Linfeng; Xia, Yuanxian; Bachelor, Paula P.; Tian, Guoxin

    2007-11-16

    The postclosure chemical environment in the proposed Yucca Mountain repository is expected to experience elevated temperatures. Predicting migration of actinides is possible if sufficient, reliable thermodynamic data on hydrolysis and complexation are available for these temperatures. Data are scarce and scattered for 25 degrees C, and nonexistent for elevated temperatures. This collaborative project between LBNL and PNNL collects thermodynamic data at elevated temperatures on actinide complexes with inorganic ligands that may be present in Yucca Mountain. The ligands include hydroxide, fluoride, sulfate, phosphate and carbonate. Thermodynamic parameters of complexation, including stability constants, enthalpy, entropy and heat capacity of complexation, are measured with a variety of techniques including solvent extraction, potentiometry, spectrophotometry and calorimetry

  9. Preliminary considerations concerning actinide solubilities

    SciTech Connect

    Newton, T.W.; Bayhurst, B.P.; Daniels, W.R.; Erdal, B.R.; Ogard, A.E.

    1980-01-01

    Work at the Los Alamos Scientific Laboratory on the fundamental solution chemistry of the actinides has thus far been confined to preliminary considerations of the problems involved in developing an understanding of the precipitation and dissolution behavior of actinide compounds under environmental conditions. Attempts have been made to calculate solubility as a function of Eh and pH using the appropriate thermodynamic data; results have been presented in terms of contour maps showing lines of constant solubility as a function of Eh and pH. Possible methods of control of the redox potential of rock-groundwater systems by the use of Eh buffers (redox couples) is presented.

  10. Oceanic and Climate phasing analysis across Marine Isotope Stage 3

    NASA Astrophysics Data System (ADS)

    Henry, G., III; McManus, J. F.; Curry, W. B.; Roberts, N. L.; Piotrowski, A. M.; Keigwin, L. D.

    2015-12-01

    Glacial climate oscillated between cold stadial periods similar to the Last Glacial Maximum and warmer periods more similar to today from 25,000 to 60,000 years BP, an envelop of time referred to as marine isotope stage three (MIS3). The sudden warmings (Dansgaard-Oeschger events) and ice sheet surges (Heinrich events) have long captured researchers' attention as a means of exploring significant perturbations to the climate system. The climate dynamics associated with these events have been recently elucidated throughhigh-resolution analysis of ice and sediment core archives. In particular, it has been recently demonstrated through synchronization of Greenlandic and Antarctic ice cores that abrupt climate events propagated from the Northern to Southern hemisphere. Likewise, during Heinrich events ice rafted detritus appeared in the Northern North Atlantic generally after cold stadial conditions had already been established. These results indict the ocean's conveyor as the vehicle hemispheric partitioning heat across these events. Here we test the phased response of multiple paleoproxies sensitive to circulation across these abrupt climate events through all of MIS3. Through correlation analysis of multiple paleoproxy records generated from a high accumulation sediment core taken from the Bermuda Rise, we examine the phase relationship of high latitude climate records with the kinematic circulation proxy Pa/Th, benthic d13C and d18O, SST, d18Osw, CaCO3 content, 230Th-normalized bulk and component fluxes in order to infer the sequence of change across these abrupt millennial events. We find that shifts in water mass composition precede increases in temperatures across the identified time interval, while the export of Pa relative to Th increases in tandem with changes in with Bermuda Rise SST estimates during warmings, but lags during cooling. Rapid shifts in thorium normalized carbonate flux supply secondary evidence for changes in preservation accompanying changes

  11. Analysis of Hydrogen Isotopic Exchange: Lava Creek Tuff Ash and Isotopically Labeled Water

    NASA Astrophysics Data System (ADS)

    Ross, A. M.; Seligman, A. N.; Bindeman, I. N.; Nolan, G. S.

    2015-12-01

    Nolan and Bindeman (2013) placed secondarily hydrated ash from the 7.7 ka eruption of Mt. Mazama (δD=-149‰, 2.3wt% H2Ot) in isotopically labeled water (+650 ‰ δD, +56 ‰ δ18O) and observed that the H2Ot and δ18O values remained constant, but the δD values of ash increased with the surrounding water at 20, 40 and 70 °C. We expand on this work by conducting a similar experiment with ash from the 640 ka Lava Creek Tuff (LCT, δD of -128 ‰; 2.1 wt.% H2Ot) eruption of Yellowstone to see if significantly older glass (with a hypothesized gel layer on the surface shielding the interior from alteration) produces the same results. We have experiments running at 70, 24, and 5 °C, and periodically remove ~1.5 mg of glass to measure the δD (‰) and H2Ot (wt.%) of water extracted from the glass on a TC/EA MAT 253 continuous flow system. After 600 hours, the δD of the samples left at 5 and 24 °C remains at -128 ‰, but increased 8‰ for the 70 °C run series. However, there is no measurable change in wt.% of H2Ot, indicating that hydrogen exchange is not dictated by the addition of water. We are measuring and will report further progress of isotope exchange. We also plan to analyze the water in the LCT glass for δ18O (‰) to see if, as is the case for the Mt. Mazama glass, the δ18O (‰) remains constant. We also analyzed Mt. Mazama glass from the Nolan and Bindeman (2013) experiments that have now been sitting in isotopically labeled water at room temperature for ~5 years. The water concentration is still unchanged (2.3 wt.% H2Ot), and the δD of the water in the glass is now -111 ‰, causing an increase of 38 ‰. Our preliminary results show that exchange of hydrogen isotopes of hydrated glass is not limited by the age of the glass, and that the testing of hydrogen isotopes of secondarily hydrated glass, regardless of age, may not be a reliable paleoclimate indicator.

  12. Actinide cross section program at ORELA

    SciTech Connect

    Dabbs, J. W.T.

    1980-01-01

    The actinide cross section program at ORELA, the Oak Ridge Electron Linear Accelerator, is aimed at obtaining accurate neutron cross sections (primarily fission, capture, and total) for actinide nuclides which occur in fission reactors. Such cross sections, measured as a function of neutron energy over as wide a range of energies as feasible, comprise a data base that permits calculated predictions of the formation and removal of these nuclides in reactors. The present program is funded by the Division of Basic Energy Sciences of DOE, and has components in several divisions at ORNL. For intensively ..cap alpha..-active nuclides, many of the existing fission cross section data have been provided by underground explosions. New measurement techniques, developed at ORELA, now permit linac measurements on fissionable nuclides with alpha half-lives as short as 28 years. Capture and capture-plus-fission measurements utilize scintillation detectors (of capture ..gamma.. rays and fission neutrons) in which pulse shape discrimination plays an important role. Total cross sections can be measured at ORELA on samples of only a few milligrams. A simultaneous program of chemical and isotopic analyses of samples irradiated in EBR-II is in progress to provide benchmarks for the existing differential measurements. These analyses are being studied with updated versions of ORIGEN and with sensitivity determinations. Calculations of the sensitivity to cross section changes of various aspects of the nuclear fuel cycle are also being made. Even in this relatively mature field, many cross sections still require improvements to provide an adequate data base. Examples of recent techniques and measurements are presented. 12 figures, 3 tables.

  13. Hardening neutron spectrum for advanced actinide transmutation experiments in the ATR.

    PubMed

    Chang, G S; Ambrosek, R G

    2005-01-01

    The most effective method for transmuting long-lived isotopes contained in spent nuclear fuel into shorter-lived fission products is in a fast neutron spectrum reactor. In the absence of a fast test reactor in the United States, initial irradiation testing of candidate fuels can be performed in a thermal test reactor that has been modified to produce a test region with a hardened neutron spectrum. Such a test facility, with a spectrum similar but somewhat softer than that of the liquid-metal fast breeder reactor (LMFBR), has been constructed in the INEEL's Advanced Test Reactor (ATR). The radial fission power distribution of the actinide fuel pin, which is an important parameter in fission gas release modelling, needs to be accurately predicted and the hardened neutron spectrum in the ATR and the LMFBR fast neutron spectrum is compared. The comparison analyses in this study are performed using MCWO, a well-developed tool that couples the Monte Carlo transport code MCNP with the isotope depletion and build-up code ORIGEN-2. MCWO analysis yields time-dependent and neutron-spectrum-dependent minor actinide and Pu concentrations and detailed radial fission power profile calculations for a typical fast reactor (LMFBR) neutron spectrum and the hardened neutron spectrum test region in the ATR. The MCWO-calculated results indicate that the cadmium basket used in the advanced fuel test assembly in the ATR can effectively depress the linear heat generation rate in the experimental fuels and harden the neutron spectrum in the test region.

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

    PubMed

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

    2016-03-01

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

  15. Development of isotope dilution gamma-ray spectrometry for plutonium analysis

    SciTech Connect

    Li, T.K.; Parker, J.L. ); Kuno, Y.; Sato, S.; Kurosawa, A.; Akiyama, T. )

    1991-01-01

    We are studying the feasibility of determining the plutonium concentration and isotopic distribution of highly radioactive, spent-fuel dissolver solutions by employing high-resolution gamma-ray spectrometry. The study involves gamma-ray plutonium isotopic analysis for both dissolver and spiked dissolver solution samples, after plutonium is eluted through an ion-exchange column and absorbed in a small resin bead bag. The spike is well characterized, dry plutonium containing {approximately}98% of {sup 239}Pu. By using measured isotopic information, the concentration of elemental plutonium in the dissolver solution can be determined. Both the plutonium concentration and the isotopic composition of the dissolver solution obtained from this study agree well with values obtained by traditional isotope dilution mass spectrometry (IDMS). Because it is rapid, easy to operate and maintain, and costs less, this new technique could be an alternative method to IDMS for input accountability and verification measurements in reprocessing plants. 7 refs., 4 figs., 4 tabs.

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

    PubMed

    Hatzinger, Paul B; Böhlke, J K; Sturchio, Neil C

    2013-06-01

    Stable isotope ratio analysis is increasingly being applied as a tool to detect, understand, and quantify biodegradation of organic and inorganic contaminants in groundwater. An important feature of this approach is that it allows degradative losses of contaminants to be distinguished from those caused by non-destructive processes such as dilution, dispersion, and sorption. Recent advances in analytical techniques, and new approaches for interpreting stable isotope data, have expanded the utility of this method while also exposing complications and ambiguities that must be considered in data interpretations. Isotopic analyses of multiple elements in a compound, and multiple compounds in the environment, are being used to distinguish biodegradative pathways by their characteristic isotope effects. Numerical models of contaminant transport, degradation pathways, and isotopic composition are improving quantitative estimates of in situ contaminant degradation rates under realistic environmental conditions. PMID:23279929

  17. Novel complexing agents for the efficient separation of actinides and remediation of actinide-contaminated sites

    SciTech Connect

    Baisden, P.; Kadkhodayan, B.

    1996-03-15

    Research into the coordination chemistry of transactinide elements should provide us with new fundamental knowledge about structure, geometry, and stability of these metal complexes. Our approach involves the design, synthesis, and characterization of {open_quotes}expanded porphyrin{close_quotes} macrocyclic ligands which coordinate the actinide metal cations with high thermodynamic affinity and kinetic stability. We can use the knowledge from understanding the fundamental coordination chemistry of these elements as a stepping stone to heavy metal detoxification, radioactive waste cleanup, and possibly radioactive isotope separation. The critical components of this research endeavor, along with the viability of metal complex formation, will be correlated to ring size and core geometry of the ligand and, the atomic radius, oxidation state, coordination geometry and coordination number of the transactinium metal ion. These chelating agents may have certain applications to the solution of some radioactive waste problems if they can be attached to polymer supports and used to chemically separate the radioactive components in waste.

  18. Separations of actinides, lanthanides and other metals

    DOEpatents

    Smith, Barbara F.; Jarvinen, Gordon D.; Ensor, Dale D.

    1995-01-01

    An organic extracting solution comprised of a bis(acylpyrazolone or a substituted bis(acylpyrazolone) and an extraction method useful for separating certain elements of the actinide series of the periodic table having a valence of four from one other, and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also useful for separating hexavalent actinides from one or more of the substances in a group consisting of trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals.

  19. Compound Specific Stable Isotope Analysis of Southern African Aerosols

    NASA Astrophysics Data System (ADS)

    Billmark, K. A.; Swap, R. J.; Macko, S. A.

    2001-12-01

    Southern Africa has recently been the focus of intensive subcontinental level study, particularly with regard to atmospheric aerosols and regional atmospheric transport. Results from these analyses have shown that emissions from extensive, often anthropogenic, biomass burning in southern Africa affects biogeochemical cycling in the region, and that emitted trace gases and aerosols as well as industrial emissions, marine aerosols and mineral dust tend to accumulate and recirculate in the well defined anticyclonic atmospheric gyre that persists for long time periods over southern Africa. The long-range transport of these materials is an important component of biogeochemical dynamics in this nutrient limited region. A recent field campaign, the Southern African Regional Science Initiative (SAFARI 2000), was conducted in part to investigate the impacts of this large-scale transport and deposition of aerosols on southern African biogeochemical cycling. As a part of the SAFARI 2000 initiative, we present data illustrating that compound specific stable isotope analysis of individual molecular components is a useful tool for the evaluation of the origins of aerosols and their generating processes. This study specifically examines fatty acids extracted from aerosols to more precisely characterize emissions produced in the high intensity biomass burning region of western Zambia, the slightly less intense biomass burning region of northeastern South Africa and a site downwind of these two regions within the gyre circulation at Sua Pan, Botswana. This discrete characterization of fatty acids contained within the organic fraction of collected aerosols establishes a means to trace biomass burning products as they are transported within the gyre and subsequently deposited on the subcontinent.

  20. Secondary Ionization Mass Spectrometric Analysis of Impurity Element Isotope Ratios in Nuclear Reactor Materials

    SciTech Connect

    Gerlach, David C.; Cliff, John B.; Hurley, David E.; Reid, Bruce D.; Little, Winston W.; Meriwether, George H.; Wickham, Anthony J.; Simmons, Tere A.

    2006-07-30

    Secondary ion mass spectrometry (SIMS) analysis has been used to measure isotope ratios of selected impurity elements in irradiated reactor materials. Samples of reactor materials such as graphite or aluminum alloys are obtained from fuel channels or supporting materials. During reactor operations and fuel burn up, some isotopic abundances change due to nuclear reactions and provide sensitive indicators of neutron fluence. The rate of change is related to cross section for a particular isotope. Different isotopes can be used as indicators of burn up during different stages in the reactor operating history. Isotope ratios of B are useful indicators for low burnup stages early in reactor operations, Ti isotope ratios are useful at later burn up stages, and Cl isotope ratios are useful in both early and later stages. Knowledge of the sample position within the reactor also yields information on the fluence shape or profile. In a sequence of samples from one reactor, 10B/11B ratios decreased from near natural values of 0.25 to < 0.03. Direct SIMS measurements of isotope ratios have been possible in materials, following shaping and surface cleaning trials which have included dry ice micropellet blasting, plasma etching, and vacuum furnace treatment.

  1. High Resolution Gamma Ray Analysis of Medical Isotopes

    NASA Astrophysics Data System (ADS)

    Chillery, Thomas

    2015-10-01

    Compton-suppressed high-purity Germanium detectors at the University of Massachusetts Lowell have been used to study medical radioisotopes produced at Brookhaven Linac Isotope Producer (BLIP), in particular isotopes such as Pt-191 used for cancer therapy in patients. The ability to precisely analyze the concentrations of such radio-isotopes is essential for both production facilities such as Brookhaven and consumer hospitals across the U.S. Without accurate knowledge of the quantities and strengths of these isotopes, it is possible for doctors to administer incorrect dosages to patients, thus leading to undesired results. Samples have been produced at Brookhaven and shipped to UML, and the advanced electronics and data acquisition capabilities at UML have been used to extract peak areas in the gamma decay spectra. Levels of Pt isotopes in diluted samples have been quantified, and reaction cross-sections deduced from the irradiation parameters. These provide both cross checks with published work, as well as a rigorous quantitative framework with high quality state-of-the-art detection apparatus in use in the experimental nuclear physics community.

  2. Study of medical isotope production facility stack emissions and noble gas isotopic signature using automatic gamma-spectra analysis platform

    NASA Astrophysics Data System (ADS)

    Zhang, Weihua; Hoffmann, Emmy; Ungar, Kurt; Dolinar, George; Miley, Harry; Mekarski, Pawel; Schrom, Brian; Hoffman, Ian; Lawrie, Ryan; Loosz, Tom

    2013-04-01

    The nuclear industry emissions of the four CTBT (Comprehensive Nuclear-Test-Ban Treaty) relevant radioxenon isotopes are unavoidably detected by the IMS along with possible treaty violations. Another civil source of radioxenon emissions which contributes to the global background is radiopharmaceutical production companies. To better understand the source terms of these background emissions, a joint project between HC, ANSTO, PNNL and CRL was formed to install real-time detection systems to support 135Xe, 133Xe, 131mXe and 133mXe measurements at the ANSTO and CRL 99Mo production facility stacks as well as the CANDU (CANada Deuterium Uranium) primary coolant monitoring system at CRL. At each site, high resolution gamma spectra were collected every 15 minutes using a HPGe detector to continuously monitor a bypass feed from the stack or CANDU primary coolant system as it passed through a sampling cell. HC also conducted atmospheric monitoring for radioxenon at approximately 200 km distant from CRL. A program was written to transfer each spectrum into a text file format suitable for the automatic gamma-spectra analysis platform and then email the file to a server. Once the email was received by the server, it was automatically analysed with the gamma-spectrum software UniSampo/Shaman to perform radionuclide identification and activity calculation for a large number of gamma-spectra in a short period of time (less than 10 seconds per spectrum). The results of nuclide activity together with other spectrum parameters were saved into the Linssi database. This database contains a large amount of radionuclide information which is a valuable resource for the analysis of radionuclide distribution within the noble gas fission product emissions. The results could be useful to identify the specific mechanisms of the activity release. The isotopic signatures of the various radioxenon species can be determined as a function of release time. Comparison of 133mXe and 133Xe activity

  3. Chemistry of lower valent actinide halides

    SciTech Connect

    Lau, K.H.; Hildenbrand, D.L.

    1992-01-01

    This research effort was concerned almost entirely with the first two members of the actinide series, thorium and uranium, although the work was later extended to some aspects of the neptunium-fluorine system in a collaborative program with Los Alamos National Laboratory. Detailed information about the lighter actinides will be helpful in modeling the properties of the heavier actinide compounds, which will be much more difficult to study experimentally. In this program, thermochemical information was obtained from high temperature equilibrium measurements made by effusion-beam mass spectrometry and by effusion-pressure techniques. Data were derived primarily from second-law analysis so as to avoid potential errors in third-law calculations resulting from uncertainties in spectroscopic and molecular constants. This approach has the additional advantage of yielding reaction entropies that can be checked for consistency with various molecular constant assignments for the species involved. In the U-F, U-Cl, and U-Br systems, all of the gaseous species UX, UX{sub 2}, UX{sub 3}, UX{sub 4}, and UX{sub 5}, where X represents the halogen, were identified and characterized; the corresponding species ThX, ThX{sub 2}, ThX{sub 3}, and ThX{sub 4} were studied in the Th-F, Th-Cl, and Th-Br systems. A number of oxyhalide species in the systems U-0-F, U-0-Cl, Th-0-F, and Th-O-Cl were studied thermochemically. Additionally, the sublimation thermodynamics of NpF{sub 4}(s) and NpO{sub 2}F{sub 2}(s) were studied by mass spectrometry.

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

    PubMed

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

    2013-12-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2009-01-01

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

  6. Synthesis and characterization of a tetrathiafulvalene-salphen actinide complex.

    PubMed

    Bejger, Christopher; Tian, Yong-Hui; Barker, Beau J; Boland, Kevin S; Scott, Brian L; Batista, Enrique R; Kozimor, Stosh A; Sessler, Jonathan L

    2013-05-21

    A new tetrathiafulvalene-salphen uranyl complex has been prepared. The system was designed to study the electronic coupling between actinides and a redox active ligand framework. Theoretical and experimental methods--including DFT calculations, single crystal X-ray analysis, cyclic voltammetry, NMR and IR spectroscopies--were used to characterize this new uranyl complex.

  7. Detection of the actinides and cesium from environmental samples

    NASA Astrophysics Data System (ADS)

    Snow, Mathew Spencer

    Detection of the actinides and cesium in the environment is important for a variety of applications ranging from environmental remediation to safeguards and nuclear forensics. The utilization of multiple different elemental concentrations and isotopic ratios together can significantly improve the ability to attribute contamination to a unique source term and/or generation process; however, the utilization of multiple elemental "signatures" together from environmental samples requires knowledge of the impact of chemical fractionation for various elements under a variety of environmental conditions (including predominantly aqueous versus arid conditions). The research reported in this dissertation focuses on three major areas: 1. Improving the understanding of actinide-mineral interactions at ultra-low concentrations. Chapter 2 reports a batch sorption and modeling study of Np(V) sorption to the mineral goethite from attomolar to micromolar concentrations. 2. Improving the detection capabilities for Thermal Ionization Mass Spectrometry (TIMS) analyses of ultra-trace cesium from environmental samples. Chapter 4 reports a new method which significantly improves the chemical yields, purification, sample processing time, and ultimately, the detection limits for TIMS analyses of femtogram quantities of cesium from a variety of environmental sample matrices. 3. Demonstrating how actinide and cesium concentrations and isotopic ratios from environmental samples can be utilized together to determine a wealth of information including environmental transport mechanisms (e.g. aqueous versus arid transport) and information on the processes which generated the original material. Chapters1, 3 and 5 demonstrate these principles using Pu, Am, Np, and Cs concentrations and isotopic ratios from contaminated soils taken near the Subsurface Disposal Area (SDA) of Idaho National Laboratory (INL) (a low level radioactive waste disposal site in southeastern Idaho).

  8. Neutron Activation Analysis and Product Isotope Inventory Code System.

    1990-10-31

    Version 00 NAC was designed to predict the neutron-induced gamma-ray radioactivity for a wide variety of composite materials. The NAC output includes the input data, a list of all reactions for each constituent element, and the end-of-irradiation disintegration rates for each reaction. NAC also compiles a product isotope inventory containing the isotope name, the disintegration rate, the gamma-ray source strength, and the absorbed dose rate at 1 meter from an unshielded point source. The inducedmore » activity is calculated as a function of irradiation and decay times; the effect of cyclic irradiation can also be calculated.« less

  9. Application of dual carbon-bromine isotope analysis for investigating abiotic transformations of tribromoneopentyl alcohol (TBNPA).

    PubMed

    Kozell, Anna; Yecheskel, Yinon; Balaban, Noa; Dror, Ishai; Halicz, Ludwik; Ronen, Zeev; Gelman, Faina

    2015-04-01

    Many of polybrominated organic compounds, used as flame retardant additives, belong to the group of persistent organic pollutants. Compound-specific isotope analysis is one of the potential analytical tools for investigating their fate in the environment. However, the isotope effects associated with transformations of brominated organic compounds are still poorly explored. In the present study, we investigated carbon and bromine isotope fractionation during degradation of tribromoneopentyl alcohol (TBNPA), one of the widely used flame retardant additives, in three different chemical processes: transformation in aqueous alkaline solution (pH 8); reductive dehalogenation by zero-valent iron nanoparticles (nZVI) in anoxic conditions; oxidative degradation by H2O2 in the presence of CuO nanoparticles (nCuO). Two-dimensional carbon-bromine isotope plots (δ(13)C/Δ(81)Br) for each reaction gave different process-dependent isotope slopes (Λ(C/Br)): 25.2 ± 2.5 for alkaline hydrolysis (pH 8); 3.8 ± 0.5 for debromination in the presence of nZVI in anoxic conditions; ∞ in the case of catalytic oxidation by H2O2 with nCuO. The obtained isotope effects for both elements were generally in agreement with the values expected for the suggested reaction mechanisms. The results of the present study support further applications of dual carbon-bromine isotope analysis as a tool for identification of reaction pathway during transformations of brominated organic compounds in the environment.

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

    PubMed Central

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Muhammad, Syahidah; Frew, Russell; Hayman, Alan

    2015-02-01

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

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

    SciTech Connect

    Duffin, Andrew M.; Springer, Kellen WE; Ward, Jesse D.; Jarman, Kenneth D.; Robinson, John W.; Endres, Mackenzie C.; Hart, Garret L.; Gonzalez, Jhanis J.; Oropeza, Dayana; Russo, Richard; Willingham, David G.; Naes, Benjamin E.; Fahey, Albert J.; Eiden, Gregory C.

    2015-02-06

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

  13. Analysis of Experimental Data for High Burnup PWR Spent Fuel Isotopic Validation - Vandellos II Reactor

    SciTech Connect

    Ilas, Germina; Gauld, Ian C

    2011-01-01

    This report is one of the several recent NUREG/CR reports documenting benchmark-quality radiochemical assay data and the use of the data to validate computer code predictions of isotopic composition for spent nuclear fuel, to establish the uncertainty and bias associated with code predictions. The experimental data analyzed in the current report were acquired from a high-burnup fuel program coordinated by Spanish organizations. The measurements included extensive actinide and fission product data of importance to spent fuel safety applications, including burnup credit, decay heat, and radiation source terms. Six unique spent fuel samples from three uranium oxide fuel rods were analyzed. The fuel rods had a 4.5 wt % {sup 235}U initial enrichment and were irradiated in the Vandellos II pressurized water reactor operated in Spain. The burnups of the fuel samples range from 42 to 78 GWd/MTU. The measurements were used to validate the two-dimensional depletion sequence TRITON in the SCALE computer code system.

  14. Quantifying plant phenotypes with isotopic labeling and metabolic flux analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Analyses of metabolic flux using stable isotopes in plants have traditionally been restricted to tissues with presumed homogeneous cell populations such as developing seeds, cell suspensions, or cultured roots and root tips. It is now possible to describe these and other more complex tissues such a...

  15. STABLE CHLORINE ISOTOPE ANALYSIS OF CHLORINATED ORGANIC CONTAMINANTS

    EPA Science Inventory

    The biogeochemical cycling of chlorinated organic contaminants in the environment is often difficult to understand because of the complex distributions of these compounds and variability of sources. To address these issues from an isotopic perspective, we have measured the, 37Cl...

  16. Studies of Nuclear Structure and Decay Properties of Actinide Nuclei

    SciTech Connect

    Kondev, F. G.; Ahmad, I.; Carpenter, M. P.; Chiara, C. J.; Greene, J. P.; Janssens, R. V. F.; Khoo, T. L.; Lauritsen, T.; Lister, C. J.; Moore, E. F.; Seweryniak, D.; Zhu, S.; Kellett, M. A.; Nichols, A. L.

    2009-01-28

    The identification of single-particle states in heavy actinide nuclei by means of studying their decay schemes plays a seminal role in understanding the structure of the heaviest elements and testing the predictive power of modern theoretical models. The heaviest odd-mass nuclides available in sufficient quantity for detailed decay spectroscopic studies are 20-h {sup 255} Fm(for neutrons) and 20-d {sup 253}Es(for protons). Decay spectra of these isotopes, together with those for the odd-odd 276-d {sup 254}Es nuclide, were measured using a variety of {alpha}-particle and {gamma}-ray spectroscopy techniques. Well-defined decay data are also essential pre-requisites for the detection and accurate characterization of fissile radionuclides. The parameters of greatest relevance include actinide half-lives, branching fractions, and {alpha}-particle and {gamma}-ray energies and emission probabilities. Their quantification to good accuracy provides the means of monitoring their presence, behavior and transport in nuclear facilities as well as any clandestine movement and usage. As a consequence of recommendations made at recent IAEA research coordination meetings on 'Updated Decay Data Library for Actinides,' measurements were undertaken to determine specific decay data of the more inadequately defined radionuclides.

  17. Isomorphism of actinides and REE in synthetic ferrite garnets

    NASA Astrophysics Data System (ADS)

    Livshits, T. S.

    2010-02-01

    The reprocessing of spent nuclear fuel (SNF) is accompanied by the formation of liquid high-level radioactive waste (HLW). To increase the safety of handling HLW, it is proposed to extract actinide isotopes (An) and REE from them. These elements may be incorporated into crystalline matrices, e.g., based on ferrites with garnet structure, and then disposed in a geologic repository. The actinide-REE fraction is characterized by a complex composition. In addition to major components (An and REE), Al, Si, Na, and Sn occur therein in small amounts (a few wt %). Possible incorporation of the admixtures into ferrite garnets, as well as their effect on the phase composition of matrices and Th, Ce, Gd, and La contents were studied. It was shown that admixtures enter into garnet by means of isomorphic replacement. The properties of samples change only when admixtures are added in amounts exceeding their concentrations in HLW. The ability of ferrite garnets to accumulate significant amounts of An, REE, and admixture elements makes them suitable for use as matrices in immobilizing actinide-REE HLW of complex composition.

  18. Mass spectrometric analysis of isotope effects in bioconversion of benzene to cyclohexanone

    NASA Astrophysics Data System (ADS)

    Nam, In-Hyun; Murugesan, Kumarasamy; Kim, Young-Mo; Yang, In-Hee; Chang, Yoon-Seok

    2006-06-01

    Pseudomonas veronii strain PH-03 has been shown to convert benzene to cyclohexanone through phenol. Mass spectrometry results revealed that unusual isotopic effects have been occurred in the transformation product, cyclohexanone. The isotopic composition was strongly depends on the compound specific hydrogen or oxygen source. The exchange of labile deuterium atoms has been investigated through electrospray ionization liquid chromatography mass spectrometry. The mass spectrometric analysis of biotransformation products enabled the proposal of a corresponding bioconversion pathway.

  19. "Computational Modeling of Actinide Complexes"

    SciTech Connect

    Balasubramanian, K

    2007-03-07

    We will present our recent studies on computational actinide chemistry of complexes which are not only interesting from the standpoint of actinide coordination chemistry but also of relevance to environmental management of high-level nuclear wastes. We will be discussing our recent collaborative efforts with Professor Heino Nitsche of LBNL whose research group has been actively carrying out experimental studies on these species. Computations of actinide complexes are also quintessential to our understanding of the complexes found in geochemical, biochemical environments and actinide chemistry relevant to advanced nuclear systems. In particular we have been studying uranyl, plutonyl, and Cm(III) complexes are in aqueous solution. These studies are made with a variety of relativistic methods such as coupled cluster methods, DFT, and complete active space multi-configuration self-consistent-field (CASSCF) followed by large-scale CI computations and relativistic CI (RCI) computations up to 60 million configurations. Our computational studies on actinide complexes were motivated by ongoing EXAFS studies of speciated complexes in geo and biochemical environments carried out by Prof Heino Nitsche's group at Berkeley, Dr. David Clark at Los Alamos and Dr. Gibson's work on small actinide molecules at ORNL. The hydrolysis reactions of urnayl, neputyl and plutonyl complexes have received considerable attention due to their geochemical and biochemical importance but the results of free energies in solution and the mechanism of deprotonation have been topic of considerable uncertainty. We have computed deprotonating and migration of one water molecule from the first solvation shell to the second shell in UO{sub 2}(H{sub 2}O){sub 5}{sup 2+}, UO{sub 2}(H{sub 2}O){sub 5}{sup 2+}NpO{sub 2}(H{sub 2}O){sub 6}{sup +}, and PuO{sub 2}(H{sub 2}O){sub 5}{sup 2+} complexes. Our computed Gibbs free energy(7.27 kcal/m) in solution for the first time agrees with the experiment (7.1 kcal

  20. Chemical preparation of an isotopically enriched superoxide dismutase and its characterization as a standard for species-specific isotope dilution analysis.

