Method to make accurate concentration and isotopic measurements for small gas samples

NASA Astrophysics Data System (ADS)

Palmer, M. R.; Wahl, E.; Cunningham, K. L.

2013-12-01

Carbon isotopic ratio measurements of CO2 and CH4 provide valuable insight into carbon cycle processes. However, many of these studies, like soil gas, soil flux, and water head space experiments, provide very small gas sample volumes, too small for direct measurement by current constant-flow Cavity Ring-Down (CRDS) isotopic analyzers. Previously, we addressed this issue by developing a sample introduction module which enabled the isotopic ratio measurement of 40ml samples or smaller. However, the system, called the Small Sample Isotope Module (SSIM), does dilute the sample during the delivery with inert carrier gas which causes a ~5% reduction in concentration. The isotopic ratio measurements are not affected by this small dilution, but researchers are naturally interested accurate concentration measurements. We present the accuracy and precision of a new method of using this delivery module which we call 'double injection.' Two portions of the 40ml of the sample (20ml each) are introduced to the analyzer, the first injection of which flushes out the diluting gas and the second injection is measured. The accuracy of this new method is demonstrated by comparing the concentration and isotopic ratio measurements for a gas sampled directly and that same gas measured through the SSIM. The data show that the CO2 concentration measurements were the same within instrument precision. The isotopic ratio precision (1σ) of repeated measurements was 0.16 permil for CO2 and 1.15 permil for CH4 at ambient concentrations. This new method provides a significant enhancement in the information provided by small samples.

LASER BIOLOGY AND MEDICINE: Laser analysis of the 13C/12C isotope ratio in CO2 in exhaled air

NASA Astrophysics Data System (ADS)

Stepanov, E. V.

2002-11-01

Tunable diode lasers (TDLs) are applied to the diagnostics of gastroenterological diseases using respiratory tests and preparations enriched with the stable 13C isotope. This method of the analysis of the 13C/12C isotope ratio in CO2 in exhaled air is based on the selective measurement of the resonance absorption at the vibrational — rotational structure of 12CO2 and 13CO2. The CO2 transmission spectra in the region of 4.35 μm were measured with a PbEuSe double-heterostructure TDL. The accuracy of carbon isotope ratio measurements in CO2 of exhaled air performed with the TDL was ~0.5%. The data of clinical tests of the developed laser-based analyser are presented.

Enzymatic Kinetic Isotope Effects from Path-Integral Free Energy Perturbation Theory.

PubMed

Gao, J

2016-01-01

Path-integral free energy perturbation (PI-FEP) theory is presented to directly determine the ratio of quantum mechanical partition functions of different isotopologs in a single simulation. Furthermore, a double averaging strategy is used to carry out the practical simulation, separating the quantum mechanical path integral exactly into two separate calculations, one corresponding to a classical molecular dynamics simulation of the centroid coordinates, and another involving free-particle path-integral sampling over the classical, centroid positions. An integrated centroid path-integral free energy perturbation and umbrella sampling (PI-FEP/UM, or simply, PI-FEP) method along with bisection sampling was summarized, which provides an accurate and fast convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. The PI-FEP method is illustrated by a number of applications, to highlight the computational precision and accuracy, the rule of geometrical mean in kinetic isotope effects, enhanced nuclear quantum effects in enzyme catalysis, and protein dynamics on temperature dependence of kinetic isotope effects. © 2016 Elsevier Inc. All rights reserved.

Selenium isotope ratios as indicators of selenium sources and oxyanion reduction

USGS Publications Warehouse

Johnson, T.M.; Herbel, M.J.; Bullen, T.D.; Zawislanski, P.T.

1999-01-01

Selenium stable isotope ratio measurements should serve as indicators of sources and biogeochemical transformations of Se. We report measurements of Se isotope fractionation during selenate reduction, selenite sorption, oxidation of reduced Se in soils, and Se volatilization by algae and soil samples. These results, combined with previous work with Se isotopes, indicate that reduction of soluble oxyanions is the dominant cause of Se isotope fractionation. Accordingly, Se isotope ratios should be useful as indicators of oxyanion reduction, which can transform mobile species to forms that are less mobile and less bioavailable. Additional investigations of Se isotope fractionation are needed to confirm this preliminary assessment. We have developed a new method for measurement of natural Se isotope ratio variation which requires less than 500 ng Se per analysis and yields ??0.2??? precision on 80Se/76Se. A double isotope spike technique corrects for isotopic fractionation during sample preparation and mass spectrometry. The small minimum sample size is important, as Se concentrations are often below 1 ppm in solids and 1 ??g/L in fluids. The Se purification process is rapid and compatible with various sample matrices, including acidic rock or sediment digests.

Selenium isotope ratios as indicators of selenium sources and oxyanion reduction

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

Johnson, T.M.; Herbel, M.J.; Bullen, T.D.

1999-09-01

Selenium stable isotope ratio measurements should serve as indicators of sources and biogeochemical transformations of Se. The authors report measurements of Se isotope fractionation during selenate reduction, selenite sorption, oxidation of reduced Se in soils, and Se volatilization by algae and soil samples. These results, combined with previous work with Se isotopes, indicate that reduction of soluble oxyanions is the dominant cause of Se isotope fractionation. Accordingly, Se isotope ratios should be useful as indicators of oxyanion reduction, which can transform mobile species to forms that are less mobile and less bioavailable. Additional investigations of Se isotope fractionation are neededmore » to confirm this preliminary assessment. The authors have developed a new method for measurement of natural Se isotope ratio variation which requires less than 500 ng Se per analysis and yields {+-}0.2% precision on {sup 80}Se/{sup 76}Se. A double isotope spike technique corrects for isotopic fractionation during sample preparation and mass spectrometry. The small minimum sample size is important, as Se concentrations are often below 1 ppm in solids and 1 {micro}g/L in fluids. The Se purification process is rapid and compatible with various sample matrices, including acidic rock or sediment digests.« less

Determination of (187)Os in molybdenite by ICP-MS with neutron-induced (186)Os and (188)Os spikes.

PubMed

Qu, W; Du, A; Zhao, D

2001-10-31

The article describes a method for the determination of (187)Os in molybdenite by isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) with neutron-induced (186)Os and (188)Os spike. The spike used in the present work was prepared in line with the principle by which artificial nuclides are produced in a nuclear reaction. The concentration and isotopic composition of osmium in the prepared spike were evaluated accurately with the isotope dilution method, using negative thermal ion mass spectrometry (N-TIMS). The advantage of this method is that using (186)Os and (188)Os double spikes can effectively compensate for the mass discrimination effects of ICP-MS. Thus, the common correction practice for mass bias in the isotope dilution method with a single spike is unnecessary. In addition, the method enables one to reduce the determined error arising from instrumental instability. The precision for the (187)Os/((186)Os+(188)Os) ratio was approximately 2% (2sigma, RSD), but in the case of (187)Os/(186)Os, (187)Os/(188)Os and (186)Os/(188)Os, precision ranged from 2.0 to 8% (2sigma, RSD). The results for (187)Os concentration in a molybdenite sample determined with this method showed good agreement with reference values.

Development of Tandem, Double-Focusing, Electron Impact, Gas Source Mass Spectrometer for Measurement of Rare Double-Substituted Isotoplogues in Geochemistry

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

Young, Edward D.

This project culminated in construction and delivery of the world’s first large-radius gas-source isotope ratio mass spectrometer that permits unparalleled analyses of the stable isotopic composition of methane gas. The instrument, referred to as the “Panorama” and installed at UCLA in March 2015, can now be used to determine the relative abundances of rare isotopic species of methane that serve as tracers of temperature of formation and/or subsequent processing of gas. With this technology we can begin to delineate different sources and sinks of methane isotopically in ways not possible until now.

Neutron induced radio-isotopes and background for Ge double beta decay experiments

NASA Astrophysics Data System (ADS)

Chu, Pinghan; Majorana Collaboration

2015-10-01

Environmental neutrons, mostly produced by muons in the cosmic rays, might contribute backgrounds to the search for neutrinoless double beta decays. These neutrons can interact with materials and generate radio-isotopes, which can decay and produce radioactive backgrounds. Some of these neutron-induced isotopes have a signature of a time-delayed coincidence, allowing us to study these infrequent events. For example, such isotopes can decay by beta decay to metastable states and then decay by gamma decay to the ground state. Considering the time-delayed coincidence of these two processes, we can determine candidates for these neutron-induced isotopes in the data and estimate the flux of neutrons in the deep underground environment. In this report, we will list possible neutron-induced isotopes and the methodology to detect them, especially those that can affect the search for neutrinoless double beta decays in 76Ge. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Nuclear Physics, the Particle Astrophysics Program of the National Science Foundation, and the Sanford Underground Research Facility. We acknowledge the support of the U.S. Department of Energy through the LANL/LDRD Program.

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

PubMed

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

2012-09-01

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

Effects of Simple Leaching of Crushed and Powdered Materials on High-precision Pb Isotope Analyses

NASA Astrophysics Data System (ADS)

Todd, E.; Stracke, A.

2013-12-01

We present new results of simple leaching experiments on the Pb isotope composition of USGS standard reference material powders and on ocean island basalt whole rock splits and powders. Rock samples were leached with 6N HCl in two steps, first hot and then in an ultrasonic bath, and washed with ultrapure H2O before conventional sample digestion and chromatographic purification of Pb. Pb isotope analyses were determined with Tl-doped MC-ICP-MS. Intra- and inter-session analytical reproducibility of repeated analyses of both synthetic Pb solutions and Pb from single digests of chemically processed natural samples were generally < 100 ppm (2 S.D.). The comparison of leached and unleached samples shows that leaching reliably removes variable amounts of different contaminants for different starting materials. For repeated digests of a single sample, the leached samples reproduce better than the unleached ones, showing that leaching effectively removes heterogeneously distributed extraneous Pb. However, the reproducibility of repeated digests of variably contaminated natural samples is up to an order of magnitude worse than the analytical reproducibility of ca. 100 ppm. More complex leaching methods (e.g., Nobre Silva et al., 2009) yield Pb isotope ratios within error of and with similar reproducibility to our method, showing that the simple leaching method is reliable. The remaining Pb isotope heterogeneity of natural samples, which typically exceeds 100 ppm, is thus attributed to inherent isotopic sample heterogeneity. Tl-doped MC-ICP-MS Pb ratio determination is therefore a sufficiently precise method for Pb isotope analyses in natural rocks. More precise Pb double- or triple-spike methods (e.g., Galer, 1999; Thirlwall, 2000), may exploit their full potential only in cases where natural isotopic sample heterogeneity is demonstrably negligible. References: Galer, S., 1999, Chem. Geol. 157, 255-274. Nobre Silva, et al. 2009, Geochemistry Geophysics Geosystems 10, Q08012. Thirlwall, M.F., 2000, Chem. Geol. 163, 299-322.

Diode-laser-based RIMS measurements of strontium-90

NASA Astrophysics Data System (ADS)

Bushaw, B. A.; Cannon, B. D.

1998-12-01

Double- and triple-resonance excitation schemes for the ionization of strontium are presented. Use of single-mode diode lasers for the resonance excitations provides a high degree of optical isotopic selectivity: with double-resonance, selectivity of >104 for 90Sr against the stable Sr isotopes has been demonstrated. Measurement of lineshapes and stable isotope shifts in the triple-resonance process indicate that optical selectivity should increase to ˜109. When combined with mass spectrometer selectivity this is sufficient for measurement of 90Sr at background environmental levels. Additionally, autoionizing resonances have been investigated for improving ionization efficiency with lower power lasers.

Optimization of scintillator loading with the tellurium-130 isotope for long-term stability

NASA Astrophysics Data System (ADS)

Duhamel, Lauren; Song, Xiaoya; Goutnik, Michael; Kaptanoglu, Tanner; Klein, Joshua; SNO+ Collaboration

2017-09-01

Tellurium-130 was selected as the isotope for the SNO + neutrinoless double beta decay search, as 130Te decays to 130Xe via double beta decay. Linear alkyl benzene(LAB) is the liquid scintillator for the SNO + experiment. To load tellurium into scintillator, it is combined with 1,2-butanediol to form an organometallic complex, commonly called tellurium butanediol (TeBD). This study focuses on maximizing the percentage of tellurium loaded into scintillator and evaluates the complex's long-term stability. Studies on the effect of nucleation due to imperfections in the detector's surface and external particulates were employed by filtration and induced nucleation. The impact of water on the stability of TeBD complex was evaluated by liquid-nitrogen sparging, variability in pH and induced humidity. Alternative loading methods were evaluated, including the addition of stability-inducing organic compounds. Samples of tellurium-loaded scintillator were synthesized, treated, and consistently monitored in a controlled environment. It was found that the hydronium ions cause precipitation in the loaded scintillator, demonstrating that water has a detrimental effect on long-term stability. Optimization of loaded scintillator stability can contribute to the SNO + double beta decay search.

On the influence of anharmonicity on the isotope effect

NASA Astrophysics Data System (ADS)

Galbaatar, T.; Drechsler, S. L.; Plakida, N. M.; Vujicic, G. M.

1991-12-01

The effect of double-well type lattice anharmonicity on the superconducting temperature and its isotope effect is investigated beyond the two-level approximation (TLA) within the Eliashberg theory. It is shown that anharmonicity can greatly modify the isotope effect; In particular anomalously large as well as negative values of the isotope effect exponent α are obtained in the strong and weak coupling limits, respectively.

Identifying stereoisomers by ab-initio calculation of secondary isotope shifts on NMR chemical shieldings.

PubMed

Böhm, Karl-Heinz; Banert, Klaus; Auer, Alexander A

2014-04-23

We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2H)ethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T) level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

Evaluation of laser ablation double-focusing SC-ICPMS for “common” lead isotopic measurements in silicate glasses and mineral

USGS Publications Warehouse

Pietruszka, Aaron J.; Neymark, Leonid

2017-01-01

An analytical method for the in situ measurement of “common” Pb isotope ratios in silicate glasses and minerals using a 193-nm excimer laser ablation (LA) system with a double-focusing single-collector (SC)-ICPMS is presented and evaluated as a possible alternative to multiple-collector (MC)-ICPMS. This LA-SC-ICPMS technique employs fast-scanning ion deflectors to sequentially place a series of flat-topped isotope peaks into a single ion-counting detector at a fixed accelerating voltage and magnetic field strength. Reference materials (including NIST, MPI-DING, and USGS glasses) are used to identify two analytical artifacts on the Pb isotope ratios (expressed here as heavier/lighter isotopes) when corrected for mass bias relative to NIST SRM610. The first artifact is characterized by anomalously low Pb isotope ratios (~0.1%/AMU) when SRM610 is analyzed in raster mode as an unknown at small spot sizes (<25 µm), which may indicate that (1) SRM610 is isotopically heterogeneous on a small length scale and/or (2) there is a non-spectral matrix effect on the Pb isotope ratios related to differences in spot size. The second artifact is characterized by anomalously high Pb isotope ratios (<0.1%/AMU) for NIST SRM612 (in raster mode) and some Fe-rich glass reference materials (BCR-2G, GOR132-G, and T1-G). These offsets are thought to be caused by one or more non-spectral matrix effects related to differences in the ablation behavior, composition, or physical properties of these reference materials compared to the bracketing SRM610 standard. The precision (±2SD) of our LA-SC-ICPMS Pb isotopic measurements is similar to (207Pb/206Pb and 208Pb/206Pb, or 20XPb/206Pb) or better than (206Pb/204Pb,207Pb/204Pb, and 208Pb/204Pb, or 20XPb/204Pb) a series of published studies that used a different type of SC-ICPMS and obtained a factor of ~3-4 higher sensitivity for Pb. An increase in the sensitivity of our LA-SC-ICPMS would likely improve the precision of the 20XPb/206Pb and 20XPb/204Pb ratios for low-Pb materials (<5 ppm), possibly making the technique broadly similar to LA-MC-ICPMS (particularly compared to methods that rely upon at least one ion-counting detector). Further improvement in the precision of the 20XPb/206Pb and 20XPb/204Pb ratios for high-Pb materials (>5 ppm) by LA-SC-ICPMS is unlikely, and in this case, LA-MC-ICPMS remains the preferable analytical technique.

Calculated differential and double differential cross section of DT neutron induced reactions on natural chromium (Cr)

NASA Astrophysics Data System (ADS)

Rajput, Mayank; Vala, Sudhirsinh; Srinivasan, R.; Abhangi, M.; Subhash, P. V.; Pandey, B.; Rao, C. V. S.; Bora, D.

2018-01-01

Chromium is an important alloying element of stainless steel (SS) and SS is the main constituent of structural material proposed for fusion reactors. Energy and double differential cross section data will be required to estimate nuclear responses in the materials used in fusion reactors. There are no experimental data of energy and double differential cross section, available for neutron induced reactions on natural chromium at 14 MeV neutron energy. In this study, energy and double differential cross section data of (n,p) and (n,α) reactions for all the stable isotopes of chromium have been estimated, using appropriate nuclear models in TALYS code. The cross section data of stable isotopes are later converted into the energy and double differential cross section data of natural Cr using the isotopic abundance. The contribution from compound, pre-equilibrium and direct nuclear reaction to total reaction have also been calculated for 52,50Cr(n,p) and 52Cr(n,α). The calculation of energy differential cross section shows that most of emitted protons and alpha particles are of 3 and 8 MeV respectively. The calculated data is compared with the data from EXFOR data library and is found to be in good agreement.

Investigation of mass dependence effects for the accurate determination of molybdenum isotope amount ratios by MC-ICP-MS using synthetic isotope mixtures.

PubMed

Malinovsky, Dmitry; Dunn, Philip J H; Petrov, Panayot; Goenaga-Infante, Heidi

2015-01-01

Methodology for absolute Mo isotope amount ratio measurements by multicollector inductively coupled plasma-mass spectrometry (MC-ICP-MS) using calibration with synthetic isotope mixtures (SIMs) is presented. For the first time, synthetic isotope mixtures prepared from seven commercially available isotopically enriched molybdenum metal powders ((92)Mo, (94)Mo, (95)Mo, (96)Mo, (97)Mo, (98)Mo, and (100)Mo) are used to investigate whether instrumental mass discrimination of Mo isotopes in MC-ICP-MS is consistent with mass-dependent isotope distribution. The parent materials were dissolved and mixed as solutions to obtain mixtures with accurately known isotope amount ratios. The level of elemental impurities in the isotopically enriched molybdenum metal powders was quantified by ICP-MS by using both high-resolution and reaction cell instruments to completely resolve spectral interferences. The Mo isotope amount ratio values with expanded uncertainty (k = 2), determined by MC-ICP-MS for a high-purity Mo rod from Johnson Matthey, were as follows: (92)Mo/(95)Mo = 0.9235(9), (94)Mo/(95)Mo = 0.5785(8), (96)Mo/(95)Mo = 1.0503(9), (97)Mo/(95)Mo = 0.6033(6), (98)Mo/(95)Mo = 1.5291(20), and (100)Mo/(95)Mo = 0.6130(7). A full uncertainty budget for the measurements is presented which shows that the largest contribution to the uncertainty budget comes from correction for elemental impurities (∼51%), followed by the contribution from weighing operations (∼26 %). The atomic weight of molybdenum was calculated to be 95.947(2); the uncertainty in parentheses is expanded uncertainty with the coverage factor of 2. A particular advantage of the developed method is that calibration factors for all six Mo isotope amount ratios, involving the (95)Mo isotope, were experimentally determined. This allows avoiding any assumption on mass-dependent isotope fractions in MC-ICP-MS, inherent to the method of double spike previously used for Mo isotope amount ratio measurements. However, data obtained in this study show that instrumental mass discrimination in MC-ICP-MS is consistent with mass-dependent Mo isotope fractionation. This was demonstrated by a good agreement between experimentally obtained and theoretically expected values of the exponent of isotope fractionation, β, for each triad of Mo isotopes.

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

NASA Astrophysics Data System (ADS)

Irrgeher, Johanna; Zitek, Andreas; Prohaska, Thomas

2014-05-01

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

Magnesium isotope compositions of Solar System materials determined by double spiking

NASA Astrophysics Data System (ADS)

Hin, R.; Lai, Y. J.; Coath, C.; Elliott, T.

2015-12-01

As a major element, magnesium is of interest for investigating large scale processes governing the formation and evolution of rocky planetary bodies. Determining the Mg isotope composition of the Earth and other planetary bodies has hence been a topic of interest ever since mass-dependent fractionation of 'non-traditional' stable isotopes has been used to study high-temperature processes. Published results, however, suffer from disagreement on the Mg isotope compositions of the Earth and chondrites [1-5], which is attributed to residual matrix effects. Nonetheless, most recent studied have converged towards a homogeneous (chondritic) Mg isotope composition in the Solar System [2-5]. However, in several of the recent studies there is a hint of a systematic difference of about 0.02-0.06‰ in the 26Mg/24Mg isotope compositions of chondrites and Earth. Such difference, however, is only resolvable by taking standard errors, which assumes robust data for homogenous sample sets. The discrepancies between various studies unfortunately undermine the confidence in such robustness and homogeneity. The issues with matrix effects during isotopic analyses can be overcome by using a double spike approach. Such methodology generally requires three isotope ratios to solve for three unknowns, a requirement that cannot be met for Mg. However, using a newly developed approach, we present Mg isotope compositions obtained by critical mixture double spiking. This new approach should allow greater confidence in the robustness of the data and hence enable improvement of. Preliminary data indicate that chondrites have a resolvable ~0.04‰ lighter 26Mg/24Mg than (ultra)mafic rocks from Earth, Mars and the eucrite parent body, which appear indistinguishable from each other. It seems implausible that this difference is caused by magmatic process such as partial melting or crystallisation. More likely, Mg isotopes are fractionated by a non-magmatic process during the formation of planets, e.g. by vapour-condensate fractionation. [1] Wiechert and Halliday, 2007. EPSL 256, 360-371. [2] Bourdon et al., 2010. GCA 74, 5069-5083. [3] Teng et al., 2010. GCA 74, 4150-4166. [4] Chakrabarti and Jacobsen, 2010. EPSl 293, 349-358. [5] Von Strandmann, 2011. GCA 75, 5247-5268.

Calcium Isotopic Composition of Bulk Silicate Earth

NASA Astrophysics Data System (ADS)

Kang, J.; Ionov, D. A.; Liu, F.; Zhang, C.; Zhang, Z.; Huang, F.

2016-12-01

Ca isotopes are used to study the accretion history of the Earth and terrestrial planets, but, Ca isotopic composition of the Bulk Silicate Earth (BSE) remains poorly constrained [1]. To better understand the Ca isotopic composition of BSE, we analyzed 22 well studied peridotite xenoliths from Tariat (Mongolia), Vitim (southern Siberia) and Udachnaya (Siberian Craton). These samples include both fertile and highly depleted garnet and spinel peridotites that show no or only minor post-melting metasomatism or alteration. Ca isotope measurements were done on a Triton-TIMS using double spike method at the Guangzhou Institute of Geochemistry, CAS. The data are reported as δ44/40Ca (relative to NIST SRM 915a). Results for geostandards are consistent with those from other laboratories. 2 standard deviations of SRM 915a analyses are 0.13‰ (n=48). δ44/40Ca of both and fertile and refractory peridotites range from 0.79 to 1.07‰ producing an average of 0.93±0.12‰ (2SD). This value defines the Ca isotopic composition of the BSE, which is consistent with the average δ44/40Ca of oceanic basalts ( 0.90‰)[2,3]. [1] Huang et al (2010) EPSL 292; [2] Valdes et al (2014) EPSL 394; [3]DePaolo (2004) RMG 55.

Iron-Isotopic Fractionation Studies Using Multiple Collector Inductively Coupled Plasma Mass Spectrometry

NASA Technical Reports Server (NTRS)

Anbar, A. D.; Zhang, C.; Barling, J.; Roe, J. E.; Nealson, K. H.

1999-01-01

The importance of Fe biogeochemistry has stimulated interest in Fe isotope fractionation. Recent studies using thermal ionization mass spectrometry (TIMS) and a "double spike" demonstrate the existence of biogenic Fe isotope effects. Here, we assess the utility of multiple-collector inductively-coupled plasma mass spectrometry(MC-ICP-MS) with a desolvating sample introduction system for Fe isotope studies, and present data on Fe biominerals produced by a thermophilic bacterium. Additional information is contained in the original extended abstract.

Absolute and Mass-Dependent Titanium Isotope Compositions of Solar System Materials

NASA Astrophysics Data System (ADS)

Williams, N. H.; Fehr, M. A.; Akram, W. M.; Parkinson, I. J.; Schönbächler, M.

2013-09-01

Mass dependent Ti isotope data for various solar system material will be presented. This data has been obtained via double spike technique using ^47 Ti and ^49Ti as spikes. Absolute nucleosynthetic anomalie data for Ti will be presented also.

Molecular Isotopic Characterization of the ALH 85013.50 Meteorite: Defining the Extraterrestrial Organic Compounds

NASA Technical Reports Server (NTRS)

Fuller, M.; Huang, Y.

2003-01-01

The Antarctic Meteorite Program has returned over 16,000 meteorites from the ice sheets of the Antarctic. This more than doubles the number of preexisting meteorite collection and adds important and rare specimens to the assemblage. The CM carbonaceous chondrites are of particular interest because of their high organic component. The Antarctic carbonaceous chondrites provide a large, previously uninvestigated suite of meteorites. Of the 161 CM chondrites listed in the Catalogue of Meteorites 138 of them have been recovered from the Antarctic ice sheets,. However, these meteorites have typically been exposed to Earth s conditions for long periods of time. The extent of terrestrial organic contamination and weathering that has taken place on these carbonaceous chondrites is unknown. In the past, stable isotope analysis was used to identify bulk organics that were extraterrestrial in origin. Although useful, this method could not exclude the possibility of terrestrial contamination contributing to the isotopic measurement. Compound specific isotope analysis of organic meteorite material has provided the opportunity to discern the terrestrial contamination from extraterrestrial organic compounds on the molecular level.

NMR studies of double proton transfer in hydrogen bonded cyclic N,N'-diarylformamidine dimers: conformational control, kinetic HH/HD/DD isotope effects and tunneling.

PubMed

Lopez, Juan Miguel; Männle, Ferdinand; Wawer, Iwona; Buntkowsky, Gerd; Limbach, Hans-Heinrich

2007-08-28

Using dynamic NMR spectroscopy, the kinetics of the degenerate double proton transfer in cyclic dimers of polycrystalline (15)N,(15)N'-di-(4-bromophenyl)-formamidine (DBrFA) have been studied including the kinetic HH/HD/DD isotope effects in a wide temperature range. This transfer is controlled by intermolecular interactions, which in turn are controlled by the molecular conformation and hence the molecular structure. At low temperatures, rate constants were determined by line shape analysis of (15)N NMR spectra obtained using cross-polarization (CP) and magic angle spinning (MAS). At higher temperatures, in the microsecond time scale, rate constants and kinetic isotope effects were obtained by a combination of longitudinal (15)N and (2)H relaxation measurements. (15)N CPMAS line shape analysis was also employed to study the non-degenerate double proton transfer of polycrystalline (15)N,(15)N'-diphenyl-formamidine (DPFA). The kinetic results are in excellent agreement with the kinetics of DPFA and (15)N,(15)N'-di-(4-fluorophenyl)-formamidine (DFFA) studied previously for solutions in tetrahydrofuran. Two large HH/HD and HD/DD isotope effects are observed in the whole temperature range which indicates a concerted double proton transfer mechanism in the domain of the reaction energy surface. The Arrhenius curves are non-linear indicating a tunneling mechanism. Arrhenius curve simulations were performed using the Bell-Limbach tunneling model. The role of the phenyl group conformation and hydrogen bond compression on the barrier of the proton transfer is discussed.

Measurement of the Carbon Isotopic Composition of Methane Using Helicoidal Laser Eigenstates

NASA Astrophysics Data System (ADS)

Jacob, D.; Le Floch, A.; Bretenaker, F.; Guenot, P.

1996-06-01

The spatially generalized Jones matrix formalism is used to design a laser cavity to make intracavity measurements of the carbon isotopic composition of methane. the method is based on a double optical lever effect for helicoidally polarized eigenstates, permitting to measure successively the ^{12}CH_4 and ^{13}CH_4 concentrations. To choose the probed isotope, one simply tunes the frequency of the laser by Zeeman effect. The experiment exhibits a good agreement with the predictions and permits to measure the ^{13}CH4/^{12}CH_4 composition ratio of methane with an uncertainty of the order of ± 0.07% for a sample containing only 6× 10^{-9} mole of methane. On utilise le formalisme des matrices de Jones généralisées spatialement pour concevoir une cavité laser permettant la mesure intra-cavité de la composition isotopique du carbone présent dans le méthane. La méthode est fondée sur une double application de l'effet de levier optique pour les états propres hélicoïdaux, permettant de mesurer successivement les concentrations de ^{12}CH_4 et de ^{13}CH_4. Pour passer d'un isotope à l'autre, on ajuste simplement la fréquence du laser par effet Zeeman. L'expérience est en bon accord avec les prédictions et permet d'effectuer la mesure du rapport isotopique ^{13}CH4/^{12}CH_4 avec une fourchette d'incertitude de ± 0,07% pour des échantillons de gaz ne contenant que 6× 10^{-9} mole de méthane.

Nuclear transition matrix elements for neutrinoless double-β decay of 76Ge and 82Se isotopes

NASA Astrophysics Data System (ADS)

Rath, P. K.

2017-10-01

Within mechanisms involving light and heavy Majorana neutrinos, the nuclear transition matrix elements (NTMEs) for the neutrinoless double-β decay of 76Ge and 82Se isotopes are calculated. Uncertainties in the average NTMEs M¯ (0 v ) and M¯ (0 N ) due to the exchange of light and heavy Majorana neutrinos, respectively, turn out to be about 10% and 37%, respectively. Limits on the effective mass of light Majorana neutrino , heavy Majorana neutrino and Majoron-neutrino coupling constant of classical Majoron model are extracted.

SIMSISH Technique Does Not Alter the Apparent Isotopic Composition of Bacterial Cells

PubMed Central

Chapleur, Olivier; Wu, Ting-Di; Guerquin-Kern, Jean-Luc; Mazéas, Laurent; Bouchez, Théodore

2013-01-01

In order to identify the function of uncultured microorganisms in their environment, the SIMSISH method, combining in situ hybridization (ISH) and nanoscale secondary ion mass spectrometry (nanoSIMS) imaging, has been proposed to determine the quantitative uptake of specific labelled substrates by uncultured microbes at the single cell level. This technique requires the hybridization of rRNA targeted halogenated DNA probes on fixed and permeabilized microorganisms. Exogenous atoms are introduced into cells and endogenous atoms removed during the experimental procedures. Consequently differences between the original and the apparent isotopic composition of cells may occur. In the present study, the influence of the experimental procedures of SIMSISH on the isotopic composition of carbon in E. coli cells was evaluated with nanoSIMS and compared to elemental analyser-isotopic ratio mass spectrometer (EA-IRMS) measurements. Our results show that fixation and hybridization have a very limited, reproducible and homogeneous influence on the isotopic composition of cells. Thereby, the SIMSISH procedure minimizes the contamination of the sample by exogenous atoms, thus providing a means to detect the phylogenetic identity and to measure precisely the carbon isotopic composition at the single cell level. This technique was successfully applied to a complex sample with double bromine – iodine labelling targeting a large group of bacteria and a specific archaea to evaluate their specific 13C uptake during labelled methanol anaerobic degradation. PMID:24204855

Laser separation of lithium isotopes by double resonance enhanced multiphoton ionization of Li/sub 2/

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

Balz, J.G.; Bernheim, R.A.; Gold, L.P.

1987-01-01

Multiphoton ionization spectra of /sup 7/Li/sub 2/, /sup 6/Li/sub 2/, and /sup 7/Li/sup 6/Li vapors have been measured in the 570--650 nm region using a single, low resolution, multimode cw dye laser. A number of wavelengths provide selective multiphoton ionization of one isotopic species demonstrating the possibility of efficient laser-driven isotopic separation in lithium in this wavelength region.

Determination of 90Sr / 238U ratio by double isotope dilution inductively coupled plasma mass spectrometer with multiple collection in spent nuclear fuel samples with in situ 90Sr / 90Zr separation in a collision-reaction cell

NASA Astrophysics Data System (ADS)

Isnard, H.; Aubert, M.; Blanchet, P.; Brennetot, R.; Chartier, F.; Geertsen, V.; Manuguerra, F.

2006-02-01

Strontium-90 is one of the most important fission products generated in nuclear industry. In the research field concerning nuclear waste disposal in deep geological environment, it is necessary to quantify accurately and precisely its concentration (or the 90Sr / 238U atomic ratio) in irradiated fuels. To obtain accurate analysis of radioactive 90Sr, mass spectrometry associated with isotope dilution is the most appropriated method. But, in nuclear fuel samples the interference with 90Zr must be previously eliminated. An inductively coupled plasma mass spectrometer with multiple collection, equipped with an hexapole collision cell, has been used to eliminate the 90Sr / 90Zr interference by addition of oxygen in the collision cell as a reactant gas. Zr + ions are converted into ZrO +, whereas Sr + ions are not reactive. A mixed solution, prepared from a solution of enriched 84Sr and a solution of enriched 235U was then used to quantify the 90Sr / 238U ratio in spent fuel sample solutions using the double isotope dilution method. This paper shows the results, the reproducibility and the uncertainties that can be obtained with this method to quantify the 90Sr / 238U atomic ratio in an UOX (uranium oxide) and a MOX (mixed oxide) spent fuel samples using the collision cell of an inductively coupled plasma mass spectrometer with multiple collection to perform the 90Sr / 90Zr separation. A comparison with the results obtained by inductively coupled plasma mass spectrometer with multiple collection after a chemical separation of strontium from zirconium using a Sr spec resin (Eichrom) has been performed. Finally, to validate the analytical procedure developed, measurements of the same samples have been performed by thermal ionization mass spectrometry, used as an independent technique, after chemical separation of Sr.

Neutron capture cross-section studies of Tellurium isotopes for neutrinoless double beta decay applications

NASA Astrophysics Data System (ADS)

Bhike, Megha; Tornow, Werner

2014-09-01

The CUORE detector at Gran Sasso, aimed at searching for neutrinoless double-beta decay of 130Te, employs an array of TeO2 bolometer modules. To understand and identify the contribution of muon and (α,n) induced neutrons to the CUORE background, fast neutron cature cross-section data of the tellurium isotopes 126Te, 128Te and 130Te have been measured with the activation method at eight different energies in the neutron energy range 0.5-7.5 MeV. Plastic pill boxes of diameter 1.6 cm and width 1 cm containing Te were irradiated with mono-energetic neutrons produced via the 3H(p,n)3He and 2H(d,n)3He reactions. The cross-sections were determined relative to the 197Au(n, γ)198Au and 115In(n,n')115m In standard cross sections. The activities of the products were measured using 60% lead-shielded HPGe detectors at TUNL's low background counting facility. The present results are compared with the evaluated data from TENDL-2012, ENDF/B-VII.1, JEFF-3.2 and JENDL-4.0, as well as with literature data.

Mid-IR enhanced laser ablation molecular isotopic spectrometry

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Measurement of the isotope shift of the 63 P 1 ↔53 D 1 transition of ytterbium by using a diode oscillator fiber amplified laser

NASA Astrophysics Data System (ADS)

Lee, L.; Park, H.; Ko, K.-H.; Jeong, D.-Y.

2010-08-01

We demonstrated a Diode Oscillator Fiber Amplification (DOFA) system in order to study the 63 P 1 ↔53 D 1 (1539 nm) transition line of a neutral ytterbium atom that is accessed by the stepwise excitation of the ground state. The frequency of the DOFA system was doubled by a MgO:PPLN crystal for the resonant excitation of the 61 S 0 ↔63 P 1 transition. The frequency of the second harmonic beam was stabilized to the 61 S 0 ↔63 P 1 transition of each isotope with the stability of about 2 MHz. We performed absorption spectroscopy on the 63 P 1 ↔53 D 1 (1539 nm) transition after the velocity selective excitation by the frequency-doubled beam. The isotope shifts in the 63 P 1 ↔53 D 1 (1539 nm) transition were directly measured for the first time. The relative isotope shifts from 174Yb were measured as -105.8 MHz and 109.7 MHz for 176Yb and 172Yb, respectively.

Uranium 238U/235U isotope ratios as indicators of reduction: Results from an in situ biostimulation experiment at Rifle, Colorado, USA

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

Bopp IV, C.J.; Lundstrom, C.C.; Johnson, T.M.

2010-02-01

The attenuation of groundwater contamination via chemical reaction is traditionally evaluated by monitoring contaminant concentration through time. However, this method can be confounded by common transport processes (e.g. dilution, sorption). Isotopic techniques bypass the limits of concentration methods, and so may provide improved accuracy in determining the extent of reaction. We apply measurements of {sup 238}U/{sup 235}U to a U bioremediation field experiment at the Rifle Integrated Field Research Challenge Site in Rifle, Colorado (USA). An array of monitoring and injection wells was installed on a 100 m{sup 2} plot where U(VI) contamination was present in the groundwater. Acetate-amended groundwatermore » was injected along an up-gradient gallery to encourage the growth of dissimilatory metal reducing bacteria (e.g. Geobacter species). During amendment, U concentration dropped by an order of magnitude in the experiment plot. We measured {sup 238}U/{sup 235}U in samples from one monitoring well by MC-ICP-MS using a double isotope tracer method. A significant {approx}1.00{per_thousand} decrease in {sup 238}U/{sup 235}U occurred in the groundwater as U(VI) concentration decreased. The relationship between {sup 238}U/{sup 235}U and concentration corresponds approximately to a Rayleigh distillation curve with an effective fractionation factor ({alpha}) of 1.00046. We attribute the observed U isotope fractionation to a nuclear field shift effect during enzymatic reduction of U(VI){sub (aq)} to U(IV){sub (s)}.« less

Platinum stable isotopes in ferromanganese crust and nodules

NASA Astrophysics Data System (ADS)

Corcoran, Loretta; Seward, Terry; Handler, Monica R.

2015-04-01

Hydrogenetic ferromanganese (Fe-Mn) crust and nodules are slow-growing chemical sediments that form by direct precipitation from seawater, resulting in a record of changing seawater chemistry. These sediments are the primary sink for platinum in the modern oxic marine environment, hosting well-documented enrichments over other platinum-group elements (PGEs): the Pt anomaly [1]. Platinum is a non-bio-essential, highly siderophile, transition metal with six stable isotopes (190Pt, 192Pt, 194Pt, 195Pt, 196Pt, and 198Pt) with several oxidation states (Pt0, Pt2+ and Pt4+). Platinum is generally considered to exist in the hydrosphere as Pt2+ although its behaviour in the marine environment is poorly constrained, and Pt4+may also be present. Variations in ocean redox state, together with changes in source fluxes to the oceans, may therefore lead to small variations (< ±1) in the stable isotopic composition of marine platinum, raising the potential of adding platinum to the growing arsenal of paleoceanographic tracers. A method has been developed to measure the platinum isotopic composition using double spike MC-ICPMS analysis [2]and applied to a global suite of modern Fe-Mn crust and nodules. Combining synchrotron XAFS analyses of platinum adsorbed onto Fe-Mn oxide and oxyhydroxide surfaces to determine oxidation state and bonding environment, with platinum stable isotopic measurements allowing us to evaluate both platinum incorporation onto these sediments and the associated degree of platinum isotopic fractionation. Leaching experiments conducted on platinum rich terrestrial materials underwent platinum stable isotopic measurement as an analogue for the Pt isotopic fractionation associated with continental weathering. [1] Hodge, V.F. et al. (1985) Earth and Planetary Science Letters, 72, 158-162. [2] Creech, J. et al. (2013) Journal of Analytical Atomic Spectrometry, 28. 853-865.

High-accuracy deep-UV Ramsey-comb spectroscopy in krypton

NASA Astrophysics Data System (ADS)

Galtier, Sandrine; Altmann, Robert K.; Dreissen, Laura S.; Eikema, Kjeld S. E.

2017-01-01

In this paper, we present a detailed account of the first precision Ramsey-comb spectroscopy in the deep UV. We excite krypton in an atomic beam using pairs of frequency-comb laser pulses that have been amplified to the millijoule level and upconverted through frequency doubling in BBO crystals. The resulting phase-coherent deep-UV pulses at 212.55 nm are used in the Ramsey-comb method to excite the two-photon 4p^6 → 4p^5 5p [1/2 ]_0 transition. For the {}^{84}Kr isotope, we find a transition frequency of 2829833101679(103) kHz. The fractional accuracy of 3.7 × 10^{-11} is 34 times better than previous measurements, and also the isotope shifts are measured with improved accuracy. This demonstration shows the potential of Ramsey-comb excitation for precision spectroscopy at short wavelengths.

The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar

2016-06-01

The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate differentiation processes, such as partial mantle melting and crystal fractionation, can cause stable Cr isotopic fractionation on Earth and other planetary bodies.

Beta-lactamase-catalyzed aminolysis of depsipeptides: Proof of the nonexistence of a specific D-phenylalanine/enzyme complex by double-label isotope trapping

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

Pazhanisamy, S.; Pratt, R.F.

The steady-state kinetics of the Enterobacter cloacae P99 beta-lactamase-catalyzed aminolysis of the depsipeptide m-(((phenylacetyl)glycyl)oxy)benzoic acid by D-phenylalanine were consistent with an ordered sequential mechanism with D-phenylalanine binding first. In terms of this mechanism, the kinetics data required that in 20 mM MOPS buffer, pH 7.5, the dissociation constant of the initially formed enzyme/D-phenylalanine complex be around 1.3 mM; at pH 9.0 in 0.1 M carbonate buffer, the complex should be somewhat more stable. Attempts to detect this complex in a binary mixture by spectroscopic methods (fluorescence, circular dichroic, and nuclear magnetic resonance spectra) failed. Kinetic methods were also unsuccessful--the presencemore » of 20 mM D-phenylalanine did not appear to affect beta-lactamase activity nor inhibition of the enzyme by phenylmethanesulfonyl fluoride, phenylboronic acid, or (3-dansylamidophenyl)boronic acid. Equilibrium dialysis experiments appeared to indicate that the dissociation constant of any binary enzyme/D-phenylalanine complex must be somewhat higher than the kinetics allowed (greater than 2 mM). Since the kinetics also required that, at high depsipeptide concentrations, and again with the assumption of the ordered sequential mechanism, the reaction of the enzyme/D-phenylalanine complex to aminolysis products be faster than its reversion to enzyme and D-phenylalanine, a double-label isotope-trapping experiment was performed.« less

The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

NASA Technical Reports Server (NTRS)

Freeman, K. H.; Boreham, C. J.; Summons, R. E.; Hayes, J. M.

1994-01-01

Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.

Purification of telluric acid for SNO+ neutrinoless double-beta decay search

NASA Astrophysics Data System (ADS)

Hans, S.; Rosero, R.; Hu, L.; Chkvorets, O.; Chan, W. T.; Guan, S.; Beriguete, W.; Wright, A.; Ford, R.; Chen, M. C.; Biller, S.; Yeh, M.

2015-09-01

Tellurium-130 has the highest natural abundance of any double-beta decay isotopes. Recently it has been developed as a promising candidate for loading in liquid scintillator to explore the Majorana or Dirac nature of the neutrino through a search for neutrinoless double beta decay (0νββ). To this end, procedures have been developed to transfer tellurium ions into the organic liquid by a water-based loading technology. However, traces of naturally occurring radioactivity and cosmic-ray induced isotopes introduced into the scintillator with tellurium could produce undesirable contaminations in the 130Te 0νββ region. Measurements using various elemental spikes prepared from different chemical forms indicate that the uses of self-scavenging as well as acid and thermal recrystallization prior to the preparation of a tellurium-loaded liquid scintillator can deplete U and Th and several cosmic-activated isotopes from Te feedstock by a factor of 102-103 in a single pass. The process is also found to improve the optical transmission in the blue region, sensible to the photomultiplier tube, by removing traces of colored impurities. In addition to the scintillator-based experiments, this cleansing scheme has potential applications to the production of radiopure tellurium crystals for other rare-event experiments.

Negative Oxygen Isotope Effect in Manganites with an Ordered Cation Arrangement in a High Magnetic Field

NASA Astrophysics Data System (ADS)

Taldenkov, A. N.; Snegirev, V. V.; Babushkina, N. A.; Kalitka, V. S.; Kaul', A. R.

2018-03-01

The oxygen isotope effect in PrBaMn2 16-18 O5.97 manganite with an ordered cation arrangement is studied. The field dependences of magnetic susceptibility and magnetization are measured in the temperature range 100-270 K and magnetic fields up to 32 T. A significant increase in the temperature of the spin-reorientation antiferromagnet-ferromagnet phase transition is detected in samples enriched in heavy oxygen 18O (negative isotope effect). The transition temperature and the isotope effect depend strongly on the magnetic field. An H-T phase diagram is plotted for samples with various isotope compositions. An analysis of the experimental results demonstrates that the detected negative isotope effect and the giant positive isotope effect revealed earlier in doped manganites have the same nature. The mechanisms of appearance of isotope effects are discussed in terms of the double exchange model under a polaron narrowing of the free carrier band.

δ-Deuterium Isotope Effects as Probes for Transition-State Structures of Isoprenoid Substrates

PubMed Central

2015-01-01

The biosynthetic pathways to isoprenoid compounds involve transfer of the prenyl moiety in allylic diphosphates to electron-rich (nucleophilic) acceptors. The acceptors can be many types of nucleophiles, while the allylic diphosphates only differ in the number of isoprene units and stereochemistry of the double bonds in the hydrocarbon moieties. Because of the wide range of nucleophilicities of naturally occurring acceptors, the mechanism for prenyltransfer reactions may be dissociative or associative with early to late transition states. We have measured δ-secondary kinetic isotope effects operating through four bonds for substitution reactions with dimethylallyl derivatives bearing deuterated methyl groups at the distal (C3) carbon atom in the double bond under dissociative and associative conditions. Computational studies with density functional theory indicate that the magnitudes of the isotope effects correlate with the extent of bond formation between the allylic moiety and the electron-rich acceptor in the transition state for alkylation and provide insights into the structures of the transition states for associative and dissociative alkylation reactions. PMID:24665882

Determination of the delta(18O/16O)of Water: RSIL Lab Code 489

USGS Publications Warehouse

Revesz, Kinga; Coplen, Tyler

2008-01-01

The purpose of the technique described by the Reston Stable Isotope Laboratory (RSIL) lab code 489 is to present a method to determine the delta(180/160), abbreviated as delta-180, of water. This delta-18O measurement of water also is a component of National Water Quality Laboratory (NWQL in USGS) schedules 1142 and 1172. Water samples are loaded into glass sample containers on a vacuum manifold to equilibrate gaseous CO2 at constant temperature (25 deg C) with water samples. After loading water samples on the vacuum manifold, air is evacuated through capillary to avoid evaporation, and CO2 is added. The samples are shaken to increase the equilibration rate of water and CO2. When isotopic equilibrium has been attained, an aliquot of CO2 is extracted sequentially from each sample container, separated from water vapor by means of a dry ice trap, and introduced into a dual-inlet isotope-ratio mass spectrometer (DI-IRMS) for determination of the delta-18O value. There is oxygen isotopic fractionation between water and CO2, but it is constant at constant temperature. The DI-IRMS is a DuPont double-focusing mass spectrometer. It has a double collector. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other ion beams are collected in the front collector. The instrument is capable of measuring mass/charge (m/z) 44 and 45 or 44 and 46 by changing the ion-accelerating voltage under computer control. The ion beams from these m/z values are as follows: m/z 44=CO2=12C16O16O, m/z 45=CO2=13C16O16O primarily, and m/z 46 = CO2=12C16O18O primarily. The data acquisition and control software calculates delta-18O values.

Sulfur-based absolute quantification of proteins using isotope dilution inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Lee, Hyun-Seok; Heun Kim, Sook; Jeong, Ji-Seon; Lee, Yong-Moon; Yim, Yong-Hyeon

2015-10-01

An element-based reductive approach provides an effective means of realizing International System of Units (SI) traceability for high-purity biological standards. Here, we develop an absolute protein quantification method using double isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) combined with microwave-assisted acid digestion for the first time. We validated the method and applied it to certify the candidate protein certified reference material (CRM) of human growth hormone (hGH). The concentration of hGH was determined by analysing the total amount of sulfur in hGH. Next, the size-exclusion chromatography method was used with ICP-MS to characterize and quantify sulfur-containing impurities. By subtracting the contribution of sulfur-containing impurities from the total sulfur content in the hGH CRM, we obtained a SI-traceable certification value. The quantification result obtained with the present method based on sulfur analysis was in excellent agreement with the result determined via a well-established protein quantification method based on amino acid analysis using conventional acid hydrolysis combined with an ID liquid chromatography-tandem mass spectrometry. The element-based protein quantification method developed here can be generally used for SI-traceable absolute quantification of proteins, especially pure-protein standards.

In situ 40K-40Ca ‘double-plus’ SIMS dating resolves Klokken feldspar 40K-40Ar paradox

NASA Astrophysics Data System (ADS)

Harrison, T. Mark; Heizler, Matthew T.; McKeegan, Kevin D.; Schmitt, Axel K.

2010-11-01

The 40K- 40Ca decay system has not been widely utilized as a geochronometer because quantification of radiogenic daughter is difficult except in old, extremely high K/Ca domains. Even these environments have not heretofore been exploited by ion microprobe analysis due to the very high mass resolving power (MRP) of 25,000 required to separate 40K + from 40Ca +. We introduce a method that utilizes doubly-charged K and Ca species which permits isotopic measurements to be made at relatively low MRP (~ 5000). We used this K-Ca 'double-plus' approach to address an enduring controversy in 40Ar/ 39Ar thermochronology revolving around exsolved alkali feldspars from the 1166 Ma Klokken syenite (southern Greenland). Ion microprobe 40K- 40Ca analysis of Klokken samples reveal both isochron and pseudoisochron behaviors that reflect episodic isotopic and chemical exchange of coarsely exsolved perthites and a near end-member K-feldspar until ≤ 719 Ma, and perhaps as late at ~ 400 Ma. Feldspar microtextures in the Klokken syenite evolved over a protracted interval by non-thermal processes (fluid-assisted recrystallization) and thus this sample makes a poor model from which to address the general validity of 40Ar/ 39Ar thermochronological methodologies.

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

Breton, J.; Berger, G.; Nabedryk, E.

The photoreduction of the secondary quinone acceptor Q{sub B} in reaction centers (RCs) of the photosynthetic bacteria Rhodobacter sphaeroides and Rhodopseudomonas viridis has been investigated by light-induced FTIR difference spectroscopy of RCs reconstituted with several isotopically labeled ubiquinones. The labels used were {sup 18}O on both carbonyls and {sup 13}C either uniformly or selectively at the 1- or the 4-position, i.e., on either one of the two carbonyls. The Q{sub B}{sup {minus}}/Q{sub B} spectra of RCs reconstituted with the isotopically labeled and unlabeled quinones as well as the double differences calculated form these spectra exhibit distinct isotopic shifts for amore » numer of bands attributed to vibrations of Q{sub B} and Q{sub B}{sup {minus}}. The vibrational modes of the quinone in the Q{sub B} site are compared to those of ubiquinone in vitro, leading to band assignments for the C{double_bond}O and C{double_bond}C vibrations of the neutral Q{sub B} and for the C---O and C---C of the semiquinone. The C{double_bond}O frequency of each of the carbonyls of the unlabeled quinone is revealed at 1641 cm{sup {minus}1} for both species. This demonstrates symmetrical and weak hydrogen bonding of the two C{double_bond}O groups to the protein at the Q{sub B} site. In contrast, the C{double_bond}C vibrations are not equivalent for selective labeling at C{sub 1} or at C{sub 4}, although they both contribute to the {approximately}1611-cm{sup {minus}1} band in the Q{sub B}{sup {minus}}/Q{sub B} spectra of the two species. Compared to the vibrations of isolated ubiquinone, the C{double_bond}C mode of Q{sub B} does not involve displacement of the C{sub 4} carbon atom, while the motion of C{sub 1} is not hindered. Further analysis of the spectra suggests that the protein at the binding site imposes a specific constraint on the methoxy and/or the methyl group proximal to the C{sub 4} carbonyl. 49 refs., 5 figs.« less

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

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

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

2010-11-16

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

Applications of New Synthetic Uranium Reference Materials for Geochemistry Research (Invited)

NASA Astrophysics Data System (ADS)

Richter, S.; Weyer, S.; Alonso, A.; Aregbe, Y.; Kuehn, H.; Eykens, R.; Verbruggen, A.; Wellum, R.

2009-12-01

For many applications in geochemistry research isotope ratio measurements play a significant role. In geochronology isotope abundances of uranium and its daughter products thorium and lead are being used to determine the age and history of various samples of geological interest. For measuring the isotopic compositions of these elements by mass spectrometry, suitable isotope reference materials are needed to validate measurement procedures and to calibrate multi-collector and ion counting detector systems. IRMM is a recognized provider for nuclear isotope reference materials to the nuclear industry and nuclear safeguards authorities, which are also being applied widely for geochemical applications. The preparation of several new synthetic uranium reference materials at IRMM during the recent five years has provided significant impacts on geochemical research. As an example, the IRMM-074 series of gravimetrically prepared uranium mixtures for linearity testing of secondary electron multipliers (SEMs) has been applied for the redetermination of the secular equilibrium 234U/238U value and the 234U half-life by Cheng et al (2009). Due to the use of IRMM-074, results with smaller uncertainties were obtained, which are shifted by about 0.04% compared to the commonly used values published earlier by Cheng et al. in 2000. This has a significant impact for U isotope measurements in geochemistry.. As a further example, the new double spike IRMM-3636 with a 233U/236U ratio of 1:1 and an expanded uncertainty as low as 0.016% (coverage factor k=2, 95% confidence level) was prepared gravimetrically. This double spike allows internal mass fractionation correction for high precision 235U/238U ratio measurements of close to natural samples. Using the new double spike IRMM-3636, the 235U/238U ratios for several commonly used natural U standard materials from NIST/NBL and IRMM, such as e.g. NBS960 (=NBL CRM-112a), NBS950a,b and IRMM-184, have been re-measured with improved precision and accuracy. The (preliminary) result of 137.836(23) for the 238U/235U ratio of NBS960, measured using the new gravimetrically prepared 233U/236U-Double Spike IRMM-3636, is deviating by -0.032% from the well-known and widely used consensus value of 137.88. For the consensus value no uncertainty has ever been assigned, but it is outside the uncertainty limits of the new measurement result. The re-measured 238U/235U ratio of 137.689(22) of IRMM-184 agrees quite well with the certified value of 137.697(41), the calculated difference is only -0.006(34)% which is insignificant. The results for both NBS960 and IRMM-184, obtained using multi-dynamic TIMS at IRMM and using high efficiency MC-ICPMS at the University of Frankfurt, agree well with each other. As a conclusion, the IRMM-3636 Double Spike has been successfully applied for measurements of important uranium isotopic standards like NBS960 and IRMM-184, with improved uncertainties at the level of 0.016%.

Diode laser based resonance ionization mass spectrometric measurement of strontium-90

NASA Astrophysics Data System (ADS)

Bushaw, B. A.; Cannon, B. D.

1997-10-01

A diode laser based scheme for the isotopically selective excitation and ionization of strontium is presented. The double-resonance excitation 5s 21S 0→5s5p 3P 1→5s6s 3S 1 is followed by photoionization at 488 nm. The isotope shifts and hyperfine structure in the resonance transitions have been accurately measured for the stable isotopes and 90Sr, with the measurement of the 90Sr shifts using sub-pg samples. Analytical tests, using graphite crucible atomization, demonstrated 90Sr detection limits of 0.8 fg and overall (optical+mass spectrometer) isotopic selectivity of >10 10 against stable strontium.

Neutrinoless double-β decay of Se82 in the shell model: Beyond the closure approximation

NASA Astrophysics Data System (ADS)

Sen'kov, R. A.; Horoi, M.; Brown, B. A.

2014-05-01

We recently proposed a method [R. A. Senkov and M. Horoi, Phys. Rev. C 88, 064312 (2013), 10.1103/PhysRevC.88.064312] to calculate the standard nuclear matrix elements for neutrinoless double-β decay (0νββ) of Ca48 going beyond the closure approximation. Here we extend this analysis to the important case of Se82, which was chosen as the base isotope for the upcoming SuperNEMO experiment. We demonstrate that by using a mixed method that considers information from closure and nonclosure approaches, one can get excellent convergence properties for the nuclear matrix elements, which allows one to avoid unmanageable computational costs. We show that in contrast with the closure approximation the mixed approach has a very weak dependence on the average closure energy. The matrix elements for the heavy neutrino-exchange mechanism that could contribute to the 0νββ decay of Se82 are also presented.

Isotopologue-selective excitation studied via optical-optical double resonance using the E3 Σ1+(63S1) ←A3Π0+(53P1) ←X1Σ0+(51S0) transitions in CdAr and CdKr van der Waals complexes

NASA Astrophysics Data System (ADS)

Urbańczyk, T.; Dudek, J.; Koperski, J.

2018-06-01

A method of experimental selection of molecular isotopologues using optical-optical double resonance (OODR) scheme and supersonic beam source of van der Waals (vdW) complexes is presented. Due to an appropriately large isotopic shift, the proper choice of a wavenumber of a sufficiently narrowband laser in the first transition of OODR scheme can lead to a selective isotopologue excitation to the intermediate state. Thanks to this approach, it is possible to select some of the isotopologues which subsequently give a contribution to laser induced fluorescence (LIF) signal originated from the final state of OODR. In this article, results of tests of the proposed method that employs the E3 Σ1+ ←A3Π0+ ←X1Σ0+ transitions in two vdW complexes, CdKr and CdAr, are presented and analysed.

Marked spatial gradient in the topographic evolution of the Andes spanning the Chilean flat-slab transition: evidence from stable isotope paleoaltimetry and zircon double dating

NASA Astrophysics Data System (ADS)

Hoke, G. D.; McPhillips, D. F.; Giambiagi, L.; Garzione, C. N.; Mahoney, J. B.; Strecker, M. R.

2015-12-01

The major changes in the subduction angle of the Nazca plate are often hypothesized to have important consequences for the tectonic evolution of the Andes. Temporal and spatial patterns of topographic growth and exhumation are indicators that should help elucidate any linkages to subduction angle. Here, we combine observations from stable isotope paleoaltimetry with detrital zircon double dating between 30 and 35°S to demonstrate a consistent increase in surface and rock uplift in the Andes south of 32°S. The stable isotope data are from Miocene pedogenic carbonates collected from seven different basin sequences spanning different tectonic and topographic positions in the range. Paleoelevations between 1 km and 1.9 km are calculated using modern local isotope-elevation gradients along with carbonate-formation temperatures determined from clumped isotope studies in modern soils. Present day, low elevation foreland localities were at their present elevations during the Miocene, while three of the intermontane basins experienced up to 2 km of surface uplift between the end of deposition during the late Miocene and present. Detrital zircon (U-Th-Sm)/He and U-Pb double dating in three modern drainage basins (Tunuyán, Arroyo Grande and Río de los Patos) reveals clear Miocene exhumation signals south of the flat slab with no recent exhumation apparent at 32°S. The exhumation pattern is consistent with paleoaltimetry results. Interestingly, the maximum inferred surface uplift is greatest where the crust is thinnest, and the timing of the observed changes in elevation and exhumation has not been linked to any documented episodes of large-magnitude crustal shortening in the eastern half of the range. The spatial pattern of surface uplift and exhumation seems to mimic the Pampean flat slab's geometry, however, it could be equally well explained by eastward migration of a crustal root via ductile deformation in the lower crust and is not related to flat-slab subduction.

Radiogenic Isotopes As Paleoceanographic Tracers in Deep-Sea Corals: Advances in TIMS Measurements of Pb Isotopes and Application to Southern Ocean Corals

NASA Astrophysics Data System (ADS)

Wilson, D. J.; van de Flierdt, T.; Bridgestock, L. J.; Paul, M.; Rehkamper, M.; Robinson, L. F.; Adkins, J. F.

2014-12-01

Deep-sea corals have emerged as a valuable archive of deep ocean paleoceanographic change, with uranium-series dating providing absolute ages and the potential for centennial resolution. In combination with measurements of radiocarbon, neodymium isotopes and clumped isotopes, this archive has recently been exploited to reconstruct changes in ventilation, water mass sourcing and temperature in relation to millennial climate change. Lead (Pb) isotopes in both corals and seawater have also been used to track anthropogenic inputs through space and time and to trace transport pathways within the oceans. Better understanding of the oceanic Pb cycle is emerging from the GEOTRACES programme. However, while Pb isotopes have been widely used in environmental studies, their full potential as a (pre-anthropogenic) paleoceanographic tracer remains to be exploited. In deep-sea corals, challenges exist from low Pb concentrations in aragonite in comparison to secondary coatings, the potential for contamination, and the efficient elemental separation required for measurement by thermal ionisation mass spectrometry (TIMS). Here we discuss progress in measuring Pb isotopes in coral aragonite using a 207Pb-204Pb double spike on a ThermoFinnigan Triton TIMS. For a 2 ng NIST-981 Pb standard, the long term reproducibility (using 1011 Ω resistors) is ~1000 ppm (2 s.d.) on 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios. We now show that using a new 1012 Ω resistor to measure the small 204Pb beam improves the internal precision on these ratios from ~500 ppm (2 s.e.) to ~250 ppm (2 s.e.) and we envisage a potential improvement in the long term reproducibility as a consequence. We further assess the internal precision and external reproducibility of our method using a BCR-2 rock standard and an in-house coral standard. Preliminary evidence on the application of this method to natural samples is derived from cleaning experiments and replication tests on deep-sea corals from the Southern Ocean.

Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

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

Frierdich, Andrew J.; Beard, Brian L.; Rosso, Kevin M.

2015-07-01

The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Femore » isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II) aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II) aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II) aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous solutions, but presents a challenge for utilizing such an approach to determine equilibrium isotope fractionation factors. Despite the uncertainty from extrapolation, there is consistency in goethite-water fractionation factors for our reversal approach to equilibrium, with final weighted average fractionation factor values of Δ¹⁸O Gth-wate r = 0.2 (±0.9‰) and 3.0 (±2.5‰) at 22 °C and -1.6 (±0.8‰) and 1.9 (±1.5‰) at 50 °C for micron-sized and nano-particulate goethite, respectively (errors at 2σ level). Reaction of ferrihydrite with Fe(II) aq in two distinct waters resulted in a quantitative conversion to goethite and complete O isotope exchange in each case, and similar fractionation factors were observed for experiments using the two waters. Comparison of our results with previous studies of O isotope fractionation between goethite and water suggests that particle size may be a contributing factor to the disparity among experimental studies.« less

Isotope effects associated with tunneling and double proton transfer in the hydrogen bonds of benzoic acid

NASA Astrophysics Data System (ADS)

Xue, Q.; Horsewill, A. J.; Johnson, M. R.; Trommsdorff, H. P.

2004-06-01

The isotope effects associated with double proton transfer in the hydrogen bonds of benzoic acid (BA) dimers have been measured using field-cycling 1H NMR relaxometry and quasielastic neutron scattering. By studying mixed isotope (hydrogen and deuterium) samples, the dynamics of three isotopologues, BA-HH, BA-HD, and BA-DD, have been investigated. Low temperature measurements provide accurate measurements of the incoherent tunneling rate, k0. This parameter scales accurately with the mass number, m, according to the formula k0=(E/m)e-F√m providing conclusive evidence that the proton transfer process is a strongly correlated motion of two hydrons. Furthermore, we conclude that the tunneling pathway is the same for the three isotopologue species. Measurements at higher temperatures illuminate the through barrier processes that are mediated via intermediate or excited vibrational states. In parallel with the investigation of proton transfer dynamics, the theoretical and experimental aspects of studying spin-lattice relaxation in single crystals of mixed isotope samples are investigated in depth. Heteronuclear dipolar interactions between 1H and 2H isotopes contribute significantly to the overall proton spin-lattice relaxation and it is shown that these must be modeled correctly to obtain accurate values for the proton transfer rates. Since the sample used in the NMR measurements was a single crystal, full account of the orientation dependence of the spin-lattice relaxation with respect to the applied B field was incorporated into the data analysis.

The search for majoron emission in xenon-136 and two-neutrino double-beta decay of xenon-134 with the enriched xenon observatory

NASA Astrophysics Data System (ADS)

Walton, Josiah

Despite neutrino oscillation experiments firmly establishing neutrinos have non-zero mass, the absolute mass scale is unknown. Moreover, it's unknown whether the neutrino is distinguishable from its antiparticle. The most promising approach for measuring the neutrino mass scale and answering the issue of neutrino-antineutrino distinguishability is by searching for neutrinoless double-beta decay, a very rare theorized process not allowed under the current theoretical framework of particle physics. Positive observation of neutrinoless double-beta decay would usher in a revolution in particle physics, since it would determine the neutrino mass scale, establish that neutrinos and antineutrinos are indistinguishable, and that the particle physics conservation law of total lepton number is violated in nature. The latter two consequences are particularly salient, as they lead to potential explanations of neutrino mass generation and the observed large asymmetry of matter over antimatter in the universe. The Enriched Xenon Observatory (EXO-200) is an international collaboration searching for the neutrinoless double-beta decay of the isotope 136 Xe. EXO-200 operates a unique world-class low-radioactivity detector containing 110 kg of liquified xenon isotopically enriched to 80.6% in 136Xe. Recently, EXO-200 published the most precise two-neutrino double-beta decay half-life ever measured and one of the strongest limits on the half-life of the neutrinoless double-beta decay mode of 136Xe. This work presents an improved experimental search for the majoron-mediated neutrinoless double-beta decay modes of 136Xe and a novel search for the yet unobserved two neutrino double-beta decay of 134Xe.

Deciphering the iron isotope message of the human body

NASA Astrophysics Data System (ADS)

Walczyk, Thomas; von Blanckenburg, Friedhelm

2005-04-01

Mass-dependent variations in isotopic composition are known since decades for the light elements such as hydrogen, carbon or oxygen. Multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS) and double-spike thermal ionization mass spectrometry (TIMS) permit us now to resolve small variations in isotopic composition even for the heavier elements such as iron. Recent studies on the iron isotopic composition of human blood and dietary iron sources have shown that lighter iron isotopes are enriched along the food chain and that each individual bears a certain iron isotopic signature in blood. To make use of this finding in biomedical research, underlying mechanisms of isotope fractionation by the human body need to be understood. In this paper available iron isotope data for biological samples are discussed within the context of isotope fractionation concepts and fundamental aspects of human iron metabolism. This includes evaluation of new data for body tissues which show that blood and muscle tissue have a similar iron isotopic composition while heavier iron isotopes are concentrated in the liver. This new observation is in agreement with our earlier hypothesis of a preferential absorption of lighter iron isotopes by the human body. Possible mechanisms for inducing an iron isotope effect at the cellular and molecular level during iron uptake are presented and the potential of iron isotope effects in human blood as a long-term measure of dietary iron absorption is discussed.

Beta-lactamase-catalyzed aminolysis of depsipeptides: proof of the nonexistence of a specific D-phenylalanine/enzyme complex by double-label isotope trapping.

PubMed

Pazhanisamy, S; Pratt, R F

1989-08-22

The steady-state kinetics of the Enterobacter cloacae P99 beta-lactamase-catalyzed aminolysis of the depsipeptide m-[[(phenylacetyl)glycyl]oxy]benzoic acid by D-phenylalanine were consistent with an ordered sequential mechanism with D-phenylalanine binding first [Pazhanisamy, S., Govardhan, C. P., & Pratt, R. F. (1989) Biochemistry (first of three papers in this issue)]. In terms of this mechanism, the kinetics data required that in 20 mM MOPS buffer, pH 7.5, the dissociation constant of the initially formed enzyme/D-phenylalanine complex be around 1.3 mM; at pH 9.0 in 0.1 M carbonate buffer, the complex should be somewhat more stable. Attempts to detect this complex in a binary mixture by spectroscopic methods (fluorescence, circular dichroic, and nuclear magnetic resonance spectra) failed. Kinetic methods were also unsuccessful--the presence of 20 mM D-phenylalanine did not appear to affect beta-lactamase activity nor inhibition of the enzyme by phenylmethanesulfonyl fluoride, phenylboronic acid, or (3-dansylamidophenyl)boronic acid. Equilibrium dialysis experiments appeared to indicate that the dissociation constant of any binary enzyme/D-phenylalanine complex must be somewhat higher than the kinetics allowed (greater than 2 mM). Since the kinetics also required that, at high depsipeptide concentrations, and again with the assumption of the ordered sequential mechanism, the reaction of the enzyme/D-phenylalanine complex to aminolysis products be faster than its reversion to enzyme and D-phenylalanine, a double-label isotope-trapping experiment was performed.(ABSTRACT TRUNCATED AT 250 WORDS)

The 238U/235U isotope ratio of the Earth and the solar system: Constrains from a gravimetrically calibrated U double spike and implications for absolute Pb-Pb ages

NASA Astrophysics Data System (ADS)

Weyer, Stefan; Noordmann, Janine; Brennecka, Greg; Richter, Stephan

2010-05-01

The ratio of 238U and 235U, the two primordial U isotopes, has been assumed to be constant on Earth and in the solar system. The commonly accepted value for the 238U/235U ratio, which has been used in Pb-Pb dating for the last ~ 30 years, was 137.88. Within the last few years, it has been shown that 1) there are considerable U isotope variations (~1.3‰) within terrestrial material produced by isotope fractionation during chemical reactions [1-3] and 2) there are even larger isotope variations (at least 3.5‰) in calcium-aluminum-rich inclusions (CAIs) in meoteorites that define the currently accepted age of the solar system [4]. These findings are dramatic for geochronology, as a known 238U/235U is a requirement for Pb-Pb dating, the most precise dating technique for absolute ages. As 238U/235U variations can greatly affect the reported absolute Pb-Pb age, understanding and accurately measuring variation of the 238U/235U ratio in various materials is critical, With these new findings, the questions also arises of "How well do we know the average U isotope composition of the Earth and the solar system?" and "How accurate can absolute Pb-Pb ages be?" Our results using a gravimetrically calibrated 233U/236U double spike IRMM 3636 [5] indicate that the U standard NBL 950a, which was commonly used to define the excepted "natural" 238U/235U isotope ratio, has a slightly lower 238U/235U of 137.836 ± 0.024. This value is indistinguishable from the U isotope compositions for NBL 960 and NBL112A, which have been determined by several laboratories, also using the newly calibrated U double spike IRMM 3636 [6]. These findings provide new implications about the average U isotope composition of the Earth and the solar system. Basalts display a very tight range of U isotope variations (~0.25-0.32‰ relative to SRM 950a). Their U isotope composition is also very similar to that of chondrites [4], which however appear to show a slightly larger spread. Accepting terrestrial basalts to be the best representation of the U isotope composition of the Earth and the solar system, and the new 238U/235U for SRM 950a of 137.836, this would result in an average 238U/235U for the Earth and the solar system of ~ 137.80. The effect of a revised 238U/235U ratio on Pb-Pb ages is age dependent. It results in an age overestimation of ~0.8 Ma for the age of the solar system and up to 1.5 Ma for very young material (with bulk Earth U isotope composition). [1] Stirling, C.H., Andersen, M.B., Potter, E.-K., et al. (2007) EPSL 264, 208-225; [2] Weyer, S., Anbar, A. D., Gerdes, A., et al. (2008) GCA 72, 345-359. [3] Bopp, C.H., Lundstrom, C.C., Johnsons, T.M., Glessner, J.G. (2009) Geology 37, 611-614. [4] Brennecka, G.A., Weyer, S., Wadhwa, et al. (2010) Science, 327, p. 449. [5] Richter, S., Alonzo-Munoz, A., Eykens, R., et al. (2008) IJMS 269, 145-148. [6] Richter, S., et al. EGU meeting 2010.

The isotopic composition of methane in polar ice cores

NASA Technical Reports Server (NTRS)

Craig, H.; Chou, C. C.; Welhan, J. A.; Stevens, C. M.; Engelkemeir, A.

1988-01-01

Air bubbles in polar ice cores indicate that about 300 years ago the atmospheric mixing ratio of methane began to increase rapidly. Today the mixing ratio is about 1.7 parts per million by volume, and, having doubled once in the past several hundred years, it will double again in the next 60 years if current rates continue. Carbon isotope ratios in methane up to 350 years in age have been measured with as little as 25 kilograms of polar ice recovered in 4-meter-long ice-core segments. The data show that: (1) in situ microbiology or chemistry has not altered the ice-core methane concentrations, and (2) that the carbon-13 to carbon-12 ratio of atmospheric CH4 in ice from 100 years and 300 years ago was about 2 per mil lower than at present. Atmospheric methane has a rich spectrum of isotopic sources: the ice-core data indicate that anthropogenic burning of the earth's biomass is the principal cause of the recent C-13H4 enrichment, although other factors may also contribute.

