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Sample records for isotopic equilibrium method

  1. The three-isotope method for equilibrium isotope fractionation factor determination: Unfounded optimism

    NASA Astrophysics Data System (ADS)

    Cao, X.; Hayles, J. A.; Bao, H.

    2015-12-01

    The equilibrium isotope fractionation factor α is a fundamental parameter in stable isotope geochemistry. Although equilibrium α can be determined by theoretical calculation or by measurement of natural samples, direct laboratory experiments are ultimately required to verify those results. The attainment of a true exchange equilibrium in experiments is often difficult, but three methods have been devised and used to ensure that an equilibrium α has been obtained in an isotope exchange experiment. These are the two-directional method, partial-exchange method, and three-isotope method. Of these, the three-isotope method is thought to be the most rigorous. Using water-water exchange as a basic unit, we have developed a set of complex exchange models to study when and why the three-isotope method may work well or not. We found that the method cannot promise to lead to an equilibrium α before the kinetic complexity of the specific exchange experiment is known. An equilibrium point in δ17O-δ18O space can be reached only when all of the isotope exchange pathways are fully reversible, i.e. there is no mass loss at any instant, and the forward and backward reactions share the same pathway. If the exchange pathways are not fully reversible, steady state may be reached, but a steady state α can be very different from the equilibrium α. Our results validated the earlier warning that the trajectory for three-isotope evolution in δ17O-δ18O space may be a distinctly curved line or contain more than one straight line due to the non-fully reversible isotope exchange reactions. The three-isotope method for equilibrium α determination is not as rigorous or as promising as it may seem. Instead, the trajectory of three-isotope evolution provides detailed insights into the kinetics of isotope exchange between compounds. If multiple components exist in the exchange system, the δ17O-δ18O evolving trajectory would be more complex.

  2. Determination of the Fe(II)aq-magnetite equilibrium iron isotope fractionation factor using the three-isotope method and a multi-direction approach to equilibrium

    NASA Astrophysics Data System (ADS)

    Frierdich, Andrew J.; Beard, Brian L.; Scherer, Michelle M.; Johnson, Clark M.

    2014-04-01

    Magnetite is ubiquitous in the Earth's crust and its presence in modern marine sediments has been taken as an indicator of biogeochemical Fe cycling. Magnetite is also the most abundant Fe oxide in banded iron formations (BIFs) that have not been subjected to ore-forming alteration. Magnetite is therefore an important target of stable Fe isotope studies, and yet interpretations are currently difficult because of large uncertainties in the equilibrium stable Fe isotope fractionation factors for magnetite relative to fluids and other minerals. In this study, we utilized the three-isotope method (57Fe-56Fe-54Fe) to explore isotopic exchange via an enriched-57Fe tracer, and natural mass-dependent fractionation using 56Fe/54Fe variations, during reaction of aqueous Fe(II) (Fe(II)aq) with magnetite. Importantly, we employed a multi-direction approach to equilibrium by reacting four 57Fe-enriched Fe(II) solutions that had distinct 56Fe/54Fe ratios, which identifies changes in the instantaneous Fe isotope fractionation factor and hence identifies kinetic isotope effects. We find that isotopic exchange can be described by two 56Fe/54Fe fractionations, where an initial rapid exchange (∼66% isotopic mixing within 1 day) involved a relatively small Fe(II)aq-magnetite 56Fe/54Fe fractionation, followed by slower exchange (∼25% isotopic mixing over 50 days) that was associated with a larger Fe(II)aq-magnetite 56Fe/54Fe fractionation; this later fractionation is interpreted to approach isotopic equilibrium between Fe(II)aq and the total magnetite. All four Fe(II) solutions extrapolate to the same final equilibrium 56Fe/54Fe fractionation for Fe(II)aq-magnetite of -1.56±0.20‰ (2σ) at 22 °C. Additional experiments that synthesized magnetite via conversion of ferrihydrite by reaction with aqueous Fe(II) yield final 56Fe/54Fe fractionations that are identical to those of the exchange experiments. Our experimental results agree well with calculated fractionation factors using

  3. Technical Note: A simple method for vaterite precipitation in isotopic equilibrium: implications for bulk and clumped isotope analysis

    NASA Astrophysics Data System (ADS)

    Kluge, T.; John, C. M.

    2014-12-01

    Calcium carbonate (CaCO3) plays an important role in the natural environment as a major constituent of the skeleton and supporting structure of marine life and has high economic importance as additive in food, chemicals and medical products. Pure CaCO3 occurs in the three different polymorphs calcite, aragonite and vaterite, whereof calcite is the most abundant and best characterized mineral. In contrast, little is known about the rare polymorph vaterite, in particular with regard to the oxygen isotope fractionation between H2O and the mineral. Synthetic precipitation of vaterite in the laboratory typically involves rapid processes and isotopic non-equilibrium, which excludes isotope studies focused on characterization of vaterite at equilibrium conditions. Here, we used a new experimental approach that enables vaterite mineral formation from an isotopically equilibrated solution. The solution consists of a ~ 0.007 mol L-1 CaCO3 solution that is saturated with NaCl at room temperature (up to 6.5 mol L-1). Vaterite precipitated as single phase or major phase (≥ 94%) in experiments performed between 23 and 91 °C. Only at 80 °C was vaterite a minor phase with a relative abundance of 27%. The high mineral yield of up to 235 mg relative to a total dissolved CaCO3 amount of 370 mg enables an investigation of the oxygen isotope fractionation between mineral and water, and the determination of clumped isotope values in vaterite.

  4. Calculation of individual isotope equilibrium constants for geochemical reactions

    USGS Publications Warehouse

    Thorstenson, D.C.; Parkhurst, D.L.

    2004-01-01

    factors. The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO2 in an acidic aqueous solution. ?? 2004 Elsevier Ltd.

  5. Calculation of individual isotope equilibrium constants for implementation in geochemical models

    USGS Publications Warehouse

    Thorstenson, Donald C.; Parkhurst, David L.

    2002-01-01

    Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

  6. Theoretical prediction for several important equilibrium Ge isotope fractionation factors

    NASA Astrophysics Data System (ADS)

    Tang, M.; Li, X.; Liu, Y.

    2008-12-01

    As a newly emerging field, the stable isotope geochemistry of germanium (Ge) needs basic equilibrium fractionation factors to explore its unknown world. In this study, the Ge isotope fractionations between systems including the aqueous Ge(OH)4 and GeO(OH)3- which are the dominant Ge species in seawater, the Ge-bearing organic complexes (e.g. Ge-catechol, Ge-oxalic acid and Ge-citric acid), the quartz- (or opal- ), albite-, K-feldspar- and olivine- like mineral structures are studied. It is the first time that some geologically important equilibrium Ge isotope fractionation factors are reported. Surprisingly, up to 5 per mil large isotopic fractionations between these Ge isotope systems are found at 25 degree. These results suggest a potentially broad application for the Ge isotope geochemistry. Our theoretical calculations are based on the Urey model (or Bigeleisen-Mayer equation) and high level quantum chemistry calculations. The B3LYP/6-311+G(d,p) level quantum chemistry method and the explicit solvent model ("water droplet" method) are used. Many different conformers are also used for the aqueous complexes in order to reduce the possible errors coming from the differences of configurations in solution. The accuracy of our calculation of the Ge isotopic fractionations is estimated about 0.2 per mil. Our results show quartz-like or opal-like structure can enrich most heavy Ge isotopes. Relative to quartz (or opal), some Ge isotopic fractionations are (at 25 C): quartz-organic Ge = 4-5,quartz-Ge(OH)4 =0.9,quartz-GeO(OH)3- =1.5,quartz-albite=0.6,quartz-K-feldspar=0.4 and quartz-olivine=3.9 per mil. The large fractionations between inorganic Ge complexes and organic Ge ones could be used to distinguish the possible bio-involving processes. Our results suggest a good explanation to the experimental observations of Siebert et al. (2006) and Rouxel et al. (2006) and provide important constraints to the study of Ge cycle in ocean.

  7. Unbiased isotope equilibrium factors from partial isotope exchange experiments in 3-exchange site systems

    NASA Astrophysics Data System (ADS)

    Agrinier, Pierre; Javoy, Marc

    2016-09-01

    Two methods are available in order to evaluate the equilibrium isotope fractionation factors between exchange sites or phases from partial isotope exchange experiments. The first one developed by Northrop and Clayton (1966) is designed for isotope exchanges between two exchange sites (hereafter, the N&C method), the second one from Zheng et al. (1994) is a refinement of the first one to account for a third isotope exchanging site (hereafter, the Z method). In this paper, we use a simple model of isotope kinetic exchange for a 3-exchange site system (such as hydroxysilicates where oxygen occurs as OH and non-OH groups like in muscovite, chlorite, serpentine, or water or calcite) to explore the behavior of the N&C and Z methods. We show that these two methods lead to significant biases that cannot be detected with the usual graphical tests proposed by the authors. Our model shows that biases originate because isotopes are fractionated between all these exchanging sites. Actually, we point out that the variable mobility (or exchangeability) of isotopes in and between the exchange sites only controls the amplitude of the bias, but is not essential to the production of this bias as previously suggested. Setting a priori two of the three exchange sites at isotopic equilibrium remove the bias and thus is required for future partial exchange experiments to produce accurate and unbiased extrapolated equilibrium fractionation factors. Our modeling applied to published partial oxygen isotope exchange experiments for 3-exchange site systems (the muscovite-calcite (Chacko et al., 1996), the chlorite-water (Cole and Ripley, 1998) and the serpentine-water (Saccocia et al., 2009)) shows that the extrapolated equilibrium fractionation factors (reported as 1000 ln(α)) using either the N&C or the Z methods lead to bias that may reach several δ per mil in a few cases. These problematic cases, may be because experiments were conducted at low temperature and did not reach high

  8. ISOTOPE METHODS IN HOMOGENEOUS CATALYSIS.

    SciTech Connect

    BULLOCK,R.M.; BENDER,B.R.

    2000-12-01

    The use of isotope labels has had a fundamentally important role in the determination of mechanisms of homogeneously catalyzed reactions. Mechanistic data is valuable since it can assist in the design and rational improvement of homogeneous catalysts. There are several ways to use isotopes in mechanistic chemistry. Isotopes can be introduced into controlled experiments and followed where they go or don't go; in this way, Libby, Calvin, Taube and others used isotopes to elucidate mechanistic pathways for very different, yet important chemistries. Another important isotope method is the study of kinetic isotope effects (KIEs) and equilibrium isotope effect (EIEs). Here the mere observation of where a label winds up is no longer enough - what matters is how much slower (or faster) a labeled molecule reacts than the unlabeled material. The most careti studies essentially involve the measurement of isotope fractionation between a reference ground state and the transition state. Thus kinetic isotope effects provide unique data unavailable from other methods, since information about the transition state of a reaction is obtained. Because getting an experimental glimpse of transition states is really tantamount to understanding catalysis, kinetic isotope effects are very powerful.

  9. Equilibrium iron isotope fractionation at core-mantle boundary conditions.

    PubMed

    Polyakov, Veniamin B

    2009-02-13

    The equilibrium iron isotope fractionation between lower mantle minerals and metallic iron at core-mantle boundary conditions can be evaluated from the high-pressure 57Fe partial vibrational density of states determined by synchrotron inelastic nuclear resonant x-ray scattering spectroscopy using a diamond anvil. Ferropericlase [(Mg,Fe)O] and (Fe,Mg)SiO3- post-perovskite are enriched in heavy iron isotopes relative to metallic iron at ultrahigh pressures, as opposed to the equilibrium iron isotope fractionation between these compounds at low pressure. The enrichment of Earth and Moon basalts in heavy iron isotopes relative to those from Mars and asteroid Vesta can be explained by the equilibrium iron isotope fractionation during the segregation of Earth's core and the assumption that Earth was already differentiated before the Moon-forming "giant impact." PMID:19213913

  10. First Principles Calculation on Equilibrium Si Isotope Fractionation Factors and its Implementation on Si Isotope Distributions in Earth Surface Environments

    NASA Astrophysics Data System (ADS)

    Liu, Y.; He, H. T.; Zhu, C.

    2014-12-01

    Several important equilibrium Si isotope fractionation factors are calculated here. We use a so-called volume-variable-cluster-model (VVCM) method for solids and the "water-droplet" method for aqueous species for isotope fractionation calculation at the same quantum chemistry level. The calculation results show that several silicate minerals, such as quartz, feldspar, kaolinite, etc., all enrich heavy Si isotopes relative to aqueous H4SiO4 and can be up to 3.3‰ at 25°C, different from most field observations. Meanwhile stable organosilicon complexes can enrich even lighter Si isotopes than aqueous H4SiO4. For explaining the difference between the calculation results and field observations, we calculate the kinetic isotope effect (KIE) associated with the formation of amorphous silica, and find that amorphous silica will enrich extremely light Si isotopes. From amorphous silica to crystalline quartz, the structural adjustment & transition needs getting rid of small amount of Si to re-organize the structure. Light Si isotopes will be preferentially lost and let the final crystalline quartz with a little bit more heavy Si isotopes. However, such late-stage Si heavy isotope enrichment cannot erase the total isotopic signal, crystalline quartz still inherit much light Si isotopic composition from amorphous quartz. That is the reason for the discrepancy between the calculation results and the field observations, because the formation of amorphous quartz is under a non-equilibrium process but theoretical calculations are for equilibrium isotope fractionations. With accurate equilibrium fractionation factors provided here, Si isotope distributions in earth surface environments including soil, groundwater and plants can be further interpreted. We find that δ30Si variations in soil are mainly driven by secondary minerals precipitation and adsorption. Also, bulk soil δ30Si maybe have a parabolic distribution with soil age, with a minimum value at where allophane is

  11. Equilibrium stable-isotope fractionation of thallium and mercury

    NASA Astrophysics Data System (ADS)

    Schauble, E. A.

    2005-12-01

    In this study first-principles quantum mechanical and empirical force-field models are used to estimate equilibrium mass-dependent isotopic fractionations among a variety of thallium and mercury compounds. High-precision MC-ICP-MS measurements have recently uncovered evidence of stable isotope fractionation for many elements, including 2-4‰ variability in the isotopic compositions of thallium[1] (atomic no. 81) and mercury[2] (atomic no. 80). The observed thallium- and mercury-isotope fractionations are remarkable, given that the magnitude of isotopic fractionation typically decreases as atomic number increases[3]. Stable isotope measurements could improve our understanding of geochemical and biogeochemical cycling of both elements, but little is known about the mechanisms driving these fractionations. A better understanding of the chemical processes controlling stable isotope compositions could help maximize the utility of these new geochemical tracers. Standard equilibrium stable isotope fractionation theory holds that the energy driving fractionation comes from isotopic effects on vibrational frequencies, which have generally not been measured. In the present study both quantum-mechanical and empirical force fields are used to estimate unknown frequencies. Results suggest that thallium and mercury fractionations of ≥ 0.5‰ are likely during the relevant redox reactions Tl+ ↔ Tl3+ and HgO ↔ Hg2+. Methyl-mercury and mercury-halide compounds like CH3HgCl will have ~ 1‰ higher 202Hg/198Hg than atomic vapor at room temperature. Fractionations between coexisting Hg2+ species appear to be much smaller, however. 205Tl/203Tl in Tl(H2O)_63+ is predicted to be ~0.5‰ higher than in coexisting Tl+-bearing substances. This result is in qualitative agreement with data from ferromanganese crusts [1], suggesting that Tl3+ in manganese-oxides will have higher 205Tl/203Tl than aqueous Tl+. Equilibrium fractionations for both elements are much smaller than the observed

  12. The oxygen isotope equilibrium fractionation between sulfite species and water

    NASA Astrophysics Data System (ADS)

    Müller, Inigo A.; Brunner, Benjamin; Breuer, Christian; Coleman, Max; Bach, Wolfgang

    2013-11-01

    Sulfite is an important sulfoxy intermediate in oxidative and reductive sulfur cycling in the marine and terrestrial environment. Different aqueous sulfite species exist, such as dissolved sulfur dioxide (SO2), bisulfite (HSO3-), pyrosulfite (S2O52-) and sulfite sensu stricto (SO32-), whereas their relative abundance in solution depends on the concentration and the pH. Conversion of one species into another is rapid and involves in many cases incorporation of oxygen from, or release of oxygen to, water (e.g. SO2 + H2O ↔ HSO3- + H+), resulting in rapid oxygen isotope exchange between sulfite species and water. Consequently, the oxygen isotope composition of sulfite is strongly influenced by the oxygen isotope composition of water. Since sulfate does not exchange oxygen isotopes with water under most earth surface conditions, it can preserve the sulfite oxygen isotope signature that it inherits via oxidative and reductive sulfur cycling. Therefore, interpretation of δO values strongly hinges on the oxygen isotope equilibrium fractionation between sulfite and water which is poorly constrained. This is in large part due to technical difficulties in extraction of sulfite from solution for oxygen isotope analysis.

  13. Plasma isotope separation methods

    SciTech Connect

    Grossman, M.W. ); Shepp, T.A. )

    1991-12-01

    Isotope separation has many important industrial, medical, and research applications. Large-scale processes have typically utilized complex cascade systems; for example, the gas centrifuge. Alternatively, high single-stage enrichment processes (as in the case of the calutron) are very energy intensive. Plasma-based methods being developed for the past 15 to 20 years have attempted to overcome these two drawbacks. In this review, six major types of isotope separation methods which involve plasma phenomena are discussed. These methods are: plasma centrifuge, AVLIS (atomic vapor laser isotope separation), ion wave, ICR (ion-cyclotron resonance), calutron, and gas discharge. The emphasis of this paper is to describe the plasma phenomena in these major categories. An attempt was made to include enough references so that more detailed study or evaluation of a particular method could readily be pursued. A brief discussion of isotope separation using mass balance concepts is also carried out.

  14. Predicting equilibrium uranium isotope fractionation in crystals and solution

    NASA Astrophysics Data System (ADS)

    Schauble, E. A.

    2015-12-01

    Despite the rapidly growing interest in using 238U/235U measurements as a proxy for changes in oxygen abundance in surface and near-surface environments, the present theoretical understanding of uranium isotope fractionation is limited to a few simple gas-phase molecules and analogues of dissolved species (e.g., 1,2,3). Understanding uranium isotope fractionation behavior in more complicated species, such as crystals and adsorption complexes, will help in the design and interpretation of experiments and field studies, and may suggest other uses for 38U/235U measurements. In this study, a recently developed first-principles method for estimating the nuclear volume component of field shift fractionation in crystals and complex molecular species (4) is combined with mass-dependent fractionation theory to predict equilibrium 38U/235U fractionations in aqueous and crystalline uranium compounds, including uraninite (UO2). The nuclear field shift effect, caused by the interaction of electrons with the finite volume of the positive charge distribution in uranium nuclei, is estimated using Density Functional Theory and the Projector Augmented Wave method (DFT-PAW). Tests against relativistic electronic structure calculations and Mössbauer isomer shift data indicate that the DFT-PAW method is reasonably accurate, while being much better suited to models of complex and crystalline species. Initial results confirm previous predictions that the nuclear volume effect overwhelms mass depdendent fractionation in U(VI)-U(IV) exchange reactions, leading to higher 238U/235U in U(IV) species (i.e., for UO2 xtal vs. UO22+aq, ln αNV ≈ +1.8‰ , ln αMD ≈ -0.8‰, ln αTotal ≈ +1.0‰ at 25ºC). UO2 and U(H2O)94+, are within ~0.4‰ of each other, while U(VI) species appear to be more variable. This suggests that speciation is likely to significantly affect natural uranium isotope fractionations, in addition to oxidation state. Tentatively, it appears that uranyl-type (UO22

  15. 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.

  16. Spinel-olivine-pryoxene equilibrium iron isotopic fractionation and applications to natural peridotites

    SciTech Connect

    Roskosz, Mathieu; Sio, Corliss K. I.; Dauphas, Nicolas; Bi, Wenli; Tissot, Francois L. H.; Hu, Michael Y.; Zhao, Jiyong; Alp, Esen E.

    2015-11-15

    Eight spinel-group minerals were synthesized by a flux-growth method producing spinels with varying composition and Fe3+/Fe-tot ratios. The mean force constants of iron bonds in these minerals were determined by synchrotron nuclear resonant inelastic X-ray scattering (NRIXS) in order to determine the reduced isotopic partition function ratios (beta-factors) of these spinels. The mean force constants are strongly dependent on the Fe3+/Fe-tot of the spinel but are independent, or weakly dependent on other structural and compositional parameters. From our spectroscopic data, it is found that a single redox-dependent calibration line accounts for the effects of Fe3+/Fe-tot on the beta-factors of spinels. This calibration successfully describes the equilibrium Fe isotopes fractionation factors between spinels and silicates (olivine and pyroxenes). Our predictions are in excellent agreement with independent determinations for the equilibrium Fe isotopic fractionations for the magnetite- fayalite and the magnetite-hedenbergite couples. Our calibration applies to the entire range of Fe3+/Fe-tot ratios found in natural spinels and provides a basis for interpreting iron isotopic variations documented in mantle peridotites. Except for a few exceptions, most of the samples measured so far are in isotopic disequilibrium, reflecting metasomatism and partial melting processes.

  17. The influence of pH on the oxygen isotope equilibrium fractionation between sulfite and water

    NASA Astrophysics Data System (ADS)

    Müller, Inigo; Brunner, Benjamin; Ferdelman, Timothy

    2010-05-01

    Currently, the value for the oxygen isotope equilibrium fractionation between water and sulfite in solution is poorly constrained. Sulfite is an important intermediate in the oxidative/reductive sulfur cycle and oxygen isotope exchange between sulfite and water is expected to leave an imprint on the isotope composition of sulfate affected by sulfur cycling. One reason for the lack of accurate information about isotope fractionation between sulfite and water are technical difficulties in extraction of sulfite from solution for oxygen isotope analysis. The pH dependent presence of multiple S(IV) species in solution, i.e. sulfur dioxide (SO2), bisulfite (HSO3-), pyrosulfite (S2O52-) and sulfite (SO32-) complicates data interpretation. For example, the oxygen isotope equilibrium fractionation between water and SO32- may be different than that between water and any of the other sulfite species in solution. We exposed sodium sulfite (Na2SO3) solutions to different pH conditions and monitored oxygen isotope exchange between sulfite and water, until isotope equilibrium was reached. The equilibrium value is determined by using two isotopically different sodium sulfite starting materials, one with a starting value lighter than the equilibrium value and one with a starting composition heavier than the equilibrium value. In this manner oxygen isotope equilibrium is approached from two directions. Sulfite from solution was precipitated as BaSO3 with a set of Ba(OH)2 solutions containing different oxygen isotope compositions. This procedure allows us to disentangle the oxygen isotope contribution from water incorporated during the precipitation from the oxygen isotope composition of sulfite in solution. We present the first results from this experimental approach and discuss the applicability of determining isotope equilibrium fractionations between water and distinct S(IV) species.