    PubMed

    Deitrich, Christian L; Raab, Andrea; Pioselli, Barbara; Thomas-Oates, Jane E; Feldmann, Jörg

    2007-11-01

    The development of methods to analyze accurately and precisely individual metalloproteins is of increasing importance. Here we describe for the first time the chemical preparation and characterization of an isotopically enriched metalloenzyme containing two different metal isotopes. Its evaluation as a standard in species-specific isotope dilution analysis by HPLC coupled to inductively coupled plasma mass spectrometry is carefully evaluated. Our model enzyme bovine superoxide dismutase (SOD) contains both Cu and Zn and is remarkably stable at high temperatures and even under denaturing conditions. The enzyme's metal cofactors were removed under a range of different conditions and replaced with isotopically enriched 65Cu and 68Zn. Depending on the conditions, various isotopic ratios differing from the natural Cu and Zn abundances were obtained for the reconstituted enzyme. Both the wild type and isotopically enriched enzyme had the same migration pattern on native 1D-PAGE. Using an enzyme activity test, we showed that the incorporated 65Cu was bound to the right SOD-binding site, since the measured activity correlated directly with the amount of Cu incorporated. Mixing the native and the isotopically enriched enzyme standard with free enriched 65Cu and 68Zn or a metal chelator did not result in any exchange or loss of the metals from the enzyme at neutral pH. This verifies the stability of the enzyme metal center under the chosen conditions. The isotopically enriched enzyme standard was spiked into a wild type SOD solution to evaluate its use for species-specific isotope dilution experiments. To our knowledge, this is the first report of the chemical preparation of a metalloenzyme containing two different isotopically enriched metals. We provide evidence that the incorporated isotopically enriched metals are bound to the right binding site of SOD using an specific enzymatic activity assay.

  1. Actinides in deer tissues at the rocky flats environmental technology site.

    PubMed

    Todd, Andrew S; Sattelberg, R Mark

    2005-11-01

    Limited hunting of deer at the future Rocky Flats National Wildlife Refuge has been proposed in U.S. Fish and Wildlife planning documents as a compatible wildlife-dependent public use. Historically, Rocky Flats site activities resulted in the contamination of surface environmental media with actinides, including isotopes of americium, plutonium, and uranium. In this study, measurements of actinides [Americium-241 (241Am); Plutonium-238 (238Pu); Plutonium-239,240 (239,240Pu); uranium-233,244 (233,234U); uranium-235,236 (235,236U); and uranium-238 (238U)] were completed on select liver, muscle, lung, bone, and kidney tissue samples harvested from resident Rocky Flats deer (N = 26) and control deer (N = 1). In total, only 17 of the more than 450 individual isotopic analyses conducted on Rocky Flats deer tissue samples measured actinide concentrations above method detection limits. Of these 17 detects, only 2 analyses, with analytical uncertainty values added, exceeded threshold values calculated around a 1 x 10(-6) risk level (isotopic americium, 0.01 pCi/g; isotopic plutonium, 0.02 pCi/g; isotopic uranium, 0.2 pCi/g). Subsequent, conservative risk calculations suggest minimal human risk associated with ingestion of these edible deer tissues. The maximum calculated risk level in this study (4.73 x 10(-6)) is at the low end of the U.S. Environmental Protection Agency's acceptable risk range. PMID:16639905

  2. ACTINIDE BIOCOLLOID FORMATION IN BRINE BY HALOPHILIC BACTERIA

    SciTech Connect

    GILLOW,J.B.; FRANCIS,A.J.; DODGE,C.J.; HARRIS,R.; BEVERIDGE,T.J.; BRADY,P.B.; PAPENGUTH,H.W.

    1998-11-09

    The authors examined the ability of a halophilic bacterium (WIPP 1A) isolated from the Waste Isolation Pilot Plant (WIPP) site to accumulate uranium in order to determine the potential for biocolloid facilitated actinide transport. The bacterial cell surface functional groups involved in the complexation of the actinide were determined by titration. Uranium, added as uranyl nitrate, was removed from solution at pH 5 by cells but at pH 7 and 9 very little uranium was removed due to its limited solubility. Although present as soluble species, uranyl citrate at pH 5, 7, and 9, and uranyl carbonate at pH 9 were not removed by the bacterium because they were not bioavailable due to their neutral or negative charge. Addition of uranyl EDTA to brine at pH 5, 7, and 9 resulted in the immediate precipitation of U. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) analysis revealed that uranium was not only associated with the cell surface but also accumulated intracellularly as uranium-enriched granules. Extended X-ray absorption fine structure (EXAFS) analysis of the bacterial cells indicated the bulk sample contained more than one uranium phase. Nevertheless these results show the potential for the formation of actinide bearing bacterial biocolloids that are strictly regulated by the speciation and bioavailability of the actinide.

  3. Actinide Biocolloid Formation in Brine by Halophilic Bacteria

    SciTech Connect

    Gillow, J.B.; Francis, A.J.; Dodge, C.J.; Harris, R.; Beveridge, T.J.; Brady, P.V.; Papenguth, H.W.

    1999-07-28

    We examined the ability of a halophilic bacterium (WFP 1A) isolated from the Waste Isolation Pilot Plant (WIPP) site to accumulate uranium in order to determine the potential for biocolloid facilitated actinide transport. The bacterial cell Surface functional groups involved in the complexation of the actinide were determined by titration. Uranium, added as uranyl nitrate, was removed from solution at pH 5 by cells but at pH 7 and 9 very little uranium was removed due to its limited volubility. Although present as soluble species, uranyl citrate at pH 5, 7, and 9, and uranyl carbonate at pH 9 were not removed by the bacterium because they were not bioavailable due to their neutral or negative charge. Addition of uranyl EDTA to brine at pH 5, 7, and 9 resulted in the immediate precipitation of U. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) analysis revealed that uranium was not only associated with the cell surface but also accumulated intracellulary as uranium-enriched granules. Extended X-ray absorption fine structure (EXAFS) analysis, of the bacterial cells indicated the bulk sample contained more than one uranium phase. Nevertheless these results show the potential for the formation of actinide bearing bacterial biocolloids that are strictly regulated by the speciation and bioavailability of the actinide.

  4. Actinide biocolloid formation in brine by halophilic bacteria

    SciTech Connect

    Gillow, J.B.; Francis, A.J.; Dodge, C.J.; Harris, R.; Beveridge, T.J.; Brady, P.V.; Papenguth, H.W.

    1998-12-31

    The authors examined the ability of a halophilic bacterium (WIPP 1A) isolated from the Waste Isolation Pilot Plant (WIPP) site to accumulate uranium in order to determine the potential for biocolloid facilitated actinide transport. The bacterial cell surface functional groups involved in the complexation of the actinide were determined by titration. Uranium, added as uranyl nitrate, was removed from solution at pH 5 by cells but at pH 7 and 9 very little uranium was removed due to its limited solubility. Although present as soluble species, uranyl citrate at pH 5, 7, and 9, and uranyl carbonate at pH 9 were not removed by the bacterium because they were not bioavailable due to their neutral or negative charge. Addition of uranyl EDTA to brine at pH 5, 7, and 9 resulted in the immediate precipitation of U. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) analysis revealed that uranium was not only associated with the cell surface but also accumulated intracellularly as uranium-enriched granules. Extended X-ray absorption fine structure (EXAFS) analysis of the bacterial cells indicated the bulk sample contained more than one uranium phase. Nevertheless these results show the potential for the formation of actinide bearing bacterial biocolloids that are strictly regulated by the speciation and bioavailability of the actinide.

  5. RAPID SEPARATION OF ACTINIDES AND RADIOSTRONTIUM IN VEGETATION SAMPLES

    SciTech Connect

    Maxwell, S.

    2010-06-01

    A new rapid method for the determination of actinides and radiostrontium in vegetation samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used in emergency response situations or for routine analysis. The actinides in vegetation method utilizes a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a streamlined column separation process with stacked TEVA, TRU and DGA Resin cartridges. Lanthanum was separated rapidly and effectively from Am and Cm on DGA Resin. Alpha emitters are prepared using rare earth microprecipitation for counting by alpha spectrometry. The purified {sup 90}Sr fractions are mounted directly on planchets and counted by gas flow proportional counting. The method showed high chemical recoveries and effective removal of interferences. The actinide and {sup 90}Sr in vegetation sample analysis can be performed in less than 8 h with excellent quality for emergency samples. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory actinide particles or vegetation residue after furnace heating is effectively digested.

  6. Quantifying plant phenotypes with isotopic labeling & metabolic flux analysis.

    PubMed

    Allen, Doug K

    2016-02-01

    Analyses of metabolic flux using stable isotopes in plants have traditionally been restricted to tissues with presumed homogeneous cell populations and long metabolic steady states such as developing seeds, cell suspensions, or cultured roots and root tips. It is now possible to describe these and other metabolically more dynamic tissues such as leaves in greater detail using novel methods in mass spectrometry, isotope labeling strategies, and transient labeling-based flux analyses. Such studies are necessary for a systems level description of plant function that more closely represents biological reality, and provides insights into the genes that will need to be modified as natural resources become ever more limited and environments change. PMID:26613198

  7. Process for recovering actinide values

    DOEpatents

    Horwitz, E. Philip; Mason, George W.

    1980-01-01

    A process for rendering actinide values recoverable from sodium carbonate scrub waste solutions containing these and other values along with organic compounds resulting from the radiolytic and hydrolytic degradation of neutral organophosphorous extractants such as tri-n butyl phosphate (TBP) and dihexyl-N,N-diethyl carbamylmethylene phosphonate (DHDECAMP) which have been used in the reprocessing of irradiated nuclear reactor fuels. The scrub waste solution is preferably made acidic with mineral acid, to form a feed solution which is then contacted with a water-immiscible, highly polar organic extractant which selectively extracts the degradation products from the feed solution. The feed solution can then be processed to recover the actinides for storage or recycled back into the high-level waste process stream. The extractant is recycled after stripping the degradation products with a neutral sodium carbonate solution.

  8. The conflict between cheetahs and humans on Namibian farmland elucidated by stable isotope diet analysis.

    PubMed

    Voigt, Christian C; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

    2014-01-01

    Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food. PMID:25162403

  9. Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane.

    PubMed

    Palau, Jordi; Shouakar-Stash, Orfan; Hunkeler, Daniel

    2014-12-16

    This study investigates dual C-Cl isotope fractionation during 1,1,1-TCA transformation by heat-activated persulfate (PS), hydrolysis/dehydrohalogenation (HY/DH) and Fe(0). Compound-specific chlorine isotope analysis of 1,1,1-TCA was performed for the first time, and transformation-associated isotope fractionation ε bulk C and ε bulk Cl values were -4.0 ± 0.2‰ and no chlorine isotope fractionation with PS, -1.6 ± 0.2‰ and -4.7 ± 0.1‰ for HY/DH, -7.8 ± 0.4‰ and -5.2 ± 0.2‰ with Fe(0). Distinctly different dual isotope slopes (Δδ13C/Δδ37Cl): ∞ with PS, 0.33 ± 0.04 for HY/DH and 1.5 ± 0.1 with Fe(0) highlight the potential of this approach to identify abiotic degradation pathways of 1,1,1-TCA in the field. The trend observed with PS agreed with a C-H bond oxidation mechanism in the first reaction step. For HY/DH and Fe(0) pathways, different slopes were obtained although both pathways involve cleavage of a C-Cl bond in their initial reaction step. In contrast to the expected larger primary carbon isotope effects relative to chlorine for C-Cl bond cleavage, ε bulk C < ε bulk Cl was observed for HY/DH and in a similar range for reduction by Fe(0), suggesting the contribution of secondary chlorine isotope effects. Therefore, different magnitude of secondary chlorine isotope effects could at least be partly responsible for the distinct slopes between HY/DH and Fe(0) pathways. Following this dual isotope approach, abiotic transformation processes can unambiguously be identified and quantified.

  10. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Horst, A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

    2015-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  11. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Hangx, S.; Pijnenburg, R. P.; Niemeijer, A. R.; Bakker, E.; Samuelson, J. E.; Spiers, C. J.

    2014-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  12. The conflict between cheetahs and humans on Namibian farmland elucidated by stable isotope diet analysis.

    PubMed

    Voigt, Christian C; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

    2014-01-01

    Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food.

  13. The Conflict between Cheetahs and Humans on Namibian Farmland Elucidated by Stable Isotope Diet Analysis

    PubMed Central

    Voigt, Christian C.; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

    2014-01-01

    Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food. PMID:25162403

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

    NASA Astrophysics Data System (ADS)

    Herzka, Sharon Z.

    2005-07-01

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

  15. Actinide Recovery Method for Large Soil Samples

    SciTech Connect

    Maxwell, S.L. III; Nichols, S.

    1998-11-01

    A new Actinide Recovery Method has been developed by the Savannah River Site Central Laboratory to preconcentrate actinides in very large soil samples. Diphonix Resin(r) is used eliminate soil matrix interferences and preconcentrate actinides after soil leaching or soil fusion. A rapid microwave digestion technique is used to remove the actinides from the Diphonix Resin(r). After the resin digestion, the actinides are recovered in a small volume of nitric acid which can be easily loaded onto small extraction-chromatography columns, such as TEVA Resin(r), U-TEVA Resin(r) or TRU Resin(r) (Eichrom Industries). This method enables the application of small, selective extraction-columns to recover actinides from very large soil samples with high selectivity, consistent tracer recoveries and minimal liquid waste.

  16. Actinide Waste Forms and Radiation Effects

    NASA Astrophysics Data System (ADS)

    Ewing, R. C.; Weber, W. J.

    Over the past few decades, many studies of actinides in glasses and ceramics have been conducted that have contributed substantially to the increased understanding of actinide incorporation in solids and radiation effects due to actinide decay. These studies have included fundamental research on actinides in solids and applied research and development related to the immobilization of the high level wastes (HLW) from commercial nuclear power plants and processing of nuclear weapons materials, environmental restoration in the nuclear weapons complex, and the immobilization of weapons-grade plutonium as a result of disarmament activities. Thus, the immobilization of actinides has become a pressing issue for the twenty-first century (Ewing, 1999), and plutonium immobilization, in particular, has received considerable attention in the USA (Muller et al., 2002; Muller and Weber, 2001). The investigation of actinides and

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

    NASA Technical Reports Server (NTRS)

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

    2008-01-01

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

  18. Isotopic analysis of Bothrops atrox in Amazonian forest

    NASA Astrophysics Data System (ADS)

    Martinez, M. G.; Silva, A. M.; Chalkidis, H.; de Oliveira Júnior, R. C.; Camargo, P. B.

    2012-12-01

    The poisoning of snakes is considered a public health problem, especially in populations from rural areas of tropical and subtropical countries. In Brazil, the 26,000 snakebites, 90% are of the genus Bothrops, and Bothrops atrox species predominant in the Amazon region including all the Brazilian Amazon. Research shows that using stable isotopes, we can verify the isotopic composition of tissues of animals that depend mainly on food, water ingested and inhaled gases. For this study, samples taken from Bothrops atrox (B. atrox), in forest using pitfall traps and fall ("Pitt-fall traps with drift fence"). The analyzes were performed by mass spectrometry, where the analytical error is 0.3‰ for carbon and 0.5‰ to nitrogen. The results of the forest animals are significantly different from results of animal vivarium. The average values of the tissues and venoms of snakes of the forest for carbon-13 and nitrogen-15 are: δ13C = -24.68‰ and δ15N = 14.22‰ and mean values of tissue and poisons snakes vivarium (Instituto Butantan) to carbon-13 and nitrogen-15 are δ13C = -20.47‰ and δ15N = 8.36‰, with a significantly different due to different sources of food animals. Based on all results isotopic δ13C and δ15N, we can suggest that changes as the power of the serpent, (nature and captivity), changes occur in relation to diet and environment as the means of the isotopic data are quite distinct, showing that these changes can also cause metabolic changes in the body of the animal itself and the different periods of turnover of each tissue analyzed.

  19. Fall MRS 2003: Actinides Symposium

    SciTech Connect

    Tobin, J

    2003-11-24

    {lg_bullet} The focus was on fundamental actinide science and its role. {lg_bullet} History- none except the Nuclear Waste Management Symposia {lg_bullet} Joint Sessions- none but we are open to it in the future. {lg_bullet} Tutorials- none but we are open to it in the future. {lg_bullet} 3 days: 16 Invited talks; 36 Contributed Talks; 10 Posters

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

    PubMed

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

    2013-12-01

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

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

    PubMed

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

    1997-11-01

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

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

    PubMed

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

    2011-03-01

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

  3. Actinides recovery from irradiated metallic fuel in LiCl-KCl melts

    NASA Astrophysics Data System (ADS)

    Murakami, T.; Rodrigues, A.; Ougier, M.; Iizuka, M.; Tsukada, T.; Glatz, J.-P.

    2015-11-01

    Electrorefining of irradiated metallic fuels was successfully demonstrated: Actinides (U, Pu, Np, Am and Cm) in the fuels were dissolved in LiCl-KCl melts with high dissolution ratios, while U was selectively deposited on a solid cathode and the simultaneous recovery of actinides in a liquid Cd cathode was confirmed. The behavior of actinides, the fuel matrix stabilizer Zr and fission products such as lanthanide, alkaline, alkaline earth and noble metal, at the electrorefining is discussed based on the ICP-MS analysis of the samples taken from molten salt electrolyte, anode fuel residues and cathode deposits.

  4. Assessment of degradation pathways in an aquifer with mixed chlorinated hydrocarbon contamination using stable isotope analysis.

    PubMed

    Hunkeler, Daniel; Aravena, Ramon; Berry-Spark, Karen; Cox, Evan

    2005-08-15

    The demonstration of monitored natural attenuation (MNA) of chlorinated hydrocarbons in groundwater is typically conducted through the evaluation of concentration trends and parent-daughter product relationships along prevailing groundwater flow paths. Unfortunately, at sites contaminated by mixtures of chlorinated ethenes, ethanes, and methanes, the evaluation of MNA by using solely concentration data and parent-daughter relationships can result in erroneous conclusions regarding the degradation mechanisms that are truly active at the site, since many of the daughter products can be derived from multiple parent compounds. Stable carbon isotope analysis was used, in conjunction with concentration data, to clarify and confirm the active degradation pathways at a former waste solvent disposal site where at least 14 different chlorinated hydrocarbons have been detected in the groundwater. The isotope data indicate that TCE, initially believed to be present as a disposed product and/or a PCE dechlorination intermediate, is attributable to dehydrochlorination of 1,1,2,2-PCA. The isotope data further support that vinyl chloride and ethene in the site groundwater result from dichloroelimination of 1,1,2-trichlorethane and 1,2-dichloroethane, respectively, rather than from reductive dechlorination of the chlorinated ethenes PCE, TCE, or 1,2-DCE. The isotope data confirm that the chlorinated ethanes and chlorinated methanes are undergoing significant intrinsic degradation, whereas degradation of the chlorinated ethenes may be limited. In addition to the classical trend of enriched isotope values of the parent compounds with increasing distance associated to biodegradation, shifts of isotope ratios of degradation byproduct in the opposite direction due to mixing of isotopically light byproducts of biodegradation with compounds from the source are shown to be of high diagnostic value. These data underline the value of stable isotope analysis in confirming transformation

  5. Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis

    SciTech Connect

    Finkelstein, Myra E.; Kuspa, Zeka E.; Welch, Alacia; Eng, Curtis; Clark, Michael; Burnett, Joseph; Smith, Donald R.

    2014-10-15

    Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot from all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ∼20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events. - Highlights: • We conducted a case-based analysis of illegal shootings of California condors. • Blood and feather Pb isotopes were used to reconstruct the illegal shooting events. • Embedded birdshot from the three condors had the same Pb isotope ratios. • Feather and blood Pb isotopes indicated that the condors were shot in a common event. • Ingested shot causes substantially greater lead exposure compared to embedded shot.

  6. Diet of spotted bats (Euderma maculatum) in Arizona as indicated by fecal analysis and stable isotopes

    EPA Science Inventory

    We assessed diet of spotted bats (Euderma maculatum (J.A. Allen, 1891)) by visual analysis of bat feces and stable carbon (δ13C) and nitrogen (δ15N) isotope analysis of bat feces, wing, hair, and insect prey. We collected 33 fecal samples from spotted bats and trapped 3755 insect...

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

    USGS Publications Warehouse

    Garbarino, J.R.; Taylor, H.E.

    1987-01-01

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

  8. Actinide partitioning-transmutation program final report. I. Overall assessment

    SciTech Connect

    Croff, A.G.; Blomeke, J.O.; Finney, B.C.

    1980-06-01

    This report is concerned with an overall assessment of the feasibility of and incentives for partitioning (recovering) long-lived nuclides from fuel reprocessing and fuel refabrication plant radioactive wastes and transmuting them to shorter-lived or stable nuclides by neutron irradiation. The principal class of nuclides considered is the actinides, although a brief analysis is given of the partitioning and transmutation (P-T) of /sup 99/Tc and /sup 129/I. The results obtained in this program permit us to make a comparison of the impacts of waste management with and without actinide recovery and transmutation. Three major conclusions concerning technical feasibility can be drawn from the assessment: (1) actinide P-T is feasible, subject to the acceptability of fuels containing recycle actinides; (2) technetium P-T is feasible if satisfactory partitioning processes can be developed and satisfactory fuels identified (no studies have been made in this area); and (3) iodine P-T is marginally feasible at best because of the low transmutation rates, the high volatility, and the corrosiveness of iodine and iodine compounds. It was concluded on the basis of a very conservative repository risk analysis that there are no safety or cost incentives for actinide P-T. In fact, if nonradiological risks are included, the short-term risks of P-T exceed the long-term benefits integrated over a period of 1 million years. Incentives for technetium and iodine P-T exist only if extremely conservative long-term risk analyses are used. Further RD and D in support of P-T is not warranted.

  9. Conservative axial burnup distributions for actinide-only burnup credit

    SciTech Connect

    Kang, C.; Lancaster, D.

    1997-11-01

    Unlike the fresh fuel approach, which assumes the initial isotopic compositions for criticality analyses, any burnup credit methodology must address the proper treatment of axial burnup distributions. A straightforward way of treating a given axial burnup distribution is to segment the fuel assembly into multiple meshes and to model each burnup mesh with the corresponding isotopic compositions. Although this approach represents a significant increase in modeling efforts compared to the uniform average burnup approach, it can adequately determine the reactivity effect of the axial burnup distribution. A major consideration is what axial burnup distributions are appropriate for use in light of many possible distributions depending on core operating conditions and histories. This paper summarizes criticality analyses performed to determine conservative axial burnup distributions. The conservative axial burnup distributions presented in this paper are included in the Topical Report on Actinide-Only Burnup Credit for Pressurized Water Reactor Spent Nuclear Fuel Packages, Revision 1 submitted in May 1997 by the US Department of Energy (DOE) to the US Nuclear Regulatory Commission (NRC). When approved by NRC, the conservative axial burnup distributions may be used to model PWR spent nuclear fuel for the purpose of gaining actinide only burnup credit.

  10. Potential for using isotopically altered metalloproteins in species-specific isotope dilution analysis of proteins by HPLC coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Harrington, Chris F; Vidler, Daniel S; Watts, Michael J; Hall, John F

    2005-07-01

    The production and evaluation of an isotopically enriched metalloprotein standard for use as a calibrant in species-specific isotope dilution analysis by HPLC coupled to inductively coupled plasma mass spectrometry is described. Using a model system involving the copper-containing protein rusticyanin (Rc) from the bacterium Acido-thiobacillus ferrooxidans, it was possible to demonstrate the analytical conditions that could be used for the measurement of metalloproteins by on-line IDMS analysis. Rc was chosen because it is a well-characterized protein with an established amino acid sequence and can be produced in suitable quantities using a bacterial recombinant system. Three different forms of the protein were studied by organic and inorganic mass spectrometry: the native form of the protein containing a natural isotopic profile for copper, an isotopically enriched species containing virtually all of its copper as the 65Cu isotope, and the nonmetalated apo form. Incorporation of the copper isotopes into the apo form of the protein was determined using a UV-vis spectrophotometric assay and shown to be complete for each of the copper-containing species. The experimental conditions required to maintain the conformational form of the protein with a nonexchangeable copper center were established using +ve electrospray mass spectrometry. A pH 7.0 buffer was found to afford the most appropriate conditions, and this was then used with HPLC-ICP-MS to verify the stability of the copper center by analysis of mixtures of different isotopic solutions. No exchange of the enriched copper isotope from Rc with an added naturally abundant inorganic copper cation was observed under a neutral pH environment, indicating that species-specific ID-MS analysis of metalloproteins is possible.

  11. Excitation functions for production of heavy actinides from interactions of /sup 18/O with /sup 248/Cm and /sup 249/Cf

    SciTech Connect

    Lee, D.; Moody, K.J.; Nurmia, M.J.; Seaborg, G.T.; von Gunten, H.R.; Hoffman, D.C.

    1983-06-01

    Excitation functions have been measured for the production of isotopes of Bk through Fm in bombardments of /sup 248/Cm with 97- to 122-MeV /sup 18/O ions and of isotopes of Bk through No in bombardments of /sup 249/Cf with 91- to 150-MeV /sup 18/O ions. The cross sections and widths of the mass distributions for the actinides produced in these reactions are very similar for transfer of the same numbers of nucleons. A semiquantitative comparison of the experimental results with calculations based on a simple model shows that calculations of this type are helpful in selection of projectile-target systems and optimum energies for production of specific actinide isotopes and for synthesis of as yet unknown heavy isotopes and elements. Comparisons of experimental results with calculations show that, in general, about half of the kinetic energy of the projectile is transferred to the actinide product.

  12. Estimating pathway-specific contributions to biodegradation in aquifers based on dual isotope analysis: theoretical analysis and reactive transport simulations.

    PubMed

    Centler, Florian; Heße, Falk; Thullner, Martin

    2013-09-01

    At field sites with varying redox conditions, different redox-specific microbial degradation pathways contribute to total contaminant degradation. The identification of pathway-specific contributions to total contaminant removal is of high practical relevance, yet difficult to achieve with current methods. Current stable-isotope-fractionation-based techniques focus on the identification of dominant biodegradation pathways under constant environmental conditions. We present an approach based on dual stable isotope data to estimate the individual contributions of two redox-specific pathways. We apply this approach to carbon and hydrogen isotope data obtained from reactive transport simulations of an organic contaminant plume in a two-dimensional aquifer cross section to test the applicability of the method. To take aspects typically encountered at field sites into account, additional simulations addressed the effects of transverse mixing, diffusion-induced stable-isotope fractionation, heterogeneities in the flow field, and mixing in sampling wells on isotope-based estimates for aerobic and anaerobic pathway contributions to total contaminant biodegradation. Results confirm the general applicability of the presented estimation method which is most accurate along the plume core and less accurate towards the fringe where flow paths receive contaminant mass and associated isotope signatures from the core by transverse dispersion. The presented method complements the stable-isotope-fractionation-based analysis toolbox. At field sites with varying redox conditions, it provides a means to identify the relative importance of individual, redox-specific degradation pathways.

  13. Microbial degradation of alpha-cypermethrin in soil by compound-specific stable isotope analysis.

    PubMed

    Xu, Zemin; Shen, Xiaoli; Zhang, Xi-Chang; Liu, Weiping; Yang, Fangxing

    2015-09-15

    To assess microbial degradation of alpha-cypermethrin in soil, attenuation of alpha-cypermethrin was investigated by compound-specific stable isotope analysis. The variations of the residual concentrations and stable carbon isotope ratios of alpha-cypermethrin were detected in unsterilized and sterilized soils spiked with alpha-cypermethrin. After an 80 days' incubation, the concentrations of alpha-cypermethrin decreased to 0.47 and 3.41 mg/kg in the unsterilized soils spiked with 2 and 10 mg/kg, while those decreased to 1.43 and 6.61 mg/kg in the sterilized soils. Meanwhile, the carbon isotope ratios shifted to -29.14 ± 0.22‰ and -29.86 ± 0.33‰ in the unsterilized soils spiked with 2 and 10 mg/kg, respectively. The results revealed that microbial degradation contributed to the attenuation of alpha-cypermethrin and induced the carbon isotope fractionation. In order to quantitatively assess microbial degradation, a relationship between carbon isotope ratios and residual concentrations of alpha-cypermethrin was established according to Rayleigh equation. An enrichment factor, ϵ = -1.87‰ was obtained, which can be employed to assess microbial degradation of alpha-cypermethrin. The significant carbon isotope fractionation during microbial degradation suggests that CSIA is a proper approach to qualitatively detect and quantitatively assess the biodegradation during attenuation process of alpha-cypermethrin in the field.

  14. In-situ monitoring of actinides and rare earth elements by electrothermal hollow cathode discharge spectrometry. Technical progress report

    SciTech Connect

    Lee, S.C.; Edelson, M.C.

    1992-12-01

    This report describes an Electrothermal Hollow Cathode Discharge Spectrometry (ET-HCDS) source being constructed for the analytical determination of actinides and rare earth elements. This work was initiated with the support of the Office of Safeguards and Security; the Buried Waste Integrated Demonstration began funding work in this area in mid-FY1992 and the work is continuing into FY1993 with funds from both sources. Special features of this instrument should permit it to be used for the determination of individual isotopic species, which is important for safeguard`s materials control and accountancy. ET-HCDS can be achieved using compact instrumentation suitable for use in field laboratories. The technique is capable of determining a suite of environmentally-important species, such as the actinides and the heavy metals, in a variety of physical forms (e.g., in solution, as found on air particulates, or in soils). ET-HCDS should be capable of very sensitive analyses and should require very small samples (e.g., microgram). Since ET-HCDS is possible in an air atmosphere (at reduced pressures), it may be useful for the real-time determination of hazardous materials, both radioactive and non radioactive, contained in dusts released during waste retrieval operations; ET-HCDS should also be useful for the rapid and sensitive analysis of metals in soils.