Calcium Isotope (δ44/40Ca) Composition of Morozovella Velascoensis During the Paleocene Eocene Thermal Maximum Ocean Acidification Event

NASA Astrophysics Data System (ADS)

Kitch, G. D.; Jacobson, A. D.; Hurtgen, M.; Sageman, B. B.; Harper, D. T.; Zachos, J. C.

2017-12-01

Ocean acidification (OA) events are transient disruptions to the carbonate chemistry of seawater that involve decreases in pH, [CO32-] and carbonate mineral saturation states (Ω). Numerical modeling studies predict that the Ca isotope (δ44/40Ca) composition of primary marine carbonate should be sensitive to OA1, and recent evidence from the rock record may support this hypothesis2. Boron isotope (δ11B) data for the planktonic foraminifera Morozovella velascoensis indicate that the Paleocene-Eocene Thermal Maximum (PETM; 55 Mya) was an interval of pronounced OA3, although the Ca isotope composition of the bulk carbonate record appears to show post-burial diagenetic effects4. To further evaluate the Ca isotope proxy, we used a high-precision (2σSD=±0.04‰), double-spike (43Ca-42Ca) TIMS method5 to measure δ44/40Ca values of well-preserved M. velascoensis tests spanning the PETM. M. velascoensis tests (250-355 µm) were picked from samples recovered during ODP Leg 198, Site 1209 on Shatsky Rise in the equatorial Pacific. Five M. velascoensis tests were combined per sample, dissolved, spiked, and analyzed using a Triton TIMS. Repeat dissolutions of ten samples gave δ44/40Ca values within ±0.04‰ of the original measurements. Method and procedural blanks were negligible. δ44/40Ca values are elevated, even before the negative carbon isotope excursion (CIE) that marks the PETM. When δ11/10B values decrease during the CIE, δ44/40Ca values remain elevated, but then decrease by 0.10‰ as δ11B values return to pre-CIE levels. The apparent inverse correlation between δ44/40Ca and δ11B values suggests that Ca isotope fractionation by M. velascoensis was sensitive to OA. A decrease in pH indicated by lower δ11B values is consistent with higher δ44/40Ca values (decreased fractionation) due to elevated [Ca2+]/[CO32-] ratios and reduced W. The Ca isotope composition of pristine foraminiferal calcite may have potential for reconstructing [CO32-]. The current, preliminary dataset may indicate changes in [CO32-] prior to the CIE. 1Nielsen et al., 2012. 2Du Vivier et al., 2015. 3Penman et al., 2014. 4Griffith et al., 2015. 5Lehn et al., 2013.

Palladium-catalyzed double carbonylation using near stoichiometric carbon monoxide: expedient access to substituted 13C2-labeled phenethylamines.

PubMed

Nielsen, Dennis U; Neumann, Karoline; Taaning, Rolf H; Lindhardt, Anders T; Modvig, Amalie; Skrydstrup, Troels

2012-07-20

A novel and general approach for (13)C(2)- and (2)H-labeled phenethylamine derivatives has been developed, based on a highly convergent single-step assembly of the carbon skeleton. The efficient incorporation of two carbon-13 isotopes into phenethylamines was accomplished using a palladium-catalyzed double carbonylation of aryl iodides with near stoichiometric carbon monoxide.

Chemical Sample Processing for Combined Selenium Isotope and Selenium-Tellurium Elemental Investigation of the Earth's Igneous Reservoirs

NASA Astrophysics Data System (ADS)

Yierpan, Aierken; König, Stephan; Labidi, Jabrane; Kurzawa, Timon; Babechuk, Michael G.; Schoenberg, Ronny

2018-02-01

The redox-sensitive, chalcophile, and volatile Se stable isotope system offers new perspectives to investigate the origin and evolution of terrestrial volatiles and the roles of magmatic and recycling processes in the development of the redox contrast between Earth's reservoirs. Selenium isotope systematics become more robust in a well-constrained petrogenetic context as can be inferred from Se-Te elemental signatures of sulfides and igneous rocks. In this study, we present a high-yield chemical sample processing method that allows the determination of Se-Te concentrations and Se isotope composition from the same sample digest of silicate rocks by hydride generation isotope dilution (ID) quadrupole inductively coupled plasma mass spectrometry (ICP-MS) and double spike (DS) multicollector (MC)-ICP-MS, respectively. Our procedure yields ˜80% Se-Te recoveries with quantitative separation of relevant interfering elements such as Ge and HG-buffering metals. Replicate analyses of selected international reference materials yield uncertainties better than 0.11‰ (2 s.d.) on δ82/76Se and 3% (r.s.d.) on Se concentration for DS MC-ICP-MS determinations for as low as ˜10 ng sample Se. The precision of Se-Te concentration measurements by ID ICP-MS is better than 3% and 5% (r.s.d.) for total amounts of ˜0.5-1 ng Se and ˜0.2-0.5 ng Te, respectively. The basaltic reference materials have variable Se-Te contents, but their δ82/76Se values are rather uniform (on average 0.23 ± 0.14‰; 2 s.d.) and different from the chondritic value. This altogether provides the methodology and potential to extend the limited data set of coupled Se isotope and Se-Te elemental systematics of samples relevant to study the terrestrial igneous inventory.

Shear heating and solid state diffusion: Constraints from clumped isotope thermometry in carbonate faults

NASA Astrophysics Data System (ADS)

Siman-Tov, S.; Affek, H. P.; Matthews, A.; Aharonov, E.; Reches, Z.

2015-12-01

Natural faults are expected to heat rapidly during seismic slip and to cool quite quickly after the event. Here we examine clumped isotope thermometry for its ability to identify short duration elevated temperature events along frictionally heated carbonate faults. This method is based on measured Δ47 values that indicate the relative atomic order of oxygen and carbon stable isotopes in the calcite lattice, which is affected by heat and thus can serve as a thermometer. We examine three types of calcite rock samples: (1) samples that were rapidly heated and then cooled in static laboratory experiments, simulating the temperature cycle experienced by fault rock during earthquake slip; (2) limestone samples that were experimentally sheared to simulate earthquake slip events; and (3) samples taken from principle slip zones of natural carbonate faults that likely experienced earthquake slip. Experimental results show that Δ47 values decrease rapidly (in the course of seconds) and systematically both with increasing temperature and shear velocity. On the other hand, carbonate shear zone from natural faults do not show such Δ47 reduction. We propose that the experimental Δ47 response is controlled by the presence of high-stressed nano-grains within the fault zone that can reduce the activation energy for diffusion by up to 60%, and thus lead to an increased rate of solid-state diffusion in the experiments. However, the lowering of activation energy is a double-edged sword in terms of clumped isotopes: In laboratory experiments, it allows for rapid disordering so that isotopic signal appears after very short heating, but in natural faults it also leads to relatively fast isotopic re-ordering after the cessation of frictional heating, thus erasing the high temperature signature in Δ47 values within relatively short geological times (<1 Ma).

Double cross polarization for the indirect detection of nitrogen-14 nuclei in magic angle spinning NMR spectroscopy

NASA Astrophysics Data System (ADS)

Carnevale, Diego; Ji, Xiao; Bodenhausen, Geoffrey

2017-11-01

Nitrogen-14 NMR spectra at fast magic-angle spinning rates can be acquired indirectly by means of two-dimensional techniques based on double cross polarization transfer 1H → 14N →1H. Experimental evidence is given for polycrystalline samples of glycine, l-histidine, and the dipeptide Ala-Gly. Either one-bond or long-range correlations can be favored by choosing the length of the cross polarization contact pulses. Longer contact pulses allow the detection of unprotonated nitrogen sites. In contrast to earlier methods that exploited second-order quadrupolar/dipolar cross-terms, cross polarization operates in the manner of the method of Hartmann and Hahn, even for 14N quadrupolar couplings up to 4 MHz. Simulations explain why amorphous samples tend to give rise to featureless spectra because the 14N quadrupolar interactions may vary dramatically with the lattice environment. The experiments are straightforward to set up and are shown to be effective for different nitrogen environments and robust with respect to the rf-field strengths and to the 14N carrier frequency during cross polarization. The efficiency of indirect detection of 14N nuclei by double cross polarization is shown to be similar to that of isotopically enriched 13C nuclei.

Determination of thiol metabolites in human urine by stable isotope labeling in combination with pseudo-targeted mass spectrometry analysis

NASA Astrophysics Data System (ADS)

Liu, Ping; Qi, Chu-Bo; Zhu, Quan-Fei; Yuan, Bi-Feng; Feng, Yu-Qi

2016-02-01

Precursor ion scan and multiple reaction monitoring scan (MRM) are two typical scan modes in mass spectrometry analysis. Here, we developed a strategy by combining stable isotope labeling (IL) with liquid chromatography-mass spectrometry (LC-MS) under double precursor ion scan (DPI) and MRM for analysis of thiols in 5 types of human cancer urine. Firstly, the IL-LC-DPI-MS method was applied for non-targeted profiling of thiols from cancer samples. Compared to traditional full scan mode, the DPI method significantly improved identification selectivity and accuracy. 103 thiol candidates were discovered in all cancers and 6 thiols were identified by their standards. It is worth noting that pantetheine, for the first time, was identified in human urine. Secondly, the IL-LC-MRM-MS method was developed for relative quantification of thiols in cancers compared to healthy controls. All the MRM transitions of light and heavy labeled thiols were acquired from urines by using DPI method. Compared to DPI method, the sensitivity of MRM improved by 2.1-11.3 folds. In addition, the concentration of homocysteine, γ-glutamylcysteine and pantetheine enhanced more than two folds in cancer patients compared to healthy controls. Taken together, the method demonstrated to be a promising strategy for identification and comprehensive quantification of thiols in human urines.

Determination of thiol metabolites in human urine by stable isotope labeling in combination with pseudo-targeted mass spectrometry analysis

PubMed Central

Liu, Ping; Qi, Chu-Bo; Zhu, Quan-Fei; Yuan, Bi-Feng; Feng, Yu-Qi

2016-01-01

Precursor ion scan and multiple reaction monitoring scan (MRM) are two typical scan modes in mass spectrometry analysis. Here, we developed a strategy by combining stable isotope labeling (IL) with liquid chromatography-mass spectrometry (LC-MS) under double precursor ion scan (DPI) and MRM for analysis of thiols in 5 types of human cancer urine. Firstly, the IL-LC-DPI-MS method was applied for non-targeted profiling of thiols from cancer samples. Compared to traditional full scan mode, the DPI method significantly improved identification selectivity and accuracy. 103 thiol candidates were discovered in all cancers and 6 thiols were identified by their standards. It is worth noting that pantetheine, for the first time, was identified in human urine. Secondly, the IL-LC-MRM-MS method was developed for relative quantification of thiols in cancers compared to healthy controls. All the MRM transitions of light and heavy labeled thiols were acquired from urines by using DPI method. Compared to DPI method, the sensitivity of MRM improved by 2.1–11.3 folds. In addition, the concentration of homocysteine, γ-glutamylcysteine and pantetheine enhanced more than two folds in cancer patients compared to healthy controls. Taken together, the method demonstrated to be a promising strategy for identification and comprehensive quantification of thiols in human urines. PMID:26888486

Heterogeneity in the 238U/235U Ratios of Angrites.

NASA Astrophysics Data System (ADS)

Tissot, F.; Dauphas, N.; Grove, T. L.

2016-12-01

Angrites are differentiated meteorites of basaltic composition, of either volcanic or plutonic origin, that display minimal post-crystallization alteration, metamorphism, shock or impact brecciation. Because quenched angrites cooled very rapidly, all radiochronometric systems closed simultaneously in these samples. Quenched angrites are thus often used as anchors for cross-calibrating short-lived dating methods (e.g., 26Al-26Mg) and the absolute dating techniques (e.g, Pb-Pb). Due to the constancy of the 238U/235U ratio in natural samples, Pb-Pb ages have long been calculated using a "consensus" 238U/235U ratio, but the discovery of resolvable variations in the 238U/235U ratio of natural samples, means that the U isotopic composition of the material to date also has to be determined in order to obtain high-precision Pb-Pb ages. We set out (a) to measure at high-precision the 238U/235U ratio of a large array of angrites to correct their Pb-Pb ages, and (b) to identify whether all angrites have a similar U isotopic composition, and, if not, what were the processes responsible for this variability. Recently, Brennecka & Wadhwa (2012) suggested that the angrite-parent body had a homogeneous 238U/235U ratio. They reached this conclusion partly because they propagated the uncertainties of the U isotopic composition of the various U double spikes that they used onto the final 238U/235U ratio the sample. Because this error is systematic (i.e., it affects all samples similarly), differences in the δ238U values of samples corrected by the same double spike are better known than one would be led to believe if uncertainties on the spike composition are propagated. At the conference, we will present the results of the high-precision U isotope analyses for six angrite samples: NWA 4590, NWA 4801, NWA 6291, Angra dos Reis, D'Orbigny, and Sahara 99555. We will show that there is some heterogeneity in the δ238U values of the angrites and will discuss the possible processes by which different angrite samples can acquire different U isotopic compositions. The U isotope data will then be used to correct Pb-Pb ages of angrites estimated using an assumed 238U/235U ratio. These ages will be used to discuss the degree of concordance between short-lived nuclides systems and the absolute Pb-Pb clock in early Solar System materials.

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

PubMed Central

Sharma, Sudhir C.; Klinman, Judith P.

2009-01-01

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

Ultra low-level measurements of actinides by sector field ICP-MS.

PubMed

Pointurier, F; Baglan, N; Hémet, P

2004-01-01

In the present work, a double-focusing sector field inductively coupled plasma-mass spectrometer was optimised for ultra trace and isotopic analyses of actinide long-lived isotopes in low concentration solutions of the fgml(-1) to the ngml(-1) range. Sensitivities of about 3GHz/(microgml(-1)), with as low a background as 0.1cps, were obtained for U using a conventional concentric pneumatic nebuliser. Detection limits are below the fg range for 239Pu and 240Pu. With natural U, a precision lower than 0.5% RSD is currently obtained for 235U/238U isotopic ratio at the 200pgml(-1) level.

Radioactive Cs capture in the early solar system

PubMed Central

Hidaka, Hiroshi; Yoneda, Shigekazu

2013-01-01

Barium isotopic compositions of primitive materials in the solar system are generally affected by s- and r-process nucleosynthetic components that hide the contribution of the isotopic excess of 135Ba formed by decay of radioactive 135Cs. However, the Ba isotopic composition of the chemical separates from chondrules in the Sayama CM2 chondrite shows an excess of 135Ba isotopic abundance up to (0.33 ± 0.06)%, which is independent of the isotopic components from s- and r-process nucleosyntheses. The isotopic excesses of 135Ba correlate with the elemental abundance of Ba relative to Cs, providing chemical and isotopic evidence for the existence of the presently extinct radionuclide 135Cs (t1/2 = 2.3 million years) in the early solar system. The estimated abundance of 135Cs/133Cs = (6.8 ± 1.9) × 10−4 is more than double that expected from the uniform production model of the short-lived radioisotopes, suggesting remobilization of Cs including 135Cs in the chondrules of the meteorite parent body. PMID:23435551

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 single-step equilibrium processes to 0.510 or even lower for kinetic processes. Rayleigh fractionation involving a kinetic process with a single-step β of 0.510 produces an effective β of 0.512. Such differences in fractionation laws can be crucial for determining excesses or deficits in isotopes relative to mass fractionation. Contrary to some assertions, Si isotope ratios can be measured with high accuracy and precision using 193 nm excimer lasers with nanosecond pulse widths (Shahar and Young, 2007). Silicon isotope ratios in CAIs measured by 193 nm LA-MC-ICPMS have been combined with Mg isotope ratios to constrain the astrophysical environments in which these oldest solar system materials formed. Accuracy of the measurements was determined using gravimetric standards of various matrix compositions. The results establish that matrix effects for Si are below detection at the ± 0.2 ‰ precision of the laser ablation technique. High mass resolving power (m/Δ m ~ 9000) is necessary to obtain accurate Si isotope ratios by laser ablation. High-precision LA-MC-ICPMS measurements of 176Hf/177Hf in zircons can be obtained by normalizing to 179Hf/177Hf assuming an exponential fractionation law and no mass-dependent Hf, Lu, or Yb stable isotope fractionation. With corrections for interfering 176Lu and 176Yb precision for this method can be on the order of 0.3 epsilon (0.03 ‰). The approach has been used to infer the existence of continental crust on Earth 4.4 billion years before present (Harrison et al., 2005).

An improved procedure for separation/purification of boron from complex matrices and high-precision measurement of boron isotopes by positive thermal ionization and multicollector inductively coupled plasma mass spectrometry.

PubMed

Wei, Hai-Zhen; Jiang, Shao-Yong; Hemming, N Gary; Yang, Jing-Hong; Yang, Tao; Wu, He-Pin; Yang, Tang-Li; Yan, Xiong; Pu, Wei

2014-06-01

In order to eliminate boron loss and potential isotopic fractionation during chemical pretreatment of natural samples with complex matrices, a three-column ion-exchange separation/purification procedure has been modified, which ensures more than 98% recovery of boron from each step for a wide range of sample matrices, and is applicable for boron isotope analysis by both TIMS and MC-ICP-MS. The PTIMS-Cs2BO2(+)-static double collection method was developed, ensuring simultaneous collection of (133)Cs2(11)B(16)O2(+)(m/z 309) and (133)Cs2(10)B(16)O2(+) (m/z 308) ions in adjacent H3-H4 Faraday cups with typical zoom optics parameters (Focus Quad: 15 V, Dispersion Quad: -85 V). The external reproducibilities of the measured (11)B/(10)B ratios of the NIST 951 boron standard solutions of 1000 ng, 100 ng and 10 ng of boron by PTIMS method are ±0.06‰, ±0.16‰ and ±0.25‰, respectively, which indicates excellent precision can be achieved for boron isotope measurement at nanogram level boron in natural samples. An on-peak zero blank correction procedure was employed to correct the residual boron signals effect in MC-ICP-MS, which gives consistent δ(11)B values with a mean of 39.66±0.35‰ for seawater in the whole range of boron content from 5 ppb to 200 ppb, ensuring accurate boron isotope analysis in few ppb boron. With the improved protocol, consistent results between TIMS and MC-ICP-MS data were obtained in typical geological materials within a wide span of δ(11)B values ranging from -25‰ to +40‰. Copyright © 2014 Elsevier B.V. All rights reserved.

Measurement of picosecond lifetimes in neutron-rich Xe isotopes

NASA Astrophysics Data System (ADS)

Ilieva, S.; Kröll, Th.; Régis, J.-M.; Saed-Samii, N.; Blanc, A.; Bruce, A. M.; Fraile, L. M.; de France, G.; Hartig, A.-L.; Henrich, C.; Ignatov, A.; Jentschel, M.; Jolie, J.; Korten, W.; Köster, U.; Lalkovski, S.; Lozeva, R.; Mach, H.; Mǎrginean, N.; Mutti, P.; Paziy, V.; Regan, P. H.; Simpson, G. S.; Soldner, T.; Thürauf, M.; Ur, C. A.; Urban, W.; Warr, N.

2016-09-01

Background: Lifetimes of nuclear excited states in fission fragments have been studied in the past following isotope separation, thus giving access mainly to the fragments' daughters and only to long-lived isomeric states in the primary fragments. For the first time now, short-lived excited states in the primary fragments, produced in neutron-induced prompt fission of 235U and 241Pu, were studied within the EXILL&FATIMA campaign at the intense neutron-beam facility of the Institute Laue-Langevin in Grenoble. Purpose: We aim to investigate the quadrupole collective properties of neutron-rich even-even 138,140,142Xe isotopes lying between the double shell closure N =82 and Z =50 and a deformed region with octupole collectivity. Method: The γ rays emitted from the excited fragments were detected with a mixed array consisting of 8 HPGe EXOGAM Clover detectors (EXILL) and 16 LaBr3(Ce) fast scintillators (FATIMA). The detector system has the unique ability to select the interesting fragment making use of the high resolution of the HPGe detectors and determine subnanosecond lifetimes using the fast scintillators. For the analysis the generalized centroid difference method was used. Results: We show that quadrupole collectivity increases smoothly with increasing neutron number above the closed N =82 neutron shell. Our measurements are complemented by state-of-the-art theory calculations based on shell-model descriptions. Conclusions: The observed smooth increase in quadrupole collectivity is similar to the evolution seen in the measured masses of the xenon isotopic chain and is well reproduced by theory. This behavior is in contrast to higher Z even-even nuclei where abrupt change in deformation occurs around N =90 .

High resolution laser spectroscopy of the [13.8]0.5 - X2Δ3/2 and [14.2]1.5 - X2Δ3/2 transitions of hafnium monofluoride (HfF)

NASA Astrophysics Data System (ADS)

Adam, A. G.; Esson, L. M.; Linton, C.; Smith, A. M.; Tokaryk, D. W.

2018-07-01

Laser-induced fluorescence (LIF) spectra of the (0, 0) and (1, 0) bands of the [13.8]0.5 - X2Δ3/2 and [14.2]1.5 - X2Δ3/2 transitions of HfF have been obtained at high resolution (∼120 MHz) using a laser ablation source. Spectra of all five isotopologues, from 180HfF to 176HfF have been clearly resolved and the two most abundant, 180HfF and 178HfF, were chosen for analysis. The rotational levels of the [13.8]0.5 state showed clear Ω - doubling closely resembling that of a 2Σ state in the v = 0 level. Irregularity in the doubling in the v = 1 level and in the isotope shift indicated a strong perturbation affecting this level. The final fit included all the previously analysed bands in the visible region and the doubling of all the Ω = 0.5 states and the isotope effect are examined and discussed.

Purification of lanthanides for double beta decay experiments

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

Polischuk, O. G.; Barabash, A. S.; Belli, P.

2013-08-08

There are several potentially double beta active isotopes among the lanthanide elements. However, even high purity grade lanthanide compounds contain {sup 238}U, {sup 226}Ra and {sup 232,228}Th typically on the level of ∼ (0.1 - 1) Bq/kg. The liquid-liquid extraction technique was used to remove traces of U, Ra and Th from CeO{sub 2}, Nd{sub 2}O{sub 3} and Gd{sub 2}O{sub 3}. The radioactive contamination of the samples before and after the purification was tested by using ultra-low-background HPGe γ spectrometry at the underground Gran Sasso National Laboratories of the INFN (Italy). After the purification the radioactive contamination of gadolinium oxidemore » by Ra and Th was decreased at least one order of magnitude. The efficiency of the approach to purify cerium oxide from Ra was on same level, while the radioactive contamination of neodymium sample before and after the purification is below the sensitivity of analytical methods. The purification method is much less efficient for chemically very similar radioactive elements like lanthanum, lutetium and actinium. R and D of the methods to remove the pollutions with improved efficiency is in progress.« less

Effectively-truncated large-scale shell-model calculations and nuclei around 100Sn

NASA Astrophysics Data System (ADS)

Gargano, A.; Coraggio, L.; Itaco, N.

2017-09-01

This paper presents a short overview of a procedure we have recently introduced, dubbed the double-step truncation method, which is aimed to reduce the computational complexity of large-scale shell-model calculations. Within this procedure, one starts with a realistic shell-model Hamiltonian defined in a large model space, and then, by analyzing the effective single particle energies of this Hamiltonian as a function of the number of valence protons and/or neutrons, reduced model spaces are identified containing only the single-particle orbitals relevant to the description of the spectroscopic properties of a certain class of nuclei. As a final step, new effective shell-model Hamiltonians defined within the reduced model spaces are derived by way of a unitary transformation of the original large-scale Hamiltonian. A detailed account of this transformation is given and the merit of the double-step truncation method is illustrated by discussing few selected results for 96Mo, described as four protons and four neutrons outside 88Sr. Some new preliminary results for light odd-tin isotopes from A = 101 to 107 are also reported.

40K-40Ca and 87Rb-86Sr Dating by SIMS: The Double-Plus Advantage

NASA Astrophysics Data System (ADS)

Harrison, T. M.; McKeegan, K. D.; Schmitt, A. K.

2009-12-01

The decay of 40K to 40Ar forms the basis of the potassium-argon dating method, although only one out of every 10 parent atoms decays to daughter 40Ar. The other 90% decay to 40Ca giving, in principle, the 40K-40Ca decay system great potential for dating samples with high K/Ca. This method, however, has not been utilized as an ion-microprobe-based geochronometer, largely because these isotopes require a very high mass resolving power (MRP) of ~25k for full separation. We found that limiting secondary ion transmission in our ims1270 ion microprobe to ~20% permits sufficient separation of 40K from 40Ca (MRP≈ 20k) to permit isotope ratio analysis, albeit with 40Ca+ on the shoulder of the more intense 40K+ peak. A pegmatitic muscovite from Jack Hills (K-Ca age = 2.54 Ga; Fletcher et al., Chem. Geol. 138, 289) yields ~104 cps of both 40K+ and 40Ca+ with a 15 μm primary spot size and O- beam current of 10 nA. The 40Ca+ signal is >90% radiogenic and reflects a “common” Ca content of ≤ 100 ppm. However, application of the relative sensitivity factor (RSF) calculated from the Jack Hills muscovite to unknowns yields relatively high age dispersion, perhaps related to the incompletely separated mass interferences. Theorizing that the noble gas electronic structure of K+ would likely resist further electron loss, we investigated an alternative approach involving analysis of Ca++/K++. The double-plus method provides an important advantage in that K++ species are suppressed by a factor of ~103 relative to K+, thereby effectively removing 40K++ from the spectrum at m/e≈ 20 and leaving 40Ca++ free from any significant interferences at an MRP≈ 4k. Measurement of the much more abundant 39K++ then permits 40Ca++/40K++ to be calculated from the known 39K/40K ratio. We applied this approach to Precambrian muscovite samples obtaining ages similar to, but generally younger than, their associated 40Ar/39Ar ages. This could reflect a minor matrix effect or a lower intrinsic retentivity of 40Ca* relative to 40Ar* in white micas. This approach offers the potential to develop a branched-decay thermochronometer (K-Ca-Ar) permitting simultaneous solution of temperature-time history from μm-scale isotopic variations. A further advantage is that even low resolution SIMS instruments (e.g., ims7f) can utilize the double-plus method. Initial investigations using the same double-plus approach for Rb-Sr dating show promise. While resolving 87Rb+ from 87Sr+ requires an MRP of ~290k, unattainable using any current SIMS instrument, 87Rb++ is so strongly suppressed that determination of 87Sr++ is possible with minor peak stripping. 87Rb/86Sr can be determined either from 85Rb+/88Sr+ at MRP≈ 8k or by the use of energy filtering. In addition to micas, these approaches may be applicable to any mineral systems enriched in alkali metals relative to alkaline earths, such as alkali feldspars, feldspathoids, and alkaline halides.

ION COMPOSITION ELUCIDATION (ICE)

EPA Science Inventory

Ion Composition Elucidation (ICE) utilizes selected ion recording with a double focusing mass spectrometer to simultaneously determine exact masses and relative isotopic abundances from mass peak profiles. These can be determined more accurately and at higher sensitivity ...

Helium isotope enrichment by resonant tunneling through nanoporous graphene bilayers.

PubMed

Mandrà, Salvatore; Schrier, Joshua; Ceotto, Michele

2014-08-21

Graphene is impermeable to gases, but introducing subnanometer pores can allow for selective gas separation. Because graphene is only one atom thick, tunneling can play an important role, especially for low-mass gases such as helium, and this has been proposed as a means of separating (3)He from (4)He. In this paper, we consider the possibility of utilizing resonant tunneling of helium isotopes through nanoporous graphene bilayers. Using a model potential fit to previously reported DFT potential energy surfaces, we calculate the thermal rate constant as a function of interlayer separation using a recently described time-independent method for arbitrary multibarrier potentials. Resonant transmission allows for the total flux rate of (3)He to remain the same as the best-known single-barrier pores but doubles the selectivity with respect to (4)He when the optimal interlayer spacing of 4.6 Å is used. The high flux rate and selectivity are robust against variations of the interlayer spacing and asymmetries in the potential that may occur in experiment.

Muon capture on light isotopes in Double Chooz

NASA Astrophysics Data System (ADS)

Strait, M.; Double Chooz Collaboration

2017-09-01

Using the Double Chooz reactor neutrino detector, we have measured the products of µ - capture on 12C, 13C, 14N and 16O. Over a period of 490 days, we collected 2.3 × 106 stopping cosmic µ -, of which 1.8 × 105 captured on these nuclei in the inner detector. The resulting isotopes were tagged using prompt neutron emission (when applicable), the subsequent beta decays, and, in some cases, β-delayed neutrons. Production of these βn isotopes, primarily 9Li, which are {{{ν _e}} \\over {{ν _μ }}} backgrounds, was found at a significance of 5.5σ. The probability of 9Li production per capture on natC is (2.4 ± 0.9(stat) ± 0.1(syst)) × 10-4. We have made the most precise measurement of the rate of 12C(µ -, ν)12B to date, 6.57 - 0.21 + 0.11 × {10^3}{{ }}{{{s}} - 1},{{ or }}≤ft( {17.35 - 0.59 + 0.35} \\right)% of nuclear captures. By tagging excited states emitting gammas, the ground state transition rate to 12B is found to be 5.68 - 0.23 + 0.14 × {10^3}{{ }}{{{s}} - 1}.

X-ray diffraction characterization of epitaxial CVD diamond films with natural and isotopically modified compositions

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

Prokhorov, I. A., E-mail: igor.prokhorov@mail.ru; Voloshin, A. E.; Ralchenko, V. G.

2016-11-15

Comparative investigations of homoepitaxial diamond films with natural and modified isotopic compositions, grown by chemical vapor deposition (CVD) on type-Ib diamond substrates, are carried out using double-crystal X-ray diffractometry and topography. The lattice mismatch between the substrate and film is precisely measured. A decrease in the lattice constant on the order of (Δa/a){sub relax} ∼ (1.1–1.2) × 10{sup –4} is recorded in isotopically modified {sup 13}C (99.96%) films. The critical thicknesses of pseudomorphic diamond films is calculated. A significant increase in the dislocation density due to the elastic stress relaxation is revealed by X-ray topography.

"Anticlumping" and Other Combinatorial Effects on Clumped Isotopes: Implications for Tracing Biogeochemical Cycling

NASA Astrophysics Data System (ADS)

Yeung, L.

2015-12-01

I present a mode of isotopic ordering that has purely combinatorial origins. It can be important when identical rare isotopes are paired by coincidence (e.g., they are neighbors on the same molecule), or when extrinsic factors govern the isotopic composition of the two atoms that share a chemical bond. By itself, combinatorial isotope pairing yields products with isotopes either randomly distributed or with a deficit relative to a random distribution of isotopes. These systematics arise because of an unconventional coupling between the formation of singly- and multiply-substituted isotopic moieties. In a random distribution, rare isotopes are symmetrically distributed: Single isotopic substitutions (e.g., H‒D and D‒H in H2) occur with equal probability, and double isotopic substitutions (e.g., D2) occur according to random chance. The absence of symmetry in a bond-making complex can yield unequal numbers of singly-substituted molecules (e.g., more H‒D than D‒H in H2), which is recorded in the product molecule as a deficit in doubly-substituted moieties and an "anticlumped" isotope distribution (i.e., Δn < 0). Enzymatic isotope pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect. Chemical-kinetic isotope effects, which are related to the bond-forming transition state, arise independently and express second-order combinatorial effects. In general, both combinatorial and chemical factors are important for calculating and interpreting clumped-isotope signatures of individual reactions. In many reactions relevant to geochemical oxygen, carbon, and nitrogen cycling, combinatorial isotope pairing likely plays a strong role in the clumped isotope distribution of the products. These isotopic signatures, manifest as either directly bound isotope clumps or as features of a molecule's isotopic anatomy, could be exploited as tracers of biogeochemistry that can relate molecular mechanisms to signals observable at environmentally relevant spatial scales.

Nuclear structure properties of the double-charge-exchange transition amplitudes

NASA Astrophysics Data System (ADS)

Auerbach, N.; Zheng, D. C.

1992-03-01

Nuclear structure aspects of the double-charge-exchange (DCX) reaction on nuclei are studied. Using a variety of DCX-type two-body transition operators, we explore the influence of two-body correlations among valence nucleons on the DCX transition amplitudes to the isobaric analog state and to other nonanalog J π=0+ states. In particular, the question of the spin dependence and of the range of the DCX transition operators is explored and the behavior of the transition amplitudes as a function of the valence nucleon number is studied. It is shown that the two-amplitude DCX formula derived by Auerbach, Gibbs, and Piasetzky for a single j n configuration holds also in some cases when configuration mixing is strong. DCX-type transitions from the Ca and Ni isotopes to the Ti and Zn isotopes and from 56Fe to 56Ni are the subject of this study.

Systematic study on the isotopic behavior of fusion barrier using the density-dependent nucleon-nucleon interactions

NASA Astrophysics Data System (ADS)

Ghodsi, O. N.; Khalaj, M.

By changing the neutron and nuclear matter incompressibility constant K, we investigate the isotopic behavior of the fusion barriers for the collision of large number of different isotopes with condition of 0.7 ≤ N/Z ≤ 1.36. Here, the double folding (DF) model which is accompanied by density-dependent (DD) versions of M3Y interactions is adopted as a basic heavy ion-ion potential. We show that the selected DD potentials predict a linear behavior for the calculated fusion barrier heights as a function of (N/Z - 1) for both proton- and neutron-rich systems. Moreover, the results indicate that the isotopic behavior of these values depend linearly on the change in the K constant. The isotopic studies conducted on the fusion cross-section also shows that the properties of the nuclear matter in the range of energy which is below the fusion barrier will quite affect the fusion process.

Redefining the utility of the three-isotope method

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Bao, Huiming

2017-09-01

The equilibrium isotope fractionation factor αeq is a fundamental parameter in the study of stable isotope effects. Experimentally, it has been difficult to establish that a system has attained equilibrium. The three-isotope method, using the initial trajectory of changing isotope ratios (e.g. 16O, 17O, and 18O) to deduce the final equilibrium point of isotope exchange, has long been hailed as the most rigorous experimental approach. However, over the years some researchers have cautioned on the limitations of this method, but the foundation of three-isotope method has not been properly examined and the method is still widely used in calibrating αeq for both traditional and increasingly non-traditional isotope systems today. Here, using water-water and dissolved CO2-water oxygen exchange as model systems, we conduct an isotopologues-specific kinetic analysis of the exchange processes and explore the underlying assumptions and validity of the three-isotope method. We demonstrate that without knowing the detailed exchange kinetics a priori the three-isotope method cannot lead to a reliable αeq. For a two-reservoir exchanging system, α determined by this method may be αeq, kinetic isotope effect, or apparent kinetic isotope effect, which can all bear different values. When multiple reservoirs exist during exchange, the evolving trajectory can be complex and hard to predict. Instead of being a tool for αeq determination, three-isotope method should be used as a tool for studying kinetic isotope effect, apparent kinetic isotope effect, and detailed exchange kinetics in diverse systems.

Method for production of an isotopically enriched compound

DOEpatents

Watrous, Matthew G.

2012-12-11

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

ALPHA SPECTROMETRIC EVALUATION OF SRM-995 AS A POTENTIAL URANIUM/THORIUM DOUBLE TRACER SYSTEM FOR AGE-DATING URANIUM MATERIALS

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

Beals, D.

2011-12-06

Uranium-233 (t{sub 1/2} {approx} 1.59E5 years) is an artificial, fissile isotope of uranium that has significant importance in nuclear forensics. The isotope provides a unique signature in determining the origin and provenance of uranium-bearing materials and is valuable as a mass spectrometric tracer. Alpha spectrometry was employed in the critical evaluation of a {sup 233}U standard reference material (SRM-995) as a dual tracer system based on the in-growth of {sup 229}Th (t{sub 1/2} {approx} 7.34E3 years) for {approx}35 years following radiochemical purification. Preliminary investigations focused on the isotopic analysis of standards and unmodified fractions of SRM-995; all samples were separatedmore » and purified using a multi-column anion-exchange scheme. The {sup 229}Th/{sup 233}U atom ratio for SRM-995 was found to be 1.598E-4 ({+-} 4.50%) using recovery-corrected radiochemical methods. Using the Bateman equations and relevant half-lives, this ratio reflects a material that was purified {approx} 36.8 years prior to this analysis. The calculated age is discussed in contrast with both the date of certification and the recorded date of last purification.« less

Determination of 90Sr and Pu isotopes in contaminated groundwater samples by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Zoriy, Miroslav V.; Ostapczuk, Peter; Halicz, Ludwik; Hille, Ralf; Becker, J. Sabine

2005-04-01

A sensitive analytical method for determining the artificial radionuclides 90Sr, 239Pu and 240Pu at the ultratrace level in groundwater samples from the Semipalatinsk Test Site area in Kazakhstan by double-focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS) was developed. In order to avoid possible isobaric interferences at m/z 90 for 90Sr determination (e.g. 90Zr+, 40Ar50Cr+, 36Ar54Fe+, 58Ni16O2+, 180Hf2+, etc.), the measurements were performed at medium mass resolution under cold plasma conditions. Pu was separated from uranium by means of extraction chromatography using Eichrom TEVA resin with a recovery of 83%. The limits of detection for 90Sr, 239Pu and 240Pu in water samples were determined as 11, 0.12 and 0.1 fg ml-1, respectively. Concentrations of 90Sr and 239Pu in contaminated groundwater samples ranged from 18 to 32 and from 28 to 856 fg ml-1, respectively. The 240Pu/239Pu isotopic ratio in groundwater samples was measured as 0.17. This isotope ratio indicates that the most probable source of contamination of the investigated groundwater samples was the nuclear weapons tests at the Semipalatinsk Test Site conducted by the USSR in the 1960s.

Effect of cancellation in neutrinoless double beta decay

NASA Astrophysics Data System (ADS)

Mitra, Manimala; Pascoli, Silvia; Wong, Steven

2014-11-01

In light of recent experimental results, we carefully analyze the effects of interference in neutrinoless double beta decay, when more than one mechanism is operative. If a complete cancellation is at work, the half-life of the corresponding isotope is infinite, and any constraint on it will automatically be satisfied. We analyze this possibility in detail assuming a cancellation in Xe 136 , and find its implications on the half-life of other isotopes, such as Ge 76 . For definiteness, we consider the role of light and heavy sterile neutrinos. In this case, the effective Majorana mass parameter can be redefined to take into account all contributions, and its value gets suppressed. Hence, larger values of neutrino masses are required for the same half-life. The canonical light neutrino contribution cannot saturate the present limits of half-lives or the positive claim of observation of neutrinoless double beta decay, once the stringent bounds from cosmology are taken into account. For the case of cancellation, where all the sterile neutrinos are heavy, the tension between the results from neutrinoless double beta decay and cosmology becomes more severe. We show that the inclusion of light sterile neutrinos in this setup can resolve this issue. Using the recent results from GERDA, we derive upper limits on the active-sterile mixing angles and compare them with the case of no cancellation. The required values of the mixing angles become larger, if a cancellation is at work. A direct test of destructive interference in Xe 136 is provided by the observation of this process in other isotopes, and we study in detail the correlation between their half-lives. Finally, we discuss the model realizations which can accommodate light and heavy sterile neutrinos and the cancellation. We show that sterile neutrinos of few hundred MeV or GeV mass range, coming from an Extended seesaw framework or a further extension, can satisfy the required cancellation.

Precise determination of δ88Sr in rocks, minerals, and waters by double-spike TIMS: A powerful tool in the study of chemical, geologic, hydrologic and biologic processes

USGS Publications Warehouse

Neymark, Leonid A.; Premo, Wayne R.; Mel'nikov, Nikolay N.; Emsbo, Poul

2014-01-01

We present strontium isotopic (88Sr/86Sr and 87Sr/86Sr) results obtained by 87Sr–84Sr double spike thermal ionization mass-spectrometry (DS-TIMS) for several standards as well as natural water samples and mineral samples of abiogenic and biogenic origin. The detailed data reduction algorithm and a user-friendly Sr-specific stand-alone computer program used for the spike calibration and the data reduction are also presented. Accuracy and precision of our δ88Sr measurements, calculated as permil (‰) deviations from the NIST SRM-987 standard, were evaluated by analyzing the NASS-6 seawater standard, which yielded δ88Sr = 0.378 ± 0.009‰. The first DS-TIMS data for the NIST SRM-607 potassium feldspar standard and for several US Geological Survey carbonate, phosphate, and silicate standards (EN-1, MAPS-4, MAPS-5, G-3, BCR-2, and BHVO-2) are also reported. Data obtained during this work for Sr-bearing solids and natural waters show a range of δ88Sr values of about 2.4‰, the widest observed so far in terrestrial materials. This range is easily resolvable analytically because the demonstrated external error (±SD, standard deviation) for measured δ88Sr values is typically ≤0.02‰. It is shown that the “true” 87Sr/86Sr value obtained by the DS-TIMS or any other external normalization method combines radiogenic and mass-dependent mass-fractionation effects, which cannot be separated. Therefore, the “true” 87Sr/86Sr and the δ87Sr parameter derived from it are not useful isotope tracers. Data presented in this paper for a wide range of naturally occurring sample types demonstrate the potential of the δ88Sr isotope tracer in combination with the traditional radiogenic 87Sr/86Sr tracer for studying a variety of biological, hydrological, and geological processes.

Development of a laser system of the laboratory AVLIS complex for producing isotopes and radionuclides

NASA Astrophysics Data System (ADS)

D'yachkov, A. B.; Gorkunov, A. A.; Labozin, A. V.; Mironov, S. M.; Panchenko, V. Ya.; Firsov, V. A.; Tsvetkov, G. O.

2018-01-01

The use of atomic vapour laser isotope separation (AVLIS) for solving a number of urgent problems (formation of 177Lu radionuclides for medical applications, 63Ni radionuclides for betavoltaic power supplies and 150Nd isotope for searching for neutrinoless double β decay and neutrino mass) is considered. An efficient three-step scheme of photoionisation of neodymium atoms through the 50474-cm-1 autoionising state with radiation wavelengths of the corresponding stages of λ1 = 6289.7 Å, λ2 = 5609.4 Å and λ3 = 5972.1 Å is developed. The average saturation intensity of the autoionising transition is ˜6 W cm-2, a value consistent with the characteristics of the previously developed photoionisation schemes for lutetium and nickel. A compact laser system for the technological AVLIS complex, designed to produce radionuclides and isotopes under laboratory conditions, is developed based on the experimental results.

Mixed quantum-classical simulation of the hydride transfer reaction catalyzed by dihydrofolate reductase based on a mapped system-harmonic bath model

NASA Astrophysics Data System (ADS)

Xu, Yang; Song, Kai; Shi, Qiang

2018-03-01

The hydride transfer reaction catalyzed by dihydrofolate reductase is studied using a recently developed mixed quantum-classical method to investigate the nuclear quantum effects on the reaction. Molecular dynamics simulation is first performed based on a two-state empirical valence bond potential to map the atomistic model to an effective double-well potential coupled to a harmonic bath. In the mixed quantum-classical simulation, the hydride degree of freedom is quantized, and the effective harmonic oscillator modes are treated classically. It is shown that the hydride transfer reaction rate using the mapped effective double-well/harmonic-bath model is dominated by the contribution from the ground vibrational state. Further comparison with the adiabatic reaction rate constant based on the Kramers theory confirms that the reaction is primarily vibrationally adiabatic, which agrees well with the high transmission coefficients found in previous theoretical studies. The calculated kinetic isotope effect is also consistent with the experimental and recent theoretical results.

Probing the experimental phonon dispersion of graphene using 12C and 13C isotopes

NASA Astrophysics Data System (ADS)

Bernard, S.; Whiteway, E.; Yu, V.; Austing, D. G.; Hilke, M.

2012-08-01

Using very uniform large-scale chemical vapor deposition grown graphene transferred onto silicon, we were able to identify 15 distinct Raman lines associated with graphene monolayers. This was possible thanks to a combination of different carbon isotopes and different Raman laser energies and extensive averaging without increasing the laser power. This allowed us to obtain a detailed experimental phonon dispersion relation for many points in the Brillouin zone. We further identified a D+D' peak corresponding to a double-phonon process involving both an inter- and intravalley phonon.

Identification of the formation of metal-vinylidene interfacial bonds of alkyne-capped platinum nanoparticles by isotopic labeling.

PubMed

Hu, Peiguang; Chen, Limei; Deming, Christopher P; Bonny, Lewis W; Lee, Hsiau-Wei; Chen, Shaowei

2016-10-07

Stable platinum nanoparticles were prepared by the self-assembly of 1-dodecyne and dodec-1-deuteroyne onto bare platinum colloid surfaces. The nanoparticles exhibited consistent core size and optical properties. FTIR and NMR measurements confirmed the formation of Pt-vinylidene (Pt[double bond, length as m-dash]C[double bond, length as m-dash]CH-) interfacial linkages rather than Pt-acetylide (Pt-C[triple bond, length as m-dash]C-) and platinum-hydride (Pt-H) bonds.

The isotope composition of inorganic germanium in seawater and deep sea sponges

NASA Astrophysics Data System (ADS)

Guillermic, Maxence; Lalonde, Stefan V.; Hendry, Katharine R.; Rouxel, Olivier J.

2017-09-01

Although dissolved concentrations of germanium (Ge) and silicon (Si) in modern seawater are tightly correlated, uncertainties still exist in the modern marine Ge cycle. Germanium stable isotope systematics in marine systems should provide additional constraints on marine Ge sources and sinks, however the low concentration of Ge in seawater presents an analytical challenge for isotopic measurement. Here, we present a new method of pre-concentration of inorganic Ge from seawater which was applied to measure three Ge isotope profiles in the Southern Ocean and deep seawater from the Atlantic and Pacific Oceans. Germanium isotopic measurements were performed on Ge amounts as low as 2.6 ng using a double-spike approach and a hydride generation system coupled to a MC-ICP-MS. Germanium was co-precipitated with iron hydroxide and then purified through anion-exchange chromatography. Results for the deep (i.e. >1000 m depth) Pacific Ocean off Hawaii (nearby Loihi Seamount) and the deep Atlantic off Bermuda (BATS station) showed nearly identical δ74/70Ge values at 3.19 ± 0.31‰ (2SD, n = 9) and 2.93 ± 0.10‰ (2SD, n = 2), respectively. Vertical distributions of Ge concentration and isotope composition in the deep Southern Ocean for water depth > 1300 m yielded an average δ74/70Ge = 3.13 ± 0.25‰ (2SD, n = 14) and Ge/Si = 0.80 ± 0.09 μmol/mol (2SD, n = 12). Significant variations in δ74/70Ge, from 2.62 to 3.71‰, were measured in the first 1000 m in one station of the Southern Ocean near Sars Seamount in the Drake Passage, with the heaviest values measured in surface waters. Isotope fractionation by diatoms during opal biomineralization may explain the enrichment in heavy isotopes for both Ge and Si in surface seawater. However, examination of both oceanographic parameters and δ74/70Ge values suggest also that water mass mixing and potential contribution of shelf-derived Ge also could contribute to the variations. Combining these results with new Ge isotope data for deep-sea sponges sampled nearby allowed us to determine a Ge isotope fractionation factor of -0.87 ± 0.37‰ (2SD, n = 12) during Ge uptake by sponges. Although Ge has long been considered as a geochemical twin of Si, this work underpins fundamental differences in their isotopic behaviors both during biomineralization processes and in their oceanic distributions. This suggests that combined with Si isotopes, Ge isotopes hold significant promise as a complementary proxy for delineating biological versus source effects in the evolution of the marine silicon cycle through time.

Site-Specific Hydrogen Isotope Composition of Propane: Mass spectrometric methods, equilibrium temperature dependence, and kinetics of exchange

NASA Astrophysics Data System (ADS)

Xie, H.; Ponton, C.; Kitchen, N.; Lloyd, M. K.; Lawson, M.; Formolo, M. J.; Eiler, J. M.

2016-12-01

Intramolecular isotope ordering can constrain temperatures of synthesis, mechanisms of formation, and/or source substrates of organic compounds. Here we explore site-specific hydrogen isotope variations of propane. Statistical thermodynamic models predict that at equilibrium methylene hydrogen (-CH2-) in propane will be 10's of per mil higher in D/H ratio than methyl hydrogen (-CH3) at geologically relevant temperatures, and that this difference is highly temperature dependent ( 0.5-1 ‰/°C). Chemical-kinetic controls on site-specific D/H in propane could constrain the mechanisms, conditions and extents of propane synthesis or destruction. We have developed a method for measuring the difference in D/H ratio between methylene and methyl hydrogen in propane by gas source mass spectrometry. The data were measured using the Thermo Fisher Double Focusing Sector high resolution mass spectrometer (DFS), and involve comparison of the D/H ratios of molecular ion (C3H8+) and the ethyl fragmental ion (C2H5+). We demonstrate the accuracy and precision of this method through analysis of D-labeled and independently analyzed propanes. In the exchange experiments, propane was heated (100-200 oC) either alone or in the presence of D-enriched water (δD=1,1419 ‰ SMOW), with or without one of several potentially catalytic substrates for hours to weeks. Propane was found to exchange hydrogen with water vigorously at 200 °C in the presence of metal catalysts. In the presence of Ni catalyst, methylene hydrogen exchanges 2.5 times faster than methyl hydrogen. Hydrogen exchange in the presence of Pd catalyst is more effective and can equilibrate hydrogen isotope distribution on propane on the order of 7 days. Isotopic exchange in the presence of natural materials have also been tested, but is only measurable in the methylene group at 200 °C. High catalytic activity of Pd permits attainment of a bracketed, time-invariant equilibrium state that we use to calibrate the site-specific thermometer; these experiments also provide a reference frame for reporting mass spectrometric data. Differential H-exchange rates of the two molecular sites in propane could be a new tool to constrain thermal history of sub-surface propane. Our experimental and mass spectrometric approaches should be generalizable to other hydrocarbon compounds.

Transfer of marine mercury to mountain lakes.

PubMed

Hansson, Sophia V; Sonke, Jeroen; Galop, Didier; Bareille, Gilles; Jean, Séverine; Le Roux, Gaël

2017-10-05

Stocking is a worldwide activity on geographical and historical scales. The rate of non-native fish introductions have more than doubled over the last decades yet the effect on natural ecosystems, in the scope of biologically mediated transport and biomagnification of Hg and Hg-isotopes, is unknown. Using geochemistry (THg) and stable isotopes (N, Sr and Hg), we evaluate natal origin and trophic position of brown trout (Salmo trutta fario), as well as mercury biomagnification trends and potential pollution sources to three high-altitude lakes. Farmed trout show Hg-isotope signatures similar to marine biota whereas wild trout shows Hg-isotope signatures typical of fresh water lakes. Stocked trout initially show Hg-isotope signatures similar to marine biota. As the stocked trout age and shifts diet to a higher trophic level, THg concentrations increase and the marine Hg isotope signatures, induced via farm fish feed, shift to locally produced MeHg with lower δ 202 Hg and higher Δ 199 Hg. We conclude that stocking acts a humanly induced biovector that transfers marine Hg to freshwater ecosystems, which is seen in the Hg-isotopic signature up to five years after stocking events occurred. This points to the need of further investigations of the role of stocking in MeHg exposure to freshwater ecosystems.

Applications of New Synthetic Uranium Reference Materials for Research in Geochemistry

NASA Astrophysics Data System (ADS)

Richter, Stephan; Alonso, Adolfo; Aregbe, Yetunde; Eykens, Roger; Jacobsson, Ulf; Kuehn, Heinz; Verbruggen, Andre; Weyer, Stefan

2010-05-01

For many applications in geochemistry research isotope ratio measurements play a significant role. In geochronology isotope abundances of uranium and its daughter products thorium and lead are being used to determine the age and history of various samples of geological interest. For measuring the isotopic compositions of these elements by mass spectrometry, suitable isotope reference materials are needed to validate measurement procedures and to calibrate multi-collector and ion counting detector systems. IRMM is a recognized provider for nuclear isotope reference materials to the nuclear industry and nuclear safeguards authorities, which are also being applied widely for geochemical applications. Firstly, the double spike IRMM-3636 with a 233U/236U ratio of 1:1 was prepared which allows internal mass fractionation correction for high precision 235U/238U ratio measurements. The 234U abundance of this double spike material is low enough to allow an accurate and precise correction of 234U/238U ratios, even for measurements of close to equilibrium uranium samples. The double spike IRMM-3636 is offered in 3 concentrations: 1mg/g, 0.1mg/g and 0.005mg/g. Secondly, the 236U single spike IRMM-3660 was prepared and is offered in 3 concentrations: 1mg/g, 0.1mg/g and 0.01mg/g. Thirdly, a "Quad"-isotope reference material, IRMM-3101, has been prepared which is characterized by 233U/235U/236U/238U=1/1/1/1. This material is useful for checking Faraday cup efficiencies and inter-calibration of MIC (multiple ion counting) detectors. The quad-IRM is offered in 3 concentrations: 1mg/g, 0.1mg/g and 0.01mg/g. As one example for the significant influence of synthetic reference materials for geochemical research, the IRMM-074 series of gravimetrically prepared uranium mixtures for linearity testing of secondary electron multipliers (SEMs) has been applied for the redetermination of the secular equilibrium 234U/238U value and the 234U half-life by Cheng et al (2009). Due to the use of IRMM-074, results with smaller uncertainties were obtained, which are shifted by about 0.04% compared to the commonly used values published earlier by Cheng et al. in 2000. This has a significant impact for U isotope measurements in geochemistry. As another example for a geochemical application, by using the new double spike IRMM-3636, the 235U/238U ratios for several commonly used natural U standard materials from NIST/NBL and IRMM, such as e.g. NBS960 (=NBL CRM-112a), NBS950a,b and IRMM-184, have been re-measured at IRMM and other laboratories with improved precision and accuracy. The (preliminary) new result of 137.839(24) for the 238U/235U ratio of NBL CRM-112a is deviating by -0.030% from the well-known and widely used old consensus value of 137.88. For this old consensus value no uncertainty has ever been assigned, but it is outside the uncertainty limits of the new measurement result. The new result is based on measurements made at several laboratories worldwide, such as University of Frankfurt (Germany), National Taiwan University, NERC (University of Nottingham, UK), UNM (University of Minnesota, US), Thermo Fisher Scientific, LLNL (Lawrence Livermore National Laboratory, US.DOE), SAL/IAEA and IRMM. The (preliminary) new result of 137.839(24) can therefore be proposed as a new consensus value for the 238U/235U ratio of NBL CRM-112a. In contrast to the older consensus value, this new result is traceable to the common SI system of units and has an uncertainty assigned to it. For the close to natural standard IRMM-184, the re-measured 238U/235U ratio of 137.683(23) agrees quite well with the certified value of 137.697(41), the calculated difference is only -0.010(35)% which is insignificant. As a conclusion, the IRMM-3636 Double Spike has been successfully applied for measurements of important uranium isotopic standards like NBL CRM-112a and IRMM-184, with improved uncertainties at the level of 0.016% and traceability to the SI system.

Development of a Field-Deployable Methane Carbon Isotope Analyzer

NASA Astrophysics Data System (ADS)

Dong, Feng; Baer, Douglas

2010-05-01

Methane is a potent greenhouse gas, whose atmospheric surface mixing ratio has almost doubled compared with preindustrial values. Methane can be produced by biogenic processes, thermogenic processes or biomass, with different isotopic signatures. As a key molecule involved in the radiative forcing in the atmosphere, methane is thus one of the most important molecules linking the biosphere and atmosphere. Therefore precise measurements of mixing ratios and isotopic compositions will help scientists to better understand methane sources and sinks. To date, high precision isotope measurements have been exclusively performed with conventional isotope ratio mass spectrometry, which involves intensive labor and is not readily field deployable. Optical studies using infrared laser spectroscopy have also been reported to measure the isotopic ratios. However, the precision of optical-based analyses, to date, is typically unsatisfactory without pre-concentration procedures. We present characterization of the performance of a portable Methane Carbon Isotope Analyzer (MCIA), based on cavity enhanced laser absorption spectroscopy technique, that provides in-situ measurements of the carbon isotope ratio (13C/12C or del_13C) and methane mixing ratio (CH4). The sample is introduced to the analyzer directly without any requirement for pretreatment or preconcentration. A typical precision of less than 1 per mill (< 0.1%) with a 10-ppm methane sample can be achieved in a measurement time of less than 100 seconds. The MCIA can report carbon isotope ratio and concentration measurements over a very wide range of methane concentrations. Results of laboratory tests and field measurements will be presented.

NMR Stratagems for the Study of Multiple Kinetic Hydrogen/Deuterium Isotope Effectsof Proton Exchange. Example: Di-p-fluorophenylformamidine/THF

NASA Astrophysics Data System (ADS)

Limbach, Hans-Heinrich; Meschede, Ludger; Scherer, Gerd

1989-05-01

Stratagems are presented for the determination of kinetic isotope effects of proton exchange reactions by dynamic NMR spectroscopy. In such experiments, lineshape analyses and/or polarization transfer experiments are performed on the exchanging protons or deuterons as well as on remote spins, as a function of the deuterium fraction in the mobile proton sites. These methods are NMR analogs of previous proton inventory techniques involving classical kinetic methods. A theory is developed in order to derive the kinetic isotope effects as well as the number of transferred protons from the experimental NMR spectra. The technique is then applied to the problem of proton exchange in the system 15N,15N'-di-p-fluorophenylibrmamidine, a nitrogen analog of formic acid, dissolved in tetrahydrofuran-d8 (THF). DFFA forms two conformers in THF to which s-trans and s-cis structures have been assigned. Only the s-trans conformer is able to dimerize and exchange protons. Lineshape simulations and magnetization transfer experiments were carried out at 189,2 K, at a concentration of 0.02 mol l-1, as a function of the deuterium fraction D in the 1H-15N sites. Using 1H NMR spectroscopy, a linear dependence of the inverse proton lifetimes on D was observed. From this it was concluded that two protons are transported in the rate limiting step of the proton exchange. This result is expected for a double proton transfer in an s-trans dimer with a cyclic structure. The full kinetic HH/HD/DD isotope effects of 233:11:1 at 189 K were determined through 19F NMR experiments on the same samples. The deviation from the rule of geometric mean, although substantial, is much smaller than found in previous studies of intramolecular HH transfer reactions. Possible causes of this effect are discussed.

Utility of γH2AX as a molecular marker of DNA double-strand breaks in nuclear medicine: applications to radionuclide therapy employing auger electron-emitting isotopes.

PubMed

Mah, Li-Jeen; Orlowski, Christian; Ververis, Katherine; El-Osta, Assam; Karagiannis, Tom C

2011-01-01

There is an intense interest in the development of radiopharmaceuticals for cancer therapy. In particular, radiopharmaceuticals which involve targeting radionuclides specifically to cancer cells with the use of monoclonal antibodies (radioimmunotherapy) or peptides (targeted radiotherapy) are being widely investigated. For example, the ultra-short range Auger electron-emitting isotopes, which are discussed in this review, are being considered in the context of DNAtargeted radiotherapy. The efficient quantitative evaluation of the levels of damage caused by such potential radiopharmaceuticals is required for assessment of therapeutic efficacy and determination of relevant doses for successful treatment. The DNA double-strand break surrogate marker, γH2AX, has emerged as a useful biomonitor of damage and thus effectiveness of treatment, offering a highly specific and sensitive means of assessment. This review will cover the potential applications of γH2AX in nuclear medicine, in particular radionuclide therapy.

Uranium Isotopes in Calcium Carbonate: A Possible Proxy for Paleo-pH and Carbonate Ion Concentration?

NASA Astrophysics Data System (ADS)

Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Wasylenki, L. E.; Anbar, A. D.

2015-12-01

Natural variations of 238U/235U in marine carbonates are being explored as a paleoredox proxy. However, in order for this proxy to be robust, it is important to understand how pH and alkalinity affect the fractionation of 238U/235U during coprecipitation with calcite and aragonite. Recent work suggests that the U/Ca ratio of foraminiferal calcite may vary with seawater [CO32-] concentration due to changes in U speciation[1]. Here we explore analogous isotopic consequences in inorganic laboratory co-precipitation experiments. Uranium coprecipitation experiments with calcite and aragonite were performed at pH 8.5 ± 0.1 and 7.5 ± 0.1 using a constant addition method [2]. Dissolved U in the remaining solution was periodically collected throughout the experiments. Samples were purified with UTEVA resin and 238U/235U was determined using a 233U-236U double-spike and MC-ICP-MS, attaining a precision of ± 0.10 ‰ [3]. Small but resolvable U isotope fractionation was observed in aragonite experiments at pH ~8.5, preferentially enriching heavier U isotopes in the solid phase. 238U/235U of the dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00002 - 1.00009. In contrast, no resolvable U isotope fractionation was detected in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among dissolved U species is the most likely mechanism driving these isotope effects. Our quantitative model of this process assumes that charged U species are preferentially incorporated into CaCO3 relative to the neutral U species Ca2UO2(CO3)3(aq), which we hypothesize to have a lighter equilibrium U isotope composition than the charged U species. According to this model, the magnitude of U isotope fractionation should scale with the fraction of the neutral U species in the solution, in agreement with our experimental results. These findings suggest that U isotope variations in abiotic CaCO3 reflect changes in aqueous U(VI) speciation, which are in turn a function of carbonate ion chemistry and pH. Hence, the door is opened to the development of a possible 238U/235U proxy for the carbonate ion system. [1] DeCarlo et al., (2015), GCA, 162,151-165. [2] Reeder et a., (2001), GCA, 65, 3491-3503. [3] Weyer et al., (2008) GCA 72, 345-359.

Metabolism of 14C-dehydroepiandrosterone in female adipose tissue and venous blood.

PubMed

Schindler, A E; Aymar, M

1975-09-01

The metabolism of dehydroepiandrosterone in female adipose tissue and venous blood in 11 patients was studied by a double isotope method which is described in detail. The main metabolite isolated, identified and quantitated was androstenediol. The conversion rate of dehydroepiandrosterone to androstenediol for adipose tissue ranged between 3.32-14.28% (X = 7.47 +/- 3.34 SD) and for venous blood between 2.88-9.60% (X = 5.84 +/- 1.80 SD). The values found for androstenedione and testostrone did not differ from the control experiments. Oestrone and oestradiol could not be detected. The contribution of the peripheral steroid metabolism to the pool of androgenic steroids is discussed.

DsRNA as a stimulator of cell pacemaker activity

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

Airapetyan, S.N.; Zakharyan, R.A.; Rychkov, G.E.

1986-03-01

The authors study the action of double-stranded RNAs (dsRNA) on the characteristics of neuron pacemaker activity which permits prediction of the character of action of dsRNA on the pacemaker activity of cells and organs, and takes the investigators closer to an understanding of the membrane mechanisms underlying the action of dsRNA on the cell. The methods for isolating and fractionating dsRNA from yeasts and the intracellular recording of the electrical activity of the snail giant neuron have been described by the authors earlier. The authors determined the dependence of Ca/sup 2 +/ entry upon dsRNA concentration using the isotope /supmore » 45/Ca. Preweighed ganglia were incubated five each for an hour in 2 ml Ringer's solution containing dsRNA and 5 microliters /sup 45/CaCl/sub 2/ of 12.5 mCi activity. After incubation, the ganglia were rinsed three times for 8 min each time in normal Ringers solution. The washed ganglia were dissolved for one day in KOH. The amount of isotope entering was counted using Brav's scintillator and an RGT counter tuned to the /sup 45/Ca isotope. The physiological saline used for the isolated ganglion contained 85 mmole NaCl, 4 mmole KCl, 8 mmole CaCl/sub 2/, 10 mmole MgCl/sub 2/, 10 mmole Tris-HCl, and 5 mmole glucose.« less

Method for enriching a middle isotope using vibration-vibration pumping

DOEpatents

Rich, Joseph W.; Homicz, Gregory F.; Bergman, Richard C.

1989-01-01

Method for producing isotopically enriched material by vibration-vibration excitation of gaseous molecules wherein a middle mass isotope of an isotopic mixture including lighter and heavier mass isotopes preferentially populates a higher vibrational mode and chemically reacts to provide a product in which it is enriched. The method can be used for vibration-vibration enrichment of .sup.17 O in a CO reactant mixture.

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

USGS Publications Warehouse

Balistrieri, L.S.; Borrok, D.M.; Wanty, R.B.; Ridley, W.I.

2008-01-01

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (65Cu/63Cu) and Zn (66Zn/64Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (??soln-solid) are 0.99927 ?? 0.00008 for Cu and 0.99948 ?? 0.00004 for Zn or, alternately, the separation factors (??soln-solid) are -0.73 ?? 0.08??? for Cu and -0.52 ?? 0.04??? for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

Laser ablation inductively coupled plasma mass spectrometry for direct isotope ratio measurements on solid samples

NASA Astrophysics Data System (ADS)

Pickhardt, Carola; Dietze, Hans-Joachim; Becker, J. Sabine

2005-04-01

Isotope ratio measurements have been increasingly used in quite different application fields, e.g., for the investigation of isotope variation in nature, in geoscience (geochemistry and geochronology), in cosmochemistry and planetary science, in environmental science, e.g., in environmental monitoring, or by the application of the isotope dilution technique for quantification purposes using stable or radioactive high-enriched isotope tracers. Due to its high sensitivity, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is today a challenging mass spectrometric technique for the direct determination of precise and accurate isotope ratios in solid samples. In comparison to laser ablation quadrupole ICP-MS (LA-ICP-QMS), laser ablation coupled to a double-focusing sector field ICP-MS (LA-ICP-SFMS) with single ion detection offers a significant improvement of sensitivity at low mass resolution, whereby isotope ratios can be measured with a precision to 0.1% relative standard deviation (R.S.D.). In LA-ICP-SFMS, many disturbing isobaric interferences of analyte and molecular ions can be separated at the required mass resolution (e.g., 40Ar16O+ and 56Fe+ for iron isotope ratio measurements). The precision on isotope ratio measurements was improved by one order of magnitude via the simultaneous detection of mass-separated ion currents of isotopes using multiple ion collectors in LA-ICP-MS (LA-MC-ICP-MS). The paper discusses the state of the art, the challenges and limits in isotope ratio measurements by LA-ICP-MS using different instrumentations at the trace and ultratrace level in different fields of application as in environmental and biological research, geochemistry and geochronology with respect to their precision and accuracy.

Oxygen Isotopic Analyses of Water Extracted from the Martian Meteorite NWA 7034

NASA Astrophysics Data System (ADS)

Nunn, M.; Agee, C. B.; Thiemens, M. H.

2012-12-01

Introduction: The NWA 7034 meteorite has been identified as Martian, but it is distinct from the Shergottite-Nakhlite-Chassignite (SNC) grouping of meteorites in its petrology (it is the only known Martian basaltic breccia) and bulk silicate oxygen isotopic composition (Δ17O = 0.56 ± 0.06 ‰, where Δ17O = δ17O - 0.528 x δ18O, compared to the average SNC Δ17O ≈ 0.3 ‰) [e.g., 1-2]. We report here measurements of the oxygen isotopic composition of water extracted from NWA 7034 by stepwise heating. Methods: A piece (~1.2g) of NWA 7034 was pumped to vacuum until outgassing had stopped before heating to 50, 150, 320, 500, and 1000°C. The sample was maintained at each temperature step for at least one hour while collecting evolved volatiles in a liquid nitrogen cold trap. Water was selectively converted to molecular oxygen, the oxygen isotopic composition of which was then measured on a double collecting isotope ratio mass spectrometer. Results: Our stepwise heating experiments indicate NWA 7034 contains 3330ppm water, and this water has an average oxygen isotopic composition of Δ17O = 0.330 ± 0.011‰. The oxygen isotopic composition of water in NWA 7034 is unlike that of the silicates from which it is extracted (Δ17O = 0.56 ± 0.06 ‰) but is comparable to the average SNC silicate composition (Δ17O ≈ 0.3 ‰). However, there is no consensus on the oxygen isotopic composition of water in SNCs because aliquots of water extracted from different samples (separate pieces of a single meteorite or from different meteorites) have different oxygen isotopic compositions [3]. Furthermore, carbonates and sulfates extracted from SNCs also possess distinct oxygen isotopic compositions [4]. The variation in oxygen isotopic composition among these phases most likely results from the existence of isotopically distinct oxygen reservoirs on Mars that were not equilibrated. On Earth, interaction of ozone (O3) and carbon dioxide (CO2) leads to a mass independent oxygen isotopic composition of atmospheric CO2 [5]. This anomaly is transferred by exchange from CO2 to water and subsequently to secondary minerals. The much larger CO2 to water ratio on Mars could allow this process to introduce a measurable oxygen isotopic anomaly to sulfates, carbonates, and water. The magnitude and variability of this anomaly would depend on the formation mechanism of the species (particularly the source of oxygen), as is consistent with measurements to date of phases in SNCs. References: [1] Franchi, I.A., et al. (1999) MAPS 34, 657-661. [2] Rumble, D. and Irving, A.J. (2009) LPSC XXXX, #2293 [3] Karlsson, H.R., et al. (1992) Science 255, 1409-1411. [4] Farquhar, J. and Thiemens, M.H. (2000) J. Geophys. Res. 105, 11991-11997. [5] Yung, Y.L., et al. (1991) Geophys. Res. Lett. 18, 13-16.

Combining multinuclear high-resolution solid-state MAS NMR and computational methods for resonance assignment of glutathione tripeptide.

PubMed

Sardo, Mariana; Siegel, Renée; Santos, Sérgio M; Rocha, João; Gomes, José R B; Mafra, Luis

2012-06-28

We present a complete set of experimental approaches for the NMR assignment of powdered tripeptide glutathione at natural isotopic abundance, based on J-coupling and dipolar NMR techniques combined with (1)H CRAMPS decoupling. To fully assign the spectra, two-dimensional (2D) high-resolution methods, such as (1)H-(13)C INEPT-HSQC/PRESTO heteronuclear correlations (HETCOR), (1)H-(1)H double-quantum (DQ), and (1)H-(14)N D-HMQC correlation experiments, have been used. To support the interpretation of the experimental data, periodic density functional theory calculations together with the GIPAW approach have been used to calculate the (1)H and (13)C chemical shifts. It is found that the shifts calculated with two popular plane wave codes (CASTEP and Quantum ESPRESSO) are in excellent agreement with the experimental results.

Determination of Mo- and Ca-isotope ratios in Ca100MoO4 crystal for AMoRE-I experiment

NASA Astrophysics Data System (ADS)

Karki, S.; Aryal, P.; Kim, H. J.; Kim, Y. D.; Park, H. K.

2018-01-01

The first phase of the AMoRE (Advanced Mo-based Rare process Experiment) is to search for neutrinoless double-beta decay of 100Mo with calcium molybdate (Ca100MoO4) crystals enriched in 100Mo and depleted in 48Ca using a cryogenic technique at Yangyang underground laboratory in Korea. It is important to know 100Mo- and 48Ca-isotope ratios in Ca100MoO4 crystal to estimate half-life of 100Mo decays and to 2 νββ background from 48Ca. We employed the ICP-MS (Inductive Coupled Plasma Mass Spectrometer) to measure 100Mo- and 48Ca-isotope ratios in Ca100MoO4 crystal. The measured results for 100Mo- and 48Ca-isotope ratios in the crystal are (94 . 6 ± 2 . 8) % and (0 . 00211 ± 0 . 00006) %, respectively, where errors are included both statistical and systematic uncertainties.