  18. 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.

  19. METHOD OF ISOTOPE CONCENTRATION

    DOEpatents

    Spevack, J.S.

    1957-04-01

    An isotope concentration process is described which consists of exchanging, at two or more different temperature stages, two isotopes of an element between substances that are physically separate from each other and each of which is capable of containing either of the isotopes, and withdrawing from a point between at least two of the temperatare stages one of the substances containing an increased concentration of the desired isotope.

  20. Iron isotope fractionation between aqueous Fe(II) and goethite revisited: New insights based on a multi-direction approach to equilibrium and isotopic exchange rate modification

    NASA Astrophysics Data System (ADS)

    Frierdich, Andrew J.; Beard, Brian L.; Reddy, Thiruchelvi R.; Scherer, Michelle M.; Johnson, Clark M.

    2014-08-01

    The Fe isotope compositions of naturally occurring Fe oxide minerals provide insights into biogeochemical processes that occur in modern and ancient environments. Key to understanding isotopic variations in such minerals is knowledge of the equilibrium Fe isotope fractionation factors between common minerals and aqueous Fe species. Because experimental measurements of isotopic fractionation may reflect a combination of kinetic and equilibrium fractionations during rapid dissolution and precipitation, even in experiments that employ the three-isotope method, assessment of the attainment of equilibrium is often difficult. Here, we re-examine Fe isotope exchange, via a 57Fe tracer, and natural mass-dependent fractionation, through changes in initial 56Fe/54Fe ratios, between aqueous Fe(II) (Fe(II)aq) and goethite. This approach uses the three-isotope method, but is distinct in its evaluation of kinetic isotope fractionation and the attainment of equilibrium by: (i) employing a multi-direction approach to equilibrium at 22 °C via reaction of three Fe(II)aq solutions that had different initial 56Fe/54Fe ratios, (ii) conducting isotopic exchange experiments at elevated temperature (50 °C), and (iii) modifying the rate of isotopic exchange through a combination of trace-element substitutions and particle coarsening to evaluate corresponding temporal changes in fractionation trajectories that may reflect changing instantaneous fractionation factors. We find that rapid isotopic exchange produces kinetic isotope effects between Fe(II)aq and goethite, which shifts the 56Fe/54Fe ratios of Fe(II)aq early in reactions toward that of goethite, indicating that the instantaneous Fe(II)aq-goethite fractionation factor under kinetic conditions is small. Importantly, however, this kinetic fractionation is “erased” with continued reaction, and this is evident by the congruence for multiple-exchange trajectories of distinct initial Fe(II)aq solutions toward the same final value

  1. Equilibrium carbon and hydrogen isotope fractionation in iron

    NASA Astrophysics Data System (ADS)

    Schauble, E. A.

    2009-12-01

    Recent theoretical and experimental studies (e.g., [1-3]) have suggested that Si- and Fe-isotopic signatures can be used to characterize the compositions and conditions of segregation of metallic cores in planetary interiors. This study expands the theoretical framework to include carbon and hydrogen, which may also be alloying elements. Hydrogen (D/H) and carbon (13C/12C) fractionations in iron-rich metallic melts are estimated by modeling analogous iron-rich crystals, i.e., dhcp-FeH and η-Fe2C. C- and H-atoms in these crystals are completely coordinated by iron. The driving energy for equilibrium fractionation is assumed to come from the reduction of vibrational frequencies when heavy isotopes are substituted for light ones; vibrations are assumed to be harmonic. This treatment is crude at high temperature, and for the relatively anharmonic vibrations typical of hydrogen-bearing substances, but may provide a reasonably accurate, semi-quantitative approximation of real fractionation behavior. Vibrational frequencies of all crystals are modeled with density functional theory, using gradient-corrected functionals and ultrasoft pseudopotentials. For both carbon and hydrogen, the models suggest that the metal phase will be strongly depleted in heavy isotopes. At 2000 K, 1 atm, η-Fe2C will have 3‰ lower 13C/12C than coexisting diamond. Combining this result with previous high-temperature theoretical and experimental studies (e.g., [4]), metal-graphite fractionation is expected to be very similar, while metal-CO2 fractionation will be almost twice as large, ca. -5‰. Deuterium/hydrogen fractionations are expected to be an order of magnitude larger, with 50-70‰ lower D/H in dhcp-FeH than in coexisting H2 gas at 2000 K, and approximately 100‰ lower D/H than water vapor. These fractionations are much larger than those inferred for silicon and iron, as expected given the differences in atomic mass. References: 1. Georg et al. (2007) Nature 447:1102; 2. Rustad & Yin

  2. A process-based model for non-equilibrium clumped isotope effects in carbonates

    NASA Astrophysics Data System (ADS)

    Watkins, J. M.; Hunt, J. D.

    2015-12-01

    The equilibrium clumped isotope composition of carbonate minerals is independent of the composition of the aqueous solution. However, many carbonate minerals grow at rates that place them in a non-equilibrium regime with respect to carbon and oxygen isotopes with unknown consequences for clumped isotopes. We develop a process-based model that allows one to calculate the oxygen, carbon, and clumped isotope composition of calcite as a function of temperature, crystal growth rate, and solution pH. In the model, carbon and oxygen isotope fractionation occurs through the mass-dependent attachment/detachment kinetics of the isotopologues of HCO-3 and CO2-3 to and from the calcite surface, which in turn, influence the clumped isotope composition of calcite. At experimental and biogenic growth rates, the mineral is expected to inherit a clumped isotopic composition that is similar to that of the DIC pool, which helps to explain (1) why different organisms share the same clumped isotope versus temperature calibration curves, (2) why many inorganic calibration curves are slightly different from one another, and (3) why foraminifera, coccoliths, and deep sea corals can have near-equilibrium clumped isotope compositions but far-from-equilibrium carbon and oxygen isotope compositions. Some aspects of the model can be generalized to other mineral systems and should serve as a useful reference in future efforts to quantify kinetic clumped isotope effects.

  3. Theoretical calculation of nitrogen isotope equilibrium exchange fractionation factors for various NOy molecules

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Michalski, Greg

    2015-09-01

    The nitrogen stable isotope ratio (15N/14N) of nitrogen oxides (NOx = NO + NO2) and its oxidation products (NOy = NOx + PAN (peroxyacetyl nitrate = C2H3NO5) + HNO3 + NO3 + HONO + N2O5 + ⋯ + particulate nitrates) has been suggested as a tool for partitioning NOx sources; however, the impact of nitrogen (N) equilibrium isotopic fractionation on 15N/14N ratios during the conversion of NOx to NOy must also be considered, but few fractionation factors for these processes have been determined. To address this limitation, computational quantum chemistry calculations of harmonic frequencies, reduced partition function ratios (15β), and N equilibrium isotope exchange fractionation factors (αA/B) were performed for various gaseous and aqueous NOy molecules in the rigid rotor and harmonic oscillator approximations using the B3LYP and EDF2 density functional methods for the mono-substitution of 15N. The calculated harmonic frequencies, 15β, and αA/B are in good agreement with available experimental measurements, suggesting the potential to use computational methods to calculate αA/B values for N isotope exchange processes that are difficult to measure experimentally. Additionally, the effects of solvation (water) on 15β and αA/B were evaluated using the IEF-PCM model, and resulted in lower 15β and αA/B values likely due to the stabilization of the NOy molecules from dispersion interactions with water. Overall, our calculated 15β and αA/B values are accurate in the rigid rotor and harmonic oscillator approximations and will allow for the estimation of αA/B involving various NOy molecules. These calculated αA/B values may help to explain the trends observed in the N stable isotope ratio of NOy molecules in the atmosphere.

  4. Group Contribution Methods for Phase Equilibrium Calculations.

    PubMed

    Gmehling, Jürgen; Constantinescu, Dana; Schmid, Bastian

    2015-01-01

    The development and design of chemical processes are carried out by solving the balance equations of a mathematical model for sections of or the whole chemical plant with the help of process simulators. For process simulation, besides kinetic data for the chemical reaction, various pure component and mixture properties are required. Because of the great importance of separation processes for a chemical plant in particular, a reliable knowledge of the phase equilibrium behavior is required. The phase equilibrium behavior can be calculated with the help of modern equations of state or g(E)-models using only binary parameters. But unfortunately, only a very small part of the experimental data for fitting the required binary model parameters is available, so very often these models cannot be applied directly. To solve this problem, powerful predictive thermodynamic models have been developed. Group contribution methods allow the prediction of the required phase equilibrium data using only a limited number of group interaction parameters. A prerequisite for fitting the required group interaction parameters is a comprehensive database. That is why for the development of powerful group contribution methods almost all published pure component properties, phase equilibrium data, excess properties, etc., were stored in computerized form in the Dortmund Data Bank. In this review, the present status, weaknesses, advantages and disadvantages, possible applications, and typical results of the different group contribution methods for the calculation of phase equilibria are presented.

  5. Methods of isotopic geochronology

    NASA Astrophysics Data System (ADS)

    Gorokhov, I. M.; Levchenkov, O. A.

    Papers are presented on such topics as the age of the chemical elements; the age of meteorites, the moon, and the earth; isotopic ages of the most ancient terrestrial formations; and the Archean evolution of Enderby Land in the Antarctic as evidenced by isotopic dating. Consideration is also given to a uranium-lead geochronology technique for investigating Precambrian ore deposits, a Pb-Pb technique of zircon dating, and the potentials and limitations of Sm-Nd geochronology.

  6. 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/.

  7. 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.

  8. Method for separating krypton isotopes

    SciTech Connect

    Porter, J.T.

    1980-10-28

    Methods and apparatus for separating krypton isotopes utilizing low temperature selective infrared excitation of 85krypton difluoride in an isotopic compound mixture. Multiphoton ir excitation and uv excitation techniques are used, as well as cryogenic matrix isolation and inert buffer gas isolation techniques.

  9. Equilibrium and kinetic Si isotope fractionation factors and their implications on Si isotope distributions in the Earth's surface environments

    NASA Astrophysics Data System (ADS)

    Tang, M.; Zhang, S.; Liu, Y.

    2015-12-01

    Several important equilibrium Si isotope fractionation factors among minerals, organic molecules and the H4SiO4 solution are complemented to facilitate explanation of distributions of Si isotope in the Earth's surface environments. The results reveal that heavy Si isotopes will be significantly enriched in the secondary silicate minerals in comparison to aqueous H4SiO4. On the contrary, quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution. The extent of 28Si-enrichment in hyper-coordinated organosilicon complexes is found the largest. In addition, the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer is calculated and the result supports previous statement that highly 28Si-enrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations. With equilibrium Si isotope fractionation factors provided here, Si isotope distributions in many surface systems of the Earth can be explained. For example, the change of bulk soil δ30Si can be predicted as a concave pattern with respect to weathering degree, with the minimum value where allophane completely dissolves and the total amount of sesqui-oxides and poorly crystalline minerals reaches its maximum. When well-crystallized clays start to precipitate from pore solutions under equilibrium conditions, the bulk soil δ30Si will increase again and reach a constant value. Similarly, the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain δ30Si variations in the ground water profile. Equilibrium Si isotope fractionations among quadra-coordinated organosilicon complexes and the H4SiO4 solution may also shed the light on the Si isotope distributions in Si-accumulating plants.

  10. Equilibrium mercury isotope fractionation between dissolved Hg(II) species and thiol-bound Hg.

    PubMed

    Wiederhold, Jan G; Cramer, Christopher J; Daniel, Kelly; Infante, Ivan; Bourdon, Bernard; Kretzschmar, Ruben

    2010-06-01

    Stable Hg isotope ratios provide a new tool to trace environmental Hg cycling. Thiols (-SH) are the dominant Hg-binding groups in natural organic matter. Here, we report experimental and computational results on equilibrium Hg isotope fractionation between dissolved Hg(II) species and thiol-bound Hg. Hg(II) chloride and nitrate solutions were equilibrated in parallel batches with varying amounts of thiol resin resulting in different fractions of thiol-bound and free Hg. Mercury isotope ratios in both fractions were analyzed by multiple collector inductively coupled plasma mass spectrometry (MC-ICPMS). Theoretical equilibrium Hg isotope effects by mass-dependent fractionation (MDF) and nuclear volume fractionation (NVF) were calculated for 14 relevant Hg(II) species. The experimental data revealed that thiol-bound Hg was enriched in light Hg isotopes by 0.53 per thousand and 0.62 per thousand (delta(202)Hg) relative to HgCl(2) and Hg(OH)(2), respectively. The computational results were in excellent agreement with the experimental data indicating that a combination of MDF and NVF was responsible for the observed Hg isotope fractionation. Small mass-independent fractionation (MIF) effects (<0.1 per thousand) were observed representing one of the first experimental evidences for MIF of Hg isotopes by NVF. Our results indicate that significant equilibrium Hg isotope fractionation can occur without redox transition, and that NVF must be considered in addition to MDF to explain Hg isotope variations.

  11. Isotope separation apparatus and method

    DOEpatents

    Feldman, Barry J.

    1985-01-01

    The invention relates to an improved method and apparatus for laser isotope separation by photodeflection. A molecular beam comprising at least two isotopes to be separated intersects, preferably 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. Because the molecules in the beam occupy various degenerate energy levels, if the laser beam comprises chirped pulses comprising selected wavelengths, the laser beam will very efficiently excite substantially all unexcited molecules and will cause stimulated emission of substantially all excited molecules of a selected one of the isotopes in the beam which such pulses encounter. Excitation caused by first direction chirped 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 chirped 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 of essentially all the molecules containing the one isotope is accomplished by a large number of chirped pulse-molecule interactions. A beam corer collects the molecules in the resulting enriched divergent portions of the beam.

  12. 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.

  13. Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

    NASA Astrophysics Data System (ADS)

    Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

    2016-10-01

    This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.

  14. Evidence for equilibrium iron isotope fractionation by nitrate-reducing iron(II)-oxidizing bacteria.

    PubMed

    Kappler, A; Johnson, C M; Crosby, H A; Beard, B L; Newman, D K

    2010-05-10

    Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)(aq) and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in (56)Fe/(54)Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ(56)Fe(Fe(OH)3 - Fe(II)aq) fractionation factor of +3.0 ‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)(aq) and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)(aq) by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)(aq) oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)(aq) and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of

  15. METHOD OF ISOTOPE CONCENTRATION

    DOEpatents

    Taylor, T.I.; Spindel, W.

    1960-02-01

    A method of concentrating N/sup 15/ in a liquid is described. Gaseous nitric oxide and at least one liquid selected from the group consisting of the aqueous oxyacids and oxides of nitrogen, wherein the atomic ratio of oxygen to nitrogen is greater than unity, are brought into intimate contact to cause an enrichment of the liquid and a depletion of the gas in N/sup 15/. The liquid is, thereafter, reacted with sulfur dioxide to produce a gas contuining nitric oxide. The gas contuining nitric oxide is then continuously passed in countercurrent contact with the liquid to cause further enrichment of the liquid.

  16. Clumped-isotope signatures at equilibrium of CH4, NH3, H2O, H2S and SO2

    NASA Astrophysics Data System (ADS)

    Liu, Qi; Liu, Yun

    2016-02-01

    High precision Δi values at equilibrium determined by theoretical methods are imperatively needed as references for the development of new clumped-isotope thermometers (or tracers). In this study, quantum chemistry methods with corrections beyond the harmonic approximation are used to obtain the clumped-isotope signatures at equilibrium of several gas-phase molecules (i.e., CH4, NH3, H2O, H2S, and SO2). Here, we consider as many corrections to the traditional Bigeleisen-Mayer equation as possible to obtain accurate Δi values at equilibrium and their temperature dependences. The corrections include anharmonic correction for zero-point energy, anharmonic correction for vibrational excited states, vibration-rotation coupling correction for zero-point energy, vibration-rotation coupling correction for vibrational excited states, quantum mechanical correction to rotation, and centrifugal distortion correction, which are important for theoretical understanding of clumped-isotope signals. Specifically, molecular constants are calculated via second-order perturbative analysis at the MP2/aug-cc-pVTZ level. The CCSD/6-311+G(3df,3pd) and CCSD/aug-cc-pVTZ levels are further employed to ensure the precision of harmonic frequencies of methane. For methane, a polynomial fit of ΔCH133D values over the temperature range of from 273.15 to 1000 K is obtained:

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

    ERIC Educational Resources Information Center

    Williams, Kathryn R.; Lipford, Levin C.

    1985-01-01

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

  18. Equilibrium Iron Isotopic Fractionation Among Ferric Chloride Complexes

    NASA Astrophysics Data System (ADS)

    Hill, P. S.; Schauble, E. A.

    2006-12-01

    Four sets of ab initio models, including Unrestricted Hartree Fock (UHF) and hybrid Density Function Theory (DFT) were calculated for each species in a series of aqueous ferric chloride complexes: (FeH2O)6{3+, FeCl(H2O)5{2+, FeCl2(H2O)4{+, FeCl3(H2O)3, FeCl3(H2O)2, FeCl4{-, FeCl5H2O{2-, FeCl5{2-, FeCl6{^{3-}) in order to determine the relative isotopic fractionation among the complexes, to compare the results of different models for the same complexes, and to examine factors that influence the magnitude of the isotopic fractionation. Relative to Fe(H2O)6{3+, all models show a nearly linear decrease in the isotopic fractionation factor as the number of Cl{- ions per Fe{3+ ion increases, with slopes of -0.8‰ to - 1.0‰ per Cl-. At 20°C, 1000 ln β56-54 (β = reduced partition function ratio relative to a dissociated Fe atom) values range from 8.93 to 9.73‰ for Fe(H2O)6{3+, 8.04 to 9.12‰ for FeCl(H2O)5{2+, 7.61 to 8.73‰ for FeCl2(H2O)4{+, 7.14 to 8.25‰ for FeCl4{-, and 3.09 to 4.41‰ for FeCl6{^{3-}. The fractionation between Fe(H2O)6{3+ and FeCl4{- ranges from 1.48 to 2.45‰, depending on the model; this is comparable to fractionation effects due to iron redox reactions. β56-54 values from the UHF models are consistently higher than those from the hybrid DFT models. Theoretical studies predict isotopic fractionation due to differences in ligand bond stiffness, coordination number, bond length, and the frequency of the asymmetric Fe-X stretching vibrational mode (Schauble et al., 2001, Geochim. et Cosmochim. Acta, 65, 15, 2487-2497; Schauble, 2004, in Reviews in Mineralogy & Geochemistry, 55, 65-111). Complexes with more Fe-OH2 bonds (see above) and/or smaller coordination numbers have higher fractionation factors (7.43‰, 4.91‰, 3.94‰ for FeCl4{-, FeCl5{2-, FeCl6{^{3-} respectively from the UHF model). The length of the Fe-Cl bonds increases as the number of chloride ligands increases while the Fe-O bond lengths decrease as the number of H2O

  19. Method for laser induced isotope enrichment

    SciTech Connect

    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.

  20. Prediction of equilibrium Li isotope fractionation between minerals and aqueous solutions at high P and T: An efficient ab initio approach

    NASA Astrophysics Data System (ADS)

    Kowalski, Piotr M.; Jahn, Sandro

    2011-10-01

    The mass-dependent equilibrium stable isotope fractionation between different materials is an important geochemical process. Here we present an efficient method to compute the isotope fractionation between complex minerals and fluids at high pressure, P, and temperature, T, representative for the Earth's crust and mantle. The method is tested by computation of the equilibrium fractionation of lithium isotopes between aqueous fluids and various Li bearing minerals such as staurolite, spodumene and mica. We are able to correctly predict the direction of the isotope fractionation as observed in the experiments. On the quantitative level the computed fractionation factors agree within 1.0‰ with the experimental values indicating predictive power of ab initio methods. We show that with ab initio methods we are able to investigate the underlying mechanisms driving the equilibrium isotope fractionation process, such as coordination of the fractionating elements, their bond strengths to the neighboring atoms, compression of fluids and thermal expansion of solids. This gives valuable insight into the processes governing the isotope fractionation mechanisms on the atomic scale. The method is applicable to any state and does not require different treatment of crystals and fluids.

  1. Ab initio calculations of Li and B equilibrium isotope fractionation between high -P and -T minerals and aqueous fluids

    NASA Astrophysics Data System (ADS)

    Kowalski, P.; Jahn, S.; Wunder, B.

    2011-12-01

    Stable isotopes are excellent geochemical tracers widely used in petrology. Among them the isotopes of light elements such as Li or B strongly fractionate between minerals and aqueous fluids during fluid-rock interaction processes, which makes them excellent tracers of mass transfer processes in the subduction cycle. In order to use the full power of isotopes tracing methods the isotope fractionation mechanisms and fractionation factors between minerals and fluids of interest must be well known and characterized. One of the most important mechanisms leading to the formation of isotopic signatures is the equilibrium isotope fractionation, which nowadays can be modeled on the atomic scale by modern computational methods. However, due to high computational requirements the current works have been limited to calculations of simple materials only. In order to overcome these limitations we develop an efficient ab initio based computational approach for prediction of the equilibrium isotope fractionation factors between high pressure and temperature materials, including fluids, which would allow for efficient calculations of the isotope fractionation factors of complex minerals and fluids containing even hundreds of atoms in the supercell. We will show our results for the Li and B stable equilibrium isotope fractionation factors between complex Li/B-bearing crystalline solids (staurolite, spodumene, tourmaline, olenite and micas) and aqueous fluids. The fractionation factors were obtained in an efficient way by simplifying the consideration to calculations of the properties of fractionating atoms only. The comparison of the calculated fractionation factors, on the qualitative and quantitative levels, with the existing experimental data show the comparable to the in situ experimental techniques, predictive power of the computations. We show that with the atomistic scale modelling we are able to reproduce correctly the experimental isotope fractionation sequences

  2. Equilibrium magnesium isotope fractionation between aqueous Mg2+ and carbonate minerals: Insights from path integral molecular dynamics

    NASA Astrophysics Data System (ADS)

    Pinilla, Carlos; Blanchard, Marc; Balan, Etienne; Natarajan, Suresh K.; Vuilleumier, Rodolphe; Mauri, Francesco

    2015-08-01

    The theoretical determination of the isotopic fractionation between an aqueous solution and a mineral is of utmost importance in Earth sciences. While for crystals, it is well established that equilibrium isotopic fractionation factors can be calculated using a statistical thermodynamic approach based on the vibrational properties, several theoretical methods are currently used to model ions in aqueous solution. In this work, we present a systematic study to determine the reduced partition function ratio (β-factor) of aqueous Mg2+ using several levels of theory within the simulations. In particular, using an empirical force field, we compare and discuss the performance of the exact results obtained from path integral molecular dynamics (PIMD) simulations, with respect to the more traditional methods based on vibrational properties and the cluster approximation. The results show the importance of including configurational disorder for the estimation of the equilibrium isotope fractionation factor. We also show that using the vibrational frequencies computed from snapshots taken from equilibrated classical molecular dynamics represents a good approximation for the study of aqueous ions. Based on these conclusions, the β-factor of aqueous Mg2+ have been estimated from a Car-Parrinello molecular dynamics (CPMD) simulation with an ab initio force field, and combined with the β-factors of carbonate minerals (magnesite, dolomite, calcite and aragonite). Mg β-factor of Mg-bearing aragonite, calculated here for the first time, displays a lower value than the three other carbonate minerals. This is explained by a strong distortion of the cationic site leading to a decrease of the coordination number during Ca-Mg substitution. Overall, the equilibrium magnesium isotope fractionation factors between aqueous Mg2+ and carbonate minerals that derive from this methodological study support the previous theoretical results obtained from embedded cluster models.