  15. Actinide Measurements by Accelerator Mass Spectrometry at Lawrence Livermore National Laboratory

    SciTech Connect

    Brown, T A; Marchetti, A A; Martinelli, R E; Cox, C C; Knezovich, J P; Hamilton, T F

    2003-09-25

    We report on the development of an accelerator mass spectrometry (AMS) system for the measurement of actinides at Lawrence Livermore National Laboratory. This AMS system is centered on a recently completed heavy isotope beam line that was designed particularly for high sensitivity, robust, high-throughput measurements of actinide concentrations and isotopic ratios. A fast isotope switching capability has been incorporated in the system, allowing flexibility in isotope selection and for the quasi-continuous normalization to a reference isotope spike. Initially, our utilization of the heavy isotope system has concentrated on the measurement of Pu isotopes. Under current operating conditions, background levels equivalent to {approx}1 x 10{sup 5} atoms are observed during routine {sup 239}Pu and {sup 240}Pu measurements. Measurements of samples containing {approx}10{sup 13} {sup 238}U atoms demonstrate that the system provides a {sup 238}U rejection factor during {sup 239}Pu measurements of {approx}10{sup 7}. Measurements of known materials, combined with results from an externally organized inter-comparison program, indicate that our {sup 239}Pu measurements are accurate and precise down to the {micro}Bq level ({approx}10{sup 6} atoms). Recently, we have investigated the performance of our heavy isotope AMS system in measurements of {sup 237}Np and {sup 236}U. Results of these investigations are discussed. The sensitivity shown by our Pu measurements, combined with the high throughput and interference rejection capabilities of our AMS system, demonstrate that AMS can provide a rapid and cost-effective measurement technique for actinides in a wide variety of studies.

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

    PubMed

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

    2014-02-15

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

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

    PubMed

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

    2010-12-15

    Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles. PMID:21111176

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

    PubMed

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

    2010-12-15

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

  19. Sr Isotope Analysis of Lacustrine Fossils Reveals Paleohydrological Reorganisation in the Turkana Basin Through the Holocene.

    NASA Astrophysics Data System (ADS)

    Vonhof, H.; Lubbe, J. V. D.; Joordens, J. J.; Feibel, C. S.; Junginger, A.; Garcin, Y.; Krause-Nehring, J.; Beck, C.; Johnson, T. C.

    2015-12-01

    Lake Turkana in northern Kenya is one of the largest lakes in the East African Rift System (EARS) that experienced significant climate-driven lake level variation over the Holocene. Arguably the most important feature of Holocene climate change in the EARS is the termination of the African Humid Period (AHP), that caused a ~70 meter lake level drop in Lake Turkana. The precise hydrological response to the termination of the AHP is potentially complex, because Lake Turkana lies at the cross roads of two large atmospheric convection systems; the Intertropical Convergence Zone (ITCZ) and the Congo Air Boundary (CAB). Shifting of these atmospheric systems around the end of the AHP dramatically rearranged spatial rainfall patterns in the Turkana Basin catchment, causing changes in relative runoff contributions from the different sub-catchments in the Turkana Basin. We here present a Holocene Turkana lake water Sr-isotope reconstruction, based on the analysis of well-dated lacustrine ostracods and shells. This reconstruction reveals consistently high Sr isotope values for the early Holocene, followed by a remarkable drop of Sr isotope ratios around the AHP termination. We interpret this pattern to represent a westward shift in the location of the CAB, leading to the reduction and eventual shutdown of runoff contribution from the Chew Bahir Basin to the Turkana Basin at the end of the AHP. The record demonstrates the exceptional suitability of Sr isotope data for this type of paleohydrological reconstructions. This is mainly due to the chemically conservative Sr-isotope mass balance in EARS lake systems, which is insensitive to environmental change at seasonal timescales that so often overprints the longer term climate signal in stable (oxygen and carbon) isotope records of these lakes. Furthermore, when Sr-isotope signatures of the contributing sub-catchments are known, the observed Sr isotope trends can be interpreted in terms of spatial shifts in climate driven runoff

  20. Micro-scale (1.5 microm) sulphur isotope analysis of contemporary and early Archean pyrite.

    PubMed

    Nishizawa, Manabu; Maruyama, Shigenori; Urabe, Tetsuro; Takahata, Naoto; Sano, Yuji

    2010-05-30

    We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5 microm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the delta(34)S value was 1.5 per thousand at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6 per thousand at the level of 1 sigma of standard deviation (named 1SD, n = 25). For each separate sample, the average delta(34)S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3 per thousand. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 microm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a (34)S-depleted core and (34)S-enriched rim, suggesting isotopic evolution of the source H(2)S from -15 to -5 per thousand. Production of H(2)S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the (34)S-depleted initial H(2)S and the progressive increase in the delta(34)S(H2S) value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth.

  1. Micro-scale (1.5 microm) sulphur isotope analysis of contemporary and early Archean pyrite.

    PubMed

    Nishizawa, Manabu; Maruyama, Shigenori; Urabe, Tetsuro; Takahata, Naoto; Sano, Yuji

    2010-05-30

    We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5 microm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the delta(34)S value was 1.5 per thousand at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6 per thousand at the level of 1 sigma of standard deviation (named 1SD, n = 25). For each separate sample, the average delta(34)S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3 per thousand. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 microm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a (34)S-depleted core and (34)S-enriched rim, suggesting isotopic evolution of the source H(2)S from -15 to -5 per thousand. Production of H(2)S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the (34)S-depleted initial H(2)S and the progressive increase in the delta(34)S(H2S) value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth. PMID:20411578

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  3. Stable isotope analysis of the karst hydrological systems in the Bay of Kvarner (Croatia).

    PubMed

    Mance, D; Hunjak, T; Lenac, D; Rubinić, J; Roller-Lutz, Z

    2014-08-01

    Here we present the results of the first systematic analysis of the stable isotope composition of the karst hydrological systems in the Bay of Kvarner. Gaussian mixture modelling, time series analysis and autoregressive integrated moving average (ARIMA) modelling were applied using the stable isotope compositions of the karst groundwater. This study revealed that the recharge is dominated by winter precipitation, the dual-porosity system is dominated by baseflow, the hinterlands of the individual springs have different degrees of karstification and the springs within the Rječina River catchment have higher recharge elevations than the springs in the Bakar Bay catchment.

  4. Compound specific 13C- and 18O-isotope analysis of organic aerosols

    NASA Astrophysics Data System (ADS)

    Blees, Jan; Saurer, Matthias; Siegwolf, Rolf T. W.; Dommen, Josef; Baltensperger, Urs

    2014-05-01

    The wide ranging environmental and health effects of aerosols are increasingly coming to light. Various studies have further highlighted the complex nature of organic aerosols, particularly oxidised organics with multiple functional groups. Source apportionment studies on aerosols are crucial to successful implementation of mitigation strategies, but this is complicated by their complex nature. Ideally, individual components of aerosols can be tracked from their source to their atmospheric sink. However, chemical alteration and the formation of secondary aerosols in the atmosphere often preclude this direct tracking on a compound specific basis. Compound specific isotope analysis could overcome these problems, as certain processes and sources impose characteristic isotope ratios on products, which may be retained even after chemical alteration in the atmosphere. Progress has been made over the past decades in the separation and identification of individual compounds that contribute to aerosol formation. Compound separation by gas chromatography (GC), coupled to mass spectrometry (MS), has enabled identification of organic compounds of various sources. On the other hand, only few studies have addressed the isotopic composition of these compounds. For successful isotopic analysis of specific compounds, using GC coupled to isotope ratio MS (GC-irMS), several challenges must be faced that go beyond the requirements for GC-MS-based compound identification. Sample extraction and handling techniques must avoid isotope fractionation. This is especially important in the light of sample extraction by e.g. thermal desorption, which may impose a temperature-induced fractionation on complex organics. Furthermore, derivatisation techniques, necessary for adequate GC compound separation, must not lead to exchange reactions of the element of interest, which would alter the measured isotope ratio. So far most studies have dealt with carbon, and other elements have been neglected

  5. Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

    USGS Publications Warehouse

    Fantle, M.S.; Bullen, T.D.

    2009-01-01

    The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a

  6. [Meta-analysis of stable carbon and nitrogen isotopic enrichment factors for aquatic animals].

    PubMed

    Guo, Liang; Sun, Cui-ping; Ren, Wei-zheng; Zhang, Jian; Tang, Jian-iun; Hu, Liana-liang; Chen, Xin

    2016-02-01

    Isotopic enrichment factor (Δ, the difference between the δ value of food and a consumer tissue) is an important parameter in using stable isotope analysis (SIA) to reconstruct diets, characterize trophic relationships, elucidate patterns of resource allocation, and construct food webs. Isotopic enrichment factor has been considered as a constancy value across a broad range of animals. However, recent studies showed that the isotopic enrichment factor differed among various types of animals although the magnitude of variation was not clear. Here, we conducted a meta-analysis to synthesize and compare Δ13C and Δ15N among four types of aquatic animals (teleosts, crustaceans, reptiles and molluscs). We searched for papers published before 2014 on Web of Science and CNKI using the key words "stable isotope or isotopic fractionation or fractionation factor or isotopic enrichment or trophic enrichment". Forty-two publications that contain 140 studies on Δ13C and 159 studies on Δ15N were obtained. We conducted three parallel meta-analyses by using three types of weights (the reciprocal of variance as weights, the sample size as weights, and equal weights). The results showed that no significant difference in Δ13C among different animal types (teleosts 1.0 per thousand, crustaceans 1.3 per thousand, reptiles 0.5 per thousand, and molluscs 1.5 per thousand), while Δ15N values were significantly different (teleosts 2.4 per thousand, crustaceans 3.6 per thousand, reptiles 1.0 per thousand and molluscs 2.5 per thousand). Our results suggested that the overall mean of Δ13C could be used as a general enrichment factor, but Δ15N should be chosen according to the type of aquatic animals in using SIA to analyze trophic relationships, patterns of resource allocation and food webs. PMID:27396136

  7. [Meta-analysis of stable carbon and nitrogen isotopic enrichment factors for aquatic animals].

    PubMed

    Guo, Liang; Sun, Cui-ping; Ren, Wei-zheng; Zhang, Jian; Tang, Jian-iun; Hu, Liana-liang; Chen, Xin

    2016-02-01

    Isotopic enrichment factor (Δ, the difference between the δ value of food and a consumer tissue) is an important parameter in using stable isotope analysis (SIA) to reconstruct diets, characterize trophic relationships, elucidate patterns of resource allocation, and construct food webs. Isotopic enrichment factor has been considered as a constancy value across a broad range of animals. However, recent studies showed that the isotopic enrichment factor differed among various types of animals although the magnitude of variation was not clear. Here, we conducted a meta-analysis to synthesize and compare Δ13C and Δ15N among four types of aquatic animals (teleosts, crustaceans, reptiles and molluscs). We searched for papers published before 2014 on Web of Science and CNKI using the key words "stable isotope or isotopic fractionation or fractionation factor or isotopic enrichment or trophic enrichment". Forty-two publications that contain 140 studies on Δ13C and 159 studies on Δ15N were obtained. We conducted three parallel meta-analyses by using three types of weights (the reciprocal of variance as weights, the sample size as weights, and equal weights). The results showed that no significant difference in Δ13C among different animal types (teleosts 1.0 per thousand, crustaceans 1.3 per thousand, reptiles 0.5 per thousand, and molluscs 1.5 per thousand), while Δ15N values were significantly different (teleosts 2.4 per thousand, crustaceans 3.6 per thousand, reptiles 1.0 per thousand and molluscs 2.5 per thousand). Our results suggested that the overall mean of Δ13C could be used as a general enrichment factor, but Δ15N should be chosen according to the type of aquatic animals in using SIA to analyze trophic relationships, patterns of resource allocation and food webs.

  8. Isotopic composition analysis and age dating of uranium samples by high resolution gamma ray spectrometry

    NASA Astrophysics Data System (ADS)

    Apostol, A. I.; Pantelica, A.; Sima, O.; Fugaru, V.

    2016-09-01

    Non-destructive methods were applied to determine the isotopic composition and the time elapsed since last chemical purification of nine uranium samples. The applied methods are based on measuring gamma and X radiations of uranium samples by high resolution low energy gamma spectrometric system with planar high purity germanium detector and low background gamma spectrometric system with coaxial high purity germanium detector. The "Multigroup γ-ray Analysis Method for Uranium" (MGAU) code was used for the precise determination of samples' isotopic composition. The age of the samples was determined from the isotopic ratio 214Bi/234U. This ratio was calculated from the analyzed spectra of each uranium sample, using relative detection efficiency. Special attention is paid to the coincidence summing corrections that have to be taken into account when performing this type of analysis. In addition, an alternative approach for the age determination using full energy peak efficiencies obtained by Monte Carlo simulations with the GESPECOR code is described.

  9. First stable isotope analysis of Asiatic wild ass tail hair from the Mongolian Gobi

    PubMed Central

    Horacek, Micha; Sturm, Martina Burnik; Kaczensky, Petra

    2015-01-01

    Stable isotope analysis has become a powerful tool to study feeding ecology, water use or movement pattern in contemporary, historic and ancient species. Certain hair and teeth grow continuously, and when sampled longitudinally can provide temporally explicit information on dietary regime and movement pattern. In an initial trial, we analysed a tail sample of an Asiatic wild ass (Equus hemionus) from the Mongolian Gobi. We found seasonal variations in H, C and N isotope patterns, likely being the result of temporal variations in available feeds, water supply and possibly physiological status. Thus stable isotope analysis shows promise to study the comparative ecology of the three autochthonous equid species in the Mongolian Gobi. PMID:26339116

  10. Prompt fission neutron spectra of actinides

    DOE PAGES

    Capote, R.; Chen, Y. -J.; Hambsch, F. -J.; Kornilov, N. V.; Lestone, J. P.; Litaize, O.; Morillon, B.; Neudecker, D.; Oberstedt, S.; Ohsawa, T.; et al

    2016-01-06

    Here, the energy spectrum of prompt neutrons emitted in fission (PFNS) plays a very important role in nuclear science and technology. A Coordinated Research Project (CRP) "Evaluation of Prompt Fission Neutron Spectra of Actinides" was established by the IAEA Nuclear Data Section in 2009, with the major goal to produce new PFNS evaluations with uncertainties for actinide nuclei.

  11. Monitoring of the aerobe biodegradation of chlorinated organic solvents by stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Horváth, Anikó; Futó, István; Palcsu, László

    2014-05-01

    Our chemical-biological basic research aims to eliminate chlorinated environmental contaminants from aquifers around industrial areas in the frame of research program supported by the European Social Fund (TÁMOP-4.2.2.A-11/1/KONV-2012-0043). The most careful and simplest way includes the in situ biodegradation with the help of cultured and compound specific strains. Numerous members of Pseudomonas bacteria are famous about function of bioremediation. They can metabolism the environmental hazardous chemicals like gas oils, dyes, and organic solvents. Our research based on the Pseudomonas putida F1 strain, because its ability to degrade halogenated hydrocarbons such as trichloroethylene. Several methods were investigated to estimate the rate of biodegradation, such as the measurement of the concentration of the pollutant along the contamination pathway, the microcosm's studies or the compound specific stable isotope analysis. In this area in the Transcarpathian basin we are pioneers in the stable isotope monitoring of biodegradation. The main goal is to find stable isotope fractionation factors by stable isotope analysis, which can help us to estimate the rate and effectiveness of the biodegradation. The subsequent research period includes the investigation of the method, testing its feasibility and adaptation in the environment. Last but not least, the research gives an opportunity to identify the producer of the contaminant based on the stable isotope composition of the contaminant.

  12. Tracing combustion-derived atmospheric pollutants using compound-specific isotope analysis

    NASA Astrophysics Data System (ADS)

    Ballentine, Donna Christine

    1997-04-01

    The use of compound specific carbon isotopic analysis (CSIA) has been investigated as a means to trace the origin and fate of organic pollutants in the atmosphere. Polycyclic aromatic hydrocarbons (PAH) and fatty acids have been suggested as two chemical classes which may serve as suitable molecular markers for anthropogenic combustion processes, such as fossil fuel combustion and biomass burning, that introduce significant quantities of organic pollutants into the atmospheric environment. First, analytical procedures for the extraction and isolation of these compounds from particulate aerosols, as well as a description of the isotopic measurement techniques, have been presented. Second, the precision and accuracy of these methods and measurements have been demonstrated. Third, the isotopic variability of PAH and fatty acids produced from different combustion processes has been investigated. In addition, in order to demonstrate the applicability of this technique as a means to monitor the fate of atmospheric pollutants, isotopic measurements of PAH, fatty acids, and alkanes isolated from a series of ambient aerosol samples have been made in a preliminary attempt to determine if compound specific isotope analysis of molecular markers in aerosols can be used in conjunction with other chemical and atmospheric data in order to reflect the transport of pollution episodes.

  13. Reactor physics input to the safety analysis report for the High Flux Isotope Reactor

    SciTech Connect

    Primm, R.T. III.

    1992-03-01

    HFIR specific, few group neutron and coupled neutron-gamma libraries have been prepared. These are based on data from ENDF/B-V and beginning-of-life (BOL) conditions. The neutron library includes actinide data for curium target rods. Six critical experiments, collectively designated HFIR critical experiment 4, were analyzed. Calculated k-effective was 2% high at BOL-typical conditions but was 1.0 at end-of-life-typical conditions. The local power density distributions were calculated for each of the critical experiments. The axially averaged values at a given radius were frequently within experimental error. However at individual points, the calculated local power densities were significantly different from the experimentally derived values (several times greater than experimental uncertainty). A reassessment of the foil activation data with transport theory techniques seems desirable. Using the results of the critical experiments study, a model of current HFIR configuration was prepared. As with the critical experiments, BOL k-effective was high (3%). However, end-of-life k-effective was high (2%). The end-of-life concentrations of fission products were compared to those generated using the ORIGEN code. Agreement was generally good through differences in the inventories of some important nuclides, Xe and I, need to be understood. End-of-cycle curium target isotopics based on measured, discharged target rods were compared to calculated values and agreement was good. Axial flux plots at various irradiation positions were generated. Time-dependent power distributions based on two-dimensional calculations were provided.

  14. Isotopic analysis of uranium in natural waters by alpha spectrometry

    USGS Publications Warehouse

    Edwards, K.W.

    1968-01-01

    A method is described for the determination of U234/U238 activity ratios for uranium present in natural waters. The uranium is coprecipitated from solution with aluminum phosphate, extracted into ethyl acetate, further purified by ion exchange, and finally electroplated on a titanium disc for counting. The individual isotopes are determined by measurement of the alpha-particle energy spectrum using a high resolution low-background alpha spectrometer. Overall chemical recovery of about 90 percent and a counting efficiency of 25 percent allow analyses of water samples containing as little as 0.10 ?g/l of uranium. The accuracy of the method is limited, on most samples, primarily by counting statistics.

  15. Separation of actinides from lanthanides

    DOEpatents

    Smith, Barbara F.; Jarvinen, Gordon D.; Ryan, Robert R.

    1989-01-01

    An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

  16. Actinide co-conversion by internal gelation

    SciTech Connect

    Robisson, Anne-Charlotte; Dauby, Jacques; Dumont-Shintu, Corinne; Machon, Estelle; Grandjean, Stephane

    2007-07-01

    Suitable microstructures and homogenous microspheres of actinide compounds are of interest for future nuclear fuel or transmutation target concepts to prevent the generation and dispersal of actinide powder. Sol-gel routes are being investigated as one of the possible solutions for producing these compounds. Preliminary work is described involving internal gelation to synthesize mixed compounds including minor actinides, particularly mixed actinide or mixed actinide-inert element compounds. A parameter study is discussed to highlight the importance of the initial broth composition for obtaining gel microspheres without major defects (cracks, craters, etc.). In particular, conditions are defined to produce gel beads from Zr(IV)/Y(III)/Ce(III) or Zr(IV)/An(III) systems. After gelation, the heat treatment of these microspheres is described for the purpose of better understanding the formation of cracks after calcination and verifying the effective synthesis of an oxide solid-solution. (authors)

  17. Actinide ion sensor for pyroprocess monitoring

    DOEpatents

    Jue, Jan-fong; Li, Shelly X.

    2014-06-03

    An apparatus for real-time, in-situ monitoring of actinide ion concentrations which comprises a working electrode, a reference electrode, a container, a working electrolyte, a separator, a reference electrolyte, and a voltmeter. The container holds the working electrolyte. The voltmeter is electrically connected to the working electrode and the reference electrode and measures the voltage between those electrodes. The working electrode contacts the working electrolyte. The working electrolyte comprises an actinide ion of interest. The reference electrode contacts the reference electrolyte. The reference electrolyte is separated from the working electrolyte by the separator. The separator contacts both the working electrolyte and the reference electrolyte. The separator is ionically conductive to the actinide ion of interest. The reference electrolyte comprises a known concentration of the actinide ion of interest. The separator comprises a beta double prime alumina exchanged with the actinide ion of interest.

  18. Exploring actinide materials through synchrotron radiation techniques.

    PubMed

    Shi, Wei-Qun; Yuan, Li-Yong; Wang, Cong-Zhi; Wang, Lin; Mei, Lei; Xiao, Cheng-Liang; Zhang, Li; Li, Zi-Jie; Zhao, Yu-Liang; Chai, Zhi-Fang

    2014-12-10

    Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of actinide-based materials. This trend is partially driven by the basic needs for multi-scale actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X-ray absorption spectroscopy, X-ray diffraction and scattering spectroscopy, which are powerful tools to characterize actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with actinides are illustrated as well.

  19. When other separation techniques fail: compound-specific carbon isotope ratio analysis of sulfonamide containing pharmaceuticals by high-temperature-liquid chromatography-isotope ratio mass spectrometry.

    PubMed

    Kujawinski, Dorothea M; Zhang, Lijun; Schmidt, Torsten C; Jochmann, Maik A

    2012-09-18

    Compound-specific isotope analysis (CISA) of nonvolatile analytes has been enabled by the introduction of the first commercial interface to hyphenate liquid chromatography with an isotope ratio mass spectrometer (LC-IRMS) in 2004, yet carbon isotope analysis of unpolar and moderately polar compounds is still a challenging task since only water as the eluent and no organic modifiers can be used to drive the separation in LC. The only way to increase the elution strength of aqueous eluents in reversed phase LC is the application of high temperatures to the mobile and stationary phases (HT-LC-IRMS). In this context we present the first method to determine carbon isotope ratios of pharmaceuticals that cannot be separated by already existing separation techniques for LC-IRMS, such as reversed phase chromatography at normal temperatures, ion-chromatography, and mixed mode chomatography. The pharmaceutical group of sulfonamides, which is generally mixed with trimethoprim in pharmaceutical products, has been chosen as probe compounds. Substance amounts as low as 0.3 μg are sufficient to perform a precise analysis. The successful applicability and reproducibility of this method is shown by the analysis of real pharmaceutical samples. The method provides the first tool to study the pharmaceutical authenticity as well as degradation and mobility of such substances in the environment by using the stable isotopic signature of these compounds.

  20. Compound-Specific Isotope Analysis of Nitroaromatic Contaminant Transformations by Nitroarene Dioxygenases

    NASA Astrophysics Data System (ADS)

    Pati, Sarah G.; Kohler, Hans-Peter E.; Hofstetter, Thomas B.

    2014-05-01

    Dioxygenation is an important biochemical reaction that often initiates the mineralization of recalcitrant organic contaminants such as nitroaromatic explosives, chlorinated benzenes, and polycyclic aromatic hydrocarbons. However, to assess the extent of dioxygenation in contaminated environments is difficult because of competing transformation processes and further reactions of the dioxygenation products. Compound-specific isotope analysis (CSIA) offers a new approach to reliably quantify biodegradation initiated by dioxygenation based on changes in stable isotope ratios of the pollutant. For CSIA it is essential to know the kinetic isotope effects (KIEs) pertinent to the dioxygenation mechanism of organic contaminants. Unfortunately, the range of KIEs of such reactions is poorly constrained although many dioxygenase enzymes with a broad substrate specificity have been reported. Dioxygenase enzymes usually exhibit complex reaction kinetics involving multiple substrates and substrate-specific binding modes which makes the determination of KIEs challenging. The goal of this study was to explore the magnitude and variability of 13C-, 2H-, and 15N-KIEs for the dioxygenation of one contaminant class, that is nitroaromatic contaminants (NACs). To this end, we investigated the C, H, and N isotope fractionation during the dioxygenation of nitrobenzene (NB), 2-nitrotoluene (2-NT), and 3-nitrotoluene (3-NT) by pure cultures, E. coli clones, cell extracts, and purified enzymes. From isotope fractionations measured in the substrates and reaction products, we determined dioxygenation KIEs for different combinations of the three substrates with nitrobenzene dioxygenase (NBDO) and 2-nitrotoluene dioxygenase (2NTDO). The 13C-, 2H-, and 15N-KIEs for the dioxygenation of NB by NBDO were consistent for all experimental systems considered (i.e., Comamonas sp. Strain JS765, E. coli clones, cell extracts of E. coli clones, and purified NBDO). This observation suggests that the isotope

  1. Enhanced understanding of ectoparasite: host trophic linkages on coral reefs through stable isotope analysis

    USGS Publications Warehouse

    Demopoulos, Amanda W. J.; Sikkel, Paul C.

    2015-01-01

    Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ13C and δ15N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15N and depleted in13C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ13C values consistent with their food source and enriched in 15N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically.

  2. Enhanced understanding of ectoparasite–host trophic linkages on coral reefs through stable isotope analysis

    PubMed Central

    Demopoulos, Amanda W.J.; Sikkel, Paul C.

    2015-01-01

    Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ13C and δ15N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15N and depleted in 13C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ13C values consistent with their food source and enriched in 15N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically. PMID:25830112

  3. Enhanced understanding of ectoparasite-host trophic linkages on coral reefs through stable isotope analysis.

    PubMed

    Demopoulos, Amanda W J; Sikkel, Paul C

    2015-04-01

    Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ(13)C and δ(15)N values similar to their host, comparable with results from the small number of other host-parasite studies that have employed stable isotopes. Adult gnathiids were enriched in (15)N and depleted in (13)C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ(13)C values consistent with their food source and enriched in (15)N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically. PMID:25830112

  4. Effects of nitrate and water on the oxygen isotopic analysis of barium sulfate precipitated from solution

    USGS Publications Warehouse

    Hannon, Janet E.; Bohlke, Johnkarl F.; Mroczkowski, Stanley J.

    2008-01-01

    BaSO4 precipitated from mixed salt solutions by common techniques for SO isotopic analysis may contain quantities of H2O and NOthat introduce errors in O isotope measurements. Experiments with synthetic solutions indicate that δ18O values of CO produced by decomposition of precipitated BaSO4 in a carbon reactor may be either too low or too high, depending on the relative concentrations of SO and NO and the δ18O values of the H2O, NO, and SO. Typical δ18O errors are of the order of 0.5 to 1‰ in many sample types, and can be larger in samples containing atmospheric NO, which can cause similar errors in δ17O and Δ17O. These errors can be reduced by (1) ion chromatographic separation of SO from NO, (2) increasing the salinity of the solutions before precipitating BaSO4 to minimize incorporation of H2O, (3) heating BaSO4 under vacuum to remove H2O, (4) preparing isotopic reference materials as aqueous samples to mimic the conditions of the samples, and (5) adjusting measured δ18O values based on amounts and isotopic compositions of coexisting H2O and NO. These procedures are demonstrated for SO isotopic reference materials, synthetic solutions with isotopically known reagents, atmospheric deposition from Shenandoah National Park, Virginia, USA, and sulfate salt deposits from the Atacama Desert, Chile, and Mojave Desert, California, USA. These results have implications for the calibration and use of O isotope data in studies of SOsources and reaction mechanisms.

  5. Isotopic Dilution Analysis and Secular Equilibrium Study: Two Complementary Radiochemistry Experiments.

    ERIC Educational Resources Information Center

    Williams, Kathryn R.; Lipford, Levin C.

    1985-01-01

    Describes a complementary pair of radiochemistry experiments for instruction of isotopic dilution analysis and secular equilibrium. Both experiments use the readily available cesium-137 nuclide and the simple precipitation technique for cesium with the tetraphenylborate anion. Procedures used and typical results obtained are provided and…

  6. Analysis of tarnished plant bug movement using carbon and nitrogen isotopes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Tarnished plant bug, Lygus lineolaris (Palisot de Beauvois), is the primary pest of cotton across the Midsouth of the United States. Movement into cotton fields occurs during the summer from other host plants, both cultivated and wild. Stable isotope analysis (SIA) has been used in other studies to ...

  7. Mucus: A new tissue fraction for rapid determination of fish diet switching using stable isotope analysis

    EPA Science Inventory

    Stable isotope analysis of diet switching by fishes often is hampered by slow turnover rates of the tissues analyzed (usually muscle or fins). We examined epidermal mucus as a potentially faster turnover “tissue” that might provide a more rapid assessment of diet switching. In a ...

  8. Mucus: a new tissue fraction for rapid determination of fish diet switching using stable isotope analysis.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Stable isotope analysis of diet switching by fishes is often hampered by slow turnover rates of the tissues analyzed (usually muscle or fins). We examined epidermal mucus as a potentially faster turnover “tissue” that might provide a more rapid assessment of diet switching. In a controlled hatchery...

  9. Grazing food web view from compound-specific stable isotope analysis of amino acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Knowledge of the trophic position (TP) of organisms in food webs allows ecologists to track energy flow and trophic linkages among organisms in complex networks of ecosystems. Compound-specific stable isotope analysis (CSIA) of amino acids has been employed as a relatively new method with the high p...

  10. Linking ramped pyrolysis isotope data to oil content through PAH analysis

    NASA Astrophysics Data System (ADS)

    Pendergraft, Matthew A.; Dincer, Zeynep; Sericano, José L.; Wade, Terry L.; Kolasinski, Joanna; Rosenheim, Brad E.