Uranium isotopic compositions of the crust and ocean: Age corrections, U budget and global extent of modern anoxia

NASA Astrophysics Data System (ADS)

Tissot, François L. H.; Dauphas, Nicolas

2015-10-01

The 238U/235U isotopic composition of uranium in seawater can provide important insights into the modern U budget of the oceans. Using the double spike technique and a new data reduction method, we analyzed an array of seawater samples and 41 geostandards covering a broad range of geological settings relevant to low and high temperature geochemistry. Analyses of 18 seawater samples from geographically diverse sites from the Atlantic and Pacific oceans, Mediterranean Sea, Gulf of Mexico, Persian Gulf, and English Channel, together with literature data (n = 17), yield a δ238U value for modern seawater of -0.392 ± 0.005‰ relative to CRM-112a. Measurements of the uranium isotopic compositions of river water, lake water, evaporites, modern coral, shales, and various igneous rocks (n = 64), together with compilations of literature data (n = 380), allow us to estimate the uranium isotopic compositions of the various reservoirs involved in the modern oceanic uranium budget, as well as the fractionation factors associated with U incorporation into those reservoirs. Because the incorporation of U into anoxic/euxinic sediments is accompanied by large isotopic fractionation (ΔAnoxic/Euxinic-SW = +0.6‰), the size of the anoxic/euxinic sink strongly influences the δ238U value of seawater. Keeping all other fluxes constant, the flux of uranium in the anoxic/euxinic sink is constrained to be 7.0 ± 3.1 Mmol/yr (or 14 ± 3% of the total flux out of the ocean). This translates into an areal extent of anoxia into the modern ocean of 0.21 ± 0.09% of the total seafloor. This agrees with independent estimates and rules out a recent uranium budget estimate by Henderson and Anderson (2003). Using the mass fractions and isotopic compositions of various rock types in Earth's crust, we further calculate an average δ238U isotopic composition for the continental crust of -0.29 ± 0.03‰ corresponding to a 238U/235U isotopic ratio of 137.797 ± 0.005. We discuss the implications of the variability of the 238U/235U ratio on Pb-Pb and U-Pb ages and provide analytical formulas to calculate age corrections as a function of the age and isotopic composition of the sample. The crustal ratio may be used in calculation of Pb-Pb and U-Pb ages of continental crust rocks and minerals when the U isotopic composition is unknown. In cosmochemistry, the search for 247Cm (t1/2 = 15.6 Myr), an extinct short-lived radionuclide that decays into 235U, is important for understanding how r-process nuclides were synthesized in stars and learning about the astrophysical context of solar system formation (Chen and Wasserburg, 1981; Wasserburg et al., 1996; Nittler and Dauphas, 2006; Brennecka et al., 2010b; Tissot et al., 2015). In both terrestrial and extraterrestrial samples, variations in the 238U/235U ratio affect Pb-Pb ages (and depending on the analytical protocols, U-Pb ages). Therefore, samples dated by these techniques need to have their U isotopic compositions measured (Stirling et al., 2005, 2006; Weyer et al., 2008; Amelin et al., 2010; Brennecka et al., 2010b; Brennecka and Wadhwa, 2012; Connelly et al., 2012; Goldmann et al., 2015) or uncertainties on the U isotopic composition should be propagated into age calculations. In low temperature aqueous geochemistry, U isotopic fractionation between U4+ and U6+ (driven in part by nuclear field shift effects; Bigeleisen, 1996; Schauble, 2007; Abe et al., 2008), makes U isotopes potential tracers of paleoredox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011a; Kendall et al., 2013, 2015; Asael et al., 2013; Andersen et al., 2014; Dahl et al., 2014; Goto et al., 2014; Noordmann et al., 2015). The present paper aims at constraining some aspects of the global budget of uranium in the modern oceans using 238U/235U isotope variations, which involves characterizing the U isotopic composition of seawater and several reservoirs involved in the uranium oceanic budget. Uranium can exist in two oxidation states in terrestrial surface environments: U4+ is insoluble in seawater while U6+ is soluble (Langmuir, 1978). The contrasting behaviors of the two oxidation states of uranium explains why the disappearance of detrital uraninite after the Archean marks the rise of oxygen in Earth's atmosphere/hydrosphere (Ramdohr, 1958; Rasmussen and Buick, 1999; Frimmel, 2005). More recently, significant effort has focused on using U isotopes to constrain the past extents of anoxic/euxinic vs. oxic or suboxic sediments in modern and ancient oceans (Montoya-Pino et al., 2010; Brennecka et al., 2011a; Asael et al., 2013; Kendall et al., 2013, 2015; Andersen et al., 2014; Dahl et al., 2014; Goto et al., 2014; Noordmann et al., 2015). A virtue of this system is that it can potentially reflect the global redox state of Earth's oceans. At the same time, several difficulties have been encountered in applying U isotopes as paleo-redox indicators. For example, detrital contributions can blur the authigenic signal and have to be corrected for (Asael et al., 2013; Andersen et al., 2014; Noordmann et al., 2015), uranium isotopes can be affected by diagenesis and exchange with porewater (Romaniello et al., 2013; Andersen et al., 2014), and the exact isotopic fractionation factors relevant to various conditions of deposition are uncertain. While significant progress has already been made to address these difficulties (Asael et al., 2013; Romaniello et al., 2013; Andersen et al., 2014; Noordmann et al., 2015), this system and others are missing some of the groundwork studies on modern environments that are needed to gain trust in their applications to ancient sediments.In the modern ocean, water-soluble uranium behaves conservatively (i.e., U concentration correlates linearly to water salinity, Ku et al., 1977; Owens et al., 2011) and has a long residence time of ∼400 kyr (Ku et al., 1977). The ocean is therefore a large repository of uranium, exceeding the total inventory of land-based deposits (Lu, 2014). The riverine input (40-46 Mmol/yr) is balanced by several sinks; including suboxic sediments, anoxic/euxinic sediments, carbonates, altered oceanic crust, salt marshes and Fe-Mn nodules. Barnes and Cochran (1990), Morford and Emerson (1999), Dunk et al. (2002), and Henderson and Anderson (2003) each proposed estimates for the oceanic uranium budget that differ substantially in the fluxes that they use. Uranium isotopes are sensitive to ocean redox conditions because uranium removal in anoxic/euxinic sediments imparts large uranium isotopic fractionation, so that the areal extent of this sink influences greatly the U isotopic composition of seawater relative to the riverine input. In the present paper, we report double-spike uranium isotopic measurements of 18 seawater samples, 18 continental crust lithologies, 7 individual minerals, 6 oyster samples, 3 modern evaporites samples, 2 lake water samples, 1 large river water sample and 1 coral sample. These measurements are supplemented by compilations of literature data. With this large data set (n = 444), we are able to constrain the flux of uranium into anoxic/euxinic sediments, as well as the global extent of anoxia in the modern ocean (percent of seafloor covered by anoxic/euxinic sediments). Our findings compare well with independent estimates and rule out the most recent U budget of Henderson and Anderson (2003).As part of our effort, we also present a data reduction method for double-spike measurements that is both comprehensive in the way the errors are propagated and simple to implement.

Isotope separation by photochromatography

DOEpatents

Suslick, Kenneth S.

1977-01-01

An isotope separation method which comprises physically adsorbing an isotopically mixed molecular species on an adsorptive surface and irradiating the adsorbed molecules with radiation of a predetermined wavelength which will selectively excite a desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thereby separate them from the unexcited undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes.

Tracing metal-silicate segregation and late veneer in the Earth and the ureilite parent body with palladium stable isotopes

NASA Astrophysics Data System (ADS)

Creech, J. B.; Moynier, F.; Bizzarro, M.

2017-11-01

Stable isotope studies of highly siderophile elements (HSE) have the potential to yield valuable insights into a range of geological processes. In particular, the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal-silicate segregation, making them sensitive tracers of planetary differentiation processes. We present the first techniques for the precise determination of palladium stable isotopes by MC-ICPMS using a 106Pd-110Pd double-spike to correct for instrumental mass fractionation. Results are expressed as the per mil (‰) difference in the 106Pd/105Pd ratio (δ106Pd) relative to an in-house solution standard (Pd_IPGP) in the absence of a certified Pd isotopic standard. Repeated analyses of the Pd isotopic composition of the chondrite Allende demonstrate the external reproducibility of the technique of ±0.032‰ on δ106Pd. Using these techniques, we have analysed Pd stable isotopes from a range of terrestrial and extraterrestrial samples. We find that chondrites define a mean δ106Pdchondrite = -0.19 ± 0.05‰. Ureilites reveal a weak trend towards heavier δ106Pd with decreasing Pd content, similar to recent findings based on Pt stable isotopes (Creech et al., 2017), although fractionation of Pd isotopes is significantly less than for Pt, possibly related to its weaker metal-silicate partitioning behaviour and the limited field shift effect. Terrestrial mantle samples have a mean δ106Pdmantle = -0.182 ± 0.130‰, which is consistent with a late-veneer of chondritic material after core formation.

Seasonal C-13 variations of methane from an anoxic marine sediment

NASA Technical Reports Server (NTRS)

Blair, Neal; Desmarais, David S.; Martens, Christopher S.

1985-01-01

Recent analyses of glacial ice suggest that the atmospheric concentration of methane has doubled in the last several hundred years, presumably due to anthropogenic perturbations of the relevant biogeochemical cycles. In principal, carbon isotopic measurements of atmospheric methane would provide information concerning changes in the sources and sinks of methane. The isotopic composition of methane is dependent on the source of the methane carbon, the mechanism of methane synthesis, and the degree and mode of oxidation which the methane has experienced. Unfortunately, few carbon isotopic measurements of atmospheric variations have been reported, so conclusions about temporal isotopic variations cannot be made. Also, before isotopic measurements of atmospheric methane can be used to identify changes in methane isotopic composition from different sources must be obtained. Methane bubbles from the anoxic sediments of Cape Lookout Bight, NC exhibit seasonal C-13 variations. The C-13 values ranged from -58 in August to -64 in the winter months with the evolution of the C-13 enriched gas occurring during periods of peak methane production. Even though a few intramolecular C-13 measurements of the pore water acetate have been made (methyl group, -26 per mil; carbonyl, -6 per mil), it is not clear how the acetate fermentation pathway affects the methane C-13/C-12 composition.

Titanium stable isotope investigation of magmatic processes on the Earth and Moon

NASA Astrophysics Data System (ADS)

Millet, Marc-Alban; Dauphas, Nicolas; Greber, Nicolas D.; Burton, Kevin W.; Dale, Chris W.; Debret, Baptiste; Macpherson, Colin G.; Nowell, Geoffrey M.; Williams, Helen M.

2016-09-01

We present titanium stable isotope measurements of terrestrial magmatic samples and lunar mare basalts with the aims of constraining the composition of the lunar and terrestrial mantles and evaluating the potential of Ti stable isotopes for understanding magmatic processes. Relative to the OL-Ti isotope standard, the δ49Ti values of terrestrial samples vary from -0.05 to +0.55‰, whereas those of lunar mare basalts vary from -0.01 to +0.03‰ (the precisions of the double spike Ti isotope measurements are ca. ±0.02‰ at 95% confidence). The Ti stable isotope compositions of differentiated terrestrial magmas define a well-defined positive correlation with SiO2 content, which appears to result from the fractional crystallisation of Ti-bearing oxides with an inferred isotope fractionation factor of ΔTi49oxide-melt = - 0.23 ‰ ×106 /T2. Primitive terrestrial basalts show no resolvable Ti isotope variations and display similar values to mantle-derived samples (peridotite and serpentinites), indicating that partial melting does not fractionate Ti stable isotopes and that the Earth's mantle has a homogeneous δ49Ti composition of +0.005 ± 0.005 (95% c.i., n = 29). Eclogites also display similar Ti stable isotope compositions, suggesting that Ti is immobile during dehydration of subducted oceanic lithosphere. Lunar basalts have variable δ49Ti values; low-Ti mare basalts have δ49Ti values similar to that of the bulk silicate Earth (BSE) while high-Ti lunar basalts display small enrichment in the heavy Ti isotopes. This is best interpreted in terms of source heterogeneity resulting from Ti stable isotope fractionation associated with ilmenite-melt equilibrium during the generation of the mantle source of high-Ti lunar mare basalts. The similarity in δ49Ti between terrestrial samples and low-Ti lunar basalts provides strong evidence that the Earth and Moon have identical stable Ti isotope compositions.

Mass dependent fractionation of stable chromium isotopes in mare basalts: Implications for the formation and the differentiation of the Moon

NASA Astrophysics Data System (ADS)

Bonnand, Pierre; Parkinson, Ian J.; Anand, Mahesh

2016-02-01

We present the first stable chromium isotopic data from mare basalts in order to investigate the similarity between the Moon and the Earth's mantle. A double spike technique coupled with MC-ICP-MS measurements was used to analyse 19 mare basalts, comprising high-Ti, low-Ti and KREEP-rich varieties. Chromium isotope ratios (δ53Cr) for mare basalts are positively correlated with indices of magmatic differentiation such as Mg# and Cr concentration which suggests that Cr isotopes were fractionated during magmatic differentiation. Modelling of the results provides evidence that spinel and pyroxene are the main phases controlling the Cr isotopic composition during fractional crystallisation. The most evolved samples have the lightest isotopic compositions, complemented by cumulates that are isotopically heavy. Two hypotheses are proposed to explain this fractionation: (i) equilibrium fractionation where heavy isotopes are preferentially incorporated into the spinel lattice and (ii) a difference in isotopic composition between Cr2+ and Cr3+ in the melt. However, both processes require magmatic temperatures below 1200 °C for appreciable Cr3+ to be present at the low oxygen fugacities found in the Moon (IW -1 to -2 log units). There is no isotopic difference between the most primitive high-Ti, low-Ti and KREEP basalts, which suggest that the sources of these basalts were homogeneous in terms of stable Cr isotopes. The least differentiated sample in our sample set is the low-Ti basalt 12016, characterised by a Cr isotopic composition of -0.222 ± 0.025‰, which is within error of the current BSE value (-0.124 ± 0.101‰). The similarity between the mantles of the Moon and Earth is consistent with a terrestrial origin for a major fraction of the lunar Cr. This similarity also suggests that Cr isotopes were not fractionated by core formation on the Moon.

A 500 year sediment lake record of anthropogenic and natural inputs to Windermere (English Lake District) using double-spike lead isotopes, radiochronology, and sediment microanalysis.

PubMed

Miller, Helen; Croudace, Ian W; Bull, Jonathan M; Cotterill, Carol J; Dix, Justin K; Taylor, Rex N

2014-07-01

A high-resolution record of pollution is preserved in recent sediments from Windermere, the largest lake in the English Lake District. Data derived from X-ray core scanning (validated against wavelength dispersive X-ray fluorescence), radiochronological techniques ((210)Pb and (137)Cs) and ultrahigh precision, double-spike mass spectrometry for lead isotopes are combined to decipher the anthropogenic inputs to the lake. The sediment record suggests that while most element concentrations have been stable, there has been a significant increase in lead, zinc, and copper concentrations since the 1930s. Lead isotope down-core variations identify three major contributory sources of anthropogenic (industrial) lead, comprising gasoline lead, coal combustion lead (most likely source is coal-fired steam ships), and lead derived from Carboniferous Pb-Zn mineralization (mining activities). Periods of metal workings do not correlate with peaks in heavy metals due to the trapping efficiency of up-system lakes in the catchment. Heavy metal increases could be due to flood-induced metal inwash after the cessation of mining and the weathering of bedrock in the catchment. The combination of sediment analysis techniques used provides new insights into the pollutant depositional history of Windermere and could be similarly applied to other lake systems to determine the timing and scale of anthropogenic inputs.

The Lamont--Doherty Geological Observatory Isolab 54 isotope ratio mass spectrometer

NASA Astrophysics Data System (ADS)

England, J. G.; Zindler, A.; Reisberg, L. C.; Rubenstone, J. L.; Salters, V.; Marcantonio, F.; Bourdon, B.; Brueckner, H.; Turner, P. J.; Weaver, S.; Read, P.

1992-12-01

The Lamont--Doherty Geological Observatory (LDGO) Isolab 54 is a double focussing isotope ratio mass spectrometer that allows the measurement of thermal ions produced on a hot filament, (thermal-ionization mass spectrometry (TIMS)), secondary ions produced by sputtering a sample using a primary ion beam, (secondary ion mass spectrometry (SIMS)), and sputtered neutrals resonantly ionized using laser radiation, (sputter-induced resonance ionization mass spectrometry (SIRIMS)). Sputtering is carried out using an Ar primary beam generated in a duoplasmatron and focussed onto the sample using a two-lens column. Resonance ionization is accomplished using a frequency-doubled dye laser pumped by an excimer laser. The Isolab's forward geometry analyzer, consisting of an electrostatic followed by a magnetic sector, allows the simultaneous collection of different isotopes of the same element. This instrument is the first to have a multicollector that contains an ion-counting system based on a microchannel plate as well as traditional Faraday cups. A second electrostatic sector after the multicollector is equipped with an ion-counting Daly detector to allow high abundance sensitivity for measurements of large dynamics range. Selectable source, collector, [alpha] and energy slits on the instrument allow analyses to be made over a range of mass resolving powers and analyzer acceptances. Recent applications of the instrument have included the analyses of U by TIMS, Hf, Th and Re by SIMS and Re and Os by SIRIMS.

DETERMINING ION COMPOSITIONS USING AN ACCURATE MASS, TRIPLE QUADRUPOLE MASS SPECTROMETER

EPA Science Inventory

For the past decade, we have used double focusing mass spectrometers to determine
compositions of ions observed in mass spectra produced from compounds introduced by GC
based on measured exact masses of the ions and their +1 and +2 isotopic profiles arising from atoms of ...

A New Method to Quantify the Isotopic Signature of Leaf Transpiration: Implications for Landscape-Scale Evapotranspiration Partitioning Studies

NASA Astrophysics Data System (ADS)

Wang, L.; Good, S. P.; Caylor, K. K.

2010-12-01

Characterizing the constituent components of evapotranspiration is crucial to better understand ecosystem-level water budgets and water use dynamics. Isotope based evapotranspiration partitioning methods are promising but their utility lies in the accurate estimation of the isotopic composition of underlying transpiration and evaporation. Here we report a new method to quantify the isotopic signature of leaf transpiration under field conditions. This method utilizes a commercially available laser-based isotope analyzer and a transparent leaf chamber, modified from Licor conifer leaf chamber. The method is based on the water mass balance in ambient air and leaf transpired air. We verified the method using “artificial leaves” and glassline extracted samples. The method provides a new and direct way to estimate leaf transpiration isotopic signatures and it has wide applications in ecology, hydrology and plant physiology.

Isotope separation by photochromatography

DOEpatents

Suslick, K.S.

1975-10-03

A photochromatographic method for isotope separation is described. An isotopically mixed molecular species is adsorbed on an adsorptive surface, and the adsorbed molecules are irradiated with radiation of a predetermined wavelength which will selectively excite desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thus separate them from the undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes. (BLM)

Thermal Ionization Mass Spectrometry Techniques for the Determination of d34S and D33S

NASA Astrophysics Data System (ADS)

Mann, J. L.; Kelly, W. R.

2006-12-01

Mass-dependent (MD) and mass-independent (MI) sulfur isotopic compositions are measured by gas source isotope ratio mass spectrometry (GIRMS) using either SO2 or SF6 gas. The variations in sulfur isotopes are used for tracing sources of sulfur and elucidating the sulfur cycle. The recent discovery of MI sulfur isotopic effects provide a tracer for atmospheric processes that may yield insight into the atmospheric sulfur cycle. Determinations of δ^{34}S and Δ^{33}S as well as sulfur concentration in low concentration (ppb) samples are now possible by multi-collector thermal ionization mass spectrometry (MCTIMS) by measuring arsenic sulfide molecular ions (AsS+) using silica gel as an emitter. δ^{34}S is determined using a ^{33}S/^{36}S double spike to correct for instrumental mass fractionation. It is added to the sample before chemical processing which permits the simultaneous determination of the natural MD isotopic fractionation and the sulfur concentration. The addition of the double spike before sample processing has the important additional advantage that any isotopic fractionation that may occur during the chemistry will be removed by the double spike correction procedure. The accuracy and precision of the double spike technique is comparable to modern GIRMS, but requires about a factor of 10 less sample. Δ^{33}S effects can also be measured by MCTIMS on unspiked samples using internal normalization. In GIRMS Δ^{33}S effects are defined by the following equation: Δ^{33}S = δ^{33}S - k δ^{34}S A resolvable effect is governed by both the precision and reproducibility of the δ^{33}S and δ^{34}S measurements and the k value. It is claimed that effects of 0.05 to 0.20 Δ^{33}S units are resolvable. MI effects in mass 33 using MCTIMS are determined on an unspiked sample using internal normalization. Because mass 33 falls between and adjacent to the masses 32 and 34 that are used for correction the interpolation correction is over the smallest possible range. A resolvable Δ^{33}S effect depends only on the precision of the measurement. It is direct in that unlike GIRMS it does not require measurement of δ^{33}S and δ^{34}S or any assumption as to the value of the parameter k. GIRMS could also potentially use the internal normalization procedure to perform direct measurements of Δ^{33}S. The double spike MCTIMS procedure was evaluated by measuring the international standards (IAEA-S-1, S-2, and S-3). The δ^{34}S values (relative to Vienna Canyon Diablo Troilite (VCDT)) determined were 0.32‰ ± 0.04‰ (1σ, n=4) and 0.31‰ ± 0.13‰ (1σ, n=8) for S-1, 22.65‰ ± 0.04‰ (1σ, n=7) and 22.60‰ ± 0.06‰ (1σ, n=5) for S-2, and 32.47‰ ± 0.07‰ (1σ, n=8) for S-3. The uncertainties reported are comparable to or better then those obtained by GIRMS. Δ^{33}S determinations for S-1, also reported relative to VCDT, ranged from -0.67‰ ± 2.2‰ (1σ) to 0.71‰ ± 2.1‰ (1σ) and averaged 0.0028‰ ± 0.55‰ (1σ, n=6) suggesting there is no MI effect (Δ^{33}S=0). Although the MCTIMS procedure requires the use of a mass fractionation law, previous work on MD standards showed that the change in fractionation during data collection was small (2 to 3‰) and thus the correction required was small and unlikely to produce measurable artifacts in Δ^{33}S.

Neutrinoless double beta decay with 82SeF6 and direct ion imaging

NASA Astrophysics Data System (ADS)

Nygren, D. R.; Jones, B. J. P.; López-March, N.; Mei, Y.; Psihas, F.; Renner, J.

2018-03-01

We present a new neutrinoless double beta decay concept: the high pressure selenium hexafluoride gas time projection chamber. A promising new detection technique is outlined which combines techniques pioneered in high pressure xenon gas, such as topological discrimination, with the high Q-value afforded by the double beta decay isotope 82Se. The lack of free electrons in SeF6 mandates the use of an ion TPC. The microphysics of ion production and drift, which have many nuances, are explored. Background estimates are presented, suggesting that such a detector may achieve background indices of better than 1 count per ton per year in the region of interest at the 100 kg scale, and still better at the ton-scale.

Evidence for cis-trans isomerization of a double bond in the fatty acids of the psychrophilic bacterium Vibrio sp. strain ABE-1.

PubMed

Morita, N; Shibahara, A; Yamamoto, K; Shinkai, K; Kajimoto, G; Okuyama, H

1993-02-01

Vibrio sp. strain ABE-1 was grown in a medium that contained as its stable isotope tracer either [2,2-2H2]cis-9-hexadecenoic or [2,2-2H2]trans-9-hexadecenoic acid. Gas chromatographic-mass spectrometric analysis of the cis-9-hexadecenoic and trans-9-hexadecenoic acid fractions from the cells revealed the formation of an intracellularly isomerized 2,2-2H2-fatty acid which differed from the tracer only in the geometrical configuration of the double bond. This observation shows that cis-trans isomerization without a shift in double-bond position between these two geometric hexadecenoic acid isomers can occur in the cells.

Evidence for cis-trans isomerization of a double bond in the fatty acids of the psychrophilic bacterium Vibrio sp. strain ABE-1.

PubMed Central

Morita, N; Shibahara, A; Yamamoto, K; Shinkai, K; Kajimoto, G; Okuyama, H

1993-01-01

Vibrio sp. strain ABE-1 was grown in a medium that contained as its stable isotope tracer either [2,2-2H2]cis-9-hexadecenoic or [2,2-2H2]trans-9-hexadecenoic acid. Gas chromatographic-mass spectrometric analysis of the cis-9-hexadecenoic and trans-9-hexadecenoic acid fractions from the cells revealed the formation of an intracellularly isomerized 2,2-2H2-fatty acid which differed from the tracer only in the geometrical configuration of the double bond. This observation shows that cis-trans isomerization without a shift in double-bond position between these two geometric hexadecenoic acid isomers can occur in the cells. PMID:8423164

High precision time calibration of the Permo-Triassic boundary mass extinction by U-Pb geochronology

NASA Astrophysics Data System (ADS)

Baresel, Björn; Bucher, Hugo; Brosse, Morgane; Schaltegger, Urs

2014-05-01

U-Pb dating using Chemical Abrasion, Isotope Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS) is the analytical method of choice for geochronologists, who are seeking highest temporal resolution and a high degree of accuracy for single grains of zircon. The use of double-isotope tracer solutions, cross-calibrated and assessed in different EARTHTIME labs, coinciding with the reassessment of the uranium decay constants and further improvements in ion counting technology led to unprecedented precision better than 0.1% for single grain, and 0.05% for population ages, respectively. These analytical innovations now allow calibrating magmatic and biological timescales at resolution adequate for both groups of processes. To construct a revised and high resolution calibrated time scale for the Permian-Triassic boundary (PTB) we use (i) high-precision U-Pb zircon age determinations of a unique succession of volcanic ash beds interbedded with shallow to deep water fossiliferous sediments in the Nanpanjiang Basin (South China) combined with (ii) accurate quantitative biochronology based on ammonoids and conodonts and (iii) carbon isotope excursions across the PTB. Using these alignments allows (i) positioning the PTB in different depositional environments and (ii) solving age/stratigraphic contradictions generated by the index, water depth-controlled conodont Hindeodus parvus, whose diachronous first occurrences are arbitrarily used for placing the base of the Triassic. This new age framework provides the basis for a combined calibration of chemostratigraphic records with high-resolution biochronozones of the Late Permian and Early Triassic. Besides the general improvement of the radio-isotopic calibration of the PTB at the ±100 ka level, this will also lead to a better understanding of cause and effect relations involved in this mass extinction.

Method for laser induced isotope enrichment

DOEpatents

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

2004-09-07

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

Method of enhancing selective isotope desorption from metals

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1984-01-01

A method of enhancing the thermal desorption of a first isotope of a diatomic gas from a metal comprises the steps of (a) establishing a partial pressure of a second isotope of the diatomic gas in vicinity of the metal; heating the metal to a temperature such that the first isotope is desorbed from the metal; and reducing the partial pressure of the desorbed first isotope while maintaining the partial pressure of the second isotope substantially constant. The method is especially useful for enhancing the desorption of tritium from the Zr-Al getter in a plasma confinement device.

An improved method for high precision measurement of chromium isotopes using double spike MC-ICP-MS

NASA Astrophysics Data System (ADS)

Zhu, J.; Wu, G. L.; Wang, X.; Zhang, L. X.; Han, G.

2017-12-01

Chormium(Cr) isotopes have been used to trace pollution processes and reconstruct paleo-redox conditions. However, the precise determination of Cr isotopes has still been challenged due to difficulties in purifying Cr from samples with low Cr content and complex matrices. Here we report an improved four-step column chromatographic procedure to separate Cr from matrix elements. Firstly, Cr in sample solution was mixed with 50Cr-54Cr double spike (the optimized 54Crspike/52Crsample = 0.4 and (50Cr/54Cr)spike = 1.3:1) was completely converted into Cr (III) in 8.5mol/L HCl and loaded onto 2ml of AG50W-X8(200-400m) resin conditioned with 11 mol/L HCl. The 2.65ml of eluent was adjusted to 4.5ml of 6mol/L HCl and immediately loaded onto a Bio-Rad column filled with 2ml of AG1-X8 anion resin (100-200m). These two steps can remove at least 99% of Ca, Fe and most matrix elements. Secondly, the 7.5ml of eluent was dried down and dissolved in 0.1ml of 0.5mol/L HNO3.before adding 2ml 4mol/L HF, which was then loaded onto 1ml of AG1-X8 anion resin (100-200m) to remove Ti and V. Finally, sample was dissolved in 0.1ml of 0.5 mol/L HNO3 and oxidized by 0.5mL 0.2 mol/L (NH4)2S2O8 and 4.4mL H2O, which was then centrifuged to remove Mn oxide, and supernatant was loaded onto AG1-X8 resin to remove SO42-, Ni, Al, Na and some Mg using 8ml H2O and 3ml 2mol/L HCl. Cr was eluted by 2 mol/L HNO3 containing 5% H2O2 and the dried Cr was dissolved in 3% HNO3for isotopic analysis. The total yield to Cr is great than 80% even for samples with low Cr content. Chromium isotopes was measured on a Neptune plus MC-ICP-MS in China University of Geosciences(Beijing). Using our improved method, the δ53/52CrSRM979 values of USGS reference materials BHVO-2, BCR-2 and SGR-1b are -0.12±0.06‰(n=15), -0.09±0.06‰ (n=5), and 0.30±0.06‰ (n=12), respectively, which agree well with previously reported values. The δ53/52CrSRM979 of carbonaceous shale CP0-1 and CP0-12 collected from Hubei, China are 2.05±0.08‰ (n=3) and 2.08±0.07‰ (n=3), respectively, identical to 2.17±0.08‰ and 2.14±0.08‰ determined at the Department of Geology, UIUC. This work was supported by the National Key Basic Research Program of China (2014CB238903) and the National Natural Science Foundation of China (41473028, 41273029).

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.

A double-stage tube furnace--acid-trapping protocol for the pre-concentration of mercury from solid samples for isotopic analysis.

PubMed

Sun, Ruoyu; Enrico, Maxime; Heimbürger, Lars-Eric; Scott, Clint; Sonke, Jeroen E

2013-08-01

High-precision mercury (Hg) stable isotopic analysis requires relatively large amounts of Hg (>10 ng). Consequently, the extraction of Hg from natural samples with low Hg concentrations (<1-20 ng/g) by wet chemistry is challenging. Combustion-trapping techniques have been shown to be an appropriate alternative. Here, we detail a modified off-line Hg pre-concentration protocol that is based on combustion and trapping. Hg in solid samples is thermally reduced and volatilized in a pure O2 stream using a temperature-programmed combustion furnace. A second furnace, kept at 1,000 °C, decomposes combustion products into H2O, CO2, SO2, etc. The O2 carrier gas, including combustion products and elemental Hg, is then purged into a 40% (v/v) acid-trapping solution. The method was optimized by assessing the variations of Hg pre-concentration efficiency and Hg isotopic compositions as a function of acid ratio, gas flow rate, and temperature ramp rate for two certified reference materials of bituminous coals. Acid ratios of 2HNO3/1HCl (v/v), 25 mL/min O2 flow rate, and a dynamic temperature ramp rate (15 °C/min for 25-150 and 600-900 °C; 2.5 °C/min for 150-600 °C) were found to give optimal results. Hg step-release experiments indicated that significant Hg isotopic fractionation occurred during sample combustion. However, no systematic dependence of Hg isotopic compositions on Hg recovery (81-102%) was observed. The tested 340 samples including coal, coal-associated rocks, fly ash, bottom ash, peat, and black shale sediments with Hg concentrations varying from <5 ng/g to 10 μg/g showed that most Hg recoveries were within the acceptable range of 80-120%. This protocol has the advantages of a short sample processing time (∼3.5 h) and limited transfer of residual sample matrix into the Hg trapping solution. This in turn limits matrix interferences on the Hg reduction efficiency of the cold vapor generator used for Hg isotopic analysis.

Neutron-capture cross-section measurements of 74Ge and 76Ge in the energy region 0.4-14.8 MeV for neutrinoless double β decay applications

NASA Astrophysics Data System (ADS)

Bhike, Megha; Tornow, Werner

2013-10-01

Fast neutron capture cross sections for the reactions 74Ge(n, γ)75Ge and 76Ge(n, γ)77Ge have been measured in the neutron energy region 0.4-14.8 MeV with the activation method. The results are important to identify backgrounds in the neutrinoless double- β decay experiments GERDA and MAJORANA, which use germanium as both source and detector. Isotopically enriched targets which consisted of 86% of 76Ge and 14% of 74Ge were irradiated with mono-energetic neutrons produced via 3H(p,n)3He, 2H(d,n)3He and 3H(d,n)4He reactions. The cross sections were determined relative to 197Au(n, γ)198Au, 115In(n,n')115mIn and 197Au(n,2n)196Au standard cross sections. The activities of the products were measured using high-resolution γ-ray spctroscopy. The present results are compared with the evaluated data from ENDF/B-VII.1 and TALYS.

Chemical purification of lanthanides for low-background experiments

NASA Astrophysics Data System (ADS)

Boiko, R. S.

2017-10-01

There are many potentially active isotopes among the lanthanide elements which are possible to use for low-background experiments to search for double β decay, dark matter, to investigate rare α and β decays. These kind of experiments require very low level of radioactive contamination, but commercially available compounds of lanthanides are always contamined by uranium, thorium, radium, potassium, etc. A simple chemical method based on liquid-liquid extraction has been applied for the purification of CeO2, Nd2O3 and Gd˙2O˙3 from radioactive traces. Detailed schemes of purification procedure are described. Measurements by using HPGe spectrometry demonstrate high efficiency in K, Ra, Th, U contaminations reduction on at least one order of magnitude.

Waves in a gas centrifuge

NASA Astrophysics Data System (ADS)

Bogovalov, S. V.; Kislov, V. A.; Tronin, I. V.

2016-09-01

Impact of the pulsed braking force on the axial gas circulation and gas content in centrifuges for uranium isotope separation was investigated by the method of numerical simulation. Pulsed brake of the rotating gas by the momentum source results into generation of the waves which propagate along the rotor of the centrifuge. The waves almost doubles the axial circulation flux in the working camera in compare with the case of the steady state breaking force with the same average power in the model under the consideration. Flux through the hole in the bottom baffle on 15% exceeds the flux in the stationary case for the same pressure and temperature in the model. We argue that the waves reduce the pressure in the GC on the same 15%.

Calcium absorbability from milk products, an imitation milk, and calcium carbonate

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

Recker, R.R.; Bammi, A.; Barger-Lux, M.J.

Whole milk, chocolate milk, yogurt, imitation milk (prepared from dairy and nondairy products), cheese, and calcium carbonate were labeled with /sup 45/Ca and administered as a series of test meals to 10 healthy postmenopausal women. Carrier Ca content of the test meals was held constant at 250 mg and subjects fasted before each meal. The absorbability of Ca from the six sources was compared by measuring fractional absorption by the double isotope method. The mean absorption values for all six sources were tightly clustered between 21 and 26% and none was significantly different from the others using one-way analysis ofmore » variance. We conclude that none of the sources was significantly superior or inferior to the others.« less

Investigation of critical parameters controlling the efficiency of associative ionization

NASA Astrophysics Data System (ADS)

Le Padellec, A.; Launoy, T.; Dochain, A.; Urbain, X.

2017-05-01

This paper compiles our merged-beam experimental findings for the associative ionization (AI) process from charged reactants, with the aim of guiding future investigations with e.g. the double electrostatic ion storage ring DESIREE in Stockholm. A reinvestigation of the isotopic effect in H-(D-) + He+ collisions is presented, along with a review of {{{H}}}3+ and NO+ production by AI involving ion pairs or excited neutrals, and put in perspective with the mutual neutralization and radiative association reactions. Critical parameters are identified and evaluated for their systematic role in controlling the magnitude of the cross section: isotopic substitution, exothermicity, electronic state density, and spin statistics.

Precise measurement of Fe isotopes in marine samples by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS).

PubMed

de Jong, Jeroen; Schoemann, Véronique; Tison, Jean-Louis; Becquevort, Sylvie; Masson, Florence; Lannuzel, Delphine; Petit, Jérôme; Chou, Lei; Weis, Dominique; Mattielli, Nadine

2007-04-18

A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)(2), and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is +/-0.07 per thousand on delta(56)Fe and +/-0.09 per thousand on delta(57)Fe while typical internal precision of a measurement (1S.E.) is +/-0.03 per thousand on delta(56)Fe and +/-0.04 per thousand on delta(57)Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of approximately 2 nmol L(-1) for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L(-1) Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. delta(56)Fe varies between -3.5 per thousand and +1.5 per thousand. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.

Double differential cross section calculations for 16O and 90Zr elements

NASA Astrophysics Data System (ADS)

Demirkol, İ.

2018-04-01

Double differential cross sections in proton induced reactions on 90Zr and O2 (inert matrix fuel) is calculated at the bombarding energies between 29 and 300 MeV. The proton-induced nuclear reaction cross section data can be used in technical applications such as the isotope production alternatives, spallation reactions for production of neutrons in spallation neutron source, etc. In this study, the cascade excition model including the effect of preequilibrium is used to calculate the differential cross section. Then, the obtained results are discussed and compared with available experimental data.

New search for double electron capture in {sup 106}Cd decay with the TGV-2 spectrometer

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

Briançon, Ch.; Brudanin, V. B.; Egorov, V. G.

2015-09-15

A new experiment devoted to searches for double electron capture in {sup 106}Cd decay is being performed at the Modane underground laboratory (4800 mwe) with the 32-detector TGV-2 spectrometer. The limit T{sub 1/2}(2νEC/EC) > 2.0×10{sup 20} yr at a 90%confidence level (C.L.) was obtained from a preliminary analysis of data obtained over 2250 h of measurements with about 23.2 g sample enriched in the isotope {sup 106}Cd to 99.57%. The limits T{sub 1/2}(KL, 2741 keV) > 0.9 × 10{sup 20} yr and T{sub 1/2}(KK, 2718 keV) ≫ 1.4 × 10{sup 20} yr at a 90% C.L. on the neutrinoless decaymore » of {sup 106}Cd were obtained from measurements performed with the Obelix low-background spectrometer from high-purity germanium (HPGe spectrometer) for a sample of mass about 23.2 g enriched in the isotope {sup 106}Cd.« less

Measurements of natural uranium concentration and isotopic composition with permil-level precision by inductively coupled plasma-quadrupole mass spectrometry

NASA Astrophysics Data System (ADS)

Shen, Chuan-Chou; Lin, Huei-Ting; Chu, Mei-Fei; Yu, Ein-Fen; Wang, Xianfeng; Dorale, Jeffrey A.

2006-09-01

A new analytical technique using inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) has been developed that produces permil-level precision in the measurement of uranium concentration ([U]) and isotopic composition (δ234U) in natural materials. A 233U-236U double spike method was used to correct for mass fractionation during analysis. To correct for ratio drifting, samples were bracketed by uranium standard measurements. A sensitivity of 6-7 × 108 cps/ppm was generated with a sample solution uptake rate of 30 μL/min. With a measurement time of 15-20 min, standards of 30-ng uranium produced a within-run precision better than 3‰ (±2 R.S.D.) for δ234U and better than 2‰ for [U]. Replicate measurements made on standards show that a between-run reproducibility of 3.5‰ for δ234U and 2‰ for [U] can be achieved. ICP-QMS data of δ234U and [U] in seawater, coral, and speleothem materials are consistent with the data measured by other ICP-MS and TIMS techniques. Advantages of the ICP-QMS method include low cost, easy maintenance, simple instrumental operation, and few sample preparation steps. Sample size requirements are small, such as 10-14 mg of coral material. The results demonstrate that this technique can be applied to natural samples with various matrices.

Selective IR multiphoton dissociation of molecules in a pulsed gas-dynamically cooled molecular flow interacting with a solid surface as an alternative to low-energy methods of molecular laser isotope separation

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

Makarov, G N; Petin, A N

2016-03-31

We report the results of studies on the isotope-selective infrared multiphoton dissociation (IR MFD) of SF{sub 6} and CF{sub 3}I molecules in a pulsed, gas-dynamically cooled molecular flow interacting with a solid surface. The productivity of this method in the conditions of a specific experiment (by the example of SF{sub 6} molecules) is evaluated. A number of low-energy methods of molecular laser isotope separation based on the use of infrared lasers for selective excitation of molecules are analysed and their productivity is estimated. The methods are compared with those of selective dissociation of molecules in the flow interacting with amore » surface. The advantages of this method compared to the low-energy methods of molecular laser isotope separation and the IR MPD method in the unperturbed jets and flows are shown. It is concluded that this method could be a promising alternative to the low-energy methods of molecular laser isotope separation. (laser separation of isotopes)« less

Method of isotope separation by chemi-ionization

DOEpatents

Wexler, Sol; Young, Charles E.

1977-05-17

A method for separating specific isotopes present in an isotopic mixture by aerodynamically accelerating a gaseous compound to form a jet of molecules, and passing the jet through a stream of electron donor atoms whereby an electron transfer takes place, thus forming negative ions of the molecules. The molecular ions are then passed through a radiofrequency quadrupole mass filter to separate the specific isotopes. This method may be used for any compounds having a sufficiently high electron affinity to permit negative ion formation, and is especially useful for the separation of plutonium and uranium isotopes.

The Majorana Demonstrator radioassay program

DOE PAGES

Abgrall, N.; Arnquist, I. J.; Avignone, F. T.; ...

2016-05-03

The Majorana collaboration is constructing the Majorana Demonstrator at the Sanford Underground Research Facility at the Homestake gold mine, in Lead, SD. The apparatus will use Ge detectors, enriched in isotope 76Ge, to demonstrate the feasibility of a large-scale Ge detector experiment to search for neutrinoless double beta decay. The long half-life of this postulated process requires that the apparatus be extremely low in radioactive isotopes whose decays may produce backgrounds to the search. The radioassay program conducted by the collaboration to ensure that the materials comprising the apparatus are sufficiently pure is described. The resulting measurements from gamma-ray counting,more » neutron activation and mass spectroscopy of the radioactive-isotope contamination for the materials studied for use in the detector are reported. In conclusion, we interpret these numbers in the context of the expected background for the experiment.« less

The graphene phonon dispersion with C12 and C13 isotopes

NASA Astrophysics Data System (ADS)

Whiteway, Eric; Bernard, Simon; Yu, Victor; Austing, D. Guy; Hilke, Michael

2013-12-01

Using very uniform large scale chemical vapor deposition grown graphene transferred onto silicon, we were able to identify 15 distinct Raman lines associated with graphene monolayers. This was possible thanks to a combination of different carbon isotopes and different Raman laser energies and extensive averaging without increasing the laser power. This allowed us to obtain a detailed experimental phonon dispersion relation for many points in the Brillouin zone. We further identified a D+D' peak corresponding to a double phonon process involving both an inter- and intra-valley phonon. In order to both eliminate substrate effects and to probe large areas, we undertook to study Raman scattering for large scale chemical vapor deposition (CVD) grown graphene using two different isotopes (C12 and C13) so that we can effectively exclude and subtract the substrate contributions, since a heavier mass downshifts only the vibrational properties, while keeping all other properties the same.

Evidence for a vibrational phase-dependent isotope effect on the photochemistry of vision.

PubMed

Schnedermann, C; Yang, X; Liebel, M; Spillane, K M; Lugtenburg, J; Fernández, I; Valentini, A; Schapiro, I; Olivucci, M; Kukura, P; Mathies, R A

2018-04-01

Vibronic coupling is key to efficient energy flow in molecular systems and a critical component of most mechanisms invoking quantum effects in biological processes. Despite increasing evidence for coherent coupling of electronic states being mediated by vibrational motion, it is not clear how and to what degree properties associated with vibrational coherence such as phase and coupling of atomic motion can impact the efficiency of light-induced processes under natural, incoherent illumination. Here, we show that deuteration of the H 11 -C 11 =C 12 -H 12 double-bond of the 11-cis retinal chromophore in the visual pigment rhodopsin significantly and unexpectedly alters the photoisomerization yield while inducing smaller changes in the ultrafast isomerization dynamics assignable to known isotope effects. Combination of these results with non-adiabatic molecular dynamics simulations reveals a vibrational phase-dependent isotope effect that we suggest is an intrinsic attribute of vibronically coherent photochemical processes.

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

USGS Publications Warehouse

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

2001-01-01

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

l-Tryptophan Radical Cation Electron Spin Resonance Studies: Connecting Solution-derived Hyperfine Coupling Constants with Protein Spectral Interpretations

PubMed Central

Connor, Henry D.; Sturgeon, Bradley E.; Mottley, Carolyn; Sipe, Herbert J.; Mason, Ronald P.

2009-01-01

Fast-flow electron spin resonance (ESR) spectroscopy has been used to detect a free radical formed from the reaction of l-tryptophan with Ce4+ in an acidic aqueous environment. Computer simulations of the ESR spectra from l-tryptophan and several isotopically modified forms strongly support the conclusion that the l-tryptophan radical cation has been detected by ESR for the first time. The hyperfine coupling constants (HFCs) determined from the well-resolved isotropic ESR spectra support experimental and computational efforts to understand l-tryptophan's role in protein catalysis of oxidation-reduction processes. l-tryptophan HFCs facilitated the simulation of fast-flow ESR spectra of free radicals from two related compounds, tryptamine and 3-methylindole. Analysis of these three compounds' β-methylene hydrogen HFC data along with equivalent l-tyrosine data has led to a new computational method that can distinguish between these two amino acid free radicals in proteins without dependence on isotope labeling, electron nuclear double resonance or high-field ESR. This approach also produces geometric parameters (dihedral angles for the β-methylene hydrogens) which should facilitate protein site assignment of observed l-tryptophan radicals as has been done for l-tyrosine radicals. PMID:18433127

Measurement of the heaviest β-delayed 2-neutron emitter: 136Sb

NASA Astrophysics Data System (ADS)

Caballero-Folch, R.; Dillmann, I.; Taín, J. L.; Agramunt, J.; Domingo-Pardo, C.; Algora, A.; Äystö, J.; Calviño, F.; Canete, L.; Cortès, G.; Eronen, T.; Ganioglu, E.; Gelletly, W.; Gorelov, D.; Guadilla, V.; Hakala, J.; Jokinen, A.; Kankainen, A.; Kolhinen, V.; Koponen, J.; Marta, M.; Mendoza, E.; Montaner-Pizá, A.; Moore, I.; Nobs, Ch.; Orrigo, S.; Penttilä, H.; Pohjalainen, I.; Reinikainen, J.; Riego, A.; Rinta-Antila, S.; Rubio, B.; Salvador-Castiñeira, P.; Simutkin, V.; Voss, A.

2017-09-01

The β-delayed neutron emission probability, Pn, of very exotic nuclei is crucial for the understanding of nuclear structure properties of many isotopes and astrophysical processes such as the rapid neutron capture process (r-process). In addition β-delayed neutrons are important in a nuclear power reactor operated in a prompt sub-critical, delayed critical condition, as they contribute to the decay heat inducing fission reactions after a shut down. The study of neutron-rich isotopes and the measurement of β-delayed one-neutron emitters (β1n) is possible thanks to the Rare Isotope Beam (RIB) facilities, where radioactive beams allow the production of exotic nuclei of interest, which can be studied and analyzed using specific detection systems. This contribution reports two recent measurements of β-delayed neutron emitters which allowed the determination of half-lives and the neutron branching ratio of isotopes in the mass region above A = 200 and N > 126, and a second experiment which confirmed 136Sb as the heaviest double neutron emitter (β2n) measured so far.

Production of radioactive isotopes through cosmic muon spallation in KamLAND

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

Abe, S.; Furuno, K.; Gando, Y.

2010-02-15

Radioactive isotopes produced through cosmic muon spallation are a background for rare-event detection in nu detectors, double-beta-decay experiments, and dark-matter searches. Understanding the nature of cosmogenic backgrounds is particularly important for future experiments aiming to determine the pep and CNO solar neutrino fluxes, for which the background is dominated by the spallation production of {sup 11}C. Data from the Kamioka liquid-scintillator antineutrino detector (KamLAND) provides valuable information for better understanding these backgrounds, especially in liquid scintillators, and for checking estimates from current simulations based upon MUSIC, FLUKA, and GEANT4. Using the time correlation between detected muons and neutron captures, themore » neutron production yield in the KamLAND liquid scintillator is measured to be Y{sub n}=(2.8+-0.3)x10{sup -4} mu{sup -1} g{sup -1} cm{sup 2}. For other isotopes, the production yield is determined from the observed time correlation related to known isotope lifetimes. We find some yields are inconsistent with extrapolations based on an accelerator muon beam experiment.« less

Study of the Production of Radioactive Isotopes through Cosmic Muon Spallation in KamLAND

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

KamLAND Collaboration; Abe, S.; Enomoto, S.

2009-06-30

Radioactive isotopes produced through cosmic muon spallation are a background for rare event detection in {nu} detectors, double-beta-decay experiments, and dark-matter searches. Understanding the nature of cosmogenic backgrounds is particularly important for future experiments aiming to determine the pep and CNO solar neutrino fluxes, for which the background is dominated by the spallation production of {sup 11}C. Data from the Kamioka Liquid scintillator Anti-Neutrino Detector (KamLAND) provides valuable information for better understanding these backgrounds, especially in liquid scintillator, and for checking estimates from current simulations based upon MUSIC, FLUKA, and Geant4. Using the time correlation between detected muons and neutronmore » captures, the neutron production yield in the KamLAND liquid scintillator is measured to be (2.8 {+-} 0.3) x 10{sup -4} n/({mu} {center_dot} (g/cm{sup 2})). For other isotopes, the production yield is determined from the observed time correlation related to known isotope lifetimes. We find some yields are inconsistent with extrapolations based on an accelerator muon beam experiment.« less

Measurement of delta13C and delta18O Isotopic Ratios of CaCO3 by a Thermoquest Finnigan GasBench II Delta Plus XL Continous Flow Isotope Ratio Mass Spectrometer with Application to Devils Hole Core DH-11 Calcite

USGS Publications Warehouse

Revesz, Kinga M.; Landwehr, Jurate Maciunas; Keybl, Jaroslav Edward

2001-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400?20 ?g) of calcium carbonate. This new method streamlines the classical phosphoric acid - calcium carbonate (H3PO4 - CaCO3) reaction method by making use of a Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. To obtain reproducible and accurate results, optimal conditions for the H3PO4 - CaCO3 reaction had to be determined. At the acid-carbonate reaction temperature suggested by the equipment manufacturer, the oxygen isotope ratio results were unsatisfactory (standard deviation () greater than 1.5 per mill), probably because of a secondary reaction. When the acid-carbonate reaction temperature was lowered to 26?C and the reaction time was increased to 24 hours, the precision of the carbon and oxygen isotope ratios for duplicate analyses improved to 0.1 and 0.2 per mill, respectively. The method was tested by analyzing calcite from Devils Hole, Nevada, which was formed by precipitation from ground water onto the walls of a sub-aqueous cavern during the last 500,000 years. Isotope-ratio values previously had been obtained by the classical method for Devils Hole core DH-11. The DH-11 core had been recently re-sampled, and isotope-ratio values were obtained using this new method. The results were comparable to those obtained by the classical method. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, a cutting error that was then independently confirmed. The reproducibility of the isotopic values is demonstrated by a correlation of approximately 0.96 for both isotopes, after correcting for an alignment offset. This result indicates that the new method is a viable alternative to the classical method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes resulting in considerable timesavings.

Isotopic composition of atmospheric moisture from pan water evaporation measurements.

PubMed

Devi, Pooja; Jain, Ashok Kumar; Rao, M Someshwer; Kumar, Bhishm

2015-01-01

A continuous and reliable time series data of the stable isotopic composition of atmospheric moisture is an important requirement for the wider applicability of isotope mass balance methods in atmospheric and water balance studies. This requires routine sampling of atmospheric moisture by an appropriate technique and analysis of moisture for its isotopic composition. We have, therefore, used a much simpler method based on an isotope mass balance approach to derive the isotopic composition of atmospheric moisture using a class-A drying evaporation pan. We have carried out the study by collecting water samples from a class-A drying evaporation pan and also by collecting atmospheric moisture using the cryogenic trap method at the National Institute of Hydrology, Roorkee, India, during a pre-monsoon period. We compared the isotopic composition of atmospheric moisture obtained by using the class-A drying evaporation pan method with the cryogenic trap method. The results obtained from the evaporation pan water compare well with the cryogenic based method. Thus, the study establishes a cost-effective means of maintaining time series data of the isotopic composition of atmospheric moisture at meteorological observatories. The conclusions drawn in the present study are based on experiments conducted at Roorkee, India, and may be examined at other regions for its general applicability.

Carbon isotope ratios and isotopic correlations between components in fruit juices

NASA Astrophysics Data System (ADS)

Wierzchnicki, Ryszard

2013-04-01

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

Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters

NASA Astrophysics Data System (ADS)

Sun, Jing; Kobayashi, Tatsuaki; Strosnider, William H. J.; Wu, Pan

2017-08-01

Karst water resources, which are extremely sensitive to mining activities, are critical for the support of human societies and ecological systems in many regions worldwide. In order to determine the sources and fate of dissolved sulfate in low-pH karst waters, hydrochemical variations of karst waters with and without acid mine drainage (AMD) impacts were investigated along with stable isotope dynamics. As expected, hydrochemical characteristics and isotopic compositions of the AMD and AMD-downstream water (ADW) were dramatically different from that of the non-AMD-impacted water (NAW). The sources of sulfur isotopes in sulfate were predominantly pyrite oxidation for the AMD and ADW, and atmospheric deposition for the NAW. Based on the general isotope-balance model, the relative proportions of sulfate oxygen derived from water and air were calculated. The mean proportion of sulfate oxygen derived from water in ADW was roughly double that of AMD. This suggests that the sulfate associated with AMD is predominantly influenced by aerobic pyrite oxidation, while that of ADW is likely affected by the dissolution of pyrite under anaerobic conditions in reservoir sediment. This observation was coincident with the noted variations of hydrochemical characteristics and was supported by principal component analysis. These results provide a better understanding of how stable isotopes of sulfate and water can be used to track mining contamination in karst aquifers, which could benefit remediation planning for these distinctive systems.

Titanium isotopes and rare earth patterns in CAIs: Evidence for thermal processing and gas-dust decoupling in the protoplanetary disk

NASA Astrophysics Data System (ADS)

Davis, Andrew M.; Zhang, Junjun; Greber, Nicolas D.; Hu, Jingya; Tissot, François L. H.; Dauphas, Nicolas

2018-01-01

Titanium isotopic compositions (mass-dependent fractionation and isotopic anomalies) were measured in 46 calcium-, aluminum-rich inclusions (CAIs) from the Allende CV chondrite. After internal normalization to 49Ti/47Ti, we found that ε50Ti values are somewhat variable among CAIs, and that ε46Ti is highly correlated with ε50Ti, with a best-fit slope of 0.162 ± 0.030 (95% confidence interval). The linear correlation between ε46Ti and ε50Ti extends the same correlation seen among bulk solar objects (slope 0.184 ± 0.007). This observation provides constraints on dynamic mixing of the solar disk and has implications for the nucleosynthetic origin of titanium isotopes, specifically on the possible contributions from various types of supernovae to the solar system. Titanium isotopic mass fractionation, expressed as δ‧49Ti, was measured by both sample-standard bracketing and double-spiking. Most CAIs are isotopically unfractionated, within a 95% confidence interval of normal, but a few are significantly fractionated and the range δ‧49Ti is from ∼-4 to ∼+4. Rare earth element patterns were measured in 37 of the CAIs. All CAIs with significant titanium mass fractionation effects have group II and related REE patterns, implying kinetically controlled volatility fractionation during the formation of these CAIs.

Measurement of O(6)-alkylguanine-DNA alkyltransferase activity in tumour cells using stable isotope dilution HPLC-ESI-MS/MS.

PubMed

Sun, Guohui; Zhao, Lijiao; Fan, Tengjiao; Ren, Ting; Zhong, Rugang

2016-10-15

The repair of DNA mediated by O(6)-alkylguanine-DNA alkyltransferase (AGT) provides protection against DNA damage from endogenous or exogenous alkylation of the O(6) position of guanine. However, this repair acts as a double-edged sword in cancer treatment, as it not only protects normal cells from chemotherapy-associated toxicities, but also results in cancer cell resistance to guanine O(6)-alkylating antitumour agents. Thus, AGT plays an important role in predicting the individual susceptibility to guanine O(6)-alkylating carcinogens and chemotherapies. Accordingly, it is necessary to establish a quantitative method for determining AGT activity with high accuracy, sensitivity and practicality. Here, we describe a novel nonradioactive method for measuring AGT activity using stable isotope dilution high-performance liquid chromatography electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). This method is based on the irreversibility of the removal of the O(6)-alkyl group from guanine by AGT and on the high affinity of O(6)-benzylguanine (O(6)-BG) as an AGT substrate. HPLC-ESI-MS/MS was used to measure the AGT activities in cell protein extracts from eight tumour lines, demonstrating that AGT activity was quite variable among different cell lines, ranging from nondetectable to 1021 fmol/mg protein. The experiments performed in intact tumour cells yielded similar results but exhibited slightly higher activities than those observed in cell protein extracts. The accuracy of this method was confirmed by an examination of AGT expression levels using western blotting analysis. To our knowledge, this method is the first mass spectrometry-based AGT activity assay, and will likely provide assistance in the screening of cancer risk or the application of chemotherapies. Copyright © 2016 Elsevier B.V. All rights reserved.

Quantitative Determination of Isotope Ratios from Experimental Isotopic Distributions

PubMed Central

Kaur, Parminder; O’Connor, Peter B.

2008-01-01

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

Fish fins as non-lethal surrogates for muscle tissues in freshwater food web studies using stable isotopes.

PubMed

Hette Tronquart, Nicolas; Mazeas, Laurent; Reuilly-Manenti, Liana; Zahm, Amandine; Belliard, Jérôme

2012-07-30

Dorsal white muscle is the standard tissue analysed in fish trophic studies using stable isotope analyses. However, sampling white muscle often implies the sacrifice of fish. Thus, we examined whether the non-lethal sampling of fin tissue can substitute muscle sampling in food web studies. Analysing muscle and fin δ(15)N and δ(13)C values of 466 European freshwater fish (14 species) with an elemental analyser coupled with an isotope ratio mass spectrometer, we compared the isotope values of the two tissues. Correlations between fin and muscle isotope ratios were examined for all fish together and specifically for 12 species. We further proposed four methods of assessing muscle from fin isotope ratios and estimated the errors made using these muscle surrogates. Despite significant differences between isotope values of the two tissues, fin and muscle isotopic signals are strongly correlated. Muscle values, estimated with raw fin isotope ratios (1st method), induce an error of ca. 1‰ for both isotopes. In comparison, specific (2nd method) or general (3rd method) correlations provide meaningful corrections of fin isotope ratios (errors <0.6‰). On the other hand, relationships, established for Australian tropical fish, only give poor muscle estimates (errors >0.8‰). There is little chance that a global model can be created. However, the 2nd and 3rd methods of estimating muscle values from fin isotope ratios should provide an acceptable level of error for the studies of European freshwater food web. We thus recommend that future studies use fin tissue as a non-lethal surrogate for muscle. Copyright © 2012 John Wiley & Sons, Ltd.

A METHOD TO IMPROVE DOSE ASSESSMENT BY RECONSTRUCTION OF THE COMPLETE ISOTOPES INVENTORY.

PubMed

Bonin, Alice; Tsilanizara, Aimé

2017-06-01

Radiation shielding assessments may underestimate the expected dose if some isotopes at trace level are not considered in the isotopes inventory of the shielded radioactive materials. Indeed, information about traces is not often available. Nevertheless, the activation of some minor isotopic traces may significantly contribute to the dose build-up. This paper presents a new method (Isotopes Inventory Reconstruction-IIR) estimating the concentration of the minor isotopes in the irradiated material at the beginning of the cooling period. The method requires the solution of the inverse problem describing the irradiated material's decay. In a mixture of an irradiated uranium-plutonium oxide shielded by a set-up made of stainless-steel, porous polyethylene plaster and lead methyl methacrylate, the comparison between different methods proves that the IIR-method allows better assessment of the dose than other approximate methods. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Transient signal isotope analysis: validation of the method for isotope signal synchronization with the determination of amplifier first-order time constants.

PubMed

Gourgiotis, Alkiviadis; Manhès, Gérard; Louvat, Pascale; Moureau, Julien; Gaillardet, Jérôme

2015-09-30

During transient signal acquisition by Multi-Collection Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS), an isotope ratio increase or decrease (isotopic drift hereafter) is often observed which is related to the different time responses of the amplifiers involved in multi-collection. This isotopic drift affects the quality of the isotopic data and, in a recent study, a method of internal amplifier signal synchronization for isotope drift correction was proposed. In this work the determination of the amplifier time constants was investigated in order to validate the method of internal amplifier signal synchronization for isotope ratio drift correction. Two different MC-ICPMS instruments, the Neptune and the Neptune Plus, were used, and both the lead transient signals and the signal decay curves of the amplifiers were investigated. Our results show that the first part of the amplifier signal decay curve is characterized by a pure exponential decay. This part of the signal decay was used for the effective calculation of the amplifier first-order time constants. The small differences between these time constants were compared with time lag values obtained from the method of isotope signal synchronization and were found to be in good agreement. This work proposes a way of determining amplifier first-order time constants. We show that isotopic drift is directly related to the amplifier first-order time constants and the method of internal amplifier signal synchronization for isotope ratio drift correction is validated. Copyright © 2015 John Wiley & Sons, Ltd.

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

USDA-ARS?s Scientific Manuscript database

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

Detecting isotopic ratio outliers

NASA Astrophysics Data System (ADS)

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

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Method for separating boron isotopes

DOEpatents

Rockwood, Stephen D.

1978-01-01

A method of separating boron isotopes .sup.10 B and .sup.11 B by laser-induced selective excitation and photodissociation of BCl.sub.3 molecules containing a particular boron isotope. The photodissociation products react with an appropriate chemical scavenger and the reaction products may readily be separated from undissociated BCl.sub.3, thus effecting the desired separation of the boron isotopes.

A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

USGS Publications Warehouse

Gulson, B.L.; Meier, A.L.; Church, S.E.; Mizon, K.J.

1989-01-01

Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS. ?? 1989.

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

USGS Publications Warehouse

Böhlke, John Karl; Mroczkowski, Stanley J.; Sturchio, Neil C.; Heraty, Linnea J.; Richman, Kent W.; Sullivan, Donald B.; Griffith, Kris N.; Gu, Baohua; Hatzinger, Paul B.

2017-01-01

RationalePerchlorate (ClO4−) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO4− source attribution and natural attenuation studies: δ37Cl, δ18O, and δ17O (or Δ17O or 17Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies.MethodsThree large batches of KClO4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O2, and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO4− to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO4 was reprecipitated as AgCl and converted into CH3Cl for DIIRMS.ResultsKClO4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO4− depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO42−, NO3−, ReO42−, and C-bearing contaminants include isotope mixing and fractionation effects on CO and O2, plus direct interference from CO2 in the mass spectrometer. The results highlight the importance of effective purification of ClO4− from environmental samples.ConclusionsKClO4 reference materials are available for testing methods and calibrating isotopic data for ClO4− and other substances with widely varying Cl or O isotopic compositions. Current ClO4−extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO4−, permitting isotopic evaluation of environmental ClO4− sources and natural attenuation.

Mechanism and stem-cell activity of 5-carboxycytosine decarboxylation determined by isotope tracing.

PubMed

Schiesser, Stefan; Hackner, Benjamin; Pfaffeneder, Toni; Müller, Markus; Hagemeier, Christian; Truss, Matthias; Carell, Thomas

2012-06-25

Eraserhead: Stem cells seem to erase epigenetic information by decarboxylation of the newly discovered epigenetic base 5-carboxycytosine (caC; see picture). This reaction is likely to involve a nucleophilic attack of the C5-C6 double bond. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

[High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

PubMed

Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

2013-05-01

In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

Experimental evidence for Mo isotope fractionation between metal and silicate liquids

NASA Astrophysics Data System (ADS)

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

2013-10-01

Stable isotope fractionation of siderophile elements may inform on the conditions and chemical consequences of core-mantle differentiation in planetary objects. The extent to which Mo isotopes fractionate during such metal-silicate segregation, however, is so far unexplored. We have therefore investigated equilibrium fractionation of Mo isotopes between liquid metal and liquid silicate to evaluate the potential of Mo isotopes as a new tool to study core formation. We have performed experiments at 1400 and 1600 °C in a centrifuging piston cylinder. Tin was used to lower the melting temperature of the Fe-based metal alloys to <1400 °C, while variable Fe-oxide contents were used to vary oxygen fugacity in graphite and MgO capsules. Isotopic analyses were performed using a double spike technique. In experiments performed at 1400 °C, the 98Mo/95Mo ratio of silicate is 0.19±0.03‰ (95% confidence interval) heavier than that of metal. This fractionation is not significantly affected by the presence or absence of carbon. Molybdenum isotope fractionation is furthermore independent of oxygen fugacity in the range IW -1.79 to IW +0.47, which are plausible values for core formation. Experiments at 1600 °C show that, at equilibrium, the 98Mo/95Mo ratio of silicate is 0.12±0.02‰ heavier than that of metal and that the presence or absence of Sn does not affect this fractionation. Equilibrium Mo isotope fractionation between liquid metal and liquid silicate as a function of temperature can therefore be described as ΔMoMetal-Silicate98/95=-4.70(±0.59)×105/T2. Our experiments show that Mo isotope fractionation may be resolvable up to metal-silicate equilibration temperatures of about 2500 °C, rendering Mo isotopes a novel tool to investigate the conditions of core formation in objects ranging from planetesimals to Earth sized bodies.

Optimization Techniques for Improving the Precision of Isotopic Analysis by Thermal Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Wang, G. Q.; Xu, J. F.; Wu-Yang, S. Q.

2016-12-01

Operation of instruments and preparation of samples are also significant factors that can affect the precision of TIMS analyses, in addition to instrument hardware. We have reviewed the isotopic data of several standard materials at our TIMS lab for 5 years. It is suggested that several optimization techniques should be used in order to obtain high-precision isotopic ratio data: (1) It is important to choose a suitable filament material for isotopic measurements. We have established that W filament is likely the most efficient for ionizing Sr when selecting from W, Re, and Ta; meanwhile, Re filament can produce a higher intensity for Nd isotopes than W and Ta filament can. It is concluded that the best TIMS signals are obtained for Sr using W signal-filaments and for Nd using Re double-filaments. (2) The preparation of the activator plays a key role in the analysis of some isotopic ratios. This study indicates that choosing a suitable activator can greatly elevate the precision of 206Pb/204Pb ratios during Pb isotopic measurements. We have suggested a new scheme to make an activator by using a mixture of 10% Si-gel + 7.5% H3PO3 + 82.5% H2O (weight %). (3) It is necessary to re-set the cup configuration to avoid cup degradation when operating for a long period of time (a year or more). We propose a new cup configuration to avoid this disadvantage during Sr isotopic analyses. (4) The contamination of 187Re and 185Re after using Re-filament could be eliminated by cleaning the ion source and baking the source housing.

The MAJORANA Demonstrator Radioassay Program

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

Abgrall, N.; Arnquist, Isaac J.; Avignone, F. T.

2016-05-03

The Majorana collaboration is constructing the Majorana Demonstrator at the Sanford Underground Research Facility at the Homestake gold mine, in Lead, SD. The apparatus will use Ge detectors, enriched in isotope 76Ge, to demonstrate the feasibility of a large-scale Ge detector experiment to search for neutrinoless double beta decay. The long half-life of this postulated process requires that the apparatus be extremely low in radioactive isotopes whose decays may produce backgrounds to the search. The radioassay program conducted by the collaboration to ensure that the materials comprising the apparatus are suffciently pure is described. The resulting measurements of the radioactiveisotopemore » contamination for a number of materials studied for use in the detector are reported.« less

Review of Nuclear Physics Experiments for Space Radiation

NASA Technical Reports Server (NTRS)

Norbury, John W.; Miller, Jack; Adamczyk, Anne M.; Heilbronn, Lawrence H.; Townsend, Lawrence W.; Blattnig, Steve R.; Norman, Ryan B.; Guetersloh, Stephen B.; Zeitlin, Cary J.

2011-01-01

Human space flight requires protecting astronauts from the harmful effects of space radiation. The availability of measured nuclear cross section data needed for these studies is reviewed in the present paper. The energy range of interest for radiation protection is approximately 100 MeV/n to 10 GeV/n. The majority of data are for projectile fragmentation partial and total cross sections, including both charge changing and isotopic cross sections. The cross section data are organized into categories which include charge changing, elemental, isotopic for total, single and double differential with respect to momentum, energy and angle. Gaps in the data relevant to space radiation protection are discussed and recommendations for future experiments are made.

Ground-State Properties of Mg Isotopes in and Beyond the Island of Inversion through Reaction Cross Sections

NASA Astrophysics Data System (ADS)

Watanabe, Shin; Minomo, Kosho; Shimada, Mitsuhiro; Tagami, Shingo; Kimura, Masaaki; Takechi, Maya; Fukuda, Mitsunori; Nishimura, Daiki; Suzuki, Takeshi; Matsumoto, Takuma; Shimizu, Yoshifumi R.; Yahiro, Masanobu

We analyze recently measured total reaction cross sections (σR) for 24-38Mg incident on 12C targets at 240 MeV/nucleon by using the microscopic framework based on the double folding model and antisymmetrized molecular dynamics (AMD). The framework reproduces not only the measured σR but also other existing measured ground-state properties of Mg Isotopes (spin parity, total binding energy, one-neutron separation energy, and 2+ and 4+ excitation energies) quite well. AMD predicts large deformation from 31Mg19 to a drip-line nucleus 40Mg28, indicating that both the N = 20 and 28 magicities disappear.

Improvement of 2,4-dinitrophenylhydrazine derivatization method for carbon isotope analysis of atmospheric acetone.

PubMed

Wen, Sheng; Yu, Yingxin; Guo, Songjun; Feng, Yanli; Sheng, Guoying; Wang, Xinming; Bi, Xinhui; Fu, Jiamo; Jia, Wanglu

2006-01-01

Through simulation experiments of atmospheric sampling, a method via 2,4-dinitrophenylhydrazine (DNPH) derivatization was developed to measure the carbon isotopic composition of atmospheric acetone. Using acetone and a DNPH reagent of known carbon isotopic compositions, the simulation experiments were performed to show that no carbon isotope fractionation occurred during the processes: the differences between the predicted and measured data of acetone-DNPH derivatives were all less than 0.5 per thousand. The results permitted the calculation of the carbon isotopic compositions of atmospheric acetone using a mass balance equation. In this method, the atmospheric acetone was collected by a DNPH-coated silica cartridge, washed out as acetone-DNPH derivatives, and then analyzed by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using this method, the first available delta13C data of atmospheric acetone are presented. Copyright 2006 John Wiley & Sons, Ltd.

[Measurements of stable isotopes in atmospheric CO2 and H2O by open-path Fourier transform infrared spectrometry].

PubMed

Wang, Wei; Liu, Wen-Qing; Zhang, Tian-Shu

2013-08-01

The development of spectroscopic techniques has offered continuous measurement of stable isotopes in the ambient air. The method of measuring environmental stable isotopes based on Fourier transform infrared spectrometry (FTIR) is described. In order to verify the feasibility of the method for continuous measurement of the stable isotopes, an open-path FTIR system was used to measure stable isotopes of CO2 and H2O in ambient air directly in a seven-day field experiment, including 12CO2, 3CO2, H2 16O and HD16 O. Also, the time course of carbon isotopic ratio delta13 C and deuterium isotope composition deltaD was calculated. The measurement precision is about 1.08 per thousand for delta13 C and 1.32 per thousand for deltaD. The measured stable isotopes of CO2 and H2O were analyzed on different time scales by Keeling plot methods, and the deuterium isotopic ratios of evapotranspiration were determined. The results of the field experiment demonstrate the potential of the open-path FTIR system for continuous measurement of stable isotopes in the air.

Inverse methods for estimating primary input signals from time-averaged isotope profiles

NASA Astrophysics Data System (ADS)

Passey, Benjamin H.; Cerling, Thure E.; Schuster, Gerard T.; Robinson, Todd F.; Roeder, Beverly L.; Krueger, Stephen K.

2005-08-01

Mammalian teeth are invaluable archives of ancient seasonality because they record along their growth axes an isotopic record of temporal change in environment, plant diet, and animal behavior. A major problem with the intra-tooth method is that intra-tooth isotope profiles can be extremely time-averaged compared to the actual pattern of isotopic variation experienced by the animal during tooth formation. This time-averaging is a result of the temporal and spatial characteristics of amelogenesis (tooth enamel formation), and also results from laboratory sampling. This paper develops and evaluates an inverse method for reconstructing original input signals from time-averaged intra-tooth isotope profiles. The method requires that the temporal and spatial patterns of amelogenesis are known for the specific tooth and uses a minimum length solution of the linear system Am = d, where d is the measured isotopic profile, A is a matrix describing temporal and spatial averaging during amelogenesis and sampling, and m is the input vector that is sought. Accuracy is dependent on several factors, including the total measurement error and the isotopic structure of the measured profile. The method is shown to accurately reconstruct known input signals for synthetic tooth enamel profiles and the known input signal for a rabbit that underwent controlled dietary changes. Application to carbon isotope profiles of modern hippopotamus canines reveals detailed dietary histories that are not apparent from the measured data alone. Inverse methods show promise as an effective means of dealing with the time-averaging problem in studies of intra-tooth isotopic variation.

Use of stable sulphur isotopes to monitor directly the behaviour of sulphur in coal during thermal desulphurization

USGS Publications Warehouse

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

1987-01-01

A method has been developed using stable sulphur isotope analyses to monitor the behaviour of sulphur forms in a coal during thermal desulphurization. In this method, the natural stable isotopic composition of the pyritic and organic sulphur in coal is used as a tracer to follow their mobility during the desulphurization process. This tracer method is based on the fact that the isotopic compositions of pyritic and organic sulphur are significantly different in some coals. Isotopic results of pyrolysis experiments at temperatures ranging from 350 to 750 ??C indicate that the sulphur released with the volatiles is predominantly organic sulphur. The pyritic sulphur is evolved in significant quantities only when pyrolysis temperatures exceed 500 ??C. The presence of pyrite seems to have no effect on the amount of organic sulphur evolved during pyrolysis. The chemical and isotopic mass balances achieved from three different samples of the Herrin (No. 6) coal of the Illinois Basin demonstrate that this stable isotope tracer method is quantitative. The main disadvantage of this tracing technique is that not all coals contain isotopically distinct organic and pyritic sulphur. ?? 1987.