  3. Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

    NASA Astrophysics Data System (ADS)

    Eldridge, D. L.; Farquhar, J.; Guo, W.

    2015-12-01

    Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate

  4. A reassessment of isotopic equilibrium (Δ47 and δ18O) in the Laghetto Basso pool carbonates

    NASA Astrophysics Data System (ADS)

    Daëron, M.; Drysdale, R.; Blamart, D.; Genty, D.; Zanchetta, G.

    2013-12-01

    To the best of our current knowledge, the overwhelming majority of modern speleothems have Δ47 values which differ significantly from those predicted for thermodynamic equilibrium. The extent to which these differences may vary temporally and spatially is still an open issue, precluding a straightforward application of clumped isotopes paleothermometry to speleothem records. Here we report on the recent results of a reassessment of isotopic equilibrium in the Laghetto Basso pool carbonates (Antro del Corchia cave, NW Italy), which offer excellent a priori conditions for equilibrium carbonate precipitation and provide a continuous or quasi-continuous isotopic record of the past million years.

  5. [Dichotomizing method applied to calculating equilibrium constant of dimerization system].

    PubMed

    Cheng, Guo-zhong; Ye, Zhi-xiang

    2002-06-01

    The arbitrary trivariate algebraic equations are formed based on the combination principle. The univariata algebraic equation of equilibrium constant kappa for dimerization system is obtained through a series of algebraic transformation, and it depends on the properties of monotonic functions whether the equation is solvable or not. If the equation is solvable, equilibrium constant of dimerization system is obtained by dichotomy and its final equilibrium constant of dimerization system is determined according to the principle of error of fitting. The equilibrium constants of trisulfophthalocyanine and biosulfophthalocyanine obtained with this method are 47,973.4 and 30,271.8 respectively. The results are much better than those reported previously.

  6. Liquid-Vapor Equilibrium Isotopic Fractionation of Water. How well can classical water models predict it?

    SciTech Connect

    Chialvo, Ariel A; Horita, Juske

    2009-01-01

    The liquid-vapor equilibrium isotopic fractionation of water is determined by molecular-based simulation, via Gibbs Ensemble Monte Carlo and isothermal-isochoric molecular dynamics involving two radically different but realistic models, the extended simple point charge (SPC/E) and the Gaussian charge polarizable (GCP) models. The predicted temperature dependence of the liquid-vapor equilibrium isotopic fractionation factors for H 2 18O / H 2 16O, H 2 17O / H 2 16O, and 2H 1H 16O / 1H 2 16O are compared against the most accurate experimental datasets to assess the ability of these intermolecular potential models to describe quantum effects according to the Kirkwood-Wigner free energy perturbation ! 2 !expansion. Predictions of the vapor pressure isotopic effect for the H 2 18O / H 2 16O and H 2 17O / H 2 16O pairs are also presented in comparison with experimental data and two recently proposed thermodynamic modeling approaches. Finally, the simulation results are used to discuss some approximations behind the microscopic interpretation of isotopic fractionation based on the underlying roto-translational coupling.

  7. Isotope exchange at equilibrium indicates a steady state ordered kinetic mechanism for human sulfotransferase.

    PubMed

    Tyapochkin, Eduard; Cook, Paul F; Chen, Guangping

    2008-11-11

    Cytosolic sulfotransferase (SULT)-catalyzed sulfation regulates biosignaling molecular biological activities and detoxifies hydroxyl-containing xenobiotics. The universal sulfuryl group donor for SULTcatalyzed sulfation is adenosine 3'-phosphate 5'-phosphosulfate (PAPS). The reaction products are a sulfated product and adenosine 3',5'-diphosphate (PAP). Although the kinetics has been reported since the 1980s,SULT-catalyzed reaction mechanisms remain unclear. Human SULT1A1 catalyzes the sulfation of xenobiotic phenols and has very broad substrate specificity. It has been recognized as one of the most important phase II drug-metabolizing enzymes. Understanding the kinetic mechanism of this isoform is important in understanding drug metabolism and xenobiotic detoxification. In this report, we investigated the SULT1A1-catalyzed phenol sulfation mechanism. The SULT1A1-catalyzed reaction was brought to equilibrium by varying substrate (1-naphthol) and PAPS initial concentrations. Equilibrium constants were determined. Two isotopic exchanges at equilibrium ([14C]1-naphthol <=>[14C]1-naphthyl sulfate and[35S]PAPS<=>[35S]1-naphthyl sulfate) were conducted. First-order kinetics, observed for all the is otopic exchange reactions studied over the entire time scale that was monitored, indicates that the system was truly at equilibrium prior to addition of an isotopic pulse. Complete suppression of the 35S isotopic exchange rate was observed with an increase in the levels of 1-naphthol and 1-naphthyl sulfate in a constant ratio,while no suppression of the 14C exchange rate was observed with an increase in the levels of PAPS and PAP in a constant ratio. Data are consistent with a steady state ordered kinetic mechanism with PAPS and PAP binding to the free enzyme.

  8. Equilibrium fractionation of H and O isotopes in water from path integral molecular dynamics

    NASA Astrophysics Data System (ADS)

    Pinilla, Carlos; Blanchard, Marc; Balan, Etienne; Ferlat, Guillaume; Vuilleumier, Rodolphe; Mauri, Francesco

    2014-06-01

    The equilibrium fractionation factor between two phases is of importance for the understanding of many planetary and environmental processes. Although thermodynamic equilibrium can be achieved between minerals at high temperature, many natural processes involve reactions between liquids or aqueous solutions and solids. For crystals, the fractionation factor α can be theoretically determined using a statistical thermodynamic approach based on the vibrational properties of the phases. These calculations are mostly performed in the harmonic approximation, using empirical or ab-initio force fields. In the case of aperiodic and dynamic systems such as liquids or solutions, similar calculations can be done using finite-size molecular clusters or snapshots obtained from molecular dynamics (MD) runs. It is however difficult to assess the effect of these approximate models on the isotopic fractionation properties. In this work we present a systematic study of the calculation of the D/H and 18O/16O equilibrium fractionation factors in water for the liquid/vapour and ice/vapour phases using several levels of theory within the simulations. Namely, we use a thermodynamic integration approach based on Path Integral MD calculations (PIMD) and an empirical potential model of water. Compared with standard MD, PIMD takes into account quantum effects in the thermodynamic modeling of systems and the exact fractionation factor for a given potential can be obtained. We compare these exact results with those of modeling strategies usually used, which involve the mapping of the quantum system on its harmonic counterpart. The results show the importance of including configurational disorder for the estimation of isotope fractionation in liquid phases. In addition, the convergence of the fractionation factor as a function of parameters such as the size of the simulated system and multiple isotope substitution is analyzed, showing that isotope fractionation is essentially a local effect in

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

    PubMed

    Yang, Sha; Liu, Yun

    2015-01-01

    The nuclear volume effects (NVEs) of Hg, Tl and Pb isotope systems are investigated with careful evaluation on quantum relativistic effects via the Dirac's formalism of full-electron wave function. Equilibrium (202)Hg/(198)Hg, (205)Tl/(203)Tl, (207)Pb/(206)Pb and (208)Pb/(206)Pb isotope fractionations are found can be up to 3.61‰, 2.54‰, 1.48‰ and 3.72‰ at room temperature, respectively, larger than fractionations predicted by classical mass-dependent isotope fractionations theory. Moreover, the NVE can cause mass-independent fractionations (MIF) for odd-mass isotopes and even-mass isotopes. The plot of [formula in text] for Hg-bearing species falls into a straight line with the slope of 1.66, which is close to previous experimental results. For the first time, Pb(4+)-bearing species are found can enrich heavier Pb isotopes than Pb(2+)-bearing species to a surprising extent, e.g., the enrichment can be up to 4.34‰ in terms of (208)Pb/(206)Pb at room temperature, due to their NVEs are in opposite directions. In contrast, fractionations among Pb(2+)-bearing species are trivial. Therefore, the large Pb fractionation changes provide a potential new tracer for redox conditions in young and closed geologic systems. The magnitudes of NVE-driven even-mass MIFs of Pb isotopes (i.e., [formula in text]) and odd-mass MIFs (i.e., [formula in text) are almost the same but with opposite signs. PMID:26224248

  10. Equilibrium and Kinetic Isotopic Fractionation Processes Recorded in δ7Li Values of Highly Evolved Granitic Pegmatites

    NASA Astrophysics Data System (ADS)

    Barnes, E. M.; Weis, D. A.; Groat, L. A.

    2010-12-01

    In geologic settings, Li isotopes are significantly influenced by both equilibrium and kinetic fractionation mechanisms. This has the potential to make δ7Li values valuable in identifying geological processes or tracing source rocks. Lithium isotopic analysis is becoming an increasingly popular geochemical tool, however, a better understanding of the mechanisms involved in Li isotopic fractionation is necessary if this method is to achieve its full potential. This study combined δ7Li values, trace element geochemistry, mineralogy and primary textural evidence from rock-forming minerals (quartz, albite, spodumene and mica) and whole rock samples taken from a coeval swarm of rare element pegmatite dikes, to look at the extent and mechanisms of Li isotopic fractionation during pegmatite formation. Pegmatite crystallization can be extremely rapid, potentially on a similar timescale to Li diffusion, as a result the influence of variable, non-equilibrium conditions during consolidation was assessed. Rock-forming minerals (given above) from the Little Nahanni Pegmatite Group (Northwest Territories, Canada) display δ7Li values that correlate with textural evidence supporting consolidation of the dikes under non-equilibrium conditions. Two examples of spodumene from different pegmatite samples have comparable δ7Li values of +3.5 and +3.7‰. In contrast, the δ7Li value of mineral separates from co-precipitated mineral assemblages varies from sample to sample. Very uniform δ7Li values for co-precipitated minerals from one sample (muscovite at +7.9‰, plagioclase at +7.9‰ and quartz at +8.7‰), contrast with very different δ7Li values for the same mineral assemblage from a different sample (muscovite at +2.2‰, plagioclase at +3.4‰ and quartz at +15.7‰). Whole rock samples from the same outcrops suggest strong Li isotope fractionation in peraluminous magma is associated with F build up in the late stages of magmatic differentiation. Pegmatites derived from the

  11. High-Temperature Equilibrium Isotope Fractionation of Non-Traditional Stable Isotopes: Experiments, Theory, and Applications (Invited)

    NASA Astrophysics Data System (ADS)

    Young, E. D.; Lazar, G. C.; Macris, C. A.; Manning, C. E.; Schauble, E. A.; Shahar, A.

    2013-12-01

    Experiments are crucial for validating our understanding of stable isotope fractionation at high temperatures. The three-isotope method has been applied with success in the Si, Mg, Fe, and Ni isotope systems to date. The results of these experiments can be compared with expectations from theory and measurements of natural samples. Qualitative insights into the partitioning of heavy and light isotopes between mineral phases are gained by treating the force constant for relevant bonds, Kf j, as electrostatic in origin. The ionic model, based on the mean bond strength as defined by Pauling, has obvious limitations but is useful for rationalizing structures and site occupancies in silicates and oxide minerals and is equally useful in formulating expectations for isotope fractionation between phases. In some cases, as in Fe isotopes in spinels, the expectations are contrary to predictions based on modeling but similar to observations in natural samples. Experimental verification is required. The force constant for a bond between cation i (Mg, Fe, etc.) and anion j (e.g., O) can be written in terms of mean bond strengths si and sj (as defined by Pauling) as Kf,ij = sisj e2 (1-n)/(4 π ɛο r3ij ) where ɛo is the electric constant (vacuum permittivity for simplicity), e is the charge of an electron, n is the exponent in the Born-Mayer formulation for ion repulsion (Born and Mayer 1932), and rij is the interatomic spacing. This equation shows explicitly that larger values for the force constant Kf correspond to smaller coordination numbers (via si and sj). We therefore expect an inverse relationship between isotope ratios (heavy/light) and coordination of its oxygen bond partners in silicate and oxides minerals and this is verified in mantle minerals. Our work with Fe isotope partitioning in mantle spinels suggests that coordination may be equally important as oxidation state, recognizing that these distinctions are not orthogonal. Recent work on the Mg isotopic

  12. Isotopic equilibrium between precipitation and water vapor: evidence from continental rains in central Kenya

    NASA Astrophysics Data System (ADS)

    Soderberg, K.; Gerlein, C.; Kemeny, P. C.; Caylor, K. K.

    2013-12-01

    An accurate understanding of the relationships between the isotopic composition of liquid water and that of water vapor in the environment can help describe hydrologic processes across many scales. One such relationship is the isotopic equilibrium between falling raindrops and the surrounding vapor. The degree of equilibration is used to model the isotopic composition of precipitation in isotope-enable general circulation models and land-atmosphere exchange models. Although this equilibrium has been a topic of isotope hydrology research for more than four decades, few studies have included vapor measurements to validate modeling efforts. Recent advances in laser technology have allowed for in situ vapor measurements at high temporal resolution (e.g., >1 Hz). Here we present concomitant rain and vapor measurements for a series of 17 rain events during the 'Continental' rainy season (June through August) at Mpala Research Center in central Kenya. Rain samples (n=218) were collected at intervals of 2 to 35 minutes (median of 3 minutes) depending on the rain rate (0.4 to 10.5 mm/hr). The volume-weighted mean rain values for δ18O, δ2H and D-excess (δ2H - 8* δ18O) were 0.1 ‰, 10.7 ‰, and 10.1 ‰. These values are more enriched than the annual weighted means reported for the area (-2.2 ‰, -7.6 ‰, and 11.0 ‰, respectively). Vapor was measured continuously at ~2Hz (DLT-100, Los Gatos Research), with an inverted funnel intake 4m above the ground surface. The mean vapor isotopic composition during the rain events was -10.0 +/- 1.2 ‰ (1 σ) for δ18O and -73.9 +/- 7.0 ‰ for δ2H. The difference between the rain sample isotopic composition and that of liquid in isotopic equilibrium with the corresponding vapor at the ambient temperature was 0.8 +/- 2.2 ‰ for δ18O and 6.2 +/- 7.0 ‰ for δ2H. This disequilibrium was found to correlate with the natural log of rain rate (R2 of 0.26 for δ18O and 0.46 for δ2H), with lower rain rates having larger

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

    PubMed

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

    2016-04-22

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

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

    PubMed Central

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

    2016-01-01

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

  15. 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.

  16. 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.

  17. Explicit Integration of Extremely Stiff Reaction Networks: Partial Equilibrium Methods

    SciTech Connect

    Guidry, Mike W; Billings, J. J.; Hix, William Raphael

    2013-01-01

    In two preceding papers [1,2] we have shown that, when reaction networks are well removed from equilibrium, explicit asymptotic and quasi-steady-state approximations can give algebraically stabilized integration schemes that rival standard implicit methods in accuracy and speed for extremely stiff systems. However, we also showed that these explicit methods remain accurate but are no longer competitive in speed as the network approaches equilibrium. In this paper we analyze this failure and show that it is associated with the presence of fast equilibration timescales that neither asymptotic nor quasi-steady-state approximations are able to remove efficiently from the numerical integration. Based on this understanding, we develop a partial equilibrium method to deal effectively with the new partial equilibrium methods, give an integration scheme that plausibly can deal with the stiffest networks, even in the approach to equilibrium, with accuracy and speed competitive with that of implicit methods. Thus we demonstrate that algebraically stabilized explicit methods may offer alternatives to implicit integration of even extremely stiff systems, and that these methods may permit integration of much larger networks than have been feasible previously in a variety of fields.

  18. Equilibrium-disequilibrium relations in the Monte Rosa Granite, Western Alps: Petrological, Rb-Sr and stable isotope data

    USGS Publications Warehouse

    Frey, M.; Hunziker, J.C.; O'Neil, J.R.; Schwander, H.W.

    1976-01-01

    Nine samples from the Monte Rosa Granite have been investigated by microscopic, X-ray, wet chemical, electron microprobe, stable isotope and Rb-Sr and K-Ar methods. Two mineral assemblages have been distinguished by optical methods and dated as Permian and mid-Tertiary by means of Rb-Sr age determinations. The Permian assemblage comprises quartz, orthoclase, oligoclase, biotite, and muscovite whereas the Alpine assemblage comprises quartz, microcline, albite+epidote or oligoclase, biotite, and phengite. Disequilibrium between the Permian and Alpine mineral assemblages is documented by the following facts: (i) Two texturally distinguishable generations of white K-mica are 2 M muscovite (Si=3.1-3.2) and 2 M or 3 T phengite (Si=3.3-3.4). Five muscovites show Permian Rb-Sr ages and oxygen isotope fractionations indicating temperatures between 520 and 560 ?? C; however, K-Ar ages are mixed or rejuvenated. Phengite always shows mid-Tertiary Rb-Sr ages, (ii) Two biotite generations can be recognized, although textural evidence is often ambiguous. Three out of four texturally old biotites show mid-Tertiary Rb-Sr cooling ages while the oxygen isotopic fractionations point to Permian, mixed or Alpine temperatures, (iii) Comparison of radiogenic and stable isotope relations indicates that the radiogenic isotopes in the interlayer positions of the micas were mobilized during Alpine time without recrystallization, that is, without breaking Al-O or Si-O bonds. High Ti contents in young muscovites and biotites also indicate that the octahedral (and tetrahedral) sites remained undisturbed during rejuvenation. (iv) 'Isotopic reversals' in the order of O18 enrichment between K-feldspar and albite exist. Arguments for equilibrium during Permian time are meagre because of Alpine overprinting effects. Texturally old muscovites show high temperatures and Permian Rb-Sr ages in concordancy with Rb-Sr whole rock ages. For the tectonically least affected samples, excellent concordance

  19. Stable isotope labeling methods for DNA.

    PubMed

    Nelissen, Frank H T; Tessari, Marco; Wijmenga, Sybren S; Heus, Hans A

    2016-08-01

    NMR is a powerful method for studying proteins and nucleic acids in solution. The study of nucleic acids by NMR is far more challenging than for proteins, which is mainly due to the limited number of building blocks and unfavorable spectral properties. For NMR studies of DNA molecules, (site specific) isotope enrichment is required to facilitate specific NMR experiments and applications. Here, we provide a comprehensive review of isotope-labeling strategies for obtaining stable isotope labeled DNA as well as specifically stable isotope labeled building blocks required for enzymatic DNA synthesis. PMID:27573183

  20. Determination and application of the equilibrium oxygen isotope effect between water and sulfite

    NASA Astrophysics Data System (ADS)

    Wankel, Scott D.; Bradley, Alexander S.; Eldridge, Daniel L.; Johnston, David T.

    2014-01-01

    The information encoded by the two stable isotope systems in sulfate (δ34SSO4 and δ18OSO4) has been widely applied to aid reconstructions of both modern and ancient environments. Interpretation of δ18OSO4 records has been complicated by rapid oxygen isotope equilibration between sulfoxyanions and water. Specifically, the apparent relationship that develops between δ18OSO4 and δ18Owater during microbial sulfate reduction is thought to result from rapid oxygen isotope equilibrium between intracellular water and aqueous sulfite - a reactive intermediate of the sulfate reduction network that can back-react to produce sulfate. Here, we describe the oxygen equilibrium isotope effect between water and sulfite (referring to all the sum of all S(IV)-oxyanions including sulfite and both isomers and the dimer of bisulfite). Based on experiments conducted over a range of pH (4.5-9.8) and temperature (2-95 °C), where ε = 1000 * (α - 1), we find εSO3-H2O=13.61-0.299∗pH-0.081∗T °C. Thus, at a pH (7.0) and temperature (25 °C) typifying commonly used experimental conditions for sulfate reducing bacterial cultures, sulfite is enriched in 18O by 9.5‰ (±0.8‰) relative to ambient water. We examine the implication of these results in a sulfate reduction network that has been revised to reflect our understanding of the reactions involving oxygen. By evaluating previously published data within this new architecture, our results are consistent with previous suggestions of high reversibility of the sulfate reduction biochemical network. We also demonstrate that intracellular exchange rates between SO32- and water must be on average 1-3 orders of magnitude more rapid than intracellular fluxes of sulfate reduction intermediates and that kinetic isotope effects upstream of SO32- are required to explain previous laboratory and environmental studies of δ18OSO4 resulting as a consequence of sulfate reduction.

  1. The early bird gets the shrimp: Confronting assumptions of isotopic equilibrium and homogeneity in a wild bird population

    USGS Publications Warehouse

    Wunder, Michael B.; Jehl, Joseph R.; Stricker, Craig A.

    2012-01-01

    1. Because stable isotope distributions in organic material vary systematically across energy gradients that exist in ecosystems, community and population structures, and in individual physiological systems, isotope values in animal tissues have helped address a broad range of questions in animal ecology. It follows that every tissue sample provides an isotopic profile that can be used to study dietary or movement histories of individual animals. Interpretations of these profiles depend on the assumption that metabolic pools are isotopically well mixed and in equilibrium with dietary resources prior to tissue synthesis, and they extend to the population level by assuming isotope profiles are identically distributed for animals using the same proximal dietary resource. As these assumptions are never fully met, studying structure in the variance of tissue isotope values from wild populations is informative. 2. We studied variation in δ13C, δ15N, δ2H and δ18O data for feathers from a population of eared grebes (Podiceps nigricollis) that migrate to Great Salt Lake each fall to moult feathers. During this time, they cannot fly and feed almost exclusively on superabundant brine shrimp (Artemia franciscana). The ecological simplicity of this situation minimized the usual spatial and trophic complexities often present in natural studies of feather isotope values. 3. Ranges and variances of isotope values for the feathers were larger than those from previously published studies that report feather isotopic variance, but they were bimodally distributed in all isotope dimensions. Isotope values for proximal dietary resources and local surface water show that some of the feathers we assumed to have been grown locally must have been grown before birds reached isotopic equilibrium with local diet or immediately prior to arrival at Great Salt Lake. 4. Our study provides novel insights about resource use strategies in eared grebes during migration. More generally, it

  2. The early bird gets the shrimp: confronting assumptions of isotopic equilibrium and homogeneity in a wild bird population.