    2013-12-01

    Ramped pyrolysis isotope (13C and 14C) analysis coupled with polycyclic aromatic hydrocarbon (PAH) analysis demonstrates the utility of ramped pyrolysis in screening for oil content in sediments. Here, sediments from Barataria Bay, Louisiana, USA that were contaminated by oil from the 2010 BP Deepwater Horizon spill display relationships between oil contamination, pyrolysis profiles, and isotopic composition. Sediment samples with low PAH concentrations are thermochemically stable until higher temperatures, while samples containing high concentrations of PAHs pyrolyze at low temperatures. High PAH samples are also depleted in radiocarbon (14C), especially in the fractions that pyrolyze at low temperatures. This lack of radiocarbon in low temperature pyrolyzates is indicative of thermochemically unstable, 14C-free oil content. This study presents a proof of concept that oil contamination can be identified by changes in thermochemical stability in organic material and corroborated by isotope analysis of individual pyrolyzates, thereby providing a basis for application of ramped pyrolysis isotope analysis to samples deposited in different environments for different lengths of time.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  12. Extending FEAST-METAL for analysis of low content minor actinide bearing and zirconium rich metallic fuels for sodium fast reactors

    NASA Astrophysics Data System (ADS)

    Karahan, Aydın

    2011-07-01

    Computational models in FEAST-METAL fuel behaviour code have been upgraded to simulate minor actinide bearing zirconium rich metallic fuels for use in sodium fast reactors. Increasing the zirconium content to 20-40 wt.% causes significant changes in fuel slug microstructure affecting thermal, mechanical, chemical, and fission gas behaviour. Inclusion of zirconium rich phase reduces the fission gas swelling rate significantly in early irradiation. Above the threshold fission gas swelling, formation of micro-cracks, and open pores increase material compliancy enhance diffusivity, leading to rapid fuel gas swelling, interconnected porosity development and release of the fission gases and helium. Production and release of helium was modelled empirically as a function of americium content and fission gas production, consistent with previous Idaho National Laboratory studies. Predicted fuel constituent redistribution is much smaller compared to typical U-Pu-10Zr fuel operated at EBR-II. Material properties such as fuel thermal conductivity, modulus of elasticity, and thermal expansion coefficient have been approximated using the available database. Creep rate and fission gas diffusivity of high zirconium fuel is lowered by an order of magnitude with respect to the reference low zirconium fuel based on limited database and in order to match experimental observations. The new code is benchmarked against the AFC-1F fuel assembly post irradiation examination results. Satisfactory match was obtained for fission gas release and swelling behaviour. Finally, the study considers a comparison of fuel behaviour between high zirconium content minor actinide bearing fuel and typical U-15Pu-6Zr fuel pins with 75% smear density. The new fuel has much higher fissile content, allowing for operating at lower neutron flux level compared to fuel with lower fissile density. This feature allows the designer to reach a much higher burnup before reaching the cladding dose limit. On the other

  13. INCA: a computational platform for isotopically non-stationary metabolic flux analysis

    PubMed Central

    2014-01-01

    Summary: 13C flux analysis studies have become an essential component of metabolic engineering research. The scope of these studies has gradually expanded to include both isotopically steady-state and transient labeling experiments, the latter of which are uniquely applicable to photosynthetic organisms and slow-to-label mammalian cell cultures. Isotopomer network compartmental analysis (INCA) is the first publicly available software package that can perform both steady-state metabolic flux analysis and isotopically non-stationary metabolic flux analysis. The software provides a framework for comprehensive analysis of metabolic networks using mass balances and elementary metabolite unit balances. The generation of balance equations and their computational solution is completely automated and can be performed on networks of arbitrary complexity. Availability and implementation: MATLAB p-code files are freely available for non-commercial use and can be downloaded at http://mfa.vueinnovations.com. Commercial licenses are also available. Contact: j.d.young@vanderbilt.edu PMID:24413674

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    NASA Astrophysics Data System (ADS)

    Adamson, Kathryn; Candy, Ian; Whitfield, Liz

    2015-04-01

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

  16. Analysis of gas centrifuge cascade for separation of multicomponent isotopes and optimal feed position

    SciTech Connect

    Chuntong Ying; Hongjiang Wu; Mingsheng Zhou; Yuguang Nie; Guangjun Liu

    1997-10-01

    Analysis of the concentration distribution in a gas centrifuge cascade for separation of multicomponent isotope mixtures is different from that in a cascade for separation of two-component mixtures. This paper presents the governing equations for a multicomponent isotope separation cascade. Numerically predicted separation factors for the gas centrifuge cascade agree well with the experimental data. A theoretical optimal feed position is derived for a short square cascade for a two-component mixture in a close-separation case. The optimal feed position for a gas centrifuge cascade for separation of multicomponent mixture is discussed.

  17. Relativistic astrophysics. [design analysis and performance tests of Cerenkov counters for detection of iron isotopes

    NASA Technical Reports Server (NTRS)

    Price, P. B.

    1976-01-01

    The design, experimental testing, and calibration (error analysis) of a high resolution Cerenkov-scintillation detector is presented. The detector is capable of detecting iron isotopes and heavy ions of cosmic rays, and of performing direct measurements of individual neighboring isotopes at charge resolution 26. It utilizes Lexan (trademark) sheets, and has been used in flight packages of balloons and on the Skylab. The detector will be able to provide more information on violet astrophysical processes, such as thermonuclear reactions on neutron stars. Ground support and display equipment which are to be used in conjunction with the detector are also discussed.

  18. Uranium Isotopic and Quantitative Analysis Using a Mechanically-Cooled HPGe Detector

    SciTech Connect

    Solodov, Alexander A

    2008-01-01

    A new, portable high-resolution spectroscopy system based on a high-purity germanium detector cooled with a miniature Stirling-cycle cooler, ORTEC trans-SPEC, has recently become commercially available. The use of a long-life mechanical cooling system eliminates the need for liquid nitrogen. The purpose of this study was to determine the applicability of this new instrument for isotopic and quantitative analyses of uranium samples. The results of the performance of the trans-SPEC with the combination of PC-FRAM and ISOTOPIC software packages are described in this paper. An optimal set of analysis parameters for uranium measurements is proposed.

  19. Evidence for a possible dietary effect on the isotopic composition of Zn in blood via isotopic analysis of food products by multi-collector ICP-mass spectrometry.

    PubMed

    Costas-Rodríguez, Marta; Van Heghe, Lana; Vanhaecke, Frank

    2014-01-01

    In this work, the hypothesis of a possible dietary effect on the isotopic composition of Zn in blood from populations with different feeding habits, i.e. lacto-ovo vegetarians and omnivores, was investigated through isotopic analysis of Zn in common food products by multi-collector ICP - mass spectrometry (MC-ICP-MS). Several certified reference materials (CRMs) were also included in the sample set for comparison purposes. For these CRMs, the isotopic composition of Zn is expressed as δ-values, calculated with respect to both IRMM-3702 and JMC-ZnLyon, as isotopic standards. The range of δ(66)Zn values observed in food products was approximately 1.9‰. In general, vegetables, cereals and derived products showed an enrichment of the heavier Zn isotopes, whereas a depletion was observed in products of animal origin (meat, fish, egg and semi-skimmed milk), relative to human blood samples. Mussel, however, showed a significant enrichment of the heavier isotopes, which is hypothetically attributed to its accumulation behaviour. Thus, the lower δ(66)Zn values found in food products of animal origin appear to be reflected in the lower δ(66)Zn value observed in blood from an omnivorous population compared to that for a vegetarian population.

  20. Compound Specific Isotope Analysis of Fatty Acids in Southern African Aerosols

    NASA Astrophysics Data System (ADS)

    Billmark, K. A.; Macko, S. A.; Swap, R. J.

    2003-12-01

    This study, conducted as a part of the Southern African Regional Science Initiative (SAFARI 2000), applied compound specific isotope analysis to describe aerosols at source regions and rural locations. Stable carbon isotopic compositions of individual fatty acids were determined for aerosol samples collected at four sites throughout southern Africa. Mongu, Zambia and Skukuza, South Africa were chosen for their location within intense seasonal Miombo woodland savanna and bushveld savanna biomass burning source regions, respectively. Urban aerosols were collected at Johannesburg, South Africa and rural samples were collected at Sua Pan, Botswana. Fatty acid isotopic compositions varied temporally. Urban aerosols showed significant isotopic enrichment of selected short chain fatty acids (C < 20) compared to aerosols produced during biomass combustion. Sua Pan short chain fatty acid signatures were significantly different from the other non-urban sites, which suggests that sources other than biomass combustion products, such as organic eolian material, impact the Sua Pan aerosol profile. However, a high degree of correlation between Sua Pan and Skukuza long chain fatty acid δ 13C values confirm atmospheric linkages between the two areas and that isotopic signatures of combusted fatty acids are unaltered during atmospheric transport highlighting their potential for use as a conservative tracer.

  1. Collection of NO and NO2 for isotopic analysis of NO(x) emissions.

    PubMed

    Fibiger, Dorothy L; Hastings, Meredith G; Lew, Audrey F; Peltier, Richard E

    2014-12-16

    There have been several measurements made of the nitrogen isotopic composition of gaseous NOx (NOx = NO + NO2) from various emission sources, utilizing a wide variety of methods to collect the NOx in solution as nitrate or nitrite. However, previous collection techniques have not been verified for complete or efficient capture of NOx such that the isotopic composition of NOx remains unaltered during collection. Here, we present a method of collecting NOx (NO + NO2) in solution as nitrate to evaluate the nitrogen isotopic composition of the NOx (δ(15)N-NOx). Using a 0.25 M KMnO4 and 0.5 M NaOH solution, quantitative NOx collection was achieved under a variety of conditions in laboratory and field settings, allowing for isotopic analysis without correcting for fractionations. The uncertainty across the entire analytic procedure is ±1.5‰ (1σ). With this method, a more robust inventory of NOx source isotopic composition is possible, which has implications for studies of air quality and acid deposition. PMID:25415365

  2. Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis.

    PubMed

    Finkelstein, Myra E; Kuspa, Zeka E; Welch, Alacia; Eng, Curtis; Clark, Michael; Burnett, Joseph; Smith, Donald R

    2014-10-01

    Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot from all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ~20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events.

  3. 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

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

    PubMed

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

    2012-11-01

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

  5. Stable Isotope Analysis Reveals Detrital Resource Base Sources of the Tree Hole Mosquito, Aedes triseriatus

    PubMed Central

    Kaufman, Michael G.; Pelz-Stelinski, Kirsten S.; Yee, Donald A.; Juliano, Steven A.; Ostrom, Peggy H.; Walker, Edward D.

    2010-01-01

    1. Detritus that forms the basis for mosquito production in tree hole ecosystems can vary in type and timing of input. We investigated the contributions of plant- and animal-derived detritus to the biomass of Aedes triseriatus (Say) pupae and adults by using stable isotope (15N and 13C) techniques in lab experiments and field collections. 2. Lab-reared mosquito isotope values reflected their detrital resource base, providing a clear distinction between mosquitoes reared on plant or animal detritus. 3. Isotope values from field-collected pupae were intermediate between what would be expected if a single (either plant or animal) detrital source dominated the resource base. However, mosquito isotope values clustered most closely with plant-derived values, and a mixed feeding model analysis indicated tree floral parts contributed approximately 80% of mosquito biomass. The mixed model also indicated that animal detritus contributed approximately 30% of mosquito tissue nitrogen. 4. Pupae collected later in the season generally had isotope values that were consistent with an increased contribution from animal detritus, suggesting this resource became more nutritionally important for mosquitoes as plant inputs declined over the summer. PMID:21132121

  6. Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis.

    PubMed

    Finkelstein, Myra E; Kuspa, Zeka E; Welch, Alacia; Eng, Curtis; Clark, Michael; Burnett, Joseph; Smith, Donald R

    2014-10-01

    Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot from all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ~20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events. PMID:25173094

  7. Actinides: How well do we know their stellar production?

    NASA Astrophysics Data System (ADS)

    Goriely, S.; Arnould, M.

    2001-12-01

    The reliable evaluation of the r-process production of the actinides and careful estimates of the uncertainties affecting these predictions are key ingredients especially in nucleo-cosmochronology studies based on the analysis of very metal-poor stars or on the composition of meteorites. This type of information is also required in order to make the best possible use of future high precision data on the actinide composition of galactic cosmic rays, of the local interstellar medium, or of meteoritic grains of presumed circumstellar origin. This paper provides the practitioners in these various fields with the most detailed and careful analysis of the r-process actinide production available to-date. This study is based on a version of the multi-event canonical model of the r-process which discards the largely used waiting point approximation. It considers also different combinations of models for the calculation of nuclear masses, beta -decay and fission rates. Two variants of the model used to predict nuclear reaction rates are adopted. In addition, the influence of the level of Pb and Bi production by the r-process on the estimated actinide production is evaluated by relying on the solar abundances of these two elements. In total, thirty-two different cases are presented, and are considered to give a fair picture of the level of reliability of the predictions of the actinide production, at least in the framework of a simple r-process model. This simplicity is imposed by our inability to identify the proper astrophysical sites for the r-process. As a guide to the practitioners, constraints on the actinide yield predictions and associated uncertainties are suggested on grounds of the measured abundances of r-nuclides, including Th and U, in the star CS 31082-001, and under the critical and questionable assumption of the ``universality'' of the r-process. We also define alternative constraints based on the nucleo-cosmochronological results derived from the present

  8. Stable isotope analysis of plant-derived nitrate - novel method for discrimination between organically and conventionally grown vegetables.

    PubMed

    Mihailova, A; Pedentchouk, N; Kelly, S D

    2014-07-01

    The lack of reliable markers for the discrimination between organic and conventional products makes the organic food market susceptible to attempted fraud. Robust analytical methodologies for organic food authentication are urgently needed. In this study a new approach, compound-specific nitrogen and oxygen isotope analysis of plant-derived nitrate, has been applied alongside bulk nitrogen isotope analysis for discrimination between organically and conventionally greenhouse-grown lettuce and retail potatoes and tomatoes. The method revealed significant differences between conventional and organic fertilisation. An intra-plant isotopic variation as well as significant impact of the fertiliser application rate on the nitrogen and oxygen isotope values of plant-derived nitrate has been observed. Nitrogen and oxygen isotope analysis of nitrate has a potential for differentiation between organic and conventional crops. Further analysis is needed to improve our understanding of the scope of application and robustness of this compound-specific approach. PMID:24518338

  9. Stable isotope analysis of plant-derived nitrate - novel method for discrimination between organically and conventionally grown vegetables.

    PubMed

    Mihailova, A; Pedentchouk, N; Kelly, S D

    2014-07-01

    The lack of reliable markers for the discrimination between organic and conventional products makes the organic food market susceptible to attempted fraud. Robust analytical methodologies for organic food authentication are urgently needed. In this study a new approach, compound-specific nitrogen and oxygen isotope analysis of plant-derived nitrate, has been applied alongside bulk nitrogen isotope analysis for discrimination between organically and conventionally greenhouse-grown lettuce and retail potatoes and tomatoes. The method revealed significant differences between conventional and organic fertilisation. An intra-plant isotopic variation as well as significant impact of the fertiliser application rate on the nitrogen and oxygen isotope values of plant-derived nitrate has been observed. Nitrogen and oxygen isotope analysis of nitrate has a potential for differentiation between organic and conventional crops. Further analysis is needed to improve our understanding of the scope of application and robustness of this compound-specific approach.

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

    NASA Astrophysics Data System (ADS)

    Mohn, J.

    2015-12-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the strongest stratospheric ozone-destroying substance released in the 21st century. Main N2O emissions are linked to different microbial pathways, therefore sources are disperse and highly variable, complicating their interpretation. Isotopic measurements have great potential to distinguish between individual source and sink processes. Developments in laser spectroscopy allow both the intramolecular distribution of 15N substitutions (15N14N16O versus 14N15N16O) and the oxygen isotopic composition of N2O to be measured in real-time, at high precision and in excellent compatibility to IRMS [1]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 2-4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. High precision isotopic analysis at ambient N2O concentration is feasible by combining laser spectroscopy with automated preconcentration. Field deployment was demonstrated by real-time monitoring of the isotopic composition of N2O emissions above an intensively managed grassland in central Switzerland. The responses of the N2O isotopic signatures were analysed with respect to management events and climatic conditions [5]. In a follow-up project we combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model of surface fluxes of N2O isotopomers. The working hypothesis is that this approach will allow us to quantify regional N2O sources, identify emission hot spots, and constrain source processes, which will significantly advance our

  11. In-situ chemical and isotopic analysis of a comet by Ptolemy

    NASA Astrophysics Data System (ADS)

    Morse, A. D.; Barber, S. J.; Leese, M. R.; Morgan, G. H.; Sheridan, S.; Wright, I. P.; Zarnecki, J. C.; Pillinger, C. T.

    2003-04-01

    Ptolemy is a Gas Chromatograph - Mass Spectrometer, one of the instruments on board the Rosetta Lander, intended to land on comet Wirtanen. Ptolemy is designed to measure the composition and isotope ratios of gases released from comet samples during pyrolysis or combustion. The total mass of the instrument is 4.6 kg and it fits into a space of 33 x 25 x 11 cm. Following touchdown on the comet nucleus, comet samples are obtained by the SD2 instrument, which drills a core sample and loads it into one of 26 ovens on a carousel. One of the ovens already contains a molecular sieve absorbent so that the comet "atmosphere" can also be sampled. The sample is then heated by the oven and the gases released are transferred to the Ptolemy instrument. Within Ptolemy, the raw sample gases can be chemically processed to convert them into molecules suitable for isotopic analysis. The processed sample mixture gas is injected into one of three GC columns to separate it into its constituent components before analysis by the mass spectrometer. An ion trap mass spectrometer has been used as this gives considerable reduction of mass, power and volume, compared to standard magnetic sector mass spectrometers normally used for isotopic analysis. Laboratory experiments have shown that an ion trap is capable of measuring carbon and nitrogen isotope ratios to a precision of +/- 20 per mil or better. We will present data from the Flight instrument plus results of ongoing characterisation studies using the identical Qualification Model.

  12. Determination of geographic provenance of cotton fibres using multi-isotope profiles and multivariate statistical analysis

    NASA Astrophysics Data System (ADS)

    Daeid, N. Nic; Meier-Augenstein, W.; Kemp, H. F.

    2012-04-01

    The analysis of cotton fibres can be particularly challenging within a forensic science context where discrimination of one fibre from another is of importance. Normally cotton fibre analysis examines the morphological structure of the recovered material and compares this with that of a known fibre from a particular source of interest. However, the conventional microscopic and chemical analysis of fibres and any associated dyes is generally unsuccessful because of the similar morphology of the fibres. Analysis of the dyes which may have been applied to the cotton fibre can also be undertaken though this can be difficult and unproductive in terms of discriminating one fibre from another. In the study presented here we have explored the potential for Isotope Ratio Mass Spectrometry (IRMS) to be utilised as an additional tool for cotton fibre analysis in an attempt to reveal further discriminatory information. This work has concentrated on un-dyed cotton fibres of known origin in order to expose the potential of the analytical technique. We report the results of a pilot study aimed at testing the hypothesis that multi-element stable isotope analysis of cotton fibres in conjunction with multivariate statistical analysis of the resulting isotopic abundance data using well established chemometric techniques permits sample provenancing based on the determination of where the cotton was grown and as such will facilitate sample discrimination. To date there is no recorded literature of this type of application of IRMS to cotton samples, which may be of forensic science relevance.

  13. 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

  14. Heavy actinide cross sections in the /sup 238/U + /sup 248/Cm reaction

    SciTech Connect

    Kratz, J V; Bruechle, W; Gaeggeler, H

    1981-01-01

    Cross sections for the production of Cf, Es, Fm, and Md isotopes in the reactions of 7.4 MeV/u /sup 238/U-ions with /sup 248/Cm targets are presented and discussed. Cross sections for the formation of heavy actinides in the reactions of 7.5 MeV/u /sup 136/Xe and /sup 238/U-projectiles with /sup 238/U-targets are presented for comparison. (WHK)

  15. Coordinated Mineralogical and Isotopic Analysis of a Cosmic Symplectite Identified in a Stardust Terminal Particle

    NASA Technical Reports Server (NTRS)

    Nguyen, A. N.; Berger, E. L.; Nakamura-Messenger, K.; Messenger, S.

    2014-01-01

    Comet Wild-2 samples returned by the Stardust spacecraft contain a chemically diverse mixture of material, underscoring the complex nature of comets. Studies of entire Stardust aerogel tracks afford the opportunity to examine the fine-grained particle fragments distributed along the length of the track as well as the terminal particles. Previous TEM characterization of a terminal particle (TP) in track #147 revealed a symplectically intergrown iron sulfide and oxide assemblage. Mineralogically similar assemblages, known as cosmic symplectites (COS, formerly termed "new-PCP"), have only been identified in the primitive carbonaceous chondrite Acfer 094. Meteoritic COS have isotopically heavy O compositions (delta (sup 17), O-18 = 180per mille) that point to interactions with early solar system primordial water. In this study we report mineralogical and O isotopic measurements of the Wild-2 COS assemblage. Experimental: Track #147 is a "bulbous"-type track (4600 microns long) containing 7 terminal particles. The TPs were removed from the track, embedded in epoxy, and ultramicrotomed. A JEOL 2500SE 200 keV field-emission scanning-transmission electron microscope was used to obtain quantitative elemental maps and detailed mineralogical characterization. Following TEM analysis, two thin sections of TP4 (12 microns) were analyzed for O isotopes by raster ion imaging with the JSC NanoSIMS 50L. All three O isotopes were measured simultaneously using electron multipliers. San Carlos olivine grains were used as isotopic standards. Results and Discussion: The COS in the Wild-2 track #147 TP4 sample consists of symplectically intergrown pentlandite and nanocrystalline maghemite which coexists with high-Ca pyroxene with Na and Cr (kosmochlor component). This kosmochlor component could have a nebular origin and be precursors to type II chondrules in ordinary chondrites. Yet pentlandite is not a stable phase in the nebula. The COS in Acfer 094 also consists of pentlandite, but

  16. Extraction and carbon isotope analysis of CO 2 from scapolite in deep crustal granulites and xenoliths

    NASA Astrophysics Data System (ADS)

    Moecher, David P.; Valley, John W.; Essene, Eric J.

    1994-01-01

    Carbon isotope compositions of scapolite from granulite facies gneisses and lower crustal xenoliths document the composition and constrain the source of carbon in scapolite from the lower crust. CO 2 is extracted from scapolite without fractionating carbon isotopes by reaction with phosphoric acid at 25 or 75°C. Thus, partial yields of CO 2 from scapolite are sufficient for accurate carbon isotopic analysis. Isotopic compositions of coexisting scapolite and calcite in high-grade calc-silicate gneisses and marbles, and consideration of the crystal chemical environment of CO 3 in the scapolite structure, indicate little fractionation of 13C /12C between scapolite and calcite (0.1 ± 1.2%.) at equilibrium conditions of 650-800°C. The carbon isotope composition of CO 2 extracted from scapolite in twenty-nine samples of regional granulite facies gneisses, amphibolites, calc-silicate gneisses, and crustal xenoliths yield values of δ 13C that range from -10 to -1%. (PDB). High-grade marbles and graphitic paragneisses are precluded as major sources of carbon for scapolite in the high grade rocks analyzed in this study, as the former are isotopically enriched, and the latter isotopically depleted in 13C /12C relative to the range of isotopic compositions determined here. The δ 13C values for mafic granulites and amphibolites in granulite terranes composed of supracrustal sequences (-10.1 to -4.0%.) may reflect the isotopic composition of diagenetic carbonate present in their basaltic protoliths. The values of δ 13C for scapolite in mafic xenoliths and some granulite facies orthogneisses (-8.2 to -1.2%.) are consistent with crystallization of the scapolite from a mafic melt or derivation of CO 2 from mafic melts emplaced in the lower crust or upper mantle. The values of δ 13C for scapolites from calc-silicate gneisses and calc-silicate xenoliths (-10.0 to -2.9%.) may result from depletion of 13C /12C as a result of decarbonation of calcite-bearing protoliths during

  17. Advances in laser ablation MC-ICPMS isotopic analysis of rock materials

    NASA Astrophysics Data System (ADS)

    Young, E. D.

    2007-12-01

    Laser ablation multiple-collector inductively coupled plasma-source mass spectrometry (LA-MC-ICPMS) is a rapid method for obtaining high-precision isotope ratio measurements in geological samples. The method has been used with success for measuring isotope ratios of numerous elements, including Pb, Hf, Mg, Si, and Fe in terrestrial and extraterrestrial samples. It fills the gap between the highest precision obtainable with acid digestion together with MC-ICPMS and thermal ionization mass spectrometry (TIMS) and the maximum spatial resolution afforded by secondary ion mass spectrometry (SIMS). Matrix effects have been shown to be negligible for Pb isotopic analysis by LA-MC-ICPMS (Simon et al., 2007). Glass standards NBS 610, 612, and 614 have Pb/matrix ratios spanning two orders of magnitude. Our sample-standard bracketing laser ablation technique gives accurate and precise 208Pb/206Pb and 207Pb/206Pb for these glasses. The accuracy is superior to that obtained when using Tl to correct for mass fractionation. Accuracy and precision (± 0.2 ‰) for Pb in feldspars is comparable to that for double-spike TIMS. Data like these have been used to distinguish distinct sources of magmas in the Long Valley silicic magma system. LA-MC-ICPMS analyses of Mg isotope ratios in calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrite meteorites have revealed a wealth of new information about the history of these objects. A byproduct of this work has been recognition of the importance of different mass fractionation laws among three isotopes of a given element. Kinetic and equilibrium processes define distinct fractionation laws. Reservoir effects can further modify these laws. The result is that the linear coefficient β that relates the logarithms of the ratios n2/n1 and n3/n1 (ni refers to the number of atoms of isotope i) of isotopes with masses m3 > m2 > m1 is not unique. Rather, it is process dependent. In the case of Mg, this coefficient ranges from 0.521 for

  18. Development of high through-put Sr isotope analysis for monitoring reservoir integrity for CO{sub 2} storage.

    SciTech Connect

    Wall, Andy; Jain, Jinesh; Stewart, Brian; Capo, Rosemary; Hakala, Alexandra J.; Hammack, Richard; Guthrie, George

    2012-01-01

    Recent innovations in multi-collector ICP-mass spectrometry (MC-ICP-MS) have allowed for rapid and precise measurements of isotope ratios in geological samples. Naturally occurring Sr isotopes has the potential for use in Monitoring, Verification, and Accounting (MVA) associated with geologic CO2 storage. Sr isotopes can be useful for: Sensitive tracking of brine migration; Determining seal rock leakage; Studying fluid/rock reactions. We have optimized separation chemistry procedures that will allow operators to prepare samples for Sr isotope analysis off site using rapid, low cost methods.

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

    PubMed

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

    1999-01-29

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

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

    PubMed Central

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

    1999-01-01

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

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

    PubMed

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

    2016-01-15

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

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

    PubMed

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

    2016-01-15

    In forensic environmental investigations the main issue concerns the inference of the original source of the pollutant for determining the liable party. Isotope measurements in geochemistry, combined with complimentary techniques for contaminant identification, have contributed significantly to source determination at polluted sites. In this work we have determined the intramolecular (13)C profiles of several molecules well-known as pollutants. By giving additional analytical parameters, position-specific isotope analysis performed by isotope ratio monitoring by (13)C nuclear magnetic resonance (irm-(13)C NMR) spectrometry gives new information to help in answering the major question: what is the origin of the detected contaminant? We have shown that isotope profiling of the core of a molecule reveals both the raw materials and the process used in its manufacture. It also can reveal processes occurring between the contamination site 'source' and the sampling site. Thus, irm-(13)C NMR is shown to be a very good complement to compound-specific isotope analysis currently performed by mass spectrometry for assessing polluted sites involving substantial spills of pollutant. PMID:26592622

  3. Advancement and application of gas chromatography isotope ratio mass spectrometry techniques for atmospheric trace gas analysis

    NASA Astrophysics Data System (ADS)

    Giebel, Brian M.

    2011-12-01

    The use of gas chromatography isotope ratio mass spectrometry (GC-IRMS) for compound specific stable isotope analysis is an underutilized technique because of the complexity of the instrumentation and high analytical costs. However stable isotopic data, when coupled with concentration measurements, can provide additional information on a compounds production, transformation, loss, and cycling within the biosphere and atmosphere. A GC-IRMS system was developed to accurately and precisely measure delta13C values for numerous oxygenated volatile organic compounds having natural and anthropogenic sources. The OVOCs include methanol, ethanol, acetone, methyl ethyl ketone, 2-pentanone, and 3-pentanone. Guided by the requirements for analysis of trace components in air, the GC-IRMS system was developed with the goals of increasing sensitivity, reducing dead-volume and peak band broadening, optimizing combustion and water removal, and decreasing the split ratio to the IRMS. The technique relied on a two-stage preconcentration system, a low-volume capillary reactor and water trap, and a balanced reference gas delivery system. Measurements were performed on samples collected from two distinct sources (i.e. biogenic and vehicle emissions) and ambient air collected from downtown Miami and Everglades National Park. However, the instrumentation and the method have the capability to analyze a variety of source and ambient samples. The measured isotopic signatures that were obtained from source and ambient samples provide a new isotopic constraint for atmospheric chemists and can serve as a new way to evaluate their models and budgets for many OVOCs. In almost all cases, OVOCs emitted from fuel combustion were enriched in 13C when compared to the natural emissions of plants. This was particularly true for ethanol gas emitted in vehicle exhaust, which was observed to have a uniquely enriched isotopic signature that was attributed to ethanol's corn origin and use as an alternative

  4. Online analysis of chlorine stable isotopes in chlorinated ethylenes: an inter-laboratory study

    NASA Astrophysics Data System (ADS)

    Bernstein, Anat; Shouakar-Stash, Orfan; Hunkeler, Daniel; Sakaguchi-Söder, Kaori; Laskov, Christine; Aravena, Ramon; Elsner, Martin

    2010-05-01

    In the last decade, compound-specific stable isotopes analysis of groundwater pollutants became an important tool to identify different sources of the same pollutant and for tracking natural attenuating processes in the sub-surface. It has been shown that trends in the isotopic composition of the target compounds can shed light on in-situ processes that are otherwise difficult to track. Analytical methods of carbon, nitrogen and hydrogen were established and are by now frequently used for a variety of organic pollutants. Yet, the motivation of introducing analytical methods for new isotopes is emerging. This motivation is further enhanced, as advantages of using two or more stable isotopes for gaining better insight on degradation pathways are well accepted. One important element which demands the development of appropriate analytical methods is chlorine, which is found in various groups of organic pollutants, among them the chlorinated ethylenes. Chlorinated ethylenes are considered as high priority environmental pollutants, and the development of suitable chlorine isotope methods for this group of pollutants is highly desired. Ideally, stable isotope techniques should have the capability to determine the isotopic composition of and individual target compound in a non-pure mixture, without the requirement of a laborious off-line treatment. Indeed, in the last years two different concepts for on-line chlorine isotope analysis methods were introduced, by using either a standard quadrapole GC/MS (Sakaguchi-Söder et al., 2007) or by using a GC/IRMS (Shouakar-Stash et al., 2006). We present a comparison of the performances of two concepts, carried out in five different laboratories: Waterloo (GC/IRMS), Neuchâtel (GC/MS), Darmstadt (GC/MS), Tübingen (GC/MS) and Munich (GC/IRMS). This comparison was performed on pure trichloroethylene and dichloroethylene products of different manufactures, as well as trichloroethylene and dichloroethylene samples that were exposed to

  5. Final Report on Actinide Glass Scintillators for Fast Neutron Detection

    SciTech Connect

    Bliss, Mary; Stave, Jean A.

    2012-10-01

    This is the final report of an experimental investigation of actinide glass scintillators for fast-neutron detection. It covers work performed during FY2012. This supplements a previous report, PNNL-20854 “Initial Characterization of Thorium-loaded Glasses for Fast Neutron Detection” (October 2011). The work in FY2012 was done with funding remaining from FY2011. As noted in PNNL-20854, the glasses tested prior to July 2011 were erroneously identified as scintillators. The decision was then made to start from “scratch” with a literature survey and some test melts with a non-radioactive glass composition that could later be fabricated with select actinides, most likely thorium. The normal stand-in for thorium in radioactive waste glasses is cerium in the same oxidation state. Since cerium in the 3+ state is used as the light emitter in many scintillating glasses, the next most common substitute was used: hafnium. Three hafnium glasses were melted. Two melts were colored amber and a third was clear. It barely scintillated when exposed to alpha particles. The uses and applications for a scintillating fast neutron detector are important enough that the search for such a material should not be totally abandoned. This current effort focused on actinides that have very high neutron capture energy releases but low neutron capture cross sections. This results in very long counting times and poor signal to noise when working with sealed sources. These materials are best for high flux applications and access to neutron generators or reactors would enable better test scenarios. The total energy of the neutron capture reaction is not the only factor to focus on in isotope selection. Many neutron capture reactions result in energetic gamma rays that require large volumes or high densities to detect. If the scintillator is to separate neutrons from gamma rays, the capture reactions should produce heavy particles and few gamma rays. This would improve the detection of a

  6. High-Precision Selenium Isotope Analysis by Hydride Generation MC-ICP-MS: Environmental Applications

    NASA Astrophysics Data System (ADS)

    Schmidberger, S.; Simonetti, A.; Gariépy, C.