Reduction of chemical formulas from the isotopic peak distributions of high-resolution mass spectra.

PubMed

Roussis, Stilianos G; Proulx, Richard

2003-03-15

A method has been developed for the reduction of the chemical formulas of compounds in complex mixtures from the isotopic peak distributions of high-resolution mass spectra. The method is based on the principle that the observed isotopic peak distribution of a mixture of compounds is a linear combination of the isotopic peak distributions of the individual compounds in the mixture. All possible chemical formulas that meet specific criteria (e.g., type and number of atoms in structure, limits of unsaturation, etc.) are enumerated, and theoretical isotopic peak distributions are generated for each formula. The relative amount of each formula is obtained from the accurately measured isotopic peak distribution and the calculated isotopic peak distributions of all candidate formulas. The formulas of compounds in simple spectra, where peak components are fully resolved, are rapidly determined by direct comparison of the calculated and experimental isotopic peak distributions. The singular value decomposition linear algebra method is used to determine the contributions of compounds in complex spectra containing unresolved peak components. The principles of the approach and typical application examples are presented. The method is most useful for the characterization of complex spectra containing partially resolved peaks and structures with multiisotopic elements.

Recurrent fever of unknown etiology: failure to demonstrate association between fever and plasma unconjugated etiocholanolone

PubMed Central

George, Jack M.; Wolff, Sheldon M.; Diller, Esther; Bartter, Frederic C.

1969-01-01

A sensitive method for determination of plasma unconjugated etiocholanolone by double-isotope-derivative dilution has been described. The mean values for normal subjects was 0.038±0.003 (SEM) μg/100 ml. 40 patients, 20 with familial Mediterranean fever and 20 with other diseases characterized by recurrent fever were studied. The over-all mean concentration of plasma unconjugated etiocholanolone for the patients (febrile or afebrile) was 0.101 ±0.012 μg/100 ml, significantly above that of normals. Mean plasma values for the patients while they were febrile did not differ from the mean values when they were afebrile. It is suggested that the concentration of plasma unconjugated etiocholanolone is not related to fever in these patients. PMID:4886315

Limit on Neutrinoless Double Beta Decay of 76Ge by GERDA

NASA Astrophysics Data System (ADS)

Agostini, M.; Allardt, M.; Andreotti, E.; Bakalyarov, A. M.; Balata, M.; Barabanov, I.; Heider, M. Barabè; Barros, N.; Baudis, L.; Bauer, C.; Becerici-Schmidt, N.; Bellotti, E.; Belogurov, S.; Belyaev, S. T.; Benato, G.; Bettini, A.; Bezrukov, L.; Bode, T.; Brudanin, V.; Brugnera, R.; Budjáš, D.; Caldwell, A.; Cattadori, C.; Chernogorov, A.; Cossavella, F.; Demidova, E. V.; Domula, A.; Egorov, V.; Falkenstein, R.; Ferella, A.; Freund, K.; Frodyma, N.; Gangapshev, A.; Garfagnini, A.; Gotti, C.; Grabmayr, P.; Gurentsov, V.; Gusev, K.; Guthikonda, K. K.; Hampel, W.; Hegai, A.; Heisel, M.; Hemmer, S.; Heusser, G.; Hofmann, W.; Hult, M.; Inzhechik, L. V.; Csáthy, J. Janicskó; Jochum, J.; Junker, M.; Kihm, T.; Kirpichnikov, I. V.; Kirsch, A.; Klimenko, A.; Knöpfle, K. T.; Kochetov, O.; Kornoukhov, V. N.; Kuzminov, V. V.; Laubenstein, M.; Lazzaro, A.; Lebedev, V. I.; Lehnert, B.; Liao, H. Y.; Lindner, M.; Lippi, I.; Lubashevskiy, A.; Lubsandorzhiev, B.; Lutter, G.; Machado, A. A.; Macolino, C.; Majorovits, B.; Maneschg, W.; Misiaszek, M.; Nemchenok, I.; Nisi, S.; Shaughnessy, C. O.'.; Pandola, L.; Pelczar, K.; Pessina, G.; Pullia, A.; Riboldi, S.; Rumyantseva, N.; Sada, C.; Salathe, M.; Schmitt, C.; Schreiner, J.; Schulz, O.; Schwingenheuer, B.; Schönert, S.; Shevchik, E.; Shirchenko, M.; Simgen, H.; Smolnikov, A.; Stanco, L.; Strecker, H.; Tarka, M.; Ur, C. A.; Vasenko, A. A.; Volynets, O.; von Sturm, K.; Wagner, V.; Walter, M.; Wegmann, A.; Wester, T.; Wojcik, M.; Yanovich, E.; Zavarise, P.; Zhitnikov, I.; Zhukov, S. V.; Zinatulina, D.; Zuber, K.; Zuzel, G.

The Gerda experiment at the Laboratori Nazionali del Gran Sasso in Italy uses germanium detectors made from material with an enriched 76Ge isotope fraction to search for neutrinoless double beta decay of this nucleus. Applying a blind analysis we find no signal after an exposure of 21.6 kg·yr and a background of about 0.01 cts/(keV·kg·yr). A half-life limit of Tov1/2> 2.1 · 1025 yr (90% C.L.) is extracted. The previous claim of a signal for 76Ge is excluded with 99% probability in a model independent way.

Method for discriminative particle selection

DOEpatents

Post, Richard F.

1992-01-01

The invention is a method and means for separating ions or providing an ion beam. The invention generates ions of the isotopes to be separated, and then provides a traveling electric potential hill created by a sequential series of quasi static electric potential hills. By regulating the velocity and potential amplitude of the traveling electric potential hill ionized isotopes are selectively positively or negatively accelerated. Since the ionized isotopes have differing final velocities, the isotopes may be collected separately or used to produce an ion beam of a selected isotope.

A novel method for rapid in vitro radiobioassay

NASA Astrophysics Data System (ADS)

Crawford, Evan Bogert

Rapid and accurate analysis of internal human exposure to radionuclides is essential to the effective triage and treatment of citizens who have possibly been exposed to radioactive materials in the environment. The two most likely scenarios in which a large number of citizens would be exposed are the detonation of a radiation dispersal device (RDD, "dirty bomb") or the accidental release of an isotope from an industrial source such as a radioisotopic thermal generator (RTG). In the event of the release and dispersion of radioactive materials into the environment in a large city, the entire population of the city -- including all commuting workers and tourists -- would have to be rapidly tested, both to satisfy the psychological needs of the citizens who were exposed to the mental trauma of a possible radiation dose, and to satisfy the immediate medical needs of those who received the highest doses and greatest levels of internal contamination -- those who would best benefit from rapid, intensive medical care. In this research a prototype rapid screening method to screen urine samples for the presence of up to five isotopes, both individually and in a mixture, has been developed. The isotopes used to develop this method are Co-60, Sr-90, Cs-137, Pu-238, and Am-241. This method avoids time-intensive chemical separations via the preparation and counting of a single sample on multiple detectors, and analyzing the spectra for isotope-specific markers. A rapid liquid-liquid separation using an organic extractive scintillator can be used to help quantify the activity of the alpha-emitting isotopes. The method provides quantifiable results in less than five minutes for the activity of beta/gamma-emitting isotopes when present in the sample at the intervention level as defined by the Centers for Disease Control and Prevention (CDC), and quantifiable results for the activity levels of alpha-emitting isotopes present at their respective intervention levels in approximately 30 minutes of sample preparation and counting time. Radiation detector spectra -- e.g. those from high-purity germanium (HPGe) gamma detectors and liquid scintillation detectors -- which contain decay signals from multiple isotopes often have overlapping signals: the counts from one isotope's decay can appear in energy channels associated with another isotope's decay, complicating the calculation of each isotope's activity. The uncertainties associated with analyzing these spectra have been traced in order to determine the effects of one isotope's count rate on the sensitivity and uncertainty associated with each other isotope. The method that was developed takes advantage of activated carbon filtration to eliminate quenching effects and to make the liquid scintillation spectra from different urine samples comparable. The method uses pulse-shape analysis to reduce the interference from beta emitters in the liquid scintillation spectrum and improve the minimum detectable activity (MDA) and minimum quantifiable activity (MQA) for alpha emitters. The method uses an HPGe detector to quantify the activity of gamma emitters, and subtract their isotopes' contributions to the liquid scintillation spectra via a calibration factor, such that the pure beta and pure alpha emitters can be identified and quantified from the resulting liquid scintillation spectra. Finally, the method optionally uses extractive scintillators to rapidly separate the alpha emitters from the beta emitters when the activity from the beta emitters is too great to detect or quantify the activity from the alpha emitters without such a separation. The method is able to detect and quantify all five isotopes, with uncertainties and biases usually in the 10-40% range, depending upon the isotopic mixtures and the activity ratios between each of the isotopes.

Results on Neutrinoless Double-β Decay of Ge76 from Phase I of the GERDA Experiment

NASA Astrophysics Data System (ADS)

Agostini, M.; Allardt, M.; Andreotti, E.; Bakalyarov, A. M.; Balata, M.; Barabanov, I.; Barnabé Heider, M.; Barros, N.; Baudis, L.; Bauer, C.; Becerici-Schmidt, N.; Bellotti, E.; Belogurov, S.; Belyaev, S. T.; Benato, G.; Bettini, A.; Bezrukov, L.; Bode, T.; Brudanin, V.; Brugnera, R.; Budjáš, D.; Caldwell, A.; Cattadori, C.; Chernogorov, A.; Cossavella, F.; Demidova, E. V.; Domula, A.; Egorov, V.; Falkenstein, R.; Ferella, A.; Freund, K.; Frodyma, N.; Gangapshev, A.; Garfagnini, A.; Gotti, C.; Grabmayr, P.; Gurentsov, V.; Gusev, K.; Guthikonda, K. K.; Hampel, W.; Hegai, A.; Heisel, M.; Hemmer, S.; Heusser, G.; Hofmann, W.; Hult, M.; Inzhechik, L. V.; Ioannucci, L.; Janicskó Csáthy, J.; Jochum, J.; Junker, M.; Kihm, T.; Kirpichnikov, I. V.; Kirsch, A.; Klimenko, A.; Knöpfle, K. T.; Kochetov, O.; Kornoukhov, V. N.; Kuzminov, V. V.; Laubenstein, M.; Lazzaro, A.; Lebedev, V. I.; Lehnert, B.; Liao, H. Y.; Lindner, M.; Lippi, I.; Liu, X.; Lubashevskiy, A.; Lubsandorzhiev, B.; Lutter, G.; Macolino, C.; Machado, A. A.; Majorovits, B.; Maneschg, W.; Misiaszek, M.; Nemchenok, I.; Nisi, S.; O'Shaughnessy, C.; Pandola, L.; Pelczar, K.; Pessina, G.; Pullia, A.; Riboldi, S.; Rumyantseva, N.; Sada, C.; Salathe, M.; Schmitt, C.; Schreiner, J.; Schulz, O.; Schwingenheuer, B.; Schönert, S.; Shevchik, E.; Shirchenko, M.; Simgen, H.; Smolnikov, A.; Stanco, L.; Strecker, H.; Tarka, M.; Ur, C. A.; Vasenko, A. A.; Volynets, O.; von Sturm, K.; Wagner, V.; Walter, M.; Wegmann, A.; Wester, T.; Wojcik, M.; Yanovich, E.; Zavarise, P.; Zhitnikov, I.; Zhukov, S. V.; Zinatulina, D.; Zuber, K.; Zuzel, G.

2013-09-01

Neutrinoless double beta decay is a process that violates lepton number conservation. It is predicted to occur in extensions of the standard model of particle physics. This Letter reports the results from phase I of the Germanium Detector Array (GERDA) experiment at the Gran Sasso Laboratory (Italy) searching for neutrinoless double beta decay of the isotope Ge76. Data considered in the present analysis have been collected between November 2011 and May 2013 with a total exposure of 21.6 kg yr. A blind analysis is performed. The background index is about 1×10-2counts/(keVkgyr) after pulse shape discrimination. No signal is observed and a lower limit is derived for the half-life of neutrinoless double beta decay of Ge76, T1/20ν>2.1×1025yr (90% C.L.). The combination with the results from the previous experiments with Ge76 yields T1/20ν>3.0×1025yr (90% C.L.).

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

PubMed

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

2010-01-27

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

Profiling and relative quantification of phosphatidylethanolamine based on acetone stable isotope derivatization.

PubMed

Wang, Xiang; Wei, Fang; Xu, Ji-Qu; Lv, Xin; Dong, Xu-Yan; Han, Xianlin; Quek, Siew-Young; Huang, Feng-Hong; Chen, Hong

2016-01-01

Phosphatidylethanolamine (PE) is considered to be one of the pivotal lipids for normal cellular function as well as disease initiation and progression. In this study, a simple, efficient, reliable, and inexpensive method for the qualitative analysis and relative quantification of PE, based on acetone stable isotope derivatization combined with double neutral loss scan-shotgun electrospray ionization tandem-quadrupole mass spectrometry analysis (ASID-DNLS-Shotgun ESI-MS/MS), was developed. The ASID method led to alkylation of the primary amino groups of PE with an isopropyl moiety. The use of acetone (d0-acetone) and deuterium-labeled acetone (d6-acetone) introduced a 6 Da mass shift that was ideally suited for relative quantitative analysis, and enhanced sensitivity for mass analysis. The DNLS model was introduced to simultaneously analyze the differential derivatized PEs by shotgun ESI-MS/MS with high selectivity and accuracy. The reaction specificity, labeling efficiency, and linearity of the ASID method were thoroughly evaluated in this study. Its excellent applicability was validated by qualitative and relative quantitative analysis of PE species presented in liver samples from rats fed different diets. Using the ASID-DNLS-Shotgun ESI-MS/MS method, 45 PE species from rat livers have been identified and quantified in an efficient manner. The level of total PEs tended to decrease in the livers of rats on high fat diets compared with controls. The levels of PE 32:1, 34:3, 34:2, 36:3, 36:2, 42:10, plasmalogen PE 36:1 and lyso PE 22:6 were significantly reduced, while levels of PE 36:1 and lyso PE 16:0 increased. Copyright © 2015 Elsevier B.V. All rights reserved.

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

DOEpatents

Harney, Robert C.; Bloom, Stewart D.

1978-01-01

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

Development of an enantiomer-specific stable carbon isotope analysis (ESIA) method for assessing the fate of α-hexachlorocyclo-hexane in the environment.

PubMed

Badea, Silviu-Laurentiu; Vogt, Carsten; Gehre, Matthias; Fischer, Anko; Danet, Andrei-Florin; Richnow, Hans-Hermann

2011-05-30

α-Hexachlorocyclohexane (α-HCH) is the only chiral isomer of the eight 1,2,3,4,5,6-HCHs and we have developed an enantiomer-specific stable carbon isotope analysis (ESIA) method for the evaluation of its fate in the environment. The carbon isotope ratios of the α-HCH enantiomers were determined for a commercially available α-HCH sample using a gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) system equipped with a chiral column. The GC-C-IRMS measurements revealed δ-values of -32.5 ± 0.8‰ and -32.3 ± 0.5‰ for (-) α-HCH and (+) α-HCH, respectively. The isotope ratio of bulk α-HCH was estimated to be -32.4 ± 0.6‰ which was in accordance with the δ-values obtained by GC-C-IRMS (-32.7 ± 0.2‰) and elemental analyzer-isotope ratio mass spectrometry (EA-IRMS) of the bulk α-HCH (-32.1 ± 0.1‰). The similarity of the isotope ratio measurements of bulk α-HCH by EA-IRMS and GC-C-IRMS indicates the accuracy of the chiral GC-C-IRMS method. The linearity of the α-HCH ESIA method shows that carbon isotope ratios can be obtained for a signal size above 100 mV. The ESIA measurements exhibited standard deviations (2σ) that were mostly < ± 0.5‰. In order to test the chiral GC-C-IRMS method, the isotope compositions of individual enantiomers in biodegradation experiments of α-HCH with Clostridium pasteurianum and samples from a contaminated field site were determined. The isotopic compositions of the α-HCH enantiomers show a range of enantiomeric and isotope patterns, suggesting that enantiomeric and isotope fractionation can serve as an indicator for biodegradation and source characterization of α-HCH in the environment. Copyright © 2011 John Wiley & Sons, Ltd.

Delta13C and delta18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite.

PubMed

Révész, Kinga M; Landwehr, Jurate M

2002-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 +/- 20 micro g) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H(3)PO(4)/CaCO(3)) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H(3)PO(4)/CaCO(3) reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 degrees C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was

Method of separating boron isotopes

DOEpatents

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

1981-01-23

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

Method of separating boron isotopes

DOEpatents

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

1984-01-01

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

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

DOE PAGES

Knowles, Justin R.; Skutnik, Steven E.; Glasgow, David C.; ...

2016-06-23

Rapid non-destructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the High Flux Isotope Reactor Neutron Activation Analysis laboratory has developed a generalized non-destructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and capitalizes off of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a holistic characterization of isotopic identification,more » mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% error have been conducted on standards of 235U and 239Pu as low as 12 nanograms in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 229 nanograms of fissile mass with less than 12% error. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. Furthermore, it is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation sources, and account for increasingly complex sample matrices.« less

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

NASA Astrophysics Data System (ADS)

Knowles, Justin; Skutnik, Steven; Glasgow, David; Kapsimalis, Roger

2016-10-01

Rapid nondestructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the Oak Ridge National Laboratory High Flux Isotope Reactor Neutron Activation Analysis facility has developed a generalized nondestructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and makes use of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a complete characterization of isotopic identification, mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% recovery bias have been conducted on standards of 235U and 239Pu as low as 12 ng in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 198 ng of fissile mass with less than 7% recovery bias. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. It is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation facilities, and account for increasingly complex sample matrices.

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

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

Knowles, Justin R.; Skutnik, Steven E.; Glasgow, David C.

Rapid non-destructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the High Flux Isotope Reactor Neutron Activation Analysis laboratory has developed a generalized non-destructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and capitalizes off of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a holistic characterization of isotopic identification,more » mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% error have been conducted on standards of 235U and 239Pu as low as 12 nanograms in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 229 nanograms of fissile mass with less than 12% error. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. Furthermore, it is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation sources, and account for increasingly complex sample matrices.« less

The role of bacterial consortium and organic amendment in Cu and Fe isotope fractionation in plants on a polluted mine site.

PubMed

Pérez Rodríguez, Nathalie; Langella, Francesca; Rodushkin, Ilia; Engström, Emma; Kothe, Erika; Alakangas, Lena; Öhlander, Björn

2014-01-01

Copper and iron isotope fractionation by plant uptake and translocation is a matter of current research. As a way to apply the use of Cu and Fe stable isotopes in the phytoremediation of contaminated sites, the effects of organic amendment and microbial addition in a mine-spoiled soil seeded with Helianthus annuus in pot experiments and field trials were studied. Results show that the addition of a microbial consortium of ten bacterial strains has an influence on Cu and Fe isotope fractionation by the uptake and translocation in pot experiments, with an increase in average of 0.99 ‰ for the δ(65)Cu values from soil to roots. In the field trial, the amendment with the addition of bacteria and mycorrhiza as single and double inoculation enriches the leaves in (65)Cu compared to the soil. As a result of the same trial, the δ(56)Fe values in the leaves are lower than those from the bulk soil, although some differences are seen according to the amendment used. Siderophores, possibly released by the bacterial consortium, can be responsible for this change in the Cu and Fe fractionation. The overall isotopic fractionation trend for Cu and Fe does not vary for pot and field experiments with or without bacteria. However, variations in specific metabolic pathways related to metal-organic complexation and weathering can modify particular isotopic signatures.

Method for separating isotopes

DOEpatents

Jepson, B.E.

1975-10-21

Isotopes are separated by contacting a feed solution containing the isotopes with a cyclic polyether wherein a complex of one isotope is formed with the cyclic polyether, the cyclic polyether complex is extracted from the feed solution, and the isotope is thereafter separated from the cyclic polyether.

Method for isotope separation by photodeflection

DOEpatents

Bernhardt, Anthony F.

1977-01-01

In the method of separating isotopes wherein a desired isotope species is selectively deflected out of a beam of mixed isotopes by irradiating the beam with a directed beam of light of narrowly defined frequency which is selectively absorbed by the desired species, the improvement comprising irradiating the deflected beam with light from other light sources whose frequencies are selected to cause the depopulation of any metastable excited states.

Isotopically nonstationary 13C flux analysis of changes in Arabidopsis thaliana leaf metabolism due to high light acclimation

PubMed Central

Ma, Fangfang; Jazmin, Lara J.; Young, Jamey D.; Allen, Doug K.

2014-01-01

Improving plant productivity is an important aim for metabolic engineering. There are few comprehensive methods that quantitatively describe leaf metabolism, although such information would be valuable for increasing photosynthetic capacity, enhancing biomass production, and rerouting carbon flux toward desirable end products. Isotopically nonstationary metabolic flux analysis (INST-MFA) has been previously applied to map carbon fluxes in photoautotrophic bacteria, which involves model-based regression of transient 13C-labeling patterns of intracellular metabolites. However, experimental and computational difficulties have hindered its application to terrestrial plant systems. We performed in vivo isotopic labeling of Arabidopsis thaliana rosettes with 13CO2 and estimated fluxes throughout leaf photosynthetic metabolism by INST-MFA. Plants grown at 200 µmol m-2s−1 light were compared with plants acclimated for 9 d at an irradiance of 500 µmol⋅m−2⋅s−1. Approximately 1,400 independent mass isotopomer measurements obtained from analysis of 37 metabolite fragment ions were regressed to estimate 136 total fluxes (54 free fluxes) under each condition. The results provide a comprehensive description of changes in carbon partitioning and overall photosynthetic flux after long-term developmental acclimation of leaves to high light. Despite a doubling in the carboxylation rate, the photorespiratory flux increased from 17 to 28% of net CO2 assimilation with high-light acclimation (Vc/Vo: 3.5:1 vs. 2.3:1, respectively). This study highlights the potential of 13C INST-MFA to describe emergent flux phenotypes that respond to environmental conditions or plant physiology and cannot be obtained by other complementary approaches. PMID:25368168

Stratigraphic and structural controls on groundwater flow in an outcropping fossil fan delta: the case of Sant Llorenç del Munt range (NE Spain)

NASA Astrophysics Data System (ADS)

Anglés, Marc; Folch, Albert; Oms, Oriol; Maestro, Eudald; Mas-Pla, Josep

2017-12-01

Hydrogeological models of mountain regions present the opportunity to understand the role of geological factors on groundwater resources. The effects of sedimentary facies and fracture distribution on groundwater flow and resource exploitation are studied in the ancient fan delta of Sant Llorenç de Munt (central Catalonia, Spain) by integrating geological field observations (using sequence stratigraphy methods) and hydrogeological data (pumping tests, hydrochemistry and environmental isotopes). A comprehensive analysis of data portrays the massif as a single unit, constituted by different compartments determined by specific layers and sets of fractures. Two distinct flow systems—local and regional—are identified based on pumping test analysis as well as hydrochemical and isotopic data. Drawdown curves derived from pumping tests indicate that the behavior of the saturated layers, whose main porosity is given by the fracture network, corresponds to a confined aquifer. Pumping tests also reflect a double porosity within the system and the occurrence of impervious boundaries that support a compartmentalized model for the whole aquifer system. Hydrochemical data and associated spatial evolution show the result of water-rock interaction along the flow lines. Concentration of magnesium, derived from dolomite dissolution, is a tracer of the flow-path along distinct stratigraphic units. Water stable isotopes indicate that evaporation (near a 5% loss) occurs in a thick unsaturated zone within the massif before infiltration reaches the water table. The hydrogeological analysis of this outcropping system provides a methodology for the conceptualization of groundwater flow in similar buried systems where logging and hydrogeological information are scarce.

Intramolecular carbon and nitrogen isotope analysis by quantitative dry fragmentation of the phenylurea herbicide isoproturon in a combined injector/capillary reactor prior to GC separation.

PubMed

Penning, Holger; Elsner, Martin

2007-11-01

Potentially, compound-specific isotope analysis may provide unique information on source and fate of pesticides in natural systems. Yet for isotope analysis, LC-based methods that are based on the use of organic solvents often cannot be used and GC-based analysis is frequently not possible due to thermolability of the analyte. A typical example of a compound with such properties is isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea), belonging to the worldwide extensively used phenylurea herbicides. To make isoproturon accessible to carbon and nitrogen isotope analysis, we developed a GC-based method during which isoproturon was quantitatively fragmented to dimethylamine and 4-isopropylphenylisocyanate. Fragmentation occurred only partially in the injector but was mainly achieved on a heated capillary column. The fragments were then chromatographically separated and individually measured by isotope ratio mass spectrometry. The reliability of the method was tested in hydrolysis experiments with three isotopically different batches of isoproturon. For all three products, the same isotope fractionation factors were observed during conversion and the difference in isotope composition between the batches was preserved. This study demonstrates that fragmentation of phenylurea herbicides does not only make them accessible to isotope analysis but even enables determination of intramolecular isotope fractionation.

THE CD ISOTOPE SIGNATURE OF THE SOUTHERN OCEAN

NASA Astrophysics Data System (ADS)

Abouchami, W.; Galer, S. J.; Middag, R.; de Baar, H.; Andreae, M. O.; Feldmann, H.; Raczek, I.

2009-12-01

The availability of micronutrients can limit and control plankton ecosystems, notably in the Southern Ocean which plays a major role in regulating the CO2 biological pump. Cadmium has a nutrient-like distribution in seawater - it is directly incorporated into living plankton in the upper water column and re-mineralised at depth. The nutritional role of Cd (Price and Morel, 1990) makes it a potentially useful tracer of biological productivity. We report Cd concentration and Cd stable isotope data obtained using a double-spike TIMS method on seawater samples collected during the Zero and Drake Passage cruise (ANTXXIV-III, IPY-GEOTRACES 2008). Four vertical profiles were collected from 40 to 70°S across the Polar Front using the ultra-clean Titan frame (De Baar et al., 2008), providing a record of changes in biological productivity from the Subantarctic to the Antarctic region. Data from two profiles from the SE Atlantic (47.66°S, 4.28W) and Drake Passage (55.13°S, 65.53°W) obtained on 1 litre-sized samples are presented. Both profiles show a increase in Cd concentration with depth, with noticeably higher concentrations in the SE Atlantic. Cd and PO4 are positively correlated with distinct slopes for the two profiles. The Cd isotope data are expressed as ɛ112/110Cd relative to our JMC Mainz standard (± 8ppm, 2SD, N=17). ɛ112/110Cd values show a continuous decrease with increasing depth and a significant shift towards heavier values in the upper 400m at both stations resolvable outside analytical error (2SE ≤ 20ppm). The sense of Cd isotope fractionation confirms previous findings of uptake of “light” Cd by phytoplankton in the upper water column (Lacan et al., 2006; Ripperger et al., 2007; Schmidt et al., 2009). Most important is the evidence for a distinctive heavier Cd isotope signature in AASW relative to AAIW. This result demonstrates that different water masses carry distinct Cd isotopic compositions reflecting changes in Cd uptake by phytoplankton. Price and Morel(1990) Nature 344, 658-660. De Baar et al.(2008) Mar. Chem. 111, 4-21 Lacan et al.(2006) Geochim. Cosmochim. Acta 70, 5104-5118. Ripperger et al.(2007) Earth Planet. Sci. Lett 261,670-684. Schmidt et al.(2009)Earth Planet. Sci. Lett 277, 262-272.

Searching Neutrinoless Double Beta Decay with GERDA Phase II

NASA Astrophysics Data System (ADS)

Agostini, M.; Bakalyarov, A. M.; Balata, M.; Barabanov, I.; Baudis, L.; Bauer, C.; Bellotti, E.; Belogurov, S.; Bettini, A.; Bezrukov, L.; Bode, T.; Brudanin, V.; Brugnera, R.; Caldwell, A.; Cattadori, C.; Chernogorov, A.; Comellato, T.; D’Andrea, V.; Demidova, E. V.; di Marco, N.; Domula, A.; Doroshkevich, E.; Egorov, V.; Falkenstein, R.; Gangapshev, A.; Garfagnini, A.; Giordano, M.; Gooch, C.; Grabmayr, P.; Gurentsov, V.; Gusev, K.; Hahne, C.; Hakenmüller, J.; Hegai, A.; Heisel, M.; Hemmer, S.; Hiller, R.; Hofmann, W.; Holl, P.; Hult, M.; Inzhechik, L. V.; Ioannucci, L.; Csáthy, J. Janicskó; Jochum, J.; Junker, M.; Kazalov, V.; Kermaidic, Y.; Kihm, T.; Kirpichnikov, I. V.; Kirsch, A.; Kish, A.; Klimenko, A.; Kneißl, R.; Knöpfle, K. T.; Kochetov, O.; Kornoukhov, V. N.; Kuzminov, V. V.; Laubenstein, M.; Lazzaro, A.; Lindner, M.; Lippi, I.; Lubashevskiy, A.; Lubsandorzhiev, B.; Lutter, G.; Macolino, C.; Majorovits, B.; Maneschg, W.; Marissens, G.; Miloradovic, M.; Mingazheva, R.; Misiaszek, M.; Moseev, P.; Nemchenok, I.; Nisi, S.; Panas, K.; Pandola, L.; Pelczar, K.; Pullia, A.; Ransom, C.; Reissfelder, M.; Riboldi, S.; Rumyantseva, N.; Sada, C.; Sala, E.; Salamida, F.; Schmitt, C.; Schneider, B.; Schreiner, J.; Schulz, O.; Schweisshelm, B.; Schwingenheuer, B.; Schönert, S.; Schütz, A.-K.; Seitz, H.; Selivanenko, O.; Shevchik, E.; Shirchenko, M.; Simgen, H.; Smolnikov, A.; Stanco, L.; Vanhoefer, L.; Vasenko, A. A.; Veresnikova, A.; von Sturm, K.; Wagner, V.; Wegmann, A.; Wester, T.; Wiesinger, C.; Wojcik, M.; Yanovich, E.; Zhitnikov, I.; Zhukov, S. V.; Zinatulina, D.; Zschocke, A.; Zsigmond, A. J.; Zuber, K.; Zuzel, G.

An observation of neutrinoless double beta (0νββ) decay would allow to shed light onto the nature of neutrinos. GERDA (GERmanium Detector Array) aims to discover this process in a background-free search using 76Ge. The experiment is located at the Laboratori Nazionali del Gran Sasso (LNGS) of the Istituto Nazionale di Fisica Nucleare (INFN) in Italy. Bare, isotopically enriched, high purity germanium detectors are operated in liquid argon. GERDA follows a staged approach. In Phase II 35.6 kg of enriched germanium detectors are operated since December 2015. The application of active background rejection methods, such as a liquid argon scintillation light read-out and pulse shape discrimination of germanium detector signals, allows to reduce the background index to the intended level of 10‑3 cts/(keVṡkgṡyr). No evidence for the 0νββ decay has been found in 23.2 kgṡyr of Phase II data, and together with data from Phase I the up-to-date most stringent half-life limit for this process in 76Ge has been established, at a median sensitivity of 5.8ṡ1025yr the 90% C.L. lower limit is 8.0ṡ1025yr.

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

PubMed

Tea, Illa; Tcherkez, Guillaume

2017-01-01

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

Integrated carbon and chlorine isotope modeling: applications to chlorinated aliphatic hydrocarbons dechlorination.

PubMed

Jin, Biao; Haderlein, Stefan B; Rolle, Massimo

2013-02-05

We propose a self-consistent method to predict the evolution of carbon and chlorine isotope ratios during degradation of chlorinated hydrocarbons. The method treats explicitly the cleavage of isotopically different C-Cl bonds and thus considers, simultaneously, combined carbon-chlorine isotopologues. To illustrate the proposed modeling approach we focus on the reductive dehalogenation of chlorinated ethenes. We compare our method with the currently available approach, in which carbon and chlorine isotopologues are treated separately. The new approach provides an accurate description of dual-isotope effects regardless of the extent of the isotope fractionation and physical characteristics of the experimental system. We successfully applied the new approach to published experimental results on dehalogenation of chlorinated ethenes both in well-mixed systems and in situations where mass-transfer limitations control the overall rate of biodegradation. The advantages of our self-consistent dual isotope modeling approach proved to be most evident when isotope fractionation factors of carbon and chlorine differed significantly and for systems with mass-transfer limitations, where both physical and (bio)chemical transformation processes affect the observed isotopic values.

Stable isotopes of nitrate reflect natural attenuation of propellant residues on military training ranges.

PubMed

Bordeleau, Geneviève; Savard, Martine M; Martel, Richard; Smirnoff, Anna; Ampleman, Guy; Thiboutot, Sonia

2013-08-06

Nitroglycerin (NG) and nitrocellulose (NC) are constituents of double-base propellants used notably for firing antitank ammunitions. Nitroglycerin was detected in soil and water samples from the unsaturated zone (pore water) at an active antitank firing position, where the presence of high nitrate (NO3(-)) concentrations suggests that natural attenuation of NG is occurring. However, concentrations alone cannot assess if NG is the source of NO3(-), nor can they determine which degradation processes are involved. To address this issue, isotopic ratios (δ(15)N, δ(18)O) were measured for NO3(-) produced from NG and NC through various controlled degradation processes and compared with ratios measured in field pore water samples. Results indicate that propellant combustion and degradation mediated by soil organic carbon produced the observed NO3(-) in pore water at this site. Moreover, isotopic results are presented for NO3(-) produced through photolysis of propellant constituents, which could be a dominant process at other sites. The isotopic data presented here constitute novel information regarding a source of NO3(-) that was practically not documented before and a basis to study the contamination by energetic materials in different contexts.

Accelerator-based method of producing isotopes

DOEpatents

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

2015-11-03

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

Quantitative non-destructive assay of PuBe neutron sources

NASA Astrophysics Data System (ADS)

Lakosi, László; Bagi, János; Nguyen, Cong Tam

2006-02-01

PuBe neutron sources were assayed, using a combination of high resolution γ-spectrometry (HRGS) and neutron correlation technique. In a previous publication [J. Bagi, C. Tam Nguyen, L. Lakosi, Nucl. Instr. and Meth. B 222 (2004) 242] a passive neutron well-counter was reported with 3He tubes embedded in a polyamide (TERRAMID) moderator (lined inside with Cd) surrounding the sources to be measured. Gross and coincidence neutron counting was performed, and the Pu content of the sources was found out from isotope analysis and by adopting specific (α, n) reaction yields of the Pu isotopes and 241Am in Be, based on supplier's information and literature data. The method was further developed and refined. Evaluation algorithm was more precisely worked out. The contribution of secondary (correlated) neutrons to the total neutron output was derived from the coincidence (doubles) count rate and taken into account in assessing the Pu content. A new evaluation of former results was performed. Assay was extended to other PuBe sources, and new results were added. In order to attain higher detection efficiency, a more efficient moderator was also applied, with and without Cd shielding around the assay chamber. Calibration seems possible using neutron measurements only (without γ-spectrometry), based on a correlation between the Pu amount and the coincidence-to-total ratio. It is expected that the method could be used for Pu accountancy and safeguards verification as well as identification and assay of seized, found, or not documented PuBe neutron sources.

Understanding the Marine Chromium Isotope Record from Modern and Ancient Carbonates

NASA Astrophysics Data System (ADS)

Parkinson, I. J.; Bonnand, P.; James, R. H.; Fairchild, I. J.; Dixon, S.

2011-12-01

Chromium isotopes may provide a powerful tool for reconstructing the redox state of ancient seawater because Cr isotope fractionation is large (up to 7% in δ53Cr) during the reduction of Cr(VI) to Cr(III) in natural waters [1]. Recent studies have demonstrated that although Cr(VI) is predicted to be the thermodynamically stable form in seawater (as CrO42-), significant amounts (5-20%) of Cr(III) may also be present in surface waters [2]. Therefore the δ53Cr of seawater could vary by up to 2%. Marine carbonates potentially provide a means to extracting information about the Cr isotopic composition of seawater in the geological past and we have developed a high-precision double-spike technique for analysing Cr isotopes in carbonates [3]. The δ53Cr of modern Bahamas Bank carbonates (+0.76%) is broadly consistent with these carbonates recording a seawater Cr signature. Moreover, these pure carbonates contain significant amounts of Cr (1-4 ppm), which indicates that Cr is strongly partitioned into calcium carbonate. Therefore carbonates are likely to provide a faithful record of the δ53Cr composition of seawater. Shallow marine carbonates from the Phanerozoic range in δ53Cr from +0.76 to +1.8%, and some Neoproterozoic carbonates also have heavy Cr isotopic compositions of +0.5 to +1.0 %. Such compositions may reflect changes in the inputs of Cr to the oceans and/or changes in the redox state of the oceans. However, to interpret Cr isotopic compositions in ancient carbonates additionally requires a careful assessment of their trace element contents. This study aims to demonstrate how a combination of redox sensitive trace elements, such as Ce, and Cr isotopes allow an assessment of the marine chromium isotope record. [1] Ellis et al., 2002, Science, 295, 2060-2062. [2] Connolly et al., 2006, Deep Sea Res. Part I, 2006 53, 1975-1988. [3] P. Bonnand, et al., 2011, J. Anal. At. Spectr., 26, 528-535.

Simultaneous determination of the quantity and isotopic ratios of uranium in individual micro-particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS).

PubMed

Park, Jong-Ho; Choi, Eun-Ju

2016-11-01

A method to determine the quantity and isotopic ratios of uranium in individual micro-particles simultaneously by isotope dilution thermal ionization mass spectrometry (ID-TIMS) has been developed. This method consists of sequential sample and spike loading, ID-TIMS for isotopic measurement, and application of a series of mathematical procedures to remove the contribution of uranium in the spike. The homogeneity of evaporation and ionization of uranium content was confirmed by the consistent ratio of n((233)U)/n((238)U) determined by TIMS measurements. Verification of the method was performed using U030 solution droplets and U030 particles. Good agreements of resulting uranium quantity, n((235)U)/n((238)U), and n((236)U)/n((238)U) with the estimated or certified values showed the validity of this newly developed method for particle analysis when simultaneous determination of the quantity and isotopic ratios of uranium is required. Copyright © 2016 Elsevier B.V. All rights reserved.

METHOD AND APPARATUS FOR COLLECTING ISOTOPES

DOEpatents

Leyshon, W.E.

1957-08-01

A method and apparatus for collecting isotopes having a high vapor pressure, such as isotopes of mercury, in a calutron are described. Heretofore, the collected material would vaporize and escape from the ion receiver as fast as it was received. By making the receiver of pure silver, the mercury isotopes form a nonvolatile amalgam with the silver at the water cooled temperature of the receiver, and the mercury is thus retained.

Uranium isotope composition of a laterite profile during extreme weathering of basalt in Guangdong, South China

NASA Astrophysics Data System (ADS)

Huang, J.; Zhou, Z.; Gong, Y.; Lundstrom, C.; Huang, F.

2015-12-01

Rock weathering and soil formation in the critical zone are important for material cycle from the solid Earth to superficial system. Laterite is a major type of soil in South China forming at hot-humid climate, which has strong effect on the global uranium cycle. Uranium is closely related to the environmental redox condition because U is stable at U(Ⅳ) in anoxic condition and U(Ⅵ) as soluble uranyl ion (UO22+) under oxic circumstance. In order to understand the behavior of U isotopes during crust weathering, here we report uranium isotopic compositions of soil and base rock samples from a laterite profile originated from extreme weathering of basalt in Guangdong, South China. The uranium isotopic data were measured on a Nu Plasma MC-ICP-MS at the University of Illinois at Urbana-Champaign using the double spike method. The δ238U of BCR-1 is -0.29±0.03‰ (relative to the international standard CRM-112A), corresponding to a 238U/235U ratio of 137.911±0.004. Our result of BCR-1 agrees with previous analyses (e.g., -0.28‰ in Weyer et al. 2008) [1]. U contents of the laterite profile decrease from 1.9 ppm to 0.9 ppm with depth, and peak at 160 - 170 cm (2.3 ppm), much higher than the U content of base rocks (~0.5 ppm). In contrary, U/Th of laterites is lower than that of base rock (0.27) except the peak at the depth of 160-170 cm (0.38), indicating significant U loss during weathering. Notably, U isotope compositions of soils show a small variation from -0.38 to -0.28‰, consistent with the base rock within analytical error (0.05‰ to 0.08‰, 2sd). Such small variation can be explained by a "rind effect" (Wang et al., 2015) [2], by which U(Ⅳ) can be completely oxidized to U(VI) layer by layer during basalt weathering by dissolved oxygen. Therefore, our study indicates that U loss during basalt weathering at the hot-humid climate does not change U isotope composition of superficial water system. [1] Weyer S. et al. (2008) Natural fractionation of 238U/235U. GCA 72,345-359 [2] Wang X. et al. (2015) Isotope fractionation during oxidation of tetravalent uranium by dissolved oxygen. GCA 150, 160-170

Mechanistic insights into a hydrate contribution to the Paleocene-Eocene carbon cycle perturbation from coupled thermohydraulic simulations

NASA Astrophysics Data System (ADS)

Minshull, T. A.; Marín-Moreno, H.; Armstrong McKay, D. I.; Wilson, P. A.

2016-08-01

During the Paleocene-Eocene Thermal Maximum (PETM), the carbon isotopic signature (δ13C) of surface carbon-bearing phases decreased abruptly by at least 2.5 to 3.0‰. This carbon isotope excursion (CIE) has been attributed to widespread methane hydrate dissociation in response to rapid ocean warming. We ran a thermohydraulic modeling code to simulate hydrate dissociation due to ocean warming for various PETM scenarios. Our results show that hydrate dissociation in response to such warming can be rapid but suggest that methane release to the ocean is modest and delayed by hundreds to thousands of years after the onset of dissociation, limiting the potential for positive feedback from emission-induced warming. In all of our simulations at least half of the dissociated hydrate methane remains beneath the seabed, suggesting that the pre-PETM hydrate inventory needed to account for all of the CIE is at least double that required for isotopic mass balance.

Electron linac for medical isotope production with improved energy efficiency and isotope recovery

DOEpatents

Noonan, John; Walters, Dean; Virgo, Matt; Lewellen, John

2015-09-08

A method and isotope linac system are provided for producing radio-isotopes and for recovering isotopes. The isotope linac is an energy recovery linac (ERL) with an electron beam being transmitted through an isotope-producing target. The electron beam energy is recollected and re-injected into an accelerating structure. The ERL provides improved efficiency with reduced power requirements and provides improved thermal management of an isotope target and an electron-to-x-ray converter.

Tellurium stable isotope fractionation in chondritic meteorites and some terrestrial samples

NASA Astrophysics Data System (ADS)

Fehr, Manuela A.; Hammond, Samantha J.; Parkinson, Ian J.

2018-02-01

New methodologies employing a 125Te-128Te double-spike were developed and applied to obtain high precision mass-dependent tellurium stable isotope data for chondritic meteorites and some terrestrial samples by multiple-collector inductively coupled plasma mass spectrometry. Analyses of standard solutions produce Te stable isotope data with a long-term reproducibility (2SD) of 0.064‰ for δ130/125Te. Carbonaceous and enstatite chondrites display a range in δ130/125Te of 0.9‰ (0.2‰ amu-1) in their Te stable isotope signature, whereas ordinary chondrites present larger Te stable isotope fractionation, in particular for unequilibrated ordinary chondrites, with an overall variation of 6.3‰ for δ130/125Te (1.3‰ amu-1). Tellurium stable isotope variations in ordinary chondrites display no correlation with Te contents or metamorphic grade. The large Te stable isotope fractionation in ordinary chondrites is likely caused by evaporation and condensation processes during metamorphism in the meteorite parent bodies, as has been suggested for other moderately and highly volatile elements displaying similar isotope fractionation. Alternatively, they might represent a nebular signature or could have been produced during chondrule formation. Enstatite chondrites display slightly more negative δ130/125Te compared to carbonaceous chondrites and equilibrated ordinary chondrites. Small differences in the Te stable isotope composition are also present within carbonaceous chondrites and increase in the order CV-CO-CM-CI. These Te isotope variations within carbonaceous chondrites may be due to mixing of components that have distinct Te isotope signatures reflecting Te stable isotope fractionation in the early solar system or on the parent bodies and potentially small so-far unresolvable nucleosynthetic isotope anomalies of up to 0.27‰. The Te stable isotope data of carbonaceous and enstatite chondrites displays a general correlation with the oxidation state and hence might provide a record of the nebular formation environment. The Te stable isotope fractionation of the carbonaceous chondrites CI and CM (and CO potentially) overlap within uncertainty with data for terrestrial Te standard solutions, sediments and ore samples. Assuming the silicate Earth displays similar Te isotope fractionation as the studied terrestrial samples, the data indicate that the late veneer might have been delivered by material similar to CI or CM (or possibly) CO carbonaceous chondrites in terms of Te isotope composition. Nine terrestrial samples display resolvable Te stable isotope fractionation of 0.85 and 0.60‰ for δ130/125Te for sediment and USGS geochemical exploration reference samples, respectively. Tellurium isotopes therefore have the potential to become a new geochemical sedimentary proxy, as well as a proxy for ore-exploration.

Extending the Boundaries of Isotope Ratio MS - Latest Technological Improvements

NASA Astrophysics Data System (ADS)

Hilkert, A.

2016-12-01

Isotope ratio mass spectrometry has a long history, which started with the analysis of the isotopes of CO2. Over several decades a broad range of IRMS techniques has been derived like multi-collector high resolution ICP-MS, TIMS, noble gas static MS and gas IRMS. These different flavors of IRMS are now building a technology tool box, which allows to derive new applications build on new capabilities by combination of specific features of these sister technologies. In the 90's inductive coupled plasma ionization was added for the high precision analysis of rare elements. In 2000 extended multicollection opened the way into clumped isotopes. In 2008 the concept of a high resolution gas source IRMS was layed out to revolutionize stable gas IRMS recently followed by the combination of this static multicollection mode with fast mass scans of the single collector double focusing high resolution GCMS. Recently new technologies were created, like the mid infrared analyzers (IRIS) based on difference frequency generation lasers, the combination of a collision cell with HR MC ICPMS as well as the use of a high resolution electrostatic ion trap for extended stable isotope analysis on individual compounds. All these building blocks for IRMS address selected requirements of sample preparation, sample introduction, referencing, ionization, mass separation, ion detection or signal amplification. Along these lines new technological improvements and applications will be shown and discussed.

Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method

USGS Publications Warehouse

Casciotti, K.L.; Sigman, D.M.; Hastings, M. Galanter; Böhlke, J.K.; Hilkert, A.

2002-01-01

We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate.1Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N2O analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N2O product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 μM NO3-), lack of interference by other solutes, and ease of sample preparation.

Double proton transfer in the complex of acetic acid with methanol: Theory versus experiment

NASA Astrophysics Data System (ADS)

Fernández-Ramos, Antonio; Smedarchina, Zorka; Rodríguez-Otero, Jesús

2001-01-01

To test the approximate instanton approach to intermolecular proton-transfer dynamics, we report multidimensional ab initio bimolecular rate constants of HH, HD, and DD exchange in the complex of acetic acid with methanol in tetrahydrofuran-d8, and compare them with the NMR (nuclear magnetic resonance) experiments of Gerritzen and Limbach. The bimolecular rate constants are evaluated as products of the exchange rates and the equilibrium rate constants of complex formation in solution. The two molecules form hydrogen-bond bridges and the exchange occurs via concerted transfer of two protons. The dynamics of this transfer is evaluated in the complete space of 36 vibrational degrees of freedom. The geometries of the two isolated molecules, the complex, and the transition states corresponding to double proton transfer are fully optimized at QCISD (quadratic configuration interaction including single and double substitutions) level of theory, and the normal-mode frequencies are calculated at MP2 (Møller-Plesset perturbation theory of second order) level with the 6-31G (d,p) basis set. The presence of the solvent is taken into account via single-point calculations over the gas phase geometries with the PCM (polarized continuum model). The proton exchange rate constants, calculated with the instanton method, show the effect of the structure and strength of the hydrogen bonds, reflected in the coupling between the tunneling motion and the other vibrations of the complex. Comparison with experiment, which shows substantial kinetic isotopic effects (KIE), indicates that tunneling prevails over classic exchange for the whole temperature range of observation. The unusual behavior of the experimental KIE upon single and double deuterium substitution is well reproduced and is related to the synchronicity of two-atom tunneling.

Cosmogenically-produced isotopes in natural and enriched high-purity germanium detectors for the MAJORANA DEMONSTRATOR

NASA Astrophysics Data System (ADS)

Gilliss, Thomas; MAJORANA DEMONSTRATOR Collaboration

2017-01-01

The MAJORANA DEMONSTRATOR advances toward measurements of the neutrinoless double-beta decay of 76Ge. Detectors employed in the DEMONSTRATOR are subject to cosmogenic spallation during production and processing, resulting in activation of certain long-lived radioisotopes. Activation of these cosmogenic isotopes is mitigated by shielded storage of detectors and through underground operation of the DEMONSTRATOR at the 4850 ft level of the Sanford Underground Research Facility. In this work, we explore the appearance and reduction of cosmogenic contributions to the DEMONSTRATOR background spectrum. This work is supported by the U.S. Department of Energy, Office of Science, Office of Nuclear Physics, the Particle Astrophysics and Nuclear Physics Programs of the National Science Foundation, and the Sanford Underground Research Facility.

Isotope effect in the organic superconductor β_H-(BEDT-TTF)2I3 where BEDT-TTF is bis (ethylenedithiotetrathiafulvalene)

NASA Astrophysics Data System (ADS)

Auban-Senzier, P.; Bourbonnais, C.; Jérome, D.; Lenoir, C.; Batail, P.; Canadell, E.; Buisson, J. P.; Lefrant, S.

1993-03-01

We have performed the simultaneous investigation of the isotope effect on the superconducting transition and on the Raman spectra in the organic superconductor β_H-(BEDT-TTF)2I3 (T_c = 8 K). For this purpose, we substitute ^{13}C for ^{12}C on the carbon sites of the central double bond of BEDT-TTF molecule. The isotope shifts measured by Raman experiments can be fairly well explained by standard molecular dynamics. However, the critical temperature is lowered by 0.2 K in the ^{13}C enriched material. We analyse the possible sources of this remarkable downward shift which leads to an isotope coefficient higher than the BCS value. The extended-Hückel calculations of the density of states for the two HOMO bands of β_H-(BEDT-TTF)2I3 do show that, within the framework of a weak coupling theory, its sizeable variation on the scale of ω_D cannot account for the observed isotope effect. On the other hand, we discuss how inelastic electronic scattering observed in resistivity measurements just above T_c can lead through a pair breaking mechanism to a sizeable increase of the isotope coefficient. Nous présentons une étude simultanée d'effet isotopique sur la transition supraconductrice et les spectres Raman dans le supraconducteur organique β_H-(BEDT-TTF)2I3 (T_c = 8 K). Pour cela, nous avons synthétisé le composé dans lequel les atomes de carbone de la double liaison centrale de la molécule BEDT-TTF sont substitués par l'isotope ^{13}C. Les déplacements isotopiques mesurés par spectroscopie Raman sont bien expliqués par la dynamique moléculaire standard. Cependant, la température critique est abaissée de 0.2 K dans le matériau enrichi en ^{13}C. Nous étudions les origines possibles de cet effet qui permet d'obtenir un coefficient isotopique supérieur à la valeur BCS. Des calculs de la densité d'états effectués par la méthode de Hückel étendue pour les deux bandes HOMO du composé montrent que, dans le cadre d'une théorie de couplage faible, son importante variation à l'échelle de ω_D ne peut expliquer l'effet observé. D'autre part, nous expliquons comment la diffusion électronique inélastique observée en résistivité juste au-dessus de T_c peut conduire via un mécanisme de brisure de paires, à une augmentation significative du coefficient isotopique.

Stable Nd isotope variations in the inner Solar System: The effect of sulfide during differentiation?

NASA Astrophysics Data System (ADS)

McCoy-West, A.

2017-12-01

Radiogenic neodymium isotopes have been widely used in studies of planetary accretion to constrain the timescales of early planetary differention [1]. Whereas stable isotope varitaions potentially provide information on the the processes that occur during planet formation. Experimental work suggests that the Earth's core contains a significant proportion of sulfide [2], and recent experimental work shows that under reducing conditions sulfide can incorporate substantial quantities of refractory lithophile elements [including Nd; 3]. If planetary embroyos also contain sulfide-rich cores, Nd stable isotopes have the potential to trace this sulfide segregation event in highly reduced environments, because there is a significant contrast in bonding environment between sulfide and silicate, where heavy isotopes should be preferentially incorporated into high force-constant bonds involving REE3+ (i.e. the silicate mantle). Here we present 146Nd/144Nd data, obtained using a double spike TIMS technique, for a range of planetary bodies formed at variable oxidation states including samples from the Moon, Mars, the asteriod 4Vesta and the Angrite and Aubrite parent bodies. Analyses of chondritic meteorites and terrestrial igneous rocks indicate that the Earth has a Nd stable isotope composition that is indistinguishable from that of chondrites [4]. Eucrites and martian meteorites also have compositons within error of the chondritic average. Significantly more variabilty is observed in the low concentration lunar samples and diogienite meteorites with Δ146Nd = 0.16‰. Preliminary results suggest that the Nd stable isotope composition of oxidised planetary bodies are homogeneous and modifications are the result of subordinate magmatic processes. [1] Boyet & Carlson, Science 309, 576 (2005) [2] Labidi et al. Nature 501, 208 (2013); [3] Wohlers &Wood, Nature 520, 337 (2015); [4] McCoy-West et al. Goldschmidt Ab. 429 (2017).

Chemical and stable-radiogenic isotope compositions of Polatlı-Haymana thermal waters (Ankara, Turkey)

NASA Astrophysics Data System (ADS)

Akilli, Hafize; Mutlu, Halim

2016-04-01

Complex tectono-magmatic evolution of the Anatolian land resulted in development of numerous geothermal areas through Turkey. The Ankara region in central Anatolia is surrounded by several basins which are filled with upper Cretaceous-Tertiary sediments. Overlying Miocene volcanics and step faulting along the margins of these basins played a significant role in formation of a number of low-enthalpy thermal waters. In this study, chemical and isotopic compositions of Polatlı and Haymana geothermal waters in the Ankara region are investigated. The Polatlı-Haymana waters with a temperature range of 24 to 43 °C are represented by Ca-(Na)-HCO3 composition implying derivation from carbonate type reservoir rocks. Oxygen-hydrogen isotope values of the waters are conformable with the Global Meteoric Water Line and point to a meteoric origin. The carbon isotopic composition in dissolved inorganic carbon (DIC) of the studied waters is between -21.8 and -1.34 permil (vs. VPDB). Marine carbonates and organic rocks are the main sources of carbon. There is a high correlation between oxygen (3.7 to 15.0 permil; VSMOW) and sulfur (-9.2 to 19.5 permil; VCDT) isotope compositions of sulfate in waters. The mixing of sulfate from dissolution of marine carbonates and terrestrial evaporite units is the chief process behind the observed sulfate isotope systematics of the samples. 87Sr/86Sr ratios of waters varying from 0.705883 to 0.707827 are consistent with those of reservoir rocks. The temperatures calculated by SO4-H2O isotope geothermometry are between 81 and 138 °C nearly doubling the estimates from chemical geothermometers.

E2C mechanism of elimination reactions. IX. Secondary deuterium isotope effects on rates of bimolecular reactions in alicyclic systems

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

Cook, D.

1976-06-11

Secondary ..cap alpha..-deuterium isotope effects on the rates of NBu/sub 4/OAc and NBu/sub 4/Cl promoted bimolecular reactions (E2 and SN2) of cyclohexyl tosylate and cyclohexyl bromide have been studied. The E2 reactions, previously categorized as E2C-like, show ..cap alpha..-deuterium isotope effects in the range 1.14--1.22, while the related SN2 reactions give values in the range 1.05--1.08. The discrepancy in the magnitude of the ..cap alpha..-deuterium isotope effect for the E2 and SN2 processes is consistent with the view that E2C-like reactions use ''looser'' transition states than those used in the concurrent SN2 reactions. While the reported ..cap alpha..-d isotope effectsmore » do not provide positive evidence to support the idea that the base interacts with C/sub ..cap alpha../ in the E2 transition states of the reactions studied, neither do they substantiate claims for dismissal of the concept. A comparison of the secondary ..gamma..-deuterium and ..beta..'-deuterium isotope effects arising in the reaction of cyclohexyl tosylate with NBu/sub 4/OAc in acetone indicates the two isotope effects to be of equivalent magnitude (k/sub ..beta..'-d/k/sub ..gamma..-d/ = 0.98). This observation can only be rationalized for this reaction in terms of a transition state structure in which there is extensive double bond development. It provides compelling evidence against the involvement of any transition state structure which accommodates extensive positive charge development at C/sub ..cap alpha../.« less

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

PubMed

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

2008-10-01

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

Methods for determination of radioactive substances in water and fluvial sediments

USGS Publications Warehouse

Thatcher, Leland Lincoln; Janzer, Victor J.; Edwards, Kenneth W.

1977-01-01

Analytical methods for the determination of some of the more important components of fission or neutron activation product radioactivity and of natural radioactivity found in water are reported. The report for each analytical method includes conditions for application of the method, a summary of the method, interferences, required apparatus and reagents, analytical procedures, calculations, reporting of results, and estimation of precision. The fission product isotopes considered are cesium-137, strontium-90, and ruthenium-106. The natural radioelements and isotopes considered are uranium, lead-210, radium-226, radium-228, tritium, and carbon-14. A gross radioactivity survey method and a uranium isotope ratio method are given. When two analytical methods are in routine use for an individual isotope, both methods are reported with identification of the specific areas of application of each. Techniques for the collection and preservation of water samples to be analyzed for radioactivity are discussed.

Influence of 13C isotopic labeling location of 13C DNP of acetate using TEMPO free radical

NASA Astrophysics Data System (ADS)

Parish, Christopher; Niedbalski, Peter; Lumata, Lloyd

2015-03-01

Dynamic nuclear polarization (DNP) via the dissolution method enhances the liquid-state magnetic resonance (NMR or MRI) signals of insensitive nuclear spins by at least 10,000-fold. The basis for all these signal enhancements at room temperature is the polarization transfer from the electrons to nuclear spins at cryogenic temperature and high magnetic field. In this work, we have studied the influence of the location of 13C isotopic labeling on the DNP of sodium acetate at 3.35 T and 1.4 K using a wide ESR linewidth free radical 4-oxo-TEMPO. The carbonyl [1-13C]acetate spins produced a polarization level that is almost twice that of the methyl [2-13C]acetate spins. On the other hand, the polarization of the methyl 13C spins doubled to reach the level of [1-13C]acetate when the methyl group was deuterated. Meanwhile, the solid-state nuclear relaxation of these samples are the same and do not correlate with the polarization levels. These behavior implies that the nuclear relaxation for these samples is dominated by the contribution from the free radicals and the polarization levels can be explained by a thermodynamic picture of DNP.

[Progress in stable isotope labeled quantitative proteomics methods].

PubMed

Zhou, Yuan; Shan, Yichu; Zhang, Lihua; Zhang, Yukui

2013-06-01

Quantitative proteomics is an important research field in post-genomics era. There are two strategies for proteome quantification: label-free methods and stable isotope labeling methods which have become the most important strategy for quantitative proteomics at present. In the past few years, a number of quantitative methods have been developed, which support the fast development in biology research. In this work, we discuss the progress in the stable isotope labeling methods for quantitative proteomics including relative and absolute quantitative proteomics, and then give our opinions on the outlook of proteome quantification methods.

δ13C and δ18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite

USGS Publications Warehouse

Revesz, Kinga M.; Landwehr, Jurate M.

2002-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 ± 20 µg) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H3PO4/CaCO3) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H3PO4/CaCO3 reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 °C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was ≤0.1 and ≤0.2 per mill or ‰, respectively, although later analysis showed that materials from one specific standard required reaction time between 34 and 54 h for δ18O to achieve this level of precision. Aliquot screening methods were shown to further minimize the total error. The accuracy and precision of the new method were analyzed and confirmed by statistical analysis. The utility of the method was verified by analyzing calcite from Devils Hole, Nevada, for which isotope-ratio values had previously been obtained by the classical method. Devils Hole core DH-11 recently had been re-cut and re-sampled, and isotope-ratio values were obtained using the new method. The results were comparable with those obtained by the classical method with correlation = +0.96 for both isotope ratios. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, and two cutting errors that occurred during re-sampling then were confirmed independently. This result indicates that the new method is a viable alternative to the classical reaction method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes resulting in considerable time savings. 

Modeling the isotopic evolution of snowpack and snowmelt: Testing a spatially distributed parsimonious approach.

PubMed

Ala-Aho, Pertti; Tetzlaff, Doerthe; McNamara, James P; Laudon, Hjalmar; Kormos, Patrick; Soulsby, Chris

2017-07-01

Use of stable water isotopes has become increasingly popular in quantifying water flow paths and travel times in hydrological systems using tracer-aided modeling. In snow-influenced catchments, snowmelt produces a traceable isotopic signal, which differs from original snowfall isotopic composition because of isotopic fractionation in the snowpack. These fractionation processes in snow are relatively well understood, but representing their spatiotemporal variability in tracer-aided studies remains a challenge. We present a novel, parsimonious modeling method to account for the snowpack isotope fractionation and estimate isotope ratios in snowmelt water in a fully spatially distributed manner. Our model introduces two calibration parameters that alone account for the isotopic fractionation caused by sublimation from interception and ground snow storage, and snowmelt fractionation progressively enriching the snowmelt runoff. The isotope routines are linked to a generic process-based snow interception-accumulation-melt model facilitating simulation of spatially distributed snowmelt runoff. We use a synthetic modeling experiment to demonstrate the functionality of the model algorithms in different landscape locations and under different canopy characteristics. We also provide a proof-of-concept model test and successfully reproduce isotopic ratios in snowmelt runoff sampled with snowmelt lysimeters in two long-term experimental catchment with contrasting winter conditions. To our knowledge, the method is the first such tool to allow estimation of the spatially distributed nature of isotopic fractionation in snowpacks and the resulting isotope ratios in snowmelt runoff. The method can thus provide a useful tool for tracer-aided modeling to better understand the integrated nature of flow, mixing, and transport processes in snow-influenced catchments.

Rapid and high-resolution stable isotopic measurement of biogenic accretionary carbonate using an online CO2 laser ablation system: Standardization of the analytical protocol.

PubMed

Sreemany, Arpita; Bera, Melinda Kumar; Sarkar, Anindya

2017-12-30

The elaborate sampling and analytical protocol associated with conventional dual-inlet isotope ratio mass spectrometry has long hindered high-resolution climate studies from biogenic accretionary carbonates. Laser-based on-line systems, in comparison, produce rapid data, but suffer from unresolvable matrix effects. It is, therefore, necessary to resolve these matrix effects to take advantage of the automated laser-based method. Two marine bivalve shells (one aragonite and one calcite) and one fish otolith (aragonite) were first analysed using a CO 2 laser ablation system attached to a continuous flow isotope ratio mass spectrometer under different experimental conditions (different laser power, sample untreated vs vacuum roasted). The shells and the otolith were then micro-drilled and the isotopic compositions of the powders were measured in a dual-inlet isotope ratio mass spectrometer following the conventional acid digestion method. The vacuum-roasted samples (both aragonite and calcite) produced mean isotopic ratios (with a reproducibility of ±0.2 ‰ for both δ 18 O and δ 13 C values) almost identical to the values obtained using the conventional acid digestion method. As the isotopic ratio of the acid digested samples fall within the analytical precision (±0.2 ‰) of the laser ablation system, this suggests the usefulness of the method for studying the biogenic accretionary carbonate matrix. When using laser-based continuous flow isotope ratio mass spectrometry for the high-resolution isotopic measurements of biogenic carbonates, the employment of a vacuum-roasting step will reduce the matrix effect. This method will be of immense help to geologists and sclerochronologists in exploring short-term changes in climatic parameters (e.g. seasonality) in geological times. Copyright © 2017 John Wiley & Sons, Ltd.

Effects of euthanasia method on stable-carbon and stable-nitrogen isotope analysis for an ectothermic vertebrate.

PubMed

Atwood, Meredith A

2013-04-30

Stable isotope analysis is a critical tool for understanding ecological food webs; however, results can be sensitive to sample preparation methods. To limit the possibility of sample contamination, freezing is commonly used to euthanize invertebrates and preserve non-lethal samples from vertebrates. For destructive sampling of vertebrates, more humane euthanasia methods are preferred to freezing and it is essential to evaluate how these euthanasia methods affect stable isotope results. Stable isotope ratios and elemental composition of carbon and nitrogen were used to evaluate whether the euthanasia method compromised the integrity of the sample for analysis. Specifically, the stable isotope and C:N ratios were compared for larval wood frogs (Rana sylvatica  =  Lithobates sylvaticus), an ectothermic vertebrate, that had been euthanized by freezing with four different humane euthanasia methods: CO2, benzocaine, MS-222 (tricaine methanesulfonate), and 70% ethanol. The euthanasia method was not related to the δ(13)C or δ(15)N values and the comparisons revealed no differences between freezing and any of the other treatments. However, there were slight (non-significant) differences in the isotope ratios of benzocaine and CO2 when each was compared with freezing. The elemental composition was altered by the euthanasia method employed. The percentage nitrogen was higher in CO2 treatments than in freezing, and similar (non-significant) trends were seen for ethanol treatments relative to freezing. The resulting C:N ratios were higher for benzocaine treatments than for both CO2 and ethanol. Similar (non-significant) trends suggested that the C:N ratios were also higher for animals euthanized by freezing than for both CO2 and ethanol euthanasia methods. The euthanasia method had a larger effect on elemental composition than stable isotope ratios. The percentage nitrogen and the subsequent C:N ratios were most affected by the CO2 and ethanol euthanasia methods, whereas non-significant trends suggested that benzocaine and CO2 altered the stable isotope ratios. It appears that the use of MS-222 and freezing with dry ice are the most appropriate euthanasia methods for ectothermic vertebrates. Copyright © 2013 John Wiley & Sons, Ltd.

Influence of sulfur-bearing polyatomic species on high precision measurements of Cu isotopic composition

USGS Publications Warehouse

Pribil, M.J.; Wanty, R.B.; Ridley, W.I.; Borrok, D.M.

2010-01-01

An increased interest in high precision Cu isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has developed recently for various natural geologic systems and environmental applications, these typically contain high concentrations of sulfur, particularly in the form of sulfate (SO42-) and sulfide (S). For example, Cu, Fe, and Zn concentrations in acid mine drainage (AMD) can range from 100??g/L to greater than 50mg/L with sulfur species concentrations reaching greater than 1000mg/L. Routine separation of Cu, Fe and Zn from AMD, Cu-sulfide minerals and other geological matrices usually incorporates single anion exchange resin column chromatography for metal separation. During chromatographic separation, variable breakthrough of SO42- during anion exchange resin column chromatography into the Cu fractions was observed as a function of the initial sulfur to Cu ratio, column properties, and the sample matrix. SO42- present in the Cu fraction can form a polyatomic 32S-14N-16O-1H species causing a direct mass interference with 63Cu and producing artificially light ??65Cu values. Here we report the extent of the mass interference caused by SO42- breakthrough when measuring ??65Cu on natural samples and NIST SRM 976 Cu isotope spiked with SO42- after both single anion column chromatography and double anion column chromatography. A set of five 100??g/L Cu SRM 976 samples spiked with 500mg/L SO42- resulted in an average ??65Cu of -3.50?????5.42??? following single anion column separation with variable SO42- breakthrough but an average concentration of 770??g/L. Following double anion column separation, the average SO42-concentration of 13??g/L resulted in better precision and accuracy for the measured ??65Cu value of 0.01?????0.02??? relative to the expected 0??? for SRM 976. We conclude that attention to SO42- breakthrough on sulfur-rich samples is necessary for accurate and precise measurements of ??65Cu and may require the use of a double ion exchange column procedure. ?? 2010.

Enhancing the gate fidelity of silicon-based singlet-triplet qubits under symmetric exchange control using optimized pulse sequences

NASA Astrophysics Data System (ADS)

Zhang, Chengxian; Throckmorton, Robert; Yang, Xu-Chen; Wang, Xin; Barnes, Edwin

We perform Randomized Benchmarking of a family of recently introduced control scheme for singlet-triplet qubits in semiconductor double quantum dots, which is optimized to have substantially shorter gate times. We study their performances under the recently introduced symmetric control scheme of changing the exchange interaction by raising and lowering the barrier between the two dots (barrier control) and compare these results to those under the traditional tilt control method in which the exchange interaction is varied by detuning. It has been suggested that the barrier control method encounters a much smaller charge noise. We found that for the cases where the charge noise is dominant, corresponding to the device made on isotopically enriched silicon, the optimized sequences offer much longer coherence time under barrier control compared to the tilt control method of the strength of the exchange interaction. This work was supported by the Research Grants Council of Hong Kong SAR (No. CityU 21300116) and the National Natural Science Foundation of China (No. 11604277), and by LPS-MPO-CMTC.

Integrating Stomach Content and Stable Isotope Analyses to Quantify the Diets of Pygoscelid Penguins

PubMed Central

Polito, Michael J.; Trivelpiece, Wayne Z.; Karnovsky, Nina J.; Ng, Elizabeth; Patterson, William P.; Emslie, Steven D.

2011-01-01

Stomach content analysis (SCA) and more recently stable isotope analysis (SIA) integrated with isotopic mixing models have become common methods for dietary studies and provide insight into the foraging ecology of seabirds. However, both methods have drawbacks and biases that may result in difficulties in quantifying inter-annual and species-specific differences in diets. We used these two methods to simultaneously quantify the chick-rearing diet of Chinstrap (Pygoscelis antarctica) and Gentoo (P. papua) penguins and highlight methods of integrating SCA data to increase accuracy of diet composition estimates using SIA. SCA biomass estimates were highly variable and underestimated the importance of soft-bodied prey such as fish. Two-source, isotopic mixing model predictions were less variable and identified inter-annual and species-specific differences in the relative amounts of fish and krill in penguin diets not readily apparent using SCA. In contrast, multi-source isotopic mixing models had difficulty estimating the dietary contribution of fish species occupying similar trophic levels without refinement using SCA-derived otolith data. Overall, our ability to track inter-annual and species-specific differences in penguin diets using SIA was enhanced by integrating SCA data to isotopic mixing modes in three ways: 1) selecting appropriate prey sources, 2) weighting combinations of isotopically similar prey in two-source mixing models and 3) refining predicted contributions of isotopically similar prey in multi-source models. PMID:22053199

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H [Idaho Falls, ID; Todd, Terry A [Aberdeen, ID; Tranter, Troy J [Idaho Falls, ID; Horwitz, E Philip [Naperville, IL

2009-10-06

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Tranter, Troy J.; Horwitz, E. Philip

2007-01-02

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

The processing of enriched germanium for the Majorana Demonstrator and R&D for a next generation double-beta decay experiment

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

Abgrall, N.; Arnquist, I. J.; Avignone III, F. T.

The Majorana Demonstrator is an array of point-contact Ge detectors fabricated from Ge isotopically enriched to 88% in 76Ge to search for neutrinoless double beta decay. The processing of Ge for germanium detectors is a well-known technology. However, because of the high cost of Ge enriched in 76Ge special procedures were required to maximize the yield of detector mass and to minimize exposure to cosmic rays. These procedures include careful accounting for the material; shielding it to reduce cosmogenic generation of radioactive isotopes; and development of special reprocessing techniques for contaminated solid germanium, shavings, grindings, acid etchant and cutting fluidsmore » from detector fabrication. Processing procedures were developed that resulted in a total yield in detector mass of 70%. However, none of the acid-etch solution and only 50% of the cutting fluids from detector fabrication were reprocessed. Had they been processed, the projections for the recovery yield would be between 80% and 85%. Maximizing yield is critical to justify a possible future ton-scale experiment. A process for recovery of germanium from the acid-etch solution was developed with yield of about 90%. All material was shielded or stored underground whenever possible to minimize the formation of 68Ge by cosmic rays, which contributes background in the double-beta decay region of interest and cannot be removed by zone refinement and crystal growth. Formation of 68Ge was reduced by a significant factor over that in natural abundance detectors not protected from cosmic rays.« less

The processing of enriched germanium for the Majorana   Demonstrator  and R&D for a next generation double-beta decay experiment

DOE PAGES

Abgrall, N.; Arnquist, I. J.; Avignone III, F. T.; ...