    PubMed

    Wunder, Michael B; Jehl, Joseph R; Stricker, Craig A

    2012-11-01

    1. Because stable isotope distributions in organic material vary systematically across energy gradients that exist in ecosystems, community and population structures, and in individual physiological systems, isotope values in animal tissues have helped address a broad range of questions in animal ecology. It follows that every tissue sample provides an isotopic profile that can be used to study dietary or movement histories of individual animals. Interpretations of these profiles depend on the assumption that metabolic pools are isotopically well mixed and in equilibrium with dietary resources prior to tissue synthesis, and they extend to the population level by assuming isotope profiles are identically distributed for animals using the same proximal dietary resource. As these assumptions are never fully met, studying structure in the variance of tissue isotope values from wild populations is informative. 2. We studied variation in δ(13) C, δ(15) N, δ(2) H and δ(18) O data for feathers from a population of eared grebes (Podiceps nigricollis) that migrate to Great Salt Lake each fall to moult feathers. During this time, they cannot fly and feed almost exclusively on superabundant brine shrimp (Artemia franciscana). The ecological simplicity of this situation minimized the usual spatial and trophic complexities often present in natural studies of feather isotope values. 3. Ranges and variances of isotope values for the feathers were larger than those from previously published studies that report feather isotopic variance, but they were bimodally distributed in all isotope dimensions. Isotope values for proximal dietary resources and local surface water show that some of the feathers we assumed to have been grown locally must have been grown before birds reached isotopic equilibrium with local diet or immediately prior to arrival at Great Salt Lake. 4. Our study provides novel insights about resource use strategies in eared grebes during migration. More generally

  3. Ab initio path-integral calculations of kinetic and equilibrium isotope effects on base-catalyzed RNA transphosphorylation models.

    PubMed

    Wong, Kin-Yiu; Xu, Yuqing; York, Darrin M

    2014-06-30

    Detailed understandings of the reaction mechanisms of RNA catalysis in various environments can have profound importance for many applications, ranging from the design of new biotechnologies to the unraveling of the evolutionary origin of life. An integral step in the nucleolytic RNA catalysis is self-cleavage of RNA strands by 2'-O-transphosphorylation. Key to elucidating a reaction mechanism is determining the molecular structure and bonding characteristics of transition state. A direct and powerful probe of transition state is measuring isotope effects on biochemical reactions, particularly if we can reproduce isotope effect values from quantum calculations. This article significantly extends the scope of our previous joint experimental and theoretical work in examining isotope effects on enzymatic and nonenzymatic 2'-O-transphosphorylation reaction models that mimic reactions catalyzed by RNA enzymes (ribozymes), and protein enzymes such as ribonuclease A (RNase A). Native reactions are studied, as well as reactions with thio substitutions representing chemical modifications often used in experiments to probe mechanism. Here, we report and compare results from eight levels of electronic-structure calculations for constructing the potential energy surfaces in kinetic and equilibrium isotope effects (KIE and EIE) computations, including a "gold-standard" coupled-cluster level of theory [CCSD(T)]. In addition to the widely used Bigeleisen equation for estimating KIE and EIE values, internuclear anharmonicity and quantum tunneling effects were also computed using our recently developed ab initio path-integral method, that is, automated integration-free path-integral method. The results of this work establish an important set of benchmarks that serve to guide calculations of KIE and EIE for RNA catalysis.

  4. Ab Initio Path-Integral Calculations of Kinetic and Equilibrium Isotope Effects on Base-Catalyzed RNA Transphosphorylation Models

    PubMed Central

    Wong, Kin-Yiu; Yuqing, Xu; York, Darrin M.

    2014-01-01

    Detailed understandings of the reaction mechanisms of RNA catalysis in various environments can have profound importance for many applications, ranging from the design of new biotechnologies to the unraveling of the evolutionary origin of life. An integral step in the nucleolytic RNA catalysis is self-cleavage of RNA strands by 2′-O-transphosphorylation. Key to elucidating a reaction mechanism is determining the molecular structure and bonding characteristics of transition state. A direct and powerful probe of transition state is measuring isotope effects on biochemical reactions, particularly if we can reproduce isotope effect values from quantum calculations. This paper significantly extends the scope of our previous joint experimental and theoretical work in examining isotope effects on enzymatic and non-enzymatic 2′-O-transphosphorylation reaction models that mimic reactions catalyzed by RNA enzymes (ribozymes), and protein enzymes such as ribonuclease A (RNase A). Native reactions are studied, as well as reactions with thio substitutions representing chemical modifications often used in experiments to probe mechanism. Here, we report and compare results from eight levels of electronic-structure calculations for constructing the potential energy surfaces in kinetic and equilibrium isotope effects (KIE and EIE) computations, including a “gold-standard” coupled-cluster level of theory [CCSD(T)]. In addition to the widely-used Bigeleisen equation for estimating KIE and EIE values, internuclear anharmonicity and quantum tunneling effects were also computed using our recently-developed ab initio path-integral method, i.e., automated integration-free path-integral (AIF-PI) method. The results of this work establish an important set of benchmarks that serve to guide calculations of KIE and EIE for RNA catalysis. PMID:24841935

  5. 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.

  6. EQUILIBRIUM AND NONEQUILIBRIUM FOUNDATIONS OF FREE ENERGY COMPUTATIONAL METHODS

    SciTech Connect

    C. JARZYNSKI

    2001-03-01

    Statistical mechanics provides a rigorous framework for the numerical estimation of free energy differences in complex systems such as biomolecules. This paper presents a brief review of the statistical mechanical identities underlying a number of techniques for computing free energy differences. Both equilibrium and nonequilibrium methods are covered.

  7. Feasibility of Isotopic Measurements: Graphite Isotopic Ratio Method

    SciTech Connect

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

    2001-04-30

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

  8. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    PubMed

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. PMID:25877865

  9. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    PubMed

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect.

  10. Stark broadening for diagnostics of the electron density in non-equilibrium plasma utilizing isotope hydrogen alpha lines

    SciTech Connect

    Yang, Lin; Tan, Xiaohua; Wan, Xiang; Chen, Lei; Jin, Dazhi; Qian, Muyang; Li, Gongping

    2014-04-28

    Two Stark broadening parameters including FWHM (full width at half maximum) and FWHA (full width at half area) of isotope hydrogen alpha lines are simultaneously introduced to determine the electron density of a pulsed vacuum arc jet. To estimate the gas temperature, the rotational temperature of the C{sub 2} Swan system is fit to 2500 ± 100 K. A modified Boltzmann-plot method with b{sub i}-factor is introduced to determine the modified electron temperature. The comparison between results of atomic and ionic lines indicates the jet is in partial local thermodynamic equilibrium and the electron temperature is close to 13 000 ± 400 K. Based on the computational results of Gig-Card calculation, a simple and precise interpolation algorithm for the discrete-points tables can be constructed to obtain the traditional n{sub e}-T{sub e} diagnostic maps of two Stark broadening parameters. The results from FWHA formula by the direct use of FWHM = FWHA and these from the diagnostic map are different. It can be attributed to the imprecise FWHA formula form and the deviation between FWHM and FWHA. The variation of the reduced mass pair due to the non-equilibrium effect contributes to the difference of the results derived from two hydrogen isotope alpha lines. Based on the Stark broadening analysis in this work, a corrected method is set up to determine n{sub e} of (1.10 ± 0.08) × 10{sup 21} m{sup −3}, the reference reduced mass μ{sub 0} pair of (3.30 ± 0.82 and 1.65 ± 0.41), and the ion kinetic temperature of 7900 ± 1800 K.

  11. Rare-event simulation methods for equilibrium and non-equilibrium events

    NASA Astrophysics Data System (ADS)

    Ziff, Robert

    2014-03-01

    Rare events are those that occur with a very low probability in experiment, or are common but difficult to sample using standard computer simulation techniques. Such processes require advanced methods in order to obtain useful results in reasonable amounts of computer time. We discuss some of those techniques here, including the ``barrier'' method, splitting methods, and a Forward-Flux Sampling in Time (FFST) algorithm, and apply them to measure the nucleation times of the first-order transition in the Ziff-Gulari-Barshad model of surface catalysis, including nucleation in finite equilibrium states, which are measured to occur with probabilities as low as 10°C(-40). We also study the transitions in the Maier-Stein model of chemical kinetics, and use the methods to find the harmonic measure in percolation and Diffusion-Limited Aggregation (DLA) clusters. co-authors: David Adams, Google, and Leonard Sander, University of Michigan.

  12. Theoretical estimation for equilibrium Mo isotope fractionations between dissolved Mo species and the adsorbed complexes on (Fe,Mn)-oxyhydroxides

    NASA Astrophysics Data System (ADS)

    Tang, M.; Liu, Y.

    2009-12-01

    Although Mo isotopes have been increasingly used as a paleoredox proxy in the study of paleo-oceanographic condition changes (Barling et al., 2001; Siebert et al., 2003, 2005,2006; Arnold et al., 2004; Poulson et al., 2006), some very basic aspects of Mo isotopes geochemistry have not been obtained yet. First, although there are several previous studies on equilibrium Mo isotope fractionation factors(Tossell,2005; Weeks et al.,2007; Wasylenki et al.,2008), these studies were dealing with situations in vacuum and we find unfortunately the solvation effects for Ge species in solution cannot be ignored. Therefore, accurate Ge fractionation factors are actually not determined yet. Second, except the dominant dissolved Mo species in seawater which is known as molybdate ion (MoO42-), the forms of possible other minor species remain elusive. Third, the Mo removal mechanisms from seawater are only known for the anoxia and euxinic conditions (e.g. Helz et al., 1996; Zheng et al., 2000), the Mo removal mechanism under oxic condition are still arguing. Fourth, the adsorption effects on Mo isotope fractionation are almost completely unknown. Especially, without the adsorption fractionation knowledge, it is difficult to understand many distinct fractionations found in a number of geologic systems and it is difficult to explain the exceptionally long residence time of Mo in seawater. Urey model or Bigeleisen-Mayer equation based theoretical method and the super-molecule clusters are used to precisely evaluate the fractionation factors. The B3LYP/(6-311+G(2df,p),LANL2DZ) level method is used for frequencies calculation. 24 water molecules are used to form the supermolecues surrounding the Mo species. At least 4 different conformers for each supermolecule are used to prevent the errors from the diversity of configurations in solution. This study provides accurate equilibrium Mo isotope fractionation factors between possible dissolved Mo species and the adsorbed Mo species on the

  13. Meshless method for solving fixed boundary problem of plasma equilibrium

    NASA Astrophysics Data System (ADS)

    Imazawa, Ryota; Kawano, Yasunori; Itami, Kiyoshi

    2015-07-01

    This study solves the Grad-Shafranov equation with a fixed plasma boundary by utilizing a meshless method for the first time. Previous studies have utilized a finite element method (FEM) to solve an equilibrium inside the fixed separatrix. In order to avoid difficulties of FEM (such as mesh problem, difficulty of coding, expensive calculation cost), this study focuses on the meshless methods, especially RBF-MFS and KANSA's method to solve the fixed boundary problem. The results showed that CPU time of the meshless methods was ten to one hundred times shorter than that of FEM to obtain the same accuracy.

  14. Evidence for deep sea hydrothermal fluid-mineral equilibrium from multiple S isotopes

    NASA Astrophysics Data System (ADS)

    McDermott, J. M.; Ono, S.; Tivey, M. K.; Seewald, J.

    2010-12-01

    in 7 out of 8 fluid-mineral pairs show <1‰ difference between fluid and chalcopyrite, with most chalcopyrite showing slightly enriched δ34S, consistent with equilibrium fluid-mineral sulfur isotope exchange at 300-400°C during precipitation [4]. Negative δ34S in fluid-mineral pairs from SuSu Knolls may be a consequence of both magmatic volatile and sedimentary sulfide mineral input, an assertion supported by observations of very high CH4 concentrations in the black smoker fluids and low temperature acid sulfate fluids emanating from the dome flanks. Additional analyses are being conducted on more SuSu Knolls vents, as well as fluid-mineral pairs from Lau Basin vent fields. [1] Ono et al. (2007) GCA 71, 1170-1182. [2] Shanks (2001) Rev. Mineral. Geochem. 43, 469-525. [3] Woodruff and Shanks (1988) J. Geophy. Res. 93, 4562-4572. [4] Ohmoto and Goldhaber (1997) Geochemistry of Hydrothermal Ore Deposits, Third Edition, pp. 517-611.

  15. Slope Stability Analysis Using Limit Equilibrium Method in Nonlinear Criterion

    PubMed Central

    Lin, Hang; Zhong, Wenwen; Xiong, Wei; Tang, Wenyu

    2014-01-01

    In slope stability analysis, the limit equilibrium method is usually used to calculate the safety factor of slope based on Mohr-Coulomb criterion. However, Mohr-Coulomb criterion is restricted to the description of rock mass. To overcome its shortcomings, this paper combined Hoek-Brown criterion and limit equilibrium method and proposed an equation for calculating the safety factor of slope with limit equilibrium method in Hoek-Brown criterion through equivalent cohesive strength and the friction angle. Moreover, this paper investigates the impact of Hoek-Brown parameters on the safety factor of slope, which reveals that there is linear relation between equivalent cohesive strength and weakening factor D. However, there are nonlinear relations between equivalent cohesive strength and Geological Strength Index (GSI), the uniaxial compressive strength of intact rock σci, and the parameter of intact rock mi. There is nonlinear relation between the friction angle and all Hoek-Brown parameters. With the increase of D, the safety factor of slope F decreases linearly; with the increase of GSI, F increases nonlinearly; when σci is relatively small, the relation between F and σci is nonlinear, but when σci is relatively large, the relation is linear; with the increase of mi, F decreases first and then increases. PMID:25147838

  16. Chemical Equilibrium: A survival strategy to cope with substrate limitation that has severe consequences for the stable isotope records

    NASA Astrophysics Data System (ADS)

    Brunner, B.

    2011-12-01

    Substrate limitation - low availability of easily metabolized substrates such as organic matter or geofuels - poses constraints on any living organism. This situation is met in the deep sub-seafloor biosphere with low availability of organic matter of refractory quality, but can also occur in environments with much higher microbial turnover, where organisms out-compete each other for substrates. An energy efficient way and thereby a valuable survival strategy to deal with substrate limitation is to operate catabolic processes close to thermodynamic equilibrium. Enzymes catalyzing catabolic processes are reversible, thus catabolic processes operating close to thermodynamic equilibrium are expected to be reversible as well. The coupling between low energy yield and high reversibility of individual steps in catabolic pathways is commonly accepted as a basic theoretical concept, and its impact on stable isotope signatures has long been acknowledged and recently confirmed for specific processes, for example dissimilatory sulfate reduction. However, the consequence of entirely reversible pathways on stable isotope signatures has not yet been addressed: the isotope composition of reactant pools becomes dependent on the isotope composition of the product pools. This renders any interpretation of the isotope pattern based on the assumption of unidirectional fluxes (e.g. Rayleigh-type equations) questionable. If this is the case, the follow-up question would be: is reversibility of entire metabolic pathways rather the rule than the exception?

  17. C-Field Methods for Non-Equilibrium Bose Gases

    NASA Astrophysics Data System (ADS)

    Davis, Matthew J.; Wright, Tod M.; Blakie, P. Blair; Bradley, Ashton S.; Ballagh, Rob J.; Gardiner, Crispin W.

    2013-02-01

    We review c-field methods for simulating the non-equilibrium dynamics of degenerate Bose gases beyond the mean-field Gross-Pitaevskii approximation. We describe three separate approaches that utilise similar numerical methods, but have distinct regimes of validity. Systems at finite temperature can be treated with either the closed-system projected Gross-Pitaevskii equation (PGPE), or the open-system stochastic projected Gross-Pitaevskii equation (SPGPE). These are both applicable in quantum degenerate regimes in which thermal fluctuations are significant. At low or zero temperature, the truncated Wigner projected Gross Pitaevskii equation (TWPGPE) allows for the simulation of systems in which spontaneous collision processes seeded by quantum fluctuations are important. We describe the regimes of validity of each of these methods, and discuss their relationships to one another, and to other simulation techniques for the dynamics of Bose gases. The utility of the SPGPE formalism in modelling non-equilibrium Bose gases is illustrated by its application to the dynamics of spontaneous vortex formation in the growth of a Bose-Einstein condensate.

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

    PubMed

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

    2011-03-01

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

  19. Study report on a double isotope method of calcium absorption

    NASA Technical Reports Server (NTRS)

    1978-01-01

    Some of the pros and cons of three methods to study gastrointestinal calcium absorption are briefly discussed. The methods are: (1) a balance study; (2) a single isotope method; and (3) a double isotope method. A procedure for the double isotope method is also included.

  20. ISOTOPE CONVERSION DEVICE AND METHOD

    DOEpatents

    Wigner, E.P.; Ohlinger, L.A.

    1958-11-11

    Homogeneous nuclear reactors are discussed, and an apparatus and method of operation are descrlbed. The apparatus consists essentially of a reaction tank, a heat exchanger connected to the reaction tank and two separate surge tanks connected to the heat exchanger. An oscillating differential pressure is applied to the surge tanks so that a portion of the homogeneous flssionable solution is circulated through the heat exchanger and reaction tank while maintaining sufficient solution in the reaction tank to sustain a controlled fission chain reaction. The reaction tank is disposed within another tank containing a neutron absorbing material through which coolant fluid is circulated, the outer tank being provided with means to permit and cause rotation thereof due to the circulation of the coolant therethrough.

  1. The procedure and results of calculations of the equilibrium isotopic composition of a demonstration subcritical molten salt reactor

    NASA Astrophysics Data System (ADS)

    Nevinitsa, V. A.; Dudnikov, A. A.; Blandinskiy, V. Yu.; Balanin, A. L.; Alekseev, P. N.; Titarenko, Yu. E.; Batyaev, V. F.; Pavlov, K. V.; Titarenko, A. Yu.

    2015-12-01

    A subcritical molten salt reactor with an external neutron source is studied computationally as a facility for incineration and transmutation of minor actinides from spent nuclear fuel of reactors of VVER-1000 type and for producing 233U from 232Th. The reactor configuration is chosen, the requirements to be imposed on the external neutron source are formulated, and the equilibrium isotopic composition of heavy nuclides and the key parameters of the fuel cycle are calculated.

  2. The procedure and results of calculations of the equilibrium isotopic composition of a demonstration subcritical molten salt reactor

    SciTech Connect

    Nevinitsa, V. A. Dudnikov, A. A.; Blandinskiy, V. Yu.; Balanin, A. L.; Alekseev, P. N.; Titarenko, Yu. E.; Batyaev, V. F.; Pavlov, K. V.; Titarenko, A. Yu.

    2015-12-15

    A subcritical molten salt reactor with an external neutron source is studied computationally as a facility for incineration and transmutation of minor actinides from spent nuclear fuel of reactors of VVER-1000 type and for producing {sup 233}U from {sup 232}Th. The reactor configuration is chosen, the requirements to be imposed on the external neutron source are formulated, and the equilibrium isotopic composition of heavy nuclides and the key parameters of the fuel cycle are calculated.

  3. Primordial radionuclides in Canadian background sites: secular equilibrium and isotopic differences.

    PubMed

    Sheppard, S C; Sheppard, M I; Ilin, M; Tait, J; Sanipelli, B

    2008-06-01

    A literature review and field sampling were done to obtain information on primordial (natural-series) radionuclide concentrations in terrestrial environments in diverse locations across Canada. Of special interest was the degree of secular equilibrium among members of decay series. The analytes measured in soils and plants were (nat)U by neutron activation-delayed neutron counting, (228)Th, (230)Th, (232)Th, (226)Ra and (210)Po by alpha spectroscopy, (210)Pb by gas flow proportional counting, (228)Ra by beta counting and (137)Cs by gamma spectroscopy. In addition, ICP-MS was used to obtain concentrations of about 50 analytes including elemental U, Pb, and Th. Samples were from seven representative background sites with a total of 162 plant samples from 38 different species. These data were supplemented by a review that gathered a large portion of the similar data from published sources. The sites chosen were semi-natural, far from any nuclear industry, although several were specifically located in areas with slightly elevated natural U concentrations. As might be expected, there were many cases of non-detectable concentrations. However, certain trends were evident. The activity ratio (210)Po/(210)Pb was unity in soils and non-annual plant tissues such as lichens. It was about 0.6 in annual plant tissues. These results are consistent with the time required for ingrowth of (210)Po to reach secular equilibrium. There was evidence from several sources that (210)Pb in plants came predominantly from deposition of (210)Pb from air after the decay of airborne (222)Rn. This was expected. Somewhat unexpected was the observation that (228)Th seemed to be much more plant available than (232)Th, even though both are in the same decay series and should be chemically similar. The difference was attributed to the combined effects of ingrowth from (228)Ra in the plant and effects of alpha recoil in mobilizing (228)Th in the soil. In general, the results of this study will benefit

  4. Theoretical calculation of oxygen equilibrium isotope fractionation factors involving various NOy molecules, radOH, and H2O and its implications for isotope variations in atmospheric nitrate

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Michalski, Greg

    2016-10-01

    The oxygen stable isotope composition (δ18O) of nitrogen oxides [NOx = nitric oxide (NO) + nitrogen dioxide (NO2)] and their oxidation products (NOy = NOx + nitric acid (HNO3) + particulate nitrate (p-NO3-) + nitrate radical (NO3) + dinitrogen pentoxide (N2O5) + nitrous acid (HONO) + …) have been shown to be a useful tool for inferring the proportion of NOx that is oxidized by ozone (O3). However, isotopic fractionation processes may have an influence on δ18O of various NOy molecules and other atmospheric O-bearing molecules pertinent to NOx oxidation chemistry. Here we have evaluated the impacts of O isotopic exchange involving NOy molecules, the hydroxyl radical (radOH), and water (H2O) using reduced partition function ratios (xβ) calculated by hybrid density functional theory. Assuming atmospheric isotopic equilibrium is achieved between NO and NO2 during the daytime, and NO2, NO3, and N2O5 during the nighttime, δ18O-δ15N compositions were predicted for the major atmospheric nitrate formation pathways using our calculated exchange fractionation factors and isotopic mass-balance. Our equilibrium model predicts that various atmospheric nitrate formation pathways, including NO2 + radOH → HNO3, N2O5 + H2O + surface → 2HNO3, and NO3 + R → HNO3 + Rrad will yield distinctive δ18O-δ15N compositions. Our calculated δ18O-δ15N compositions match well with previous atmospheric nitrate measurements, and will potentially help better understand the role oxidation chemistry plays on the N and O isotopic composition of atmospheric nitrate.

  5. A Variational Method in Out-of-Equilibrium Physical Systems

    PubMed Central

    Pinheiro, Mario J.