    2003-04-01

    The global cycle and the natural isotopic variation of Se in the lithosphere, biosphere, hydrosphere and atmosphere are currently little constrained. The study of Se isotope systematics by negative thermal ionization mass spectrometry (NTIMS) has documented large Se isotope variations up to 15 ppm in various natural samples (δ80Se/76Se; Johnson et al., 1999), indicating its important potential as a tracer in geological and biological processes. Recently, Se isotope measurements on sulfide deposits from hydrothermal systems were obtained using a Micromass IsoProbe multicollector inductively coupled plasma mass spectrometer coupled to a hydride generator (Rouxel et al. 2002). This technique allows for high-precision Se isotope analysis on small sample sizes (<= 100 ng), and thus is a prerequisite for precise Se isotope measurements in low abundance samples such as precipitations, freshwaters and atmospheric aerosols (1 ppb or less). We have developed a 74-82Se double spike technique, which corrects for instrumental mass fractionation during both isotopic analysis and chemical processing. During double spike calibration, mass discrimination was monitored using a Germanium Specpuretextregistered standard (25 ppb). The isotopic composition of the Ge standard was accurately determined using a 10 ppb solution of the isotopic Gallium standard SRM 994. Repeated measurements (n=8) of the Ge standard yielded an external reproducibility of 0.13 ppm and a 74Ge/72Ge ratio of 1.32987. Instrumental mass bias evaluated with the Ge standard was essentially invariant over a three-month period. Our results yield an external reproducibility of 0.4 ppm (80Se/76Se) for a 100 ppb solution of the Se standard SRM 3149 (˜100 ng of total Se consumed). This ongoing study focuses on determining the Se isotopic compositions of precipitations and aerosol samples from remote and urban areas in northeastern North America. The preliminary results for precipitation samples (˜100 to 300 ml of rain

  7. In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy

    PubMed Central

    Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

    2016-01-01

    Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. 6Li and 7Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy. PMID:27350565

  8. In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy.

    PubMed

    Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

    2016-01-01

    Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. (6)Li and (7)Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy. PMID:27350565

  9. In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy

    NASA Astrophysics Data System (ADS)

    Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

    2016-06-01

    Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. 6Li and 7Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy.

  10. Simultaneous Analysis of Nitrogen, Carbon and Sulfur Stable Isotopes and Concentrations in Organics and Soils

    NASA Astrophysics Data System (ADS)

    Mambelli, S.; Brooks, P. D.; Sutka, R.; Hughes, S.; Finstad, K. M.; Pakes, M. J.; Dawson, T. E.

    2014-12-01

    To date, analysis of diet, food web complexities, biogeochemical cycles, and ecosystem functioning have largely focused on using variation in carbon (C) and nitrogen (N) stable isotope ratios. This is because a great deal is understood about what leads to this variation and because the dual stable isotope analysis of these two elements using continuous flow isotope ratio mass spectrometry (IRMS) is now commonplace. However, the aforementioned studies may all greatly benefit from the additional information one can get from also having sulfur (S) stable isotopes ratio data. Until very recently the analysis of δ34S has traditionally required an additional and often more difficult analytical procedure. Here, we report on the development of a new method that simultaneously analyzes the elemental and isotopic composition of N, C and S in a single sample. The new commercially available instrument includes a modified NCS elemental analyzer in line with an IRMS outfitted with 100 volt AD converters for wide dynamic range. We tested, and modified, this instrument to achieve maximum accuracy and precision for the isotopic measurements of all three elements. We found that the original design needed improvements to achieve our goals by: a) including a component (originally designed for trapping water) as buffer to reduce S memory and obtain reliable δ34S analysis; b) adding an external furnace for complete reduction of nitrogen oxides to N2 gas for accurate δ15N; c) adding a magnesium perchlorate water trap immediately after the reduction tube to minimize any water condensation that could also influence S memory. We analyzed a selection of organic materials and soils with approximately a 1:2 standards versus unknowns ratio per run. Using this NCS set-up, the precision of the N and C isotopic measurements was comparable to the one usually attained in NC mode alone (standard deviation of ± 0.13 δ15N in the range 30 to 400 µg N, and of ± 0.12 δ13C in the range 0.20 to 4 mg

  11. Experimental studies of actinides in molten salts

    SciTech Connect

    Reavis, J.G.

    1985-06-01

    This review stresses techniques used in studies of molten salts containing multigram amounts of actinides exhibiting intense alpha activity but little or no penetrating gamma radiation. The preponderance of studies have used halides because oxygen-containing actinide compounds (other than oxides) are generally unstable at high temperatures. Topics discussed here include special enclosures, materials problems, preparation and purification of actinide elements and compounds, and measurements of various properties of the molten volts. Property measurements discussed are phase relationships, vapor pressure, density, viscosity, absorption spectra, electromotive force, and conductance. 188 refs., 17 figs., 6 tabs.

  12. Decontamination of matrices containing actinide oxides

    SciTech Connect

    Villarreal, Robert

    1997-12-01

    There is provided a method for removing actinides and actinide oxides, particularly fired actinides, from soil and other contaminated matrices, comprising: (a) contacting a contaminated material with a solution of at least one inhibited fluoride and an acid to form a mixture; (b) heating the mixture of contaminated material and solution to a temperature in the range from about 30 C to about 90 C while stirring; (c) separating the solution from any undissolved matrix material in the mixture; (d) washing the undissolved matrix material to remove any residual materials; and (e) drying and returning the treated matrix material to the environment.

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

    NASA Astrophysics Data System (ADS)

    Sugiura, Shinji; Ikeda, Hiroshi

    2014-03-01

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

  14. Stable isotope analysis of molecular oxygen from silicates and oxides using CO2 laser extraction

    NASA Technical Reports Server (NTRS)

    Perry, Eugene

    1996-01-01

    A laser-excited system for determination of the oxygen isotope composition of small quantities of silicate and oxide minerals was constructed and tested at JSC. This device is the first reported to use a commercially available helium cryostat to transfer and purify oxygen gas quantitatively within the system. The system uses oxygen gas instead of the conventional CO2 for mass spectrometer analyses. This modification of technique permits determination of all three stable oxygen isotopes, an essential requirement for oxygen isotope analysis of meteoritic material. Tests of the system included analysis of standard silicate materials NBS 28 and UWMG2 garnet, six SNC meteorites, and inclusions and chondrules from the Allende meteorite. Calibration with terrestrial standards was excellent. Meteorite values are close to published values and show no evidence of terrestrial oxygen contamination. The one limitation observed is that, in some runs on fine-grained SNC matrix material, sample results were affected by other samples in the sample holder within the reaction chamber. This reemphasizes the need for special precautions in dealing with fine-grained, reactive samples. Performance of the JSC instrument compares favorably with that of any other instrument currently producing published oxygen isotope data.

  15. Investigating Actinide Molecular Adducts From Absorption Edge Spectroscopy

    SciTech Connect

    Den Auwer, C.; Conradson, S.D.; Guilbaud, P.; Moisy, P.; Mustre de Leon, J.; Simoni, E.; /SLAC, SSRL

    2006-10-27

    Although Absorption Edge Spectroscopy has been widely applied to the speciation of actinide elements, specifically at the L{sub III} edge, understanding and interpretation of actinide edge spectra are not complete. In that sense, semi-quantitative analysis is scarce. In this paper, different aspects of edge simulation are presented, including semi-quantitative approaches. Comparison is made between various actinyl (U, Np) aquo or hydroxy compounds. An excursion into transition metal osmium chemistry allows us to compare the structurally related osmyl and uranyl hydroxides. The edge shape and characteristic features are discussed within the multiple scattering picture and the role of the first coordination sphere as well as contributions from the water solvent are described.

  16. Compound-Specific Stable Carbon Isotope Analysis of Chlorofluorocarbons in Groundwater.

    PubMed

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2015-10-20

    Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), controlled substances due to their role in stratospheric ozone loss, also occur as dissolved contaminants in groundwaters. Stable carbon isotopic signatures may provide valuable new information on the fate of these compounds as has been seen for other priority hydrocarbon contaminants, but to date no method for extraction and isotopic analysis of dissolved CFCs from groundwaters has been developed. Here we describe a cryogenic purge and trap system coupled to continuous flow compound-specific stable carbon isotope analysis mass spectrometry for concentrations as low as 35 μg/L. The method is validated by comparing isotopic signatures from water extracted CFCs against a new suite of isotopic CFC standards. Fractionation of CFCs in volatilization experiments from pure-phase CFC-11 and CFC-113 resulted in enrichment factors (ε) of +1.7 ± 0.1‰ and +1.1 ± 0.1‰, respectively, indicating that such volatile loss, if significant, would produce a more (13)C depleted signature in the remaining CFCs. Importantly, no significant fractionation was observed during volatile extraction of dissolved CFCs from aqueous solutions. δ(13)C values for groundwaters from a CFC-contaminated site were, on average, more enriched than δ(13)C values for pure compounds. Such enriched δ(13)C values have been seen in other hydrocarbon contaminants such as chlorinated ethenes and ethanes due to in situ degradation, but definitive interpretation of such enriched signatures in field samples requires additional experiments to characterize fractionation of CFCs during biodegradation. The establishment of a robust and sensitive method of extraction and analysis, as described here, provides the foundation for such future directions. PMID:26383531

  17. Compound-Specific Stable Carbon Isotope Analysis of Chlorofluorocarbons in Groundwater.

    PubMed

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2015-10-20

    Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), controlled substances due to their role in stratospheric ozone loss, also occur as dissolved contaminants in groundwaters. Stable carbon isotopic signatures may provide valuable new information on the fate of these compounds as has been seen for other priority hydrocarbon contaminants, but to date no method for extraction and isotopic analysis of dissolved CFCs from groundwaters has been developed. Here we describe a cryogenic purge and trap system coupled to continuous flow compound-specific stable carbon isotope analysis mass spectrometry for concentrations as low as 35 μg/L. The method is validated by comparing isotopic signatures from water extracted CFCs against a new suite of isotopic CFC standards. Fractionation of CFCs in volatilization experiments from pure-phase CFC-11 and CFC-113 resulted in enrichment factors (ε) of +1.7 ± 0.1‰ and +1.1 ± 0.1‰, respectively, indicating that such volatile loss, if significant, would produce a more (13)C depleted signature in the remaining CFCs. Importantly, no significant fractionation was observed during volatile extraction of dissolved CFCs from aqueous solutions. δ(13)C values for groundwaters from a CFC-contaminated site were, on average, more enriched than δ(13)C values for pure compounds. Such enriched δ(13)C values have been seen in other hydrocarbon contaminants such as chlorinated ethenes and ethanes due to in situ degradation, but definitive interpretation of such enriched signatures in field samples requires additional experiments to characterize fractionation of CFCs during biodegradation. The establishment of a robust and sensitive method of extraction and analysis, as described here, provides the foundation for such future directions.

  18. Subsurface interactions of actinide species and microorganisms : implications for the bioremediation of actinide-organic mixtures.

    SciTech Connect

    Banaszak, J.E.; Reed, D.T.; Rittmann, B.E.

    1999-02-12

    By reviewing how microorganisms interact with actinides in subsurface environments, we assess how bioremediation controls the fate of actinides. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. We describe how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility. We explain why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. We describe the development of mathematical models that link microbiological and geochemical reactions. Throughout, we identify the key research needs.

  19. Actinide removal from spent salts

    DOEpatents

    Hsu, Peter C.; von Holtz, Erica H.; Hipple, David L.; Summers, Leslie J.; Adamson, Martyn G.

    2002-01-01

    A method for removing actinide contaminants (uranium and thorium) from the spent salt of a molten salt oxidation (MSO) reactor is described. Spent salt is removed from the reactor and analyzed to determine the contaminants present and the carbonate concentration. The salt is dissolved in water, and one or more reagents are added to precipitate the thorium as thorium oxide and/or the uranium as either uranium oxide or as a diuranate salt. The precipitated materials are filtered, dried and packaged for disposal as radioactive waste. About 90% of the thorium and/or uranium present is removed by filtration. After filtration, salt solutions having a carbonate concentration >20% can be dried and returned to the reactor for re-use. Salt solutions containing a carbonate concentration <20% require further clean-up using an ion exchange column, which yields salt solutions that contain less than 0.1 ppm of thorium or uranium.

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

    PubMed

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

    2016-04-22

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

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

    PubMed Central

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

    2016-01-01

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

  2. Tungsten isotope analysis of meteorite samples using electrothermal vaporization (ETV)-MC-ICPMS technique

    NASA Astrophysics Data System (ADS)

    Okabayashi, S.; Sakata, S.; Hirata, T.

    2013-05-01

    Hf-W chronometer is based on the decay of 182Hf to 182W with a half-life of 8.9 ± 0.1 Myr. Hf is strongly lithophile elements, whereas W is moderately siderophile elements. Thus, the Hf-W age can provide critical information about the timing of metal-silicate differentiation (core formation) processes at the early stage of the planetary formation. Moreover, both the Hf and W is strongly refractory elements, the Hf-W age can reflect the timing of condensation or segregation of the metallic nuggets from chondritic reservoir at the early sequence of the solar system. The thermal ionization mass spectrometry (TIMS) is widely used for W isotope analysis. However, a micro-gram amount of W is desired for Hf-W chronological studies in this technique. The ICP-MS technique coupled with the conventional nebulization technique is also used for W isotope measurement. With this technique, total amount of W required for the isotopic ratio measurements could be 50 - 100 ng. On the other hand, typical ion transmission efficiency from sample to ion collector would be <0.1% under the sample introduction using the nebulizer. This suggests that the sample introduction efficiency (i.e., high transmission efficiency) can be dramatically improved when the loss of sample mist could be minimized. To achieve this, we have developed a sample introduction technique using the electrothermal vaporization (ETV) technique for W isotope analysis. In this study, W sample in 2% HNO3 solution is loaded on the Re filament located in a small volume ETV chamber to achieve minimum loss of W vapor and also to reduce the memory of W within the chamber. Temperature of the Re filament is controlled by the incident current (0 - 4 A). The W evaporation is carried out under the two different ambient gasses, Ar or He. We found that W signal intensity profile obtained under the Ar carrier gas is spiky and unstable, and this is not suitable for the precise isotopic analysis. In strike contrast, the signal

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  4. Isotopic Analysis of Fingernails as a USGS Open House Demonstration of the Use of Stable Isotopes in Foodweb Studies

    NASA Astrophysics Data System (ADS)

    Silva, S. R.; Kendall, C.; Young, M. B.; Choy, D.

    2011-12-01

    The USGS Isotope Tracers Project uses stable isotopes and tritium to add a unique dimension of chemical information to a wide range of environmental investigations. The use and application of isotopes is usually an unfamiliar and even esoteric topic to the general public. Therefore during three USGS open house events, as a public outreach effort, we demonstrated the use of stable isotopes by analyzing nitrogen and carbon isotopes from very small fragments of fingernail from willing participants. We titled the exhibit "You Are What You Eat". The results from all participants were plotted on a graph indicating the general influence of different food groups on the composition of body tissues as represented by fingernails. All participants were assigned a number and no personal-identification information was collected. A subset of participants provided us with an estimate of the number of days a week various foods were eaten and if they were vegetarians, vegans or non-vegetarians. Volunteers from our research group were on hand to explain and discuss fundamental concepts such as how foods attain their isotopic composition, the difference between C3 and C4 plants, the effects of assimilation, trophic enrichment, and the various uses of stable isotopes in environmental studies. The results of the fingernail analyses showed the variation of the range of isotopic compositions among about 400 people at each event, the distinct influence of C4 plants (mainly corn and cane sugar) on our carbon isotopic composition, and the isotopic differences between vegetarians and non vegetarians among other details (http://wwwrcamnl.wr.usgs.gov/isoig/projects/fingernails/). A poll of visitors attending the open house event in 2006 indicated that "You Are What You Eat" was among the most popular exhibits. Following the first two open house events we were contacted by a group of researchers from Brazil who had completed a very similar study. Our collaboration resulted in a publication in

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

    PubMed Central

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

    2014-01-01

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

  6. Overview of actinide chemistry in the WIPP

    SciTech Connect

    Borkowski, Marian; Lucchini, Jean - Francois; Richmann, Michael K; Reed, Donald T; Khaing, Hnin; Swanson, Juliet

    2009-01-01

    The year 2009 celebrates 10 years of safe operations at the Waste Isolation Pilot Plant (WIPP), the only nuclear waste repository designated to dispose defense-related transuranic (TRU) waste in the United States. Many elements contributed to the success of this one-of-the-kind facility. One of the most important of these is the chemistry of the actinides under WIPP repository conditions. A reliable understanding of the potential release of actinides from the site to the accessible environment is important to the WIPP performance assessment (PA). The environmental chemistry of the major actinides disposed at the WIPP continues to be investigated as part of the ongoing recertification efforts of the WIPP project. This presentation provides an overview of the actinide chemistry for the WIPP repository conditions. The WIPP is a salt-based repository; therefore, the inflow of brine into the repository is minimized, due to the natural tendency of excavated salt to re-seal. Reducing anoxic conditions are expected in WIPP because of microbial activity and metal corrosion processes that consume the oxygen initially present. Should brine be introduced through an intrusion scenario, these same processes will re-establish reducing conditions. In the case of an intrusion scenario involving brine, the solubilization of actinides in brine is considered as a potential source of release to the accessible environment. The following key factors establish the concentrations of dissolved actinides under subsurface conditions: (1) Redox chemistry - The solubility of reduced actinides (III and IV oxidation states) is known to be significantly lower than the oxidized forms (V and/or VI oxidation states). In this context, the reducing conditions in the WIPP and the strong coupling of the chemistry for reduced metals and microbiological processes with actinides are important. (2) Complexation - For the anoxic, reducing and mildly basic brine systems in the WIPP, the most important

  7. Joint Actinide Shock Physics Experimental Research - JASPER

    ScienceCinema

    None

    2016-07-12

    Commonly known as JASPER the Joint Actinide Shock Physics Experimental Research facility is a two stage light gas gun used to study the behavior of plutonium and other materials under high pressures, temperatures, and strain rates.

  8. BWR Assembly Optimization for Minor Actinide Recycling

    SciTech Connect

    G. Ivan Maldonado; John M. Christenson; J.P. Renier; T.F. Marcille; J. Casal

    2010-03-22

    The Primary objective of the proposed project is to apply and extend the latest advancements in LWR fuel management optimization to the design of advanced boiling water reactor (BWR) fuel assemblies specifically for the recycling of minor actinides (MAs).

  9. Joint Actinide Shock Physics Experimental Research - JASPER

    SciTech Connect

    2014-10-31

    Commonly known as JASPER the Joint Actinide Shock Physics Experimental Research facility is a two stage light gas gun used to study the behavior of plutonium and other materials under high pressures, temperatures, and strain rates.

  10. Advanced Aqueous Separation Systems for Actinide Partitioning

    SciTech Connect

    Nash, Kenneth L.; Clark, Sue; Meier, G Patrick; Alexandratos, Spiro; Paine, Robert; Hancock, Robert; Ensor, Dale

    2012-03-21

    One of the most challenging aspects of advanced processing of spent nuclear fuel is the need to isolate transuranium elements from fission product lanthanides. This project expanded the scope of earlier investigations of americium (Am) partitioning from the lanthanides with the synthesis of new separations materials and a centralized focus on radiochemical characterization of the separation systems that could be developed based on these new materials. The primary objective of this program was to explore alternative materials for actinide separations and to link the design of new reagents for actinide separations to characterizations based on actinide chemistry. In the predominant trivalent oxidation state, the chemistry of lanthanides overlaps substantially with that of the trivalent actinides and their mutual separation is quite challenging.

  11. Preparation of actinide targets by electrodeposition

    NASA Astrophysics Data System (ADS)

    Trautmann, N.; Folger, H.

    1989-10-01

    Actinide targets with varying thicknesses on different substrates have been prepared by electrodeposition either from aqueous solutions or from solutions of their nitrates in isopropyl alcohol. With these techniques the actinides can be deposited almost quantitatively on various backing materials within 15 to 30 min. Targets of thorium, uranium, neptunium, plutonium, americium, curium and californium with areal densities from almost carrier-free up to 1.4 mg/cm 2 on thin beryllium, carbon, titanium, tantalum and platinum foils have been prepared. In most cases, prior to the deposition, the actinides had to be purified chemically and for some of them, due to the limited amount of material available, recycling procedures were required. Applications of actinide targets in heavy-ion reactions are briefly discussed.

  12. Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Mahaffy, P.; Niemann, Hasso (Technical Monitor)

    2001-01-01

    Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

  13. A refined sampling strategy for intra-tooth stable isotope analysis of mammalian enamel

    NASA Astrophysics Data System (ADS)

    Zazzo, A.; Bendrey, R.; Vella, D.; Moloney, A. P.; Monahan, F. J.; Schmidt, O.

    2012-05-01

    Serial sampling and stable isotope analysis performed along the growth axis of vertebrate tooth enamel records differences attributed to seasonal variation in diet, climate or animal movement. Because several months are required to obtain mature enamel in large mammals, modifications in the isotopic composition of environmental parameters are not instantaneously recorded, and stable isotope analysis of tooth enamel returns a time-averaged signal attenuated in its amplitude relative to the input signal. For convenience, stable isotope profiles are usually determined on the side of the tooth where enamel is thickest. Here we investigate the possibility of improving the time resolution by targeting the side of the tooth where enamel is thinnest. Observation of developing third molars (M3) in sheep shows that the tooth growth rate is not constant but decreases exponentially, while the angle between the first layer of enamel deposited and the enamel-dentine junction increases as a tooth approaches its maximal length. We also noted differences in thickness and geometry of enamel growth between the mesial side (i.e., the side facing the M2) and the buccal side (i.e., the side facing the cheek) of the M3. Carbon and oxygen isotope variations were measured along the M3 teeth from eight sheep raised under controlled conditions. Intra-tooth variability was systematically larger along the mesial side and the difference in amplitude between the two sides was proportional to the time of exposure to the input signal. Although attenuated, the mesial side records variations in the environmental signal more faithfully than the buccal side. This approach can be adapted to other mammals whose teeth show lateral variation in enamel thickness and could potentially be used as an internal check for diagenesis.

  14. Compound-specific carbon, nitrogen, and hydrogen isotope analysis of N-nitrosodimethylamine in aqueous solutions.

    PubMed

    Spahr, Stephanie; Bolotin, Jakov; Schleucher, Jürgen; Ehlers, Ina; von Gunten, Urs; Hofstetter, Thomas B

    2015-03-01

    Mitigation of N-nitrosodimethylamine (NDMA) and other hazardous water disinfection byproducts (DBP) is currently hampered by a limited understanding of DBP formation mechanisms. Because variations of the stable isotope composition of NDMA can potentially reveal reaction pathways and precursor compounds, we developed a method for the compound-specific isotope analysis (CSIA) of (13)C/(12)C, (15)N/(14)N, and (2)H/(1)H ratios of NDMA by gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS). Method quantification limits for the accurate isotope analysis of NDMA, N-nitrosodiethyl-, -dipropyl-, and -dibutylamine as well as N-nitrosopyrrolidine were between 0.18 to 0.60 nmol C, 0.40 to 0.80 nmol N, and 2.2 to 5.8 nmol H injected on column. Coupling solid phase extraction (SPE) to GC/IRMS enabled the precise quantification of C, N, and H isotope ratios of NDMA in aqueous samples at concentrations of 0.6 μM (45 μg L(-1)). We validated the proposed method with a laboratory experiment, in which NDMA was formed with stoichiometric yield (97 ± 4%) through chloramination of the pharmaceutical ranitidine (3 μM). δ(13)C and δ(2)H values of NDMA remained constant during NDMA formation while its δ(15)N increased due to a reaction at a N atom in the rate-limiting step of NDMA formation. The δ(2)H value of NDMA determined by SPE-GC/IRMS also corresponded well to the δ(2)H value of the N(CH3)2-group of ranitidine measured by quantitative deuterium nuclear magnetic resonance spectroscopy. This observation implies that the N(CH3)2-moiety of ranitidine is transferred to NDMA without being chemically altered and illustrates the accuracy of the proposed method.

  15. Technical Note: A simple method for vaterite precipitation in isotopic equilibrium: implications for bulk and clumped isotope analysis

    NASA Astrophysics Data System (ADS)

    Kluge, T.; John, C. M.

    2014-12-01

    Calcium carbonate (CaCO3) plays an important role in the natural environment as a major constituent of the skeleton and supporting structure of marine life and has high economic importance as additive in food, chemicals and medical products. Pure CaCO3 occurs in the three different polymorphs calcite, aragonite and vaterite, whereof calcite is the most abundant and best characterized mineral. In contrast, little is known about the rare polymorph vaterite, in particular with regard to the oxygen isotope fractionation between H2O and the mineral. Synthetic precipitation of vaterite in the laboratory typically involves rapid processes and isotopic non-equilibrium, which excludes isotope studies focused on characterization of vaterite at equilibrium conditions. Here, we used a new experimental approach that enables vaterite mineral formation from an isotopically equilibrated solution. The solution consists of a ~ 0.007 mol L-1 CaCO3 solution that is saturated with NaCl at room temperature (up to 6.5 mol L-1). Vaterite precipitated as single phase or major phase (≥ 94%) in experiments performed between 23 and 91 °C. Only at 80 °C was vaterite a minor phase with a relative abundance of 27%. The high mineral yield of up to 235 mg relative to a total dissolved CaCO3 amount of 370 mg enables an investigation of the oxygen isotope fractionation between mineral and water, and the determination of clumped isotope values in vaterite.

  16. PREPARATION OF ACTINIDE-ALUMINUM ALLOYS

    DOEpatents

    Moore, R.H.

    1962-09-01

    BS>A process is given for preparing alloys of aluminum with plutonium, uranium, and/or thorium by chlorinating actinide oxide dissolved in molten alkali metal chloride with hydrochloric acid, chlorine, and/or phosgene, adding aluminum metal, and passing air and/or water vapor through the mass. Actinide metal is formed and alloyed with the aluminum. After cooling to solidification, the alloy is separated from the salt. (AEC)

  17. Transmutation of actinides in power reactors.

    PubMed

    Bergelson, B R; Gerasimov, A S; Tikhomirov, G V

    2005-01-01

    Power reactors can be used for partial short-term transmutation of radwaste. This transmutation is beneficial in terms of subsequent storage conditions for spent fuel in long-term storage facilities. CANDU-type reactors can transmute the main minor actinides from two or three reactors of the VVER-1000 type. A VVER-1000-type reactor can operate in a self-service mode with transmutation of its own actinides.

  18. The Actinide Transition Revisited by Gutzwiller Approximation

    NASA Astrophysics Data System (ADS)

    Xu, Wenhu; Lanata, Nicola; Yao, Yongxin; Kotliar, Gabriel

    2015-03-01

    We revisit the problem of the actinide transition using the Gutzwiller approximation (GA) in combination with the local density approximation (LDA). In particular, we compute the equilibrium volumes of the actinide series and reproduce the abrupt change of density found experimentally near plutonium as a function of the atomic number. We discuss how this behavior relates with the electron correlations in the 5 f states, the lattice structure, and the spin-orbit interaction. Our results are in good agreement with the experiments.

  19. Transmutation of actinides in power reactors.

    PubMed

    Bergelson, B R; Gerasimov, A S; Tikhomirov, G V

    2005-01-01

    Power reactors can be used for partial short-term transmutation of radwaste. This transmutation is beneficial in terms of subsequent storage conditions for spent fuel in long-term storage facilities. CANDU-type reactors can transmute the main minor actinides from two or three reactors of the VVER-1000 type. A VVER-1000-type reactor can operate in a self-service mode with transmutation of its own actinides. PMID:16604724

  20. Entropy analysis of stable isotopes in precipitation: tracing the monsoon systems in China

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Chen, Jiansheng; Li, Ling

    2016-08-01

    Due to the complexity of monsoon systems and random behaviors of isotope tracers, conventional methods are not adequate for uncovering detailed information about monsoon activities from typically limited precipitation isotope data. We developed a new approach based on the entropy theory to analyze such data with a focus on the monsoon systems in China, dealing with the complexity of these systems and data deficiency. Using precipitation isotope data from 42 selected stations in and around China within the GNIP network, we computed entropies associated with D and 18O. These entropies were found to relate linearly to each other with a proportionality factor close to unity. The spatial variations of the D and 18O entropy in the study area revealed the origins, extents and pathways of the Chinese monsoon systems, as well as their interactions. While further investigation is needed at a greater (global) scale, this study has demonstrated how the entropy theory enables an in-depth analysis of precipitation isotope data to trace the pathway and determine the range of a monsoon system.

  1. Entropy analysis of stable isotopes in precipitation: tracing the monsoon systems in China

    PubMed Central

    Wang, Tao; Chen, Jiansheng; Li, Ling

    2016-01-01

    Due to the complexity of monsoon systems and random behaviors of isotope tracers, conventional methods are not adequate for uncovering detailed information about monsoon activities from typically limited precipitation isotope data. We developed a new approach based on the entropy theory to analyze such data with a focus on the monsoon systems in China, dealing with the complexity of these systems and data deficiency. Using precipitation isotope data from 42 selected stations in and around China within the GNIP network, we computed entropies associated with D and 18O. These entropies were found to relate linearly to each other with a proportionality factor close to unity. The spatial variations of the D and 18O entropy in the study area revealed the origins, extents and pathways of the Chinese monsoon systems, as well as their interactions. While further investigation is needed at a greater (global) scale, this study has demonstrated how the entropy theory enables an in-depth analysis of precipitation isotope data to trace the pathway and determine the range of a monsoon system. PMID:27507656

  2. Comparing evapotranspiration partitioning after different types of rain events using stable isotopes and lagrangian dispersion analysis

    NASA Astrophysics Data System (ADS)

    Hogan, Patrick; Parajka, Juraj

    2016-04-01

    The eddy covariance method has become one of the standard methods for measuring evapotranspiration (ET) at the field scale, however it cannot separate transpiration from evaporation and it is also limited within plant canopies due to distortion of the turbulent wind fields. Possible solutions to these limitations include combining EC measurements made above the canopy coupled with either source/sink distribution models or stable isotope ET partitioning models. During the summer of 2014 the concentration and isotopic ratio of water vapour within the canopy of a growing maize field at the Hydrological Open Air Laboratory (HOAL) catchment was measured using a Picarro field sampling device. A tripod mounted eddy covariance device was used to calculate the ET value for the field. The first objective of this experiment is to compare the ET partitioning results made using the stable isotope Keeling Plot method within a canopy to two different lagrangian dispersion analysis methods, the Localised Near Field theory of Raupach (1989a) and the Warland and Thurtell (2000) dispersion model. Preliminary results show good agreement during dry conditions with the dispersion methods overestimating the fraction of transpiration directly after a rain event. The second objective is then to analyse and compare the soil evaporation response for two different kinds of rain events using the stable isotope results.