2017-10-07

The Majorana Demonstrator is an array of point-contact Ge detectors fabricated from Ge isotopically enriched to 88% in 76Ge to search for neutrinoless double beta decay. The processing of Ge for germanium detectors is a well-known technology. However, because of the high cost of Ge enriched in 76Ge special procedures were required to maximize the yield of detector mass and to minimize exposure to cosmic rays. These procedures include careful accounting for the material; shielding it to reduce cosmogenic generation of radioactive isotopes; and development of special reprocessing techniques for contaminated solid germanium, shavings, grindings, acid etchant and cutting fluidsmore » from detector fabrication. Processing procedures were developed that resulted in a total yield in detector mass of 70%. However, none of the acid-etch solution and only 50% of the cutting fluids from detector fabrication were reprocessed. Had they been processed, the projections for the recovery yield would be between 80% and 85%. Maximizing yield is critical to justify a possible future ton-scale experiment. A process for recovery of germanium from the acid-etch solution was developed with yield of about 90%. All material was shielded or stored underground whenever possible to minimize the formation of 68Ge by cosmic rays, which contributes background in the double-beta decay region of interest and cannot be removed by zone refinement and crystal growth. Formation of 68Ge was reduced by a significant factor over that in natural abundance detectors not protected from cosmic rays.« less

The processing of enriched germanium for the MAJORANA DEMONSTRATOR and R&D for a next generation double-beta decay experiment

NASA Astrophysics Data System (ADS)

Abgrall, N.; Arnquist, I. J.; Avignone, F. T., III; Barabash, A. S.; Bertrand, F. E.; Bradley, A. W.; Brudanin, V.; Busch, M.; Buuck, M.; Caja, J.; Caja, M.; Caldwell, T. S.; Christofferson, C. D.; Chu, P.-H.; Cuesta, C.; Detwiler, J. A.; Dunagan, C.; Dunstan, D. T.; Efremenko, Yu.; Ejiri, H.; Elliott, S. R.; Gilliss, T.; Giovanetti, G. K.; Goett, J.; Green, M. P.; Gruszko, J.; Guinn, I. S.; Guiseppe, V. E.; Haufe, C. R. S.; Henning, R.; Hoppe, E. W.; Jasinski, B. R.; Kidd, M. F.; Konovalov, S. I.; Kouzes, R. T.; Lopez, A. M.; MacMullin, J.; Martin, R. D.; Massarczyk, R.; Meijer, S. J.; Mertens, S.; Meyer, J. H.; Myslik, J.; O'Shaughnessy, C.; Poon, A. W. P.; Radford, D. C.; Rager, J.; Reine, A. L.; Reising, J. A.; Rielage, K.; Robertson, R. G. H.; Shanks, B.; Shirchenko, M.; Suriano, A. M.; Tedeschi, D.; Toth, L. M.; Trimble, J. E.; Varner, R. L.; Vasilyev, S.; Vetter, K.; Vorren, K.; White, B. R.; Wilkerson, J. F.; Wiseman, C.; Xu, W.; Yakushev, E.; Yu, C.-H.; Yumatov, V.; Zhitnikov, I.; Zhu, B. X.

2018-01-01

The MAJORANA DEMONSTRATOR is an array of point-contact Ge detectors fabricated from Ge isotopically enriched to 88% in 76 Ge to search for neutrinoless double beta decay. The processing of Ge for germanium detectors is a well-known technology. However, because of the high cost of Ge enriched in 76 Ge special procedures were required to maximize the yield of detector mass and to minimize exposure to cosmic rays. These procedures include careful accounting for the material; shielding it to reduce cosmogenic generation of radioactive isotopes; and development of special reprocessing techniques for contaminated solid germanium, shavings, grindings, acid etchant and cutting fluids from detector fabrication. Processing procedures were developed that resulted in a total yield in detector mass of 70%. However, none of the acid-etch solution and only 50% of the cutting fluids from detector fabrication were reprocessed. Had they been processed, the projections for the recovery yield would be between 80% and 85%. Maximizing yield is critical to justify a possible future ton-scale experiment. A process for recovery of germanium from the acid-etch solution was developed with yield of about 90%. All material was shielded or stored underground whenever possible to minimize the formation of 68Ge by cosmic rays, which contributes background in the double-beta decay region of interest and cannot be removed by zone refinement and crystal growth. Formation of 68Ge was reduced by a significant factor over that in natural abundance detectors not protected from cosmic rays.

The processing of enriched germanium for the Majorana Demonstrator and R&D for a next generation double-beta decay experiment

DOE PAGES

Abgrall, N.; Arnquist, I. J.; Avignone III, F. T.; ...

2017-10-07

The Majorana Demonstrator is an array of point-contact Ge detectors fabricated from Ge isotopically enriched to 88% in 76Ge to search for neutrinoless double beta decay. The processing of Ge for germanium detectors is a well-known technology. However, because of the high cost of Ge enriched in 76Ge special procedures were required to maximize the yield of detector mass and to minimize exposure to cosmic rays. These procedures include careful accounting for the material; shielding it to reduce cosmogenic generation of radioactive isotopes; and development of special reprocessing techniques for contaminated solid germanium, shavings, grindings, acid etchant and cutting fluidsmore » from detector fabrication. Processing procedures were developed that resulted in a total yield in detector mass of 70%. However, none of the acid-etch solution and only 50% of the cutting fluids from detector fabrication were reprocessed. Had they been processed, the projections for the recovery yield would be between 80% and 85%. Maximizing yield is critical to justify a possible future ton-scale experiment. A process for recovery of germanium from the acid-etch solution was developed with yield of about 90%. All material was shielded or stored underground whenever possible to minimize the formation of 68Ge by cosmic rays, which contributes background in the double-beta decay region of interest and cannot be removed by zone refinement and crystal growth. Formation of 68Ge was reduced by a significant factor over that in natural abundance detectors not protected from cosmic rays.« less

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

USDA-ARS?s Scientific Manuscript database

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

Carbon isotope analyses of n-alkanes released from rapid pyrolysis of oil asphaltenes in a closed system.

PubMed

Chen, Shasha; Jia, Wanglu; Peng, Ping'an

2016-08-15

Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ(13) C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oil-source' correlations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Device and method for separating oxygen isotopes

DOEpatents

Rockwood, Stephen D.; Sander, Robert K.

1984-01-01

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

Novel methods for estimating 3D distributions of radioactive isotopes in materials

NASA Astrophysics Data System (ADS)

Iwamoto, Y.; Kataoka, J.; Kishimoto, A.; Nishiyama, T.; Taya, T.; Okochi, H.; Ogata, H.; Yamamoto, S.

2016-09-01

In recent years, various gamma-ray visualization techniques, or gamma cameras, have been proposed. These techniques are extremely effective for identifying "hot spots" or regions where radioactive isotopes are accumulated. Examples of such would be nuclear-disaster-affected areas such as Fukushima or the vicinity of nuclear reactors. However, the images acquired with a gamma camera do not include distance information between radioactive isotopes and the camera, and hence are "degenerated" in the direction of the isotopes. Moreover, depth information in the images is lost when the isotopes are embedded in materials, such as water, sand, and concrete. Here, we propose two methods of obtaining depth information of radioactive isotopes embedded in materials by comparing (1) their spectra and (2) images of incident gamma rays scattered by the materials and direct gamma rays. In the first method, the spectra of radioactive isotopes and the ratios of scattered to direct gamma rays are obtained. We verify experimentally that the ratio increases with increasing depth, as predicted by simulations. Although the method using energy spectra has been studied for a long time, an advantage of our method is the use of low-energy (50-150 keV) photons as scattered gamma rays. In the second method, the spatial extent of images obtained for direct and scattered gamma rays is compared. By performing detailed Monte Carlo simulations using Geant4, we verify that the spatial extent of the position where gamma rays are scattered increases with increasing depth. To demonstrate this, we are developing various gamma cameras to compare low-energy (scattered) gamma-ray images with fully photo-absorbed gamma-ray images. We also demonstrate that the 3D reconstruction of isotopes/hotspots is possible with our proposed methods. These methods have potential applications in the medical fields, and in severe environments such as the nuclear-disaster-affected areas in Fukushima.

High accuracy method for the application of isotope dilution to gas chromatography/mass spectrometric analysis of gases.

PubMed

Milton, Martin J T; Wang, Jian

2003-01-01

A new isotope dilution mass spectrometry (IDMS) method for high-accuracy quantitative analysis of gases has been developed and validated by the analysis of standard mixtures of carbon dioxide in nitrogen. The method does not require certified isotopic reference materials and does not require direct measurements of the highly enriched spike. The relative uncertainty of the method is shown to be 0.2%. Reproduced with the permission of Her Majesty's Stationery Office. Copyright Crown copyright 2003.

Novel hybrid isotope separation scheme and apparatus

DOEpatents

Maya, Jakob

1991-01-01

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

Study of five-dimensional potential-energy surfaces for actinide isotopes by the macroscopic-microscopic method

NASA Astrophysics Data System (ADS)

Fan, T. S.; Wang, Z. M.; Zhu, X.; Zhu, W. J.; Zhong, C. L.

2017-09-01

In this work, the nuclear potential-energy of the deformed nuclei as a function of shape coordinates is calculated in a five-dimensional (5D) parameter space of the axially symmetric generalized Lawrence shapes, on the basis of the macroscopic-microscopic method. The liquid-drop part of the nuclear energy is calculated according to the Myers-Swiatecki model and the Lublin-Strasbourg-drop (LSD) formula. The Woods-Saxon and the folded-Yukawa potentials for deformed nuclei are used for the shell and pairing corrections of the Strutinsky-type. The pairing corrections are calculated at zero temperature, T, related to the excitation energy. The eigenvalues of Hamiltonians for protons and neutrons are found by expanding the eigen-functions in terms of harmonic-oscillator wave functions of a spheroid. Then the BCS pair is applied on the smeared-out single-particle spectrum. By comparing the results obtained by different models, the most favorable combination of the macroscopic-microscopic model is known as the LSD formula with the folded-Yukawa potential. Potential-energy landscapes for actinide isotopes are investigated based on a grid of more than 4,000,000 deformation points and the heights of static fission barriers are obtained in terms of a double-humped structure on the full 5D parameter space. In order to locate the ground state shapes, saddle points, scission points and optimal fission path on the calculated 5D potential-energy surface, the falling rain algorithm and immersion method are designed and implemented. The comparison of our results with available experimental data and others' theoretical results confirms the reliability of our calculations.

Testing sequential extraction methods for the analysis of multiple stable isotope systems from a bone sample

NASA Astrophysics Data System (ADS)

Sahlstedt, Elina; Arppe, Laura

2017-04-01

Stable isotope composition of bones, analysed either from the mineral phase (hydroxyapatite) or from the organic phase (mainly collagen) carry important climatological and ecological information and are therefore widely used in paleontological and archaeological research. For the analysis of the stable isotope compositions, both of the phases, hydroxyapatite and collagen, have their more or less well established separation and analytical techniques. Recent development in IRMS and wet chemical extraction methods have facilitated the analysis of very small bone fractions (500 μg or less starting material) for PO43-O isotope composition. However, the uniqueness and (pre-) historical value of each archaeological and paleontological finding lead to preciously little material available for stable isotope analyses, encouraging further development of microanalytical methods for the use of stable isotope analyses. Here we present the first results in developing extraction methods for combining collagen C- and N-isotope analyses to PO43-O-isotope analyses from a single bone sample fraction. We tested sequential extraction starting with dilute acid demineralization and collection of both collagen and PO43-fractions, followed by further purification step by H2O2 (PO43-fraction). First results show that bone sample separates as small as 2 mg may be analysed for their δ15N, δ13C and δ18OPO4 values. The method may be incorporated in detailed investigation of sequentially developing skeletal material such as teeth, potentially allowing for the investigation of interannual variability in climatological/environmental signals or investigation of the early life history of an individual.

An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry.

PubMed

Rua-Ibarz, Ana; Bolea-Fernandez, Eduardo; Vanhaecke, Frank

2016-01-01

Mercury (Hg) isotopic analysis via multi-collector inductively coupled plasma (ICP)-mass spectrometry (MC-ICP-MS) can provide relevant biogeochemical information by revealing sources, pathways, and sinks of this highly toxic metal. In this work, the capabilities and limitations of two different sample introduction systems, based on pneumatic nebulization (PN) and cold vapor generation (CVG), respectively, were evaluated in the context of Hg isotopic analysis via MC-ICP-MS. The effect of (i) instrument settings and acquisition parameters, (ii) concentration of analyte element (Hg), and internal standard (Tl)-used for mass discrimination correction purposes-and (iii) different mass bias correction approaches on the accuracy and precision of Hg isotope ratio results was evaluated. The extent and stability of mass bias were assessed in a long-term study (18 months, n = 250), demonstrating a precision ≤0.006% relative standard deviation (RSD). CVG-MC-ICP-MS showed an approximately 20-fold enhancement in Hg signal intensity compared with PN-MC-ICP-MS. For CVG-MC-ICP-MS, the mass bias induced by instrumental mass discrimination was accurately corrected for by using either external correction in a sample-standard bracketing approach (SSB) or double correction, consisting of the use of Tl as internal standard in a revised version of the Russell law (Baxter approach), followed by SSB. Concomitant matrix elements did not affect CVG-ICP-MS results. Neither with PN, nor with CVG, any evidence for mass-independent discrimination effects in the instrument was observed within the experimental precision obtained. CVG-MC-ICP-MS was finally used for Hg isotopic analysis of reference materials (RMs) of relevant environmental origin. The isotopic composition of Hg in RMs of marine biological origin testified of mass-independent fractionation that affected the odd-numbered Hg isotopes. While older RMs were used for validation purposes, novel Hg isotopic data are provided for the latest generations of some biological RMs.

Salinity increases in the navajo aquifer in southeastern Utah

USGS Publications Warehouse

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

1994-01-01

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

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.

Results on neutrinoless double-β decay of 76Ge from phase I of the GERDA experiment.

PubMed

Agostini, M; Allardt, M; Andreotti, E; Bakalyarov, A M; Balata, M; Barabanov, I; Barnabé Heider, M; Barros, N; Baudis, L; Bauer, C; Becerici-Schmidt, N; Bellotti, E; Belogurov, S; Belyaev, S T; Benato, G; Bettini, A; Bezrukov, L; Bode, T; Brudanin, V; Brugnera, R; Budjáš, D; Caldwell, A; Cattadori, C; Chernogorov, A; Cossavella, F; Demidova, E V; Domula, A; Egorov, V; Falkenstein, R; Ferella, A; Freund, K; Frodyma, N; Gangapshev, A; Garfagnini, A; Gotti, C; Grabmayr, P; Gurentsov, V; Gusev, K; Guthikonda, K K; Hampel, W; Hegai, A; Heisel, M; Hemmer, S; Heusser, G; Hofmann, W; Hult, M; Inzhechik, L V; Ioannucci, L; Janicskó Csáthy, J; Jochum, J; Junker, M; Kihm, T; Kirpichnikov, I V; Kirsch, A; Klimenko, A; Knöpfle, K T; Kochetov, O; Kornoukhov, V N; Kuzminov, V V; Laubenstein, M; Lazzaro, A; Lebedev, V I; Lehnert, B; Liao, H Y; Lindner, M; Lippi, I; Liu, X; Lubashevskiy, A; Lubsandorzhiev, B; Lutter, G; Macolino, C; Machado, A A; Majorovits, B; Maneschg, W; Misiaszek, M; Nemchenok, I; Nisi, S; O'Shaughnessy, C; Pandola, L; Pelczar, K; Pessina, G; Pullia, A; Riboldi, S; Rumyantseva, N; Sada, C; Salathe, M; Schmitt, C; Schreiner, J; Schulz, O; Schwingenheuer, B; Schönert, S; Shevchik, E; Shirchenko, M; Simgen, H; Smolnikov, A; Stanco, L; Strecker, H; Tarka, M; Ur, C A; Vasenko, A A; Volynets, O; von Sturm, K; Wagner, V; Walter, M; Wegmann, A; Wester, T; Wojcik, M; Yanovich, E; Zavarise, P; Zhitnikov, I; Zhukov, S V; Zinatulina, D; Zuber, K; Zuzel, G

2013-09-20

Neutrinoless double beta decay is a process that violates lepton number conservation. It is predicted to occur in extensions of the standard model of particle physics. This Letter reports the results from phase I of the Germanium Detector Array (GERDA) experiment at the Gran Sasso Laboratory (Italy) searching for neutrinoless double beta decay of the isotope (76)Ge. Data considered in the present analysis have been collected between November 2011 and May 2013 with a total exposure of 21.6 kg yr. A blind analysis is performed. The background index is about 1 × 10(-2) counts/(keV kg yr) after pulse shape discrimination. No signal is observed and a lower limit is derived for the half-life of neutrinoless double beta decay of (76)Ge, T(1/2)(0ν) >2.1 × 10(25) yr (90% C.L.). The combination with the results from the previous experiments with (76)Ge yields T(1/2)(0ν)>3.0 × 10(25) yr (90% C.L.).

Isotopic tracing of perchlorate in the environment

USGS Publications Warehouse

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

2012-01-01

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

Determination of compound-specific Hg isotope ratios from transient signals using gas chromatography coupled to multicollector inductively coupled plasma mass spectrometry (MC-ICP/MS).

PubMed

Dzurko, Mark; Foucher, Delphine; Hintelmann, Holger

2009-01-01

MeHg and inorganic Hg compounds were measured in aqueous media for isotope ratio analysis using aqueous phase derivatization, followed by purge-and-trap preconcentration. Compound-specific isotope ratio measurements were performed by gas chromatography interfaced to MC-ICP/MS. Several methods of calculating isotope ratios were evaluated for their precision and accuracy and compared with conventional continuous flow cold vapor measurements. An apparent fractionation of Hg isotopes was observed during the GC elution process for all isotope pairs, which necessitated integration of signals prior to the isotope ratio calculation. A newly developed average peak ratio method yielded the most accurate isotope ratio in relation to values obtained by a continuous flow technique and the best reproducibility. Compound-specific isotope ratios obtained after GC separation were statistically not different from ratios measured by continuous flow cold vapor measurements. Typical external uncertainties were 0.16 per thousand RSD (n = 8) for the (202)Hg(/198)Hg ratio of MeHg and 0.18 per thousand RSD for the same ratio in inorganic Hg using the optimized operating conditions. Using a newly developed reference standard addition method, the isotopic composition of inorganic Hg and MeHg synthesized from this inorganic Hg was measured in the same run, obtaining a value of delta (202)Hg = -1.49 +/- 0.47 (2SD; n = 10). For optimum performance a minimum mass of 2 ng per Hg species should be introduced onto the column.

THEORETICAL AND EXPERIMENTAL ASPECTS OF ISOTOPIC FRACTIONATION.

USGS Publications Warehouse

O'Neil, James R.

1986-01-01

Essential to the interpretation of natural variations of light stable isotope ratios is knowledge of the magnitude and temperature dependence of isotopic fractionation factors between the common minerals and fluids. These fractionation factors are obtained in three ways: (1) Semi-empirical calculations using spectroscopic data and the methods of statistical mechanics. (2) Laboratory calibration studies. (3) Measurements of natural samples whose formation conditions are well-known or highly constrained. In this chapter methods (1) and (2) are evaluated and a review is given of the present state of knowledge of the theory of isotopic fractionation and the fraction that influence the isotopic properties of minerals.

Precise and traceable carbon isotope ratio measurements by multicollector ICP-MS: what next?

PubMed

Santamaria-Fernandez, Rebeca

2010-06-01

This article reviews recent developments in the use of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) to provide high-precision carbon isotope ratio measurements. MC-ICP-MS could become an alternative method to isotope ratio mass spectrometry (IRMS) for rapid carbon isotope ratio determinations in organic compounds and characterisation and certification of isotopic reference materials. In this overview, the advantages, drawbacks and potential of the method for future applications are critically discussed. Furthermore, suggestions for future improvements in terms of precision and sensitivity are made. No doubt, this is an exciting analytical challenge and, as such, hurdles will need to be cleared.

On microscopic theory of radiative nuclear reaction characteristics

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

Kamerdzhiev, S. P.; Achakovskiy, O. I., E-mail: oachakovskiy@ippe.ru; Avdeenkov, A. V.

2016-07-15

A survey of some results in the modern microscopic theory of properties of nuclear reactions with gamma rays is given. First of all, we discuss the impact of Phonon Coupling (PC) on the Photon Strength Function (PSF) because it represents the most natural physical source of additional strength found for Sn isotopes in recent experiments that could not be explained within the standard HFB + QRPA approach. The self-consistent version of the Extended Theory of Finite Fermi Systems in the Quasiparticle Time Blocking Approximation is applied. It uses the HFB mean field and includes both the QRPA and PC effectsmore » on the basis of the SLy4 Skyrme force. With our microscopic E1 PSFs, the following properties have been calculated for many stable and unstable even–even semi-magic Sn and Ni isotopes as well as for double-magic {sup 132}Sn and {sup 208}Pb using the reaction codes EMPIRE and TALYS with several Nuclear Level Density (NLD) models: (1) the neutron capture cross sections; (2) the corresponding neutron capture gamma spectra; (3) the average radiative widths of neutron resonances. In all the properties considered, the PC contribution turned out to be significant, as compared with the standard QRPA one, and necessary to explain the available experimental data. The results with the phenomenological so-called generalized superfluid NLD model turned out to be worse, on the whole, than those obtained with the microscopic HFB + combinatorial NLD model. The very topical question about the M1 resonance contribution to PSFs is also discussed.Finally, we also discuss the modern microscopic NLD models based on the self-consistent HFB method and show their relevance to explain the experimental data as compared with the phenomenological models. The use of these self-consistent microscopic approaches is of particular relevance for nuclear astrophysics, but also for the study of double-magic nuclei.« less

Escherichia coli cell-free protein synthesis and isotope labeling of mammalian proteins.

PubMed

Terada, Takaho; Yokoyama, Shigeyuki

2015-01-01

This chapter describes the cell-free protein synthesis method, using an Escherichia coli cell extract. This is a cost-effective method for milligram-scale protein production and is particularly useful for the production of mammalian proteins, protein complexes, and membrane proteins that are difficult to synthesize by recombinant expression methods, using E. coli and eukaryotic cells. By adjusting the conditions of the cell-free method, zinc-binding proteins, disulfide-bonded proteins, ligand-bound proteins, etc., may also be produced. Stable isotope labeling of proteins can be accomplished by the cell-free method, simply by using stable isotope-labeled amino acid(s) in the cell-free reaction. Moreover, the cell-free protein synthesis method facilitates the avoidance of stable isotope scrambling and dilution over the recombinant expression methods and is therefore advantageous for amino acid-selective stable isotope labeling. Site-specific stable isotope labeling is also possible with a tRNA molecule specific to the UAG codon. By the cell-free protein synthesis method, coupled transcription-translation is performed from a plasmid vector or a PCR-amplified DNA fragment encoding the protein. A milligram quantity of protein can be produced with a milliliter-scale reaction solution in the dialysis mode. More than a thousand solution structures have been determined by NMR spectroscopy for uniformly labeled samples of human and mouse functional domain proteins, produced by the cell-free method. Here, we describe the practical aspects of mammalian protein production by the cell-free method for NMR spectroscopy. © 2015 Elsevier Inc. All rights reserved.

Reconciling Isotopic Partitioning Estimates of Moisture Fluxes in Semi-arid Landscapes Through a New Modeling Approach for Evaporation

NASA Astrophysics Data System (ADS)

Kaushik, A.; Berkelhammer, M. B.; O'Neill, M.; Noone, D.

2017-12-01

The partitioning of land surface latent heat flux into evaporation and transpiration remains a challenging problem despite a basic understanding of the underlying mechanisms. Water isotopes are useful tracers for separating evaporation and transpiration contributions because E and T have distinct isotopic ratios. Here we use the isotope-based partitioning method at a semi-arid grassland tall-tower site in Colorado. Our results suggest that under certain conditions evaporation cannot be isotopically distinguished from transpiration without modification of existing partitioning techniques. Over a 4-year period, we measured profiles of stable oxygen and hydrogen isotope ratios of water vapor from the surface to 300 m and soil water down to 1 m along with standard meteorological fluxes. Using these data, we evaluated the contributions of rainfall, equilibration, surface water vapor exchange and sub-surface vapor diffusion to the isotopic composition of evapotranspiration (ET). Applying the standard isotopic approach to find the transpiration portion of ET (i.e., T/ET), we see a significant discrepancy compared with a method to constrain T/ET based on gross primary productivity (GPP). By evaluating the kinetic fractionation associated with soil evaporation and vapor diffusion we find that a significant proportion (58-84%) of evaporation following precipitation is non-fractionating. This is possible when water from isolated soil layers is being nearly completely evaporated. Non-fractionating evaporation looks isotopically like transpiration and therefore leads to an overestimation of T/ET. Including non-fractionating evaporation reconciles the isotope-based partitioning estimates of T/ET with the GPP method, and may explain the overestimation of T/ET from isotopes compared to other methods. Finally, we examine the application of non-fractionating evaporation to other boundary layer moisture flux processes such as rain evaporation, where complete evaporation of smaller drop pools may produce a similarly weaker kinetic effect.

Novel hybrid isotope separation scheme and apparatus

DOEpatents

Maya, J.

1991-06-18

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

Formation of Kokumi-Enhancing γ-Glutamyl Dipeptides in Parmesan Cheese by Means of γ-Glutamyltransferase Activity and Stable Isotope Double-Labeling Studies.

PubMed

Hillmann, Hedda; Behr, Jürgen; Ehrmann, Matthias A; Vogel, Rudi F; Hofmann, Thomas

2016-03-02

Recently, γ-glutamyl dipeptides (γ-GPs) were found to be responsible for the attractive kokumi flavor of Parmesan cheese (PC). Quantitation of γ-GPs and their parent amino acids in 13-, 24-, and 30-month ripened PC samples by LC-MS/MS and stable isotope dilution analysis (SIDA), in-cheese (13)C-labeling studies, followed by analysis of the γ-glutamyl transferase (GGT) activity revealed γ-GPs to be generated most efficiently after 24 months of ripening by a GGT-catalyzed transfer of the γ-glutamyl moiety of L-glutamine onto various acceptor amino acids released upon casein proteolysis. Following the identification of milk as a potential GGT source in PC, the functionality of the milk's GGT to generate the target γ-GPs was validated by stable isotope double-labeling (SIDL) experiments. Therefore, raw and heat-treated milk samples were incubated with L-glutamine-[U-(13)C] and acceptor amino acids (X) and the hetero- (γ-Glu-[(13)C5]-X) and homotranspeptidation products (γ-Glu-Gln-[(13)C10]) were quantitated by LC-MS/MS-SIDA using γ-Glu-Ala-[(13)C3] as the internal standard. High GGT activity to generate the γ-GPs and preference for L-phenylalanine and L-methionine as acceptor amino acids were found in raw milk and milk samples heat-treated for 10 min up to a maximum of 65 °C. In comparison, GGT activity and SIDL studies performed with inoculated Lactobacillus strains, including Lactobacillus harbinensis and Lactobacillus casei identified in PC by means of 16S rRNA gene sequencing, did not show any significant GGT activity and unequivocally demonstrated unpasteurized cow's milk, rather than microorganisms, as a key factor in γ-glutamyl dipeptide generation in Parmesan cheese.

Isotopically nonstationary 13C flux analysis of changes in Arabidopsis thaliana leaf metabolism due to high light acclimation

DOE PAGES

Ma, Fangfang; Jazmin, Lara J.; Young, Jamey D.; ...

2014-11-03

Improving plant productivity is an important aim for metabolic engineering. There are few comprehensive methods that quantitatively describe leaf metabolism, although such information would be valuable for increasing photosynthetic capacity, enhancing biomass production, and rerouting carbon flux toward desirable end products. Isotopically nonstationary metabolic flux analysis (INST-MFA) has been previously applied to map carbon fluxes in photoautotrophic bacteria, which involves model-based regression of transient 13C-labeling patterns of intracellular metabolites. However, experimental and computational difficulties have hindered its application to terrestrial plant systems. Here, we performed in vivo isotopic labeling of Arabidopsis thaliana rosettes with 13CO 2 and estimated fluxes throughoutmore » leaf photosynthetic metabolism by INST-MFA. Plants grown at 200 µmol m $-$2s $-$1 light were compared with plants acclimated for 9 d at an irradiance of 500 µmol∙m $-$2∙s $-$1. Approximately 1,400 independent mass isotopomer measurements obtained from analysis of 37 metabolite fragment ions were regressed to estimate 136 total fluxes (54 free fluxes) under each condition. The results provide a comprehensive description of changes in carbon partitioning and overall photosynthetic flux after long-term developmental acclimation of leaves to high light. Despite a doubling in the carboxylation rate, the photorespiratory flux increased from 17 to 28% of net CO 2 assimilation with high-light acclimation (Vc/Vo: 3.5:1 vs. 2.3:1, respectively). In conclusion, this study highlights the potential of 13C INST-MFA to describe emergent flux phenotypes that respond to environmental conditions or plant physiology and cannot be obtained by other complementary approaches.« less

Equilibrium properties of dense hydrogen isotope gases based on the theory of simple fluids.

PubMed

Kowalczyk, Piotr; MacElroy, J M D

2006-08-03

We present a new method for the prediction of the equilibrium properties of dense gases containing hydrogen isotopes. The proposed approach combines the Feynman-Hibbs effective potential method and a deconvolution scheme introduced by Weeks et al. The resulting equations of state and the chemical potentials as functions of pressure for each of the hydrogen isotope gases depend on a single set of Lennard-Jones parameters. In addition to its simplicity, the proposed method with optimized Lennard-Jones potential parameters accurately describes the equilibrium properties of hydrogen isotope fluids in the regime of moderate temperatures and pressures. The present approach should find applications in the nonlocal density functional theory of inhomogeneous quantum fluids and should also be of particular relevance to hydrogen (clean energy) storage and to the separation of quantum isotopes by novel nanomaterials.

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

PubMed

Centler, Florian; Heße, Falk; Thullner, Martin

2013-09-01

At field sites with varying redox conditions, different redox-specific microbial degradation pathways contribute to total contaminant degradation. The identification of pathway-specific contributions to total contaminant removal is of high practical relevance, yet difficult to achieve with current methods. Current stable-isotope-fractionation-based techniques focus on the identification of dominant biodegradation pathways under constant environmental conditions. We present an approach based on dual stable isotope data to estimate the individual contributions of two redox-specific pathways. We apply this approach to carbon and hydrogen isotope data obtained from reactive transport simulations of an organic contaminant plume in a two-dimensional aquifer cross section to test the applicability of the method. To take aspects typically encountered at field sites into account, additional simulations addressed the effects of transverse mixing, diffusion-induced stable-isotope fractionation, heterogeneities in the flow field, and mixing in sampling wells on isotope-based estimates for aerobic and anaerobic pathway contributions to total contaminant biodegradation. Results confirm the general applicability of the presented estimation method which is most accurate along the plume core and less accurate towards the fringe where flow paths receive contaminant mass and associated isotope signatures from the core by transverse dispersion. The presented method complements the stable-isotope-fractionation-based analysis toolbox. At field sites with varying redox conditions, it provides a means to identify the relative importance of individual, redox-specific degradation pathways. © 2013.

Structural phase transition in d-benzil characterised by capacitance measurements and neutron powder diffraction

NASA Astrophysics Data System (ADS)

Goossens, D. J.; Wu, Xiaodong; Prior, M.

2005-12-01

The ferroelectric phase transition in deuterated benzil, C 14H 10O 2, has been studied using capacitance measurements and neutron powder diffraction. Hydrogenous benzil shows a phase transition at 83.5 K from a high temperature P3 121 phase to a cell-doubled P2 1 phase. The phase transition in d-benzil occurs at 88.1 K, a small isotope effect. Neutron powder diffraction was consistent with a low temperature phase of space group P2 1. Upon deuteration the transition remained first-order and the dynamics of the phenyl ring dominated the behaviour. The isotope effect can be attributed to the difference in mass and moment of inertia between C 6H 5 and C 6D 5.

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

PubMed

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

2008-10-01

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

Barium Tagging n Solid Xenon for nEXO Neutrinoless Double Beta Decay

NASA Astrophysics Data System (ADS)

Walton, Tim; Chambers, Chris; Craycraft, Adam; Fairbank, William; nEXO Collaboration

2015-04-01

nEXO is a next-generation experiment designed to search for neutrinoless double beta decay of the isotope Xe136 in a liquid xenon time projection chamber. Positive observation of this decay would determine the nature of the neutrino to be a Majorana particle. Since the daughter of this decay is barium (Ba136), detecting the presence of Ba136 at a decay site (called ``barium tagging'') would provide strong rejection of backgrounds in the search for this decay. This would involve detecting a single barium ion from within a macroscopic volume of liquid xenon. This technique may be available for a second phase of the nEXO detector and sensitivity beyond the inverted hierarchy to neutrino oscillations. Several methods of barium tagging are being explored by the nEXO collaboration, but here we present a method of trapping the barium ion/atom (it may neutralize) in solid xenon (SXe) at the end of a cold probe, and then detecting the ion/atom by its fluorescence in the SXe. Our group at CSU has been studying the fluorescence of Ba in SXe by laser excitation, in order to ultimately detect a single Ba +/Ba in a SXe sample. We present studies of fluorescence signals, as well as recent results on imaging small numbers of Ba atoms in SXe, in a focused laser region. This work is supported by grants from the National Science Foundation and the Department of Energy.

On-line Differential Thermal Isotope Analysis: A New Method for Measuring Oxygen and Hydrogen Isotopes of Hydration Water in Minerals

NASA Astrophysics Data System (ADS)

Bauska, T.; Hodell, D. A.; Walters, G.

2016-12-01

Oxygen (16O,17O,18O) and hydrogen (H,D) isotopes of hydration water in minerals provide a rich source of information about the conditions under which hydrated minerals form on Earth and other planetary bodies (e.g. Mars). We have developed a new method for measuring different types of bonded water (e.g., molecular, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves step heating a mineral sample, precisely measuring the weight loss and enthalpy as the sample undergoes dehydration and dehydroxylation, whilst simultaneously determining the oxygen and hydrogen isotopes of the water vapor evolved from the mineral sample by cavity ring-down laser spectroscopy (CRDS). Nitrogen carrier gas is used to transfer the sample from the TG to the CRDS via a heated line and interface box. The interface includes the capability of (i) cryogenic trapping discrete types of water for samples containing small amounts of water; (ii) injecting small quantities of water of known isotopic value for calibration; and (iii) converting volatile organic compounds to nascent amounts of water using a catalyst. The CRDS continually measures water vapor concentration in the optical cavity and hydrogen and oxygen isotope ratios. Isotopic values are calculated by integrating the product of the water amount and its isotopic value for the separated peaks after correcting for background. Precision of the method was estimated by comparing isotope results of total water for gypsum measured by DTIA with our conventional method of extraction and analysis (Gázquez et al., 2015. Rapid Communications in Mass Spectrometry, 29, 1997-2006). Errors for the isotopic values of total hydration water vary between ±0.08 and ±0.34 ‰ for δ18O and between ±0.16 and ±0.86 ‰ for δD. We demonstrate the application of the DTIA method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous silica (opal, glass, chert). The DTIA method has wide ranging application for addressing fundamental problems across many disciplines in Earth and Planetary Sciences, including: paleoclimatology, sedimentology, volcanology, water exchange between the solid earth and hydrosphere, and water on Mars and other planetary bodies.

Comparing floral and isotopic paleoelevation estimates: Examples from the western United States

NASA Astrophysics Data System (ADS)

Hyland, E. G.; Huntington, K. W.; Sheldon, N. D.; Smith, S. Y.; Strömberg, C. A. E.

2016-12-01

Describing paleoelevations is crucial to understanding tectonic processes and deconvolving the effects of uplift and climate on environmental change in the past. Decades of work has gone into estimating past elevation from various proxy archives, particularly using modern relationships between elevation and temperature, floral assemblage compositions, or oxygen isotope values. While these methods have been used widely and refined through time, they are rarely applied in tandem; here we provide two examples from the western United States using new multiproxy methods: 1) combining clumped isotopes and macrofloral assemblages to estimate paleoelevations along the Colorado Plateau, and 2) combining oxygen isotopes and phytolith methods to estimate paleoelevations within the greater Yellowstone region. Clumped isotope measurements and refined floral coexistence methods from sites on the northern Colorado Plateau like Florissant and Creede (CO) consistently estimate low (< 2km) elevations through the Eocene/Oligocene, suggesting slower uplift and a south-north propagation of the plateau. Oxygen isotope measurements and C4 phytolith estimates from sites surrounding the Yellowstone hotspot consistently estimate moderate uplift (0.2-0.7km) propagating along the hotspot track, suggesting migrating dynamic topography associated with the region. These examples provide support for the emerging practice of using multiproxy methods to estimate paleoelevations for important time periods, and can help integrate environmental and tectonic records of the past.

Carbon and Nitrogen Sources for Shrimp Postlarvae Fed Natural Diets from a Tropical Mangrove System

NASA Astrophysics Data System (ADS)

Dittel, A. I.; Epifanio, C. E.; Cifuentes, L. A.; Kirchman, D. L.

1997-11-01

Postlarvae ofPenaeus vannameiwere fed various diets in order to examine the importance of detritus and other possible prey items in supporting postlarval growth. Stable isotopes (C and N) were used to determine the carbon and nitrogen source of the prey in the various diets. The zooplankton diet contained mostly copepods. The subtidal detritus treatment consisted mostly of plant material whereas the diets from both intertidal sites contained a mixture of plant detritus and associated meiofauna. Postlarvae reared on zooplankton and detritus plus meiofauna diets more than tripled their weight during a 6-day period. In contrast, postlarvae fed the detritus diet barely doubled their weight. Based on isotopic composition, postlarvae appear to obtain their carbon and nitrogen from various food sources. Postlarvae were enriched by 0·4‰ in13C and 2·7‰ in15N relative to the zooplankton diet, which is consistent with isotopic fractionation between successive trophic levels. In turn, the isotopic signal of the zooplankton was consistent with phytoplankton being the initial source of organic matter. In contrast, mean δ13C values of the shrimp fed detritus plus meiofauna were significantly different from their respective diets. Isotopic ratios of the postlarvae fed the mixed diet from Chomes were two trophic levels above benthic algae suggesting that the shrimp preyed on organisms that derived their carbon and nitrogen from benthic algae and/or phytoplankton.

Palaeoclimate signal recorded by stable isotopes in cave ice: a modeling approach

NASA Astrophysics Data System (ADS)

Perşoiu, A.; Bojar, A.-V.

2012-04-01

Ice accumulations in caves preserve a large variety of geochemical information as candidate proxies for both past climate and environmental changes, one of the most significant being the stable isotopic composition of the ice. A series of recent studies have targeted oxygen and hydrogen stable isotopes in cave ice as proxies for past air temperatures, but the results are far from being as straightforward as they are in high latitude and altitude glaciers and ice caps. The main problems emerging from these studies are related to the mechanisms of cave ice formation (i.e., freezing of water) and post-formation processes (melting and refreezing), which both alter the original isotopic signal in water. Different methods have been put forward to solve these issues and a fair understanding of the present-day link between stable isotopes in precipitation and cave ice exists now. However, the main issues still lays unsolved: 1) is it possible to extend this link to older ice and thus reconstruct past changes in air temperature?; 2) to what extent are ice dynamics processes modifying the original climatic signal and 3) what is the best method to be used in extracting a climatic signal from stable isotopes in cave ice? To respond to these questions, we have conducted a modeling experiment, in which a theoretical cave ice stable isotope record was constructed using present-day observations on stable isotope behavior in cave ice and ice dynamics, and different methods (presently used for both polar and cave glaciers), were used to reconstruct the original, known, isotopic values. Our results show that it is possible to remove the effects of ice melting and refreezing on stable isotope composition of cave ice, and thus reconstruct the original isotopic signal, and further the climatic one.

A novel ion-exclusion chromatography-mass spectrometry method to measure concentrations and cycling rates of carbohydrates and amino sugars in freshwaters.

PubMed

Horňák, Karel; Pernthaler, Jakob

2014-10-24

The concentrations of free neutral carbohydrates and amino sugars were determined in freshwater samples of distinct matrix complexity, including meso-, eu- and dystrophic lakes and ponds, using high-performance ion-exclusion chromatography (HPIEC) coupled to mass spectrometry (MS). In contrast to other methods, our approach allowed the quantification of free neutral carbohydrates and amino sugars at low nM concentrations without derivatization, de-salting or pre-concentration. New sample preparation procedures were applied prior to injection employing syringe and hollow fiber filtration. Analytes were separated on a strong cation exchange resin under 100% aqueous conditions using 0.1% formic acid as a mobile phase. To minimize background noise in MS, analytes were detected in a multiple reaction monitoring scan mode with double ion filtering. Detection limits of carbohydrates and amino sugars ranged between 0.2 and 2nM at a signal-to-noise ratio >5. Error ranged between 1 and 12% at 0.5-500nM levels. Using a stable isotope dilution approach, both the utilization and recycling of glucose in Lake Zurich was observed. In contrast, N-acetyl-glucosamine was equally rapidly consumed but there was no visible de novo production. The simple and rapid sample preparation makes our protocol suitable for routine analyses of organic compounds in freshwater samples. Application of stable isotope tracers along with accurate measures of carbohydrate and amino sugar concentrations enables novel insights into the compound in situ dynamics. Copyright © 2014 Elsevier B.V. All rights reserved.

Sterols and stanols as novel tracers of waterbird population dynamics in freshwater ponds.

PubMed

Hargan, Kathryn E; Stewart, Emily M; Michelutti, Neal; Grooms, Christopher; Kimpe, Linda E; Mallory, Mark L; Smol, John P; Blais, Jules M

2018-04-25

With the expansion of urban centres in the mid-twentieth century and the post-1970 decrease in pesticides, populations of double-crested cormorants ( Phalacrocorax auritus ) and ring-billed gulls ( Larus delawarensis ) around Lake Ontario (Canada and USA) have rapidly rebounded, possibly to unprecedented numbers. Along with the use of traditional palaeolimnological methods (e.g. stable isotopes, biological proxies), we now have the capacity to develop specific markers for directly tracking the presence of waterbirds on nesting islands. Here, we apply the use of lipophilic sterols and stanols from both plant and animal-faecal origins as a reliable technique, independent of traditional isotopic methods, for pinpointing waterbird arrival and population growth over decadal timescales. Sterol and stanol concentrations measured in the guano samples of waterbird species were highly variable within a species and between the three species of waterbirds examined. However, cholesterol was the dominant sterol in guano, and phytosterols were also high in ring-billed gull guano. This variability highlights a specialist piscivorous diet for cormorants compared to a generalist, omnivorous diet for gulls, which may now often include grain and invertebrates from agricultural fields. A ratio that includes cholesterol and sitosterol plus their aerobically reduced products (cholestanol, stigmastanol) best explained the present range of bird abundance across the islands and was significantly correlated to sedimentary δ 15 N. Overall, we demonstrate the use of sterols and stanols as a direct means for tracking the spatial and temporal presence of waterbirds on islands across Lake Ontario, and probably elsewhere. © 2018 The Author(s).

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, Christopher A.; Worden, Earl F.

1995-01-01

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

The MAJORANA DEMONSTRATOR Neutrinoless Double-Beta Decay Experiment

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

Abgrall, N.; Aguayo, Estanislao; Avignone, Frank T.

2014-06-01

The MAJORANA DEMONSTRATOR will search for the neutrinoless double-beta (ββ(0ν)) decay of the isotope 76Ge with a mixed array of enriched and natural germanium detectors. The observation of this rare decay would indicate that the neutrino is its own antiparticle, demonstrate that lepton number is not conserved, and provide information on the absolute mass scale of the neutrino. The DEMONSTRATOR is being assembled at the 4850-foot level of the Sanford Underground Research Facility in Lead, South Dakota. The array will be situated in a low-background environment and surrounded by passive and active shielding. Here we describe the science goals ofmore » the DEMONSTRATOR and the details of its design.« less

The MAJORANA DEMONSTRATOR Neutrinoless Double-Beta Decay Experiment

DOE PAGES

Abgrall, N.; Aguayo, E.; Avignone, F. T.; ...

2014-01-29

Tmore » he M ajorana D emonstrator will search for the neutrinoless double-beta ( β β 0 ν ) decay of the isotope Ge with a mixed array of enriched and natural germanium detectors. he observation of this rare decay would indicate that the neutrino is its own antiparticle, demonstrate that lepton number is not conserved, and provide information on the absolute mass scale of the neutrino. he D emonstrator is being assembled at the 4850-foot level of the Sanford Underground Research Facility in Lead, South Dakota. he array will be situated in a low-background environment and surrounded by passive and active shielding. Here we describe the science goals of the D emonstrator and the details of its design.« less

Water isotope partitioning and ecohydrologic separation in mixed conifer forest explored with a centrifugation water extraction method

NASA Astrophysics Data System (ADS)

Bowers, W.; Mercer, J.; Pleasants, M.; Williams, D. G.

2017-12-01

Isotopic partitioning of water within soil into tightly and loosely bound fractions has been proposed to explain differences between isotopic water sources used by plants and those that contribute to streams and ground water, the basis for the "two water worlds" hypothesis. We examined the isotope ratio values of water in trees, bulk soil, mobile water collected from soil lysimeters, stream water, and GW at three different hillslopes in a mixed conifer forest in southeastern Wyoming, USA. Hillslopes differed in aspect and topographic position with corresponding differences in surface energy balance, snowmelt timing, and duration of soil moisture during the dry summer. The isotopic results support the partitioning of water within the soil; trees apparently used a different pool of water for transpiration than that recovered from soil lysimeters and the source was not resolved with the isotopic signature of the water that was extracted from bulk soil via cryogenic vacuum distillation. Separating and measuring the isotope ratios values in these pools would test the assumption that the tightly bound water within the soil has the same isotopic signature as the water transpired by the trees. We employed a centrifugation approach to separate water within the soil held at different tensions by applying stepwise increases in rotational velocity and pressures to the bulk soil samples. Effluent and the remaining water (cryogenically extracted) at each step were compared. We first applied the centrifugation method in a simple lab experiment using sandy loam soil and separate introductions of two isotopically distinct waters. We then applied the method to soil collected from the montane hillslopes. For the lab experiment, we predicted that effluents would have distinct isotopic signatures, with the last effluent and extracted water more closely representing the isotopic signature of the first water applied. For our field samples, we predicted that the isotopic signature of the water discharged in the last centrifuge step and final extraction would more closely represent the isotopic signature of water extracted from trees. Understanding the isotopic partitioning of water within soil is important for interpreting plant water isotope values within the context of the "two water worlds" hypothesis.

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.

SAIL--stereo-array isotope labeling.

PubMed

Kainosho, Masatsune; Güntert, Peter

2009-11-01

Optimal stereospecific and regiospecific labeling of proteins with stable isotopes enhances the nuclear magnetic resonance (NMR) method for the determination of the three-dimensional protein structures in solution. Stereo-array isotope labeling (SAIL) offers sharpened lines, spectral simplification without loss of information and the ability to rapidly collect and automatically evaluate the structural restraints required to solve a high-quality solution structure for proteins up to twice as large as before. This review gives an overview of stable isotope labeling methods for NMR spectroscopy with proteins and provides an in-depth treatment of the SAIL technology.

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 of biological isotope fractionation in medical studies, paleoclimatic and paleoceanographic, and other terrestrial as well as extraterrestrial investigations. 2009 Wiley Periodicals, Inc.

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 biodegradation. This study sets standards for further application of these techniques to distinguish sources and track degradation processes in the sub-surface.

On the Use of Biomineral Oxygen Isotope Data to Identify Human Migrants in the Archaeological Record: Intra-Sample Variation, Statistical Methods and Geographical Considerations

PubMed Central

Lightfoot, Emma; O’Connell, Tamsin C.

2016-01-01

Oxygen isotope analysis of archaeological skeletal remains is an increasingly popular tool to study past human migrations. It is based on the assumption that human body chemistry preserves the δ18O of precipitation in such a way as to be a useful technique for identifying migrants and, potentially, their homelands. In this study, the first such global survey, we draw on published human tooth enamel and bone bioapatite data to explore the validity of using oxygen isotope analyses to identify migrants in the archaeological record. We use human δ18O results to show that there are large variations in human oxygen isotope values within a population sample. This may relate to physiological factors influencing the preservation of the primary isotope signal, or due to human activities (such as brewing, boiling, stewing, differential access to water sources and so on) causing variation in ingested water and food isotope values. We compare the number of outliers identified using various statistical methods. We determine that the most appropriate method for identifying migrants is dependent on the data but is likely to be the IQR or median absolute deviation from the median under most archaeological circumstances. Finally, through a spatial assessment of the dataset, we show that the degree of overlap in human isotope values from different locations across Europe is such that identifying individuals’ homelands on the basis of oxygen isotope analysis alone is not possible for the regions analysed to date. Oxygen isotope analysis is a valid method for identifying first-generation migrants from an archaeological site when used appropriately, however it is difficult to identify migrants using statistical methods for a sample size of less than c. 25 individuals. In the absence of local previous analyses, each sample should be treated as an individual dataset and statistical techniques can be used to identify migrants, but in most cases pinpointing a specific homeland should not be attempted. PMID:27124001

Isotope-ratio measurements of lead in NIST standard reference materials by multiple-collector inductively coupled plasma mass spectrometry.

PubMed

Platzner, I; Ehrlich, S; Halicz, L

2001-07-01

The capability of a second-generation Nu Instruments multiple collector inductively coupled plasma mass spectrometer (MC-ICP-MS) has been evaluated for precise and accurate isotope-ratio determinations of lead. Essentially the mass spectrometer is a double-focusing instrument of Nier-Johnson analyzer geometry equipped with a newly designed variable-dispersion ion optical device, enabling the measured ion beams to be focused into a fixed array of Faraday collectors and an ion-counting assembly. NIST SRM Pb 981, 982, and 983 isotopic standards were used. Addition of thallium to the lead standards and subsequent simultaneous measurement of the thallium and lead isotopes enabled correction for mass discrimination, by use of the exponential correction law and 205Tl/203Tl = 2.3875. Six measurements of SRM Pb-982 furnished the results 206Pb/204Pb = 36.7326(68), 207Pb/204Pb = 17.1543(30), 208Pb/204Pb = 36.7249(69), 207Pb/206Pb = 0.46700(1), and 208Pb/206Pb = 0.99979(2); the NIST-certified values were 36.738(37), 17.159(25), 36.744(50), 0.46707(20), and 1.00016(36), respectively. Direct isotope lead analysis in silicates can be performed without any chemical separation. NIST SRM 610 glass was dissolved and introduced into the MC-ICP-MS by means of a micro concentric nebulizer. The ratios observed were in excellent agreement with previously reported data obtained by TIMS and laser ablation MC-ICP-MS, despite the high Ca/Pb concentration ratio (200/1) and the presence of many other elements at levels comparable with that of lead. Approximately 0.2 microg lead are sufficient for isotope analysis with ratio uncertainties between 240 and 530 ppm.

Evaluation of UV-fs-LA-MC-ICP-MS for precise in situ copper isotopic microanalysis of cubanite.

PubMed

Ikehata, Kei; Hirata, Takafumi

2013-01-01

We evaluated the capabilities of an in situ method for measuring copper isotopes of cubanite using UV-fs-LA-MC-ICP-MS. A comparison of the UV-fs laser results with those obtained from the NIR-fs laser system shows that there is obviously an improvement in the precision (<0.10‰, 2SE) when using the UV-fs laser. In both wavelength modes, matrix-matched standards are required for reliable in situ copper isotope analysis of cubanite. This method was applied to determinations for copper isotopes of minute cubanite grains in a skarn ore. Copper isotopic ratios of cubanite grains near a weathered surface of the sample are lower than those of intact cubanite grains within the sample, suggesting that selective leaching of heavier copper isotope in primary minerals occurred during weathering.

Method and apparatus for tritiated water separation

DOEpatents

Nelson, David A.; Duncan, James B.; Jensen, George A.

1995-01-01

The present invention is a membrane method and apparatus for separating isotopic water constituents from light water. The method involves providing a supported membrane of an aromatic polyphosphazene and pressurizing the water on one side of the membrane thereby forcing the light water through the supported membrane while isotopic water constituents are retained or vice versa. The apparatus of the present invention includes an aromatic polyphosphazene placed on a porous support and means for pressurizing water through the membrane while certain isotopic water constituents are retained.

Method and apparatus for tritiated water separation

DOEpatents

Nelson, D.A.; Duncan, J.B.; Jensen, G.A.

1995-09-19

The present invention is a membrane method and apparatus for separating isotopic water constituents from light water. The method involves providing a supported membrane of an aromatic polyphosphazene and pressurizing the water on one side of the membrane thereby forcing the light water through the supported membrane while isotopic water constituents are retained or vice versa. The apparatus of the present invention includes an aromatic polyphosphazene placed on a porous support and means for pressurizing water through the membrane while certain isotopic water constituents are retained. 1 fig.

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.

Measurement of longitudinal sulfur isotopic variations by laser ablation MC-ICP-MS in single human hair strands.

PubMed

Santamaria-Fernandez, Rebeca; Giner Martínez-Sierra, Justo; Marchante-Gayón, J M; García-Alonso, J Ignacio; Hearn, Ruth

2009-05-01

A new method for the measurement of longitudinal variations of sulfur isotope amount ratios in single hair strands using a laser ablation system coupled to a multicollector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) is reported here for the first time. Ablation parameters have been optimized for the measurement of sulfur isotope ratios in scalp human hair strands of 80-120-microm thickness and different washing procedures have been evaluated. The repeatability of the method has been tested and the ability to measure sulfur isotopic variations in 1,000-microm-long hair segments has been evaluated. A horse hair sample previously characterized for carbon and nitrogen isotope ratios in an interlaboratory study has been characterized by LA-MC-ICP-MS to be used as an in-house standard for the bracketing of human hair strands. (34)S/(32)S isotope amount ratios have been measured and corrected for instrumental mass bias adopting the external standardization approach using National Institute of Standards and Technology (NIST) RM8553 and full uncertainty budgets have been calculated using the Kragten approach. Results are reported as both (34)S/(32)S isotope amount ratios and deltaS(V-CDT) values (sulfur isotopic differences relative to a reference sample expressed in the Vienna Canyon Diablo Troilite (V-CDT) scale) calculated using NIST RM8553, NIST RM8554, and NIST RM8556 to anchor results to the V-CDT scale. The main advantage of the new method versus conventional gas source isotope ratio mass spectrometry measurements is that longitudinal variations in sulfur isotope amount ratios can be resolved. Proof of concept is shown with human scalp hair strands from three individuals, two UK residents and one traveler (long periods of time abroad). The method enables monitoring of longitudinal isotope ratio variations in single hair strands. Absolute ratios are reported and delta(34)S(V-CDT) values are plotted for comparison. Slight variations of <1.2 per thousand were detected in the hair strands from UK residents whereas the traveler presented a variation of >5 per thousand. Thus, the measurement of sulfur isotopic variations in hair samples has potential to be an indicator of geographical origin and recent movements and could be used in combination with isotope ratio measurements in water/foodstuffs from different geographical locations to provide important information in nutritional and geographical studies.

Doubly labeled water method: in vivo oxygen and hydrogen isotope fractionation

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

Schoeller, D.A.; Leitch, C.A.; Brown, C.

The accuracy and precision of the doubly labeled water method for measuring energy expenditure are influenced by isotope fractionation during evaporative water loss and CO/sub 2/ excretion. To characterize in vivo isotope fractionation, we collected and isotopically analyzed physiological fluids and gases. Breath and transcutaneous water vapor were isotopically fractionated. The degree of fractionation indicated that the former was fractionated under equilibrium control at 37/sup 0/C, and the latter was kinetically fractionated. Sweat and urine were unfractionated. By use of isotopic balance models, the fraction of water lost via fractionating routes was estimated from the isotopic abundances of body water,more » local drinking water, and dietary solids. Fractionated water loss averaged 23% (SD = 10%) of water turnover, which agreed with our previous estimates based on metabolic rate, but there was a systematic difference between the results based on O/sub 2/ and hydrogen. Corrections for isotopic fractionation of water lost in breath and (nonsweat) transcutaneous loss should be made when using labeled water to measure water turnover or CO/sub 2/ production.« less

Laser isotope separation of erbium and other isotopes

DOEpatents

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

1995-08-22

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

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Study of Fission Barrier Heights of Uranium Isotopes by the Macroscopic-Microscopic Method

NASA Astrophysics Data System (ADS)

Zhong, Chun-Lai; Fan, Tie-Shuan

2014-09-01

Potential energy surfaces of uranium nuclei in the range of mass numbers 229 through 244 are investigated in the framework of the macroscopic-microscopic model and the heights of static fission barriers are obtained in terms of a double-humped structure. The macroscopic part of the nuclear energy is calculated according to Lublin—Strasbourg-drop (LSD) model. Shell and pairing corrections as the microscopic part are calculated with a folded-Yukawa single-particle potential. The calculation is carried out in a five-dimensional parameter space of the generalized Lawrence shapes. In order to extract saddle points on the potential energy surface, a new algorithm which can effectively find an optimal fission path leading from the ground state to the scission point is developed. The comparison of our results with available experimental data and others' theoretical results confirms the reliability of our calculations.

Studies on the reduction of radon plate-out

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

Bruemmer, M.; Nakib, M.; Calkins, R.

The decay of common radioactive gases, such as radon, produces stable isotopes by a sequence of daughter particles with varied half-lives. These daughter particles are a significant source of gamma, neutron, and alpha (α) particle backgrounds that can mimic desired signals in dark matter and neutrinoless double beta decay experiments. In the LUMINA Laboratory at Southern Methodist University (SMU), studies of radon plate-out onto copper samples are conducted using one of XIA’s first five UltraLo 1800 alpha counters. We present results from investigations into various mitigation approaches. A custom-built copper holder (in either plastic or metal) has been designed andmore » produced to maximize the copper’s exposure to {sup 220}Rn. The {sup 220}Rn source is a collection of camping lantern mantles. We present the current status of control and experimental methods for addressing radon exposure levels.« less

Statistical properties of Pu 243 , and Pu 242 ( n , γ ) cross section calculation

DOE PAGES

Laplace, T. A.; Zeiser, F.; Guttormsen, M.; ...

2016-01-29

The level density and γ-ray strength function (γSF) of 243Pu have been measured in the quasicontinuum using the Oslo method. Excited states in 243Pu were populated using the 242Pu(d,p) reaction. The level density closely follows the constant-temperature level density formula for excitation energies above the pairing gap. The γSF displays a double-humped resonance at low energy as also seen in previous investigations of actinide isotopes. The structure is interpreted as the scissors resonance and has a centroid of ω SR = 2.42(5) MeV and a total strength of B SR = 10.1(15) μ 2 N, which is in excellent agreementmore » with sum-rule estimates. Lastly, the measured level density and γSF were used to calculate the 242Pu(n,γ) cross section in a neutron energy range for which there were previously no measured data.« less

Liquid-phase thermal diffusion isotope separation apparatus and method having tapered column

DOEpatents

Rutherford, William M.

1988-05-24

A thermal diffusion counterflow method and apparatus for separating isotopes in solution in which the solution is confined in a long, narrow, vertical slit which tapers from bottom to top. The variation in the width of the slit permits maintenance of a stable concentration distribution with relatively long columns, thus permitting isotopic separation superior to that obtainable in the prior art.

Liquid-phase thermal diffusion isotope separation apparatus and method having tapered column

DOEpatents

Rutherford, W.M.

1985-12-04

A thermal diffusion counterflow method and apparatus for separating isotopes in solution in which the solution is confined in a long, narrow, vertical slit which tapers from bottom to top. The variation in the width of the slit permits maintenance of a stable concentration distribution with relatively long columns, thus permitting isotopic separation superior to that obtained in the prior art.

Experimental assessment of the purity of α-cellulose produced by variations of the Brendel method: Implications for stable isotope (δ13C, δ18O) dendroclimatology

NASA Astrophysics Data System (ADS)

Brookman, Tom; Whittaker, Thomas

2012-09-01

Stable isotope dendroclimatology using α-cellulose has unique potential to deliver multimillennial-scale, sub-annually resolved, terrestrial climate records. However, lengthy processing and analytical methods often preclude such reconstructions. Variants of the Brendel extraction method have reduced these limitations, providing fast, easy methods of isolating α-cellulose in some species. Here, we investigate application of Standard Brendel (SBrendel) variants to resinous soft-woods by treating samples of kauri (Agathis australis), ponderosa pine (Pinus ponderosa) and huon pine (Lagarastrobus franklinii), varying reaction vessel, temperature, boiling time and reagent volume. Numerous samples were visibly `under-processed' and Fourier Transform infrared spectroscopic (FTIR) investigation showed absorption peaks at 1520 cm-1 and ˜1600 cm-1 in those fibers suggesting residual lignin and retained resin respectively. Replicate analyses of all samples processed at high temperature yielded consistent δ13C and δ18O despite color and spectral variations. Spectra and isotopic data revealed that α-cellulose δ13C can be altered during processing, most likely due to chemical contamination from insufficient acetone removal, but is not systematically affected by methodological variation. Reagent amount, temperature and extraction time all influence δ18O, however, and our results demonstrate that different species may require different processing methods. FTIR prior to isotopic analysis is a fast and cost effective way to determine α-cellulose extract purity. Furthermore, a systematic isotopic test such as we present here can also determine sensitivity of isotopic values to methodological variables. Without these tests, isotopic variability introduced by the method could obscure or `create' climatic signals within a data set.

Reliability of a new technique for the determination of vitamin B12 absorption in children: single stool sample test--a double isotope technique

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

Hjelt, K.

1986-03-01

The fractional vitamin B12 absorption (FAB12) was determined in 39 patients with various gastrointestinal diseases by a double-isotope technique, employing a single stool sample test (SSST), as well as a complete stool collection. The age of the patients ranged from 2.5 months to 16.2 years (mean 5.0 years). The test dose was administered orally and consisted of 0.5-4.5 micrograms of /sup 57/CoB12 (approximately 0.05 microCi), carmine powder, and 2 mg /sup 51/CrCl/sub 3/ (approximately 1.25 microCi) as the inabsorbable tracer. The wholebody radiation to a 1-year-old child averaged only 20 mrad. The stool and napkin was collected and homogenized bymore » addition of 300 ml chromium sulfuric acid. A 300-ml sample of the homogenized stool and napkin, as well as 300 ml chromium sulfuric acid (75% v/v) containing the standards, were counted in a broad-based well counter. The FAB12 determined by SSST employing the stool with the highest content of /sup 51/Cr (which corresponded to the most carmine-colored stool) correlated closely to the FAB12 based on complete stool collection (r = 0.98, n = 39, p less than 0.001). The reproducibility of FAB12 determined by SSST was assessed from double assays in 19 patients. For a mean value of 12%, the SD was 3%, which corresponded to a coefficient of variation (CV) of 25%. The excretion of /sup 57/Co and /sup 51/Cr in the urine was examined in six patients with moderate to severe mucosal damage and was found to be low.« less

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

PubMed

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

2010-09-01

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

Enzymatic Kinetic Isotope Effects from First-Principles Path Sampling Calculations.

PubMed

Varga, Matthew J; Schwartz, Steven D

2016-04-12

In this study, we develop and test a method to determine the rate of particle transfer and kinetic isotope effects in enzymatic reactions, specifically yeast alcohol dehydrogenase (YADH), from first-principles. Transition path sampling (TPS) and normal mode centroid dynamics (CMD) are used to simulate these enzymatic reactions without knowledge of their reaction coordinates and with the inclusion of quantum effects, such as zero-point energy and tunneling, on the transferring particle. Though previous studies have used TPS to calculate reaction rate constants in various model and real systems, it has not been applied to a system as large as YADH. The calculated primary H/D kinetic isotope effect agrees with previously reported experimental results, within experimental error. The kinetic isotope effects calculated with this method correspond to the kinetic isotope effect of the transfer event itself. The results reported here show that the kinetic isotope effects calculated from first-principles, purely for barrier passage, can be used to predict experimental kinetic isotope effects in enzymatic systems.

First-principles investigations of equilibrium Ca, Mg, Si and O isotope fractionations between silicate melts and minerals

NASA Astrophysics Data System (ADS)

Qi, Y.; Liu, X.; Kang, J.; He, L.

2017-12-01

Equilibrium isotope fractionation factors are essential for using stable isotope data to study many geosciences processes such as planetary differentiation and mantle evolution. The mass-dependent equilibrium isotope fractionation is primarily controlled by the difference in bond energies triggered by the isotope substitution. With the recent advances in computational capabilities, first-principles calculation has become a reliable tool to investigate equilibrium isotopic fractionations, greatly improving our understanding of the factors controlling isotope fractionations. It is important to understand the isotope fractionation between melts and minerals because magmatism is critical for creating and shaping the Earth. However, because isotope fractionation between melts and minerals is small at high temperature, it is difficult to experimentally calibrate such small signature. Due to the disordered and dynamic character of melts, calculations of equilibrium isotope fractionation of melts are more challenging than that for gaseous molecules or minerals. Here, we apply first-principles molecular dynamics method to calculate equilibrium Ca, Mg, Si, and O isotope fractionations between silicate melts and minerals. Our results show that equilibrium Mg, Si, and O isotope fractionations between olivine and pure Mg2SiO4 melt are close to zero at high temperature (e.g. δ26Mgmelt-ol = 0.03 ± 0.04‰, δ30Simelt-ol = -0.06 ± 0.07‰, δ18Omelt-ol = 0.07‰ ± 0.08 at 1500 K). Equilibrium Ca, Mg, Si, and O isotope fractionations between diopside and basalt melt (67% CaMgSi2O6 + 33% CaAl2Si2O8) are also negligible at high temperature (e.g. δ44/40Camelt-cpx = -0.01 ± 0.02‰, δ26Mgmelt-cpx = -0.05 ± 0.14‰, δ30Simelt-cpx = 0.04 ± 0.04‰, δ18Omelt-cpx = 0.03 ± 0.07‰ at 1500 K). These results are consistent with the observations in natural samples that there is no significant Ca, Mg, Si, and O isotope fractionation during mantle partial melting, demonstrating the reliability of our methods. Thus, our results can be used to understand stable isotope fractionation during partial melting of mantle peridotite or fractional crystallization during magmatic differentiation. The first-principles molecular dynamics method is a promising tool to obtain equilibrium fractionation of more isotope systems for complicate liquids.

Tracing redox processes during paleoclimatic changes in the Neoproterozoic: Stable chromium isotopic results from the Arroyo del Soldado Group (Ediacaran, Uruguay)

NASA Astrophysics Data System (ADS)

Frei, R.; Gaucher, C.

2007-12-01

Positive δ13C carbonate values, combined with the occurrence of Fe-rich cherts (oxide-facies BIF) and organic-rich black shales within the late Ediacaran (ca. 580-560 Ma) Yerbal Fm. of the Arroyo del Soldato Group (Uruguay) are compatible with paleoclimatic models which postulate that enhanced bioproductivity due to higher availability of nutrient (P, N, Fe) was essential for controlling Neoproterozoic glaciations. Tracing of associated redox processes (f.e. linked to oxygenation of bottom waters in restricted basins) that might have been responsible for the deposition of Fe-rich cherts (BIFs) is therefore an important tool to better understand the seawater changes during cold-warm periods. Besides the traditionally used Fe and Mo isotopic systems, the redox-sensitive element Cr (Cr(III); Cr(IV)) and its stable isotopes offer another complementary system to trace paleo-redox processes. We have applied Cr stable isotope systematics to a sequence of samples from a late Ediacaran sedimentary sequence in Uruguay, using a 52Cr-54Cr double spike (Schoenberg et al., Chem..Geol., subm.). The middle Yerbal Fm. is dominated by organic-rich, black shales and black dolostones (δ53Cr = -0.05‰), followed by organic-rich cherts (δ53Cr = +1.83 - +4.49 ‰) and BIF (δ53Cr = -0.31 +0.90 ‰) gradually changing into Fe-bearing, organic-rich cherts and shales (δ53Cr = -0.28 - -0.01 ‰), and another sequence with BIF and organic-rich cherts topped by carbonates of the lower Polanco Fm. (δ53Cr = -0.17 to -0.27 ‰). The strongly positively fractionated Cr isotopic signatures in organic-rich and Fe-rich cherts in the Yerbal Fm. may point to significant oxidation processes either directly in the seawater column and/or during early diagenetic processes at the sediment-water interface. While these strongly positive δ53Cr values are the first to be reported from Neoproterozoic sedimentary sequence, the exact nature of the chemical process that produced these anomalies is not yet understood. However, the occurrence of these anomalies in organic-rich and Fe-rich chemical sediments that were deposited in a period following a glacial (Gaskiers?) event is compatible with "Snowball Earth" scenarios whereby impulsive oxidation of the upper seawater was in response to ice cover retraction which allowed booming of the biosphere and concomitant oxidation of accumulated Fe2+ and subsequent precipitation of the Fe-oxyhydroxides to form the "BIF" during such epochs. Schoenberg et al. (subm.) The stable Cr isotope inventory of solid earth reservoirs determined by double-spike MC-ICP-MS. Chemical Geology

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

Park, HyangKyu

The AMoRE (Advanced Mo based Rare process Experiment) collaboration is going to use calcium molybdate crystals to search for neutrinoless double beta decay of {sup 100}Mo isotope. In order to make the crystal, we use calcium carbonate and molybdenum oxide powders as raw materials. Therefore it is highly necessary to reduce potential sources for radioactive backgrounds such as U and Th in the powders. In this talk, we will present our studies for purification of calcium carbonate and molybdenum oxide powders.

EPR investigation of Ti2+ in SrCl2 single crystals.

NASA Technical Reports Server (NTRS)

Herrington, J. R.; Estle, T. L.; Boatner, L. A.

1972-01-01

The observation of 'double quantum' transitions which made it possible to determine the charge state of Ti as 2+ is reported. The EPR spectrum observed at 1.2 K is presented in a graph. The first derivative of the absorption is shown vs the magnetic field. The hyperfine patterns for the Ti-47 and Ti-49 isotopes are identified. Spin-Hamiltonian parameters for Ti(2+) in various cubic hosts are listed.

Understanding the SNO+ Detector

DOE PAGES

Kamdin, K.

2015-03-24

SNO+, a large liquid scintillator experiment, is the successor of the Sudbury Neutrino Observatory (SNO) experiment. The scintillator volume will be loaded with large quantities of 130Te, an isotope that undergoes double beta decay, in order to search for neutrinoless double beta decay. In addition to this search, SNO+ has a broad physics program due to its sensitivity to solar and supernova neutrinos, as well as reactor and geo anti-neutrinos. SNO+ can also place competitive limits on certain modes of invisible nucleon decay during its first phase. The detector is currently undergoing commissioning in preparation for its first phase, inmore » which the detector is filled with ultra pure water. This will be followed by a pure scintillator phase, and then a Tellurium-loaded scintillator phase to search for neutrinoless double beta decay. Here we present the work done to model detector aging, which was first observed during SNO. The aging was found to reduce the optical response of the detector. We also describe early results from electronics calibration of SNO+.« less

Nuclear applications of inorganic mass spectrometry.

PubMed

De Laeter, John

2010-01-01

There are several basic characteristics of mass spectrometry that are not always fully appreciated by the science community. These characteristics include the distinction between relative and absolute isotope abundances, and the influence of isotope fractionation on the accuracy of isotopic measurements. These characteristics can be illustrated in the field of nuclear physics with reference to the measurement of nuclear parameters, which involve the use of enriched isotopes, and to test models of s-, r-, and p-process nucleosynthesis. The power of isotope-dilution mass spectrometry (IDMS) to measure trace elements in primitive meteorites to produce accurate Solar System abundances has been essential to the development of nuclear astrophysics. The variety of mass spectrometric instrumentation used to measure the isotopic composition of elements has sometimes been accompanied by a lack of implementation of basic mass spectrometric protocols which are applicable to all instruments. These metrological protocols are especially important in atomic weight determinations, but must also be carefully observed in cases where the anomalies might be very small, such as in studies of the daughter products of extinct radionuclides to decipher events in the early history of the Solar System. There are occasions in which misleading conclusions have been drawn from isotopic data derived from mass spectrometers where such protocols have been ignored. It is important to choose the mass spectrometer instrument most appropriate to the proposed experiment. The importance of the integrative nature of mass spectrometric measurements has been demonstrated by experiments in which long, double beta decay and geochronological decay half-lives have been measured as an alternative to costly radioactive-counting experiments. This characteristic is also illustrated in the measurement of spontaneous fission yields, which have accumulated over long periods of time. Mass spectrometry is also a valuable tool in the determination of neutron capture cross-section measurements and the application of such determinations in Planetary Science. 2009 Wiley Periodicals, Inc.

Boron isotopes at the catchment scale, a new potential tool to infer critical zone processes.

NASA Astrophysics Data System (ADS)

Gaillardet, J.; Noireaux, J.; Braun, J. J.; Riotte, J.; Louvat, P.; Bouchez, J.; Lemarchand, D.; Muddu, S.; Mohan Kumar, M.; Candaudap, F.