    2013-01-01

    We propose a new variational principle for out-of-equilibrium dynamic systems that are fundamentally based on the method of Lagrange multipliers applied to the total entropy of an ensemble of particles. However, we use the fundamental equation of thermodynamics on differential forms, considering U and S as 0-forms. We obtain a set of two first order differential equations that reveal the same formal symplectic structure shared by classical mechanics, fluid mechanics and thermodynamics. From this approach, a topological torsion current emerges of the form , where Aj and ωk denote the components of the vector potential (gravitational and/or electromagnetic) and where ω denotes the angular velocity of the accelerated frame. We derive a special form of the Umov-Poynting theorem for rotating gravito-electromagnetic systems. The variational method is then applied to clarify the working mechanism of particular devices. PMID:24316718

  6. Minimizing the Free Energy: A Computer Method for Teaching Chemical Equilibrium Concepts.

    ERIC Educational Resources Information Center

    Heald, Emerson F.

    1978-01-01

    Presents a computer method for teaching chemical equilibrium concepts using material balance conditions and the minimization of the free energy. Method for the calculation of chemical equilibrium, the computer program used to solve equilibrium problems and applications of the method are also included. (HM)

  7. Effect of parent body evolution on equilibrium and kinetic isotope fractionation: a combined Ni and Fe isotope study of iron and stony-iron meteorites

    NASA Astrophysics Data System (ADS)

    Chernonozhkin, Stepan M.; Goderis, Steven; Costas-Rodríguez, Marta; Claeys, Philippe; Vanhaecke, Frank

    2016-08-01

    resolvable differences, similar in magnitude but opposite in sign (Δ56/54Femet-oliv of +0.178 ± 0.092‰ and Δ60/58Nimet-oliv of -0.212 ± 0.082‰, 2SD). As such, the heavier Fe isotope ratios for the metal (δ56/54Fe = +0.023‰ to +0.247‰) and lighter values for the corresponding olivines (δ56/54Fe = -0.155‰ to -0.075‰) are interpreted to reflect later-stage Fe isotopic re-equilibration between these phases, rather than a pristine record of mantle-core differentiation. In the case of mesosiderites, the similarly lighter Ni and Fe isotopic signatures found for the silicate phase (-0.149‰ to +0.023‰ for δ60/58Ni, -0.214‰ to -0.149‰ for δ56/54Fe) compared to the metal phase (+0.168‰ to +0.191‰ for δ60/58Ni, +0.018‰ to +0.120‰ for δ56/54Fe) likely result from Fe and Ni diffusion. Overall, the Fe and Ni isotopic compositions of iron-rich meteorites reflect multiple, often superimposed, processes of equilibrium or kinetic nature, illustrating convoluted parent body histories and late-stage interaction between early-formed planetesimal reservoirs.

  8. Isotopic ratio method for determining uranium contamination

    SciTech Connect

    Miles, R.E.; Sieben, A.K.

    1994-02-03

    The presence of high concentrations of uranium in the subsurface can be attributed either to contamination from uranium processing activities or to naturally occurring uranium. A mathematical method has been employed to evaluate the isotope ratios from subsurface soils at the Rocky Flats Nuclear Weapons Plant (RFP) and demonstrates conclusively that the soil contains uranium from a natural source and has not been contaminated with enriched uranium resulting from RFP releases. This paper describes the method used in this determination which has widespread application in site characterizations and can be adapted to other radioisotopes used in manufacturing industries. The determination of radioisotope source can lead to a reduction of the remediation effort.

  9. A survey of upwind methods for flows with equilibrium and non-equilibrium chemistry and thermodynamics

    NASA Technical Reports Server (NTRS)

    Grossman, B.; Garrett, J.; Cinnella, P.

    1989-01-01

    Several versions of flux-vector split and flux-difference split algorithms were compared with regard to general applicability and complexity. Test computations were performed using curve-fit equilibrium air chemistry for an M = 5 high-temperature inviscid flow over a wedge, and an M = 24.5 inviscid flow over a blunt cylinder for test computations; for these cases, little difference in accuracy was found among the versions of the same flux-split algorithm. For flows with nonequilibrium chemistry, the effects of the thermodynamic model on the development of flux-vector split and flux-difference split algorithms were investigated using an equilibrium model, a general nonequilibrium model, and a simplified model based on vibrational relaxation. Several numerical examples are presented, including nonequilibrium air chemistry in a high-temperature shock tube and nonequilibrium hydrogen-air chemistry in a supersonic diffuser.

  10. Yang-Yang equilibrium statistical mechanics: A brilliant method

    NASA Astrophysics Data System (ADS)

    Guan, Xi-Wen; Chen, Yang-Yang

    2016-03-01

    Yang and Yang in 1969 [J. Math. Phys. 10, 1115 (1969)] for the first time proposed a rigorous approach to the thermodynamics of the one-dimensional system of bosons with a delta-function interaction. This paper was a breakthrough in exact statistical mechanics, after Yang [Phys. Rev. Lett. 19, 1312 (1967)] published his seminal work on the discovery of the Yang-Baxter equation in 1967. Yang and Yang’s brilliant method yields significant applications in a wide range of fields of physics. In this paper, we briefly introduce the method of the Yang-Yang equilibrium statistical mechanics and demonstrate a fundamental application of the Yang-Yang method for the study of thermodynamics of the Lieb-Liniger model with strong and weak interactions in a whole temperature regime. We also consider the equivalence between the Yang-Yang’s thermodynamic Bethe ansatz equation and the thermodynamics of the ideal gas with the Haldane’s generalized exclusion statistics.

  11. Yang-Yang Equilibrium Statistical Mechanics: A Brilliant Method

    NASA Astrophysics Data System (ADS)

    Guan, Xi-Wen; Chen, Yang-Yang

    C. N. Yang and C. P. Yang in 1969 (J. Math. Phys. 10, 1115 (1969)) for the first time proposed a rigorous approach to the thermodynamics of the one-dimensional system of bosons with a delta-function interaction. This paper was a breakthrough in exact statistical mechanics, after C. N. Yang (Phys. Rev. Lett. 19, 1312 (1967)) published his seminal work on the discovery of the Yang-Baxter equation in 1967. Yang and Yang's brilliant method yields significant applications in a wide range of fields of physics. In this communication, we briefly introduce the method of the Yang-Yang equilibrium statistical mechanics and demonstrate a fundamental application of the Yang-Yang method for the study of thermodynamics of the Lieb-Liniger model with strong and weak interactions in a whole temperature regime. We also consider the equivalence between the Yang-Yang's thermodynamic Bethe ansatz equation and the thermodynamics of the ideal gas with the Haldane's generalized exclusion statistics.

  12. Method for production of an isotopically enriched compound

    SciTech Connect

    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.

  13. 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.

  14. A new nonlocal thermodynamical equilibrium radiative transfer method for cool stars. Method and numerical implementation

    NASA Astrophysics Data System (ADS)

    Lambert, J.; Josselin, E.; Ryde, N.; Faure, A.

    2015-08-01

    Context. The solution of the nonlocal thermodynamical equilibrium (non-LTE) radiative transfer equation usually relies on stationary iterative methods, which may falsely converge in some cases. Furthermore, these methods are often unable to handle large-scale systems, such as molecular spectra emerging from, for example, cool stellar atmospheres. Aims: Our objective is to develop a new method, which aims to circumvent these problems, using nonstationary numerical techniques and taking advantage of parallel computers. Methods: The technique we develop may be seen as a generalization of the coupled escape probability method. It solves the statistical equilibrium equations in all layers of a discretized model simultaneously. The numerical scheme adopted is based on the generalized minimum residual method. Results: The code has already been applied to the special case of the water spectrum in a red supergiant stellar atmosphere. This demonstrates the fast convergence of this method, and opens the way to a wide variety of astrophysical problems.

  15. Current Methods in Sedimentation Velocity and Sedimentation Equilibrium Analytical Ultracentrifugation

    PubMed Central

    Zhao, Huaying; Brautigam, Chad A.; Ghirlando, Rodolfo; Schuck, Peter

    2013-01-01

    Significant progress in the interpretation of analytical ultracentrifugation (AUC) data in the last decade has led to profound changes in the practice of AUC, both for sedimentation velocity (SV) and sedimentation equilibrium (SE). Modern computational strategies have allowed for the direct modeling of the sedimentation process of heterogeneous mixtures, resulting in SV size-distribution analyses with significantly improved detection limits and strongly enhanced resolution. These advances have transformed the practice of SV, rendering it the primary method of choice for most existing applications of AUC, such as the study of protein self- and hetero-association, the study of membrane proteins, and applications in biotechnology. New global multi-signal modeling and mass conservation approaches in SV and SE, in conjunction with the effective-particle framework for interpreting the sedimentation boundary structure of interacting systems, as well as tools for explicit modeling of the reaction/diffusion/sedimentation equations to experimental data, have led to more robust and more powerful strategies for the study of reversible protein interactions and multi-protein complexes. Furthermore, modern mathematical modeling capabilities have allowed for a detailed description of many experimental aspects of the acquired data, thus enabling novel experimental opportunities, with important implications for both sample preparation and data acquisition. The goal of the current commentary is to supplement previous AUC protocols, Current Protocols in Protein Science 20.3 (1999) and 20.7 (2003), and 7.12 (2008), and provide an update describing the current tools for the study of soluble proteins, detergent-solubilized membrane proteins and their interactions by SV and SE. PMID:23377850

  16. Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures

    PubMed Central

    Loyd, S. J.; Sample, J.; Tripati, R. E.; Defliese, W. F.; Brooks, K.; Hovland, M.; Torres, M.; Marlow, J.; Hancock, L. G.; Martin, R.; Lyons, T.; Tripati, A. E.

    2016-01-01

    Methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ∼0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings. PMID:27447820

  17. Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures

    NASA Astrophysics Data System (ADS)

    Loyd, S. J.; Sample, J.; Tripati, R. E.; Defliese, W. F.; Brooks, K.; Hovland, M.; Torres, M.; Marlow, J.; Hancock, L. G.; Martin, R.; Lyons, T.; Tripati, A. E.

    2016-07-01

    Methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ~0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings.

  18. Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures.

    PubMed

    Loyd, S J; Sample, J; Tripati, R E; Defliese, W F; Brooks, K; Hovland, M; Torres, M; Marlow, J; Hancock, L G; Martin, R; Lyons, T; Tripati, A E

    2016-01-01

    Methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ∼0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings. PMID:27447820

  19. The impact of evaporation to the isotope composition of DIC in calcite precipitating water films in equilibrium and kinetic fractionation models

    NASA Astrophysics Data System (ADS)

    Dreybrodt, Wolfgang; Deininger, Michael

    2014-01-01

    To understand the effects of processes that influence the stable carbon and oxygen isotope ratios of DIC in a small planar water film, two model approaches have been developed in the past, a classical Rayleigh-approach and a kinetic model approach. Here we compare the effect of evaporation on the stable carbon and oxygen isotope ratios 13/12 and 18/16 of DIC, based on calculation with the two model approaches. For the Rayleigh-model, the isotope ratio increases, with increasing evaporation rate. For the kinetic-model the evolution of the isotope ratio, depends, in addition to the evaporation rate, on a fractionation parameter γ ≈ 1, which results from different equilibrium concentrations with respect to calcite for the heavy and light isotopes in the DIC. In dependence on the evaporation rate, the isotope ratio increases faster, with increasing evaporation rate and reaches a maximum. After the maximum is reached it converges to an equilibrium isotope ratio, which is determined by γ. Both models results indicate, that the effect of evaporation on the stable carbon and oxygen isotope composition can be neglected for relative humidities greater than 85% and wind velocities smaller than 0.2 m/s. Close to ventilated cave sites, however, where humidity can be low and high wind speeds are possible significant changes of the isotope signal may arise.

  20. 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.

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

    SciTech Connect

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

    1986-12-01

    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, 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.

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

    PubMed

    Wong, William W; Clarke, Lucinda L

    2012-11-01

    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 hydrogen gas (H(2)) for mass spectrometric analysis are labor intensive, require special reagent, and involve memory effect and potential isotope fractionation. The objective of this study was to determine the accuracy and precision of a platinum catalyzed H(2)-water equilibration method for stable hydrogen isotope ratio measurements. Time to reach isotopic equilibrium, day-to-day and week-to-week reproducibility, accuracy, and precision of stable hydrogen isotope ratio measurements by the H(2)-water equilibration method were assessed using a Thermo DELTA V Advantage continuous-flow isotope ratio mass spectrometer. It took 3 h to reach isotopic equilibrium. The day-to-day and week-to-week measurements on water and urine samples with natural abundance and enriched levels of deuterium were highly reproducible. The method was accurate to within 2.8 (o)/oo and reproducible to within 4.0 (o)/oo based on analysis of international references. All the outcome variables, whether in urine samples collected in 10 doubly labeled water studies or plasma samples collected in 26 body water studies, did not differ from those obtained using the reference zinc reduction method. The method produced highly accurate estimation on ad libitum energy intakes, body composition, and water turnover rates. The method greatly reduces the analytical cost and could easily be adopted by laboratories equipped with a continuous-flow isotope ratio mass spectrometer.

  3. A Hydrogen Gas-Water Equilibration Method Produces Accurate and Precise Stable Hydrogen Isotope Ratio Measurements in Nutrition Studies12

    PubMed Central

    Wong, William W.; Clarke, Lucinda L.

    2012-01-01

    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 hydrogen gas (H2) for mass spectrometric analysis are labor intensive, require special reagent, and involve memory effect and potential isotope fractionation. The objective of this study was to determine the accuracy and precision of a platinum catalyzed H2-water equilibration method for stable hydrogen isotope ratio measurements. Time to reach isotopic equilibrium, day-to-day and week-to-week reproducibility, accuracy, and precision of stable hydrogen isotope ratio measurements by the H2-water equilibration method were assessed using a Thermo DELTA V Advantage continuous-flow isotope ratio mass spectrometer. It took 3 h to reach isotopic equilibrium. The day-to-day and week-to-week measurements on water and urine samples with natural abundance and enriched levels of deuterium were highly reproducible. The method was accurate to within 2.8 o/oo and reproducible to within 4.0 o/oo based on analysis of international references. All the outcome variables, whether in urine samples collected in 10 doubly labeled water studies or plasma samples collected in 26 body water studies, did not differ from those obtained using the reference zinc reduction method. The method produced highly accurate estimation on ad libitum energy intakes, body composition, and water turnover rates. The method greatly reduces the analytical cost and could easily be adopted by laboratories equipped with a continuous-flow isotope ratio mass spectrometer. PMID:23014490

  4. 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.

  5. Stable isotope geochemical study of Pamukkale travertines: New evidences of low-temperature non-equilibrium calcite-water fractionation

    NASA Astrophysics Data System (ADS)

    Kele, Sándor; Özkul, Mehmet; Fórizs, István; Gökgöz, Ali; Baykara, Mehmet Oruç; Alçiçek, Mehmet Cihat; Németh, Tibor

    2011-06-01

    In this paper we present the first detailed geochemical study of the world-famous actively forming Pamukkale and Karahayit travertines (Denizli Basin, SW-Turkey) and associated thermal waters. Sampling was performed along downstream sections through different depositional environments (vent, artificial channel and lake, terrace-pools and cascades of proximal slope, marshy environment of distal slope). δ 13C travertine values show significant increase (from + 6.1‰ to + 11.7‰ PDB) with increasing distance from the spring orifice, whereas the δ 18O travertine values show only slight increase downstream (from - 10.7‰ to - 9.1‰ PDB). Mainly the CO 2 outgassing caused the positive downstream shift (~ 6‰) in the δ 13C travertine values. The high δ 13C values of Pamukkale travertines located closest to the spring orifice (not affected by secondary processes) suggest the contribution of CO 2 liberated by thermometamorphic decarbonation besides magmatic sources. Based on the gradual downstream increase of the concentration of the conservative Na +, K +, Cl -, evaporation was estimated to be 2-5%, which coincides with the moderate effect of evaporation on the water isotope composition. Stable isotopic compositions of the Pamukkale thermal water springs show of meteoric origin, and indicate a Local Meteoric Water Line of Denizli Basin to be between the Global Meteoric Water Line (Craig, 1961) and Western Anatolian Meteoric Water Line (Şimşek, 2003). Detailed evaluation of several major and trace element contents measured in the water and in the precipitated travertine along the Pamukkale MM section revealed which elements are precipitated in the carbonate or concentrated in the detrital minerals. Former studies on the Hungarian Egerszalók travertine (Kele et al., 2008a, b, 2009) had shown that the isotopic equilibrium is rarely maintained under natural conditions during calcite precipitation in the temperature range between 41 and 67 °C. In this paper

  6. Temperature dependency of the triple isotope fractionation relationship for equilibrium processes

    NASA Astrophysics Data System (ADS)

    Hayles, J. A.; Cao, X.; Bao, H.

    2015-12-01

    The use of an approximation to the Bigeleisen-Mayer-Urey model for isotope fractionation has led to the concept of a constant, and later constrained, mass fractionation law for multiple isotopes of the same element. This concept has brought new insights to investigation in photochemistry, radical chemistry, or the contribution of quantum tunneling to chemical and biological processes. Despite previous work indicating that these mass fractionation laws can be highly variable, the concept of a constant relationship remains common in these fields. Using the diatomic case as a first-order approximation, we demonstrate generically that the mass fractionation exponent, θ, can take any value for small fractionations but is less variable for large fractionations. The predicted variability is larger than both theoretical and analytical precision. These deviations from the traditional range of mass-dependence exponents are the largest under cross-over scenarios, but can occur for any scenario with small fractionations. We advocate the use of ∆∆‡M or "change in cap-delta", defined strictly with a slope of at the high-temperature limit, as a necessary, more reliable and more useful descriptor of mass-dependent fractionation. This work can bring new insights and a conventional explanation to low temperature experiments yielding traditionally unusual mass fractionation laws.

  7. A new method for carbon isotopic analysis of protein

    SciTech Connect

    Nelson, D.E. )

    1991-02-01

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

  8. A regularized Newton method for solving equilibrium programming problems with an inexactly specified set

    NASA Astrophysics Data System (ADS)

    Antipin, A. S.; Vasil'Ev, F. P.; Stukalov, A. S.

    2007-01-01

    Unstable equilibrium problems are examined in which the objective function and the set where the equilibrium point is sought are specified inexactly. A regularized Newton method, combined with penalty functions, is proposed for solving such problems, and its convergence is analyzed. A regularizing operator is constructed.

  9. Out-of-equilibrium finite-size method for critical behavior analyses.

    PubMed

    Lulli, Matteo; Parisi, Giorgio; Pelissetto, Andrea

    2016-03-01

    We present a dynamic off-equilibrium method for the study of continuous transitions, which represents a dynamic generalization of the usual equilibrium cumulant method. Its main advantage is that critical parameters are derived from numerical data obtained much before equilibrium has been attained. Therefore, the method is particularly useful for systems with long equilibration times, like spin glasses. We apply it to the three-dimensional Ising spin-glass model, obtaining accurate estimates of the critical exponents and of the critical temperature with a limited computational effort. PMID:27078311

  10. Revised method for calculating cloud densities in equilibrium models

    NASA Astrophysics Data System (ADS)

    Wong, M. H.; Atreya, S. K.; Kuhn, W. R.

    2013-12-01

    Models of cloud condensation under thermodynamic equilibrium in planetary atmospheres are simple but still useful for several reasons. They calculate the wet adiabatic lapse rate, they determine saturation-limited mixing ratios of condensing species, and they calculate the stabilizing effect of latent heat release and molecular weight stratification. Equilibrium cloud condensation models (ECCMs) also calculate a type of condensate density---a condensate "unit density"---that only equates to cloud density under specific circumstances, because microphysics and dynamics are not considered in ECCMs. Unit densities are calculated for every model altitude by requiring that condensed material remains at the level where it condenses. Many ECCMs in use trace their heritage to Weidenschilling and Lewis (1973; Icarus 20, 465--476; hereafter WL73), which contains an error that affects only the calculation of condensate unit density. The error led to densities too high by a factor of the atmospheric scale height divided by unit length, which is about 3x10^6 at Jupiter's ammonia cloud level. We will describe the condensate unit density calculation error in WL73, and provide a new algorithm based on the local change in vapor mixing ratio, rather than the difference between integrated column masses as in WL73. The new algorithm satisfies conservation of mass. Using a simple scaling law to parameterize dynamics in terms of updraft speed and duration, condensate unit densities from ECCMs can be converted to cloud densities. We validate the technique for the terrestrial case, by comparing model predictions with representative densities of cirrus and cumulus clouds. For cirrus and cumulus updraft parameters, respectively, we find cloud densities of 0.01--0.2 g m-3 and 0.8--7 g m-3, in excellent agreement with observations and models of terrestrial clouds of these types. Implications for models of planetary and exoplanetary atmospheres will be discussed. [This material is based upon

  11. Estimating of equilibrium formation temperature by curve fitting method and it's problems

    SciTech Connect

    Kenso Takai; Masami Hyodo; Shinji Takasugi

    1994-01-20

    Determination of true formation temperature from measured bottom hole temperature is important for geothermal reservoir evaluation after completion of well drilling. For estimation of equilibrium formation temperature, we studied non-linear least squares fitting method adapting the Middleton Model (Chiba et al., 1988). It was pointed out that this method was applicable as simple and relatively reliable method for estimation of the equilibrium formation temperature after drilling. As a next step, we are studying the estimation of equilibrium formation temperature from bottom hole temperature data measured by MWD (measurement while drilling system). In this study, we have evaluated availability of nonlinear least squares fitting method adapting curve fitting method and the numerical simulator (GEOTEMP2) for estimation of the equilibrium formation temperature while drilling.

  12. A rapid method for the computation of equilibrium chemical composition of air to 15000 K

    NASA Technical Reports Server (NTRS)

    Prabhu, Ramadas K.; Erickson, Wayne D.

    1988-01-01

    A rapid computational method has been developed to determine the chemical composition of equilibrium air to 15000 K. Eleven chemically reacting species, i.e., O2, N2, O, NO, N, NO+, e-, N+, O+, Ar, and Ar+ are included. The method involves combining algebraically seven nonlinear equilibrium equations and four linear elemental mass balance and charge neutrality equations. Computational speeds for determining the equilibrium chemical composition are significantly faster than the often used free energy minimization procedure. Data are also included from which the thermodynamic properties of air can be computed. A listing of the computer program together with a set of sample results are included.

  13. Reconciling Empirical Carbonate Clumped Isotope Calibrations: A Comparison of Calcite Precipitation and Acid Digestion Methods

    NASA Astrophysics Data System (ADS)

    Kelson, J.; Huntington, K. W.; Schauer, A. J.; Saenger, C.; Lechler, A. R.