  3. Entropy analysis of stable isotopes in precipitation: tracing the monsoon systems in China.

    PubMed

    Wang, Tao; Chen, Jiansheng; Li, Ling

    2016-01-01

    Due to the complexity of monsoon systems and random behaviors of isotope tracers, conventional methods are not adequate for uncovering detailed information about monsoon activities from typically limited precipitation isotope data. We developed a new approach based on the entropy theory to analyze such data with a focus on the monsoon systems in China, dealing with the complexity of these systems and data deficiency. Using precipitation isotope data from 42 selected stations in and around China within the GNIP network, we computed entropies associated with D and (18)O. These entropies were found to relate linearly to each other with a proportionality factor close to unity. The spatial variations of the D and (18)O entropy in the study area revealed the origins, extents and pathways of the Chinese monsoon systems, as well as their interactions. While further investigation is needed at a greater (global) scale, this study has demonstrated how the entropy theory enables an in-depth analysis of precipitation isotope data to trace the pathway and determine the range of a monsoon system. PMID:27507656

  4. Entropy analysis of stable isotopes in precipitation: tracing the monsoon systems in China.

    PubMed

    Wang, Tao; Chen, Jiansheng; Li, Ling

    2016-08-10

    Due to the complexity of monsoon systems and random behaviors of isotope tracers, conventional methods are not adequate for uncovering detailed information about monsoon activities from typically limited precipitation isotope data. We developed a new approach based on the entropy theory to analyze such data with a focus on the monsoon systems in China, dealing with the complexity of these systems and data deficiency. Using precipitation isotope data from 42 selected stations in and around China within the GNIP network, we computed entropies associated with D and (18)O. These entropies were found to relate linearly to each other with a proportionality factor close to unity. The spatial variations of the D and (18)O entropy in the study area revealed the origins, extents and pathways of the Chinese monsoon systems, as well as their interactions. While further investigation is needed at a greater (global) scale, this study has demonstrated how the entropy theory enables an in-depth analysis of precipitation isotope data to trace the pathway and determine the range of a monsoon system.

  5. Ancient bronze coins from Mediterranean basin: LAMQS potentiality for lead isotopes comparative analysis with former mineral

    NASA Astrophysics Data System (ADS)

    Torrisi, L.; Italiano, A.; Torrisi, A.

    2016-11-01

    Bronze coins coming from the area of the Mediterranean basin, dated back the II-X Cent. A.D., were analyzed using different physical analytical techniques. Characteristic X-ray fluorescence was used with electrons and photons, in order to investigate the elemental composition of both the surface layers and bulk. Moreover, the quadrupole mass spectrometry coupled to laser ablation (LAMQS technique) in high vacuum was used to analyse typical material compounds from surface contamination. Mass spectrometry, at high resolution and sensitivity, extended up to 300 amu, allowed measuring the 208Pb/206Pb and 207Pb/206Pb isotopic ratios into the coins. Quantitative relative analyses of these isotopic ratios identify the coin composition such as a "fingerprint" depending on the mineral used to extract the lead. Isotopic ratios in coins can be compared to those of the possible minerals used to produce the bronze alloy. A comparison between the measured isotope ratios in the analyzed coins and the literature database, related to the mineral containing Pb as a function of its geological and geophysical extraction mine, is presented. The analysis, restricted to old coins and the mines of the Mediterranean basin, indicates a possible correlation between the coin compositions and the possible geological sites of the extracted mineral.

  6. Source apportionment of aerosol iron in the marine environment using iron isotope analysis

    NASA Astrophysics Data System (ADS)

    Mead, Chris; Herckes, Pierre; Majestic, Brian J.; Anbar, Ariel D.

    2013-11-01

    (Fe) is a critical nutrient for phytoplankton. In the open ocean, this demand coupled with scarce supply often makes Fe the limiting factor in phytoplankton growth. The largest source, by mass, of Fe to the open ocean is windblown soil dust, but this Fe is much less soluble than Fe from other aerosol sources. Therefore, to fully understand how Fe reaches this ecosystem, it is necessary to understand the range of sources of aerosol Fe. To do this, we collected size-segregated aerosol samples from Bermuda and analyzed them to determine their Fe isotope composition. From this analysis, we found clear evidence in the fine size fraction (< 2.5 µm) of an important non-soil-dust Fe source. Our isotope analysis of multiple oil and coal fly ashes shows that those materials cannot explain our finding. We suggest biomass burning as the most likely source.

  7. Authentication of fishery and aquaculture products by multi-element and stable isotope analysis.

    PubMed

    Li, Li; Boyd, Claude E; Sun, Zhenlong

    2016-03-01

    The market of fishery and aquaculture products is globalized with increasing numbers of mislabeled products. This highlights the need for approaches to indentify the origin of these products. Among the measures used to identify the origin of other agro-products, multi-element and stable isotope analysis are promising approaches to identify the authenticity and traceability of fishery and aquaculture products. The present paper reviews the use of multi-element and stable isotope analysis to determine the origin of fishery and aquaculture products. Principles and limitations of each method will be illustrated and perspectives for traceability of fishery and aquaculture products will be discussed. The aim of this review is to mediate fundamental knowledge for the interpretation of experimental data on authentication of aquaculture products.

  8. Authentication of fishery and aquaculture products by multi-element and stable isotope analysis.

    PubMed

    Li, Li; Boyd, Claude E; Sun, Zhenlong

    2016-03-01

    The market of fishery and aquaculture products is globalized with increasing numbers of mislabeled products. This highlights the need for approaches to indentify the origin of these products. Among the measures used to identify the origin of other agro-products, multi-element and stable isotope analysis are promising approaches to identify the authenticity and traceability of fishery and aquaculture products. The present paper reviews the use of multi-element and stable isotope analysis to determine the origin of fishery and aquaculture products. Principles and limitations of each method will be illustrated and perspectives for traceability of fishery and aquaculture products will be discussed. The aim of this review is to mediate fundamental knowledge for the interpretation of experimental data on authentication of aquaculture products. PMID:26471677

  9. Gamma isotopic analysis of the coals and ashes from coal fired power plants of Turkey

    NASA Astrophysics Data System (ADS)

    Akyuz, T.; Varinlioglu, A.; Kose, A.

    1999-01-01

    Gamma-isotopic analysis of the ashes produced by the combustion of lignite in power stations of Turkey together with the parent coal samples was performed with the aim to estimate its potential adverse impacts on human health. Gamma-isotopic analysis indicated that all samples contained226Ra (coal samples: 89 148 Bq kg-1; ash samples: 15 26 Bq kg-1),238U (coal samples: 2 4 μg g-1; ash samples: 9 33 μg g-1),232Th (coal samples: 1 9 μg g-1; ash samples: 8 12μg g-1), and40K (coal samples: 26 67 Bq kg-1; ash samples: not detected).134Cs and137Cs have not been found in the samples.

  10. Gamma isotopic analysis of the coals and ashes from coal fired power plants of Turkey

    NASA Astrophysics Data System (ADS)

    Akyuz, T.; Varinlioglu, A.; Kose, A.

    1999-01-01

    Gamma-isotopic analysis of the ashes produced by the combustion of lignite in power stations of Turkey together with the parent coal samples was performed with the aim to estimate its potential adverse impacts on human health. Gamma-isotopic analysis indicated that all samples contained226Ra (coal samples: 89-148 Bq kg-1; ash samples: 15-26 Bq kg-1),238U (coal samples: 2-4 μg g-1; ash samples: 9-33 μg g-1),232Th (coal samples: 1-9 μg g-1; ash samples: 8-12μg g-1), and40K (coal samples: 26-67 Bq kg-1; ash samples: not detected).134Cs and137Cs have not been found in the samples.

  11. Actinide speciation in relation to biological processes.

    PubMed

    Ansoborlo, Eric; Prat, Odette; Moisy, Philippe; Den Auwer, Christophe; Guilbaud, Philippe; Carriere, M; Gouget, Barbara; Duffield, John; Doizi, Denis; Vercouter, Thomas; Moulin, Christophe; Moulin, Valérie

    2006-11-01

    In case of accidental release of radionuclides into the environment, actinides represent a severe health risk to human beings following internal contamination (inhalation, ingestion or wound). For a better understanding of the actinide behaviour in man (in term of metabolism, retention, excretion) and in specific biological systems (organs, cells or biochemical pathways), it is of prime importance to have a good knowledge of the relevant actinide solution chemistry and biochemistry, in particular of the thermodynamic constants needed for computing actinide speciation. To a large extent, speciation governs bioavailability and toxicity of elements and has a significant impact on the mechanisms by which toxics accumulate in cell compartments and organs and by which elements are transferred and transported from cell to cell. From another viewpoint, speciation is the prerequisite for the design and success of potential decorporation therapies. The purpose of this review is to present the state of the art of actinide knowledge within biological media. It is also to discuss how actinide speciation can be determined or predicted and to highlight the areas where information is lacking with the aim to encourage new research efforts.

  12. Recent progress in actinide borate chemistry

    SciTech Connect

    Wang, Shuao; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

    2011-01-01

    The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB₅O₆(OH)₆][BO(OH)₂]·2.5H₂O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO4- Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials.

  13. Recent progress in actinide borate chemistry.

    PubMed

    Wang, Shuao; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2011-10-21

    The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB(5)O(6)(OH)(6)][BO(OH)(2)]·2.5H(2)O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO(4)(-). Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials.

  14. Contrasting behavior of oxygen and iron isotopes in banded iron formation revealed by in situ analysis

    NASA Astrophysics Data System (ADS)

    Beard, B.; Li, W.; Kita, N.; Valley, J. W.; Johnson, C.

    2012-12-01

    Banded iron formations (BIFs) record a period of dramatic secular change in Earth's geologic history, when abundant aqueous Fe(II) was removed from Archean and Proterozoic oceans by oxidation. BIFs are characterized by co-existing of quartz and iron minerals, including oxides and carbonates, and alternating iron-rich and iron-poor layers range from m to isotope ratios in minerals in BIFs provide valuable information about the origin of BIFs, as well as diagenetic and metamorphic effects that were superimposed on primary layering. We analyzed O and Fe isotope compositions of magnetite and hematite in BIFs from the 2.5 Ga Dales Gorge Member of the Brockman Iron Formation, Hamersley Group, Western Australia. Oxygen isotope ratios were measured by Secondary Ion Mass Spectrometry (SIMS), and Fe isotope ratios were measured by femtosecond Laser ablation Multi-Collector ICP-MS (fs-LA-MC-ICP-MS), with spatial resolutions of 15 mm (O) and 30-50 mm (Fe), and external precisions (2s) of +0.7 ‰ for δ18O and +0.2 ‰ for δ56Fe, respectively. Analysis of δ18O in iron oxides by SIMS employed special tuning with a 3kV primary beam to minimize orientation effects (Huberty et al. 2010 ). For hematite, δ18O values range from -7.1 ‰ to -0.6 ‰, with the majority of data clustering around -4.5 ‰, and δ56Fe values range from -0.50 ‰ to +1.53‰. Magnetite has a δ18O range of -5.6 ‰ to +5.6 ‰ and a δ56Fe range of -0.76 ‰ to +1.33 ‰. Notably, magnetite shows significant O isotope heterogeneity at a mineral grain scale, and the highest δ18O values were commonly measured from Si-rich (1-3 wt% SiO2) magnetite overgrowths or magnetite grains that have a recrystallization texture. In contrast, lowest δ18O values were measured from magnetite that contains less than 1 wt% SiO2. Individual magnetite grains can have up to 6 ‰ variation in δ18O values between low-Si core and Si-rich overgrowth. Iron

  15. Evaluating gull diets: A comparison of conventional methods and stable isotope analysis

    USGS Publications Warehouse

    Weiser, E.L.; Powell, A.N.

    2011-01-01

    Samples such as regurgitated pellets and food remains have traditionally been used in studies of bird diets, but these can produce biased estimates depending on the digestibility of different foods. Stable isotope analysis has been developed as a method for assessing bird diets that is not biased by digestibility. These two methods may provide complementary or conflicting information on diets of birds, but are rarely compared directly. We analyzed carbon and nitrogen stable isotope ratios of feathers of Glaucous Gull (Larus hyperboreus) chicks from eight breeding colonies in northern Alaska, and used a Bayesian mixing model to generate a probability distribution for the contribution of each food group to diets. We compared these model results with probability distributions from conventional diet samples (pellets and food remains) from the same colonies and time periods. Relative to the stable isotope estimates, conventional analysis often overestimated the contributions of birds and small mammals to gull diets and often underestimated the contributions of fish and zooplankton. Both methods gave similar estimates for the contributions of scavenged caribou, miscellaneous marine foods, and garbage to diets. Pellets and food remains therefore may be useful for assessing the importance of garbage relative to certain other foods in diets of gulls and similar birds, but are clearly inappropriate for estimating the potential impact of gulls on birds, small mammals, or fish. However, conventional samples provide more species-level information than stable isotope analysis, so a combined approach would be most useful for diet analysis and assessing a predator's impact on particular prey groups. ?? 2011 Association of Field Ornithologists.

  16. Quantifying RDX biodegradation in groundwater using delta15N isotope analysis.

    PubMed

    Bernstein, Anat; Adar, Eilon; Ronen, Zeev; Lowag, Harald; Stichler, Willibald; Meckenstock, Rainer U

    2010-01-15

    Isotope analysis was used to examine the extent of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) biodegradation in groundwater along a ca. 1.35-km contamination plume. Biodegradation was proposed as a natural attenuating remediation method for the contaminated aquifer. By isotope analysis of RDX, the extent of biodegradation was found to reach up to 99.5% of the initial mass at a distance of 1.15-1.35km down gradient from the contamination sources. A range of first-order biodegradation rates was calculated based on the degradation extents, with average half-life values ranging between 4.4 and 12.8years for RDX biodegradation in the upper 15m of the aquifer, assuming purely aerobic biodegradation, and between 10.9 and 31.2years, assuming purely anaerobic biodegradation. Based on the geochemical data, an aerobic biodegradation pathway was suggested as the dominant attenuation process at the site. The calculated biodegradation rate was correlated with depth, showing decreasing degradation rates in deeper groundwater layers. Exceptionally low first-order kinetic constants were found in a borehole penetrating the bottom of the aquifer, with half life ranging between 85.0 to 161.5years, assuming purely aerobic biodegradation, and between 207.5 and 394.3years, assuming purely anaerobic biodegradation. The study showed that stable isotope fractionation analysis is a suitable tool to detect biodegradation of RDX in the environment. Our findings clearly indicated that RDX is naturally biodegraded in the contaminated aquifer. To the best of our knowledge, this is the first reported use of RDX isotope analysis to quantify its biodegradation in contaminated aquifers.

  17. Trace, isotopic analysis of micron-sized grains -- Mo, Zr analysis of stardust (SiC and graphite grains).

    SciTech Connect

    Pellin, M. J.; Nicolussi, G. K.

    1998-02-19

    Secondary Neutral Mass Spectrometry using resonant laser ionization can provide for both high useful yields and high discrimination while maintaining high lateral and depth resolutions. An example of the power of the method is measurement of the isotopic composition of Mo and Zr in 1-5 {micro}m presolar SiC and graphite grains isolated from the Murchison CM2 meteorite for the first time. These grains have survived the formation of the Solar System and isotopic analysis reveals a record of the stellar nucleosynthesis present during their formation. Mo and Zr, though present at less than 10 ppm in some grains, are particularly useful in that among their isotopes are members that can only be formed by distinct nucleosynthetic processes known as s-, p-, and r-process. Successful isotopic analysis of these elements requires both high selectivity (since these are trace elements) and high efficiency (since the total number of atoms available are limited). Resonant Ionization Spectroscopy is particularly useful and flexible in this application. While the sensitivity of this t.edmique has often been reported in the past, we focus hereon the very low noise properties of the technique. We further demonstrate the efficacy of noise removal by two complimentary methods. First we use the resonant nature of the signal to subtract background signal. Second we demonstrate that by choosing the appropriate resonance scheme background can often be dramatically reduced.

  18. Performance Comparison of Metallic, Actinide Burning Fuel in Lead-Bismuth and Sodium Cooled Fast Reactors

    SciTech Connect

    Weaver, Kevan Dean; Herring, James Stephen; Mac Donald, Philip Elsworth

    2001-04-01

    Various methods have been proposed to “incinerate” or “transmutate” the current inventory of trans-uranic waste (TRU) that exits in spent light-water-reactor (LWR) fuel, and weapons plutonium. These methods include both critical (e.g., fast reactors) and non-critical (e.g., accelerator transmutation) systems. The work discussed here is part of a larger effort at the Idaho National Engineering and Environmental Laboratory (INEEL) and at the Massachusetts Institute of Technology (MIT) to investigate the suitability of lead and lead-alloy cooled fast reactors for producing low-cost electricity as well as for actinide burning. The neutronics of non-fertile fuel loaded with 20 or 30-wt% light water reactor (LWR) plutonium plus minor actinides for use in a lead-bismuth cooled fast reactor are discussed in this paper, with an emphasis on the fuel cycle life and isotopic content. Calculations show that the average actinide burn rate is similar for both the sodium and lead-bismuth cooled cases ranging from -1.02 to -1.16 g/MWd, compared to a typical LWR actinide generation rate of 0.303 g/MWd. However, when using the same parameters, the sodium-cooled case went subcritical after 0.2 to 0.8 effective full power years, and the lead-bismuth cooled case ranged from 1.5 to 4.5 effective full power years.

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  20. Stable carbon isotope analysis in a South Texas cave: Investigating sources of CO2 production

    NASA Astrophysics Data System (ADS)

    Thompson, Reece

    Studies of interactions between modern local climate, cave atmosphere, and ?13C ratios are needed to determine sources of CO2 in caves, and the cycles of seasonal variations that alter karst geochemistry. A seasonal study, focusing on the analysis of stable isotopes collected from a modern cave system, was conducted in Robber Baron Cave (RBC) in order to identify sources of CO2 in its atmosphere. Determining what conditions affect cave morphology and the transfer path of carbon through a cave system is necessary in order to assess the role of caves in the carbon cycle and correctly interpret past ecological changes. This study investigates the extent that stable isotopic values of carbon in CO2 are affected by CO2 sourced from soils, bedrock, atmospheric air, and vegetation, and how ?13C signals are transmitted in a modern cave system. This study also measures how ventilation affects CO2 concentration and ?13C on seasonal scales. In-cave air grab samples were collected monthly at various transects located in RBC in order to measure CO2 composition in addition to factors such as temperature, and barometric pressure. Soil gas and limestone bedrock were also collected and tested for ?13C composition. Air samples were analyzed using an Ambient Air-Model G2101-I Picarro Cavity Ring-Down Spectroscopy Analyzer for both the concentration and ?13C isotopic value of CO2. These values were then compared to isotopic values of known sources of CO2 in order to determine possible sources of CO2 that result in high CO2 concentrations found in RBC. The background stable isotopic value of carbon from CO2 measured in RBC is -19.1‰ VPDB.

  1. Tracing fetal and childhood exposure to lead using isotope analysis of deciduous teeth.

    PubMed

    Shepherd, Thomas J; Dirks, Wendy; Roberts, Nick M W; Patel, Jaiminkumar G; Hodgson, Susan; Pless-Mulloli, Tanja; Walton, Pamela; Parrish, Randall R

    2016-04-01

    We report progress in using the isotopic composition and concentration of Pb in the dentine and enamel of deciduous teeth to provide a high resolution time frame of exposure to Pb during fetal development and early childhood. Isotope measurements (total Pb and (208)Pb/(206)Pb, (207)Pb/(206)Pb ratios) were acquired by laser ablation inductively coupled mass spectrometry at contiguous 100 micron intervals across thin sections of the teeth; from the outer enamel surface to the pulp cavity. Teeth samples (n=10) were selected from two cohorts of children, aged 5-8 years, living in NE England. By integrating the isotope data with histological analysis of the teeth, using the daily incremental lines in dentine, we were able to assign true estimated ages to each ablation point (first 2-3 years for molars, first 1-2 years for incisors+pre-natal growth). Significant differences were observed in the isotope composition and concentration of Pb between children, reflecting differences in the timing and sources of exposure during early childhood. Those born in 2000, after the withdrawal of leaded petrol in 1999, have the lowest dentine Pb levels (<0.2µgPb/g) with (208)Pb/(206)Pb (mean ±2σ: 2.126-2.079) (208)Pb/(206)Pb (mean ±2σ: 0.879-0.856) ratios that correlate very closely with modern day Western European industrial aerosols (PM10, PM2.5) suggesting that diffuse airborne pollution was probably the primary source and exposure pathway. Legacy lead, if present, is insignificant. For those born in 1997, dentine lead levels are typically higher (>0.4µgPb/g) with (208)Pb/(206)Pb (mean ±2σ: 2.145-2.117) (208)Pb/(206)Pb (mean ±2σ: 0.898-0.882) ratios that can be modelled as a binary mix between industrial aerosols and leaded petrol emissions. Short duration, high intensity exposure events (1-2 months) were readily identified, together with evidence that dentine provides a good proxy for childhood changes in the isotope composition of blood Pb. Our pilot study confirms that

  2. Tracing fetal and childhood exposure to lead using isotope analysis of deciduous teeth.

    PubMed

    Shepherd, Thomas J; Dirks, Wendy; Roberts, Nick M W; Patel, Jaiminkumar G; Hodgson, Susan; Pless-Mulloli, Tanja; Walton, Pamela; Parrish, Randall R

    2016-04-01

    We report progress in using the isotopic composition and concentration of Pb in the dentine and enamel of deciduous teeth to provide a high resolution time frame of exposure to Pb during fetal development and early childhood. Isotope measurements (total Pb and (208)Pb/(206)Pb, (207)Pb/(206)Pb ratios) were acquired by laser ablation inductively coupled mass spectrometry at contiguous 100 micron intervals across thin sections of the teeth; from the outer enamel surface to the pulp cavity. Teeth samples (n=10) were selected from two cohorts of children, aged 5-8 years, living in NE England. By integrating the isotope data with histological analysis of the teeth, using the daily incremental lines in dentine, we were able to assign true estimated ages to each ablation point (first 2-3 years for molars, first 1-2 years for incisors+pre-natal growth). Significant differences were observed in the isotope composition and concentration of Pb between children, reflecting differences in the timing and sources of exposure during early childhood. Those born in 2000, after the withdrawal of leaded petrol in 1999, have the lowest dentine Pb levels (<0.2µgPb/g) with (208)Pb/(206)Pb (mean ±2σ: 2.126-2.079) (208)Pb/(206)Pb (mean ±2σ: 0.879-0.856) ratios that correlate very closely with modern day Western European industrial aerosols (PM10, PM2.5) suggesting that diffuse airborne pollution was probably the primary source and exposure pathway. Legacy lead, if present, is insignificant. For those born in 1997, dentine lead levels are typically higher (>0.4µgPb/g) with (208)Pb/(206)Pb (mean ±2σ: 2.145-2.117) (208)Pb/(206)Pb (mean ±2σ: 0.898-0.882) ratios that can be modelled as a binary mix between industrial aerosols and leaded petrol emissions. Short duration, high intensity exposure events (1-2 months) were readily identified, together with evidence that dentine provides a good proxy for childhood changes in the isotope composition of blood Pb. Our pilot study confirms that

  3. An application of nitrogen microwave-induced plasma mass spectrometry to isotope dilution analysis of selenium in marine organisms.

    PubMed

    Shirasaki, T; Yoshinaga, J; Morita, M; Okumoto, T; Oishi, K

    1996-01-01

    Nitrogen microwave-induced plasma mass spectrometry was studied for its applicability to the isotope dilution analysis of selenium in biological samples. Spectroscopic interference by calcium, which is present in high concentrations in biological samples, was investigated. No detectable background spectrum was observed for the major selenium isotopes of 78Se and 80Se. No detectable interferences by sodium, potassium, calcium and phosphorus on the isotope ratio 80Se/78Se were observed up to concentration of 200 mg/ml. The method was applied to the analysis of selenium in biological reference materials of marine organisms. The results showed good agreement between the certified and found values. PMID:8848792

  4. Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective.

    PubMed

    Wu, Q-Y; Lan, J-H; Wang, C-Z; Cheng, Z-P; Chai, Z-F; Gibson, J K; Shi, W-Q

    2016-02-21

    Recently, the +2 formal oxidation state in soluble molecular complexes for lanthanides (La-Nd, Sm-Lu) and actinides (Th and U) has been discovered [W. J. Evans, et al., J. Am. Chem. Soc., 2011, 133, 15914; J. Am. Chem. Soc., 2012, 134, 8420; J. Am. Chem. Soc., 2013, 135, 13310; Chem. Sci., 2015, 6, 517]. To explore the nature of the bonding and stabilities of the low-valent actinide complexes, a series of divalent actinide species, [AnCp'3](-) (An[double bond, length as m-dash]Th-Am, Cp' = [η(5)-C5H4(SiMe3)](-)) have been investigated in THF solution using scalar relativistic density functional theory. The electronic structures and electron affinity properties were systematically studied to identify the interactions between the +2 actinide ions and Cp' ligands. The ground state electron configurations for the [AnCp'3](-) species are [ThCp'3](-) 6d(2), [PaCp'3](-) 5f(2)6d(1), [UCp'3](-) 5f(3)6d(1), [NpCp'3](-) 5f(5), [PuCp'3](-) 5f(6), and [AmCp'3](-) 5f(7), respectively, according to the MO analysis. The total bonding energy decreases from the Th- to the Am-complex and the electrostatic interactions mainly dominate the bonding between the actinide atom and ligands. The electron affinity analysis suggests that the reduction reaction of AnCp'3→ [AnCp'3](-) should become increasingly facile across the actinide series from Th to Am, in accord with the known An(iii/ii) reduction potentials. This work expands the knowledge on the low oxidation state chemistry of actinides, and further motivates and guides the synthesis of related low oxidation state compounds of 5f elements.

  5. Examination of the kinetic isotopic effect to the acetylation derivatization for the gas chromatographic-combustion-isotope ratio mass spectrometric doping control analysis of endogenous steroids.

    PubMed

    Angelis, Yiannis S; Kioussi, Maroula K; Kiousi, Polyxeni; Brenna, J Thomas; Georgakopoulos, Costas G

    2012-12-01

    In gas chromatographic-combustion-isotope ratio mass spectrometry (GC-C-IRMS) doping control analysis, endogenous androgenic anabolic steroids and their metabolites are commonly acetylated using acetic anhydride reagent, thus incorporating exogenous carbon that contributes to the measured isotope ratio. Comparison of the endogenous δ(13)C of free, mono-, and di-acetylated steroids requires application of corrections, typically through straightforward use of the mass balance equation. Variability in kinetic isotope effects (KIE) due to steroid structures could cause fractionation of endogenous steroid carbon, resulting in inaccurate results. To test for possible KIE influence on δ(13)C, acetic anhydride of graded isotope ratio within the natural abundance range was used under normal derivatization conditions to test for linearity. In all cases, plots of measured steroid acetate δ(13)C versus acetic anhydride δ(13)C were linear and slopes were not significantly different. Regression analysis of the Δδ(13)C of enriched acetic anhydrides versus Δδ(13)C of derivatized steroids shows that KIE are similar in all cases. We conclude that δ(13)C calculated from the mass balance equation is independent of the δ(13)C of the acetic anhydride reagent, and that net KIE under normal derivatization conditions do not bias the final reported steroid δ(13)C.

  6. Congener-specific carbon isotopic analysis of technical PCB and PCN mixtures using two-dimensional gas chromatography-isotope ratio mass spectrometry.

    PubMed

    Horii, Yuichi; Kannan, Kurunthachalam; Petrick, Gert; Gamo, Toshitaka; Falandysz, Jerzy; Yamashita, Nobuyoshi

    2005-06-01

    Analysis of stable carbon isotope fractionation is a useful method to study the sources and fate of anthropogenic organic contaminants such as polychlorinated biphenyls (PCBs) in the environment. To evaluate the utility of carbon isotopes, determination of isotopic ratios of 13C/12C in source materials, for example, technical PCB preparations, is needed. In this study, we determined delta13C values of 31 chlorobiphenyl (CB) congeners in 18 technical PCB preparations and 15 chloronaphthalene (CN) congeners in 6 polychlorinated naphthalene preparations using two-dimensional gas chromatography-combustion furnace-isotope ratio mass spectrometry (2DGC-C-IRMS). Development of 2DGC-IRMS enabled improved resolution and sensitivity of compound-specific carbon isotope analysis (CSIA) of CB or CN congeners. Delta13C values of PCB congeners ranged from -34.4 (Delors) to -22.0/1000 (Sovol). Analogous PCB preparations with similar chlorine content, but different geographical origin, had different delta13C values. PCB preparations from Eastern European countries--Delors, Sovol, Trichlorodiphenyl, and Chlorofen--had distinct delta13C values. PCB mixtures showed increased 13C depletion with increasing chlorine content. Delta13C values for individual CB congeners varied depending on the degree of chlorination in technical mixtures. Delta13C values of CN congeners in Halowaxes ranged from -26.3 to -21.7/1000 and these values are within the ranges observed for PCBs. This study establishes the range of delta13C values in technical PCB and PCN preparations, which may prove to be useful in the determination of sources of these compounds in the environment. This is the first study to employ 2DGC-IRMS analysis of delta13C values in technical PCB and PCN preparations.

  7. Stable isotopic analysis of pyrogenic organic matter in soils by liquid chromatography-isotope-ratio mass spectrometry of benzene polycarboxylic acids.

    PubMed

    Yarnes, Christopher; Santos, Fernanda; Singh, Nimisha; Abiven, Samuel; Schmidt, Michael W I; Bird, Jeffrey A

    2011-12-30

    Pyrogenic organic matter (PyOM), the incomplete combustion product of organic materials, is considered stable in soils and represents a potentially important terrestrial sink for atmospheric carbon dioxide. One well-established method of measuring PyOM in the environment is as benzene polycarboxylic acids (BPCAs), a compound-specific method, which allows both qualitative and quantitative estimation of PyOM. Until now, stable isotope measurement of PyOM carbon involved measurement of the trimethylsilyl (TMS) or methyl (Me) polycarboxylic acid derivatives by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). However, BPCA derivatives can contain as much as 150% derivative carbon, necessitating post-analysis correction for the accurate measurement of δ¹³C values, leading to increased measurement error. Here, we describe a method for δ¹³C isotope ratio measurement and quantification of BPCAs from soil-derived PyOM, based on ion-exchange chromatography (IEC-IRMS). The reproducibility of the δ¹³C measurement of individual BPCAs by IEC-IRMS was better than 0.35‰ (1σ). The δ¹³C-BPCA analysis of PyOM in soils, including at natural and artificially enriched ¹³C-abundance, produced accurate and precise δ¹³C measurements. Analysis of samples that differed in δ¹³C by as much as 900‰ revealed carryover of <1‰ between samples. The weighted sum of individual δ¹³C-BPCA measurements was correlated with previous isotopic measurements of whole PyOM, providing complementary information for bulk isotopic measurements. We discuss potential applications of δ¹³C-BPCA measurements, including the study of turnover rates of PyOM in soils and the partitioning of PyOM sources based on photosynthetic pathways. PMID:22468329

  8. Neutron-Induced Fission Cross Section Measurements for Full Suite of Uranium Isotopes

    NASA Astrophysics Data System (ADS)

    Laptev, Alexander; Tovesson, Fredrik; Hill, Tony

    2010-11-01

    A well established program of neutron-induced fission cross section measurement at Los Alamos Neutron Science Center (LANSCE) is supporting the Fuel Cycle Research program (FC R&D). The incident neutron energy range spans energies from sub-thermal energies up to 200 MeV by measuring both the Lujan Center and the Weapons Neutron Research center (WNR). Conventional parallel-plate fission ionization chambers with actinide deposited foils are used as a fission detector. The time-of-flight method is implemented to measure neutron energy. Counting rate ratio from investigated and standard U-235 foils is translated into fission cross section ratio. Different methods of normalization for measured ratio are employed, namely, using of actinide deposit thicknesses, normalization to evaluated data, etc. Finally, ratios are converted to cross sections based on the standard U-235 fission cross section data file. Preliminary data for newly investigated isotopes U-236 and U-234 will be reported. Those new data complete a full suite of Uranium isotopes, which were investigated with presented experimental approach. When analysis of the new measured data will is completed, data will be delivered to evaluators. Having data for full set of Uranium isotopes will increase theoretical modeling capabilities and make new data evaluations much more reliable.