2017-12-01

Boron is a mid-mass element that has two isotopes, 10B and 11B. These isotopes are largely fractioned by a number of chemical, biological and physical processes. Boron as a great affinity for clays and is useful for life, making it a double tracer of critical zone processes. This study focuses on the Mule Hole Critical Zone Observatory in South India. This is part of the French Research Infrastructure OZCAR and has benefited from the fruitful Indo-French collaboration (Indo-French Cell for Water Sciences) for more that 15 years. Boron and its isotopes were measured in the different compartment of the CZ in Mule Hole, vegetation, atmosphere, throughfall, soil, soil water, river water and compared to the behavior of other elements. The well constrained hydrology in Mule Hole allowed us to calculate the main fluxes affecting boron in the Critical Zone and came to the first order conclusion that the recycling of boron by vegetation is by far the most important flux within the system, reaching 15-20 times the catchment outlet flux. From an isotopic point of view, the total range of variation is measured between -3 ‰ and 77‰, with a bedrock value at 10‰ in classical delta unit, making boron a well suited tracer for constraining CZ processes. The flux of boron most enriched in heavy boron is the throughfall, showing the importance of biological processes in controlling the boron isotopic composition of the stream. Boron in soils in depleted in the heavy isotope but is enriched in boron compared to the bedrock, a surprising situation that we interpret as the legacy of a previous stage of transient weathering. These results indicate a strong decoupling between the behaviors of boron at the surface of the CZ and at depth.

Strontium stable isotope behaviour accompanying basalt weathering

NASA Astrophysics Data System (ADS)

Burton, K. W.; Parkinson, I. J.; Gíslason, S. G. R.

2016-12-01

The strontium (Sr) stable isotope composition of rivers is strongly controlled by the balance of carbonate to silicate weathering (Krabbenhöft et al. 2010; Pearce et al. 2015). However, rivers draining silicate catchments possess distinctly heavier Sr stable isotope values than their bedrock compositions, pointing to significant fractionation during weathering. Some have argued for preferential release of heavy Sr from primary phases during chemical weathering, others for the formation of secondary weathering minerals that incorporate light isotopes. This study presents high-precision double-spike Sr stable isotope data for soils, rivers, ground waters and estuarine waters from Iceland, reflecting both natural weathering and societal impacts on those environments. The bedrock in Iceland is dominantly basaltic, d88/86Sr ≈ +0.27, extending to lighter values for rhyolites. Geothermal waters range from basaltic Sr stable compositions to those akin to seawater. Soil pore waters reflect a balance of input from primary mineral weathering, precipitation and litter recycling and removal into secondary phases and vegetation. Rivers and ground waters possess a wide range of d88/86Sr compositions from +0.101 to +0.858. Elemental and isotope data indicate that this fractionation primarily results from the formation or dissolution of secondary zeolite (d88/86Sr ≈ +0.10), but also carbonate (d88/86Sr ≈ +0.22) and sometimes anhydrite (d88/86Sr ≈ -0.73), driving the residual waters to heavier or lighter values, respectively. Estuarine waters largely reflect mixing with seawater, but are also be affected by adsorption onto particulates, again driving water to heavy values. Overall, these data indicate that the stability and nature of secondary weathering phases, exerts a strong control on the Sr stable isotope composition of silicate rivers. [1] Krabbenhöft et al. (2010) Geochim. Cosmochim. Acta 74, 4097-4109. [2] Pearce et al. (2015) Geochim. Cosmochim. Acta 157, 125-146.

Chromium Stable Isotope Fractionation - An Indicator of Hexavalent Chromium Reduction.

NASA Astrophysics Data System (ADS)

Ellis, A.; Johnson, T. M.; Bullen, T. D.

2001-12-01

Chromium is a common anthropogenic contaminant in surface water and ground water, and is also of interest in oceanography. It is redox-active; the two common valences in natural waters are Cr(VI), which is highly soluble and toxic, and Cr(III), which is relatively insoluble. Redox reactions thus control Cr mobility in aqueous solutions, and reduction of Cr(VI) to Cr(III) is the most important reaction controlling attenuation of Cr in groundwater. Our results show that Cr(VI) reduction favors the lighter isotopes and leads to enrichment of heavier isotopes in the remaining Cr(VI). Cr isotope measurements thus show great promise as indicators of Cr(VI) reduction. We report here the first measurements of the magnitude of Cr isotope fractionation during Cr(VI) reduction and variations in δ 53Cr values obtained from three contaminated sites. Experiments were conducted to measure Cr isotope fractionation during Cr(VI) reduction by suspensions of magnetite and unamended sediments from a local pond, Urbana, IL and San Francisco Estuary near Martinez, CA. Suspensions were incubated anaerobically with constant shaking, and complete Cr(VI) reduction occurred within a few days. Cr(VI) from intermediate time points in the experiments was purified via ion exchange and 53Cr/52Cr ratios were measured via TIMS with a double isotope spike. The instantaneous per mil fractionation, ɛ , was calculated assuming a Rayleigh fractionation model. The ɛ for Cr(VI) reduction on magnetite surfaces yielded a fractionation of -3.5 ‰ . The ɛ values for the pond and estuary sediments were -3.5 ‰ and -3.3 ‰ respectively. The size of this Cr isotope fractionation is encouraging, as current precision is 0.2 \\permil. δ 53Cr values in dissolved Cr(VI) from three contaminated sites range from 1.1 ‰ to 5.8 ‰ , suggesting that Cr(VI) reduction has occurred and has induced isotopic fractionation in these settings. δ 53Cr values measured from Cr(VI) in plating baths show little or no fractionation during plating operations during up to 5 years of use. These results demonstrate that Cr stable isotope analyses should be a highly practical indicator of the critical chromate reduction reaction, and an otherwise useful geologic and oceanographic tool.

The Influence of Non-spectral Matrix Effects on the Accuracy of Isotope Ratio Measurement by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Barling, J.; Shiel, A.; Weis, D.

2006-12-01

Non-spectral interferences in ICP-MS are caused by matrix elements effecting the ionisation and transmission of analyte elements. They are difficult to identify in MC-ICP-MS isotopic data because affected analyses exhibit normal mass dependent isotope fractionation. We have therefore investigated a wide range of matrix elements for both stable and radiogenic isotope systems using a Nu Plasma MC-ICP-MS. Matrix elements commonly enhance analyte sensitivity and change the instrumental mass bias experienced by analyte elements. These responses vary with element and therefore have important ramifications for the correction of data for instrumental mass bias by use of an external element (e.g. Pb and many non-traditional stable isotope systems). For Pb isotope measurements (Tl as mass bias element), Mg, Al, Ca, and Fe were investigated as matrix elements. All produced signal enhancement in Pb and Tl. Signal enhancement varied from session to session but for Ca and Al enhancement in Pb was less than for Tl while for Mg and Fe enhancement levels for Pb and Tl were similar. After correction for instrumental mass fractionation using Tl, Mg effected Pb isotope ratios were heavy (e.g. ^{208}Pb/204Pbmatrix > ^{208}Pb/204Pbtrue) for both moderate and high [Mg] while Ca effected Pb showed little change at moderate [Ca] but were light at high [Ca]. ^{208}Pb/204Pbmatrix - ^{208}Pb/204Pbtrue for all elements ranged from +0.0122 to - 0.0177. Isotopic shifts of similar magnitude are observed between Pb analyses of samples that have seen either one or two passes through chemistry (Nobre Silva et al, 2005). The double pass purified aliquots always show better reproducibility. These studies show that the presence of matrix can have a significant effect on the accuracy and reproducibility of replicate Pb isotope analyses. For non-traditional stable isotope systems (e.g. Mo(Zr), Cd(Ag)), the different responses of analyte and mass bias elements to the presence of matrix can result in del/amu for measured & mass bias corrected data that disagree outside of error. Either or both values can be incorrect. For samples, unlike experiments, the correct del/amu is not known in advance. Therefore, for sample analyses to be considered accurate, both measured and exponentially corrected del/amu should agree.

Stable isotope phenotyping via cluster analysis of NanoSIMS data as a method for characterizing distinct microbial ecophysiologies and sulfur-cycling in the environment

NASA Astrophysics Data System (ADS)

Dawson, K.; Scheller, S.; Dillon, J. G.; Orphan, V. J.

2016-12-01

Stable isotope probing (SIP) is a valuable tool for gaining insights into ecophysiology and biogeochemical cycling of environmental microbial communities by tracking isotopically labeled compounds into cellular macromolecules as well as into byproducts of respiration. SIP, in conjunction with nanoscale secondary ion mass spectrometry (NanoSIMS), allows for the visualization of isotope incorporation at the single cell level. In this manner, both active cells within a diverse population as well as heterogeneity in metabolism within a homogeneous population can be observed. The ecophysiological implications of these single cell stable isotope measurements are often limited to the taxonomic resolution of paired fluorescence in situ hybridization (FISH) microscopy. Here we introduce a taxonomy-independent method using multi-isotope SIP and NanoSIMS for identifying and grouping phenotypically similar microbial cells by their chemical and isotopic fingerprint. This method was applied to SIP experiments in a sulfur-cycling biofilm collected from sulfidic intertidal vents amended with 13C-acetate, 15N-ammonium, and 33S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope (13C/12C, 15N/14N, and 33S/32S) and elemental ratio (C/CN and S/CN) profiles, our analysis partitioned 2200 cellular regions of interest (ROIs) into 5 distinct groups. These isotope phenotype groupings are reflective of the variation in labeled substrate uptake by cells in a multispecies metabolic network dominated by Gamma- and Deltaproteobacteria. Populations independently grouped by isotope phenotype were subsequently compared with paired FISH data, demonstrating a single coherent deltaproteobacterial cluster and multiple gammaproteobacterial groups, highlighting the distinct ecophysiologies of spatially-associated microbes within the sulfur-cycling biofilm from White Point Beach, CA.

Dual-isotope PET using positron-gamma emitters.

PubMed

Andreyev, A; Celler, A

2011-07-21

Positron emission tomography (PET) is widely recognized as a highly effective functional imaging modality. Unfortunately, standard PET cannot be used for dual-isotope imaging (which would allow for simultaneous investigation of two different biological processes), because positron-electron annihilation products from different tracers are indistinguishable in terms of energy. Methods that have been proposed for dual-isotope PET rely on differences in half-lives of the participating isotopes; these approaches, however, require making assumptions concerning kinetic behavior of the tracers and may not lead to optimal results. In this paper we propose a novel approach for dual-isotope PET and investigate its performance using GATE simulations. Our method requires one of the two radioactive isotopes to be a pure positron emitter and the second isotope to emit an additional high-energy gamma in a cascade simultaneously with positron emission. Detection of this auxiliary prompt gamma in coincidence with the annihilation event allows us to identify the corresponding 511 keV photon pair as originating from the same isotope. Two list-mode datasets are created: a primary dataset that contains all detected 511 keV photon pairs from both isotopes, and a second, tagged (much smaller) dataset that contains only those PET events for which a coincident prompt gamma has also been detected. An image reconstructed from the tagged dataset reflects the distribution of the second positron-gamma radiotracer and serves as a prior for the reconstruction of the primary dataset. Our preliminary simulation study with partially overlapping (18)F/(22)Na and (18)F/(60)Cu radiotracer distributions showed that in these two cases the dual-isotope PET method allowed for separation of the two activity distributions and recovered total activities with relative errors of about 5%.

Stable Isotope Phenotyping via Cluster Analysis of NanoSIMS Data As a Method for Characterizing Distinct Microbial Ecophysiologies and Sulfur-Cycling in the Environment

PubMed Central

Dawson, Katherine S.; Scheller, Silvan; Dillon, Jesse G.; Orphan, Victoria J.

2016-01-01

Stable isotope probing (SIP) is a valuable tool for gaining insights into ecophysiology and biogeochemical cycling of environmental microbial communities by tracking isotopically labeled compounds into cellular macromolecules as well as into byproducts of respiration. SIP, in conjunction with nanoscale secondary ion mass spectrometry (NanoSIMS), allows for the visualization of isotope incorporation at the single cell level. In this manner, both active cells within a diverse population as well as heterogeneity in metabolism within a homogeneous population can be observed. The ecophysiological implications of these single cell stable isotope measurements are often limited to the taxonomic resolution of paired fluorescence in situ hybridization (FISH) microscopy. Here we introduce a taxonomy-independent method using multi-isotope SIP and NanoSIMS for identifying and grouping phenotypically similar microbial cells by their chemical and isotopic fingerprint. This method was applied to SIP experiments in a sulfur-cycling biofilm collected from sulfidic intertidal vents amended with 13C-acetate, 15N-ammonium, and 33S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope (13C/12C, 15N/14N, and 33S/32S) and elemental ratio (C/CN and S/CN) profiles, our analysis partitioned ~2200 cellular regions of interest (ROIs) into five distinct groups. These isotope phenotype groupings are reflective of the variation in labeled substrate uptake by cells in a multispecies metabolic network dominated by Gamma- and Deltaproteobacteria. Populations independently grouped by isotope phenotype were subsequently compared with paired FISH data, demonstrating a single coherent deltaproteobacterial cluster and multiple gammaproteobacterial groups, highlighting the distinct ecophysiologies of spatially-associated microbes within the sulfur-cycling biofilm from White Point Beach, CA. PMID:27303371

Correlated optical and isotopic nanoscopy

NASA Astrophysics Data System (ADS)

Saka, Sinem K.; Vogts, Angela; Kröhnert, Katharina; Hillion, François; Rizzoli, Silvio O.; Wessels, Johannes T.

2014-04-01

The isotopic composition of different materials can be imaged by secondary ion mass spectrometry. In biology, this method is mainly used to study cellular metabolism and turnover, by pulsing the cells with marker molecules such as amino acids labelled with stable isotopes (15N, 13C). The incorporation of the markers is then imaged with a lateral resolution that can surpass 100 nm. However, secondary ion mass spectrometry cannot identify specific subcellular structures like organelles, and needs to be correlated with a second technique, such as fluorescence imaging. Here, we present a method based on stimulated emission depletion microscopy that provides correlated optical and isotopic nanoscopy (COIN) images. We use this approach to study the protein turnover in different organelles from cultured hippocampal neurons. Correlated optical and isotopic nanoscopy can be applied to a variety of biological samples, and should therefore enable the investigation of the isotopic composition of many organelles and subcellular structures.

Using phylogenetic probes for quantification of stable isotope labeling and microbial community analysis

DOEpatents

Brodie, Eoin L; DeSantis, Todd Z; Karaoz, Ulas; Andersen, Gary L

2014-12-09

Herein is described methods for a high-sensitivity means to measure the incorporation of stable isotope labeled substrates into RNA following stable isotope probing experiments (SIP). RNA is hybridized to a set of probes such as phylogenetic microarrays and isotope incorporation is quantified such as by secondary ion mass spectrometer imaging (NanoSIMS).

Configuration-constrained cranking Hartree-Fock pairing calculations for sidebands of nuclei

NASA Astrophysics Data System (ADS)

Liang, W. Y.; Jiao, C. F.; Wu, Q.; Fu, X. M.; Xu, F. R.

2015-12-01

Background: Nuclear collective rotations have been successfully described by the cranking Hartree-Fock-Bogoliubov (HFB) model. However, for rotational sidebands which are built on intrinsic excited configurations, it may not be easy to find converged cranking HFB solutions. The nonconservation of the particle number in the BCS pairing is another shortcoming. To improve the pairing treatment, a particle-number-conserving (PNC) pairing method was suggested. But the existing PNC calculations were performed within a phenomenological one-body potential (e.g., Nilsson or Woods-Saxon) in which one has to deal the double-counting problem. Purpose: The present work aims at an improved description of nuclear rotations, particularly for the rotations of excited configurations, i.e., sidebands. Methods: We developed a configuration-constrained cranking Skyrme Hartree-Fock (SHF) calculation with the pairing correlation treated by the PNC method. The PNC pairing takes the philosophy of the shell model which diagonalizes the Hamiltonian in a truncated model space. The cranked deformed SHF basis provides a small but efficient model space for the PNC diagonalization. Results: We have applied the present method to the calculations of collective rotations of hafnium isotopes for both ground-state bands and sidebands, reproducing well experimental observations. The first up-bendings observed in the yrast bands of the hafnium isotopes are reproduced, and the second up-bendings are predicted. Calculations for rotational bands built on broken-pair excited configurations agree well with experimental data. The band-mixing between two Kπ=6+ bands observed in 176Hf and the K purity of the 178Hf rotational state built on the famous 31 yr Kπ=16+ isomer are discussed. Conclusions: The developed configuration-constrained cranking calculation has been proved to be a powerful tool to describe both the yrast bands and sidebands of deformed nuclei. The analyses of rotational moments of inertia help to understand the structures of nuclei, including rotational alignments, configurations, and competitions between collective and single-particle excitations.

Estimation of evapotranspiration rate in irrigated lands using stable isotopes

NASA Astrophysics Data System (ADS)

Umirzakov, Gulomjon; Windhorst, David; Forkutsa, Irina; Brauer, Lutz; Frede, Hans-Georg

2013-04-01

Agriculture in the Aral Sea basin is the main consumer of water resources and due to the current agricultural management practices inefficient water usage causes huge losses of freshwater resources. There is huge potential to save water resources in order to reach a more efficient water use in irrigated areas. Therefore, research is required to reveal the mechanisms of hydrological fluxes in irrigated areas. This paper focuses on estimation of evapotranspiration which is one of the crucial components in the water balance of irrigated lands. Our main objective is to estimate the rate of evapotranspiration on irrigated lands and partitioning of evaporation into transpiration using stable isotopes measurements. Experiments has done in 2 different soil types (sandy and sandy loam) irrigated areas in Ferghana Valley (Uzbekistan). Soil samples were collected during the vegetation period. The soil water from these samples was extracted via a cryogenic extraction method and analyzed for the isotopic ratio of the water isotopes (2H and 18O) based on a laser spectroscopy method (DLT 100, Los Gatos USA). Evapotranspiration rates were estimated with Isotope Mass Balance method. The results of evapotranspiration obtained using isotope mass balance method is compared with the results of Catchment Modeling Framework -1D model results which has done in the same area and the same time.

Specificity and sensitivity of noninvasive measurement of pulmonary vascular protein leak.

PubMed

Dauber, I M; Pluss, W T; VanGrondelle, A; Trow, R S; Weil, J V

1985-08-01

Noninvasive techniques employing external counting of radiolabeled protein have the potential for measuring pulmonary vascular protein permeability, but their specificity and sensitivity remain unclear. We tested the specificity and sensitivity of a double-radioisotope method by injecting radiolabeled albumin (131I) and erythrocytes (99mTc) into anesthetized dogs and measuring the counts of each isotope for 150 min after injection with an external gamma probe fixed over the lung. We calculated the rate of increase of albumin counts measured by the probe (which reflects the rate at which protein leaks into the extravascular space). To assess permeability we normalized the rate of increase in albumin counts for changes in labeled erythrocyte signal to minimize influence of changes in vascular surface area and thus derived an albumin leak index. We measured the albumin leak index and gravimetric lung water during hydrostatic edema (acutely elevating left atrial pressure by left atrial balloon inflation: mean pulmonary arterial wedge pressure = 22.6 Torr) and in lung injury edema induced by high- (1.0 g/kg) and low-dose (0.25 g/kg) intravenous thiourea. To test specificity we compared hydrostatic and high-dose thiourea edema. The albumin leak index increased nearly fourfold from control after thiourea injury (27.2 +/- 2.3 X 10-4 vs. 7.6 +/- 0.9 X 10-4 min-1) but did not change from control levels after elevating left atrial pressure (8.9 +/- 1.2 X 10-4 min-1) despite comparable increases in gravimetric lung water. To test sensitivity we compared low-dose thiourea with controls. Following low-dose thiourea, the albumin leak index nearly doubled despite the absence of a measurable increase in lung water. We conclude that a noninvasive double radioisotope measurement of pulmonary vascular protein leak, employing external counting techniques and a simplified method of calculation, is specific for lung injury and is also sensitive enough to detect lung injury insufficient to produce detectable pulmonary edema.

Stable isotope measurements of evapotranspiration partitioning in a maize field

NASA Astrophysics Data System (ADS)

Hogan, Patrick; Parajka, Juraj; Oismüller, Markus; Strauss, Peter; Heng, Lee; Blöschl, Günter

2017-04-01

Evapotranspiration (ET) is one of the most important processes in describing land surface - atmosphere interactions as it connects the energy and water balances. Furthermore knowledge of the individual components of evapotranspiration is important for ecohydrological modelling and agriculture, particularly for irrigation efficiency and crop productivity. In this study, we tested the application of the stable isotope method for evapotranspiration partitioning to a maize crop during the vegetative stage, using sap flow sensors as a comparison technique. Field scale ET was measured using an eddy covariance device and then partitioned using high frequency in-situ measurements of the isotopic signal of the canopy water vapor. The fraction of transpiration (Ft) calculated with the stable isotope method showed good agreement with the sap flow method. High correlation coefficient values were found between the two techniques, indicating the stable isotope method can successfully be applied in maize. The results show the changes in transpiration as a fraction of evapotranspiration after rain events and during the subsequent drying conditions as well as the relationship between transpiration and solar radiation and vapor pressure deficit.

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

PubMed

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

2016-10-04

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

Evaluation of Direct Vapour Equilibration for Stable Isotope Analysis of Plant Water.

NASA Astrophysics Data System (ADS)

Millar, C. B.; McDonnell, J.; Pratt, D.

2017-12-01

The stable isotopes of water (2H and 18O), extracted from plants, have been utilized in a variety of ecohydrological, biogeochemical and climatological studies. The array of methods used to extract water from plants are as varied as the studies themselves. Here we perform a comprehensive inter-method comparison of six plant water extraction techniques: direct vapour equilibration, microwave extraction, two unique versions of cryogenic extraction, centrifugation, and high pressure mechanical squeezing. We applied these methods to four isotopically unique plant portions (heads, stems, leaves and root crown) of spring wheat (Triticum aestivum L.). The spring wheat was grown under controlled conditions with irrigation inputs of a known isotopic composition. Our results show that the methods of extraction return significantly different plant water isotopic signals. Centrifugation, microwave extraction, direct vapour equilibration, and squeezing returned more enriched results. Both cryogenic systems and squeezing returned more depleted results, depending upon the plant portion extracted. While cryogenic extraction is currently the most widely used method in the literature, our results suggest that direct vapor equilibration method outperforms it in terms of accuracy, sample throughput and replicability. More research is now needed with other plant species (especially woody plants) to see how far the findings from this study could be extended.

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

PubMed

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

2017-08-18

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

Chloroformate derivatization for tracing the fate of Amino acids in cells and tissues by multiple stable isotope resolved metabolomics (mSIRM).

PubMed

Yang, Ye; Fan, Teresa W-M; Lane, Andrew N; Higashi, Richard M

2017-07-11

Amino acids have crucial roles in central metabolism, both anabolic and catabolic. To elucidate these roles, steady-state concentrations of amino acids alone are insufficient, as each amino acid participates in multiple pathways and functions in a complex network, which can also be compartmentalized. Stable Isotope-Resolved Metabolomics (SIRM) is an approach that uses atom-resolved tracking of metabolites through biochemical transformations in cells, tissues, or whole organisms. Using different elemental stable isotopes to label multiple metabolite precursors makes it possible to resolve simultaneously the utilization of these precursors in a single experiment. Conversely, a single precursor labeled with two (or more) different elemental isotopes can trace the allocation of e.g. C and N atoms through the network. Such dual-label experiments however challenge the resolution of conventional mass spectrometers, which must distinguish the neutron mass differences among different elemental isotopes. This requires ultrahigh resolution Fourier transform mass spectrometry (UHR-FTMS). When combined with direct infusion nano-electrospray ion source (nano-ESI), UHR-FTMS can provide rapid, global, and quantitative analysis of all possible mass isotopologues of metabolites. Unfortunately, very low mass polar metabolites such as amino acids can be difficult to analyze by current models of UHR-FTMS, plus the high salt content present in typical cell or tissue polar extracts may cause unacceptable ion suppression for sources such as nano-ESI. Here we describe a modified method of ethyl chloroformate (ECF) derivatization of amino acids to enable rapid quantitative analysis of stable isotope labeled amino acids using nano-ESI UHR-FTMS. This method showed excellent linearity with quantifiable limits in the low nanomolar range represented in microgram quantities of biological specimens, which results in extracts with total analyte abundances in the low to sub-femtomole range. We have applied this method to profile amino acids and their labeling patterns in 13 C and 2 H doubly labeled PC9 cell extracts, cancerous and non-cancerous tissue extracts from a lung cancer patient and their protein hydrolysates as well as plasma extracts from mice fed with a liquid diet containing 13 C 6 -glucose (Glc). The multi-element isotopologue distributions provided key insights into amino acid metabolism and intracellular pools in human lung cancer tissues in high detail. The 13 C labeling of Asp and Glu revealed de novo synthesis of these amino acids from 13 C 6 -Glc via the Krebs cycle, specifically the elevated level of 13 C 3 -labeled Asp and Glu in cancerous versus non-cancerous lung tissues was consistent with enhanced pyruvate carboxylation. In addition, tracking the fate of double tracers, ( 13 C 6 -Glc +  2 H 2 -Gly or 13 C 6 -Glc +  2 H 3 -Ser) in PC9 cells clearly resolved pools of Ser and Gly synthesized de novo from 13 C 6 -Glc ( 13 C 3 -Ser and 13 C 2 -Gly) versus Ser and Gly derived from external sources ( 2 H 3 -Ser, 2 H 2 -Gly). Moreover the complex 2 H labeling patterns of the latter were results of Ser and Gly exchange through active Ser-Gly one-carbon metabolic pathway in PC9 cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Impact-induced devolatilization and hydrogen isotopic fractionation of serpentine: Implications for planetary accretion

NASA Technical Reports Server (NTRS)

Tyburczy, James A.; Krishnamurthy, R. V.; Epstein, Samuel; Ahrens, Thomas J.

1988-01-01

Impact-induced devolatilization of porous serpentine was investigated using two independent experimental methods, the gas recovery and the solid recovery method, each yielding nearly identical results. For shock pressures near incipient devolatilization, the hydrogen isotopic composition of the evolved H2O is very close to that of the starting material. For shock pressures at which up to 12 percent impact-induced devolatilization occurs, the bulk evolved gas is significantly lower in deuterium than the starting material. There is also significant reduction of H2O to H2 in gases recovered at these higher shock pressures, probably caused by reaction of evolved H2O with the metal gas recovery fixture. Gaseous H2O-H2 isotopic fractionation suggests high temperature isotopic equilibrium between the gaseous species, indicating initiation of devolatilization at sites of greater than average energy deposition. Bulk gas-residual solid isotopic fractionations indicate nonequilibrium, kinetic control of gas-solid isotopic ratios. Impact-induced hydrogen isotopic fractionation of hydrous silicates during accretion can strongly affect the long-term planetary isotopic ratios of planetary bodies, leaving the interiors enriched in deuterium. Depending on the model used for extrapolation of the isotopic fractionation to devolatilization fractions greater than those investigated experimentally can result from this process.

Sulphur tracer experiments in laboratory animals using 34S-labelled yeast.

PubMed

Martínez-Sierra, J Giner; Moreno Sanz, F; Herrero Espílez, P; Marchante Gayón, J M; Rodríguez Fernández, J; García Alonso, J I

2013-03-01

We have evaluated the use of (34)S-labelled yeast to perform sulphur metabolic tracer experiments in laboratory animals. The proof of principle work included the selection of the culture conditions for the preparation of sulphur labelled yeast, the study of the suitability of this labelled yeast as sulphur source for tracer studies using in vitro gastrointestinal digestion and the administration of the (34)S-labelled yeast to laboratory animals to follow the fate and distribution of (34)S in the organism. For in vitro gastrointestinal digestion, the combination of sodium dodecyl sulphate-polyacrylamide gel electrophoresis and high-performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICP-MS) showed that labelled methionine, cysteine and other low molecular weight sulphur-containing biomolecules were the major components in the digested extracts of the labelled yeast. Next, in vivo kinetic experiments were performed in healthy Wistar rats after the oral administration of (34)S-labelled yeast. The isotopic composition of total sulphur in tissues, urine and faeces was measured by double-focusing inductively coupled plasma mass spectrometry after microwave digestion. It was observed that measurable isotopic enrichments were detected in all samples. Finally, initial investigations on sulphur isotopic composition of serum and urine samples by HPLC-ICP-MS have been carried out. For serum samples, no conclusive data were obtained. Interestingly, chromatographic analysis of urine samples showed differential isotope enrichment for several sulphur-containing biomolecules.

Towards absolute laser spectroscopic CO2 isotope ratio measurements

NASA Astrophysics Data System (ADS)

Anyangwe Nwaboh, Javis; Werhahn, Olav; Ebert, Volker

2017-04-01

Knowledge of isotope composition of carbon dioxide (CO2) in the atmosphere is necessary to identify sources and sinks of this key greenhouse gas. In the last years, laser spectroscopic techniques such as cavity ring-down spectroscopy (CRDS) and tunable diode laser absorption spectroscopy (TDLAS) have been shown to perform accurate isotope ratio measurements for CO2 and other gases like water vapour (H2O) [1,2]. Typically, isotope ratios are reported in literature referring to reference materials provided by e.g. the International Atomic Energy Agency (IAEA). However, there could be some benefit if field deployable absolute isotope ratio measurement methods were developed to address issues such as exhausted reference material like the Pee Dee Belemnite (PDB) standard. Absolute isotope ratio measurements would be particularly important for situations where reference materials do not even exist. Here, we present CRDS and TDLAS-based absolute isotope ratios (13C/12C ) in atmospheric CO2. We demonstrate the capabilities of the used methods by measuring CO2 isotope ratios in gas standards. We compare our results to values reported for the isotope certified gas standards. Guide to the expression of uncertainty in measurement (GUM) compliant uncertainty budgets on the CRDS and TDLAS absolute isotope ratio measurements are presented, and traceability is addressed. We outline the current impediments in realizing high accuracy absolute isotope ratio measurements using laser spectroscopic methods, propose solutions and the way forward. Acknowledgement Parts of this work have been carried out within the European Metrology Research Programme (EMRP) ENV52 project-HIGHGAS. The EMRP is jointly funded by the EMRP participating countries within EURAMET and the European Union. References [1] B. Kühnreich, S. Wagner, J. C. Habig,·O. Möhler, H. Saathoff, V. Ebert, Appl. Phys. B 119:177-187 (2015). [2] E. Kerstel, L. Gianfrani, Appl. Phys. B 92, 439-449 (2008).

Stable isotope monitoring of ionic trapping of CO2 in deep brines

NASA Astrophysics Data System (ADS)

Myrttinen, A.; Barth, J. A. C.; Becker, V.; Blum, P.; Grathwohl, P.

2009-04-01

CO2 injection into a depleted gas-reservoir is used as a combined method for Enhanced Gas Recovery (EGR) and CO2 storage. In order to safeguard this process, monitoring the degree of dissolution and potential further precipitation and mineral interactions are a necessity. Here a method is introduced, in which stable isotope and geochemical data can be used as a monitoring technique to quantify ionic trapping of injected CO2. Isotope and geochemical data of dissolved inorganic carbon (DIC) can be used to distinguish between already present and to be injected inorganic carbon. Injected CO2, for instance, is formed during combustion of former plant material and is expected to have a different isotope ratio (δ13C value) than the baseline data of the aquifer. This is because combusted CO2 originates from organic material, such as coal and oil with a predominant C3 plant signature. Mixing the injected CO2 with groundwater is therefore expected to change the isotope, as well as the geochemical composition of the groundwater. Mass balance calculations with stable isotope ratios can serve to quantify ionic trapping of CO2 as DIC in groundwater. However, depending on the composition of the aquifer, weathering of carbonate or silicates may occur. Enhanced weathering processes due to CO2 injection can also further influence the isotopic composition. Such interactions between dissolved CO2 and minerals depend on the temperature and pressure regimes applied. Field data, as well as laboratory experiments are planned to quantify isotope ratios of dissolved inorganic carbon as well as oxygen isotope ratios of the water. These are indicative of geochemical processes before, during and after EGR. The isotope method should therefore provide a new tool to quantify the efficiency of ionic trapping under various temperatures and pressures. Keywords: Enhanced Gas Recovery, monitoring of CO2 dissolution, stable isotopes

EPA Method: Rapid Radiochemical Method for Americium-241, Radium-226, Plutonium-238/-239, Radiostronium, and Isotopic Uranium in Water for Environmental Restoration Following Homeland Security Events

EPA Pesticide Factsheets

SAM lists this method for the qualitative determination of Americium-241, Radium-226, Plutonium-238, Plutonium-239 and isotopic uranium in drinking water samples using alpha spectrometry and radiostrontium using beta counting.

A segmented, enriched N-type germanium detector for neutrinoless double beta-decay experiments

NASA Astrophysics Data System (ADS)

Leviner, L. E.; Aalseth, C. E.; Ahmed, M. W.; Avignone, F. T.; Back, H. O.; Barabash, A. S.; Boswell, M.; De Braeckeleer, L.; Brudanin, V. B.; Chan, Y.-D.; Egorov, V. G.; Elliott, S. R.; Gehman, V. M.; Hossbach, T. W.; Kephart, J. D.; Kidd, M. F.; Konovalov, S. I.; Lesko, K. T.; Li, Jingyi; Mei, D.-M.; Mikhailov, S.; Miley, H.; Radford, D. C.; Reeves, J.; Sandukovsky, V. G.; Umatov, V. I.; Underwood, T. A.; Tornow, W.; Wu, Y. K.; Young, A. R.

2014-01-01

We present data characterizing the performance of the first segmented, N-type Ge detector, isotopically enriched to 85% 76Ge. This detector, based on the Ortec PT6×2 design and referred to as SEGA (Segmented, Enriched Germanium Assembly), was developed as a possible prototype for neutrinoless double beta-decay measurements by the MAJORANA collaboration. We present some of the general characteristics (including bias potential, efficiency, leakage current, and integral cross-talk) for this detector in its temporary cryostat. We also present an analysis of the resolution of the detector, and demonstrate that for all but two segments there is at least one channel that reaches the MAJORANA resolution goal below 4 keV FWHM at 2039 keV, and all channels are below 4.5 keV FWHM.

Liquid xenon purification, de-radonation (and de-kryptonation)

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

Pocar, Andrea, E-mail: pocar@umass.edu; Physics Division, Lawrence Livermore National Laboratory, Livermore, California 94550

Liquid xenon detectors are at the forefront of rare event physics, including searches for neutrino-less double beta decay and WIMP dark matter. The xenon for these experiments needs to be purified from chemical impurities such as electronegative atoms and molecules, which absorb ionization electrons, and VUV (178 nm) scintillation light-absorbing chemical species. In addition, superb purification from radioactive impurities is required. Particularly challenging are radioactive noble isotopes ({sup 85}Kr,{sup 39,42}Ar,{sup 220,222}Rn). Radon is a particularly universal problem, due to the extended decay sequence of its daughters and its ubiquitous presence in detector materials. Purification and de-radonation of liquid xenon aremore » addressed with particular focus on the experience gained with the EXO-200 neutrino-less double beta decay detector.« less

First array of enriched Zn$$^{82}$$Se bolometers to search for double beta decay

DOE PAGES

Artusa, D. R.; Balzoni, A.; Beeman, J. W.; ...

2016-07-01

The R&D activity performed during the last years proved the potential of ZnSe scintillating bolometers to the search for neutrino-less double beta decay, motivating the realization of the first large-mass experiment based on this technology: CUPID-0. The isotopic enrichment in 82Se, the Zn 82Se crystals growth, as well as the light detectors production have been accomplished, and the experiment is now in construction at Laboratori Nazionali del Gran Sasso (Italy). In this paper we present the results obtained testing the first three Zn 82Se crystals operated as scintillating bolometers, and we prove that their performance in terms of energy resolution,more » background rejection capability and intrinsic radio-purity complies with the requirements of CUPID-o.« less

(90)Y microspheres prepared by sol-gel method, promising medical material for radioembolization of liver malignancies.

PubMed

Łada, Wiesława; Iller, Edward; Wawszczak, Danuta; Konior, Marcin; Dziel, Tomasz

2016-10-01

A new technology for the production of radiopharmaceutical (90)Y microspheres in the form of spherical yttrium oxide grains obtained by sol-gel method has been described. The authors present and discuss the results of investigations performed in the development of new production technology of yttrium microspheres and determination of their physic-chemical properties. The final product has the structure of spherical yttrium oxide grains with a diameter 25-100μm, is stable and free from contaminants. Irradiation of 20mg samples of grains with diameter of 20-50μm in the thermal neutron flux of 1.7×10(14)cm(-2)s(-1) at the core of MARIA research nuclear reactor allowed to obtain microspheres labelled with the (90)Y isotope on the way of the nuclear reaction (89)Y(n, ɤ)(90)Y. Specific activity of irradiated microspheres has been determined by application of absolute triple to double coincidence ratio method (TDCR) and has been evaluated at 190MBq/mg Y. (90)Y microspheres prepared by the proposed technique can be regarded as a promising medical material for radioembolization of liver malignancies. Copyright © 2016 Elsevier B.V. All rights reserved.

First-excited state g factor of Te 136 by the recoil in vacuum method

DOE PAGES

Stuchbery, A. E.; Allmond, J. M.; Danchev, M.; ...

2017-07-27

The g factor of the first 2 + state of radioactive 136Te with two valence protons and two valence neutrons beyond double-magic 132Sn has been measured by the recoil in vacuum (RIV) method. The lifetime of this state is an order of magnitude longer than the lifetimes of excited states recently measured by the RIV method in Sn and Te isotopes, requiring a new evaluation of the free-ion hyperfine interactions and methodology used to determine the g factor. In this paper, the calibration data are reported and the analysis procedures are described in detail. The resultant g factor has amore » similar magnitude to the g factors of other nuclei with an equal number of valence protons and neutrons in the major shell. However, an unexpected trend is found in the g factors of the N = 84 isotones, which decrease from 136Te to 144Nd. Finally, shell model calculations with interactions derived from the CD Bonn potential show good agreement with the g factors and E2 transition rates of 2 + states around 132Sn, confirming earlier indications that 132Sn is a good doubly magic core.« less

First-excited state g factor of Te 136 by the recoil in vacuum method

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

Stuchbery, A. E.; Allmond, J. M.; Danchev, M.

The g factor of the first 2 + state of radioactive 136Te with two valence protons and two valence neutrons beyond double-magic 132Sn has been measured by the recoil in vacuum (RIV) method. The lifetime of this state is an order of magnitude longer than the lifetimes of excited states recently measured by the RIV method in Sn and Te isotopes, requiring a new evaluation of the free-ion hyperfine interactions and methodology used to determine the g factor. In this paper, the calibration data are reported and the analysis procedures are described in detail. The resultant g factor has amore » similar magnitude to the g factors of other nuclei with an equal number of valence protons and neutrons in the major shell. However, an unexpected trend is found in the g factors of the N = 84 isotones, which decrease from 136Te to 144Nd. Finally, shell model calculations with interactions derived from the CD Bonn potential show good agreement with the g factors and E2 transition rates of 2 + states around 132Sn, confirming earlier indications that 132Sn is a good doubly magic core.« less

Large Carbon Dioxide Fluxes from Headwater Boreal and Sub-Boreal Streams

PubMed Central

Venkiteswaran, Jason J.; Schiff, Sherry L.; Wallin, Marcus B.

2014-01-01

Half of the world's forest is in boreal and sub-boreal ecozones, containing large carbon stores and fluxes. Carbon lost from headwater streams in these forests is underestimated. We apply a simple stable carbon isotope idea for quantifying the CO2 loss from these small streams; it is based only on in-stream samples and integrates over a significant distance upstream. We demonstrate that conventional methods of determining CO2 loss from streams necessarily underestimate the CO2 loss with results from two catchments. Dissolved carbon export from headwater catchments is similar to CO2 loss from stream surfaces. Most of the CO2 originating in high CO2 groundwaters has been lost before typical in-stream sampling occurs. In the Harp Lake catchment in Canada, headwater streams account for 10% of catchment net CO2 uptake. In the Krycklan catchment in Sweden, this more than doubles the CO2 loss from the catchment. Thus, even when corrected for aquatic CO2 loss measured by conventional methods, boreal and sub-boreal forest carbon budgets currently overestimate carbon sequestration on the landscape. PMID:25058488

Effect of SiO2 coating in bolometric Ge light detectors for rare event searches

NASA Astrophysics Data System (ADS)

Beeman, J. W.; Gentils, A.; Giuliani, A.; Mancuso, M.; Pessina, G.; Plantevin, O.; Rusconi, C.

2013-05-01

In germanium-based light detectors for scintillating bolometers, a SiO2 anti-reflective coating is often applied on the side of the germanium wafer exposed to light with the aim to improve its light collection efficiency. In this paper, we report about a measurement, performed in the temperature range 25-35 mK, of the light-collection increase obtained thanks to this method, which resulted to be of the order of 20%. The procedure followed has been carefully selected in order to minimize systematic effects. The employed light sources have the same spectral features (peaking at ˜630 nm wavelength) that will characterize future neutrinoless double beta decay experiments on the isotope 82Se and based on ZnSe crystals, such as LUCIFER. The coupling between source and light detector reproduces the configuration used in scintillating bolometers. The present measurement clarifies the role of SiO2 coating and describes a method and a set-up that can be extended to the study of other types of coatings and luminescent materials.

MATHEMATICS PANEL QUARTERLY PROGRESS REPORT FOR PERIOD ENDING JULY 31, 1952

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

Perry, C.L. ed.

1952-10-27

The background and status of the following projects of the Mathematics Panel are reported: test problems for the ORAC arithmetic units errors in matrix operations; basic studies in the Monte Carlo methods A Sturm-Liouville problems approximate steady-state solution of the equation of continuity; estimation of volume of lymph space; xradiation effects on respiration rates in grasshopper embnyos; temperature effects in irradiation experiments with yeast; LD/sub 50/ estimation for burros and swine exposed to gamma radiation; thermal-neutron penetration in tissues; kinetics of HBr-HBrO/sub 3/ reaction; isotope effect in reaction rate constants; experimental determination of diffusivity coefficientss Dirac wave equationss fitting amore » calibration curves beta decay (field factors); neutron decay theorys calculation of internal conversion coefficients with screening; estimation of alignment ratios; optimum allocation of counting times calculation of coincidence probabilities for a double-crystal detectors reactor inequalities; heat flow in long rectangular tubes; solving an equation by numerical methods; numerical integration; evalvation of a functions depigmentation of a biological dosimeter. (L.M.T.)« less

Large carbon dioxide fluxes from headwater boreal and sub-boreal streams.

PubMed

Venkiteswaran, Jason J; Schiff, Sherry L; Wallin, Marcus B

2014-01-01

Half of the world's forest is in boreal and sub-boreal ecozones, containing large carbon stores and fluxes. Carbon lost from headwater streams in these forests is underestimated. We apply a simple stable carbon isotope idea for quantifying the CO2 loss from these small streams; it is based only on in-stream samples and integrates over a significant distance upstream. We demonstrate that conventional methods of determining CO2 loss from streams necessarily underestimate the CO2 loss with results from two catchments. Dissolved carbon export from headwater catchments is similar to CO2 loss from stream surfaces. Most of the CO2 originating in high CO2 groundwaters has been lost before typical in-stream sampling occurs. In the Harp Lake catchment in Canada, headwater streams account for 10% of catchment net CO2 uptake. In the Krycklan catchment in Sweden, this more than doubles the CO2 loss from the catchment. Thus, even when corrected for aquatic CO2 loss measured by conventional methods, boreal and sub-boreal forest carbon budgets currently overestimate carbon sequestration on the landscape.

A quantum cascade laser infrared spectrometer for CO2 stable isotope analysis: Field implementation at a hydrocarbon contaminated site under bio-remediation.

PubMed

Guimbaud, Christophe; Noel, Cécile; Chartier, Michel; Catoire, Valéry; Blessing, Michaela; Gourry, Jean Christophe; Robert, Claude

2016-02-01

Real-time methods to monitor stable isotope ratios of CO2 are needed to identify biogeochemical origins of CO2 emissions from the soil-air interface. An isotope ratio infra-red spectrometer (IRIS) has been developed to measure CO2 mixing ratio with δ(13)C isotopic signature, in addition to mixing ratios of other greenhouse gases (CH4, N2O). The original aspects of the instrument as well as its precision and accuracy for the determination of the isotopic signature δ(13)C of CO2 are discussed. A first application to biodegradation of hydrocarbons is presented, tested on a hydrocarbon contaminated site under aerobic bio-treatment. CO2 flux measurements using closed chamber method is combined with the determination of the isotopic signature δ(13)C of the CO2 emission to propose a non-intrusive method to monitor in situ biodegradation of hydrocarbons. In the contaminated area, high CO2 emissions have been measured with an isotopic signature δ(13)C suggesting that CO2 comes from petroleum hydrocarbon biodegradation. This first field implementation shows that rapid and accurate measurement of isotopic signature of CO2 emissions is particularly useful in assessing the contribution of contaminant degradation to the measured CO2 efflux and is promising as a monitoring tool for aerobic bio-treatment. Copyright © 2016. Published by Elsevier B.V.

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

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

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

New Technique for Barium Daughter Ion Identification in a Liquid Xe-136 Double Beta Decay Experiment

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

Fairbank, William

2016-06-08

This work addresses long-standing issues of fundamental interest in elementary particle physics. The most important outcome of this work is a new limit on neutrinoless double beta decay. This is an extremely rare and long-sought-after type of radioactive decay. If discovered, it would require changes in the standard model of the elementary constituents of matter, and would prove that neutrinos and antineutrinos are the same, a revolutionary concept in particle physics. Neutrinos are major components of the matter in the universe that are so small and so weakly interacting with other matter that their masses have not yet been discovered.more » A discovery of neutrinoless double beta decay could help determine the neutrino masses. An important outcome of the work on this project was the Colorado State University role in operating the EXO-200 neutrinoless double beta decay experiment and in analysis of the data from this experiment. One type of double beta decay of the isotope 136Xe, the two-neutrino variety, was discovered in this work. Although the other type of double beta decay, the neutrinoless variety, was not yet discovered in this work, a world’s best sensitivity of 1.9x10 25 year half-life was obtained. This result rules out a previous claim of a positive result in a different isotope. This work also establishes that the masses of the neutrinos are less than one millionth of that of electrons. A unique EXO-200 analysis, in which the CSU group had a leading role, has established for the first time ever in a liquid noble gas the fraction of daughter atoms from alpha and beta decay that are ionized. This result has important impact on other pending studies, including nucleon decay and barium tagging. Novel additional discoveries include multiphoton ionization of liquid xenon with UV pulsed lasers, which may find application in calibration of future noble liquid detectors, and studies of association and dissociation reactions of Ba + ions in gaseous xenon. Through this project, we are substantially closer to demonstrating “barium tagging”, i.e., detection of single daughter 136Ba atoms from 136Xe double beta decay. Milestones achieved include obtaining spectra of small numbers of Ba atoms and cryoprobe advances toward trapping single 136Ba atoms in solid xenon and probe extraction for detection. One of the other benefits to society is the training of six Ph.D. students in a variety of state-of-the-art technologies, half under primary support of this grant and half with partial support, with four finishing their Ph.D. degrees and two well on their way.« less

Carbon Stable Isotope Fractionation of Sulfamethoxazole during Biodegradation by Microbacterium sp. Strain BR1 and upon Direct Photolysis.

PubMed

Birkigt, Jan; Gilevska, Tetyana; Ricken, Benjamin; Richnow, Hans-Hermann; Vione, Davide; Corvini, Philippe F-X; Nijenhuis, Ivonne; Cichocka, Danuta

2015-05-19

Carbon isotope fractionation of sulfamethoxazole (SMX) during biodegradation by Microbacterium sp. strain BR1 (ipso-hydroxylation) and upon direct photolysis was investigated. Carbon isotope signatures (δ(13)C) of SMX were measured by LC-IRMS (liquid chromatography coupled to isotope ratio mass spectrometry). A new LC-IRMS method for the SMX metabolite, 3-amino-5-methylisoxazole (3A5MI), was established. Carbon isotope enrichment factors for SMX (ε(C)) were -0.6 ± 0.1‰ for biodegradation and -2.0 ± 0.1‰ and -3.0 ± 0.2‰ for direct photolysis, at pH 7.4 and pH 5, respectively. The corresponding apparent kinetic isotope effects (AKIE) for ipso-hydroxylation were 1.006 ± 0.001; these fall in the same range as AKIE in previously studied hydroxylation reactions. The differences in SMX and 3A5MI fractionation upon biotic and abiotic degradation suggest that compound specific stable isotope analysis (CSIA) is a suitable method to distinguish SMX reaction pathways. In addition, the study revealed that the extent of isotope fractionation during SMX photolytic cleavage is pH-dependent.

SRS-sensor 13C/12C isotops measurements for detecting Helicobacter Pylori

NASA Astrophysics Data System (ADS)

Grishkanich, Aleksandr; Chubchenko, Yan; Elizarov, Valentin; Zhevlakov, Aleksandr; Konopelko, Leonid

2018-02-01

We developed SRS-sensor 13C/12C isotops measurements detecting Helicobacter Pylori for medical diagnostics of human health. Measuring of absolute 13C/12C isotope amount ratios allows to explore the topical problems of the modern world, alcoholic beverages and tobacco, medical diagnostics of human health. SRS method is used to measure the ratio of carbon isotopes in the exhaled carbon dioxide, which is used to diagnose the human infection of Helicobacter pylori and the influence of the Helicobacter pylori bacterium on the occurrence of gastritis, gastric and duodenal ulcers. A method for the analysis of human infection with Helicobacter pylori was developed on the basis of measurements of the ratio of 13C / 12C carbon isotopes in human exhaled air with a high level of measurement accuracy. The article reviews the work in the field of provision comparability of absolute 13C/12C isotope amount ratios in the environment and food. The analysis of the technical and metrological characteristics of traditional and perspective instruments for measuring isotope ratios is presented. The provision of comparability of absolute 13C/12C isotope amount ratios is carried by gravimetrically prepared reference standards. The key features and emerging issues are discussed.

The first investigation of Wilms' tumour atomic structure-nitrogen and carbon isotopic composition as a novel biomarker for the most individual approach in cancer disease

PubMed Central

Taran, Katarzyna; Frączek, Tomasz; Sikora-Szubert, Anita; Sitkiewicz, Anna; Młynarski, Wojciech; Kobos, Józef; Paneth, Piotr

2016-01-01

The paper describes a novel approach to investigating Wilms' tumour (nephroblastoma) biology at the atomic level. Isotope Ratio Mass Spectrometry (IRMS) was used to directly assess the isotope ratios of nitrogen and carbon in 84 Wilms' tumour tissue samples from 28 cases representing the histological spectrum of nephroblastoma. Marked differences in nitrogen and carbon isotope ratios were found between nephroblastoma histological types and along the course of cancer disease, with a breakout in isotope ratio of the examined elements in tumour tissue found between stages 2 and 3. Different isotopic compositions with regard to nitrogen and carbon content were observed in blastemal Wilms' tumour, with and without focal anaplasia, and in poorly- and well-differentiated epithelial nephroblastoma. This first assessment of nitrogen and carbon isotope ratio reveals the previously unknown part of Wilms' tumour biology and represents a potential novel biomarker, allowing for a highly individual approach to treating cancer. Furthermore, this method of estimating isotopic composition appears to be the most sensitive tool yet for cancer tissue evaluation, and a valuable complement to established cancer study methods with prospective clinical impact. PMID:27732932

Cryogenic separation of an oxygen-argon mixture in natural air samples for the determination of isotope and molecular ratios.

PubMed

Keedakkadan, Habeeb Rahman; Abe, Osamu

2015-04-30

The separation and purification of oxygen-argon mixtures are critical in the high-precision analysis of Δ(17) O and δ(O2 /Ar) for geochemical applications. At present, chromatographic methods are used for the separation and purification of oxygen-argon mixtures or pure oxygen, but these methods require the use of high-purity helium as a carrier gas. Considerable interest has been expressed in the development of a helium-free cryogenic separation of oxygen-argon mixtures in natural air samples. The precise and simplified cryogenic separation of oxygen-argon mixtures from natural air samples presented here was made possible using a single 5A (30/60 mesh) molecular sieve column. The method involves the trapping of eluted gases using molecular sieves at liquid nitrogen temperature, which is associated with isotopic fractionation. We tested the proposed method for the determination of isotopic fractionations during the gas exchange between water and atmospheric air at equilibrium. The dependency of fractionation was studied at different water temperatures and for different methods of equilibration (bubbling and stirring). Isotopic and molecular fractionations during gas desorption from molecular sieves were studied for different amounts and types of molecular sieves. Repeated measurements of atmospheric air yielded a reproducibility (±SD) of 0.021 ‰, 0.044 ‰, 15 per meg and 1.9 ‰ for δ(17) O, δ(18) O, Δ(17) O and δ(O2 /Ar) values, respectively. We applied the method to determine equilibrium isotope fractionation during gas exchange between air and water. Consistent δ(18) O and Δ(17) O results were obtained with the latest two studies, whereas there was a significant difference in δ(18) O values between seawater and deionized water. We have revised a helium-free, cryogenic separation of oxygen-argon mixtures in natural air samples for isotopic and molecular ratio analysis. The use of a single 13X (1/8" pellet) molecular sieve yielded the smallest isotopic and molecular fractionations, and this fractionation by molecular sieves can be corrected by the amount of molecular sieve used in the experiment. The reproducibility of the method was tested by the measurement of the oxygen isotope ratios of dissolved oxygen at equilibrium with atmospheric air. We confirmed that the choice of methods for making air-equilibrated water was not related to the magnitude of isotope fractionation, whereas there was a difference between seawater and deionized water. Copyright © 2015 John Wiley & Sons, Ltd.

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

Kathawa, J.; Fry, C.; Thoennessen, M., E-mail: thoennessen@nscl.msu.edu

Currently, thirty-eight palladium, thirty-eight antimony, thirty-nine tellurium, thirty-eight iodine, and forty xenon isotopes have been observed and the discovery of these isotopes is described here. For each isotope a brief synopsis of the first refereed publication, including the production and identification method, is presented.

Isotopic analysis of N and O in nitrite and nitrate by sequential selective bacterial reduction to N2O

USGS Publications Warehouse

Böhlke, J.K.; Smith, R.L.; Hannon, J.E.

2007-01-01

Nitrite is an important intermediate species in the biogeochemical cycling of nitrogen, but its role in natural aquatic systems is poorly understood. Isotopic data can be used to study the sources and transformations of NO2- in the environment, but methods for independent isotopic analyses of NO2- in the presence of other N species are still new and evolving. This study demonstrates that isotopic analyses of N and O in NO2- can be done by treating whole freshwater or saltwater samples with the denitrifying bacterium Stenotrophomonas nitritireducens, which selectively reduces NO2- to N2O for isotope ratio mass spectrometry. When calibrated with solutions containing NO2- with known isotopic compositions determined independently, reproducible δ15N and δ18O values were obtained at both natural-abundance levels (±0.2−0.5‰ for δ15N and ±0.4−1.0‰ for δ18O) and moderately enriched 15N tracer levels (±20−50‰ for δ15N near 5000‰) for 5−20 nmol of NO2- (1−20 μmol/L in 1−5 mL aliquots). This method is highly selective for NO2-and was used for mixed samples containing both NO2- and NO3- with little or no measurable cross-contamination. In addition, mixed samples that were analyzed with S. nitritireducens were treated subsequently with Pseudomonas aureofaciens to reduce the NO3- in the absence of NO2-, providing isotopic analyses of NO2- and NO3- separately in the same aliquot. Sequential bacterial reduction methods like this one should be useful for a variety of isotopic studies aimed at understanding nitrogen cycling in aquatic environments. A test of these methods in an agricultural watershed in Indiana provides isotopic evidence for both nitrification and denitrification as sources of NO2- in a small stream.

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

NASA Astrophysics Data System (ADS)

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

2005-01-01

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

Mono-isotope Prediction for Mass Spectra Using Bayes Network.

PubMed

Li, Hui; Liu, Chunmei; Rwebangira, Mugizi Robert; Burge, Legand

2014-12-01

Mass spectrometry is one of the widely utilized important methods to study protein functions and components. The challenge of mono-isotope pattern recognition from large scale protein mass spectral data needs computational algorithms and tools to speed up the analysis and improve the analytic results. We utilized naïve Bayes network as the classifier with the assumption that the selected features are independent to predict mono-isotope pattern from mass spectrometry. Mono-isotopes detected from validated theoretical spectra were used as prior information in the Bayes method. Three main features extracted from the dataset were employed as independent variables in our model. The application of the proposed algorithm to publicMo dataset demonstrates that our naïve Bayes classifier is advantageous over existing methods in both accuracy and sensitivity.

The variation of molybdenum isotopes within the weathering system of the black shales

NASA Astrophysics Data System (ADS)

Jianming, Z.

2016-12-01

Jian-Ming Zhu 1,2, De-Can Tan 2, Liang Liang 2, Wang Jing21 State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing, 100083, China 2 State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang, 550002, China Molybdenum (Mo) stable isotopes have been developed as a tracer to indicate the evolution of the atmospheric and oceanic oxygenation related with continent weathering, and to reveal the extent of ancient oceanic euxinia. Molybdenum isotopic variation within the weathering system of basalts has been studied, and was presented the whole trend with heavier isotopes preferentially removed during weathering processes. However, there are few researches to study the variation of Mo isotopes during black shale weathering, especiall on the behavoir of Mo isotopes within the perfect shales' profiles. Here, the weathering profiles of Mo and selenium(Se)-rich carbonaceous rocks in Enshi southwest Hubei Province were selected. The Mo isotopes was measured on Nu Plasma II's MC-ICP-MS using 97Mo-100Mo double spike, and δ98/95Mo was reported relative to NIST 3134. A comprehensive set of Mo isotopic composition and concentration data from the unweathered, weakly and intensely weathered rocks were collected. The δ98/95Mo in fresh shales (220±248 mg/kg Mo, 1SD, n=41) from Shadi and Yutangba drill cores varies from 0.41‰ to 0.99‰ with an average of 0.67±0.16‰, while the strongly weathered shales (19.9±5.8 mg/kg Mo, 1SD, n=5) from Shadi profiles are isotopically heavier with average δ98/95Mo values of 1.03±0.10‰ (1SD, n=5). The Locally altered shales exposed in a quarry at Yutangba are highly enriched in Mo, varing from 31 to 2377 mg/kg with an average of 428 ±605mg/kg (1SD, n=24), approximately 2 times greater than that in fresh shales samples. These rocks are presented a significant variation in δ98/95Mo values varing from -0.24 ‰ to -3.99 ‰ with average -1.67±1.57‰, showing the extremely negative δ98/95Mo values existed in natural samples. This suggested that Mo isotopes can be fractionated during shales weathering processes, with lighter isotopes preferentially removed. This finding is in contrast to the previous knowledge from basalt weathering, and requires further study.

Method of preparing mercury with an arbitrary isotopic distribution

DOEpatents

Grossman, Mark W.; George, William A.

1986-01-01

This invention provides for a process for preparing mercury with a predetermined, arbitrary, isotopic distribution. In one embodiment, different isotopic types of Hg.sub.2 Cl.sub.2, corresponding to the predetermined isotopic distribution of Hg desired, are placed in an electrolyte solution of HCl and H.sub.2 O. The resulting mercurous ions are then electrolytically plated onto a cathode wire producing mercury containing the predetermined isotopic distribution. In a similar fashion, Hg with a predetermined isotopic distribution is obtained from different isotopic types of HgO. In this embodiment, the HgO is dissolved in an electrolytic solution of glacial acetic acid and H.sub.2 O. The isotopic specific Hg is then electrolytically plated onto a cathode and then recovered.

Method of preparing mercury with an arbitrary isotopic distribution

DOEpatents

Grossman, M.W.; George, W.A.

1986-12-16

This invention provides for a process for preparing mercury with a predetermined, arbitrary, isotopic distribution. In one embodiment, different isotopic types of Hg[sub 2]Cl[sub 2], corresponding to the predetermined isotopic distribution of Hg desired, are placed in an electrolyte solution of HCl and H[sub 2]O. The resulting mercurous ions are then electrolytically plated onto a cathode wire producing mercury containing the predetermined isotopic distribution. In a similar fashion, Hg with a predetermined isotopic distribution is obtained from different isotopic types of HgO. In this embodiment, the HgO is dissolved in an electrolytic solution of glacial acetic acid and H[sub 2]O. The isotopic specific Hg is then electrolytically plated onto a cathode and then recovered. 1 fig.

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

PubMed

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

2014-11-18

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

Lipid Extraction Techniques for Stable Isotope Analysis and Ecological Assays.

PubMed

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

2017-01-01

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

Stable isotope methodology in the pharmacokinetic studies of androgenic steroids in humans.

PubMed

Shinohara, Y; Baba, S

1990-04-01

The use of stable isotopically labeled steroids combined with gas chromatography/mass spectrometry (GC/MS) has found a broad application in pharmacologic studies. Initially, stable isotopically labeled steroids served as the ideal analytic internal standard for GC/MS analysis; however, their in vivo use has expanded and has proven to be a powerful pharmacokinetic tool. We have successfully used stable isotope methodology to study the pharmacokinetic/bioavailability of androgens. The primary advantage of the technique is that endogenous and exogenous steroids with the same basic structure can be differentiated by using stable isotopically labeled analogs. The method was used to examine the pharmacokinetics of testosterone and testosterone propionate, and to clarify the influence of endogenous testosterone. Another advantage of the isotope methods is that steroidal drugs can be administered concomitantly in two formulations (e.g., solution and solid dosage). A single set of blood samples serves to describe the time course of the formulations being compared. This stable isotope coadministration technique was used to estimate the relative bioavailability of 17 alpha-methyltestosterone.

Congener-specific determination of ultratrace levels of chlorinated and brominated polycyclic aromatic hydrocarbons in atmosphere and industrial stack gas by isotopic dilution gas chromatography/high resolution mass spectrometry method.

PubMed

Jin, Rong; Liu, Guorui; Zheng, Minghui; Fiedler, Heidelore; Jiang, Xiaoxu; Yang, Lili; Wu, Xiaolin; Xu, Yang

2017-08-04

Isotopic dilution gas chromatography combined with high resolution mass spectrometry (GC/HRMS) has overwhelming advantages with respect to the accuracy of congener-specific ultratrace analysis of complex persistent organic pollutants (POPs) in environmental matrices. However, an isotopic dilution GC/HRMS method for analysis of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs) using 13 C-labelled congeners as internal standards has not been established. In this study, a method for identification and quantification of 38 congeners of Cl-PAHs and Br-PAHs in atmosphere and stack gas samples from waste incinerators was developed using the isotopic dilution GC/HRMS technique. The instrumental detection limits of the GC/HRMS method ranged from 0.2pg to 1.8pg for Cl-PAH congeners, and 0.7pg to 2.7pg for Br-PAH congeners, which were about three orders of magnitude lower than those of the GC/quadrupole MS method. This new method developed was also the first to enable determination of Cl-PAH and Br-PAH homologs comprising congeners with the same molecular skeleton and chlorine or bromine substitution numbers. Among the detected congeners, seven Cl-PAH congeners and thirteen Br-PAH congeners that were abundant in the atmosphere and stack gases released from waste incinerators were firstly detected in real samples and reported using the established isotopic dilution GC/HRMS method. The developed isotopic dilution GC/HRMS is significant and needed for better studying the environmental behavior and health risk of Cl-PAHs and Br-PAHs. Copyright © 2017 Elsevier B.V. All rights reserved.

Rat brain-uptake index for phenylethylamine and various monomethylated derivatives.

PubMed

Mosnaim, Aron D; Callaghan, Owen H; Hudzik, Thomas; Wolf, Marion E

2013-04-01

Phenylethylamine and its monomethylated derivatives p-methylphenylethylamine, α-methylphenylethylamine, phenylethylamine itself, N-methylphenylethylamine, o-methylphenylethylamine, and β-methylphenylethylamine, readily cross the blood-brain barrier showing a brain-uptake index (%) ± SD (water considered 100 %), of 108 ± 11, 98 ± 14, 83 ± 6, 78 ± 11, 62 ± 7 and 56 ± 6, respectively (injection of tritiated water and 100 μg standard amine, which was measured by gas-liquid chromatography). Similar brain-uptake index values (determined by double isotope counting) were obtained for phenylethylamine and α-methylphenylethylamine (amphetamine) after the injection of tritiated water and C(14)-labeled amine (either 3 μg or when added 100 μg standard compound), suggesting that they entered the brain via passive diffusion. Accordingly, both amines distributed rather evenly in the various rat brain areas examined: uptake index (%) ± SD (double isotope counting; non-, and diluted labeled amine) for phenylethylamine (89 ± 8 and 78 ± 7, 83 ± 9 and 86 ± 9, 96 ± 6 and 84 ± 7) and for α-methylphenylethylamine (88 ± 11 and 87 ± 9, 93 ± 14 and 87 ± 11, 97 ± 12 and 87 ± 9) for the cerebellum, frontal cortex, and striatum, respectively. These results will aid a greater understanding of the pharmacological and behavioral effects observed after the administration of phenylethylamine and methylphenylethylamine derivatives.

Isospin splitting of nucleon effective mass and symmetry energy in isotopic nuclear reactions

NASA Astrophysics Data System (ADS)

Guo, Ya-Fei; Chen, Peng-Hui; Niu, Fei; Zhang, Hong-Fei; Jin, Gen-Ming; Feng, Zhao-Qing

2017-10-01

Within an isospin and momentum dependent transport model, the dynamics of isospin particles (nucleons and light clusters) in Fermi-energy heavy-ion collisions are investigated for constraining the isospin splitting of nucleon effective mass and the symmetry energy at subsaturation densities. The impacts of the isoscalar and isovector parts of the momentum dependent interaction on the emissions of isospin particles are explored, i.e., the mass splittings of and (). The single and double neutron to proton ratios of free nucleons and light particles are thoroughly investigated in the isotopic nuclear reactions of 112Sn+112Sn and 124Sn+124Sn at incident energies of 50 and 120 MeV/nucleon, respectively. It is found that both the effective mass splitting and symmetry energy impact the kinetic energy spectra of the single ratios, in particular at the high energy tail (larger than 20 MeV). The isospin splitting of nucleon effective mass slightly impacts the double ratio spectra at the energy of 50 MeV/nucleon. A soft symmetry energy with stiffness coefficient of γ s=0.5 is constrained from the experimental data with the Fermi-energy heavy-ion collisions. Supported by Major State Basic Research Development Program in China (2014CB845405, 2015CB856903), National Natural Science Foundation of China (11722546, 11675226, 11675066, U1332207) and Youth Innovation Promotion Association of Chinese Academy of Sciences

Method for isotope enrichment by photoinduced chemiionization

DOEpatents

Dubrin, James W.

1985-01-01

Isotope enrichment, particularly .sup.235 U enrichment, is achieved by irradiating an isotopically mixed vapor feed with radiant energy at a wavelength or wavelengths chosen to selectively excite the species containing a desired isotope to a predetermined energy level. The vapor feed if simultaneously reacted with an atomic or molecular reactant species capable of preferentially transforming the excited species into an ionic product by a chemiionization reaction. The ionic product, enriched in the desired isotope, is electrostatically or electromagnetically extracted from the reaction system.

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

PubMed

Fischer, Anko; Manefield, Mike; Bombach, Petra

2016-10-01

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

Method and apparatus for separation of heavy and tritiated water

DOEpatents

Lee, Myung W.

2001-01-01

The present invention is a bi-thermal membrane process for separating and recovering hydrogen isotopes from a fluid containing hydrogen isotopes, such as water and hydrogen gas. The process in accordance with the present invention provides counter-current cold and hot streams of the fluid separated with a thermally insulating and chemically transparent proton exchange membrane (PEM). The two streams exchange hydrogen isotopes through the membrane: the heavier isotopes migrate into the cold stream, while the lighter isotopes migrate into the hot stream. The heavy and light isotopes are continuously withdrawn from the cold and hot streams respectively.

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

PubMed

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

2015-01-06

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

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

PubMed

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

2007-06-01

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

Improved characterization of the botanical origin of sugar by carbon-13 SNIF-NMR applied to ethanol.

PubMed

Thomas, Freddy; Randet, Celia; Gilbert, Alexis; Silvestre, Virginie; Jamin, Eric; Akoka, Serge; Remaud, Gerald; Segebarth, Nicolas; Guillou, Claude

2010-11-24

Until now, no analytical method, not even isotopic ones, had been able to differentiate between sugars coming from C4-metabolism plants (cane, maize, etc.) and some crassulacean acid metabolism plants (e.g., pineapple, agave) because in both cases the isotope distributions of the overall carbon-13/carbon-12 and site-specific deuterium/hydrogen isotope ratios are very similar. Following recent advances in the field of quantitative isotopic carbon-13 NMR measurements, a procedure for the analysis of the positional carbon-13/carbon-12 isotope ratios of ethanol derived from the sugars of pineapples and agave using the site-specific natural isotopic fractionation-nuclear magnetic resonance (SNIF-NMR) method is presented. It is shown that reproducible results can be obtained when appropriate analytical conditions are used. When applied to pineapple juice, this new method demonstrates a unique ability to detect cane and maize sugar, which are major potential adulterants, with a detection limit in the order of 15% of the total sugars, which provides an efficient mean of controlling the authenticity of juices made from this specific fruit. When applied to tequila products, this new method demonstrates a unique ability to unambiguously differentiate authentic 100% agave tequila, as well as misto tequila (made from at least 51% agave), from products made from a larger proportion of cane or maize sugar and therefore not complying with the legal definition of tequila.

Toward a simple, repeatable, non-destructive approach to measuring stable-isotope ratios of water within tree stems

NASA Astrophysics Data System (ADS)

Raulerson, S.; Volkmann, T.; Pangle, L. A.

2017-12-01

Traditional methodologies for measuring ratios of stable isotopes within the xylem water of trees involve destructive coring of the stem. A recent approach involves permanently installed probes within the stem, and an on-site assembly of pumps, switching valves, gas lines, and climate-controlled structure for field deployment of a laser spectrometer. The former method limits the possible temporal resolution of sampling, and sample size, while the latter may not be feasible for many research groups. We present results from initial laboratory efforts towards developing a non-destructive, temporally-resolved technique for measuring stable isotope ratios within the xylem flow of trees. Researchers have used direct liquid-vapor equilibration as a method to measure isotope ratios of the water in soil pores. Typically, this is done by placing soil samples in a fixed container, and allowing the liquid water within the soil to come into isotopic equilibrium with the headspace of the container. Water can also be removed via cryogenic distillation or azeotropic distillation, with the resulting liquid tested for isotope ratios. Alternatively, the isotope ratios of the water vapor can be directly measured using a laser-based water vapor isotope analyzer. Well-established fractionation factors and the isotope ratios in the vapor phase are then used to calculate the isotope ratios in the liquid phase. We propose a setup which would install a single, removable chamber onto a tree, where vapor samples could non-destructively and repeatedly be taken. These vapor samples will be injected into a laser-based isotope analyzer by a recirculating gas conveyance system. A major part of what is presented here is in the procedure of taking vapor samples at 100% relative humidity, appropriately diluting them with completely dry N2 calibration gas, and injecting them into the gas conveyance system without inducing fractionation in the process. This methodology will be helpful in making temporally resolved measurements of the stable isotopes in xylem water, using a setup that can be easily repeated by other research groups. The method is anticipated to find broad application in ecohydrological analyses, and in tracer studies aimed at quantifying age distributions of soil water extracted by plant roots.

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

PubMed

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

2015-01-01

Research that uses stable isotope analysis often involves a delay between sample collection in the field and laboratory processing, therefore requiring preservation to prevent or reduce tissue degradation and associated isotopic compositions. Although there is a growing literature describing the effects of various preservation techniques, the results are often contextual, unpredictable and vary among taxa, suggesting the need to treat each species individually. We conducted a controlled experiment to test the effects of four preservation methods of muscle tissue from four species of upper trophic-level reef fish collected from the eastern Gulf of Mexico (Red Grouper Epinephelus morio, Gag Mycteroperca microlepis, Scamp Mycteroperca phenax, and Red Snapper Lutjanus campechanus). We used a paired design to measure the effects on isotopic values for carbon and nitrogen after storage using ice, 95% ethanol, and sodium chloride (table salt), against that in a liquid nitrogen control. Mean offsets for both δ (13)C and δ (15)N values from controls were lowest for samples preserved on ice, intermediate for those preserved with salt, and highest with ethanol. Within species, both salt and ethanol significantly enriched the δ (15)N values in nearly all comparisons. Ethanol also had strong effects on the δ (13)C values in all three groupers. Conversely, for samples preserved on ice, we did not detect a significant offset in either isotopic ratio for any of the focal species. Previous studies have addressed preservation-induced offsets in isotope values using a mass balance correction that accounts for changes in the isotope value to that in the C/N ratio. We tested the application of standard mass balance corrections for isotope values that were significantly affected by the preservation methods and found generally poor agreement between corrected and control values. The poor performance by the correction may have been due to preferential loss of lighter isotopes and corresponding low levels of mass loss with a substantial change in the isotope value of the sample. Regardless of mechanism, it was evident that accounting for offsets caused by different preservation methods was not possible using the standard correction. Caution is warranted when interpreting the results from specimens stored in either ethanol or salt, especially when using those from multiple preservation techniques. We suggest the use of ice as the preferred preservation technique for muscle tissue when conducting stable isotope analysis as it is widely available, inexpensive, easy to transport and did not impart a significant offset in measured isotopic values. Our results provide additional evidence that preservation effects on stable isotope analysis can be highly contextual, thus requiring their effects to be measured and understood for each species and isotopic ratio of interest before addressing research questions.