    2015-12-01

    An accurate empirical calibration is necessary to confidently apply the carbonate clumped isotope (Δ47) thermometer. Previous synthetic carbonate calibrations disagree in temperature sensitivity, with one group of calibrations displaying a shallow Δ47-temperature slope (e.g., Dennis & Schrag, GCA, 2010), and the other a steep slope (e.g., Zaarur et al., EPSL, 2013). These calibrations differ in both the method of mineral precipitation and the temperature of the phosphoric acid used to digest carbonates for analysis, making it difficult to isolate the cause of the discrepancy. Here, we precipitate synthetic carbonates at temperatures of 6-80ºC using 4 different precipitation methods, and analyze the samples using both 90 and 25°C acid digestion. Precipitation experiments varied the use of salts (NaHCO3 and CaCl2) vs. dissolved CaCO3 as a starting solution, the use of carbonic anhydrase to promote isotopic equilibrium among dissolved inorganic carbon species in solution, and the method by which CO2 degasses to force carbonate precipitation. Carbonates precipitated by using salts and allowing CO2 to passively degas produce a shallow calibration slope that we hypothesize to approach isotopic equilibrium. Precipitation methods that bubble CO2 into solution then degas that CO2 (either passively or actively by bubbling N2) produce carbonates with consistently lower Δ47 and higher δ18O values for a given growth temperature. We infer that these carbonates grew in disequilibrium during rapid CO2 degassing. Varying acid digestion temperature does not change the results; acid fractionation factor is not correlated with grain size, Δ47, or d47 values. No precipitation method produces a steep calibration slope. Our large sample set of >60 carbonates lend confidence to a shallow slope calibration, and inform interpretations of Δ47 and δ18O values of natural carbonates that grow under conditions of isotopic disequilibrium.

  14. Non-Equilibrium Allele Frequency Spectra Via Spectral Methods

    PubMed Central

    Hey, Jody; Chen, Kevin

    2011-01-01

    A major challenge in the analysis of population genomics data consists of isolating signatures of natural selection from background noise caused by random drift and gene flow. Analyses of massive amounts of data from many related populations require high-performance algorithms to determine the likelihood of different demographic scenarios that could have shaped the observed neutral single nucleotide polymorphism (SNP) allele frequency spectrum. In many areas of applied mathematics, Fourier Transforms and Spectral Methods are firmly established tools to analyze spectra of signals and model their dynamics as solutions of certain Partial Differential Equations (PDEs). When spectral methods are applicable, they have excellent error properties and are the fastest possible in high dimension; see [15]. In this paper we present an explicit numerical solution, using spectral methods, to the forward Kolmogorov equations for a Wright-Fisher process with migration of K populations, influx of mutations, and multiple population splitting events. PMID:21376069

  15. 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.

  16. 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.

  17. Computational methods for reactive transport modeling: A Gibbs energy minimization approach for multiphase equilibrium calculations

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg

    2016-02-01

    We present a numerical method for multiphase chemical equilibrium calculations based on a Gibbs energy minimization approach. The method can accurately and efficiently determine the stable phase assemblage at equilibrium independently of the type of phases and species that constitute the chemical system. We have successfully applied our chemical equilibrium algorithm in reactive transport simulations to demonstrate its effective use in computationally intensive applications. We used FEniCS to solve the governing partial differential equations of mass transport in porous media using finite element methods in unstructured meshes. Our equilibrium calculations were benchmarked with GEMS3K, the numerical kernel of the geochemical package GEMS. This allowed us to compare our results with a well-established Gibbs energy minimization algorithm, as well as their performance on every mesh node, at every time step of the transport simulation. The benchmark shows that our novel chemical equilibrium algorithm is accurate, robust, and efficient for reactive transport applications, and it is an improvement over the Gibbs energy minimization algorithm used in GEMS3K. The proposed chemical equilibrium method has been implemented in Reaktoro, a unified framework for modeling chemically reactive systems, which is now used as an alternative numerical kernel of GEMS.

  18. [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.

  19. a Proposal for a General Method for Determining Semi-Experimental Equilibrium Structures of Carbon Atom Backbones

    NASA Astrophysics Data System (ADS)

    Craig, Norman C.

    2010-06-01

    Semi-experimental equilibrium structures are determined from ground state rotational constants derived from the analysis of rotational transitions in high-resolution spectra and from the quantum chemical calculation of spectroscopic alphas. In the full application of this method, spectra of numerous isotopic species must be investigated. Most of these isotopic species require specialized synthesis. We now propose focusing on the carbon atoms, for which microwave spectroscopy routinely yields spectra for polar molecules with 13C substitution in natural abundance. Needed spectroscopic alphas can be computed with Gaussian software. Application of the Kraitchman substitution relationships gives Cartesian coordinates for the carbon atoms and thence bond parameters for the carbon backbone. This method will be evaluated with ethylene, 1,1-difluoroethylene, 1,1-difluorocyclopropane, propene, and butadiene. The method will then be applied to cis-hexatriene and the two conformers of glycidol. R. D. Suenram, B. H. Pate, A. Lessari, J. L. Neill, S. Shipman, R. A. Holmes, M. C. Leyden, and N. C. Craig, J. Phys. Chem. A 113, 1864-1868 (2009). A. R. Conrad, N. H. Teumelsan, P. E. Wang, and M. J. Tubergen, J. Phys. Chem. A 114, 336-342 (2010).

  20. Predicting equilibrium vapour pressure isotope effects by using artificial neural networks or multi-linear regression - A quantitative structure property relationship approach.

    PubMed

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

    2015-09-01

    We aim at predicting the effect of structure and isotopic substitutions on the equilibrium vapour pressure isotope effect of various organic compounds (alcohols, acids, alkanes, alkenes and aromatics) at intermediate temperatures. We attempt to explore quantitative structure property relationships by using artificial neural networks (ANN); the multi-layer perceptron (MLP) and compare the performances of it with multi-linear regression (MLR). These approaches are based on the relationship between the molecular structure (organic chain, polar functions, type of functions, type of isotope involved) of the organic compounds, and their equilibrium vapour pressure. A data set of 130 equilibrium vapour pressure isotope effects was used: 112 were used in the training set and the remaining 18 were used for the test/validation dataset. Two sets of descriptors were tested, a set with all the descriptors: number of(12)C, (13)C, (16)O, (18)O, (1)H, (2)H, OH functions, OD functions, CO functions, Connolly Solvent Accessible Surface Area (CSA) and temperature and a reduced set of descriptors. The dependent variable (the output) is the natural logarithm of the ratios of vapour pressures (ln R), expressed as light/heavy as in classical literature. Since the database is rather small, the leave-one-out procedure was used to validate both models. Considering higher determination coefficients and lower error values, it is concluded that the multi-layer perceptron provided better results compared to multi-linear regression. The stepwise regression procedure is a useful tool to reduce the number of descriptors. To our knowledge, a Quantitative Structure Property Relationship (QSPR) approach for isotopic studies is novel.

  1. Predicting equilibrium vapour pressure isotope effects by using artificial neural networks or multi-linear regression - A quantitative structure property relationship approach.

    PubMed

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

    2015-09-01

    We aim at predicting the effect of structure and isotopic substitutions on the equilibrium vapour pressure isotope effect of various organic compounds (alcohols, acids, alkanes, alkenes and aromatics) at intermediate temperatures. We attempt to explore quantitative structure property relationships by using artificial neural networks (ANN); the multi-layer perceptron (MLP) and compare the performances of it with multi-linear regression (MLR). These approaches are based on the relationship between the molecular structure (organic chain, polar functions, type of functions, type of isotope involved) of the organic compounds, and their equilibrium vapour pressure. A data set of 130 equilibrium vapour pressure isotope effects was used: 112 were used in the training set and the remaining 18 were used for the test/validation dataset. Two sets of descriptors were tested, a set with all the descriptors: number of(12)C, (13)C, (16)O, (18)O, (1)H, (2)H, OH functions, OD functions, CO functions, Connolly Solvent Accessible Surface Area (CSA) and temperature and a reduced set of descriptors. The dependent variable (the output) is the natural logarithm of the ratios of vapour pressures (ln R), expressed as light/heavy as in classical literature. Since the database is rather small, the leave-one-out procedure was used to validate both models. Considering higher determination coefficients and lower error values, it is concluded that the multi-layer perceptron provided better results compared to multi-linear regression. The stepwise regression procedure is a useful tool to reduce the number of descriptors. To our knowledge, a Quantitative Structure Property Relationship (QSPR) approach for isotopic studies is novel. PMID:25559176

  2. An experimental study on the effect of carbonic anhydrase on the oxygen isotope exchange kinetics and equilibrium in the carbonic acid system

    NASA Astrophysics Data System (ADS)

    Uchikawa, J.; Zeebe, R. E.

    2011-12-01

    Stable oxygen isotopes of marine biogenic carbonates are often depleted in 18O relative to the values expected for thermodynamic equilibrium with ambient seawater. One possibility is that 18O-depletion in carbonates is kinetically controlled. The kinetic isotope effect associated with the hydration of CO2 results in 18O-depleted HCO3-. If the HCO3- is utilized before re-establishing equilibrium with ambient water under rapid calcification, the 18O-depletion will be recorded in carbonates. But one caveat in this kinetic model is the fact that many marine calcifiers posses carbonic anhydrase, a zinc-bearing enzyme that catalyzes the CO2 hydration reaction. It is expected that this enzyme accelerates 18O-equilibration in the carbonic acid system by facilitating direct oxygen isotope exchange between HCO3- and H2O via CO2 hydration. Clearly this argues against the conceptual framework of the kinetic model. Yet the critical variable here is the effectiveness of the carbonic anhydrase, which is likely to depend on its concentration and the carbonate chemistry of the aqueous medium. It is also hitherto unknown whether the presence of carbonic anhydrase alters the equilibrium oxygen isotope fractionations between dissolved carbonate species and water. We performed a series of quantitative inorganic carbonate precipitation experiments to examine the changes in the oxygen isotope equilibration time as a function of carbonic anhydrase concentrations. We conducted experiments at pH 8.3 and 8.9. These pH values are similar to the average surface ocean pH and the elevated pH levels observed within calcification microenvironments of certain corals and planktonic foraminifera. A summary of our new experimental results will be presented.

  3. Distance, Dialogue and Reflection: Interpersonal Reflective Equilibrium as Method for Professional Ethics Education

    ERIC Educational Resources Information Center

    van den Hoven, Mariëtte; Kole, Jos

    2015-01-01

    The method of reflective equilibrium (RE) is well known within the domain of moral philosophy, but hardly discussed as a method in professional ethics education. We argue that an interpersonal version of RE is very promising for professional ethics education. We offer several arguments to support this claim. The first group of arguments focus on a…

  4. Multigrid method for the equilibrium equations of elasticity using a compact scheme

    NASA Technical Reports Server (NTRS)

    Taasan, S.

    1986-01-01

    A compact difference scheme is derived for treating the equilibrium equations of elasticity. The scheme is inconsistent and unstable. A multigrid method which takes into account these properties is described. The solution of the discrete equations, up to the level of discretization errors, is obtained by this method in just two multigrid cycles.

  5. Impact of the carbon pore size and topology on the equilibrium quantum sieving of hydrogen isotopes at zero coverage and finite pressures.

    PubMed

    Kowalczyk, Piotr; Gauden, Piotr A; Terzyk, Artur P; Furmaniak, Sylwester

    2009-04-01

    Carbonaceous slit-shaped and square-shaped pores efficiently differentiate adsorbed hydrogen isotopes at 77 and 33 K. Extensive path integral Monte Carlo simulations revealed that the square-shaped carbon pores enhanced the selectivity of deuterium over hydrogen in comparison to equivalent slit-shaped carbon pores at zero coverage as well as at finite pressures (i.e. quantum sieving of hydrogen isotopes is pore-topology-dependent). We show that this enhancement of the D(2)/H(2) equilibrium selectivity results from larger localization of hydrogen isotopes in square-shaped pores. The operating pressures for efficient quantum sieving of hydrogen isotopes are strongly dependent on the topology as well as on the size of the carbon pores. However, for both considered carbon pore topologies the highest D(2)/H(2) separation factor is observed at zero-coverage limit. Depending on carbon pore size and topology we predicted monotonic decreasing and non-monotonic shape of the D(2)/H(2) equilibrium selectivity at finite pressures. For both kinds of carbonaceous pores of molecular sizes we predict high compression of hydrogen isotopes at 77 and 33 K (for example, the pore density of compressed hydrogen isotopes at 77 K and 0.25 MPa in a square-shaped carbon pore of size 2.6 Å exceeds 60 mmol cm(-3); for comparison, the liquid density of para-H(2) at 30 K and 30 MPa is 42 mmol cm(-3)). Finally, by direct comparison of simulation results with experimental data it is explained why 'ordinary' carbonaceous materials are not efficient quantum sieves.

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

    PubMed

    Mead, Chris; Johnson, Thomas M

    2010-06-01

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

  7. Study of plasma equilibrium in toroidal fusion devices using mesh-free numerical calculation method

    NASA Astrophysics Data System (ADS)

    Rasouli, C.; Abbasi Davani, F.; Rokrok, B.

    2016-08-01

    Plasma confinement using external magnetic field is one of the successful ways leading to the controlled nuclear fusion. Development and validation of the solution process for plasma equilibrium in the experimental toroidal fusion devices is the main subject of this work. Solution of the nonlinear 2D stationary problem as posed by the Grad-Shafranov equation gives quantitative information about plasma equilibrium inside the vacuum chamber of hot fusion devices. This study suggests solving plasma equilibrium equation which is essential in toroidal nuclear fusion devices, using a mesh-free method in a condition that the plasma boundary is unknown. The Grad-Shafranov equation has been solved numerically by the point interpolation collocation mesh-free method. Important features of this approach include truly mesh free, simple mathematical relationships between points and acceptable precision in comparison with the parametric results. The calculation process has been done by using the regular and irregular nodal distribution and support domains with different points. The relative error between numerical and analytical solution is discussed for several test examples such as small size Damavand tokamak, ITER-like equilibrium, NSTX-like equilibrium, and typical Spheromak.

  8. Three applications of path integrals: equilibrium and kinetic isotope effects, and the temperature dependence of the rate constant of the [1,5] sigmatropic hydrogen shift in (Z)-1,3-pentadiene.

    PubMed

    Zimmermann, Tomáš; Vaníček, Jiří

    2010-11-01

    Recent experiments have confirmed the importance of nuclear quantum effects even in large biomolecules at physiological temperature. Here we describe how the path integral formalism can be used to describe rigorously the nuclear quantum effects on equilibrium and kinetic properties of molecules. Specifically, we explain how path integrals can be employed to evaluate the equilibrium (EIE) and kinetic (KIE) isotope effects, and the temperature dependence of the rate constant. The methodology is applied to the [1,5] sigmatropic hydrogen shift in pentadiene. Both the KIE and the temperature dependence of the rate constant confirm the importance of tunneling and other nuclear quantum effects as well as of the anharmonicity of the potential energy surface. Moreover, previous results on the KIE were improved by using a combination of a high level electronic structure calculation within the harmonic approximation with a path integral anharmonicity correction using a lower level method.

  9. Computational methods for multiphase equilibrium and kinetics calculations for geochemical and reactive transport applications

    NASA Astrophysics Data System (ADS)

    Leal, Allan; Saar, Martin

    2016-04-01

    Computational methods for geochemical and reactive transport modeling are essential for the understanding of many natural and industrial processes. Most of these processes involve several phases and components, and quite often requires chemical equilibrium and kinetics calculations. We present an overview of novel methods for multiphase equilibrium calculations, based on both the Gibbs energy minimization (GEM) approach and on the solution of the law of mass-action (LMA) equations. We also employ kinetics calculations, assuming partial equilibrium (e.g., fluid species in equilibrium while minerals are in disequilibrium) using automatic time stepping to improve simulation efficiency and robustness. These methods are developed specifically for applications that are computationally expensive, such as reactive transport simulations. We show how efficient the new methods are, compared to other algorithms, and how easy it is to use them for geochemical modeling via a simple script language. All methods are available in Reaktoro, a unified open-source framework for modeling chemically reactive systems, which we also briefly describe.

  10. A method for determining the nitrogen isotopic composition of porphyrins.

    PubMed

    Higgins, Meytal B; Robinson, Rebecca S; Casciotti, Karen L; McIlvin, Matthew R; Pearson, Ann

    2009-01-01

    We describe a new method for analysis of the nitrogen isotopic composition of sedimentary porphyrins. This method involves separation and purification of geoporphyrins from sediment samples using liquid chromatography and HPLC, oxidation of the nitrogen within porphyrin-enriched fractions using a two-step process, and isotopic analysis of the resulting nitrate using the denitrifier method. By analysis of these degradation products of chlorophylls, we are able to measure an isotopic signature that reflects the nitrogen utilized by primary producers. The high sensitivity of the denitrifier method allows measurement of small samples that contain low concentrations of porphyrins. Extraction of only 50 nmol of nitrogen (nmol N) allows the following five analyses to be made (each on approximately 10 nmol N): nitrogen concentration, an assessment of potential contamination by nonporphyrin N, and three replicate isotopic measurements. The measured values of delta15N have an average analytical precision of +/-0.5 per thousand (1sigma) and an average contribution from Rayleigh fractionation of 0.7 per thousand from incomplete oxidation of porphyrin N to nitrate. The overall method will enable high-resolution records of delta15N values to be obtained for geological and ecological applications.

  11. Teasing Cellulose Isotopic Signals Apart by Chemical Methods

    NASA Astrophysics Data System (ADS)

    Sternberg, L. D.; Anderson, W. T.; Morrison, K.

    2002-12-01

    The δ18O and δD values of precipitation water correlates with changes in atmospheric circulation patterns and temperature. This has been the basis of many attempts to use fossil tree ring cellulose as a proxy for paleoclimate. Ideally by measuring δ18O and δD values of tree ring cellulose one would infer isotopic composition of water available for plant uptake, which presumably is the least isotopically altered from precipitation. Subsequently, paleo-temperatures or atmospheric circulation patterns at the time of cellulose formation could then be inferred. However, this goal is confounded by isotopic exchange processes occurring in the leaf. Our current understanding of the physiological/biochemical mechanisms operating during the labeling of carbohydrates by water during tree ring cellulose synthesis indicates that the isotopic composition of tree ring cellulose is a mixture of isotopic signals coming from source (CA 35 to 45%) and leaf (CA 55 to 65%) water. The isotopic composition of the latter component is radically modified from that of the original source water by factors such as relative humidity and leaf properties. Here we present a chemical method of derivatizing cellulose to tease these two signals apart. We analyze the isotopic composition of cellulose and its derivative and calculate the δ18O value of the oxygen attached to the second carbon of the glucose moieties in cellulose (2C-OH). A one to one relationship between δ18O values of this oxygen and that of water available for cellulose synthesis in seeds germinated in the presence of water having different δ18O values was observed. Indicating that 2C-OH undergoes complete exchange with water during the synthesis of cellulose from sucrose. This technique can potentially be an analytical tool in paleo-climatic and ecological studies, once the analytical techniques are refined so as to increase precision.

  12. Online Method for Oxygen Triple Isotope Analyses of Nitrate

    NASA Astrophysics Data System (ADS)

    Kaiser, J.; Hastings, M. G.; Houlton, B.; Roeckmann, T.; Sigman, D. M.

    2004-12-01

    Combined 17O/16O and 18O/16O isotope ratio analyses of nitrate in ground and surface waters help to understand the partitioning between atmospheric and terrestrial nitrate sources because only terrestrial nitrate shows mass-dependent relative enrichments in 17O and 18O, whereas atmospheric nitrate displays an anomalous enrichment in 17O. The 17O isotope anomaly of nitrate is therefore a sensitive tracer of fresh water pollution. Furthermore, isotope measurements of atmospheric nitrate in aerosols and precipitation provide insight into the partitioning between atmospheric NOx cycling pathways via ozone or hydroxy/peroxy radicals because only ozone has a significant non-mass dependent enrichment in 17O. Previous methods to analyze the oxygen triple isotope composition of nitrate rely on offline thermal decomposition of AgNO3 amounts in the µ mol range. We have recently developed an online (coupled gas chromatography-mass spectrometry) method that requires two to three orders of magnitude less material to achieve essentially the same analytical precision: 30 nmol of nitrate give a 1σ uncertainty of 1.0 ‰ for the δ ^{18}O value and 0.3 \\permil for the ^{17}O anomaly (\\Delta17O). The method uses a strain of bacterial denitrifiers to convert nitrate to N2O [Casciotti et al., 2002], which is then quantitatively converted to elemental nitrogen and oxygen in a gold furnace at 800° C. Both gases are separated on a molecular sieve capillary column and introduced into the isotope ratio mass spectrometer. There is no significant memory effect, but calibration via nitrate or N2O standards is required for scale normalization. This novel method was used to analyze nitrate isotopes in rain water and streams and, thanks to the low sample size requirements, will also be suitable for ice core samples, which have very low nitrate concentrations. A tight correlation between Δ 17O and δ 18O in rain water was found with a slope of about 0.3 (R2 = 0.86), which reflects the

  13. Semiexperimental equilibrium structure of the lower energy conformer of glycidol by the mixed estimation method.

    PubMed

    Demaison, Jean; Craig, Norman C; Conrad, Andrew R; Tubergen, Michael J; Rudolph, Heinz Dieter

    2012-09-13

    Rotational constants were determined for (18)O-substituted isotopologues of the lower energy conformer of glycidol, which has an intramolecular inner hydrogen bond from the hydroxyl group to the oxirane ring oxygen. Rotational constants were previously determined for the (13)C and the OD species. These rotational constants have been corrected with the rovibrational constants calculated from an ab initio cubic force field. The derived semiexperimental equilibrium rotational constants have been supplemented by carefully chosen structural parameters, including those for hydrogen atoms, from medium level ab initio calculations. The combined data have been used in a weighted least-squares fit to determine an equilibrium structure for the glycidol H-bond inner conformer. This work shows that the mixed estimation method allows us to determine a complete and reliable equilibrium structure for large molecules, even when the rotational constants of a number of isotopologues are unavailable.

  14. RECTIFIED ABSORPTION METHOD FOR THE SEPARATION OF HYDROGEN ISOTOPES

    DOEpatents

    Hunt, C.D.; Hanson, D.N.

    1961-10-17

    A method is described for separating and recovering heavy hydrogen isotopes from gaseous mixtures by multiple stage cyclic absorption and rectification from an approximate solvent. In particular, it is useful for recovering such isoteoes from ammonia feedstock streams containing nitrogen solvent. Modifications of the process ranging from isobaric to isothermal are provided. Certain impurities are tolerated, giving advantages over conventional fractional distillation processes. (AEC)

  15. 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.

  16. Efficient methods and practical guidelines for simulating isotope effects

    NASA Astrophysics Data System (ADS)

    Ceriotti, Michele; Markland, Thomas E.