  9. Technical Note: A simple method for vaterite precipitation for isotopic studies: implications for bulk and clumped isotope analysis

    NASA Astrophysics Data System (ADS)

    Kluge, T.; John, C. M.

    2015-06-01

    Calcium carbonate (CaCO3) plays an important role in the natural environment as a major constituent of the skeleton and supporting structure of marine life and has high economic importance as an additive in food, chemicals and medical products. Anhydrous CaCO3 occurs in the three different polymorphs calcite, aragonite and vaterite, whereof calcite is the most abundant and best characterized mineral. In contrast, little is known about the rare polymorph vaterite, in particular with regard to the oxygen isotope fractionation between H2O and the mineral. Synthetic precipitation of vaterite in the laboratory typically involves rapid processes and isotopic non-equilibrium, which excludes isotope studies focused on the characterization of vaterite under equilibrium conditions. Here, we used a new experimental approach that enables vaterite mineral formation from an isotopically equilibrated solution. The solution consists of a ~0.007 mol L-1 CaCO3 solution that is saturated with NaCl at room temperature (up to 6.4 mol L-1). Vaterite precipitated as single phase or major phase (≥94%) in experiments performed between 23 and 91 °C. Only at 80 °C was vaterite a minor phase with a relative abundance of 27%. The high mineral yield per experiment of up to 235 mg relative to the initially dissolved CaCO3 amount of on average 360 mg enables an investigation of the oxygen isotope fractionation between the mineral and water, and the determination of clumped isotope values in vaterite.

  10. Automated CO2 extraction from air for clumped isotope analysis in the atmo- and biosphere

    NASA Astrophysics Data System (ADS)

    Hofmann, Magdalena; Ziegler, Martin; Pons, Thijs; Lourens, Lucas; Röckmann, Thomas

    2015-04-01

    The conventional stable isotope ratios 13C/12C and 18O/16O in atmospheric CO2 are a powerful tool for unraveling the global carbon cycle. In recent years, it has been suggested that the abundance of the very rare isotopologue 13C18O16O on m/z 47 might be a promising tracer to complement conventional stable isotope analysis of atmospheric CO2 [Affek and Eiler, 2006; Affek et al. 2007; Eiler and Schauble, 2004; Yeung et al., 2009]. Here we present an automated analytical system that is designed for clumped isotope analysis of atmo- and biospheric CO2. The carbon dioxide gas is quantitatively extracted from about 1.5L of air (ATP). The automated stainless steel extraction and purification line consists of three main components: (i) a drying unit (a magnesium perchlorate unit and a cryogenic water trap), (ii) two CO2 traps cooled with liquid nitrogen [Werner et al., 2001] and (iii) a GC column packed with Porapak Q that can be cooled with liquid nitrogen to -30°C during purification and heated up to 230°C in-between two extraction runs. After CO2 extraction and purification, the CO2 is automatically transferred to the mass spectrometer. Mass spectrometric analysis of the 13C18O16O abundance is carried out in dual inlet mode on a MAT 253 mass spectrometer. Each analysis generally consists of 80 change-over-cycles. Three additional Faraday cups were added to the mass spectrometer for simultaneous analysis of the mass-to-charge ratios 44, 45, 46, 47, 48 and 49. The reproducibility for δ13C, δ18O and Δ47 for repeated CO2 extractions from air is in the range of 0.11o (SD), 0.18o (SD) and 0.02 (SD)o respectively. This automated CO2 extraction and purification system will be used to analyse the clumped isotopic signature in atmospheric CO2 (tall tower, Cabauw, Netherlands) and to study the clumped isotopic fractionation during photosynthesis (leaf chamber experiments) and soil respiration. References Affek, H. P., Xu, X. & Eiler, J. M., Geochim. Cosmochim. Acta 71, 5033

  11. Recent developments in stable isotope dilution assays in mycotoxin analysis with special regard to Alternaria toxins.

    PubMed

    Asam, Stefan; Rychlik, Michael

    2015-10-01

    Stable isotope dilution assays (SIDAs) are becoming ever commoner in mycotoxin analysis, and the number of synthesized or commercially available isotopically labelled compounds has greatly increased in the 7 years since our last review dealing with this topic. Thus, this review is conceived as an update for new applications or improvements of SIDAs for compounds discussed earlier, but the main focus is on newly introduced labelled substances and the development of SIDAs for, for example, fusarin C, moniliformin or the enniatins. Mycotoxin research has concentrated on the emerging group of Alternaria toxins in recent years, and a series of SIDAs have been developed, including ones for tenuazonic acid, alternariol, altertoxins and tentoxin that are discussed in detail in this review. Information about synthetic routes, isotopic purity and mass-spectrometric characterization of labelled compounds is given, as well as about the development and validation of SIDAs and their application to foods, feeds or biological samples. As the number of commercially available labelled standards is increasing continuously, a general tendency for the use of analytical methods based on liquid chromatography coupled with mass spectrometry capable of identifying a series of mycotoxins simultaneously ("multimethods") and using one or more labelled internal standards can be observed. An overview of these applications is given, thus demonstrating that SIDAs are increasingly being used in routine analysis.

  12. A rapid method for the sampling of atmospheric water vapour for isotopic analysis.

    PubMed

    Peters, Leon I; Yakir, Dan

    2010-01-01

    Analysis of the stable isotopic composition of atmospheric moisture is widely applied in the environmental sciences. Traditional methods for obtaining isotopic compositional data from ambient moisture have required complicated sampling procedures, expensive and sophisticated distillation lines, hazardous consumables, and lengthy treatments prior to analysis. Newer laser-based techniques are expensive and usually not suitable for large-scale field campaigns, especially in cases where access to mains power is not feasible or high spatial coverage is required. Here we outline the construction and usage of a novel vapour-sampling system based on a battery-operated Stirling cycle cooler, which is simple to operate, does not require any consumables, or post-collection distillation, and is light-weight and highly portable. We demonstrate the ability of this system to reproduce delta(18)O isotopic compositions of ambient water vapour, with samples taken simultaneously by a traditional cryogenic collection technique. Samples were collected over 1 h directly into autosampler vials and were analysed by mass spectrometry after pyrolysis of 1 microL aliquots to CO. This yielded an average error of < +/-0.5 per thousand, approximately equal to the signal-to-noise ratio of traditional approaches. This new system provides a rapid and reliable alternative to conventional cryogenic techniques, particularly in cases requiring high sample throughput or where access to distillation lines, slurry maintenance or mains power is not feasible. PMID:19960497

  13. Diffusion sampler for compound specific carbon isotope analysis of dissolved hydrocarbon contaminants.

    PubMed

    Passeport, Elodie; Landis, Richard; Mundle, Scott O C; Chu, Katrina; Mack, E Erin; Lutz, Edward; Lollar, Barbara Sherwood

    2014-08-19

    Compound Specific Isotope Analysis (CSIA) is widely utilized to study the fate of organic contaminants in groundwater. To date, however, no method is available to obtain CSIA samples at a fine (cm) spatial scale across the sediment-surface water interface (SWI), a key boundary for discharge of contaminated groundwater to surface water. Dissolved contaminants in such discharged zones undergo rapid temporal and spatial changes due to heterogeneity in redox conditions and microbial populations. The compatibility of a passive sediment pore water sampler ("peeper") to collect 40 mL samples for CSIA of benzene, toluene, monochlorobenzene, and 1,2-dichlorobenzene at field-relevant concentrations (0.1-5 mg L(-1)) was evaluated in laboratory experiments. Results demonstrate that physical diffusion across the polysulfone membrane does not alter the carbon isotope values (±0.5‰). Measured δ(13)C values also remain invariant despite significant adsorption of the compounds on the peeper material, an effect which increased with higher numbers of chlorine atoms and sorption coefficient (Koc) values. In addition, isotope equilibrium between the peeper chamber and the sediment pore water occurred in less than a day, indicating the peeper method can be used to provide samples for CSIA analysis at fine spatial and temporal sampling resolutions in contaminated sediments. PMID:25058598

  14. Compound-specific carbon isotope analysis of a contaminant plume in Kingsford, Michigan, USA

    USGS Publications Warehouse

    Michel, R.L.; Silva, S.R.; Bemis, B.; Godsy, E.M.; Warren, E.

    2001-01-01

    Compound-specific isotope analysis was used to study a contaminated site near Kingsford, Michigan, USA. Organic compounds at three of the sites studied had similar ??13C values indicating that the contaminant source is the same for all sites. At a fourth site, chemical and ??13C values had evolved due to microbial degradation of organics, with the ??13C being much heavier than the starting materials. A microcosm experiment was run to observe isotopic changes with time in the methane evolved and in compounds remaining in the water during degradation. The ??13C values of the methane became heavier during the initial period of the run when volatile fatty acids were being consumed. There was an abrupt decrease in the ??13C values when fatty acids had been consumed and phenols began to be utilized. The ??13C value of the propionate remaining in solution also increased, similar to the results found in the field.

  15. INTERACTION BETWEEN INLAND AND SEA THROUGH RAUSU RIVER USING ISOTOPE ANALYSIS

    NASA Astrophysics Data System (ADS)

    Aynur, Abliz; Nakayama, Keisuke; Maruya, Yasuyuki; Kuwae, Tomohiro; Okada, Tomonari; Ishida, Tetsuya

    The Shiretoko is a pennusla where a unique interaction occurs between the terrestrial and oceanic systems, which are linked by nutrient exchange processes. Nutrient rich floating sea ice is transported to the coast from the Okhotsk Sea and salmon and trout move upstream and feed inland animals, such as bears and birds. Conversely, nutrients flow into the ocean through rivers. It has been reported that this unique nutrient circulation is being disrupted by climate change and it is thus important to understand what mechanisms drive nutrient circulation in Shiretoko and maintain a unique ecological system. In this study, stable isotope analysis is used in combination to determine the contribution of land-derived (LDN) and marine-derived nutrients (MDN) in the Rausu River basin. Stable isotopes ratios, δ13C and δ15N, show a higher contribution of MDN before the snow-melt floods, and that MDN are distributed largely in the downstream region of the basin.

  16. Preparative separation of underivatized amino acids for compound-specific stable isotope analysis and radiocarbon dating of hydrolyzed bone collagen.

    PubMed

    Tripp, Jennifer A; McCullagh, James S O; Hedges, Robert E M

    2006-01-01

    Analysis of stable and radioactive isotopes from bone collagen provides useful information to archaeologists about the origin and age of bone artifacts. Isolation and analysis of single amino acids from the proteins can provide additional and more accurate information by removing contamination and separating a bulk isotope signal into its constituent parts. In this paper, we report a new method for the separation and isolation of underivatized amino acids from bone collagen, and their analysis by isotope ratio MS and accelerator MS. RP chromatography is used to separate the amino acids with nonpolar side chains, followed by an ion pair separation to isolate the remaining amino acids. The method produces single amino acids with little or no contamination from the separation process and allows for the measurement of accurate stable isotope ratios and pure samples for radiocarbon dating.

  17. Determination of Atto- to Femtogram Levels of Americium and Curium Isotopes in Large-Volume Urine Samples by Compact Accelerator Mass Spectrometry.

    PubMed

    Dai, Xiongxin; Christl, Marcus; Kramer-Tremblay, Sheila; Synal, Hans-Arno

    2016-03-01

    Ultralow level analysis of actinides in urine samples may be required for dose assessment in the event of internal exposures to these radionuclides at nuclear facilities and nuclear power plants. A new bioassay method for analysis of sub-femtogram levels of Am and Cm in large-volume urine samples was developed. Americium and curium were co-precipitated with hydrous titanium oxide from the urine matrix and purified by column chromatography separation. After target preparation using mixed titanium/iron oxides, the final sample was measured by compact accelerator mass spectrometry. Urine samples spiked with known quantities of Am and Cm isotopes in the range of attogram to femtogram levels were measured for method evaluation. The results are in good agreement with the expected values, demonstrating the feasibility of compact accelerator mass spectrometry (AMS) for the determination of minor actinides at the levels of attogram/liter in urine samples to meet stringent sensitivity requirements for internal dosimetry assessment. PMID:26822907

  18. Stable-isotope dilution LC–MS for quantitative biomarker analysis

    PubMed Central

    Ciccimaro, Eugene; Blair, Ian A

    2010-01-01

    The ability to conduct validated analyses of biomarkers is critically important in order to establish the sensitivity and selectivity of the biomarker in identifying a particular disease. The use of stable-isotope dilution (SID) methodology in combination with LC–MS/MS provides the highest possible analytical specificity for quantitative determinations. This methodology is now widely used in the discovery and validation of putative exposure and disease biomarkers. This review will describe the application of SID LC–MS methodology for the analysis of small-molecule and protein biomarkers. It will also discuss potential future directions for the use of this methodology for rigorous biomarker analysis. PMID:20352077

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

    PubMed

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

    2013-03-01

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

  20. Actinide production in /sup 136/Xe bombardments of /sup 249/Cf

    SciTech Connect

    Gregorich, K.E.

    1985-08-01

    The production cross sections for the actinide products from /sup 136/Xe bombardments of /sup 249/Cf at energies 1.02, 1.09, and 1.16 times the Coulomb barrier were determined. Fractions of the individual actinide elements were chemically separated from recoil catcher foils. The production cross sections of the actinide products were determined by measuring the radiations emitted from the nuclides within the chemical fractions. The chemical separation techniques used in this work are described in detail, and a description of the data analysis procedure is included. The actinide production cross section distributions from these /sup 136/Xe + /sup 249/Cf bombardments are compared with the production cross section distributions from other heavy ion bombardments of actinide targets, with emphasis on the comparison with the /sup 136/Xe + /sup 248/Cm reaction. A technique for modeling the final actinide cross section distributions has been developed and is presented. In this model, the initial (before deexcitation) cross section distribution with respect to the separation energy of a dinuclear complex and with respect to the Z of the target-like fragment is given by an empirical procedure. It is then assumed that the N/Z equilibration in the dinuclear complex occurs by the transfer of neutrons between the two participants in the dinuclear complex. The neutrons and the excitation energy are statistically distributed between the two fragments using a simple Fermi gas level density formalism. The resulting target-like fragment initial cross section distribution with respect to Z, N, and excitation energy is then allowed to deexcite by emission of neutrons in competition with fission. The result is a final cross section distribution with respect to Z and N for the actinide products. 68 refs., 33 figs., 6 tabs.

  1. Quantum Chemical Studies of Actinides and Lanthanides: From Small Molecules to Nanoclusters

    NASA Astrophysics Data System (ADS)

    Vlaisavljevich, Bess

    Research into actinides is of high interest because of their potential applications as an energy source and for the environmental implications therein. Global concern has arisen since the development of the actinide concept in the 1940s led to the industrial scale use of the commercial nuclear energy cycle and nuclear weapons production. Large quantities of waste have been generated from these processes inspiring efforts to address fundamental questions in actinide science. In this regard, the objective of this work is to use theory to provide insight and predictions into actinide chemistry, where experimental work is extremely challenging because of the intrinsic difficulties of the experiments themselves and the safety issues associated with this type of chemistry. This thesis is a collection of theoretical studies of actinide chemistry falling into three categories: quantum chemical and matrix isolation studies of small molecules, the electronic structure of organoactinide systems, and uranyl peroxide nanoclusters and other solid state actinide compounds. The work herein not only spans a wide range of systems size but also investigates a range of chemical problems. Various quantum chemical approaches have been employed. Wave function-based methods have been used to study the electronic structure of actinide containing molecules of small to middle-size. Among these methods, the complete active space self consistent field (CASSCF) approach with corrections from second-order perturbation theory (CASPT2), the generalized active space SCF (GASSCF) approach, and Moller-Plesset second-order perturbation theory (MP2) have been employed. Likewise, density functional theory (DFT) has been used along with analysis tools like bond energy decomposition, bond orders, and Bader's Atoms in Molecules. From these quantum chemical results, comparison with experimentally obtained structures and spectra are made.

  2. A new method of tree xylem water extraction for isotopic analysis

    NASA Astrophysics Data System (ADS)

    Gierke, C.; Newton, B. T.

    2011-12-01

    The Sacramento Mountain Watershed Study in the southern Sacramento Mountains of New Mexico is designed to assess the forest restoration technique of tree thinning in mountain watersheds as an effective method of increasing local and regional groundwater recharge. The project is using a soil water balance approach to quantify the partitioning of local precipitation within this watershed before and after thinning trees. Understanding what sources trees extract their water from (e.g. shallow groundwater, unsaturated fractured bedrock, and soils) is difficult due to a complex hydrologic system and heterogeneous distribution of soil thicknesses. However, in order to accurately quantify the soil water balance and to assess how thinning trees will affect this water balance, it is important determine the sources from which trees extract their water. We plan to use oxygen and hydrogen stable isotopic analysis of various end member waters to identify these different sources. We are in the process of developing a new method of determining the isotopic composition of tree water that has several advantages over conventional methods. Within the tree there is the xylem which transports water from the roots to the leaves and the phloem which transports starches and sugars in a water media throughout the tree. Previous studies have shown that the isotopic composition of xylem water accurately reflects that of source water, while phloem water has undergone isotopic fractionation during photosynthesis and metabolism. The distillation of water from twigs, which is often used to extract tree water for isotopic analysis, is very labor intensive. Other disadvantages to distillation methods include possible fractionation due to phase changes and the possible extraction of fractionated phloem waters. Employing a new mixing method, the composition of the twig water (TW) can be determined by putting twigs of unknown isotopic water composition into waters of known compositions or initial

  3. In situ SIMS oxygen isotope analysis of olivine in the Tibetan mantle xenoliths

    NASA Astrophysics Data System (ADS)

    Zhao, Zhidan; Zhu, Di-Cheng; Liu, Dong; Mo, Xuanxue

    2016-04-01

    Although the mantle-derived xenoliths from Lhasa terrane provide a means of directly investigating the mantle underlying the southern part of the plateau, they were rarely found in the region. The only case of mantle xenoliths came from the Sailipu ultrapotassic volcanic rocks, erupted at ˜17 Ma, which have indicated that the subcontinental mantle of southern Tibetan Plateau is hot and strongly influenced by metasomatism (Zhao et al., 2008a, b; Liu et al., 2011). A further study by Liu et al.(2014) of in-situ oxygen isotope of olivine crystals in Sailipu mantle xenoliths identify a metasomatized mantle reservoir that interpreted as the sub-arc lithospheric mantle, with anomalously enriched oxygen isotopes (δ18O=8.03). Here we present oxygen isotopes data on the Sailipu mantle xenolith olivines, using different method of sample preparation. Mantle xenoliths (less than 1 cm in diameter) together originally with their host volcanic rocks were prepared in epoxy adjacent to grains of a San Carlos olivine intralaboratory standard and then polished to a flat and smooth surface. Oxygen isotope compositions of olivines occurs both in mantle xenolith and as phenocryst in the host rock, were analyzed in situ using CAMECA SIMS-1280 ion microprobe at the Institute of Geology and Geophysics, Chinese Academy of Sciences. We also performed traditional oxygen isotope analysis on three olivine phenocrysts separates from the host lava. Our new data show: (1) The mantle xenolith olivines have typical mantle oxygen isotopic composition (δ18O=4.8-8.0‰ with average of 5.5±0.2‰ n=105) with variety Fo#(78-90), (2) Oxygen isotopes of situ olivine phenocrysts in the Sailipu lavas (δ18O=7.1-9.2‰ Fo#=70-84, n=66), are similar to that of the whole rock (δ18O=7.0-9.4‰ Fo#=64-74, n=8, Zhao et al., 2009), and three olivine phenocryst grains (δ18O=7.2-7.8); (3) The intralaboratory standard of San Carlos olivine can be a suitable standard using for analyzing olivines with Fo not only

  4. Detection of Human Sewage in Urban Stormwater Using DNA Based Methods and Stable Isotope Analysis

    NASA Astrophysics Data System (ADS)

    McLellan, S. L.; Malet, N.; Sauer, E.; Mueller-Spitz, S.; Borchardt, M.

    2008-12-01

    related to the mixed organic matter sources in polluted stormwater runoff, and that this signal will distinct from untreated sanitary sewage. Stable isotope signatures of stormwater and untreated sewage were determined and compared with the rivers. Isotopic values of stormwater was delta 15N = 1.1 ± 2 %; delta 13C = -25.5 ± 3 % and sewage was delta 15N = -1.9 ± 0.2 %; delta 13C = -23.6 ± 0.3. Suspended particular organic matter (SPOM) of Milwaukee River showed depleted delta 13C (-28.6 ± 1.6 %) and enriched delta 15N (7.7 ± 1.9 %) values. SPOM of the KK River exhibited the most depleted delta 15N (0.2 ± 1.6 %) and enriched delta 13C (-24.8 ± 1.8 %) isotopic values. Menomonee River SPOM showed intermediate isotopic values. The delta 13C values of each river and the estuary enriched significantly throughout the summer storm periods. The isotope signals in the KK and Menomonee were indicative of stormwater runoff and sewage contamination. These results suggest that unrecognized sewage inputs are chronically present and may be delivered through urban stormwater systems. DNA based methods combined with isotope analysis may provide a useful tool for urban watershed assessments and to identify sewage inputs. Delineating the relative contribution of stormwater and sewage to overall degraded water quality might give the first indication of the impact of these sources on the Michigan Lake waters.

  5. Matrix Effects on the MC-ICPMS Analysis of Zn and Cd Isotopes

    NASA Astrophysics Data System (ADS)

    Shiel, A. E.; Weis, D.; Barling, J.; Orians, K. J.

    2006-12-01

    In order to understand fractionation in heavy stable isotope systems, matrix and auto-matrix effects need to be carefully monitored as they have a major impact on the precision and accuracy of isotope measurement by MC-ICP-MS. Understanding their impact for any given isotopic system is an important aspect of method development. In this study we look at auto-matrix and matrix effects for Zn (Cu mass bias correction) and Cd (Ag mass bias correction). Zn and Cd have similarly high ionization potentials, 9.4 and 9.0 respectively, and ionization potentials for Cu and Ag are similar, 7.7 and 7.6 respectively, making for an interesting comparison. All experiments were performed on a Nu Plasma MC-ICP-MS with 5x molar concentration of matrix elements. Experiments were also performed at concentrations more representative of those likely to be found in purified samples. In addition, we tested auto-matrix effects for Cd and Zn by varying the concentration of the analyte and mass bias correcting element. Cd sensitivity is enhanced in the presence of Rb and Pb, and is suppressed in the presence of Al, Sr and Cs. Spiked Cd runs are isotopically lighter than un-spiked runs, as light as 0.4‰/amu. Ag sensitivity was enhanced by all matrix elements. Cu sensitivity is enhanced by Al, Sr and Ba, and Zn sensitivity is enhanced by the latter two and Pb. Zn spiked with Al, Sr and Pb, or with poorly matched Cu intensities is isotopically lighter than un-spiked standards, as light as 1.0‰/amu. Auto-matrix effects for Cd and Ag, if present, are within the analytical error. We demonstrate that the presence of matrix elements or differences in concentration of analyte and mass bias correcting element between sample and standard can produce fractionation that is not true. The matrix effect is also found to be variable, as replicate analyses do not always agree. Cd and Zn react differently to different matrix elements, demonstrating the need for independent evaluation of each isotopic system

  6. Least destructive sampling of human remains using laser drilling for Sr isotope analysis by TIMS

    NASA Astrophysics Data System (ADS)

    Willmes, Malte; Moffat, Ian; Grün, Rainer; Armstrong, Richard; Kinsley, Les; McMorrow, Linda

    2013-04-01

    Strontium isotope ratios (87Sr/86Sr) measured in ancient human remains can be used to reconstruct migration patterns of ancient human populations. This application is based on the fact that different geologic regions have distinct Sr isotope signatures that are cycled through the soils, plants and rivers, and eventually enter the food cycle. Sr isotope ratios measured in skeletal remains (bones and teeth) reflect the average of dietary Sr that was consumed when the tissue was formed, allowing the investigation of human migration between geologically distinct terrains. The analysis of human remains is always a sensitive topic requiring minimal damage to the sample, while at the same time providing highly precise and accurate results. Samples can be analysed either by solution methods like thermal ionisation mass spectrometry (TIMS), or by in-situ laser ablation MC-ICP-MS. For TIMS a drill is used to extract a small amount of sample, which is then digested in acid and Sr is separated out using ion exchange chromatography. This technique provides highly precise and accurate results, because any isobaric interferences are removed during chemical separation. The drawback is that drilling may cause visible damage to the sample, restricting access to precious human remains. LA-MC-ICP-MS analysis is very fast and nearly destruction free. However, the accuracy and precision of LA-MC-ICP-MS is limited by a number of factors including large instrumental mass discrimination, laser-induced isotopic and elemental fractionations and molecular interferences on 87Sr. Its application thus requires rigorous data reduction, which can introduce significant uncertainties into the analysis. This is especially true for samples with relatively low Sr concentrations such as human teeth (e.g., Woodhead et al., 2005; Horstwood et al., 2008; Vroon et al., 2008). In addition, LA-MC-ICP-MS has traditionally required a flat sample surface, thus an unbroken tooth needs to be cut, which is rather

  7. Nonaqueous method for dissolving lanthanide and actinide metals

    DOEpatents

    Crisler, L.R.

    1975-11-11

    Lanthanide and actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a lanthanide or actinide element in the elemental metallic state in a mixture of carbon tetrachloride and methanol.

  8. TUCS/phosphate mineralization of actinides

    SciTech Connect

    Nash, K.L.

    1997-10-01

    This program has as its objective the development of a new technology that combines cation exchange and mineralization to reduce the concentration of heavy metals (in particular actinides) in groundwaters. The treatment regimen must be compatible with the groundwater and soil, potentially using groundwater/soil components to aid in the immobilization process. The delivery system (probably a water-soluble chelating agent) should first concentrate the radionuclides then release the precipitating anion, which forms thermodynamically stable mineral phases, either with the target metal ions alone or in combination with matrix cations. This approach should generate thermodynamically stable mineral phases resistant to weathering. The chelating agent should decompose spontaneously with time, release the mineralizing agent, and leave a residue that does not interfere with mineral formation. For the actinides, the ideal compound probably will release phosphate, as actinide phosphate mineral phases are among the least soluble species for these metals. The most promising means of delivering the precipitant would be to use a water-soluble, hydrolytically unstable complexant that functions in the initial stages as a cation exchanger to concentrate the metal ions. As it decomposes, the chelating agent releases phosphate to foster formation of crystalline mineral phases. Because it involves only the application of inexpensive reagents, the method of phosphate mineralization promises to be an economical alternative for in situ immobilization of radionuclides (actinides in particular). The method relies on the inherent (thermodynamic) stability of actinide mineral phases.

  9. Fabrication and Pre-irradiation Characterization of a Minor Actinide and Rare Earth Containing Fast Reactor Fuel Experiment for Irradiation in the Advanced Test Reactor

    SciTech Connect

    Timothy A. Hyde

    2012-06-01

    The United States Department of Energy, seeks to develop and demonstrate the technologies needed to transmute the long-lived transuranic actinide isotopes contained in spent nuclear fuel into shorter lived fission products, thereby decreasing the volume of material requiring disposal and reducing the long-term radiotoxicity and heat load of high-level waste sent to a geologic repository. This transmutation of the long lived actinides plutonium, neptunium, americium and curium can be accomplished by first separating them from spent Light Water Reactor fuel using a pyro-metalurgical process, then reprocessing them into new fuel with fresh uranium additions, and then transmuted to short lived nuclides in a liquid metal cooled fast reactor. An important component of the technology is developing actinide-bearing fuel forms containing plutonium, neptunium, americium and curium isotopes that meet the stringent requirements of reactor fuels and materials.

  10. Stable isotope analysis of vertebrae reveals ontogenetic changes in habitat in an endothermic pelagic shark.

    PubMed

    Carlisle, Aaron B; Goldman, Kenneth J; Litvin, Steven Y; Madigan, Daniel J; Bigman, Jennifer S; Swithenbank, Alan M; Kline, Thomas C; Block, Barbara A

    2015-01-22

    Ontogenetic changes in habitat are driven by shifting life-history requirements and play an important role in population dynamics. However, large portions of the life history of many pelagic species are still poorly understood or unknown. We used a novel combination of stable isotope analysis of vertebral annuli, Bayesian mixing models, isoscapes and electronic tag data to reconstruct ontogenetic patterns of habitat and resource use in a pelagic apex predator, the salmon shark (Lamna ditropis). Results identified the North Pacific Transition Zone as the major nursery area for salmon sharks and revealed an ontogenetic shift around the age of maturity from oceanic to increased use of neritic habitats. The nursery habitat may reflect trade-offs between prey availability, predation pressure and thermal constraints on juvenile endothermic sharks. The ontogenetic shift in habitat coincided with a reduction of isotopic niche, possibly reflecting specialization upon particular prey or habitats. Using tagging data to inform Bayesian isotopic mixing models revealed that adult sharks primarily use neritic habitats of Alaska yet receive a trophic subsidy from oceanic habitats. Integrating the multiple methods used here provides a powerful approach to retrospectively study the ecology and life history of migratory species throughout their ontogeny.

  11. Stable isotope analysis of 1987-1991 zooplankton samples and bowhead whale tissues. Final report

    SciTech Connect

    Schell, D.M.

    1992-06-01

    Stable isotope analyses of bowhead whale tissue samples and bowhead whale prey organisms collected over the years 1987 to 1991 were used to provide detail on the isotope ratio gradients evident in the arctic Alaskan zooplankton and to verify previous findings regarding the growth rates and age determination techniques developed for bowhead whales. Zooplankton of the Bering and Chukchi seas are enriched in (13)C relative to the eastern Beaufort Sea. The analysis of baleen from bowhead whales taken between 1987 to 1990 indicate that the whales are slow-growing and the young animals between year one and about six to seven years of age, undergo a period of little or no linear growth. The authors estimate that bowheads require 16-18 years to reach the length of sexual maturity, i.e., 13-14 m. From baleen Delta(13C) cycles, a 20 year record of the isotope ratios in the phytoplankton of the northern Bering and Chukchi seas was constructed. The long-term record has been compared with the temperature anomalies in surface waters of the Bering Sea. The Delta(13C) of the zooplankton is inversely correlated with temperature and refutes current models attempting to relate ocean temperature, and atmospheric carbon dioxide levels with the Delta(13C) of ocean sediment organic matter.