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

NASA Astrophysics Data System (ADS)

Parkes, Stephen; Wang, Lixin; McCabe, Matthew

2015-04-01

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

System for recovery of daughter isotopes from a source material

DOEpatents

Tranter, Troy J [Idaho Falls, ID; Todd, Terry A [Aberdeen, ID; Lewis, Leroy C [Idaho Falls, ID; Henscheid, Joseph P [Idaho Falls, ID

2009-08-04

A method of separating isotopes from a mixture containing at least two isotopes in a solution is disclosed. A first isotope is precipitated and is collected from the solution. A daughter isotope is generated and collected from the first isotope. The invention includes a method of producing an actinium-225/bismuth-213 product from a material containing thorium-229 and thorium-232. A solution is formed containing nitric acid and the material containing thorium-229 and thorium-232, and iodate is added to form a thorium iodate precipitate. A supernatant is separated from the thorium iodate precipitate and a second volume of nitric acid is added to the thorium iodate precipitate. The thorium iodate precipitate is stored and a decay product comprising actinium-225 and bismuth-213 is generated in the second volume of nitric acid, which is then separated from the thorium iodate precipitate, filtered, and treated using at least one chromatographic procedure. A system for producing an actinium-225/bismuth-213 product is also disclosed.

Testing of an automated online EA-IRMS method for fast and simultaneous carbon content and stable isotope measurement of aerosol samples

NASA Astrophysics Data System (ADS)

Major, István; Gyökös, Brigitta; Túri, Marianna; Futó, István; Filep, Ágnes; Hoffer, András; Molnár, Mihály

2016-04-01

Comprehensive atmospheric studies have demonstrated that carbonaceous aerosol is one of the main components of atmospheric particulate matter over Europe. Various methods, considering optical or thermal properties, have been developed for quantification of the accurate amount of both organic and elemental carbon constituents of atmospheric aerosol. The aim of our work was to develop an alternative fast and easy method for determination of the total carbon content of individual aerosol samples collected on prebaked quartz filters whereby the mass and surface concentration becomes simply computable. We applied the conventional "elemental analyzer (EA) coupled online with an isotope ratio mass spectrometer (IRMS)" technique which is ubiquitously used in mass spectrometry. Using this technique we are able to measure simultaneously the carbon stable isotope ratio of the samples, as well. During the developing process, we compared the EA-IRMS technique with an off-line catalytic combustion method worked out previously at Hertelendi Laboratory of Environmental Studies (HEKAL). We tested the combined online total carbon content and stable isotope ratio measurement both on standard materials and real aerosol samples. Regarding the test results the novel method assures, on the one hand, at least 95% of carbon recovery yield in a broad total carbon mass range (between 100 and 3000 ug) and, on the other hand, a good reproducibility of stable isotope measurements with an uncertainty of ± 0.2 per mill. Comparing the total carbon results obtained by the EA-IRMS and the off-line catalytic combustion method we found a very good correlation (R2=0.94) that proves the applicability of both preparation method. Advantages of the novel method are the fast and simplified sample preparation steps and the fully automated, simultaneous carbon stable isotope ratio measurement processes. Furthermore stable isotope ratio results can effectively be applied in the source apportionment investigations of atmospheric carbonaceous aerosol. This research was supported by the European Union and the State of Hungary, co-financed by the European Social Fund in the framework of TÁMOP 4.2.4.A/2-11-1-2012-0001 'National Excellence Program.

Trace Element Study of MORB Glasses from 14¡ã-16¡ãN along Mid-Atlantic Ridge by LA-ICP- MS

NASA Astrophysics Data System (ADS)

Barzoi, C. A.; Casey, J. F.; Gao, Y.; Lapen, T.

2007-12-01

A comparison of 20 MORB glasses from 14°-16° N along the Mid-Atlantic Ridge using both solution-based and in situ laser ablation-based ICP-MS trace element analyses on the same samples was conducted. Li, Be, Sc, Ti, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Tb, Gd, Dy, Ho, Er, Tm, Yb,Lu, Hf, Ta, Pb, Th, and U were analyzed using the Varian 810 quadrupole ICP-MS. The instrument features a 90 degree ion mirror and low noise double-off-axis quadrupole that allows high sensitivity and low backgrounds. Precision in term of relative standard deviation (RSD) of the measurements for both methods based on repeated analyses of USGS BIR-1G and BHVO-2G glass standards and Max Planck KL-2G glass standard is within 5 % for all trace elements with the exception of Pb, which averaged 12 %. Measured trace element abundances are within 2% of recommended standard values using both solution and laser ablation methods. Comparison between the analyte concentrations obtained by solution-based ICP-MS and in situ microanalysis by laser ablation reveals little systematic differences in abundances(<5% for all elements). The two-method correlation and strong repeatability of the results indicate that rapid in situ trace element analysis by laser ablation ICP-MS is likely to become a preferred method of trace element analysis for MORB glasses. Our geochemical results and previous studies of MORB glasses in the region of the MAR between 14°-16°N show that basalts are characterized isotopic and incompatible element enrichment.The nature of the enrichment has been the topic of significant discussion and speculation because a specific mantle plume is not well defined in the region. Likewise the magma supply is probably small in the region as the magmatic crust is interpreted to be very thin in most of the area studied. Integrated studies of major element, trace element, and isotopic variations among basalts, gabbroic rocks and igneous and residual ultramafic rocks in the region indicate that 1) the enriched basalts have positive Ta-Nb anomalies, enriched relative to U, Th, and La 2) basalts have relatively high SiO2 abundances compared to the global average, 3) basalts show a HIMU isotopic signature, and 4) bulk major element abundances and mineral chemistry in mantle rocks indicate that they are among the most depleted,although variably refertilized, residual mantle assemblages sampled to date along MORs.We suggest that much of the regional variation in major and trace element data, as well as isotopic data and the unusual regional geology (multiple core complexes) can be explained by melting of a sub-axial mantle that contains two end members, one highly depleted and the other enriched. These components appear to involve ancient recycled ocean crust and lithospheric mantle.

Isotopic investigation of rivers runoff in glaciated regions of the central Asian arid highlands (southeastern Altai)

NASA Astrophysics Data System (ADS)

Bantcev, Dmitrii; Ganushkin, Dmitriy; Ekaykin, Alexey; Chistyakov, Kirill

2017-04-01

Stable isotopes investigations were carried out during fieldwork in glacier basins of the Mongun-Taiga (southwestern Tuva) and Tsambagarav (northwestern Mongolia) mountain massifs in July, 2016. These Arid highlands are problematic in the context of provision of water resources, and glaciers here play a large part in nourishment of the rivers. Concentrations of the oxygen 18, deuterium and the mineralization were measured in the samples of meltwater, precipitation, water from streams, ice and snow. Sable isotope method was used for separation of the glacier runoff. Average isotopic characteristics for different water sources, such as glacier ice, snow patches and precipitation, were calculated and the contribution of these sources in total runoff was valued. Isotopic method was also used for estimation of contribution of buried ice meltwater from rock glaciers ice cores.

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

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

v, Mitroshkov; JV, Ryan

2016-04-07

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

Use of Isotope Ratio Determination (13C/12C) to Assess the Production Method of Sparkling Wine.

PubMed

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

2016-01-01

The production of a sparkling wine can be performed with different methods taking from a few weeks to several years, which often justifies a difference in added value for the consumer. This paper presents the use of isotope ratio δ(13)C measurements combined with physico-chemical analyses for the determination of mislabelling of sparkling wines produced by 'ancestral', 'traditional', 'closed tank' or 'gasification' methods. This work shows that the isotope composition of CO(2) compared with that of the corresponding dried residue of wine (DRW) can assess whether carbonate CO(2) in a sparkling wine originates from alcohol fermentation or from artificial gas addition. Isotopic ratios expressed as δ(13)C(CO2) and δ(13)C(DRW) measurements have been obtained for each wine by gasbench isotopic ratio mass spectroscopy and cavity ring down infrared spectroscopy, respectively. When the difference between δ(13)C(CO2) and δ(13)C(DRW) is negative, the presence of artificial CO(2) can be undoubtedly inferred, which would exclude the production methods 'ancestral' or 'traditional' for instance. Other parameters such as alcohol content, sugar and acid distributions are also important to complete the analytical panel to aid fraud tracking.

Experimental determination of the Mo isotope fractionation factor between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, R. C.; Burkhardt, C.; Schmidt, M. W.; Bourdon, B.

2011-12-01

The conditions and chemical consequences of core formation have mainly been reconstructed from experimentally determined element partition coefficients between metal and silicate liquids. However, first order questions such as the mode of core formation or the nature of the light element(s) in the Earth's core are still debated [1]. In addition, the geocentric design of most experimental studies leaves the conditions of core formation on other terrestrial planets and asteroids even more uncertain than for Earth. Through mass spectrometry, records of mass-dependent stable isotope fractionation during high-temperature processes such as metal-silicate segregation are detectable. Stable isotope fractionation may thus yield additional constrains on core formation conditions and its consequences for the chemical evolution of planetary objects. Experimental investigations of equilibrium mass-dependent stable isotope fractionation have shown that Si isotopes fractionate between metal and silicate liquids at temperatures of 1800°C and pressures of 1 GPa, while Fe isotopes leave no resolvable traces of core formation processes [2,3]. Molybdenum is a refractory and siderophile trace element in the Earth, and thus much less prone to complications arising from mass balancing core and mantle and from potential volatile behaviour than other elements. To determine equilibrium mass-dependent Mo isotope fractionation during metal-silicate segregation, we have designed piston cylinder experiments with a basaltic silicate composition and an iron based metal with ~8 wt% Mo, using both graphite and MgO capsules. Metal and silicate phases are completely segregated by the use of a centrifuging piston cylinder at ETH Zurich, thus preventing analysis of mixed metal and silicate signatures. Molybdenum isotope compositions were measured using a Nu Instruments 1700 MC-ICP-MS at ETH Zurich. To ensure an accurate correction of analytical mass fractionation a 100Mo-97Mo double spike was admixed before chemical purification. Initial results provide an equilibrium 98Mo/95Mo isotope fractionation factor between metal and silicate liquids of -0.18±0.10% (2σ) at 1400°C and 1 GPa. Although the relative mass difference of these Mo isotopes is smaller than for Fe isotopes, this result implies that metal-silicate segregation may have led to mass-dependent stable Mo isotope fractionation, as opposed to Fe isotopes. A possible explanation is that the bonding environment of Mo may counterbalance its relatively small mass separation. At reducing conditions, Mo occurs in 4+ valence state in silicates [4] and thus its bond strength difference between metal and silicate may be more similar to that of Si than Fe. Stable Mo isotopes may thus become an important tool for constraining the conditions of core formation in asteroids and terrestrial planets. [1] Rubie et al. (2011) EPSL 301, 31-42. [2] Shahar et al. (2009) EPSL 288, 228-234. [3] Poitrasson et al. (2009) EPSL 278, 376-385. [4] Farges et al. (2006) Can. Min. 44, 731-753.

Theoretical studies for the rates and kinetic isotope effects of the excited-state double proton transfer in the 1:1 7-azaindole:H2O complex using variational transition state theory including multidimensional tunneling.

PubMed

Duong, My Phu Thi; Kim, Yongho

2010-03-18

Variational transition state theory calculations including multidimensional tunneling (VTST/MT) for excited-state tautomerization in the 1:1 7-azaindole:H(2)O complex were performed. Electronic structures and energies for reactant, product, transition state, and potential energy curves along the reaction coordinate were computed at the CASSCF(10,9)/6-31G(d,p) level of theory. The potential energies were corrected by second-order multireference perturbation theory to take the dynamic electron correlation into consideration. The final potential energy curves along the reaction coordinate were generated at the MRPT2//CASSCF(10,9)/6-31G(d,p) level. Two protons in the excited-state tautomerization are transferred concertedly, albeit asynchronously. The position of the variational transition state is very different from the conventional transition state, and is highly dependent on isotopic substitution. Rate constants were calculated using VTST/MT, and were on the order of 10(-6) s(-1) at room temperature. The HH/DD kinetic isotope effects are consistent with experimental observations; consideration of both tunneling and variational effects was essential to predict the experimental values correctly.

A new derivatization method for δ18O analysis of individual carbohydrates with GC-Pyrolysis-IRMS

NASA Astrophysics Data System (ADS)

Lehmann, M. M.; Siegwolf, R. T.; Saurer, M.; Blees, J.; Fischer, M.; Zech, M.

2015-12-01

Compound specific isotope analysis (CSIA) with gas chromatography coupled to an isotope ratio mass spectrometer (GC-Pyr-IRMS) is nowadays a powerful tool that is widely used by a broad spectrum of research fields to investigate the isotopic signature of diverse metabolites. While many CSIA methods for carbon, hydrogen, and nitrogen isotopes are known, CSIA methods for the analysis of oxygen isotopes (δ18O) are still not widely established. Especially, reliable and precise methods for the δ18O analyses of individual carbohydrates are scarce, which is caused by the highly sensitive nature of the sugars. However, carbohydrates are important components of living organisms, source for many biochemical reactions, and can be found in all organisms, in soils, sediments, and in air. Thus, a method, allowing the investigation of the 18O/16O ratio in carbohydrates will enhance the scope of research using isotopes. We developed a new and easy to handle derivatization method to determine δ18O in carbohydrates with GC-Pyr-IRMS that consists of a catalyzed one-pot reaction in acetonitrile, resulting in complete methylation of all sugar hydroxyl groups within 24 hours, with silver oxide as the proton acceptor and methyl iodide as the methyl group carrier. Results derived from standard material show unrivalled δ18O precision ranging from about 0.2 to 1.1 ‰ for different individual carbohydrates of different classes and a generally very good accuracy, with a narrow range of 0.2 ‰ around the reference value, despite of high area variations. We applied this method on real samples, demonstrating that the method can commonly be used for analyzing honey samples, and for the analyses of more complex carbohydrate mixtures from plant leaves, including glucose, fructose, pinitol, and sucrose. Our new method may be used for food, beverage, and medical applications, as well as for biogeochemical and paleoclimatic sciences.

Isotope effect on blob-statistics in gyrofluid simulations of scrape-off layer turbulence

NASA Astrophysics Data System (ADS)

Meyer, O. H. H.; Kendl, A.

2017-12-01

In this contribution we apply a recently established stochastic model for scrape-off layer fluctuations to long time series obtained from gyrofluid simulations of fusion edge plasma turbulence. Characteristic parameters are estimated for different fusion relevant isotopic compositions (protium, deuterium, tritium and singly charged helium) by means of conditional averaging. It is shown that large amplitude fluctuations associated with radially propagating filaments in the scrape-off layer feature double-exponential wave-forms. We find increased pulse duration and longer waiting times between peaks for heavier ions, while the amplitudes are similar. The associated radial blob velocity is shown to be reduced for heavier ions. A parabolic relation between skewness and kurtosis of density fluctuations seems to be present. Improved particle confinement in terms of reduced mean value close to the outermost radial boundary and blob characteristics for heavier plasmas is presented.

Rainfall and cave water isotopic relationships in two South-France sites

NASA Astrophysics Data System (ADS)

Genty, D.; Labuhn, I.; Hoffmann, G.; Danis, P. A.; Mestre, O.; Bourges, F.; Wainer, K.; Massault, M.; Van Exter, S.; Régnier, E.; Orengo, Ph.; Falourd, S.; Minster, B.

2014-04-01

This article presents isotopic measurements (δ18O and δD) of precipitation and cave drip water from two sites in southern France in order to investigate the link between rainfall and seepage water, and to characterize regional rainfall isotopic variability. These data, which are among the longest series in France, come from two rainfall stations in south-west France (Le Mas 1996-2012, and Villars 1998-2012; typically under Atlantic influence), and from one station in the south-east (Orgnac 2000-2012; under both Mediterranean and Atlantic influence). Rainfall isotopic composition is compared to drip water collected under stalactites from the same sites: Villars Cave (four drip stations 1999-2012) in the south-west, and Chauvet Cave (two drip stations 2000-2012) in the south-east, near Orgnac. The study of these isotopic data sets allows the following conclusions to be drawn about the rainfall/drip water relationships and about rainfall variability: (1) the cave drip water isotopic composition does not show any significant changes since the beginning of measurements; in order to explain its isotopic signature it is necessary to integrate weighted rainfall δ18O of all months during several years, which demonstrates that, even at shallow depths (10-50 m), cave drip water is a mixture of rain water integrated over relatively long periods, which give an apparent time residence from several months to up to several years. These results have important consequences on the interpretation of proxies like speleothem fluid inclusions and tree-ring cellulose isotopic composition, which are used for paleoclimatic studies; (2) in the Villars Cave, where drip stations at two different depths were studied, lower δ18O values were observed in the lower galleries, which might be due to winter season overflows during infiltration and/or to older rain water with a different isotopic composition that reaches the lower galleries after years; (3) local precipitation is characterized by local meteoric water lines, LMWL, with δ18O/δD slopes close to 7 in both areas, and correlations between air temperature and precipitation δ18O are low at both monthly and annual scales, even with temperature weighted by the amount of precipitation; (4) the mesoscale climate model REMOiso, equipped with a water isotope module, allows the direct comparison of modeled and observed long term water isotope records. The model slightly overestimates rainfall δ18O at the respective sampling stations. However, it simulates very well not only the seasonal rainfall isotopic signal but also some intra-seasonal patterns such as a typical double-peak δ18O pattern in winter time.

Using stable isotopes to monitor forms of sulfur during desulfurization processes: A quick screening method

USGS Publications Warehouse

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

1987-01-01

A method using stable isotope ratio analysis to monitor the reactivity of sulfur forms in coal during thermal and chemical desulfurization processes has been developed at the Illinois State Geological Survey. The method is based upon the fact that a significant difference exists in some coals between the 34S/32S ratios of the pyritic and organic sulfur. A screening method for determining the suitability of coal samples for use in isotope ratio analysis is described. Making these special coals available from coal sample programs would assist research groups in sorting out the complex sulfur chemistry which accompanies thermal and chemical processing of high sulfur coals. ?? 1987.

Trophic hierarchies revealed via amino acid isotopic analysis

USDA-ARS?s Scientific Manuscript database

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

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

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

A new rapid fusion method for the determination of plutonium in large rice samples has been developed at the Savannah River National Laboratory (Aiken, SC, USA) that can be used to determine very low levels of plutonium isotopes in rice. The recent accident at Fukushima Nuclear Power Plant in March, 2011 reinforces the need to have rapid, reliable radiochemical analyses for radionuclides in environmental and food samples. Public concern regarding foods, particularly foods such as rice in Japan, highlights the need for analytical techniques that will allow very large sample aliquots of rice to be used for analysis so thatmore » very low levels of plutonium isotopes may be detected. The new method to determine plutonium isotopes in large rice samples utilizes a furnace ashing step, a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a column separation process with TEVA Resin cartridges. The method can be applied to rice sample aliquots as large as 5 kg. Plutonium isotopes can be determined using alpha spectrometry or inductively-coupled plasma mass spectrometry (ICP-MS). The method showed high chemical recoveries and effective removal of interferences. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory plutonium particles are effectively digested. The MDA for a 5 kg rice sample using alpha spectrometry is 7E-5 mBq g{sup -1}. The method can easily be adapted for use by ICP-MS to allow detection of plutonium isotopic ratios.« less

Liquid chromatography/electrospray ionization/isotopic dilution mass spectrometry analysis of n-(phosphonomethyl) glycine and mass spectrometry analysis of aminomethyl phosphonic acid in environmental water and vegetation matrixes.

PubMed

Grey, L; Nguyen, B; Yang, P

2001-01-01

A liquid chromatography/electrospray/mass spectrometry (LC/ES/MS) method was developed for the analysis of glyphosate (n-phosphonomethyl glycine) and its metabolite, aminomethyl phosphonic acid (AMPA) using isotope-labelled glyphosate as a method surrogate. Optimized parameters were achieved to derivatize glyphosate and AMPA using 9-fluorenylmethyl chloroformate (FMOC-Cl) in borate buffer prior to a reversed-phase LC analysis. Method spike recovery data obtained using laboratory and real world sample matrixes indicated an excellent correlation between the recovery of the native and isotope-labelled glyphosate. Hence, the first performance-based, isotope dilution MS method with superior precision, accuracy, and data quality was developed for the analysis of glyphosate. There was, however, no observable correlation between the isotope-labelled glyphosate and AMPA. Thus, the use of this procedure for the accurate analysis of AMPA was not supported. Method detection limits established using standard U.S. Environmental Protection Agency protocol were 0.06 and 0.30 microg/L, respectively, for glyphosate and AMPA in water matrixes and 0.11 and 0.53 microg/g, respectively, in vegetation matrixes. Problems, solutions, and the method performance data related to the analysis of chlorine-treated drinking water samples are discussed. Applying this method to other environmental matrixes, e.g., soil, with minimum modifications is possible, assuring accurate, multimedia studies of glyphosate concentration in the environment and the delivery of useful multimedia information for regulatory applications.

Hybrid isotope separation scheme

DOEpatents

Maya, Jakob

1991-01-01

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

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

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

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

1982-02-02

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

Effects of cleaning methods upon preservation of stable isotopes and trace elements in shells of Cyprideis torosa (Crustacea, Ostracoda): Implications for palaeoenvironmental reconstruction

NASA Astrophysics Data System (ADS)

Roberts, L. R.; Holmes, J. A.; Leng, M. J.; Sloane, H. J.; Horne, D. J.

2018-06-01

The trace element (Sr/Ca and Mg/Ca) and stable isotope (δ18O and δ13C) geochemistry of fossil ostracod valves provide valuable information, particularly in lacustrine settings, on palaeo-water composition and palaeotemperature. The removal of sedimentary and organic contamination prior to geochemical analysis is essential to avoid bias of the results. Previous stable isotope and trace element work on ostracod shells has, however, employed different treatments for the removal of contamination beyond simple 'manual' cleaning using a paint brush and methanol under a low-power binocular microscope. For isotopic work pre-treatments include chemical oxidation, vacuum roasting and plasma ashing, and for trace element work sonication, chemical oxidation and reductive cleaning. The impact of different treatments on the geochemical composition of the valve calcite has not been evaluated in full, and a universal protocol has not been established. Here, a systematic investigation of the cleaning methods is undertaken using specimens of the ubiquitous euryhaline species, Cyprideis torosa. Cleaning methods are evaluated by undertaking paired analyses on a single carapace (comprising two valves); in modern ostracods, whose valves are assumed to be unaltered, the two valves should have identical geochemical and isotopic composition. Hence, when one valve is subjected to the chosen treatment and the other to simple manual cleaning any difference in composition can confidently be assigned to the treatment method. We show that certain cleaning methods have the potential to cause alteration to the geochemical signal, particularly Mg/Ca and δ18O, and hence have implications for palaeoenvironmental reconstructions. For trace-element determinations we recommend cleaning by sonication and for stable isotope analysis, oxidation by hydrogen peroxide. These methods remove contamination, yet do not significantly alter the geochemical signal.

Laser Ablation in situ (U-Th-Sm)/He and U-Pb Double-Dating of Apatite and Zircon: Techniques and Applications

NASA Astrophysics Data System (ADS)

McInnes, B.; Danišík, M.; Evans, N.; McDonald, B.; Becker, T.; Vermeesch, P.

2015-12-01

We present a new laser-based technique for rapid, quantitative and automated in situ microanalysis of U, Th, Sm, Pb and He for applications in geochronology, thermochronometry and geochemistry (Evans et al., 2015). This novel capability permits a detailed interrogation of the time-temperature history of rocks containing apatite, zircon and other accessory phases by providing both (U-Th-Sm)/He and U-Pb ages (+trace element analysis) on single crystals. In situ laser microanalysis offers several advantages over conventional bulk crystal methods in terms of safety, cost, productivity and spatial resolution. We developed and integrated a suite of analytical instruments including a 193 nm ArF excimer laser system (RESOlution M-50A-LR), a quadrupole ICP-MS (Agilent 7700s), an Alphachron helium mass spectrometry system and swappable flow-through and ultra-high vacuum analytical chambers. The analytical protocols include the following steps: mounting/polishing in PFA Teflon using methods similar to those adopted for fission track etching; laser He extraction and analysis using a 2 s ablation at 5 Hz and 2-3 J/cm2fluence; He pit volume measurement using atomic force microscopy, and U-Th-Sm-Pb (plus optional trace element) analysis using traditional laser ablation methods. The major analytical challenges for apatite include the low U, Th and He contents relative to zircon and the elevated common Pb content. On the other hand, apatite typically has less extreme and less complex zoning of parent isotopes (primarily U and Th). A freeware application has been developed for determining (U-Th-Sm)/He ages from the raw analytical data and Iolite software was used for U-Pb age and trace element determination. In situ double-dating has successfully replicated conventional U-Pb and (U-Th)/He age variations in xenocrystic zircon from the diamondiferous Ellendale lamproite pipe, Western Australia and increased zircon analytical throughput by a factor of 50 over conventional methods.Reference: Evans NJ, McInnes BIA, McDonald B, Becker T, Vermeesch P, Danisik M, Shelley M, Marillo-Sialer E and Patterson D. An in situ technique for (U-Th-Sm)/He and U-Pb double dating. J Analytical Atomic Spectrometry, 30, 1636 - 1645.

Evaluation of the plasma hydrogen isotope content by residual gas analysis at JET and AUG

NASA Astrophysics Data System (ADS)

Drenik, A.; Alegre, D.; Brezinsek, S.; De Castro, A.; Kruezi, U.; Oberkofler, M.; Panjan, M.; Primc, G.; Reichbauer, T.; Resnik, M.; Rohde, V.; Seibt, M.; Schneider, P. A.; Wauters, T.; Zaplotnik, R.; ASDEX-Upgrade, the; EUROfusion MST1 Teams; contributors, JET

2017-12-01

The isotope content of the plasma reflects on the dynamics of isotope changeover experiments, efficiency of wall conditioning and the performance of a fusion device in the active phase of operation. The assessment of the isotope ratio of hydrogen and methane molecules is used as a novel method of assessing the plasma isotope ratios at JET and ASDEX-Upgrade (AUG). The isotope ratios of both molecules in general shows similar trends as the isotope ratio detected by other diagnostics. At JET, the absolute values of RGA signals are in relatively good agreement with each other and with spectroscopy data, while at AUG the deviation from neutral particle analyser data are larger, and the results show a consistent spatial distribution of the isotope ratio. It is further shown that the isotope ratio of the hydrogen molecule can be used to study the degree of dissociation of the injected gas during changeover experiments.

A simple distillation method to extract bromine from natural water and salt samples for isotope analysis by multi-collector inductively coupled plasma mass spectrometry.

PubMed

Eggenkamp, H G M; Louvat, P

2018-04-30

In natural samples bromine is present in trace amounts, and measurement of stable Br isotopes necessitates its separation from the matrix. Most methods described previously need large samples or samples with high Br/Cl ratios. The use of metals as reagents, proposed in previous Br distillation methods, must be avoided for multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) analyses, because of risk of cross-contamination, since the instrument is also used to measure stable isotopes of metals. Dedicated to water and evaporite samples with low Br/Cl ratios, the proposed method is a simple distillation that separates bromide from chloride for isotopic analyses by MC-ICP-MS. It is based on the difference in oxidation potential between chloride and bromide in the presence of nitric acid. The sample is mixed with dilute (1:5) nitric acid in a distillation flask and heated over a candle flame for 10 min. The distillate (bromine) is trapped in an ammonia solution and reduced to bromide. Chloride is only distilled to a very small extent. The obtained solution can be measured directly by MC-ICP-MS for stable Br isotopes. The method was tested for a variety of volumes, ammonia concentrations, pH values and distillation times and compared with the classic ion-exchange chromatography method. The method more efficiently separates Br from Cl, so that samples with lower Br/Cl ratios can be analysed, with Br isotope data in agreement with those obtained by previous methods. Unlike other Br extraction methods based on oxidation, the distillation method presented here does not use any metallic ion for redox reactions that could contaminate the mass spectrometer. It is efficient in separating Br from samples with low Br/Cl ratios. The method ensures reproducible recovery yields and a long-term reproducibility of ±0.11‰ (1 standard deviation). The distillation method was successfully applied to samples with low Br/Cl ratios and low Br amounts (down to 20 μg). Copyright © 2018 John Wiley & Sons, Ltd.

Probiotic strain Lactobacillus plantarum 299v increases iron absorption from an iron-supplemented fruit drink: a double-isotope cross-over single-blind study in women of reproductive age.

PubMed

Hoppe, Michael; Önning, Gunilla; Berggren, Anna; Hulthén, Lena

2015-10-28

Iron deficiency is common, especially among young women. Adding probiotics to foods could be one way to increase iron absorption. The aim of this study was to test the hypothesis that non-haem iron absorption from a fruit drink is improved by adding Lactobacillus plantarum 299v (Lp299v). Iron absorption was studied in healthy women of reproductive age using a single-blind cross-over design in two trials applying the double-isotope (55Fe and 59Fe) technique. In Trial 1, iron absorption from a fruit drink containing 109 colony-forming units (CFU) Lp299v was compared with that from a control drink without Lp299v. Trial 2 had the same design but 1010 CFU were used. The test and control drinks contained approximately 5 mg of iron as ferrous lactate and were labelled with 59Fe (B) and 55Fe (A), respectively, and consumed on 4 consecutive days in the order AABB. Retention of the isotopes was measured with whole-body counting and in blood. Mean iron absorption from the drink containing 109 CFU Lp299v (28·6(sd 12·5) %) was significantly higher than from the control drink (18·5(sd 5·8) %), n 10, P<0·028). The fruit drink with 1010 CFU Lp299v gave a mean iron absorption of 29·1(sd 17·0) %, whereas the control drink gave an absorption of (20·1(sd 6·4) %) (n 11, P<0·080). The difference in iron absorption between the 109 CFU Lp299v and the 1010 CFU Lp299v drinks was not significant (P=0·941). In conclusion, intake of probiotics can increase iron absorption by approximately 50 % from a fruit drink having an already relatively high iron bioavailability.

Method of enhancing selective isotope desorption from metals

DOEpatents

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

1983-07-26

This invention relates generally to the field of gas desorption from metals; and, more particularly, to a method of enhancing the selective desorption of a particular isotope of a gas from metals. Enhanced selective desorption is especially useful in the operation of fusion devices.

ISOTOPIC STUDY OF THE INHALATION TOXICOLOGY OF OXIDANTS

EPA Science Inventory

The purpose of these studies was to develop novel methods to investigate the biological fate of inhaled ozone and other oxygen-containing pollutants in animal and human tissues using the heavy isotope of oxygen, oxygen-18 (18O). Methods were developed which facilitated the conver...

Research on the properties and interactions of simple atomic and ionic systems

NASA Technical Reports Server (NTRS)

Novick, R.

1972-01-01

Simple ionic systems were studied, such as metastable autoionizing states of the negative He ion, two-photon decay spectrum of metastable He ion, optical excitation with low energy ions, and lifetime measurements of singly ionized Li and metastable He ion. Simple atomic systems were also investigated. Metastable autoionizing atomic energy levels in alkali elements were included, along with lifetime measurements of Cr-53, group 2A isotopes, and alkali metal atoms using level crossing and optical double resonance spectroscopy.

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

Agnes, P.; et al.

The DarkSide-50 experiment, located at the “Laboratori Nazionali del Gran Sasso (INFN)”, is based on low-radioactivity argon double phase time projection chamber, surrounded by an active liquid scintillator veto, designed for the zero background achievement. The liquid argon features sufficient self shielding and easy scalability to multi-tons scale. The impressive reduction of the 39Ar isotope (compared to the atmospheric argon), along with the excellent pulse shape discrimination, make this technology a possible candidate for the forthcoming generation of multi-ton Dark Matter experiments.

Development of a Method to Isolate Glutamic Acid from Foodstuffs for a Precise Determination of Their Stable Carbon Isotope Ratio.

PubMed

Kobayashi, Kazuhiro; Tanaka, Masaharu; Yatsukawa, Yoichi; Tanabe, Soichi; Tanaka, Mitsuru; Ohkouchi, Naohiko

2018-01-01

Recent growing health awareness is leading to increasingly conscious decisions by consumers regarding the production and traceability of food. Stable isotopic compositions provide useful information for tracing the origin of foodstuffs and processes of food production. Plants exhibit different ratios of stable carbon isotopes (δ 13 C) because they utilized different photosynthetic (carbon fixation) pathways and grow in various environments. The origins of glutamic acid in foodstuffs can be differentiated on the basis of these photosynthetic characteristics. Here, we have developed a method to isolate glutamic acid in foodstuffs for determining the δ 13 C value by elemental analyzer-isotope-ratio mass spectrometry (EA/IRMS) without unintended isotopic fractionation. Briefly, following acid-hydrolysis, samples were defatted and passed through activated carbon and a cation-exchange column. Then, glutamic acid was isolated using preparative HPLC. This method is applicable to measuring, with a low standard deviation, the δ 13 C values of glutamic acid from foodstuffs derived from C3 and C4 plants and marine algae.

Liquid chromatography coupled to isotope ratio mass spectrometry: a new perspective on honey adulteration detection.

PubMed

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

2006-12-27

A new procedure to determine individual sugar (sucrose, glucose, and fructose) 13C isotope ratios, using liquid chromatography-isotope ratio mass spectrometry (HPLC-IRMS), has been developed to improve isotopic methods devoted to the study of honey authenticity. For this purpose 79 commercial honey samples from various origins were analyzed. Values of delta13Choney ranged from -14.2 to -27.2", and delta13Cprotein ranged from -23.6 to -26.9". A very strong correlation is observed between the individual sugar 13C ratios, which are altered in the event of sugar addition, even at low levels. The use of Deltadelta13C [fruct-glu], Deltadelta13C [fruct-suc], and Deltadelta13C [gluc-suc] systematic differences as an authenticity criterion permits the sugar addition [C3, beet sugar; or C4, cane sugar, cane syrup, isoglucose syrup, and high-fructose corn syrup (HFCS)] to be reliably detected (DL = 1-10%). The new procedure has advantages over existing methods in terms of analysis time and sensitivity. In addition, it is the first isotopic method developed that allows beet sugar addition detection.

Uranium isotopes quantitatively determined by modified method of atomic absorption spectrophotometry

NASA Technical Reports Server (NTRS)

Lee, G. H.

1967-01-01

Hollow-cathode discharge tubes determine the quantities of uranium isotopes in a sample by using atomic absorption spectrophotometry. Dissociation of the uranium atoms allows a large number of ground state atoms to be produced, absorbing the incident radiation that is different for the two major isotopes.

Site-Specific Carbon Isotopes in Organics

NASA Astrophysics Data System (ADS)

Piasecki, A.; Eiler, J. M.

2012-12-01

Natural organic molecules exhibit a wide range of internal site-specific isotope variation (i.e., molecules with same isotopic substitution type but different site). Such variations are generally unconstrained by bulk isotopic measurements. If known, site-specific variations might constrain temperatures of equilibrium, mechanisms of formation or consumption reactions, and possibly other details. For example, lipids can exhibit carbon isotope differences of up to 30‰ between adjacent carbon sites as a result of fractionations arising during decarboxylation of pyruvate and other steps in lipid biosynthesis(1). We present a method for site-specific carbon isotope analysis of propane, based on high-resolution, multi-collector gas source mass spectrometry, using a novel prototype instrument - the Thermo MAT 253 Ultra. This machine has an inlet system and electron bombardment ion source resembling those in conventional stable isotope gas source mass spectrometers, and the energy filter, magnet, and detector array resembling those in multi-collector ICPMS and TIMS. The detector array has 7 detector positions, 6 of which are movable, and each of which can collect ions with either a faraday cup (read through amplifiers ranging from 107-1012 ohms) or an SEM. High mass resolving power (up to 27,000, MRP = M/dM definition) is achieved through a narrow entrance slit, adjustable from 250 to 5 μm. Such resolution can cleanly separate isobaric interferences between isotopologues of organic molecules having the same cardinal mass (e.g., 13CH3 and 12CH2D). We use this technology to analyze the isotopologues and fragments of propane, and use such data to solve for the site-specific carbon isotope fractionation. By measuring isotopologues of both the one-carbon (13CH3) and the two-carbon (13C12CH4) fragment ion, we can solve for both bulk δ13C and the difference in δ13C between the terminal and central carbon position. We tested this method by analyzing mixtures between natural propane and labeled propane (13CH3-12CH2-12CH3). Results are consistent with the expected relative fractionations between the two fragments, indicating limited 'scrambling' of carbon positions of less than 2% in the source. The limits of precision of this method are currently ~0.5 ‰, sufficient to resolve known or suspected position-specific isotope effects in propane. We have explored the expected temperature-dependent equilibrium isotopic distributions of propane using density functional theory and quantum mechanical models of vibrational isotope effects. These models predict the homogeneous isotope exchange equilibria among the various isotopologues of propane, which include several of a wide range of effects that should be measurable by our methods. At 300 K we predict that the central carbon site is 15‰ higher in δ13C and 95 ‰ higher in δD than the terminal carbon site; similarly the molecule containing both a 13C and D in the central site is enriched by ~120 ‰ relative to a random isotopic distribution at 300 K. These predictions present targets for future experimental and empirical studies of the temperature dependence of isotopic ordering in propane. More generally, the methods we are developing for the study of intramolecular isotopic distributions in propane will serve as a model for future study of similar effects in other organic compounds. [1]DeNiro, Epstein (1977) Science Volume 197, 261-263.

A New Pb Isotope Perspective on Oceanic Basalts: Reading Between the Lines

NASA Astrophysics Data System (ADS)

Galer, S. J.; Abouchami, W.; Eisele, J.; Haase, K.; Moller, H.; Regelous, M.; Hofmann, A. W.

2001-12-01

Recent high-precision Pb isotope analyses ( ~100 ppm) obtained using double and triple spikes demonstrate that much of the scatter in previous, conventionally obtained data is analytical in origin. Here we pool together all the currently available high-precision Pb isotope data on oceanic basalts to provide a new "sharpened up" picture of the gross Pb isotope heterogeneity in the mantle. These Pb isotope data are from MORB glasses from the East Pacific Rise (EPR) and South Atlantic (26° S, Ascension), seven Hawaiian volcanoes, Pitcairn, Rurutu, the Azores (all MPI data), Mangaia (Woodhead, 1996), and St. Helena and Iceland (Thirlwall, 2000), totalling around 250 samples. The high-precision data for a given location do not form the "clouds" in Pb-Pb isotope space seen in conventional literature data. Rather, each data set forms tight linear arrays in both Pb isotope spaces. More surprising, though, is that the samples lying on a given array cover a limited geographic extent: (1) In the case of the EPR, six distinct arrays are found, each of which is confined to a particular range in latitude along the ridge, corresponding to length-scales of ~100 to 5000 km. The same is true of MORB samples from the South Atlantic (2) Distinct arrays are resolved for individual volcanoes along the Hawaiian chain, indicating that the heterogeneities within the Hawaiian plume are tapped in a long-lived and highly systematic fashion. It is also quite clear that these data are not readily interpretable in terms of mixing between notional end-member "components" in the mantle. For example, the EM1 "component" present in Pitcairn is quite clearly different in Pb isotope space from that sampled by Koolau. Similarly, the HIMU "component" present in the Austral-Cook chain is distinct in the islands Mangaia and Rurutu, and is not the same as that found in St. Helena. In all of these cases it is impossible to find common crossing points of the arrays in both Pb isotope spaces. Moreover, none of the arrays "point" towards any of the putative end-member "mantle components." If such common end-members do exist in the mantle, almost perfect premixing between them would be required to form viable intermediate end-members to each of the arrays observed. Overall, these new Pb isotope data pose the questions: (1) What is the significance of the linear arrays and why are there so many of them?, and (2) how can such heterogeneities survive intact in the convecting mantle over long periods of time?

Carbon stable isotope composition of DNA isolated from an incipient paleosol

NASA Astrophysics Data System (ADS)

Jahren, A. Hope; Kelm, Kellie; Wendland, Beverly; Petersen, Gitte; Seberg, Ole

2006-05-01

We determined the carbon isotope (δ13C) value of double-stranded DNA (dsDNA) isolated from the organic horizons of a Delaware soil that is actively being covered by an encroaching sand dune. The soil belongs to a Nymphaea odorata Ait. (water lily) wetland, and we regard its active acquisition of a thick (˜24 cm) surface mantle to embody the process of paleopedogenesis; therefore, we have termed it an “incipient paleosol.” In this study, we compared the δ13C value of paleosol dsDNA to the bulk δ13C value of N. odorata, as well as to the δ13C value of plants that had colonized the surface mantle. The isotopic offset between paleosol δ13CdsDNA and N. odorata δ13Ctissue was identical to the relationship between δ13CdsDNA and δ13Ctissue for tracheophytes, which we had previously determined. In contrast, the isotopic offset between paleosol δ13CdsDNA and the δ13Ctissue of plants colonizing the surface mantle differed from this relationship by as much as 4‰. Similarly, the δ13C value of bulk paleosol organic matter was extremely heterogeneous and varied across 6‰. All paleosol DNA polymerase chain reaction (PCR) products produced clear, sharp, 350 base-pair (bp) fragments of rbcL, a gene shared by all photosynthetic organisms. These results open the exciting possibility that stable isotope analysis of dsDNA isolated from paleosol organic matter can be used to infer the δ13C value of the plant that dominated the nucleic acid contribution.

Molecular beam electric resonance study of KCN, K 13CN and KC 15N

NASA Astrophysics Data System (ADS)

van Vaals, J. J.; Leo Meerts, W.; Dymanus, A.

1984-08-01

The microwave spectra of the isotopic species K 13CN and KC 15N have been investigated by molecular beam electric resonance spectroscopy, using the seeded beam technique. For both isotopic species about 20 rotational transitions originating in the ground vibrational state were observed in the frequency range 9-38 GHz. The observed transitions were fitted to an asymmetric rotor model to determine the three rotational, as well as the five quartic and three sextic centrifugal distortion constants. The hyperfine spectrum of KCN has been unravelled with the help of microwave-microwave double-resonance techniques. One hundred and forty hyperfine transitions in 11 rotational transitions have been assigned. The hyperfine structures of K 13CN and KC 15N were also studied. For all three isotopic species the quadrupole coupling constants and some spin-rotation coupling constants could be deduced. The rotational constants of the 13C and 15N isotopically substituted species of potassium cyanide, combined with those of the normal isotopic species (determined more accurately in this work), allowed an accurate and unambiguous evaluation of the structure, which was confirmed to be T shaped. Both the effective structure of the ground vibrational state and the substitution structure were evaluated. The results for the effective structural parameters are r CN = 1.169(3) Å, r KC = 2.716(9) Å, and r KN = 2.549(9) Å. The values obtained for the principal hyperfine coupling constant eQqz(N), the angle between the CN axis and zN, and the bond length rCN indicate that in gaseous potassium cyanide the CN group can be considered as an almost unperturbed CN - ion.

A Formation Timescale of the Galactic Halo from Mg Isotopes in Dwarf Stars

NASA Astrophysics Data System (ADS)

Carlos, Marília; Karakas, Amanda I.; Cohen, Judith G.; Kobayashi, Chiaki; Meléndez, Jorge

2018-04-01

We determine magnesium isotopic abundances of metal-poor dwarf stars from the galactic halo, to shed light on the onset of asymptotic giant branch (AGB) star nucleosynthesis in the galactic halo and constrain the timescale of its formation. We observed a sample of eight new halo K dwarfs in a metallicity range of ‑1.9 < [Fe/H] < ‑0.9 and 4200 < T eff(K) < 4950, using the HIRES spectrograph at the Keck Observatory (R ≈ 105 and 200 ≤ S/N ≤ 300). We obtain magnesium isotopic abundances by spectral synthesis on three MgH features and compare our results with galactic chemical evolution models. With the current sample, we almost double the number of metal-poor stars with Mg isotopes determined from the literature. The new data allow us to determine the metallicity when the 26Mg abundances start to become important, [Fe/H] ∼ ‑1.4 ± 0.1. The data with [Fe/H] > ‑1.4 are somewhat higher (1–3σ) than previous chemical evolution model predictions, indicating perhaps higher yields of the neutron-rich isotopes. Our results using only AGB star enrichment suggest a timescale for formation for the galactic halo of about 0.3 Gyr, but considering also supernova enrichment, the upper limit for the timescale formation is about 1.5 Gyr. The data presented herein were obtained at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California and the National Aeronautics and Space Administration. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

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.

Strontium isotope measurement of basaltic glasses by laser ablation multiple collector inductively coupled plasma mass spectrometry based on a linear relationship between analytical bias and Rb/Sr ratios.

PubMed

Zhang, Le; Ren, Zhong-Yuan; Wu, Ya-Dong; Li, Nan

2018-01-30

In situ strontium (Sr) isotope analysis of geological samples by laser ablation multiple collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) provides useful information about magma mixing, crustal contamination and crystal residence time. Without chemical separation, during Sr isotope analysis with laser ablation, many kinds of interference ions (such as Rb + and Kr + ) are on the Sr isotope spectrum. Most previous in situ Sr isotope studies only focused on Sr-enriched minerals (e.g. plagioclase, calcite). Here we established a simple method for in situ Sr isotope analysis of basaltic glass with Rb/Sr ratio less than 0.14 by LA-MC-ICP-MS. Seven Faraday cups, on a Neptune Plus MC-ICP-MS instrument, were used to receive the signals on m/z 82, 83, 84, 85, 86, 87 and 88 simultaneously for the Sr isotope analysis of basaltic glass. The isobaric interference of 87 Rb was corrected by the peak stripping method. The instrumental mass fractionation of 87 Sr/ 86 Sr was corrected to 86 Sr/ 88 Sr = 0.1194 with an exponential law. Finally, the residual analytical biases of 87 Sr/ 86 Sr were corrected with a relationship between the deviation of 87 Sr/ 86 Sr from the reference values and the measured 87 Rb/ 86 Sr. The validity of the protocol present here was demonstrated by measuring the Sr isotopes of four basaltic glasses, a plagioclase crystal and a piece of modern coral. The measured 87 Sr/ 86 Sr ratios of all these samples agree within 100 ppm with the reference values. In addition, the Sr isotopes of olivine-hosted melt inclusions from the Emeishan large igneous province (LIP) were measured to show the application of our method to real geological samples. A simple but accurate approach for in situ Sr isotope measurement by LA-MC-ICP-MS has been established, which should greatly facilitate the wider application of in situ Sr isotope geochemistry, especially to volcanic rock studies. Copyright © 2017 John Wiley & Sons, Ltd.

A novel procedure for Rubidium separation and its isotope measurements on geological samples by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Ma, J.; Zhang, Z.; Wei, G.; Zhang, L.

2017-12-01

A method including a novel column Rb separation procedure and high-precision Rb isotope measurement in geological materials by using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in standard-sample-bracketing (SSB) mode has been developed. Sr-Spec resin was employed, in which the distribution coefficients for Rb, K, Ba and Sr are different in nitric acid, to sequentially separate them from the matrix. The dissolved samples were loaded on the column in 3 M HNO3, the main matrix such as Al, Ca, Fe, Mg, Mn and Na were removed by rinsing with 4.5 mL HNO3, Rb and K were then sequentially eluted by 3 M HNO3 in different volumes. After that, Ba was eluted by 8 M HNO3, and Sr was finally eluted by Milli-Q water. This enable us to collect the pure Rb, K, Ba and Sr one by one with recovery close to 100% for their isotopic compositions measurement on MC-ICP-MS. We here focus on Rb isotope measurement. The measurement using MC-ICP-MS yielded an internal precision for δ87Rb of < ± 0.03‰ (2SE), and the external precision was generally better than ± 0.06‰ (2SD) based on the long-term results of the Rb standard solutions NIST SRM 984. A series of geological rock standards, were analyzed using this method, and the results indicate significant Rb isotope differences in different geologic materials. This will provide a powerful tool to investigate Rb isotope fractionation during geological processes.Based on this method, Rb isotope compositions from a basaltic weathering profile were carried out. The data show the lighter Rb (85Rb) isotope is preferentially leached from the weathering profile and remains heavy Rb isotope (87Rb) in the weathered residues during the incipient weathering stage. From the moderate to advanced weathering stage, the significant variations of Rb isotope were observed and multiple factors, such as leaching, adsorption, desorption, and precipitation, should play important role in fractionating Rb isotope.

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

PubMed

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

2014-08-19

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

A new dimethyl labeling-based SID-MRM-MS method and its application to three proteases involved in insulin maturation.

PubMed

Cheng, Dongwan; Zheng, Li; Hou, Junjie; Wang, Jifeng; Xue, Peng; Yang, Fuquan; Xu, Tao

2015-01-01

The absolute quantification of target proteins in proteomics involves stable isotope dilution coupled with multiple reactions monitoring mass spectrometry (SID-MRM-MS). The successful preparation of stable isotope-labeled internal standard peptides is an important prerequisite for the SID-MRM absolute quantification methods. Dimethyl labeling has been widely used in relative quantitative proteomics and it is fast, simple, reliable, cost-effective, and applicable to any protein sample, making it an ideal candidate method for the preparation of stable isotope-labeled internal standards. MRM mass spectrometry is of high sensitivity, specificity, and throughput characteristics and can quantify multiple proteins simultaneously, including low-abundance proteins in precious samples such as pancreatic islets. In this study, a new method for the absolute quantification of three proteases involved in insulin maturation, namely PC1/3, PC2 and CPE, was developed by coupling a stable isotope dimethyl labeling strategy for internal standard peptide preparation with SID-MRM-MS quantitative technology. This method offers a new and effective approach for deep understanding of the functional status of pancreatic β cells and pathogenesis in diabetes.

Determination of Glyphosate, its Degradation Product Aminomethylphosphonic Acid, and Glufosinate, in Water by Isotope Dilution and Online Solid-Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry

USGS Publications Warehouse

Meyer, Michael T.; Loftin, Keith A.; Lee, Edward A.; Hinshaw, Gary H.; Dietze, Julie E.; Scribner, Elisabeth A.

2009-01-01

The U.S. Geological Survey method (0-2141-09) presented is approved for the determination of glyphosate, its degradation product aminomethylphosphonic acid (AMPA), and glufosinate in water. It was was validated to demonstrate the method detection levels (MDL), compare isotope dilution to standard addition, and evaluate method and compound stability. The original method USGS analytical method 0-2136-01 was developed using liquid chromatography/mass spectrometry and quantitation by standard addition. Lower method detection levels and increased specificity were achieved in the modified method, 0-2141-09, by using liquid chromatography/tandem mass spectrometry (LC/MS/MS). The use of isotope dilution for glyphosate and AMPA and pseudo isotope dilution of glufosinate in place of standard addition was evaluated. Stable-isotope labeled AMPA and glyphosate were used as the isotope dilution standards. In addition, the stability of glyphosate and AMPA was studied in raw filtered and derivatized water samples. The stable-isotope labeled glyphosate and AMPA standards were added to each water sample and the samples then derivatized with 9-fluorenylmethylchloroformate. After derivatization, samples were concentrated using automated online solid-phase extraction (SPE) followed by elution in-line with the LC mobile phase; the compounds separated and then were analyzed by LC/MS/MS using electrospray ionization in negative-ion mode with multiple-reaction monitoring. The deprotonated derivatized parent molecule and two daughter-ion transition pairs were identified and optimized for glyphosate, AMPA, glufosinate, and the glyphosate and AMPA stable-isotope labeled internal standards. Quantitative comparison between standard addition and isotope dilution was conducted using 473 samples analyzed between April 2004 and June 2006. The mean percent difference and relative standard deviation between the two quantitation methods was 7.6 plus or minus 6.30 (n = 179), AMPA 9.6 plus or minus 8.35 (n = 206), and glufosinate 9.3 plus or minus 9.16 (n = 16). The analytical variation of the method, comparison of quantitation by isotope dilution and multipoint linear regressed standard curves, and method detection levels were evaluated by analyzing six sets of distilled-water, groundwater, and surface-water samples spiked in duplicate at 0.0, 0.05, 0.10 and 0.50 microgram per liter and analyzed on 6 different days during 1 month. The grand means of the normalized concentration percentage recovery for glyphosate, AMPA, and glufosinate among all three matrices and spiked concentrations ranged from 99 to 114 plus or minus 2 to 7 percent of the expected spiked concentration. The grand mean of the percentage difference between concentrations calculated by standard addition and linear regressed multipoint standard curves ranged from 8 to 15 plus or minus 2 to 9 percent for the three compounds. The method reporting levels calculated from all the 0.05- microgram per liter spiked samples were 0.02 microgram per liter for all three compounds. Compound stability experiments were conducted on 10 samples derivatized four times for periods between 136 to 269 days. The glyphosate and AMPA concentrations remained relatively constant in samples held up to 136 days before derivatization. The half life of glyphosate varied from 169 to 223 days in the underivatized samples. Derivatized samples were analyzed the day after derivitization, and again 54 and 64 days after derivatization. The derivatized samples analyzed at days 52 and 64 were within 20 percent of the concentrations of the derivatized samples analyzed the day after derivatization.

Precise determination of triple Sr isotopes (δ⁸⁷Sr and δ⁸⁸Sr) using MC-ICP-MS.

PubMed

Liu, Hou-Chun; You, Chen-Feng; Huang, Kuo-Fang; Chung, Chuan-Hsiung

2012-01-15

The non-traditional stable strontium (Sr) isotopes have received increasing attention recently as new geochemical tracers for studying Sr isotopic fractionation and source identification. This has been attributed to the advancement in multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), allows to determine precisely and simultaneously of the triple Sr isotopes. In this study, we applied a modified empirical external normalization (EEN) MC-ICPMS procedure for mass bias correction in Sr isotopic measurement using (92)Zr/(90)Zr. High-purity Zr Standard was spiked into sample solutions and the degree of fractionation was calculated off-line using an exponential law. The long-term external reproducibility for NIST SRM 987 δ(87)Sr and δ(88)Sr was better than 0.040‰ and 0.018‰ (2SD), respectively. The IAPSO standard seawater was used as a secondary standard to validate the analytical protocol and the absolute ratios measured were 0.709161±0.000018 for (87)Sr/(86)Sr, 0.177±0.021‰ for δ(87)Sr, and 0.370±0.026‰ for δ(88)Sr (2SD, n=7). These values are in good agreement with the literature data analyzed by thermal ionization mass spectrometry (TIMS) double spike technique. Rock standards, BHVO-2, BCR-2 and AGV-2 were also analyzed to validate the robustness of the methodology and showed identical results with literature data. Compared to previous (91)Zr/(90)Zr correction, we obtained improved results based on (92)Zr/(90)Zr, probably due to similar mass difference between (92)Zr/(90)Zr and measured Sr isotopes. The new analytical protocol presented in this study not only improves the analytical precision but also increases sample efficiency by omitting the use of the standard-sample bracketing (SSB) procedure. Copyright © 2011 Elsevier B.V. All rights reserved.

Determination of uranium isotopic composition and 236U content of soil samples and hot particles using inductively coupled plasma mass spectrometry.

PubMed

Boulyga, S F; Becker, J S

2001-07-01

As a result of the accident at the Chernobyl nuclear power plant (NPP) the environment was contaminated with spent nuclear fuel. The 236U isotope was used in this study to monitor the spent uranium from nuclear fallout in soil samples collected in the vicinity of the Chernobyl NPP. Nuclear track radiography was applied for the identification and extraction of hot radioactive particles from soil samples. A rapid and sensitive analytical procedure was developed for uranium isotopic ratio measurement in environmental samples based on double-focusing inductively coupled plasma mass spectrometry (DF-ICP-MS) with a MicroMist nebulizer and a direct injection high-efficiency nebulizer (DIHEN). The performance of the DF-ICP-MS with a quartz DIHEN and plasma shielded torch was studied. Overall detection efficiencies of 4 x 10(-4) and 10(-3) counts per atom were achieved for 238U in DF-ICP-QMS with the MicroMist nebulizer and DIHEN, respectively. The rate of formation of uranium hydride ions UH+/U+ was 1.2 x 10(-4) and 1.4 x 10(-4), respectively. The precision of short-term measurements of uranium isotopic ratios (n = 5) in 1 microg L(-1) NBS U-020 standard solution was 0.11% (238U/235U) and 1.4% (236U/238U) using a MicroMist nebulizer and 0.25% (235U/238U) and 1.9% (236U/P38U) using a DIHEN. The isotopic composition of all investigated Chernobyl soil samples differed from those of natural uranium; i.e. in these samples the 236U/238U ratio ranged from 10(-5) to 10(-3). Results obtained with ICP-MS, alpha- and gamma-spectrometry showed differences in the migration properties of spent uranium, plutonium, and americium. The isotopic ratio of uranium was also measured in hot particles extracted from soil samples.

Variation in fluxes estimated from nitrogen isotope discrimination corresponds with independent measures of nitrogen flux in Populus balsamifera L.

PubMed

Kalcsits, Lee A; Guy, Robert D

2016-02-01

Acquisition of mineral nitrogen by roots from the surrounding environment is often not completely efficient, in which a variable amount of leakage (efflux) relative to gross uptake (influx) occurs. The efflux/influx ratio (E/I) is, therefore, inversely related to the efficiency of nutrient uptake at the root level. Time-integrated estimates of E/I and other nitrogen-use traits may be obtainable from variation in stable isotope ratios or through compartmental analysis of tracer efflux (CATE) using radioactive or stable isotopes. To compare these two methods, Populus balsamifera L. genotypes were selected, a priori, for high or low nitrogen isotope discrimination. Vegetative cuttings were grown hydroponically, and E/I was calculated using an isotope mass balance model (IMB) and compared to E/I calculated using (15) N CATE. Both methods indicated that plants grown with ammonium had greater E/I than nitrate-grown plants. Genotypes with high or low E/I using CATE also had similarly high or low estimates of E/I using IMB, respectively. Genotype-specific means were linearly correlated (r = 0.77; P = 0.0065). Discrepancies in E/I between methods may reflect uncertainties in discrimination factors for the assimilatory enzymes, or temporal differences in uptake patterns. By utilizing genotypes with known variation in nitrogen isotope discrimination, a relationship between nitrogen isotope discrimination and bidirectional nitrogen fluxes at the root level was observed. © 2015 John Wiley & Sons Ltd.

GasBench/isotope ratio mass spectrometry: a carbon isotope approach to detect exogenous CO(2) in sparkling drinks.

PubMed

Cabañero, Ana I; San-Hipólito, Tamar; Rupérez, Mercedes

2007-01-01

A new procedure for the determination of carbon dioxide (CO(2)) (13)C/(12)C isotope ratios, using direct injection into a GasBench/isotope ratio mass spectrometry (GasBench/IRMS) system, has been developed to improve isotopic methods devoted to the study of the authenticity of sparkling drinks. Thirty-nine commercial sparkling drink samples from various origins were analyzed. Values of delta(13)C(cava) ranged from -20.30 per thousand to -23.63 per thousand, when C3 sugar addition was performed for a second alcoholic fermentation. Values of delta(13)C(water) ranged from -5.59 per thousand to -6.87 per thousand in the case of naturally carbonated water or water fortified with gas from the spring, and delta(13)C(water) ranged from -29.36 per thousand to -42.09 per thousand when industrial CO(2) was added. It has been demonstrated that the addition of C4 sugar to semi-sparkling wine (aguja) and industrial CO(2) addition to sparkling wine (cava) or water can be detected. The new procedure has advantages over existing methods in terms of analysis time and sample treatment. In addition, it is the first isotopic method developed that allows (13)C/(12)C determination directly from a liquid sample without previous CO(2) extraction. No significant isotopic fractionation was observed nor any influence by secondary compounds present in the liquid phase. Copyright (c) 2007 John Wiley & Sons, Ltd.

Hybrid isotope separation scheme

DOEpatents

Maya, J.

1991-06-18

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

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

PubMed

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

2017-10-01

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

Copper isotope fractionation between aqueous compounds relevant to low temperature geochemistry and biology

NASA Astrophysics Data System (ADS)

Fujii, Toshiyuki; Moynier, Frédéric; Abe, Minori; Nemoto, Keisuke; Albarède, Francis

2013-06-01

Isotope fractionation between the common Cu species present in solution (Cu+, Cu2+, hydroxide, chloride, sulfide, carbonate, oxalate, and ascorbate) has been investigated using both ab initio methods and experimental solvent extraction techniques. In order to establish unambiguously the existence of equilibrium isotope fractionation (as opposed to kinetic isotope fractionation), we first performed laboratory-scale liquid-liquid distribution experiments. Upon exchange between HCl medium and a macrocyclic complex, the 65Cu/63Cu ratio fractionated by -1.06‰ to -0.39‰. The acidity dependence of the fractionation was appropriately explained by ligand exchange reactions between hydrated H2O and Cl- via intramolecular vibrations. The magnitude of the Cu isotope fractionation among important Cu ligands was also estimated by ab initio methods. The magnitude of the nuclear field shift effect to the Cu isotope fractionation represents only ˜3% of the mass-dependent fractionation. The theoretical estimation was expanded to chlorides, hydroxides, sulfides, sulfates, and carbonates under different conditions of pH. Copper isotope fractionation of up to 2‰ is expected for different forms of Cu present in seawater and for different sediments (carbonates, hydroxides, and sulfides). We found that Cu in dissolved carbonates and sulfates is isotopically much heavier (+0.6‰) than free Cu. Isotope fractionation of Cu in hydroxide is minimal. The relevance of these new results to the understanding of metabolic processes was also discussed. Copper is an essential element used by a large number of proteins for electron transfer. Further theoretical estimates of δ65Cu in hydrated Cu(I) and Cu(II) ions, Cu(II) ascorbates, and Cu(II) oxalate predict Cu isotope fractionation during the breakdown of ascorbate into oxalate and account for the isotopically heavy Cu found in animal kidneys.

Lagrangian process attribution of isotopic variations in near-surface water vapour in a 30-year regional climate simulation over Europe

NASA Astrophysics Data System (ADS)

Dütsch, Marina; Pfahl, Stephan; Meyer, Miro; Wernli, Heini

2018-02-01

Stable water isotopes are naturally available tracers of moisture in the atmosphere. Due to isotopic fractionation, they record information about condensation and evaporation processes during the transport of air parcels, and therefore present a valuable means for studying the global water cycle. However, the meteorological processes driving isotopic variations are complex and not very well understood so far, in particular on short (hourly to daily) timescales. This study presents a Lagrangian method for attributing the isotopic composition of air parcels to meteorological processes, which provides new insight into the isotopic history of air parcels. It is based on the temporal evolution of the isotope ratios, the humidity, the temperature, and the location of the air parcels. Here these values are extracted along 7-day backward trajectories started every 6 hours from near the surface in a 30-year regional climate simulation over Europe with the isotope-enabled version of the model of the Consortium for Small-Scale Modelling (COSMOiso). The COSMOiso simulation has a horizontal resolution of 0.25° and is driven at the lateral boundaries by a T106 global climate simulation with the isotope-enabled version of the European Centre Hamburg model (ECHAMwiso). Both simulations are validated against measurements from the Global Network of Isotopes in Precipitation (GNIP), which shows that nesting COSMOiso within ECHAMwiso improves the representation of δ2H and deuterium excess in monthly accumulated precipitation. The method considers all isotopic changes that occur inside the COSMOiso model domain, which, on average, correspond to more than half of the mean and variability in both δ2H and deuterium excess at the air parcels' arrival points. Along every trajectory, the variations in the isotope values are quantitatively decomposed into eight process categories (evaporation from the ocean, evapotranspiration from land, mixing with moister air, mixing with drier air, liquid cloud formation, mixed phase cloud formation, ice cloud formation, and no process). The results show that for air parcels arriving over the ocean, evaporation from the ocean is the primary factor controlling δ2H and deuterium excess. Over land, evapotranspiration from land and mixing with moister air are similarly important. Liquid and mixed phase cloud formation contribute to the variability of δ2H and deuterium excess, especially over continental Europe. In summary, the presented method helps to better understand the linkage between the meteorological history of air parcels and their isotopic composition, and may support the interpretation of stable water isotope measurements in future.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

In this study, we attempted to establish quinone-stable-isotope probing (SIP) technique to link substrate-utilizing bacterial group to chemotaxonomic group in bacterial community. To identify metabolically active bacterial group in various environments, SIP techniques combined with biomarkers have been widely utilized as an attractive method for environmental study. Quantitative approaches of the SIP technique have unique advantage to assess substrate-incorporation into bacteria. As a most major quantitative approach, SIP technique based on phospholipid-derived fatty acids (PLFA) have been applied to simultaneously assess substrate-incorporation rate into bacteria and microbial community structure. This approach is powerful to estimate the incorporation rate because of the high sensitivity due to the detection by a gas chromatograph-combustion interface-isotope ratio mass spectrometer (GC-c-IRMS). However, its phylogenetic resolution is limited by specificity of a compound-specific marker. We focused on respiratory quinone as a biomarker. Our previous study found a good correlation between concentrations of bacteria-specific PLFAs and quinones over several orders of magnitude in various marine sediments, and the quinone method has a higher resolution (bacterial phylum level) for resolving differences in bacterial community composition more than that of bacterial PLFA. Therefore, respiratory quinones are potentially good biomarkers for quantitative approaches of the SIP technique. The LC-APCI-MS method as molecular-mass based detection method for quinone was developed and provides useful structural information for identifying quinone molecular species in environmental samples. LC-MS/MS on hybrid triple quadrupole/linear ion trap, which enables to simultaneously identify and quantify compounds in a single analysis, can detect high molecular compounds with their isotope ions. Use of LC-MS/MS allows us to develop quinone-SIP based on molecular mass differences due to 13C abundance in the quinone. In this study, we verified carbon stable isotope of quinone compared with bulk carbon stable isotope of bacterial culture. Results indicated a good correlation between carbon stable isotope of quinone compared with bulk carbon stable isotope. However, our measurement conditions for detection of quinone isotope-ions incurred underestimation of 13C abundance in the quinone. The quinone-SIP technique needs further optimization for measurement conditions of LC-MS/MS.

On-line hydrogen-isotope measurements of organic samples using elemental chromium: An extension for high temperature elemental-analyzer techniques

USGS Publications Warehouse

Gehre, Matthias; Renpenning, Julian; Gilevska, Tetyana; Qi, Haiping; Coplen, Tyler B.; Meijer, Harro A.J.; Brand, Willi A.; Schimmelmann, Arndt

2015-01-01

The high temperature conversion (HTC) technique using an elemental analyzer with a glassy carbon tube and filling (temperature conversion/elemental analysis, TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ2H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1‰) from the true value for some materials. We show that a single-oven, chromium-filled elemental analyzer coupled to an IRMS substantially improves the measurement quality and reliability for hydrogen isotopic compositions of organic substances (Cr-EA method). Hot chromium maximizes the yield of molecular hydrogen in a helium carrier gas by irreversibly and quantitatively scavenging all reactive elements except hydrogen. In contrast, under TC/EA conditions, heteroelements like nitrogen or chlorine (and other halogens) can form hydrogen cyanide (HCN) or hydrogen chloride (HCl) and this can cause isotopic fractionation. The Cr-EA technique thus expands the analytical possibilities for on-line hydrogen-isotope measurements of organic samples significantly. This method yielded reproducibility values (1-sigma) for δ2H measurements on water and caffeine samples of better than 1.0 and 0.5 mUr, respectively. To overcome handling problems with water as the principal calibration anchor for hydrogen isotopic measurements, we have employed an effective and simple strategy using reference waters or other liquids sealed in silver-tube segments. These crimped silver tubes can be employed in both the Cr-EA and TC/EA techniques. They simplify considerably the normalization of hydrogen-isotope measurement data to the VSMOW-SLAP (Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation) scale, and their use improves accuracy of the data by eliminating evaporative loss and associated isotopic fractionation while handling water as a bulk sample. The calibration of organic samples, commonly having high δ2H values, will benefit from the availability of suitably 2H-enriched reference waters, extending the VSMOW-SLAP scale above zero.

The Majorana Demonstrator: Progress towards showing the feasibility of a tonne-scale 76Ge neutrinoless double-beta decay experiment

NASA Astrophysics Data System (ADS)

Finnerty, P.; Aguayo, E.; Amman, M.; Avignone, F. T., Iii; Barabash, A. S.; Barton, P. J.; Beene, J. R.; Bertrand, F. E.; Boswell, M.; Brudanin, V.; Busch, M.; Chan, Y.-D.; Christofferson, C. D.; Collar, J. I.; Combs, D. C.; Cooper, R. J.; Detwiler, J. A.; Doe, P. J.; Efremenko, Yu; Egorov, V.; Ejiri, H.; Elliott, S. R.; Esterline, J.; Fast, J. E.; Fields, N.; Fraenkle, F. M.; Galindo-Uribarri, A.; Gehman, V. M.; Giovanetti, G. K.; Green, M. P.; Guiseppe, V. E.; Gusey, K.; Hallin, A. L.; Hazama, R.; Henning, R.; Hoppe, E. W.; Horton, M.; Howard, S.; Howe, M. A.; Johnson, R. A.; Keeter, K. J.; Kidd, M. F.; Knecht, A.; Kochetov, O.; Konovalov, S. I.; Kouzes, R. T.; LaFerriere, B. D.; Leon, J.; Leviner, L. E.; Loach, J. C.; Luke, P. N.; MacMullin, S.; Marino, M. G.; Martin, R. D.; Merriman, J. H.; Miller, M. L.; Mizouni, L.; Nomachi, M.; Orrell, J. L.; Overman, N. R.; Perumpilly, G.; Phillips, D. G., Ii; Poon, A. W. P.; Radford, D. C.; Rielage, K.; Robertson, R. G. H.; Ronquest, M. C.; Schubert, A. G.; Shima, T.; Shirchenko, M.; Snavely, K. J.; Steele, D.; Strain, J.; Timkin, V.; Tornow, W.; Varner, R. L.; Vetter, K.; Vorren, K.; Wilkerson, J. F.; Yakushev, E.; Yaver, H.; Young, A. R.; Yu, C.-H.; Yumatov, V.; Majorana Collaboration

2014-03-01

The Majorana Demonstrator will search for the neutrinoless double-beta decay (0vββ) of the 76Ge isotope with a mixed array of enriched and natural germanium detectors. The observation of this rare decay would indicate the neutrino is its own anti-particle, demonstrate that lepton number is not conserved, and provide information on the absolute mass-scale of the neutrino. The Demonstrator is being assembled at the 4850 foot level of the Sanford Underground Research Facility in Lead, South Dakota. The array will be contained in a low-background environment and surrounded by passive and active shielding. The goals for the Demonstrator are: demonstrating a background rate less than 3 t-1 y-1 in the 4 keV region of interest (ROI) surrounding the 2039 keV 76Ge endpoint energy; establishing the technology required to build a tonne-scale germanium based double-beta decay experiment; testing the recent claim of observation of 0vββ [1]; and performing a direct search for light WIMPs (3-10 GeV/c2).

The Majorana Demonstrator: Progress towards showing the feasibility of a 76Ge neutrinoless double-beta decay experiment

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

Finnerty, P.; Aguayo, Estanislao; Amman, M.

2014-03-24

The Majorana Demonstrator will search for the neutrinoless double-beta decay (0*) of the 76Ge isotope with a mixed array of enriched and natural germanium detectors. The observation of this rare decay would indicate the neutrino is its own anti-particle, demonstrate that lepton number is not conserved, and provide information on the absolute mass-scale of the neutrino. The Demonstrator is being assembled at the 4850 foot level of the Sanford Underground Research Facility in Lead, South Dakota. The array will be contained in a lowbackground environment and surrounded by passive and active shielding. The goals for the Demonstrator are: demonstrating amore » background rate less than 3 counts tonne -1 year-1 in the 4 keV region of interest (ROI) surrounding the 2039 keV 76Ge endpoint energy; establishing the technology required to build a tonne-scale germanium based double-beta decay experiment; testing the recent claim of observation of 0; and performing a direct search for lightWIMPs (3-10 GeV/c2).« less

'Trophic' and 'source' amino acids in trophic estimation: a likely metabolic explanation.

PubMed

O'Connell, T C

2017-06-01

Amino acid nitrogen isotopic analysis is a relatively new method for estimating trophic position. It uses the isotopic difference between an individual's 'trophic' and 'source' amino acids to determine its trophic position. So far, there is no accepted explanation for the mechanism by which the isotopic signals in 'trophic' and 'source' amino acids arise. Yet without a metabolic understanding, the utility of nitrogen isotopic analyses as a method for probing trophic relations, at either bulk tissue or amino acid level, is limited. I draw on isotopic tracer studies of protein metabolism, together with a consideration of amino acid metabolic pathways, to suggest that the 'trophic'/'source' groupings have a fundamental metabolic origin, to do with the cycling of amino-nitrogen between amino acids. 'Trophic' amino acids are those whose amino-nitrogens are interchangeable, part of a metabolic amino-nitrogen pool, and 'source' amino acids are those whose amino-nitrogens are not interchangeable with the metabolic pool. Nitrogen isotopic values of 'trophic' amino acids will reflect an averaged isotopic signal of all such dietary amino acids, offset by the integrated effect of isotopic fractionation from nitrogen cycling, and modulated by metabolic and physiological effects. Isotopic values of 'source' amino acids will be more closely linked to those of equivalent dietary amino acids, but also modulated by metabolism and physiology. The complexity of nitrogen cycling suggests that a single identifiable value for 'trophic discrimination factors' is unlikely to exist. Greater consideration of physiology and metabolism should help in better understanding observed patterns in nitrogen isotopic values.