    2013-01-01

    The shift in chemical equilibria due to isotope substitution is frequently exploited to obtain insight into a wide variety of chemical and physical processes. It is a purely quantum mechanical effect, which can be computed exactly using simulations based on the path integral formalism. Here we discuss how these techniques can be made dramatically more efficient, and how they ultimately outperform quasi-harmonic approximations to treat quantum liquids not only in terms of accuracy, but also in terms of computational cost. To achieve this goal we introduce path integral quantum mechanics estimators based on free energy perturbation, which enable the evaluation of isotope effects using only a single path integral molecular dynamics trajectory of the naturally abundant isotope. We use as an example the calculation of the free energy change associated with H/D and 16O/18O substitutions in liquid water, and of the fractionation of those isotopes between the liquid and the vapor phase. In doing so, we demonstrate and discuss quantitatively the relative benefits of each approach, thereby providing a set of guidelines that should facilitate the choice of the most appropriate method in different, commonly encountered scenarios. The efficiency of the estimators we introduce and the analysis that we perform should in particular facilitate accurate ab initio calculation of isotope effects in condensed phase systems.

  17. Efficient methods and practical guidelines for simulating isotope effects.

    PubMed

    Ceriotti, Michele; Markland, Thomas E

    2013-01-01

    The shift in chemical equilibria due to isotope substitution is frequently exploited to obtain insight into a wide variety of chemical and physical processes. It is a purely quantum mechanical effect, which can be computed exactly using simulations based on the path integral formalism. Here we discuss how these techniques can be made dramatically more efficient, and how they ultimately outperform quasi-harmonic approximations to treat quantum liquids not only in terms of accuracy, but also in terms of computational cost. To achieve this goal we introduce path integral quantum mechanics estimators based on free energy perturbation, which enable the evaluation of isotope effects using only a single path integral molecular dynamics trajectory of the naturally abundant isotope. We use as an example the calculation of the free energy change associated with H/D and (16)O/(18)O substitutions in liquid water, and of the fractionation of those isotopes between the liquid and the vapor phase. In doing so, we demonstrate and discuss quantitatively the relative benefits of each approach, thereby providing a set of guidelines that should facilitate the choice of the most appropriate method in different, commonly encountered scenarios. The efficiency of the estimators we introduce and the analysis that we perform should in particular facilitate accurate ab initio calculation of isotope effects in condensed phase systems. PMID:23298033

  18. Equilibrium vs. kinetic fractionation of oxygen isotopes in two low-temperature travertine-depositing systems with differing hydrodynamic conditions at Baishuitai, Yunnan, SW China

    NASA Astrophysics Data System (ADS)

    Yan, Hao; Sun, Hailong; Liu, Zaihua

    2012-10-01

    In order to understand the behavior of oxygen isotopic fractionation and obtain more reliable paleoclimatic data from surficial travertine deposits, the hydrochemistry, carbonate precipitation rates, and the temporal and spatial variations in δ18O values of the modern travertine in two low-temperature travertine-depositing systems (canal and pool) with differing hydrodynamic conditions at Baishuitai, Yunnan, SW China, were investigated during the warm rainy season (May 24 to November 2) in 2010. It was found that the oxygen isotopic composition of travertine in the two systems showed distinct controlling mechanisms mainly due to different carbonate precipitation rates and water residence times. For the canal system with fast flow, large deviations between the calculated and measured temperatures indicated that travertine precipitated out of isotopic equilibrium. This was due to rapid carbonate precipitation with intense CO2 degassing. δ18Otravertine values and water temperature increased downstream (˜1‰ and 4 °C, respectively) while δ18Owater values remained relatively stable. It was shown that the δ18O values of travertine in the canal system recorded the δ18O values of dissolved carbonates (HCO3-) which also increased along the canal, controlled by Rayleigh-distillation effects. In contrast, in the pools system with slow flow, oxygen isotopic equilibrium between dissolved carbonates (HCO3-) and H2O was achieved and the δ18Otravertine values did not display spatial variations. Calculated water temperatures using the equilibrium fractionation factors of Coplen (2007) were identical to the measured ones, which indicates that travertine in such pools system is suitable for the reconstruction of paleo-precipitating temperatures. Finally, by comparing these two systems we have obtained a simple criterion to determine the suitability of travertine to estimate temperatures - the δ18O value of BaCO3 precipitated from water samples is compared with the

  19. METHOD TO TEST ISOTOPIC SEPARATION EFFICIENCY OF PALLADIUM PACKED COLUMNS

    SciTech Connect

    Heung, L; Gregory Staack, G; James Klein, J; William Jacobs, W

    2007-06-27

    The isotopic effect of palladium has been applied in different ways to separate hydrogen isotopes for many years. At Savannah River Site palladium deposited on kieselguhr (Pd/k) is used in a thermal cycling absorption process (TCAP) to purify tritium for over ten years. The need to design columns for different throughputs and the desire to advance the performance of TCAP created the need to evaluate different column designs and packing materials for their separation efficiency. In this work, columns with variations in length, diameter and metal foam use, were tested using an isotope displacement method. A simple computer model was also developed to calculate the number of theoretical separation stages using the test results. The effects of column diameter, metal foam and gas flow rate were identified.

  20. 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.

  1. Modeling Equilibrium Fe Isotope Fractionation in Fe-Organic Complexes: Implications for the use of Fe Isotopes as a Biomarker and Trends Based on the Properties of Bound Ligands

    NASA Astrophysics Data System (ADS)

    Domagal-Goldman, S.; Kubicki, J. D.

    2006-05-01

    Fe Isotopes have been proposed as a useful tracer of biological and geochemical processes. Key to understanding the effects these various processes have on Fe isotopes is accurate modeling of the reactions responsible for the isotope fractionations. In this study, we examined the theoretical basis for the claims that Fe isotopes can be used as a biomarker. This was done by using molecular orbital/density functional theory (MO/DFT) calculations to predict the equilibrium fractionation of Fe isotopes due to changes in the redox state and the bonding environment of Fe. Specifically, we predicted vibrational frequencies for iron desferrioxamine (Fe-DFOB), iron triscatechol (Fe(cat)3), iron trisoxalate (Fe(ox)3), and hexaaquo iron (Fe(H2O)6) for complexes containing both ferrous (Fe2+) and ferric (Fe3+) iron. Using these vibrational frequencies, we then predicted fractionation factors between these six complexes. The predicted fractionation factors resulting from changes in the redox state of Fe fell in the range 2.5- 3.5‰. The fractionation factors resulting from changes in the bonding environment of Fe ranged from 0.2 to 1.4‰. These results indicate that changes in the bonding strength of Fe ligands are less important to Fe isotope fractionation processes than are changes to the redox state of Fe. The implications for use of Fe as a tracer of biological processes is clear: abiological redox changes must be ruled out in a sample before Fe isotopes are considered as a potential biomarker. Furthermore, the use of Fe isotopes to measure the redox state of the Earths surface environment through time is supported by this work, since changes in the redox state of Fe appear to be the more important driver of isotopic fractionations. In addition to the large differences between redox-driven fractionations and ligand-driven fractionations, we will also show general trends in the demand for heavy Fe isotopes as a function of properties of the bound ligand. This will help the

  2. Combining sources in stable isotope mixing models: alternative methods.

    PubMed

    Phillips, Donald L; Newsome, Seth D; Gregg, Jillian W

    2005-08-01

    Stable isotope mixing models are often used to quantify source contributions to a mixture. Examples include pollution source identification; trophic web studies; analysis of water sources for soils, plants; or water bodies, and many others. A common problem is having too many sources to allow a unique solution. We discuss two alternative procedures for addressing this problem. One option is a priori to combine sources with similar signatures so the number of sources is small enough to provide a unique solution. Aggregation should be considered only when isotopic signatures of clustered sources are not significantly different, and sources are related so the combined source group has some functional significance. For example, in a food web analysis, lumping several species within a trophic guild allows more interpretable results than lumping disparate food sources, even if they have similar isotopic signatures. One result of combining mixing model sources is increased uncertainty of the combined end-member isotopic signatures and consequently the source contribution estimates; this effect can be quantified using the IsoError model (http://www.epa.gov/wed/pages/models/isotopes/isoerror1_04.htm). As an alternative to lumping sources before a mixing analysis, the IsoSource mixing model (http://www.epa.gov/wed/pages/models/isosource/isosource.htm) can be used to find all feasible solutions of source contributions consistent with isotopic mass balance. While ranges of feasible contributions for each individual source can often be quite broad, contributions from functionally related groups of sources can be summed a posteriori, producing a range of solutions for the aggregate source that may be considerably narrower. A paleo-human dietary analysis example illustrates this method, which involves a terrestrial meat food source, a combination of three terrestrial plant foods, and a combination of three marine foods. In this case, a posteriori aggregation of sources allowed

  3. Stable isotope method to measure drug release from nanomedicines.

    PubMed

    Skoczen, Sarah; McNeil, Scott E; Stern, Stephan T

    2015-12-28

    Existing methods to measure nanomedicine drug release in biological matrices are inadequate. A novel drug release method utilizing a stable isotope tracer has been developed. Stable isotope-labeled drug is spiked into plasma containing nanomedicine. The labeled drug equilibrates with plasma components identical to the normoisotopic drug released from the nanomedicine formulation. Therefore, the ultrafilterable fraction of the isotope-labeled drug represents a reliable measure of free normoisotopic drug fraction in plasma, and can be used to calculate nanomedicine encapsulated and unencapsulated drug fractions. To demonstrate the utility of this method, we performed a plasma drug release study with both a fast releasing commercial docetaxel formulation, Taxotere®, and a delayed releasing nanomicellar formulation of a docetaxel prodrug, Procet 8. The instability of the unencapsulated prodrug in plasma allowed us to compare our calculated prodrug release and docetaxel conversion with the actual docetaxel concentration measured directly without fractionation. Drug release estimates for the fast releasing Taxotere formulation demonstrated accuracy deviation and precision (%CV) of <15%. For the controlled release Procet 8 formulation, we calculated a slow release and conversion of the prodrug in rat plasma that was highly correlated with the direct docetaxel measurement (R(2)=0.98). We believe that this method will have tremendous utility in the development and regulatory evaluation of nanomedicines, and aid in determination of generic bioequivalence.

  4. Technical Note: A simple method for vaterite precipitation for isotopic studies: implications for bulk and clumped isotope analysis

    NASA Astrophysics Data System (ADS)

    Kluge, T.; John, C. M.

    2015-06-01

    Calcium carbonate (CaCO3) plays an important role in the natural environment as a major constituent of the skeleton and supporting structure of marine life and has high economic importance as an additive in food, chemicals and medical products. Anhydrous CaCO3 occurs in the three different polymorphs calcite, aragonite and vaterite, whereof calcite is the most abundant and best characterized mineral. In contrast, little is known about the rare polymorph vaterite, in particular with regard to the oxygen isotope fractionation between H2O and the mineral. Synthetic precipitation of vaterite in the laboratory typically involves rapid processes and isotopic non-equilibrium, which excludes isotope studies focused on the characterization of vaterite under equilibrium conditions. Here, we used a new experimental approach that enables vaterite mineral formation from an isotopically equilibrated solution. The solution consists of a ~0.007 mol L-1 CaCO3 solution that is saturated with NaCl at room temperature (up to 6.4 mol L-1). Vaterite precipitated as single phase or major phase (≥94%) in experiments performed between 23 and 91 °C. Only at 80 °C was vaterite a minor phase with a relative abundance of 27%. The high mineral yield per experiment of up to 235 mg relative to the initially dissolved CaCO3 amount of on average 360 mg enables an investigation of the oxygen isotope fractionation between the mineral and water, and the determination of clumped isotope values in vaterite.

  5. A new method for stable lead isotope extraction from seawater.

    PubMed

    Zurbrick, Cheryl M; Gallon, Céline; Flegal, A Russell

    2013-10-24

    A new technique for stable lead (Pb) isotope extraction from seawater is established using Toyopearl AF-Chelate 650M(®) resin (Tosoh Bioscience LLC). This new method is advantageous because it is semi-automated and relatively fast; in addition it introduces a relatively low blank by minimizing the volume of chemicals used in the extraction. Subsequent analyses by HR ICP-MS have a good relative external precision (2σ) of 3.5‰ for (206)Pb/(207)Pb, while analyses by MC-ICP-MS have a better relative external precision of 0.6‰. However, Pb sample concentrations limit MC-ICP-MS analyses to (206)Pb, (207)Pb, and (208)Pb. The method was validated by processing the common Pb isotope reference material NIST SRM-981 and several GEOTRACES intercalibration samples, followed by analyses by HR ICP-MS, all of which showed good agreement with previously reported values.

  6. METHOD FOR PRODUCING ISOTOPIC METHANES AND PARTIALLY HALOGENATED DERIVATIVES THEROF

    DOEpatents

    Frazer, J.W.

    1959-08-18

    A method is given for producing isotopic methanes and/ or partially halogenated derivatives. Lithium hydride, deuteride, or tritide is reacted with a halogenated methane or with a halogenated methane in combination with free halogen. The process is conveniently carried out by passing a halogenated methane preferably at low pressures or in an admixture with an inert gas through a fixed bed of finely divided lithium hydride heated initially to temperatures of 100 to 200 deg C depending upon the halogenated methane used.

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

    NASA Astrophysics Data System (ADS)

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

    2000-10-01

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

  8. An Analytical Investigation of Three General Methods of Calculating Chemical-Equilibrium Compositions

    NASA Technical Reports Server (NTRS)

    Zeleznik, Frank J.; Gordon, Sanford

    1960-01-01

    The Brinkley, Huff, and White methods for chemical-equilibrium calculations were modified and extended in order to permit an analytical comparison. The extended forms of these methods permit condensed species as reaction products, include temperature as a variable in the iteration, and permit arbitrary estimates for the variables. It is analytically shown that the three extended methods can be placed in a form that is independent of components. In this form the Brinkley iteration is identical computationally to the White method, while the modified Huff method differs only'slightly from these two. The convergence rates of the modified Brinkley and White methods are identical; and, further, all three methods are guaranteed to converge and will ultimately converge quadratically. It is concluded that no one of the three methods offers any significant computational advantages over the other two.

  9. A new method of tree xylem water extraction for isotopic analysis

    NASA Astrophysics Data System (ADS)

    Gierke, C.; Newton, B. T.

    2011-12-01

    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.

  10. Method of rapid determination of MHD equilibrium properties with the modified version of the SURFAS code

    SciTech Connect

    Lee, D.K.; Hirshman, S.P.; Okabayashi, M.; Reusch, M.F.; Sun, Y.C.

    1993-09-01

    Rapid determination of MHD eqilibrium properties of tokamak plasmas is carried out by means of an approximation method based on the use of database files. These are computed a priori from MHD equilibrium solutions obtained by performing reconstruction to match experimental measurements, which include motional Stark effect (MSE) data. The procedure carries out a single iteration of Newton`s method to determine the poloidal variation of the toroidal plasma current density in the equilibrium form j{sub {phi}} = {minus}2{pi}({mu}{sub 0}Rp{prime} + FF{prime}/R) by representing p{prime}({psi}) and F({psi})F{prime}({psi}) in series expansions of Chebyshev polynomials. The polynominal expansion coefficients are obtained through a least-squares data fitting process similar to that used in the equilibrium reconstruction. Knowing the current density j{phi} allows the determination of the internal q-profile from the MSE data. This important stability parameter is generally unavailable from a current filament model. Numerical results calculated in this approach are compared with those determined from an accurate solution of the Grad-Shafranov equation, subject to a similar set of magnetic and pressure measurement constraints.

  11. An approximate method for calculating composition of the non-equilibrium explosion products of hydrocarbons and oxygen

    NASA Astrophysics Data System (ADS)

    Shargatov, V. A.; Gubin, S. A.; Okunev, D. Yu

    2016-09-01

    We develop a method for calculating the changes in composition of the explosion products in the case where the complete chemical equilibrium is absent but the bimolecular reactions are in quasi-equilibrium with the exception bimolecular reactions with one of the components of the mixture. We investigate the possibility of using the method of "quasiequilibrium" for mixtures of hydrocarbons and oxygen. The method is based on the assumption of the existence of the partial chemical equilibrium in the explosion products. Without significant loss of accuracy to the solution of stiff differential equations detailed kinetic mechanism can be replaced by one or two differential equation and a system of algebraic equations. This method is always consistent with the detailed mechanism and can be used separately or in conjunction with the solution of a stiff system for chemically non-equilibrium mixtures replacing it when bimolecular reactions are near to equilibrium.

  12. Quantification of metabotropic glutamate subtype 5 receptors in brain by an equilibrium method using 18F-SP203

    PubMed Central

    Kimura, Yasuyuki; Siméon, Fabrice G.; Zoghbi, Sami S.; Zhang, Yi; Hatazawa, Jun; Pike, Victor W.; Innis, Robert B.; Fujita, Masahiro

    2011-01-01

    A new PET ligand, 3-fluoro-5-(2-(2-18F-(fluoromethyl)-thiazol-4-yl)ethynyl)benzonitrile (18F-SP203) can quantify metabotropic glutamate subtype 5 receptors (mGluR5) in human brain by a bolus injection and kinetic modeling. As an alternative approach to a bolus injection, binding can simply be measured as a ratio of tissue to metabolite-corrected plasma at a single time point under equilibrium conditions achieved by administering the radioligand with a bolus injection followed by a constant infusion. The purpose of this study was to validate the equilibrium method as an alternative to the standard kinetic method for measuring 18F-SP203 binding in brain. Nine healthy subjects were injected with 18F-SP203 using a bolus plus constant infusion for 300 minutes. A single ratio of bolus-to-constant infusion (the activity of bolus equaled to that of infusion over 219 minutes) was applied to all subjects to achieve equilibrium in approximately 120 minutes. As a measure of ligand binding, we compared total distribution volume (VT) calculated by the equilibrium and kinetic methods in each scan. The equilibrium method calculated VT by the ratio of radioactivity in brain to the concentration of 18 F-SP203 in arterial plasma at 120 minutes, and the kinetic method calculated VT by a two-tissue compartment model using brain and plasma dynamic data from 0 to 120 minutes. VT obtained via the equilibrium method was highly correlated with VT obtained via kinetic modeling. Inter-subject variability of VT obtained via the equilibrium method was slightly smaller than VT obtained via the kinetic method. VT obtained via the equilibrium method was ~10% higher than VT obtained via the kinetic method, indicating a small difference between the measurements. Taken together, the results of this study show that using the equilibrium method is an acceptable alternative to the standard kinetic method when using 18F-SP203 to measure mGluR5. Although small differences in the measurements obtained via

  13. Quantification of metabotropic glutamate subtype 5 receptors in the brain by an equilibrium method using 18F-SP203.

    PubMed

    Kimura, Yasuyuki; Siméon, Fabrice G; Zoghbi, Sami S; Zhang, Yi; Hatazawa, Jun; Pike, Victor W; Innis, Robert B; Fujita, Masahiro

    2012-02-01

    A new PET ligand, 3-fluoro-5-(2-(2-(18)F-(fluoromethyl)-thiazol-4-yl)ethynyl)benzonitrile (18F-SP203) can quantify metabotropic glutamate subtype 5 receptors (mGluR5) in human brain by a bolus injection and kinetic modeling. As an alternative approach to a bolus injection, binding can simply be measured as a ratio of tissue to metabolite-corrected plasma at a single time point under equilibrium conditions achieved by administering the radioligand with a bolus injection followed by a constant infusion. The purpose of this study was to validate the equilibrium method as an alternative to the standard kinetic method for measuring 18F-SP203 binding in the brain. Nine healthy subjects were injected with 18F-SP203 using a bolus plus constant infusion for 300 min. A single ratio of bolus-to-constant infusion (the activity of bolus equaled to that of infusion over 219 min) was applied to all subjects to achieve equilibrium in approximately 120 min. As a measure of ligand binding, we compared total distribution volume (VT) calculated by the equilibrium and kinetic methods in each scan. The equilibrium method calculated VT by the ratio of radioactivity in the brain to the concentration of 18F-SP203 in arterial plasma at 120 min, and the kinetic method calculated VT by a two-tissue compartment model using brain and plasma dynamic data from 0 to 120 min. VT obtained via the equilibrium method was highly correlated with VT obtained via kinetic modeling. Inter-subject variability of VT obtained via the equilibrium method was slightly smaller than VT obtained via the kinetic method. VT obtained via the equilibrium method was ~10% higher than VT obtained via the kinetic method, indicating a small difference between the measurements. Taken together, the results of this study show that using the equilibrium method is an acceptable alternative to the standard kinetic method when using 18F-SP203 to measure mGluR5. Although small differences in the measurements obtained via the

  14. Prospects of lithium enrichment on 7Li isotope by method of controlled ions electro-migration

    NASA Astrophysics Data System (ADS)

    Martoyan, G. A.; Kalugin, M. M.; Gabrielyan, A. V.; Martoyan, A. G.

    2016-01-01

    This paper deals with a new electro-membrane method of enrichment of 7Li isotope. The data are presented on the importance and application fields regarding the use of 7Li isotopes. Existing methods and criteria of separation of lithium isotopes are discussed. The principle of new technology, regimes of enrichment experiments, and analysis details of obtained products are briefly described.

  15. Thermodynamic equilibrium solubility measurements in simulated fluids by 96-well plate method in early drug discovery.

    PubMed

    Bharate, Sonali S; Vishwakarma, Ram A

    2015-04-01

    An early prediction of solubility in physiological media (PBS, SGF and SIF) is useful to predict qualitatively bioavailability and absorption of lead candidates. Despite of the availability of multiple solubility estimation methods, none of the reported method involves simplified fixed protocol for diverse set of compounds. Therefore, a simple and medium-throughput solubility estimation protocol is highly desirable during lead optimization stage. The present work introduces a rapid method for assessment of thermodynamic equilibrium solubility of compounds in aqueous media using 96-well microplate. The developed protocol is straightforward to set up and takes advantage of the sensitivity of UV spectroscopy. The compound, in stock solution in methanol, is introduced in microgram quantities into microplate wells followed by drying at an ambient temperature. Microplates were shaken upon addition of test media and the supernatant was analyzed by UV method. A plot of absorbance versus concentration of a sample provides saturation point, which is thermodynamic equilibrium solubility of a sample. The established protocol was validated using a large panel of commercially available drugs and with conventional miniaturized shake flask method (r(2)>0.84). Additionally, the statistically significant QSPR models were established using experimental solubility values of 52 compounds.

  16. The mass dependent and independent equilibrium fractionation of stable mercury isotopes during laboratory synthesis of metacinnabar and other mercury-bearing phases

    NASA Astrophysics Data System (ADS)

    Smith, R. S.; Wiederhold, J. G.; Bourdon, B.; Kretzschmar, R.