  12. Stable isotope analysis of vertebrae reveals ontogenetic changes in habitat in an endothermic pelagic shark

    PubMed Central

    Carlisle, Aaron B.; Goldman, Kenneth J.; Litvin, Steven Y.; Madigan, Daniel J.; Bigman, Jennifer S.; Swithenbank, Alan M.; Kline, Thomas C.; Block, Barbara A.

    2015-01-01

    Ontogenetic changes in habitat are driven by shifting life-history requirements and play an important role in population dynamics. However, large portions of the life history of many pelagic species are still poorly understood or unknown. We used a novel combination of stable isotope analysis of vertebral annuli, Bayesian mixing models, isoscapes and electronic tag data to reconstruct ontogenetic patterns of habitat and resource use in a pelagic apex predator, the salmon shark (Lamna ditropis). Results identified the North Pacific Transition Zone as the major nursery area for salmon sharks and revealed an ontogenetic shift around the age of maturity from oceanic to increased use of neritic habitats. The nursery habitat may reflect trade-offs between prey availability, predation pressure and thermal constraints on juvenile endothermic sharks. The ontogenetic shift in habitat coincided with a reduction of isotopic niche, possibly reflecting specialization upon particular prey or habitats. Using tagging data to inform Bayesian isotopic mixing models revealed that adult sharks primarily use neritic habitats of Alaska yet receive a trophic subsidy from oceanic habitats. Integrating the multiple methods used here provides a powerful approach to retrospectively study the ecology and life history of migratory species throughout their ontogeny. PMID:25621332

  13. Stable isotope analysis of vertebrae reveals ontogenetic changes in habitat in an endothermic pelagic shark.

    PubMed

    Carlisle, Aaron B; Goldman, Kenneth J; Litvin, Steven Y; Madigan, Daniel J; Bigman, Jennifer S; Swithenbank, Alan M; Kline, Thomas C; Block, Barbara A

    2015-01-22

    Ontogenetic changes in habitat are driven by shifting life-history requirements and play an important role in population dynamics. However, large portions of the life history of many pelagic species are still poorly understood or unknown. We used a novel combination of stable isotope analysis of vertebral annuli, Bayesian mixing models, isoscapes and electronic tag data to reconstruct ontogenetic patterns of habitat and resource use in a pelagic apex predator, the salmon shark (Lamna ditropis). Results identified the North Pacific Transition Zone as the major nursery area for salmon sharks and revealed an ontogenetic shift around the age of maturity from oceanic to increased use of neritic habitats. The nursery habitat may reflect trade-offs between prey availability, predation pressure and thermal constraints on juvenile endothermic sharks. The ontogenetic shift in habitat coincided with a reduction of isotopic niche, possibly reflecting specialization upon particular prey or habitats. Using tagging data to inform Bayesian isotopic mixing models revealed that adult sharks primarily use neritic habitats of Alaska yet receive a trophic subsidy from oceanic habitats. Integrating the multiple methods used here provides a powerful approach to retrospectively study the ecology and life history of migratory species throughout their ontogeny. PMID:25621332

  14. An approach for assessing total instrumental uncertainty in compound-specific carbon isotope analysis: implications for environmental remediation studies.

    PubMed

    Lollar, Barbara Sherwood; Hirschorn, Sarah K; Chartrand, Michelle M G; Lacrampe-Couloume, Georges

    2007-05-01

    Determination of compound-specific carbon isotope values by continuous flow isotope ratio mass spectrometry is impacted by variation in several routine operating parameters of which one of the most important is signal size, or linearity. Experiments were carried out to evaluate the implications of these operating parameters on both reproducibility and accuracy of delta13C measurements. A new method is described for assessing total instrumental uncertainty of routine compound-specific delta13C analysis, incorporating both accuracy and reproducibility. These findings have important implications for application of compound-specific isotope analysis in environmental geochemistry and in particular for the rapidly developing field of isotopic investigation of biodegradation and remediation of organic chemicals in contaminant hydrogeology. PMID:17391005

  15. An approach for assessing total instrumental uncertainty in compound-specific carbon isotope analysis: implications for environmental remediation studies.

    PubMed

    Lollar, Barbara Sherwood; Hirschorn, Sarah K; Chartrand, Michelle M G; Lacrampe-Couloume, Georges

    2007-05-01

    Determination of compound-specific carbon isotope values by continuous flow isotope ratio mass spectrometry is impacted by variation in several routine operating parameters of which one of the most important is signal size, or linearity. Experiments were carried out to evaluate the implications of these operating parameters on both reproducibility and accuracy of delta13C measurements. A new method is described for assessing total instrumental uncertainty of routine compound-specific delta13C analysis, incorporating both accuracy and reproducibility. These findings have important implications for application of compound-specific isotope analysis in environmental geochemistry and in particular for the rapidly developing field of isotopic investigation of biodegradation and remediation of organic chemicals in contaminant hydrogeology.

  16. Collection of Lanthanides and Actinides from Natural Waters with Conventional and Nanoporous Sorbents

    SciTech Connect

    Johnson, Bryce E.; Santschi, Peter H.; Chuang, Chia-Ying; Otosaka, Shigeyoshi; Addleman, Raymond S.; Douglas, Matthew; Rutledge, Ryan D.; Chouyyok, Wilaiwan; Davidson, Joseph D.; Fryxell, Glen E.; Schwantes, Jon M.

    2012-10-16

    Effective collection of trace-level lanthanides and actinides is advantageous for recovery and recycling of valuable resources, environmental remediation, chemical separations and in-situ monitoring. Using isotopic tracers, we have evaluated a number of conventional and nanoporous sorbent materials for their ability to capture and remove selected lanthanides (Ce and Eu) and actinides (Th, Pa, U, and Np) from fresh and salt water systems. In general, the nanostructured materials demonstrated a higher level of performance and consistency. Nanoporous silica surface modified with 3,4- hydroxypyridinone provided excellent collection and consistency in both river water and seawater. The MnO2 materials, particular the high surface area small particle material also demonstrated good performance. Other conventional sorbents typically performed at the levels below the nanostructured sorbents and demonstrate a larger variability and matrix dependency.

  17. Collection of lanthanides and actinides from natural waters with conventional and nanoporous sorbents.

    PubMed

    Johnson, Bryce E; Santschi, Peter H; Chuang, Chia-Ying; Otosaka, Shigeyoshi; Addleman, Raymond Shane; Douglas, Matt; Rutledge, Ryan D; Chouyyok, Wilaiwan; Davidson, Joseph D; Fryxell, Glen E; Schwantes, Jon M

    2012-10-16

    Effective collection of trace-level lanthanides and actinides is advantageous for recovery and recycling of valuable resources, environmental remediation, chemical separations, and in situ monitoring. Using isotopic tracers, we have evaluated a number of conventional and nanoporous sorbent materials for their ability to capture and remove selected lanthanides (Ce and Eu) and actinides (Th, Pa, U, and Np) from fresh and salt water systems. In general, the nanostructured materials demonstrated a higher level of performance and consistency. Nanoporous silica surface modified with 3,4-hydroxypyridinone provided excellent collection and consistency in both river water and seawater. The MnO(2) materials, in particular the high surface area small particle material, also demonstrated good performance. Other conventional sorbents typically performed at levels below the nanostructured sorbents and demonstrate a larger variability and matrix dependency.

  18. High Precision Fe Isotope Analysis in low Concentration Samples by High Resolution MC-ICPMS

    NASA Astrophysics Data System (ADS)

    Chung, C.; Wu, J.; You, C.

    2009-12-01

    Iron availability has been shown to be the main limitation factor for phytoplankton growth in the ocean. However, due to the limitation of analytical technique, the database of dissolved Fe concentrations and isotope ratio distribution in the ocean is still very limited. In particular, the iron sources to the ocean remain uncertain. Aeolian dust from the continental is considered as the primary source, also the digenetic dissolution at the continental margins is proposed to contribute significant portion of iron content of the sea surface water. The field of Fe isotope geochemistry has seen important developments in methodology and scope since the advent of Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS). Although increasing the number of replicates in High Resolution MC-ICPMS reduces the uncertainty related to instability in instrumental mass bias and counting statistics, many other parameters include mass fractionation during column separation, matrix effect in ICPMS analysis and the presence of isobaric interferences can affect the precision and accuracy of Fe isotopic analyses. In this study, a high precision analytical method of Fe isotope measurement for low concentration samples was developed using HR-MC-ICPMS. Several parameters that may affect the accuracy and precision of 56Fe/54Fe result such as background, instrumental mass discrimination, isobaric interferences, type of introduction system and acid molarity were identified and evaluated. External precisions better than 0.04‰ for δ56Fe can be achieve using only 10ng of iron sample with APEX and X-cone as introduction system. Significant improvement in terms of sample size was made. This method can be applied on very low concentration samples such as coral and seawater.

  19. Improved method for isotopic and quantitative analysis of dissolved inorganic carbon in natural water samples.

    PubMed

    Assayag, Nelly; Rivé, Karine; Ader, Magali; Jézéquel, Didier; Agrinier, Pierre

    2006-01-01

    We present here an improved and reliable method for measuring the concentration of dissolved inorganic carbon (DIC) and its isotope composition (delta(13)C(DIC)) in natural water samples. Our apparatus, a gas chromatograph coupled to an isotope ratio mass spectrometer (GCIRMS), runs in a quasi-automated mode and is able to analyze about 50 water samples per day. The whole procedure (sample preparation, CO(2(g))-CO(2(aq)) equilibration time and GCIRMS analysis) requires 2 days. It consists of injecting an aliquot of water into a H(3)PO(4)-loaded and He-flushed 12 mL glass tube. The H(3)PO(4) reacts with the water and converts the DIC into aqueous and gaseous CO(2). After a CO(2(g))-CO(2(aq)) equilibration time of between 15 and 24 h, a portion of the headspace gas (mainly CO(2)+He) is introduced into the GCIRMS, to measure the carbon isotope ratio of the released CO(2(g)), from which the delta(13)C(DIC) is determined via a calibration procedure. For standard solutions with DIC concentrations ranging from 1 to 25 mmol . L(-1) and solution volume of 1 mL (high DIC concentration samples) or 5 mL (low DIC concentration samples), delta(13)C(DIC) values are determined with a precision (1sigma) better than 0.1 per thousand. Compared with previously published headspace equilibration methods, the major improvement presented here is the development of a calibration procedure which takes the carbon isotope fractionation associated with the CO(2(g))-CO(2(aq)) partition into account: the set of standard solutions and samples has to be prepared and analyzed with the same 'gas/liquid' and 'H(3)PO(4)/water' volume ratios. A set of natural water samples (lake, river and hydrothermal springs) was analyzed to demonstrate the utility of this new method. PMID:16810706

  20. Job/task analysis for I C (Instrumentation and Controls) instrument technicians at the High Flux Isotope Reactor

    SciTech Connect

    Duke, L.L.

    1989-09-01

    To comply with Department of Energy Order 5480.XX (Draft), a job/task analysis was initiated by the Maintenance Management Department at Oak Ridge National Laboratory (ORNL). The analysis was applicable to instrument technicians working at the ORNL High Flux Isotope Reactor (HFIR). This document presents the procedures and results of that analysis. 2 refs., 2 figs.

  1. Spatially-resolved stable isotope analysis of a hypersaline microbial mat

    NASA Astrophysics Data System (ADS)

    Moran, J.; Cory, A. B.; Lindemann, S. R.; Fredrickson, J. K.

    2012-12-01

    Hot Lake is a hypersaline, meromictic lake located in north-central Washington. High rates of evapotranspiration coupled with its location in an endorrheic basin contribute to the lake's high salinity. The predominant dissolved salt is magnesium sulfate; hypolimnion waters may seasonally exceed 2 M magnesium sulfate concentrations. In addition to extreme salinity, horizons within the lake seasonally exceed 50 °C, in part due to the enhanced light absorption by magnesium sulfate-saturated water. Despite extreme and highly variable seasonal conditions (salinity, temperature, photon flux), dense benthic microbial mats composed of cyanobacteria and bacterial heterotroph populations develop annually at the lake. These mats may exceed 5 mm in thickness and display stratification observable by eye associated with dominant bacterial phototrophic pigments. Typical mat stratification includes an orange surface layer followed by green and purple layers at increasing depth into the mat. Carbonates including aragonite and magnesite are observed within the mat and their formation is likely induced or influenced by microbial activities. While not exclusively limited to the green stratum in the mat, maximum carbonate content is within this layer. We are exploring the role Hot Lake's microbial mats play in carbon cycling within the system. Namely, we seek to understand the rates of carbon accumulation in the mat and associated sediments and the various forms this carbon takes (organic or inorganic species). We are assessing mat development, community composition, and carbon accumulation in pre-cleaned devices installed at the lake as they are colonized by native mat. We are using laser ablation isotope ratio mass spectrometry (LA-IRMS) to provide spatially-resolved stable isotope analysis of mat cross-sections. Currently, this technique permits isotope analysis at the 50 μm scale, and can provide multiple isotope analyses within the thickness of each major layer of the mat. We

  2. Complexation of Actinides in Solution: Thermodynamic Measurementsand Structural Characterization

    SciTech Connect

    Rao, L.

    2007-02-01

    This paper presents a brief introduction of the studies of actinide complexation in solution at Lawrence Berkeley National Laboratory. An integrated approach of thermodynamic measurements and structural characterization is taken to obtain fundamental understanding of actinide complexation in solution that is of importance in predicting the behavior of actinides in separation processes and environmental transport.

  3. The Actinide-Lanthanide Separation Process

    SciTech Connect

    Lumetta, Gregg J.; Gelis, Artem V.; Carter, Jennifer C.; Niver, Cynthia M.; Smoot, Margaret R.

    2014-02-21

    The Actinide-Lanthanide SEParation (ALSEP) process is described. The process uses an extractant phase consisting of either N,N,N',N'-tetraoctyldiglycolamide (TODGA) or N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) combined with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). The neutral TODGA or T2EHDGA serves to co-extract the trivalent actinide and lanthanide ions from nitric acid media. Switching the aqueous phase chemistry to a citrate buffered diethylenetriaminepentaacetic acid (DTPA) solution at pH 2.5 to 4 results in selective transfer of the actinides to the aqueous phase, thus resulting in separation of these two groups of elements.

  4. THEORY FOR THE XPS OF ACTINIDES

    SciTech Connect

    Bagus, Paul S.; Ilton, Eugene S.

    2013-08-01

    Two aspects of the electronic structure of actinide oxides that significantly affect the XPS spectra are described; these aspects are also important for the materials properties of the oxides. The two aspects considered are: (1) The spin-orbit coupling of the open 5f shell electrons in actinide cations and how this coupling affects the electronic structure. And, (2) the covalent character of the metal oxygen interaction in actinide compounds. Because of this covalent character, there are strong departures from the nominal oxidation states that are significantly larger in core-hole states than in the ground state. The consequences for the XPS of this covalent character are examined. A proper understanding of the way in which they influence the XPS makes it possible to use the XPS to correctly characterize the electronic structure of the oxides.

  5. Actinide separations by supported liquid membranes

    SciTech Connect

    Danesi, P.R.; Horwitz, E.P.; Rickert, P.; Chiarizia, R.

    1984-01-01

    The work has demonstrated that actinide removal from synthetic waste solutions using both flat-sheet and hollow-fiber SLM's is a feasible chemical process at the laboratory scale level. The process is characterized by the typical features of SLM's processes: very small quantities of extractant required; the potential for operations with high feed/strip volume ratios, resulting in a corresponding concentration factor of the actinides; and simplicity of operation. Major obstacles to the implementation of the SLM technology to the decontamination of liquid nuclear wastes are the probable low resistance of polypropylene supports to high radiation fields, which may prevent the application to high-level nuclear wastes; the unknown lifetime of the SLM; and the high Na content of the separated actinide solution.

  6. A Flow-through Reaction Cell that Couples Time-resolved X-ray Diffraction with Stable Isotope Analysis

    SciTech Connect

    Hanson, J.C.; Wall, A.J.; Heaney, P.J.; Mathur, R.; Post, J.E.; Eng, P.J.

    2011-04-01

    A non-metallic flow-through reaction cell is described, designed for in situ time-resolved X-ray diffraction coupled with stable isotope analysis. The experimental setup allows the correlation of Cu isotope fractionation with changes in crystal structure during copper sulfide dissolution. This flow-through cell can be applied to many classes of fluid-mineral reactions that involve dissolution or ion exchange.

  7. Ultra-Sensitive Elemental and Isotope Measurements with Compact Plasma Source Cavity Ring-Down Spectroscopy

    SciTech Connect

    Wang, Chuji

    2004-12-01

    The proposed research is to develop a new class of instruments for actinide isotopes and hazardous element analysis through coupling highly sensitive cavity ring-down spectroscopy to a compact microwave plasma source. The research work will combine advantages of CRDS measurement with a low power, low flow rate, tubing-type microwave plasma source to reach breakthrough sensitivity for elemental analysis and unique capability of isotope measurement. The project has several primary goals: (1) Explore the feasibility of marrying CRDS with a new microwave plasma source; (2) Provide quantitative evaluation of CMP-CRDS for ultra-trace elemental and actinide isotope analysis; (3) Approach a breakthrough detection limit of ca. 10-13 g/ml or so, which are orders of magnitude better than currently available best values; (4) Demonstrate the capability of CMP-CRD S technology for isobaric measurements, such as 238U and 238Pu isotopes. (5) Design and assemble the first compact, field portable CMP-CRDS instrument with a high-resolution diode laser for DOE/EM on-site demonstration. With all these unique capabilities and sensitivities, we expect CMPCRDS will bring a revolutionary change in instrument design and development, and will have great impact and play critical roles in supporting DOE's missions in environmental remediation, environmental emission control, waste management and characterization, and decontamination and decommissioning. The ultimate goals of the proposed project are to contribute to environmental management activities that would decrease risk for the public and workers, increase worker productivity with on-site analysis, and tremendously reduce DOE/EM operating costs.

  8. Probing the population of the spin-orbit split levels in the actinide 5f states.

    PubMed

    Moore, K T; van der Laan, G; Tobin, J G; Chung, B W; Wall, M A; Schwartz, A J

    2006-03-01

    Spin-orbit interaction in the 5f states is believed to strongly influence exotic behaviors observed in actinide metals and compounds. Understanding these interactions and how they relate to the actinide series is of considerable importance. To address this issue, the branching ratio of the white-line peaks of the N4,5 edge for the light actinide metals, alpha-Th, alpha-U, and alpha-Pu were recorded using electron energy-loss spectroscopy (EELS) in a transmission electron microscope (TEM) and synchrotron-radiation-based X-ray absorption spectroscopy (XAS). Using the spin-orbit sum rule and the branching ratios from both experimental spectra and many-electron atomic spectral calculations, accurate values of the spin-orbit interaction, and thus the relative occupation of the j = 5/2 and 7/2 levels, are determined for the actinide 5f states. Results show that the spin-orbit sum rule works very well with both EELS and XAS spectra, needing little or no correction. This is important, since the high spatial resolution of a TEM can be used to overcome the problems of single-crystal growth often encountered with actinide metals, allowing acquisition of EELS spectra, and subsequent spin-orbit analysis, from nm-sized regions. The relative occupation numbers obtained by our method have been compared with recent theoretical results and they show a good agreement in their trend.

  9. Experimental and simulated assay of actinides in a real waste package

    NASA Astrophysics Data System (ADS)

    Saurel, N.; Capdevila, J. M.; Huot, N.; Gmar, M.

    2005-09-01

    The non-destructive control of nuclear wastes is important for their management and the non-proliferation. Among the methods using the nuclear radiation as an investigation, the Instrumental Photon Activation Analysis (IPAA) seems to be a promising way to quantify the masses of actinides present in bulky packages of nuclear waste. The IPAA method consists in irradiating actinides with photons of high energy to produce photofission reactions. The counting of the delayed neutrons, produced by these photofission reactions, allows to locate and to quantify the mass of actinides by tomography. At this end, we use a simulation tool named OPERA to obtain the information necessary for the tomographic restitution and an experimental installation based on a LINear ACcelerator (LINAC) to perform the measurements. The high-energy photons (11 MeV) are produced by Bremsstrahlung, thanks to a tungsten target placed in front of the LINAC. In this paper, we present the first experimental results obtained on a real package of nuclear waste. We establish that, for this waste package, the limit of detection, in terms of mass of actinides, is about 1 g. Furthermore, these results show the good agreement between the experiment and the simulation that provides a localization of actinides by tomography.

  10. Coenzyme F430, quantification and isotope analysis from the Eel River Basin California

    NASA Astrophysics Data System (ADS)

    Bird, L. R.; Fulton, J. M.; Dawson, K.; Orphan, V. J.; Freeman, K. H.

    2012-12-01

    Large amounts of methane are oxidized by communities of methanotrophic archaea and sulphate-reducing bacteria, preventing this greenhouse gas from reaching the atmosphere (Orphan et al., 2001; Scheller et al., 2010). Methyl-coenzyme M reductase, an enzyme traditionally associated with methanogenesis, has recently been linked to the anaerobic oxidation of methane suggesting methane oxidation follows a pathway similar to reverse methanogenesis. Coenzyme F430, a tetrapyrrole-nickel complex within the active site of methyl-coenzyme M, is used in methanogenesis and is hypothesized to play a key role in archaeal methanotrophy (Scheller et al., 2010). We recently developed a method to extract and isolate F430 from natural sediments so it can be purified for carbon and nitrogen stable isotope analysis. Sediments are extracted using an ultrasonic homogenizer, first in water (pH 7), then twice in dilute formic acid (pH 3). The combined extract is neutralized and the F430-containing fraction is isolated using Sephadex and Amberlite column chromatography. Further purification is performed using two dimensional high performance liquid chromatography, first with a reverse phase C-18 column followed by separation on a ThermoFisher Hypercarb column. F430 is then quantified using photo diode array detection with fractions collected for isotope analysis using a nano-scale elemental analyzer isotope ratio mass spectrometer (nano-EA-IRMS; Polissar et al., 2009). Compound identity and purity are confirmed using molar C:N ratios, UV absorbance and MSn detection of the parent ion (m/z 905). Here, we report F430 concentrations and isotopic data determined from active seep sediment cores from the Eel River Basin (California), a site where the anoxic oxidation of methane occurs. A spike in the concentration of F430 is observed at the 3-6 cm depth horizon corresponding with peak abundance in ANME-2/Desulfosarcina/Desulfococcus aggregate counts. Carbon isotope values of F430 are significantly

  11. Actinide Lanthanide Separation Process – ALSEP

    SciTech Connect

    Gelis, Artem V.; Lumetta, Gregg J.

    2014-01-29

    Separation of the minor actinides (Am, Cm) from the lanthanides at an industrial scale remains a significant technical challenge for closing the nuclear fuel cycle. To increase the safety of used nuclear fuel (UNF) reprocessing, as well as reduce associated costs, a novel solvent extraction process has been developed. The process allows for partitioning minor actinides, lanthanides and fission products following uranium/plutonium/neptunium removal; minimizing the number of separation steps, flowsheets, chemical consumption, and waste. This new process, Actinide Lanthanide SEParation (ALSEP), uses an organic solvent consisting of a neutral diglycolamide extractant, either N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) or N,N,N',N'-tetraoctyldiglycolamide (TODGA), and an acidic extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]), dissolved in an aliphatic diluent (e.g. n-dodecane). The An/Ln co-extraction is conducted from moderate-to-strong nitric acid, while the selective stripping of the minor actinides from the lanthanides is carried out using a polyaminocarboxylic acid/citrate buffered solution at pH anywhere between 3 and 4.5. The extraction and separation of the actinides from the fission products is very effective in a wide range of HNO3 concentrations and the minimum separation factors for lanthanide/Am exceed 30 for Nd/Am, reaching > 60 for Eu/Am under some conditions. The experimental results presented here demonstrate the great potential for a combined system, consisting of a neutral extractant such as T2EHDGA or TODGA, and an acidic extractant such as HEH[EHP], for separating the minor actinides from the lanthanides.

  12. Source Attribution of Cyanides Using Anionic Impurity Profiling, Stable Isotope Ratios, Trace Elemental Analysis and Chemometrics.

    PubMed

    Mirjankar, Nikhil S; Fraga, Carlos G; Carman, April J; Moran, James J

    2016-02-01

    Chemical attribution signatures (CAS) for chemical threat agents (CTAs), such as cyanides, are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. Herein, stocks of KCN and NaCN were analyzed for trace anions by high performance ion chromatography (HPIC), carbon stable isotope ratio (δ(13)C) by isotope ratio mass spectrometry (IRMS), and trace elements by inductively coupled plasma optical emission spectroscopy (ICP-OES). The collected analytical data were evaluated using hierarchical cluster analysis (HCA), Fisher-ratio (F-ratio), interval partial least-squares (iPLS), genetic algorithm-based partial least-squares (GAPLS), partial least-squares discriminant analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminant analysis (SVMDA). HCA of anion impurity profiles from multiple cyanide stocks from six reported countries of origin resulted in cyanide samples clustering into three groups, independent of the associated alkali metal (K or Na). The three groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries each having one known solid cyanide factory: Czech Republic, Germany, and United States. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). Classification errors for two validation studies using anion impurity profiles collected over five years on different instruments were as low as zero for KNN and SVMDA, demonstrating the excellent reliability associated with using anion impurities for matching a cyanide sample to its factory using our current cyanide stocks. Variable selection methods reduced errors for those classification methods having errors greater than zero; iPLS-forward selection and F-ratio typically provided the lowest errors. Finally, using anion profiles to classify cyanides to a specific stock

  13. Biodilution of heavy metals in a stream macroinvertebrate food web: evidence from stable isotope analysis.

    PubMed

    Watanabe, Kozo; Monaghan, Michael T; Takemon, Yasuhiro; Omura, Tatsuo

    2008-05-01

    Analysis of carbon (delta13C) and nitrogen (delta15N) stable isotopes provides an increasingly important means of understanding the complex trophic structure of macroinvertebrate communities in streams. We coupled a stable isotope approach with a contaminant analysis of six metals (Pb, Ag, Zn, Hg, Cu, As) to trace the accumulation and dilution of metals from an abandoned mine across trophic levels of the benthic community in Ginzan Creek, Japan. The delta15N signature increased with trophic level, with mean increases of 4.70 per thousand from producers to primary consumers and 3.06 per thousand from primary to secondary consumers. Tissue Pb and Ag concentrations were negatively correlated with delta15N, indicating biodilution of both metals through the food web. Although macroinvertebrate taxon body mass was negatively correlated with tissue metal concentration at several sites, it did not increase with trophic level (as delta15N) in any of the sites, suggesting that changes in body mass were not the cause of biodilution. Our findings suggest invertebrates at higher trophic levels may exhibit increasingly efficient excretion of metals. Autotrophic epilithon (mean delta13C= -21.3 per thousand) had a much higher concentration of mined metals than did riparian vegetation (mean delta13C= -29.3 per thousand); nonetheless, a carbon-mixing model indicated that taxa feeding on autochthonous carbon sources did not accumulate more metal than allochthonous feeders. It is likely that the notably high metal concentration of allochthonous FPOM plays an important role in the trophic transfer of metals. Our data suggest the strong potential for stable isotope analysis to enhance our understanding of metal transfer through stream macroinvertebrate food webs.

  14. Source Attribution of Cyanides Using Anionic Impurity Profiling, Stable Isotope Ratios, Trace Elemental Analysis and Chemometrics.

    PubMed

    Mirjankar, Nikhil S; Fraga, Carlos G; Carman, April J; Moran, James J

    2016-02-01

    Chemical attribution signatures (CAS) for chemical threat agents (CTAs), such as cyanides, are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. Herein, stocks of KCN and NaCN were analyzed for trace anions by high performance ion chromatography (HPIC), carbon stable isotope ratio (δ(13)C) by isotope ratio mass spectrometry (IRMS), and trace elements by inductively coupled plasma optical emission spectroscopy (ICP-OES). The collected analytical data were evaluated using hierarchical cluster analysis (HCA), Fisher-ratio (F-ratio), interval partial least-squares (iPLS), genetic algorithm-based partial least-squares (GAPLS), partial least-squares discriminant analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminant analysis (SVMDA). HCA of anion impurity profiles from multiple cyanide stocks from six reported countries of origin resulted in cyanide samples clustering into three groups, independent of the associated alkali metal (K or Na). The three groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries each having one known solid cyanide factory: Czech Republic, Germany, and United States. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). Classification errors for two validation studies using anion impurity profiles collected over five years on different instruments were as low as zero for KNN and SVMDA, demonstrating the excellent reliability associated with using anion impurities for matching a cyanide sample to its factory using our current cyanide stocks. Variable selection methods reduced errors for those classification methods having errors greater than zero; iPLS-forward selection and F-ratio typically provided the lowest errors. Finally, using anion profiles to classify cyanides to a specific stock

  15. Measurement of Actinides in Environmental Samples at Micro-Becquerel Levels by Accelerator Mass Spectrometry

    SciTech Connect

    Brown, T A; Knezovich, J P; Marchetti, A A; Hamilton, T F

    2002-09-03

    The need for ultra-sensitive actinide measurements continues to expand in the fields of environmental stewardship, nuclear isotope forensics, radiobioassay and environmental research. We have developed a heavy isotope accelerator mass spectrometry (AMS) system at Lawrence Livermore National Laboratory's Center for Accelerator Mass Spectrometry (CAMS). The system was designed particularly for the measurement of actinide concentrations and isotopic ratios. A fast isotope switching capability has been incorporated in the system, allowing flexibility in isotope selection and for the quasi-continuous normalization to a reference isotope spike. Initially, our utilization of the system has concentrated on the measurement of Pu isotopes. Under current operating conditions, background levels equivalent to <10{sup 6} atoms are observed during routine {sup 239}Pu and {sup 240}Pu measurements. Measurements of samples containing 10{sup 13} {sup 238}U atoms demonstrate that the system provides a {sup 238}U rejection factor of >10{sup 7}. Recently, we have utilized the high dynamic range of the AMS system in measuring samples whose Pu contents ranged from <10{sup 6} (background) to >10{sup 11} Pu atoms. Measurements of known materials, combined with results from an externally organized intercomparison program, indicate that our {sup 239}Pu measurements are accurate and precise down to the {mu}Bq level ({approx}10{sup 6} atoms). The development of the heavy isotope system was undertaken with particular interest in the measurement of environmental samples, including soils, sediments, waters, air filters, tissue samples, and human urine. The high rejection of interferences, including molecular interferences, and low susceptibility to matrix components, provided by the AMS technique are of particular relevance for such complex samples. These two factors significantly reduce demands on sample preparation chemistry for Pu analyses, allowing relatively simple, cost-effective procedures