Nitrogen isotopic baselines and implications for estimating foraging habitat and trophic position of yellowfin tuna in the Indian and Pacific Oceans

NASA Astrophysics Data System (ADS)

Lorrain, Anne; Graham, Brittany S.; Popp, Brian N.; Allain, Valérie; Olson, Robert J.; Hunt, Brian P. V.; Potier, Michel; Fry, Brian; Galván-Magaña, Felipe; Menkes, Christophe E. R.; Kaehler, Sven; Ménard, Frédéric

2015-03-01

Assessment of isotopic compositions at the base of food webs is a prerequisite for using stable isotope analysis to assess foraging locations and trophic positions of marine organisms. Our study represents a unique application of stable-isotope analyses across multiple trophic levels (primary producer, primary consumer and tertiary consumer) and over a large spatial scale in two pelagic marine ecosystems. We found that δ15N values of particulate organic matter (POM), barnacles and phenylalanine from the muscle tissue of yellowfin tuna all showed similar spatial patterns. This consistency suggests that isotopic analysis of any of these can provide a reasonable proxy for isotopic variability at the base of the food web. Secondly, variations in the δ15N values of yellowfin tuna bulk-muscle tissues paralleled the spatial trends observed in all of these isotopic baseline proxies. Variation in isotopic composition at the base of the food web, rather than differences in tuna diet, explained the 11‰ variability observed in the bulk-tissue δ15N values of yellowfin tuna. Evaluating the trophic position of yellowfin tuna using amino-acid isotopic compositions across the western Indian and equatorial Pacific Oceans strongly suggests these tuna occupy similar trophic positions, albeit absolute trophic positions estimated by this method were lower than expected. This study reinforces the importance of considering isotopic baseline variability for diet studies, and provides new insights into methods that can be applied to generate nitrogen isoscapes for worldwide comparisons of top predators in marine ecosystems.

A double-tracer technique to characterize absorption, distribution, metabolism and excretion (ADME) of [14C]-basimglurant and absolute bioavailability after oral administration and concomitant intravenous microdose administration of [13C6]-labeled basimglurant in humans.

PubMed

Guerini, Elena; Schadt, Simone; Greig, Gerard; Haas, Ruth; Husser, Christophe; Zell, Manfred; Funk, Christoph; Hartung, Thomas; Gloge, Andreas; Mallalieu, Navita L

2017-02-01

1. The emerging technique of employing intravenous microdose administration of an isotope tracer concomitantly with an [ 14 C]-labeled oral dose was used to characterize the disposition and absolute bioavailability of a novel metabotropic glutamate 5 (mGlu5) receptor antagonist under clinical development for major depressive disorder (MDD). 2. Six healthy volunteers received a single 1 mg [ 12 C/ 14 C]-basimglurant (2.22 MBq) oral dose and a concomitant i.v. tracer dose of 100 μg of [ 13 C 6 ]-basimglurant. Concentrations of [ 12 C]-basimglurant and the stable isotope [ 13 C 6 ]-basimglurant were determined in plasma by a specific LC/MS-MS method. Total [ 14 C] radioactivity was determined in whole blood, plasma, urine and feces by liquid scintillation counting. Metabolic profiling was conducted in plasma, urine, blood cell pellet and feces samples. 3. The mean absolute bioavailability after oral administration (F) of basimglurant was ∼67% (range 45.7-77.7%). The major route of [ 14 C]-radioactivity excretion, primarily in form of metabolites, was in urine (mean recovery 73.4%), with the remainder excreted in feces (mean recovery 26.5%). The median t max for [ 12 C]-basimglurant after the oral administration was 0.71 h (range 0.58-1.00) and the mean terminal half-life was 77.2 ± 38.5 h. Terminal half-life for the [ 14 C]-basimglurant was 178 h indicating presence of metabolites with a longer terminal half-life. Five metabolites were identified with M1-Glucuronide as major and the others in trace amounts. There was minimal binding of drug to RBCs. IV pharmacokinetics was characterized with a mean ± SD CL of 11.8 ± 7.4 mL/h and a Vss of 677 ± 229 L. 4. The double-tracer technique used in this study allowed to simultaneously characterize the absolute bioavailability and disposition characteristics of the new oral molecular entity in a single study.

Determination of the δ13C of dissolved inorganic carbon in water; RSIL lab code 1710

USGS Publications Warehouse

Singleton, Glenda L.; Revesz, Kinga; Coplen, Tyler B.

2012-01-01

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1710 is to present a method to determine the δ13C of dissolved inorganic carbon (DIC) of water. The DIC of water is precipitated using ammoniacal strontium chloride (SrCl2) solution to form strontium carbonate (SrCO3). The δ13C is analyzed by reacting SrCO3 with 100-percent phosphoric acid (H3PO4) to liberate carbon quantitatively as carbon dioxide (CO2), which is collected, purified by vacuum sublimation, and analyzed by dual inlet isotope-ratio mass spectrometry (DI-IRMS). The DI-IRMS is a DuPont double-focusing mass spectrometer. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other measurable ion beams are collected in the front collector. By changing the ion-accelerating voltage under computer control, the instrument is capable of measuring mass/charge (m/z) 45 or 46 in the rear collector and m/z 44 and 46 or 44 and 45, respectively, in the front collector. The ion beams from these m/z values are as follows: m/z 44 = CO2 = 12C16O16O, m/z 45 = CO2 = 13C16O16O primarily, and m/z 46 = CO2 = 12C16O18O primarily. The data acquisition and control software calculates δ13C values.

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

PubMed

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

2015-04-30

Dacryoconarids are extinct marine zooplankton known from abundant, globally distributed calcite microfossils in the Devonian, but their shell stable isotope composition has not been previously explored. Devonian stable isotope stratigraphy is currently limited to less common invertebrates or bulk rock analyses of uncertain provenance. As with Cenozoic planktonic foraminifera, isotopic analysis of dacryoconarid shells could facilitate higher-resolution, geographically widespread stable isotope records of paleoenvironmental change, including marine hypoxia events, climate changes, and biocrises. We explored the use of Dacryoconarid isotope stratigraphy as a viable method in interpreting paleoenvironments. We applied an established method for determining stable isotope ratios (δ(13) C, δ(18) O values) of small carbonate microfossils to very well-preserved dacryoconarid shells. We analyzed individual calcite shells representing five common genera using a Kiel carbonate device coupled to a MAT 253 isotope ratio mass spectrometer. Calcite shell δ(13) C and δ(18) O values were compared by taxonomic group, rock unit, and locality. Single dacryoconarid calcite shells are suitable for stable isotope analysis using a Kiel-IRMS setup. The dacryoconarid shell δ(13) C values (-4.7 to 2.3‰) and δ(18) O values (-10.3 to -4.8‰) were consistent across taxa, independent of shell size or part, but varied systematically through time. Lower fossil δ(18) O values were associated with warmer water temperature and more variable δ(13) C values were associated with major bioevents. Dacryoconarid δ(13) C and δ(18) O values differed from bulk rock carbonate values. Dacryoconarid individual microfossil δ(13) C and δ(18) O values are highly sensitive to paleoenvironmental changes, thus providing a promising avenue for stable isotope chemostratigraphy to better resolve regional to global paleoceanographic changes throughout the upper Silurian to the upper Devonian. Our results warrant further exploration of dacryoconarid stable isotope proxy sensitivity, the isotopic contrast among dacryoconarids, other taxa, and bulk rock, as well as other potential dacryoconarid proxies (Mg/Ca, Sr/Ca, (87) Sr/(86) Sr, microlaser and ion microprobe isotope techniques, and clumped isotopes) for stratigraphic research. Copyright © 2015 John Wiley & Sons, Ltd.

Testing isotopic labeling with [¹³C₆]glucose as a method of advanced glycation sites identification.

PubMed

Kielmas, Martyna; Kijewska, Monika; Stefanowicz, Piotr; Szewczuk, Zbigniew

2012-12-01

The Maillard reaction occurring between reducing sugars and reactive amino groups of biomolecules leads to the formation of a heterogeneous mixture of compounds: early, intermediate, and advanced glycation end products (AGEs). These compounds could be markers of certain diseases and of the premature aging process. Detection of Amadori products can be performed by various methods, including MS/MS techniques and affinity chromatography on immobilized boronic acid. However, the diversity of the structures of AGEs makes detection of these compounds more difficult. The aim of this study was to test a new method of AGE identification based on isotope (13)C labeling. The model protein (hen egg lysozyme) was modified with an equimolar mixture of [(12)C(6)]glucose and [(13)C(6)]glucose and then subjected to reduction of the disulfide bridges followed by tryptic hydrolysis. The digest obtained was analyzed by LC-MS. The glycation products were identified on the basis of characteristic isotopic patterns resulting from the use of isotopically labeled glucose. This method allowed identification of 38 early Maillard reaction products and five different structures of the end glycation products. This isotopic labeling technique combined with LC-MS is a sensitive method for identification of advanced glycation end products even if their chemical structure is unknown. Copyright © 2012 Elsevier Inc. All rights reserved.

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS for isotope analysis of long-lived radionuclides

NASA Astrophysics Data System (ADS)

Becker, J. Sabine

2005-04-01

For a few years now inductively coupled plasma mass spectrometry has been increasingly used for precise and accurate determination of isotope ratios of long-lived radionuclides at the trace and ultratrace level due to its excellent sensitivity, good precision and accuracy. At present, ICP-MS and also laser ablation ICP-MS are applied as powerful analytical techniques in different fields such as the characterization of nuclear materials, recycled and by-products (e.g., spent nuclear fuel or depleted uranium ammunitions), radioactive waste control, in environmental monitoring and in bioassay measurements, in health control, in geochemistry and geochronology. Especially double-focusing sector field ICP mass spectrometers with single ion detector or with multiple ion collector device have been used for the precise determination of long-lived radionuclides isotope ratios at very low concentration levels. Progress has been achieved by the combination of ultrasensitive mass spectrometric techniques with effective separation and enrichment procedures in order to improve detection limits or by the introduction of the collision cell in ICP-MS for reducing disturbing interfering ions (e.g., of 129Xe+ for the determination of 129I). This review describes the state of the art and the progress of ICP-MS and laser ablation ICP-MS for isotope ratio measurements of long-lived radionuclides in different sample types, especially in the main application fields of characterization of nuclear and radioactive waste material, environmental research and health controls.

Biomedical applications of laser photoionization

NASA Astrophysics Data System (ADS)

Xiong, Xiaoxiong; Moore, Larry J.; Fassett, John R.; O'Haver, Thomas C.

1991-07-01

Trace elements are important for many essential metabolic functions. Zinc is a structural/functional component in more than 200 enzymes active in the biochemistry of cell division and tissue growth, neurology and endocrine control. Calcium is involved in intracellular control mechanisms and in skeletal bone building and resorption processes related to osteoporosis. Sensitive and selective laser photoionization is being developed to understand mechanisms in smaller samples and biological units approaching the cellular domain. Zinc has an ionization potential of 9.4 eV, or 75766.8 cm-1. Several processes are being explored, including two-photon resonant, three- photon ionization utilizing sequential UV transitions, e.g., 4s2 1S0 yields 4s4p 3P1 and 4s4p 3P1 yields 4s5d 3D1. Preliminary zinc stable isotope ratio data obtained by thermal atomization and laser photoionization agree with accepted values within 2 to 5%, except for anomalous 67Zn. Photoionization of calcium is being studied for isotope enrichment and ratio measurement using narrow and medium bandwidth lasers. Several ionization pathways, e.g., 4s2 1S0 - 2hv1 yields 4s10s - hv2 yields Ca+ (4s2S), are being investigated for isotopically selective ionization. Auto-ionization pathways are explored for greater efficiency in isotopic analysis. All studies have utilized a Nd:YAG- pumped laser system with one or two frequency-doubled tunable dye lasers coupled either to a magnetic sector or time-of-flight mass spectrometer.

Efficacy of passive sampler collection for atmospheric NO2 isotopes under simulated environmental conditions.

PubMed

Coughlin, Justin G; Yu, Zhongjie; Elliott, Emily M

2017-07-30

Nitrogen oxides or NO x (NO x = NO + NO 2 ) play an important role in air quality, atmospheric chemistry, and climate. The isotopic compositions of anthropogenic and natural NO 2 sources are wide-ranging, and they can be used to constrain sources of ambient NO 2 and associated atmospheric deposition of nitrogen compounds. While passive sample collection of NO 2 isotopes has been used in field studies to determine NO x source influences on atmospheric deposition, this approach has not been evaluated for accuracy or precision under different environmental conditions. The efficacy of NO 2 passive sampler collection for NO 2 isotopes was evaluated under varied temperature and relative humidity (RH) conditions in a dynamic flux chamber. The precision and accuracy of the filter NO 2 collection as nitrite (NO 2 - ) for isotopic analysis were determined using a reference NO 2 gas tank and through inter-calibration with a modified EPA Method 7. The bacterial denitrifer method was used to convert 20 μM of collected NO 2 - or nitrate (NO 3 - ) into N 2 O and was carried out on an Isoprime continuous flow isotope ratio mass spectrometer. δ 15 N-NO 2 values determined from passive NO 2 collection, in conditions of 11-34 °C, 1-78% RH, have an overall accuracy and precision of ±2.1 ‰, and individual run precision of ±0.6 ‰. δ 18 O-NO 2 values obtained from passive NO 2 sampler collection, under the same conditions, have an overall precision of ± 1.3 ‰. Suitable conditions for passive sampler collection of NO 2 isotopes are in environments ranging from 11 to 34 °C and 1 to 78% RH. The passive NO 2 isotope measurement technique provides an accurate method to determine variations in atmospheric δ 15 N-NO 2 values and a precise method for determining atmospheric δ 18 O-NO 2 values. The ability to measure NO 2 isotopes over spatial gradients at the same temporal resolution provides a unique perspective on the extent and seasonality of fluctuations in atmospheric NO 2 isotopic compositions. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

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 mixtures and c) transformation of pesticides in lysimeters during the year 2014. 1 Elsner, M. Stable isotope fractionation to investigate natural transformation mechanisms of organic contaminants: principles, prospects and limitations. J. Environ. Monit. 12, 2005-2031 (2010). 2 Hofstetter, T. B. & Berg, M. Assessing transformation processes of organic contaminants by compound-specific stable isotope analysis. TrAC Trends in Analytical Chemistry 30, 618-627 (2011). 3 Elsner, M. et al. Current challenges in compound-specific stable isotope analysis of environmental organic contaminants. Anal. Bioanal. Chem. 403, 2471-2491, doi:10.1007/s00216-011-5683-y (2012).

High Throughput Strontium Isotope Method for Monitoring Fluid Flow Related to Geological CO2 Storage

NASA Astrophysics Data System (ADS)

Capo, R. C.; Wall, A. J.; Stewart, B. W.; Phan, T. T.; Jain, J. C.; Hakala, J. A.; Guthrie, G. D.

2012-12-01

Natural isotope tracers, such as strontium (Sr), can be a unique and powerful component of a monitoring strategy at a CO2 storage site, facilitating both the quantification of reaction progress for fluid-rock interactions and the tracking of brine migration caused by CO2 injection. Several challenges must be overcome, however, to enable the routine use of isotopic tracers, including the ability to rapidly analyze numerous aqueous samples with potentially complex chemical compositions. In a field situation, it might be necessary to analyze tens of samples over a short period of time to identify subsurface reactions and respond to unexpected fluid movement in the host formation. These conditions require streamlined Sr separation chemistry for samples ranging from pristine groundwaters to those containing high total dissolved solids, followed by rapid measurement of isotope ratios with high analytical precision. We have optimized Sr separation chemistry and MC-ICP-MS methods to provide rapid and precise measurements of isotope ratios in geologic, hydrologic, and environmental samples. These improvements will allow an operator to independently prepare samples for Sr isotope analysis off-site using fast, low cost chemical separation procedures and commercially available components. Existing vacuum-assisted Sr separation procedures were modified by using inexpensive disposable parts to eliminate cross contamination. Experimental results indicate that the modified columns provide excellent separation of Sr from chemically complex samples and that Sr can be effectively isolated from problematic matrix elements (e.g., Ca, Ba, K) associated with oilfield brines and formation waters. The separation procedure is designed for high sample throughput in which batches of 24 samples can be processed in approximately 2 hours, and are ready for Sr isotope measurements by MC-ICP-MS immediately after collection from the columns. Precise Sr isotope results can be achieved by MC-ICP-MS with a throughput of 4 to 5 samples per hour. Our mean measured value of NIST Sr isotope standard SRM 987 is 0.710265 ± 0.000014 (2σ, n = 94). A range of brines and CO2-rich fluids analyzed by this method yielded results within the analytical uncertainty of 87Sr/86Sr ratios previously determined by standard column separation and thermal ionization mass spectrometry. This method provides a fast and effective way to use Sr isotopes for monitoring purposes related to geological CO2 storage.

A Method to Determine 18O Kinetic Isotope Effects in the Hydrolysis of Nucleotide Triphosphates

PubMed Central

Du, Xinlin; Ferguson, Kurt; Sprang, Stephen R.

2007-01-01

A method to determine 18O kinetic isotope effects (KIE) in the hydrolysis of GTP is described that is generally applicable to reactions involving other nucleotide triphosphates. Internal competition, wherein the substrate of the reaction is a mixture of 18O-labeled and unlabeled nucleotides, is employed and the change in relative abundance of the two species in the course of the reaction is used to calculate KIE. The nucleotide labeled with 18O at sites of mechanistic interest also contains 13C at all carbon positions, while the 16O-nucleotide is depleted of 13C. The relative abundance of the labeled and unlabeled substrates or products is reflected in the carbon isotope ratio (13C/12C) in GTP or GDP, which is determined by use of a liquid chromatography-coupled isotope ratio mass spectrometer (LC-coupled IRMS). The LC is coupled to the IRMS by an Isolink™ interface (ThermoFinnigan). Carbon isotope ratios can be determined with accuracy and precision greater than 0.04%, and are consistent over an order of magnitude in sample amount. KIE values for Ras/NF1333-catalyzed hydrolysis of [β18O3,13C]GTP were determined by change in the isotope ratio of GTP or GDP or the ratio of the isotope ratio of GDP to that of GTP. KIE values computed in the three ways agree within 0.1%, although the method using the ratio of isotope ratios of GDP and GTP gives superior precision (< 0.1%). A single KIE measurement can be conducted in 25 minutes with less than 5 μg nucleotide reaction product. PMID:17963711

Compound-specific nitrogen isotope analysis of D-alanine, L-alanine, and valine: application of diastereomer separation to delta15N and microbial peptidoglycan studies.

PubMed

Takano, Yoshinori; Chikaraishi, Yoshito; Ogawa, Nanako O; Kitazato, Hiroshi; Ohkouchi, Naohiko

2009-01-01

We have developed an analytical method to determine the compound-specific nitrogen isotope compositions of individual amino acid enantiomers using gas chromatography/combustion/isotope ratio mass spectrometry. A novel derivatization of amino acid diastereomers by optically active (R)-(-)-2-butanol or (S)-(+)-2-butanol offers two advantages for nitrogen isotope analysis. First, chromatographic chiral separation can be achieved without the use of chiral stationary-phase columns. Second, the elution order of these compounds on the chromatogram can be switched by a designated esterification reaction. We applied the method to the compound-specific nitrogen isotope analysis of D- and L-alanine in a peptidoglycan derived from the cell walls of cultured bacteria (Firmicutes and Actinobacteria; Enterococcus faecalis, Staphylococcus aureus, Staphylococcus staphylolyticus, Lactobacillus acidophilus, Bacillus subtilis, Micrococcus luteus, and Streptomyces sp.), natural whole bacterial cells (Bacillus subtilis var. natto), (pseudo)-peptidoglycan from archaea (Methanobacterium sp.), and cell wall from eukaryota (Saccharomyces cerevisiae). We observed statistically significant differences in nitrogen isotopic compositions; e.g., delta15N ( per thousand vs air) in Staphylococcus staphylolyticus for d-alanine (19.2 +/- 0.5 per thousand, n = 4) and L-alanine (21.3 +/- 0.8 per thousand, n = 4) and in Bacillus subtilis for D-alanine (6.2 +/- 0.2 per thousand, n = 3) and L-alanine (8.2 +/- 0.4 per thousand, n = 3). These results suggest that enzymatic reaction pathways, including the alanine racemase reaction, produce a nitrogen isotopic difference in amino acid enantiomers, resulting in 15N-depleted D-alanine. This method is expected to facilitate compound-specific nitrogen isotope studies of amino acid stereoisomers.

Evaluation strategies for isotope ratio measurements of single particles by LA-MC-ICPMS.

PubMed

Kappel, S; Boulyga, S F; Dorta, L; Günther, D; Hattendorf, B; Koffler, D; Laaha, G; Leisch, F; Prohaska, T

2013-03-01

Data evaluation is a crucial step when it comes to the determination of accurate and precise isotope ratios computed from transient signals measured by multi-collector-inductively coupled plasma mass spectrometry (MC-ICPMS) coupled to, for example, laser ablation (LA). In the present study, the applicability of different data evaluation strategies (i.e. 'point-by-point', 'integration' and 'linear regression slope' method) for the computation of (235)U/(238)U isotope ratios measured in single particles by LA-MC-ICPMS was investigated. The analyzed uranium oxide particles (i.e. 9073-01-B, CRM U010 and NUSIMEP-7 test samples), having sizes down to the sub-micrometre range, are certified with respect to their (235)U/(238)U isotopic signature, which enabled evaluation of the applied strategies with respect to precision and accuracy. The different strategies were also compared with respect to their expanded uncertainties. Even though the 'point-by-point' method proved to be superior, the other methods are advantageous, as they take weighted signal intensities into account. For the first time, the use of a 'finite mixture model' is presented for the determination of an unknown number of different U isotopic compositions of single particles present on the same planchet. The model uses an algorithm that determines the number of isotopic signatures by attributing individual data points to computed clusters. The (235)U/(238)U isotope ratios are then determined by means of the slopes of linear regressions estimated for each cluster. The model was successfully applied for the accurate determination of different (235)U/(238)U isotope ratios of particles deposited on the NUSIMEP-7 test samples.

Isotope dilution ICP-MS with laser-assisted sample introduction for direct determination of sulfur in petroleum products.

PubMed

Boulyga, Sergei F; Heilmann, Jens; Heumann, Klaus G

2005-08-01

Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with direct laser-assisted introduction of isotope-diluted samples into the plasma, using a laser ablation system with high ablation rates, was developed for accurate sulfur determinations in different petroleum products such as 'sulfur-free' premium gasoline, diesel fuel, and heating oil. Two certified gas oil reference materials were analyzed for method validation. Two different 34S-enriched spike compounds, namely, elementary sulfur dissolved in xylene and dibenzothiophene in hexane, were synthesized and tested for their usefulness in this isotope dilution technique. The isotope-diluted sample was adsorbed on a filter-paper-like material, which was fixed in a special holder for irradiation by the laser beam. Under these conditions no time-dependent spike/analyte fractionation was only observed for the dibenzothiophene spike during the laser ablation process, which means that the measured 34S/32S isotope ratio of the isotope-diluted sample remained constant-a necessary precondition for accurate results with the isotope dilution technique. A comparison of LA-ICP-IDMS results with the certified values of the gas oil reference materials and with results obtained from ICP-IDMS analyses with wet sample digestion demonstrated the accuracy of the new LA-ICP-IDMS method in the concentration range of 9.2 microg g(-1) ('sulfur-free' premium gasoline) to 10.4 mg g(-1) (gas oil reference material BCR 107). The detection limit for sulfur by LA-ICP-IDMS is 0.04 microg g(-1) and the analysis time is only about 10 min, which therefore also qualifies this method for accurate determinations of low sulfur contents in petroleum products on a routine level.

Testing the Late-Veneer hypothesis with selenium isotopes

NASA Astrophysics Data System (ADS)

Labidi, J.; Koenig, S.; Bennett, N.; Kurzawa, T.; Aierken, E.; Shahar, A.; Schoenberg, R.

2016-12-01

Selenium (Se) is a siderophile element displaying an excess abundance in Earth's mantle compared to experimental predictions [1], which may be attributed to the Late-Veneer. As Se is also volatile, testing the late-veneer addition of Se can constrain the origin of other volatile elements on Earth. Here we combine high-precision Se isotope measurements of metal-silicate partitioning experiments and chondrites to assess whether planetary differentiation could leave a measurable Se isotopic signature on planetary mantles. We performed Se isotopic measurements of 5 metal-silicate partitioning experiments and 20 chondrites of all major classes. Experiments were conducted at 1 GPa and 1650 C for 1 to 4 hours using the piston-cylinder apparatus at Carnegie's Geophysical Laboratory. After wet chemistry, data were obtained on a ThermoFisher Scientific™ NeptunePlus MC-ICP-MS at the University of Tübingen with a 74Se/77Se double spike technique. δ82/76Se values are given relative to NIST SRM-3149 and the external reproducibility calculated from duplicate meteorite analyses is ≤ 0.1‰ (2 s.d.). Chondrites vary over a 0.8‰ range of δ82/76Se values. CIs and CMs show evidence for heavier 82Se/76Se ratios, likely due to mixing processes in the proto-planetary nebula. When these isotopically heavier meteorites are excluded, remaining chondrites have δ82/76Se values varying over a 0.3‰ range, within uncertainty of previous results [2]. We suggest that these chondrites may be used to estimate a δ82/76Se value of bulk planets. At the conditions of our experiments, the partition coefficients for Se log Dmetal-silicate range from 0.7±0.1 to 1.9±0.1, consistent with previous work [1]. A small but resolvable Se isotopic fractionation was observed: 82Se/76Se ratios were enriched by ≤ 0.5‰ in the silicates relative to the metals. Thus, given current uncertainties for Se isotopic measurements, marginal differences between planetary mantles and chondrites may be resolved. [1] Rose-Weston et al. 2009, GCA, 73(15), 4598-4615. [2] Vollstaedt et al. 2016, 450, 372-380.

Guideline on Isotope Dilution Mass Spectrometry

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

Gaffney, Amy

Isotope dilution mass spectrometry is used to determine the concentration of an element of interest in a bulk sample. It is a destructive analysis technique that is applicable to a wide range of analytes and bulk sample types. With this method, a known amount of a rare isotope, or ‘spike’, of the element of interest is added to a known amount of sample. The element of interest is chemically purified from the bulk sample, the isotope ratio of the spiked sample is measured by mass spectrometry, and the concentration of the element of interest is calculated from this result. Thismore » method is widely used, although a mass spectrometer required for this analysis may be fairly expensive.« less

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

USGS Publications Warehouse

Garbarino, John R.; Taylor, Howard E.

1987-01-01

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

Theoretical calculation of polarizability isotope effects.

PubMed

Moncada, Félix; Flores-Moreno, Roberto; Reyes, Andrés

2017-03-01

We propose a scheme to estimate hydrogen isotope effects on molecular polarizabilities. This approach combines the any-particle molecular orbital method, in which both electrons and H/D nuclei are described as quantum waves, with the auxiliary density perturbation theory, to calculate analytically the polarizability tensor. We assess the performance of method by calculating the polarizability isotope effect for 20 molecules. A good correlation between theoretical and experimental data is found. Further analysis of the results reveals that the change in the polarizability of a X-H bond upon deuteration decreases as the electronegativity of X increases. Our investigation also reveals that the molecular polarizability isotope effect presents an additive character. Therefore, it can be computed by counting the number of deuterated bonds in the molecule.

Long-term nitrogen additions and the intrinsic water-use efficiency of boreal Scots pine.

NASA Astrophysics Data System (ADS)

Marshall, John; Wallin, Göran; Linder, Sune; Lundmark, Tomas; Näsholm, Torgny

2015-04-01

Nitrogen fertilization nearly always increases productivity in boreal forests, at least in terms of wood production, but it is unclear how. In a mature (80 yrs. old) Scots pine forest in northern Sweden, we tested the extent to which nitrogen fertilization increased intrinsic photosynthetic water-use efficiency. We measured δ13C both discretely, in biweekly phloem sampling, and continuously, by monitoring of bole respiration. The original experiment was designed as a test of eddy covariance methods and is not therefore strictly replicated. Nonetheless, we compared phloem contents among fifteen trees from each plot and stem respiration from four per plot. The treatments included addition of 100 kg N/ha for eight years and a control. Phloem contents have the advantage of integrating over the whole canopy and undergoing complete and rapid turnover. Their disadvantage is that some have observed isotopic drift with transport down the length of the stem, presumably as a result of preferential export and/or reloading. We also measured the isotopic composition of stem respiration from four trees on each plot using a Picarro G1101-I CRDS attached to the vent flow from a continuous gas-exchange system. We detected consistent differences in δ13C between the treatments in phloem contents. Within each treatment, the phloem δ13C was negatively correlated with antecedent temperature (R2= 0.65) and no other measured climate variable. The isotopic composition of stem CO2 efflux will be compared to that of phloem contents. However, when converted to intrinsic water-use efficiency, the increase amounted to only about 4%. This is a small relative to the near doubling in wood production. Although we were able to detect a clear and consistent increase in water-use efficiency with N-fertilization, it constitutes but a minor cause of the observed increase in wood production.

Environmental isotope investigation of groundwater flow in the Honey Lake Basin, California and Nevada

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

Rose, T.P.; Davisson, M.L.; Hudson, G.B.

The hydrology of Honey Lake Basin was studied using environmental isotope measurements of approximately 130 water samples collected during 1995 and 1996. The principal analytical methods included hydrogen, oxygen and carbon stable isotope ratio measurements, radiocarbon and tritium dating, and measurements of dissolved noble gas abundances.

INTERLABORATORY COMPARISON OF MASS SPECTROMETRIC METHODS FOR LEAD ISOTOPES AND TRACE ELEMENTS IN NIST SRM 1400 BONE ASH

EPA Science Inventory

The results of an interlaboratory comparison are reported for he lead isotope composition and for trace element concentrations in NIST SRM 1400 Bone Ash obtained using quadrupole and magnetic-sector inductively coupled plasma mass spectrometry (ICP-MS) and (for the Pb isotopes on...

Localization of groundwater infiltration in the combined sewers of Brussels by stable isotopes measurements (δ18O, δD) by Cavity Ring Down Spectroscopy.

NASA Astrophysics Data System (ADS)

De Bondt, Kevin; Claeys, Philippe

2014-05-01

In the last 20 years research has been conducted to quantify the infiltration of groundwater into the sewers. This groundwater, called parasitic water, increases the volume of waste-water to be treated and consequently the cost of this treatment. Moreover, in the case of combined sewer systems, the parasitic water also limits the sewer capacity and indirectly increases the risks of combined sewer overflows and floods. The infiltration of groundwater occurs trough cracks, sewer collapses and from direct connections with old springs. Different methods quantify the intrusion of parasitic water. Among these, the use of the stable isotopes of water (δ18O & δD) shows good result in catchments or cities close to Mountainous regions (example from Lyon, Zurich), where isotopic signals vary significantly because of continental and altitude effects. However many cities, such as Brussels, are located in more oceanic settings and theoretically offer less potential for the application of the stable isotopes method. In the case of Brussels, river-water from the Meuse is used to produce domestic-water. The catchment of this river extends into the Ardennes, which are affected by slightly different climatic conditions. δ18O & δD analyzes of groundwater from the main aquifer (Ledo-Paniselian-Brusselian) and domestic-water from the Callois reservoir fed by the Meuse River show sufficient isotopic differences in the south of Brussels, but only during the summer. The discrimination potential is better with δD than with δ18O. The improvement of δD measurements (precision, costs,...) brought by Cavity Ring Down Spectroscopy largely contributes to the potential of using stable isotopes method to trace water in Brussels. The first campaigns in the sewers also show a little enrichment (in heavy isotopes) of the waste-water in comparison with the reservoir waters and tap waters. This increases the potential of the method but constrains the sampling to pure waste-water in sewer segments without infiltration generally localized upstream. Anyway, it is in the localization of parasitic water entrance from upstream to downstream that the stable isotopes method is the most powerful. Other methods (e.g. minimum night flow,...) are available at the treatment plants or at flow measurement stations downstream but will not be able to localize parasitic water intrusion towards old springs.

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

PubMed Central

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

2013-01-01

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

Stable isotopes in barnacles as a tool to understand green sea turtle (Chelonia mydas) regional movement patterns

NASA Astrophysics Data System (ADS)

Detjen, M.; Sterling, E.; Gómez, A.

2015-12-01

Sea turtles are migratory animals that travel long distances between their feeding and breeding grounds. Traditional methods for researching sea turtle migratory behavior have important disadvantages, and the development of alternatives would enhance our ability to monitor and manage these globally endangered species. Here we report on the isotope signatures in green sea-turtle (Chelonia mydas) barnacles (Platylepas sp.) and discuss their potential relevance as tools with which to study green sea turtle migration and habitat use patterns. We analyzed oxygen (δ18O) and carbon (δ13C) isotope ratios in barnacle calcite layers from specimens collected from green turtles captured at the Palmyra Atoll National Wildlife Refuge (PANWR) in the central Pacific. Carbon isotopes were not informative in this study. However, the oxygen isotope results suggest likely regional movement patterns when mapped onto a predictive oxygen isotope map of the Pacific. Barnacle proxies could therefore complement other methods in understanding regional movement patterns, informing more effective conservation policy that takes into account connectivity between populations.

Stable isotopes in barnacles as a tool to understand green sea turtle (Chelonia mydas) regional movement patterns

NASA Astrophysics Data System (ADS)

Detjen, M.; Sterling, E.; Gómez, A.

2015-03-01

Sea turtles are migratory animals that travel long distances between their feeding and breeding grounds. Traditional methods for researching sea turtle migratory behavior have important disadvantages, and the development of alternatives would enhance our ability to monitor and manage these globally endangered species. Here we report on the isotope signatures in green sea turtle (Chelonia mydas) barnacles (Platylepas sp.) and discuss their potential relevance as tools with which to study green sea turtle migration and habitat use patterns. We analyzed oxygen (δ18O) and carbon (δ13C) isotope ratios in barnacle calcite layers from specimens collected from green turtles captured at the Palmyra Atoll National Wildlife Refuge (PANWR) in the Central Pacific. Carbon isotopes were not informative in this study. However, the oxygen isotope results suggest likely regional movement patterns when mapped onto a predictive oxygen isotope map of the Pacific. Barnacle proxies could therefore complement other methods in understanding regional movement patterns, informing more effective conservation policy that takes into account connectivity between populations.

Development of a compound-specific isotope analysis method for acetone via 2,4-dinitrophenylhydrazine derivatization.

PubMed

Wen, Sheng; Feng, Yanli; Wang, Xinming; Sheng, Guoying; Fu, Jiamo; Bi, Xinhui

2004-01-01

A novel method has been developed for compound-specific isotope analysis for acetone via DNPH (2,4-dinitrophenylhydrazine) derivatization together with combined gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Acetone reagents were used to assess delta13C fractionation during the DNPH derivatization process. Reduplicate delta13C analyses were designed to evaluate the reproducibility of the derivatization, with an average error (1 standard deviation) of 0.17 +/- 0.05 per thousand, and average analytical error of 0.28 +/- 0.09 per thousand. The derivatization process introduces no isotopic fractionation for acetone (the average difference between the predicted and analytical delta13C values was 0.09 +/- 0.20 per thousand, within the precision limits of the GC/C/IRMS measurements), which permits computation of the delta13C values for the original underivatized acetone through a mass balance equation. Together with further studies of the carbon isotopic effect during the atmospheric acetone-sampling procedure, it will be possible to use DNPH derivatization for carbon isotope analysis of atmospheric acetone. Copyright (c) 2004 John Wiley & Sons, Ltd.

Isotope separation apparatus and method

DOEpatents

Cotter, Theodore P.

1982-12-28

The invention relates to a method and apparatus for laser isotope separation by photodeflection. A molecular beam comprising at least two isotopes to be separated intersects, preferable substantially perpendicular to one broad side of the molecular beam, with a laser beam traveling in a first direction. The laser beam is reflected back through the molecular beam, preferably in a second direction essentially opposite to the first direction. The laser beam comprises .pi.-pulses of a selected wavelength which excite unexcited molecules, or cause stimulated emission of excited molecules of one of the isotopes. Excitation caused by first direction .pi.-pulses moves molecules of the isotope excited thereby in the first direction. Stimulated emission of excited molecules of the isotope is brought about by returning .pi.-pulses traveling in the second direction. Stimulated emission moves emitting molecules in a direction opposite to the photon emitted. Because emitted photons travel in the second direction, emitting molecules move in the first direction. Substantial molecular movement is accomplished by a large number of .pi.-pulse-molecule interactions. A beam corer collects the molecules in the resulting enriched divergent portions of the beam.

Multi-element compound specific stable isotope analysis of volatile organic compounds at trace levels in groundwater samples

NASA Astrophysics Data System (ADS)

Herrero-Martín, Sara; Nijenhuis, Ivonne; Schmidt, Marie; Wolfram, Diana; Richnow, Hans. H.; Gehre, Matthias

2013-04-01

Groundwater pollution remains one of the major environmental and health concerns. A thorough understanding of sources, sinks and transformation processes of groundwater contaminants is needed to improve risk management evaluation, and to design efficient remediation and water treatment strategies. Isotopic tools provide unique information for an in-depth understanding of the fate of organic chemicals in the environment. During the last decades compound specific isotope analysis (CSIA) of complex mixtures, using gas chromatography-isotope ratio mass spectrometry (GC-IRMS), has gained popularity for the characterization and risk assessment of hazardous waste sites and for isotope forensics of organic contaminants. Multi-element isotope fingerprinting of organic substances provides a more robust framework for interpretation than the isotope analysis of only one element. One major challenge for application of CSIA is the analysis of trace levels of organic compounds in environmental matrices. It is necessary to inject 1 nmol carbon or 8 nmol hydrogen on column, to obtain an accurate and precise measurement of the isotope ratios, which is between two and three orders of magnitude larger than the amount of compound needed for conventional analysis of compound concentrations. Therefore, efficient extraction and pre-concentration techniques have to be integrated with GC-IRMS. Further research is urgently needed in this field, to evaluate the potential of novel and environmental-friendly sample pre-treatment techniques for CSIA to lower the detection limits and extending environmental applications. In this study, the novel coupling of a headspace autosampler (HS) with a programmed temperature vaporizer (PTV), allowing large volume injection of headspace samples, is proposed to improve the sensitivity of CSIA. This automatic, fast and solvent free strategy provides a significant increase on the sensitivity of GC-based methods maintaining the simple headspace instrumentation. The method was developed for the multi-element isotope analysis (carbon and hydrogen) of priority volatile organic groundwater pollutants (methyl tert-butyl ether (MTBE), benzene, toluene, ethylbenzene and o-xylene (BTEX)), and for carbon isotope analysis of chlorinated benzenes and ethenes. The extraction and injection conditions were optimized in terms of maximum sensitivity and minimum isotope effects. During the injection of the headspace sample, the liner is maintained at a low temperature, such that the compounds are retained in a hydrophobic insert packing while the water vapor is eliminated through the split line. With the optimized conditions, it was possible to inject up to 5mL headspace sample with no significant carbon or hydrogen isotopic effects except for the most hydrophobic substance (MTBE), which was subject to a small and reproducible isotope fractionation for hydrogen. The increment on method sensitivity was at least 20 fold in comparison with conventional static headspace analysis. The environmental applicability of the HS-PTV-GC-IRMS method was evaluated by the analysis of groundwater samples from different contaminated field sites, containing BTEX and chlorinated volatile organic contaminants in the low µg/L range. The results obtained demonstrate that this pre-concentration technique is highly promising to enhance the limits of detection of current CSIA methods and broaden its possibilities.

Quantification of isotopic turnover in agricultural systems

NASA Astrophysics Data System (ADS)

Braun, A.; Auerswald, K.; Schnyder, H.

2012-04-01

The isotopic turnover, which is a proxy for the metabolic rate, is gaining scientific importance. It is quantified for an increasing range of organisms, from microorganisms over plants to animals including agricultural livestock. Additionally, the isotopic turnover is analyzed on different scales, from organs to organisms to ecosystems and even to the biosphere. In particular, the quantification of the isotopic turnover of specific tissues within the same organism, e.g. organs like liver and muscle and products like milk and faeces, has brought new insights to improve understanding of nutrient cycles and fluxes, respectively. Thus, the knowledge of isotopic turnover is important in many areas, including physiology, e.g. milk synthesis, ecology, e.g. soil retention time of water, and medical science, e.g. cancer diagnosis. So far, the isotopic turnover is quantified by applying time, cost and expertise intensive tracer experiments. Usually, this comprises two isotopic equilibration periods. A first equilibration period with a constant isotopic input signal is followed by a second equilibration period with a distinct constant isotopic input signal. This yields a smooth signal change from the first to the second signal in the object under consideration. This approach reveals at least three major problems. (i) The input signals must be controlled isotopically, which is almost impossible in many realistic cases like free ranging animals. (ii) Both equilibration periods may be very long, especially when the turnover rate of the object under consideration is very slow, which aggravates the first problem. (iii) The detection of small or slow pools is improved by large isotopic signal changes, but large isotopic changes also involve a considerable change in the input material; e.g. animal studies are usually carried out as diet-switch experiments, where the diet is switched between C3 and C4 plants, since C3 and C4 plants differ strongly in their isotopic signal. The additional change in nutrition induces changes in physiology that are likely to bias the estimation of the isotopic turnover. We designed an experiment with lactating cows which were successively exposed to the diet's natural isotopic variation and a diet-switch. We examined whether the same turnover information can be obtained from the natural (uncontrolled, short-term) isotopic variation as from the diet-switch experiment. Statistical methods to retrieve the turnover characteristics comprised multi-pool compartmental modeling for the diet-switch experiment as well as correlation analysis to perform wiggle-matching and quantification of autocorrelation (geostatistics) for the analysis of the natural variation. All three methods yielded similar results but differed in their strengths and weaknesses that will be highlighted. Combining the strengths of the new methods can make this tool even more advantageous than diet-switch experiments in many cases. In particular, the new approach empowers studying isotope turnover under a wider range of keepings, wildlife conditions and species, yielding turnover estimates that are not biased by changes in nutrition.

Isotope exchange in oxide-containing catalyst

NASA Technical Reports Server (NTRS)

Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

1989-01-01

A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

Advanced Doubling Adding Method for Radiative Transfer in Planetary Atmospheres

NASA Astrophysics Data System (ADS)

Liu, Quanhua; Weng, Fuzhong

2006-12-01

The doubling adding method (DA) is one of the most accurate tools for detailed multiple-scattering calculations. The principle of the method goes back to the nineteenth century in a problem dealing with reflection and transmission by glass plates. Since then the doubling adding method has been widely used as a reference tool for other radiative transfer models. The method has never been used in operational applications owing to tremendous demand on computational resources from the model. This study derives an analytical expression replacing the most complicated thermal source terms in the doubling adding method. The new development is called the advanced doubling adding (ADA) method. Thanks also to the efficiency of matrix and vector manipulations in FORTRAN 90/95, the advanced doubling adding method is about 60 times faster than the doubling adding method. The radiance (i.e., forward) computation code of ADA is easily translated into tangent linear and adjoint codes for radiance gradient calculations. The simplicity in forward and Jacobian computation codes is very useful for operational applications and for the consistency between the forward and adjoint calculations in satellite data assimilation.

High-Throughput Method for Strontium Isotope Analysis by Multi-Collector-Inductively Coupled Plasma-Mass Spectrometer

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

Wall, Andrew J.; Capo, Rosemary C.; Stewart, Brian W.

2016-09-22

This technical report presents the details of the Sr column configuration and the high-throughput Sr separation protocol. Data showing the performance of the method as well as the best practices for optimizing Sr isotope analysis by MC-ICP-MS is presented. Lastly, this report offers tools for data handling and data reduction of Sr isotope results from the Thermo Scientific Neptune software to assist in data quality assurance, which help avoid issues of data glut associated with high sample throughput rapid analysis.

High-Throughput Method for Strontium Isotope Analysis by Multi-Collector-Inductively Coupled Plasma-Mass Spectrometer

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

Hakala, Jacqueline Alexandra

2016-11-22

This technical report presents the details of the Sr column configuration and the high-throughput Sr separation protocol. Data showing the performance of the method as well as the best practices for optimizing Sr isotope analysis by MC-ICP-MS is presented. Lastly, this report offers tools for data handling and data reduction of Sr isotope results from the Thermo Scientific Neptune software to assist in data quality assurance, which help avoid issues of data glut associated with high sample throughput rapid analysis.

Method for the purification of noble gases, nitrogen and hydrogen

DOEpatents

Baker, J.D.; Meikrantz, D.H.; Tuggle, D.G.

1997-09-23

A method and apparatus are disclosed for the purification and collection of hydrogen isotopes in a flowing inert gaseous mixture containing impurities, wherein metal alloy getters having the capability of sorbing non-hydrogen impurities such as oxygen, carbon dioxide, carbon monoxide, methane, ammonia, nitrogen and water vapor are utilized to purify the gaseous mixture of impurities. After purification hydrogen isotopes may be more efficiently collected. A plurality of parallel process lines utilizing metal getter alloys can be used to provide for the continuous purification and collection of the hydrogen isotopes. 15 figs.

Method for the purification of noble gases, nitrogen and hydrogen

DOEpatents

Baker, John D.; Meikrantz, David H.; Tuggle, Dale G.

1997-01-01

A method and apparatus for the purification and collection of hydrogen isotopes in a flowing inert gaseous mixture containing impurities, wherein metal alloy getters having the capability of sorbing non-hydrogen impurities such as oxygen, carbon dioxide, carbon monoxide, methane, ammonia, nitrogen and water vapor are utilized to purify the gaseous mixture of impurities. After purification hydrogen isotopes may be more efficiently collected. A plurality of parallel process lines utilizing metal getter alloys can be used to provide for the continuous purification and collection of the hydrogen isotopes.

System and method for high precision isotope ratio destructive analysis

DOEpatents

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

2013-07-02

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

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

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

2018-04-20

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

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

DOE PAGES

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

2018-04-20

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

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

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

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

Polyatomic interferences on high precision uranium isotope ratio measurements by MC-ICP-MS: Applications to environmental sampling for nuclear safeguards

DOE PAGES

Pollington, Anthony D.; Kinman, William S.; Hanson, Susan K.; ...

2015-09-04

Modern mass spectrometry and separation techniques have made measurement of major uranium isotope ratios a routine task; however accurate and precise measurement of the minor uranium isotopes remains a challenge as sample size decreases. One particular challenge is the presence of isobaric interferences and their impact on the accuracy of minor isotope 234U and 236U measurements. Furthermore, we present techniques used for routine U isotopic analysis of environmental nuclear safeguards samples and evaluate polyatomic interferences that negatively impact accuracy as well as methods to mitigate their impacts.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

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

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

Development of high through-put Sr isotope analysis for monitoring reservoir integrity for CO{sub 2} storage.

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

Wall, Andy; Jain, Jinesh; Stewart, Brian

2012-01-01

Recent innovations in multi-collector ICP-mass spectrometry (MC-ICP-MS) have allowed for rapid and precise measurements of isotope ratios in geological samples. Naturally occurring Sr isotopes has the potential for use in Monitoring, Verification, and Accounting (MVA) associated with geologic CO2 storage. Sr isotopes can be useful for: Sensitive tracking of brine migration; Determining seal rock leakage; Studying fluid/rock reactions. We have optimized separation chemistry procedures that will allow operators to prepare samples for Sr isotope analysis off site using rapid, low cost methods.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

DOE PAGES

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

2018-06-01

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

A novel tandem mass spectrometry method for first-line screening of mainly beta-thalassemia from dried blood spots.

PubMed

Yu, Chaowen; Huang, Shuodan; Wang, Ming; Zhang, Juan; Liu, Hao; Yuan, Zhaojian; Wang, Xingbin; He, Xiaoyan; Wang, Jie; Zou, Lin

2017-02-10

Traditional methods for thalassemia screening are time-consuming and easily affected by cell hemolysis or hemoglobin degradation in stored blood samples. Tandem mass spectrometry (MS/MS) proved to be an effective technology for sickle cell disorders (SCD) screening. Here, we developed a novel MS/MS method for β-thalassemia screening from dried blood spots (DBS). Stable isotopic-labeled peptides were used as internal standards for quantification and calculation of the α:β-globin ratios. We used the α:β-globin ratio cutoffs to differentiate between normal individuals and patients with thalassemia. About 781 patients and 300 normal individuals were analyzed. The α:β-globin ratios showed significant difference between normal and β-thalassemia patients (P<0.01), particularly when the disease was homozygous or double heterozygous with another α- or β-thalassemia mutation. In the parallel study, all cases screened for suspected thalassemia from six hundred DBS samples by using this MS/MS method were successfully confirmed by genotyping. The intra-assay and inter-assay CVs of the ratios ranged from 2.4% to 3.9% and 4.7% to 7.1%, and there was no significant sample carryover or matrix effect for this MS/MS method. Combined with SCD screening, this MS/MS method could be used as a first-line screening assay for both structural and expression abnormalities of human hemoglobin. Traditional methods for thalassemia screening were depending on the structural integrity of tetramers and could be affected by hemolysis and degradation of whole blood samples, especially when stored. We used proteospecific peptides produced by the tryptic digestion of each globin to evaluate the production ratio between α- and β-globin chains, which turned out to be quite stable even when stored for more than two months. Though most of the peptides were specific to α-globin or β-globin, we only chose four most informative peptides and its stable isotopic-labeled peptides as internal standards for analysis, which could obtain a high accuracy. Currently, we are the first to address the application of MS/MS for thalassemia screening, when combined with SCD screening, this MS/MS method could be used as a first-line screening assay for both structural and expression abnormalities of human hemoglobin. Copyright © 2016. Published by Elsevier B.V.

Potassium Isotopic Compositions of NIST Potassium Standards and 40Ar/39Ar Mineral Standards

NASA Technical Reports Server (NTRS)

Morgan, Leah; Tappa, Mike; Ellam, Rob; Mark, Darren; Higgins, John; Simon, Justin I.

2013-01-01

Knowledge of the isotopic ratios of standards, spikes, and reference materials is fundamental to the accuracy of many geochronological methods. For example, the 238U/235U ratio relevant to U-Pb geochronology was recently re-determined [1] and shown to differ significantly from the previously accepted value employed during age determinations. These underlying values are fundamental to accurate age calculations in many isotopic systems, and uncertainty in these values can represent a significant (and often unrecognized) portion of the uncertainty budget for determined ages. The potassium isotopic composition of mineral standards, or neutron flux monitors, is a critical, but often overlooked component in the calculation of K-Ar and 40Ar/39Ar ages. It is currently assumed that all terrestrial materials have abundances indistinguishable from that of NIST SRM 985 [2]; this is apparently a reasonable assumption at the 0.25per mille level (1s) [3]. The 40Ar/39Ar method further relies on the assumption that standards and samples (including primary and secondary standards) have indistinguishable 40K/39K values. We will present data establishing the potassium isotopic compositions of NIST isotopic K SRM 985, elemental K SRM 999b, and 40Ar/39Ar biotite mineral standard GA1550 (sample MD-2). Stable isotopic compositions (41K/39K) were measured by the peak shoulder method with high resolution MC-ICP-MS (Thermo Scientific NEPTUNE Plus), using the accepted value of NIST isotopic SRM 985 [2] for fractionation [4] corrections [5]. 40K abundances were measured by TIMS (Thermo Scientific TRITON), using 41K/39K values from ICP-MS measurements (or, for SRM 985, values from [2]) for internal fractionation corrections. Collectively these data represent an important step towards a metrologically traceable calibration of 40K concentrations in primary 40Ar/39Ar mineral standards and improve uncertainties by ca. an order of magnitude in the potassium isotopic compositions of standards.

Quantifying the isotopic composition of NOx emission sources: An analysis of collection methods

NASA Astrophysics Data System (ADS)

Fibiger, D.; Hastings, M.

2012-04-01

We analyze various collection methods for nitrogen oxides, NOx (NO2 and NO), used to evaluate the nitrogen isotopic composition (δ15N). Atmospheric NOx is a major contributor to acid rain deposition upon its conversion to nitric acid; it also plays a significant role in determining air quality through the production of tropospheric ozone. NOx is released by both anthropogenic (fossil fuel combustion, biomass burning, aircraft emissions) and natural (lightning, biogenic production in soils) sources. Global concentrations of NOx are rising because of increased anthropogenic emissions, while natural source emissions also contribute significantly to the global NOx burden. The contributions of both natural and anthropogenic sources and their considerable variability in space and time make it difficult to attribute local NOx concentrations (and, thus, nitric acid) to a particular source. Several recent studies suggest that variability in the isotopic composition of nitric acid deposition is related to variability in the isotopic signatures of NOx emission sources. Nevertheless, the isotopic composition of most NOx sources has not been thoroughly constrained. Ultimately, the direct capture and quantification of the nitrogen isotopic signatures of NOx sources will allow for the tracing of NOx emissions sources and their impact on environmental quality. Moreover, this will provide a new means by which to verify emissions estimates and atmospheric models. We present laboratory results of methods used for capturing NOx from air into solution. A variety of methods have been used in field studies, but no independent laboratory verification of the efficiencies of these methods has been performed. When analyzing isotopic composition, it is important that NOx be collected quantitatively or the possibility of fractionation must be constrained. We have found that collection efficiency can vary widely under different conditions in the laboratory and fractionation does not vary predictably with collection efficiency. For example, prior measurements frequently utilized triethanolamine solution for collecting NOx, but the collection efficiency was found to drop quickly as the solution aged. The most promising method tested is a NaOH/KMnO4 solution (Margeson and Knoll, Anal. Chem., 1985) which can collect NOx quantitatively from the air. Laboratory tests of previously used methods, along with progress toward creating a suitable and verifiable field deployable collection method will be presented.

A new method and application for determining the nitrogen isotopic composition of NOx

NASA Astrophysics Data System (ADS)

Hastings, M. G.; Miller, D. J.; Wojtal, P.; O'Connor, M.

2015-12-01

Atmospheric nitrogen oxides (NOx = NO + NO2) play key roles in atmospheric chemistry, air quality, and radiative forcing, and contribute to nitric acid deposition. Sources of NOx include both natural and anthropogenic emissions, which vary significantly in space and time. NOx isotopic signatures offer a potentially valuable tool to trace source impacts on atmospheric chemistry and regional acid deposition. Previous work on NOx isotopic signatures suggests large ranges in values, even from the same emission source, as well as overlapping ranges amongst different sources, making it difficult to use the isotopic composition as a quantitative tracer of source influences. These prior measurements have utilized a variety of methods for collecting the NOx as nitrate or nitrite for isotopic analysis, and testing of some of these methods (including active and passive collections) reveal inconsistencies in efficiency of collection, as well as issues related to changes in conditions such as humidity, temperature, and NOx fluxes. A recently developed method allows for accurately measuring the nitrogen isotopic composition of NOx (NOx = NO + NO2) after capturing the NOx in a potassium permanganate/sodium hydroxide solution as nitrate (Fibiger et al., Anal. Chem., 2014). The method has been thoroughly tested in the laboratory and field, and efficiently collects NO and NO2 under a variety of conditions. There are several advantages to collecting NOx actively, including the ability to collect over minutes to hourly time scales, and the ability to collect in environments with highly variable NOx sources and concentrations. Challenges include a nitrate background present in potassium permanganate (solid and liquid forms), accurately deriving ambient NOx concentrations based upon flow rate and solution concentrations above this variable background, and potential interferences from other nitrogen species. This method was designed to collect NOx in environments with very different emission source loadings in an effort to isotopically characterize NOx sources. Results to date suggest very different values, and less variability than previous work, particularly for vehicle emissions. Ultimately, we aim to determine whether the influence of NOx sources can be quantitatively tracked in the environment.

Characterization of high-purity 82Se-enriched ZnSe for double-beta decay bolometer/scintillation detectors

NASA Astrophysics Data System (ADS)

Silva, B. C.; de Oliveira, R.; Ribeiro, G. M.; Cury, L. A.; Leal, A. S.; Nagorny, S.; Krambrock, K.

2018-02-01

Zinc selenide (ZnSe), when enriched with 82Se isotope, is one of the most promising materials for the construction of a bolometer/scintillation detector to study neutrinoless double beta decay (0νDBD). Because the 0νDBD is a very rare event, a high quantity of high-purity monocrystalline ZnSe is needed, which means high costs. Therefore, the knowledge of the best material parameters, especially the presence of point defects, is essential to make feasible the construction of such a detector. In this work, both the as-grown and thermally annealed ZnSe enriched to 95% with the 82Se isotope grown by the Bridgman technique from high-purity starting materials were characterized by electron paramagnetic resonance (EPR), photo-EPR, neutron activation, photoluminescence, and electrical measurements. It is shown that although thermal annealing increases crystal homogeneity and reduces microcracks, the scintillation efficiency is much better for the as-grown material. The higher scintillation efficiency is due to the presence of donor acceptor pairs in the as-grown material, which are responsible for strong luminescence/scintillation in the red spectral region. By photo-EPR, the donor acceptor pairs are identified as closed VZn - AlZn pairs which are lost during the annealing procedure. Electrical characterization shows that the as-grown material is of good quality as it has high electron mobility at low temperatures. Excellent material parameters for the construction of the bolometer/scintillation detector based on enriched Zn82Se are discussed.

GraXe, graphene and xenon for neutrinoless double beta decay searches

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

Gómez-Cadenas, J.J.; Martín-Albo, J.; Monrabal, F.

2012-02-01

We propose a new detector concept, GraXe (to be pronounced as grace), to search for neutrinoless double beta decay in {sup 136}XE. GraXe combines a popular detection medium in rare-event searches, liquid xenon, with a new, background-free material, graphene. In our baseline design of GraXe, a sphere made of graphene-coated titanium mesh and filled with liquid xenon (LXe) enriched in the {sup 136}XE isotope is immersed in a large volume of natural LXe instrumented with photodetectors. Liquid xenon is an excellent scintillator, reasonably transparent to its own light. Graphene is transparent over a large frequency range, and impermeable to themore » xenon. Event position could be deduced from the light pattern detected in the photosensors. External backgrounds would be shielded by the buffer of natural LXe, leaving the ultra-radiopure internal volume virtually free of background. Industrial graphene can be manufactured at a competitive cost to produce the sphere. Enriching xenon in the isotope {sup 136}XE is easy and relatively cheap, and there is already near one ton of enriched xenon available in the world (currently being used by the EXO, KamLAND-Zen and NEXT experiments). All the cryogenic know-how is readily available from the numerous experiments using liquid xenon. An experiment using the GraXe concept appears realistic and affordable in a short time scale, and its physics potential is enormous.« less

A Novel Method for Relative Quantitation of N-Glycans by Isotopic Labeling Using 18O-Water

PubMed Central

Tao, Shujuan; Orlando, Ron

2014-01-01

Quantitation is an essential aspect of comprehensive glycomics study. Here, a novel isotopic-labeling method is described for N-glycan quantitation using 18O-water. The incorporation of the 18O-labeling into the reducing end of N-glycans is simply and efficiently achieved during peptide-N4-(N-acetyl-β-glucosaminyl) asparagine amidase F release. This process provides a 2-Da mass difference compared with the N-glycans released in 16O-water. A mathematical calculation method was also developed to determine the 18O/16O ratios from isotopic peaks. Application of this method to several standard glycoprotein mixtures and human serum demonstrated that this method can facilitate the relative quantitation of N-glycans over a linear dynamic range of two orders, with high accuracy and reproducibility. PMID:25365792

Two-step extraction method for lead isotope fractionation to reveal anthropogenic lead pollution.

PubMed

Katahira, Kenshi; Moriwaki, Hiroshi; Kamura, Kazuo; Yamazaki, Hideo

2018-05-28

This study developed the 2-step extraction method which eluted the Pb adsorbing on the surface of sediments in the first solution by aqua regia and extracted the Pb absorbed inside particles into the second solution by mixed acid of nitric acid, hydrofluoric acid and hydrogen peroxide solution. We applied the method to sediments in the enclosed water area and found out that the isotope ratios of Pb in the second solution represented those of natural origin. This advantage of the method makes it possible to distinguish the Pb between natural origin and anthropogenic source on the basis of the isotope ratios. The results showed that the method was useful to discuss the Pb sources and that anthropogenic Pb in the sediment samples analysed was mainly derived from China because of transboundary air pollution.

Experimenting with mixing and layered convection in phono-trachytic magmas: Implications on reservoir dynamics

NASA Astrophysics Data System (ADS)

de Campos, C. P.; Civetta, L.; Dingwell, D. B.; Perugini, D.; Petrelli, M.; Fehr, T. K.

2006-12-01

Abundant geochemical and volcanological data on the Campanian Ignimbrite, (>200 km3, 39 ka) Phlegrean Fields, Italy, support the existence of a layered magmatic reservoir, which evolved via 1) replenishment of the chamber with trachytic magma and 2) short-term pre-eruptive mixing between new trachytic and phono- trachytic resident magmas. We have initiated an experimental program in order to constrain the dynamics of such mingling/mixing events. We used melted natural products from these two magmas of sub-equal but distinct composition, which are thought to have been involved in the origin of this magmatic system as end-members (phono-trachyte = end- member A and trachyte = end-member B). The two were then stirred together and sampled by experiment termination as a time series, ranging from 1-hour up to 1-week. Stirring under constant low flow velocity (0.5 rotations per minute) generated at first homogenization and mixing of the starting compositions. Then separate convection cells and compositional layering for major and minor elements emerged. Calculated density distributions along sections from the experimental glasses, after decoupling, are very similar to density distributions in aqueous systems under double-diffusive convection. In order to test double- diffusive decoupled convection in this system, we performed 87Sr/86Sr-isotopic and Sr- LA-ICP-MS- measurements, using the 25-hour experimental glasses. The effective chemical separation of different convection cells has been confirmed with clearly distinct isotopic signatures for both bottom and top cells. Comparison with natural samples from the Campanian Ignimbrite strengthens the importance of the role of a double-diffusive similar convection as a major differentiation process leading to layering in this system. Our results support the effectiveness of a DDC-driven fractionation for moderately high-silica magmas under high near-liquidus temperatures, before the onset of fractional crystallization.

A New Method of Obtaining High-Resolution Paleoclimate Records from Speleothem Fluid Inclusions

NASA Astrophysics Data System (ADS)

Logan, A. J.; Horton, T. W.

2010-12-01

We present a new method for stable hydrogen and oxygen isotope analysis of ancient drip water trapped within cave speleothems. Our method improves on existing fluid inclusion isotopic analytical techniques in that it decreases the sample size by a factor of ten or more, dramatically improving the spatial and temporal precision of fluid inclusion-based paleoclimatology. Published thermal extraction methods require large samples (c. 150 mg) and temperatures high enough (c. 500-900°C) to cause calcite decomposition, which is also associated with isotopic fractionation of the trapped fluids. Extraction by crushing faces similar challenges, where the failure to extract all the trapped fluid can result in isotopic fractionation, and samples in excess of 500 mg are required. Our new method combines the strengths of these published thermal and crushing methods using continuous-flow isotope ratio analytical techniques. Our method combines relatively low-temperature (~250°C) thermal decrepitation with cryogenic trapping across a switching valve sample loop. In brief, ~20 mg carbonate samples are dried (75°C for >1 hour) and heated (250°C for >1 hour) in a quartz sample chamber under a continuously flowing stream of ultra-high purity helium. Heating of the sample chamber is achieved by use of a tube furnace. Fluids released during the heating step are trapped in a coiled stainless steel cold trap (~ -98°C) serving as the sample loop in a 6-way switching valve. Trapped fluids are subsequently injected into a high-temperature conversion elemental analyzer by switching the valve and rapidly thawing the trap. This approach yielded accurate and precise measurements of injected liquid water IAEA reference materials (GISP; SMOW2; SLAP2) for both hydrogen and oxygen isotopic compositions. Blanking tests performed on the extraction line demonstrate extremely low line-blank peak heights (<50mv). Our tests also demonstrate that complete recovery of liquid water is possible and that a minimum quantity of ~100nL water was required. In contrast to liquid water analyses, carbonate inclusion waters gave highly variable results. As plenty of signal was produced from relatively small sample sizes (~20 mg), the observed isotopic variation most likely reflects fractionation during fluid extraction, or natural isotopic variability. Additional tests and modifications to the extraction procedure are in progress, using a recently collected New Zealand stalagmite from a West Coast cave (DOC collection permit WC-27462-GEO). U-Th age data will accompany a paleoclimate record from this stalagmite obtained using standard carbonate analytical techniques, and compared to the results from our new fluid inclusion analyses.

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 waters (IW), allowing diffusive processes to proceed to equilibrium, measuring the composition of the resulting mixture or final water (FW) then, solving a simple mixing equation. To evaluate this method, we collected several twig samples from Douglas Firs in the Sacramento Mountains. Twig water was prepared for isotopic analysis both by cryogenic distillation and the mixing method. Soil in close proximity to these trees was also sampled and water was extracted by cryogenic distillation. Preliminary results show that the isotopic composition of distilled twig water and soil waters plot to the right of the local meteoric water line (LMWL) suggesting that trees are extracting shallow evaporated soil water. Twig water obtained from the mixing method plot near the LMWL within the range expected for local snow melt, suggesting a possibly deeper non-evaporated source. In general, distillation values are approximately 4% heavier with respect to delta 18O than waters obtained from the mixing method. It is possible that this difference is due to the contribution of the fractionated water of the twig phloem that is released during the distillation process. This difference is quite significant and can lead to very different interpretations. These results are being addressed with additional experiments.

Discovering Mercury Protein Modifications in Whole Proteomes Using Natural Isotope Distributions Observed in Liquid Chromatography-Tandem Mass Spectrometry

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

Polacco, Benjamin J.; Purvine, Samuel O.; Zink, Erika M.

2011-08-01

The identification of peptides that result from post-translational modifications is critical for understanding normal pathways of cellular regulation as well as identifying damage from, or exposures to xenobiotics, i.e. the exposome. However, because of their low abundance in proteomes, effective detection of modified peptides by mass spectrometry (MS) typically requires enrichment to eliminate false identifications. We present a new method for confidently identifying peptides with mercury (Hg)-containing adducts that is based on the influence of mercury’s seven stable isotopes on peptide isotope distributions detected by high-resolution MS. Using a pure protein and E. coli cultures exposed to phenyl mercuric acetate,more » we show the pattern of peak heights in isotope distributions from primary MS single scans efficiently identified Hg adducts in data from chromatographic separation coupled with tandem mass spectrometry with sensitivity and specificity greater than 90%. Isotope distributions are independent of peptide identifications based on peptide fragmentation (e.g. by SEQUEST), so both methods can be combined to eliminate false positives. Summing peptide isotope distributions across multiple scans improved specificity to 99.4% and sensitivity above 95%, affording identification of an unexpected Hg modification. We also illustrate the theoretical applicability of the method for detection of several less common elements including the essential element, selenium, as selenocysteine in peptides.« less

Stable Isotope Labeling Strategy for Curcumin Metabolite Study in Human Liver Microsomes by Liquid Chromatography-Tandem Mass Spectrometry

NASA Astrophysics Data System (ADS)

Gao, Dan; Chen, Xiaowu; Yang, Xiaomei; Wu, Qin; Jin, Feng; Wen, Hongliang; Jiang, Yuyang; Liu, Hongxia

2015-04-01

The identification of drug metabolites is very important in drug development. Nowadays, the most widely used methods are isotopes and mass spectrometry. However, the commercial isotopic labeled reagents are usually very expensive, and the rapid and convenient identification of metabolites is still difficult. In this paper, an 18O isotope labeling strategy was developed and the isotopes were used as a tool to identify drug metabolites using mass spectrometry. Curcumin was selected as a model drug to evaluate the established method, and the 18O labeled curcumin was successfully synthesized. The non-labeled and 18O labeled curcumin were simultaneously metabolized in human liver microsomes (HLMs) and analyzed by liquid chromatography/mass spectrometry (LC-MS). The two groups of chromatograms obtained from metabolic reaction mixture with and without cofactors were compared and analyzed using Metabolynx software (Waters Corp., Milford, MA, USA). The mass spectra of the newly appearing chromatographic peaks in the experimental sample were further analyzed to find the metabolite candidates. Their chemical structures were confirmed by tandem mass spectrometry. Three metabolites, including two reduction products and a glucuronide conjugate, were successfully detected under their specific HLMs metabolic conditions, which were in accordance with the literature reported results. The results demonstrated that the developed isotope labeling method, together with post-acquisition data processing using Metabolynx software, could be used for fast identification of new drug metabolites.

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

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

PubMed

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

2012-11-01

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

Rate-dependent carbon and nitrogen kinetic isotope fractionation in hydrolysis of isoproturon.

PubMed

Penning, Holger; Cramer, Christopher J; Elsner, Martin

2008-11-01

Stable isotope fractionation permits quantifying contaminant degradation in the field when the transformation reaction is associated with a consistent isotope enrichment factor epsilon. When interpreted in conjunction with dual isotope plots, isotope fractionation is also particularly useful for elucidating reaction mechanisms. To assess the consistency of epsilon and dual isotope slopes in a two-step reaction, we investigated the abiotic hydrolysis of the herbicide isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) using a fragmentation method that allows measuring isotope ratios in different parts of the molecule. Carbon and nitrogen position-specific isotope fractionation, as well as slopes in dual isotope plots, varied linearly with rate constants k(obs) depending on the presence of buffers that mediate the initial zwitterion formation. The correlation can be explained by two consecutive reaction steps (zwitterion formation followed by dimethylamine elimination) each of which has a different kinetic isotope effect and may be rate-limiting. Intrinsic isotope effects for both steps, extracted from our kinetic data using a novel theoretical treatment, agree well with values computed from density functional calculations. Our study therefore demonstrates that more variable isotope fractionation may be observed in simple chemical reactions than commonly thought, but that consistent epsilon or dual isotope slopes may nonetheless be encountered in certain molecular fragments.

Progress in the Use of Isotopes: The Atomic Triad - Reactors, Radioisotopes and Radiation

DOE R&D Accomplishments Database

Libby, W. F.

1958-08-04

Recent years have seen a substantial growth in the use of isotopes in medicine, agriculture, and industry: up to the minute information on the production and use of isotopes in the U.S. is presented. The application of radioisotopes to industrial processes and manufacturing operations has expanded more rapidly than any one except its most ardent advocates expected. New uses and new users are numerous. The adoption by industry of low level counting techniques which make possible the use of carbon-14 and tritium in the control of industrial processes and in certain exploratory and research problems is perhaps most promising of current developments. The latest information on savings to industry will be presented. The medical application of isotopes has continued to develop at a rapid pace. The current trend appears to be in the direction of improvements in technique and the substitution of more effective isotopes for those presently in use. Potential and actual benefits accruing from the use of isotopes in agriculture are reviewed. The various methods of production of radioisotopes are discussed. Not only the present methods but also interesting new possibilities are covered. Although isotopes are but one of the many peaceful uses of the atom, it is the first to pay its way. (auth)

Applications of Cavity Ring-Down Spectroscopy (CRDS) to Analysis of Carbon Stable Isotope Composition of Groundwater

NASA Astrophysics Data System (ADS)

Jeong, T.; Woo, N. C.; Choi, H.

2014-12-01

Carbon Capture and Storage (CCS) has been considered as an effective strategy to reduce atmospheric carbon dioxide (CO2) concentration. However, unintended leakage of CO2 leakage from storage sites could occur through highly permeable conduits such as fractures in low-K formations during the injection and storage of SCCO2 (supercritical phase CO2). Therefore, prediction and detection of CO2 leakage and relevant analysis of carbon isotope are crucial to assure environmental and public safety. Until recently, Isotope Ratio Mass Spectrometry (IRMS) has been utilized to measure the stable isotope ratio of water. However, IRMS is time-consuming operation due to complicated pretreatment, and thus not a practical methodology under field conditions. Carbon Isotope Analyzer (CCIA), which is a kind of Cavity Ring-Down Spectroscopy (CRDS) and has a wide measurement range from 300 to 25000 ppmv, can facilitate the rate of measurements up to 1 Hz by using continuous flow method so that it can be readily applied to field. In this study, carbon stable isotope ratio of groundwater will be analyzed using CCIA. Then, the CCIA results will be compared with IRMS to validate its accuracy and stability. This research will provide an appropriate method for analyzing carbon stable isotope in groundwater, using a continuous flow mode.