    2010-12-01

    that precipitates created from the Hg-nitrate had a Hg:S stoichiometry greater than 1:1 suggesting the formation of mixed Hg-S-nitrate phases. In contrast, the stoichiometry of the precipitates from the Hg-acetate experiments was close to 1:1. XRD analysis of the precipitates from the Hg-acetate system confirmed that metacinnabar was formed. The similarity of the concentration and isotope results obtained from the two time steps suggests that reactant and product were in equilibrium for both Hg systems. In all experimental samples, the precipitates were isotopically lighter than the corresponding supernatants. Small negative MIF anomalies for the odd mass Hg isotopes were found in the supernatants of the Hg-acetate. The observed MDF and MIF signatures can be explained by the change from Hg-O to Hg-S coordination during precipitation and are consistent in direction and magnitude with the predictions for equilibrium isotope effects caused by a combination of MDF and nuclear volume fractionation (Wiederhold et al., ES&T, 2010, 44:4191-4197). Additional experiments will be performed to confirm these findings.

  17. 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.

  18. A refined method for calculating paleotemperatures from linear correlations in bamboo coral carbon and oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Saenger, Casey; Watkins, James M.

    2016-06-01

    Bamboo corals represent an emerging paleoclimate archive with the potential to record variability at intermediate depths throughout much of the global ocean. Realizing this potential has been complicated by biologically mediated vital effects, which are evident in linear correlations of skeletal carbon (δ13C) and oxygen (δ18O) isotope composition. Previous efforts to develop a bamboo coral δ18O paleothermometer by accounting for such vital effects have not been completely successful as they still rely on empirical calibrations that are offset from the temperature dependence of abiogenic experiments. Here we describe an approach that better corrects for bamboo coral vital effects and allows paleotemperatures to be calculated directly from the abiogenic temperature dependence. The success of the method lies in calculating apparent equilibrium carbon and oxygen isotope fractionation at the temperature, pH, and growth rate of each coral, as well as in the use of model II regressions. Rigorous propagation of uncertainty suggests typical errors of ±2-3°C, but in select cases errors as low as ±0.65°C can be achieved for densely sampled and strongly correlated data sets. This lower limit approaches the value attributed to uncertainty in pH and growth rate estimates alone, as predicted by a series of pseudoproxy experiments. The incorporation of isotopically light metabolic CO2 appears to be negligible in most Pacific corals, but may be significant in Atlantic specimens, potentially requiring an additional correction. The success of the method therefore hinges on how well complex environmental systems and biomineralization strategies are constrained, with the most reliable temperatures occurring when calcifying fluid pH, growth rate, and incorporation of metabolic carbon into skeletal calcite are constrained using multiple geochemical proxies.

  19. Analysis of Price Equilibriums in the Aspen Economic Model under Various Purchasing Methods

    SciTech Connect

    SLEPOY, NATASHA; PRYOR, RICHARD J.

    2002-11-01

    Aspen, a powerful economic modeling tool that uses agent modeling and genetic algorithms, can accurately simulate the economy. In it, individuals are hired by firms to produce a good that households then purchase. The firms decide what price to charge for this good, and based on that price, the households determine which firm to purchase from. We will attempt to discover the Nash Equilibrium price found in this model under two different methods of determining how many orders each firm receives. To keep it simple, we will assume there are only two firms in our model, and that these firms compete for the sale of one identical good.

  20. Methods for separating medical isotopes using ionic liquids

    DOEpatents

    Luo, Huimin; Boll, Rose Ann; Bell, Jason Richard; Dai, Sheng

    2014-10-21

    A method for extracting a radioisotope from an aqueous solution, the method comprising: a) intimately mixing a non-chelating ionic liquid with the aqueous solution to transfer at least a portion of said radioisotope to said non-chelating ionic liquid; and b) separating the non-chelating ionic liquid from the aqueous solution. In preferred embodiments, the method achieves an extraction efficiency of at least 80%, or a separation factor of at least 1.times.10.sup.4 when more than one radioisotope is included in the aqueous solution. In particular embodiments, the method is applied to the separation of medical isotopes pairs, such as Th from Ac (Th-229/Ac-225, Ac-227/Th-227), or Ra from Ac (Ac-225 and Ra-225, Ac-227 and Ra-223), or Ra from Th (Th-227 and Ra-223, Th-229 and Ra-225).

  1. Evaluation of soil water stable isotope analysis by H2O(liquid)-H2O(vapor) equilibration method

    NASA Astrophysics Data System (ADS)

    Gralher, Benjamin; Stumpp, Christine

    2014-05-01

    Environmental tracers like stable isotopes of water (δ18O, δ2H) have proven to be valuable tools to study water flow and transport processes in soils. Recently, a new technique for soil water isotope analysis has been developed that employs a vapor phase being in isothermal equilibrium with the liquid phase of interest. This has increased the potential application of water stable isotopes in unsaturated zone studies as it supersedes laborious extraction of soil water. However, uncertainties of analysis and influencing factors need to be considered. Therefore, the objective of this study was to evaluate different methodologies of analysing stable isotopes in soil water in order to reduce measurement uncertainty. The methodologies included different preparation procedures of soil cores for equilibration of vapor and soil water as well as raw data correction. Two different inflatable sample containers (freezer bags, bags containing a metal layer) and equilibration atmospheres (N2, dry air) were tested. The results showed that uncertainties for δ18O were higher compared to δ2H that cannot be attributed to any specific detail of the processing routine. Particularly, soil samples with high contents of organic matter showed an apparent isotope enrichment which is indicative for fractionation due to evaporation. However, comparison of water samples obtained from suction cups with the local meteoric water line indicated negligible fractionation processes in the investigated soils. Therefore, a method was developed to correct the raw data reducing the uncertainties of the analysis.. We conclude that the evaluated method is advantageous over traditional methods regarding simplicity, resource requirements and sample throughput but careful consideration needs to be made regarding sample handling and data processing. Thus, stable isotopes of water are still a good tool to determine water flow and transport processes in the unsaturated zone.

  2. Meshless Method for Solving Fixed Boundary Problem of Axisymmetric Plasma Equilibrium

    NASA Astrophysics Data System (ADS)

    Imazawa, Ryota; Kawano, Yasunori; Itami, Kiyoshi

    2013-10-01

    This study is to solve Grad-Shafranov (GS) equation with the fixed plasma boundary by utilizing the meshless method for the first time. The previous studies have utilized the finite element method (FEM) to solve the equilibrium inside the fixed separatrix. In order to avoid the difficulty of FEM (e.g. mesh problem, difficulty of coding, expensive calculation cost, etc.), this study proposes the new method to apply the meshless methods, especially RBF-MFS and Kansa's method to inhomogeneous and nonlinear partial differential equations (PDE). Although the RBF-MFS and Kansa's method are applicable to the inhomogeneous PDE, the application of these methods to the GS equation is not straight-forward. Since the current profile is usually parameterized by the normalized poloidal flux, the inhomogeneous term of the GS equation contains the normalized poloidal flux, not just a poloidal flux. This is the difficulty for solving the GS equation. Accuracy and calculation time of the meshless method and FEM are compared in the condition of the same total number of nodes. The results show that the error of magnetic field obtained by the meshless methods is one hundredth of that by FEM and that the calculation time of the meshless method is one tenth of that of FEM. Moreover, this study shows that the meshless methods can be easily accelerated by parallel computing.

  3. Kinetic isotope effects calculated with the instanton method.

    PubMed

    Meisner, Jan; Rommel, Judith B; Kästner, Johannes

    2011-12-01

    The ring-opening reaction of the cyclopropylcarbinyl radical proceeds via heavy-atom tunneling at low temperature. We used instanton theory to calculate tunneling rates and kinetic isotope effects with on-the-fly calculation of energies by density functional theory (B3LYP). The accuracy was verified by explicitly correlated coupled-cluster calculations (UCCSD(T)-F12). At cryogenic temperatures, we found protium/deuterium KIEs up to 13 and inverse KIEs down to 0.2. We also studied an intramolecular tautomerization reaction. A simple and computationally efficient method is proposed to calculate KIEs with the instanton method: the instanton path is assumed to be independent of the atomic masses. This results in surprisingly good estimates of the KIEs for the cyclopropylcarbinyl radical and for the secondary KIEs of the tautomerization. Challenges and capabilities of the instanton method for calculating KIEs are discussed.

  4. Rotational spectra of rare isotopic species of fluoroiodomethane: determination of the equilibrium structure from rotational spectroscopy and quantum-chemical calculations.

    PubMed

    Puzzarini, Cristina; Cazzoli, Gabriele; López, Juan Carlos; Alonso, José Luis; Baldacci, Agostino; Baldan, Alessandro; Stopkowicz, Stella; Cheng, Lan; Gauss, Jürgen

    2012-07-14

    Supported by accurate quantum-chemical calculations, the rotational spectra of the mono- and bi-deuterated species of fluoroiodomethane, CHDFI and CD(2)FI, as well as of the (13)C-containing species, (13)CH(2)FI, were recorded for the first time. Three different spectrometers were employed, a Fourier-transform microwave spectrometer, a millimeter/submillimter-wave spectrometer, and a THz spectrometer, thus allowing to record a huge portion of the rotational spectrum, from 5 GHz up to 1.05 THz, and to accurately determine the ground-state rotational and centrifugal-distortion constants. Sub-Doppler measurements allowed to resolve the hyperfine structure of the rotational spectrum and to determine the complete iodine quadrupole-coupling tensor as well as the diagonal elements of the iodine spin-rotation tensor. The present investigation of rare isotopic species of CH(2)FI together with the results previously obtained for the main isotopologue [C. Puzzarini, G. Cazzoli, J. C. López, J. L. Alonso, A. Baldacci, A. Baldan, S. Stopkowicz, L. Cheng, and J. Gauss, J. Chem. Phys. 134, 174312 (2011); G. Cazzoli, A. Baldacci, A. Baldan, and C. Puzzarini, Mol. Phys. 109, 2245 (2011)] enabled us to derive a semi-experimental equilibrium structure for fluoroiodomethane by means of a least-squares fit procedure using the available experimental ground-state rotational constants together with computed vibrational corrections. Problems related to the missing isotopic substitution of fluorine and iodine were overcome thanks to the availability of an accurate theoretical equilibrium geometry (computed at the coupled-cluster singles and doubles level augmented by a perturbative treatment of triple excitations).

  5. Rotational spectra of rare isotopic species of fluoroiodomethane: Determination of the equilibrium structure from rotational spectroscopy and quantum-chemical calculations

    NASA Astrophysics Data System (ADS)

    Puzzarini, Cristina; Cazzoli, Gabriele; López, Juan Carlos; Alonso, José Luis; Baldacci, Agostino; Baldan, Alessandro; Stopkowicz, Stella; Cheng, Lan; Gauss, Jürgen

    2012-07-01

    Supported by accurate quantum-chemical calculations, the rotational spectra of the mono- and bi-deuterated species of fluoroiodomethane, CHDFI and CD2FI, as well as of the 13C-containing species, 13CH2FI, were recorded for the first time. Three different spectrometers were employed, a Fourier-transform microwave spectrometer, a millimeter/submillimter-wave spectrometer, and a THz spectrometer, thus allowing to record a huge portion of the rotational spectrum, from 5 GHz up to 1.05 THz, and to accurately determine the ground-state rotational and centrifugal-distortion constants. Sub-Doppler measurements allowed to resolve the hyperfine structure of the rotational spectrum and to determine the complete iodine quadrupole-coupling tensor as well as the diagonal elements of the iodine spin-rotation tensor. The present investigation of rare isotopic species of CH2FI together with the results previously obtained for the main isotopologue [C. Puzzarini, G. Cazzoli, J. C. López, J. L. Alonso, A. Baldacci, A. Baldan, S. Stopkowicz, L. Cheng, and J. Gauss, J. Chem. Phys. 134, 174312 (2011);, 10.1063/1.3583498 G. Cazzoli, A. Baldacci, A. Baldan, and C. Puzzarini, Mol. Phys. 109, 2245 (2011)], 10.1080/00268976.2011.609142 enabled us to derive a semi-experimental equilibrium structure for fluoroiodomethane by means of a least-squares fit procedure using the available experimental ground-state rotational constants together with computed vibrational corrections. Problems related to the missing isotopic substitution of fluorine and iodine were overcome thanks to the availability of an accurate theoretical equilibrium geometry (computed at the coupled-cluster singles and doubles level augmented by a perturbative treatment of triple excitations).

  6. Using (18)O/(16)O exchange to probe an equilibrium space-charge layer at the surface of a crystalline oxide: method and application.

    PubMed

    De Souza, Roger A; Martin, Manfred

    2008-05-01

    The use of an (18)O/(16)O exchange experiment as a means for probing surface space-charge layers in oxides is examined theoretically and experimentally. On the basis of a theoretical treatment, isotope penetration profiles are calculated for (18)O/(16)O exchange across a gas-solid interface and subsequent diffusion of the labelled isotope through an equilibrium space-charge layer depleted of mobile oxygen vacancies and into a homogeneous bulk phase. Profiles calculated for a range of conditions all have a characteristic shape: a sharp drop in isotope fraction close to the surface followed by a normal bulk diffusion profile. Experimental (18)O profiles in an exchanged (001) oriented single crystal of Fe-doped SrTiO(3) were measured by time-of-flight secondary ion mass spectrometry (ToF-SIMS). By extracting the space-charge potential from such profiles, we demonstrate that this method allows the spatially resolved characterization of space-charge layers at the surfaces of crystalline oxides under thermodynamically well-defined conditions.

  7. Non-equilibrium simulation of CH4 production through the depressurization method from gas hydrate reservoirs

    NASA Astrophysics Data System (ADS)

    Qorbani, Khadijeh; Kvamme, Bjørn

    2016-04-01

    as non-equilibrium processes under local constraint of mass and heat fluxes. In this work, we have extended RCB by adding another route for dissociation or reformation of CH4-hydrate towards CH4 into the aqueous phase and water. CH4-hydrate formation and dissociation is resolved by looking at supersaturation and undersaturation with respect to thermodynamics variables. Hydrate instability due to undersaturation of CH4 in the contacting water phase is also considered. A complete non-equilibrium thermodynamic package, developed in-house, was combined with RCB to account for competing phase transitions by considering the minimization of Gibb's free energy. The energy differences were calculated from variations in chemical potentials of hydrate and hydrate formers. Mass transport, heat transport and non-equilibrium thermodynamic effects were implemented through classical nucleation theory to model the kinetic rate of hydrate phase transitions. To illustrate our implementations we ran simulations covering time-spans in the order of hundred years. CH4 production was modelled using the depressurization method, where we employed the Messoyakha field data. We discuss our implementations, as well as results obtained from simulations utilizing our modifications.

  8. Non-equilibrium Green function method: theory and application in simulation of nanometer electronic devices

    NASA Astrophysics Data System (ADS)

    Do, Van-Nam

    2014-09-01

    We review fundamental aspects of the non-equilibrium Green function method in the simulation of nanometer electronic devices. The method is implemented into our recently developed computer package OPEDEVS to investigate transport properties of electrons in nano-scale devices and low-dimensional materials. Concretely, we present the definition of the four real-time Green functions, the retarded, advanced, lesser and greater functions. Basic relations among these functions and their equations of motion are also presented in detail as the basis for the performance of analytical and numerical calculations. In particular, we review in detail two recursive algorithms, which are implemented in OPEDEVS to solve the Green functions defined in finite-size opened systems and in the surface layer of semi-infinite homogeneous ones. Operation of the package is then illustrated through the simulation of the transport characteristics of a typical semiconductor device structure, the resonant tunneling diodes.

  9. Air-snow transfer of nitrate on the East Antarctic Plateau - Part 1: Isotopic evidence for a photolytically driven dynamic equilibrium

    NASA Astrophysics Data System (ADS)

    Erbland, J.; Vicars, W. C.; Savarino, J.; Morin, S.; Frey, M. M.; Frosini, D.; Vince, E.; Martins, J. M. F.

    2012-10-01

    Here we report the measurement of the comprehensive isotopic composition (δ15N, Δ17O and δ18O) of nitrate at the air-snow interface at Dome C, Antarctica (DC, 75° 06' S, 123° 19' E) and in snow pits along a transect across the East Antarctic Ice Sheet (EAIS) between 66° S and 78° S. For each of the East Antarctic snow pits in most of which nitrate loss is observed, we derive apparent fractionation constants associated with this loss as well as asymptotic values of nitrate concentration and isotopic ratios below the photic zone. Nitrate collected from snow pits on the plateau have average apparent fractionation constants of (-59±10)‰, (+2.0±1.0)‰ and (+8.7±2.4)‰, for δ15N, Δ17O and δ18O, respectively. In contrast, snow pits sampled on the coast show distinct isotopic signatures with average apparent fractionation constants of (-16±14)‰, (-0.2±1.5)‰ and (+3.1±5.8)‰, for δ15N, Δ17O and δ18O, respectively. From a lab experiment carried out at DC in parallel to the field investigations, we find that the 15N/14N fractionation associated with the physical release of nitrate is (-8.5±2.5)‰, a value significantly different from the modelled estimate previously found for photolysis (-48‰, Frey et al., 2009) when assuming a Rayleigh-type process. Our observations corroborate that photolysis is the dominant nitrate loss process on the East Antarctic Plateau, while on the coast the loss is less pronounced and could involve both physical release and photochemical processes. Year-round isotopic measurements at DC show a close relationship between the Δ17O of atmospheric nitrate and Δ17O of nitrate in skin layer snow, suggesting a photolytically-driven isotopic equilibrium imposed by nitrate recycling at this interface. The 3-4 weeks shift observed for nitrate concentration in these two compartments may be explained by the different sizes of the nitrate reservoirs and by deposition from the atmosphere to the snow. Atmospheric nitrate

  10. 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.

  11. 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.

  12. The invariant constrained equilibrium edge preimage curve method for the dimension reduction of chemical kinetics

    NASA Astrophysics Data System (ADS)

    Ren, Zhuyin; Pope, Stephen B.; Vladimirsky, Alexander; Guckenheimer, John M.

    2006-03-01

    This work addresses the construction and use of low-dimensional invariant manifolds to simplify complex chemical kinetics. Typically, chemical kinetic systems have a wide range of time scales. As a consequence, reaction trajectories rapidly approach a hierarchy of attracting manifolds of decreasing dimension in the full composition space. In previous research, several different methods have been proposed to identify these low-dimensional attracting manifolds. Here we propose a new method based on an invariant constrained equilibrium edge (ICE) manifold. This manifold (of dimension nr) is generated by the reaction trajectories emanating from its (nr-1)-dimensional edge, on which the composition is in a constrained equilibrium state. A reasonable choice of the nr represented variables (e.g., nr "major" species) ensures that there exists a unique point on the ICE manifold corresponding to each realizable value of the represented variables. The process of identifying this point is referred to as species reconstruction. A second contribution of this work is a local method of species reconstruction, called ICE-PIC, which is based on the ICE manifold and uses preimage curves (PICs). The ICE-PIC method is local in the sense that species reconstruction can be performed without generating the whole of the manifold (or a significant portion thereof). The ICE-PIC method is the first approach that locally determines points on a low-dimensional invariant manifold, and its application to high-dimensional chemical systems is straightforward. The "inputs" to the method are the detailed kinetic mechanism and the chosen reduced representation (e.g., some major species). The ICE-PIC method is illustrated and demonstrated using an idealized H2/O system with six chemical species. It is then tested and compared to three other dimension-reduction methods for the test case of a one-dimensional premixed laminar flame of stoichiometric hydrogen/air, which is described by a detailed mechanism

  13. Application of the non-equilibrium statistical operator method (NESOM) to dissipation atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Mo, M. Y.; Kantorovich, L.

    2001-02-01

    We apply the non-equilibrium statistical operator method to non-contact atomic force microscopy, considering explicitly the statistical effects of (classical) vibrations of surface atoms and associated energy transfer from the tip to the surface. We derive several, physically and mathematically equivalent, forms of the equation of motion for the tip, each containing a friction term due to the so-called intrinsic mechanism of energy dissipation first suggested by Gauthier and Tsukada. Our exact treatment supports the results of some earlier work which were all approximate. We also demonstrate, using the same theory, that the distribution function of the tip in the coordinate-momentum phase subspace is governed by the Fokker-Planck equation and should be considered as strongly peaked around the exact values t and t of the momentum and the position of the tip, respectively.

  14. Isotope-ratio-monitoring gas chromatography-mass spectrometry: methods for isotopic calibration

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

    In trial analyses of a series of n-alkanes, precise determinations of 13C contents were based on isotopic standards introduced by five different techniques and results were compared. Specifically, organic-compound standards were coinjected with the analytes and carried through chromatography and combustion with them; or CO2 was supplied from a conventional inlet and mixed with the analyte in the ion source, or CO2 was supplied from an auxiliary mixing volume and transmitted to the source without interruption of the analyte stream. Additionally, two techniques were investigated in which the analyte stream was diverted and CO2 standards were placed on a near-zero background. All methods provided accurate results. Where applicable, methods not involving interruption of the analyte stream provided the highest performance (sigma = 0.00006 at.% 13C or 0.06% for 250 pmol C as CO2 reaching the ion source), but great care was required. Techniques involving diversion of the analyte stream were immune to interference from coeluting sample components and still provided high precision (0.0001 < or = sigma < or = 0.0002 at.% or 0.1 < or = sigma < or = 0.2%).

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

    SciTech Connect

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

    2013-07-02

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

  16. A moving mesh finite difference method for equilibrium radiation diffusion equations

    NASA Astrophysics Data System (ADS)

    Yang, Xiaobo; Huang, Weizhang; Qiu, Jianxian

    2015-10-01

    An efficient moving mesh finite difference method is developed for the numerical solution of equilibrium radiation diffusion equations in two dimensions. The method is based on the moving mesh partial differential equation approach and moves the mesh continuously in time using a system of meshing partial differential equations. The mesh adaptation is controlled through a Hessian-based monitor function and the so-called equidistribution and alignment principles. Several challenging issues in the numerical solution are addressed. Particularly, the radiation diffusion coefficient depends on the energy density highly nonlinearly. This nonlinearity is treated using a predictor-corrector and lagged diffusion strategy. Moreover, the nonnegativity of the energy density is maintained using a cutoff method which has been known in literature to retain the accuracy and convergence order of finite difference approximation for parabolic equations. Numerical examples with multi-material, multiple spot concentration situations are presented. Numerical results show that the method works well for radiation diffusion equations and can produce numerical solutions of good accuracy. It is also shown that a two-level mesh movement strategy can significantly improve the efficiency of the computation.

  17. A moving mesh finite difference method for equilibrium radiation diffusion equations

    SciTech Connect

    Yang, Xiaobo; Huang, Weizhang; Qiu, Jianxian

    2015-10-01

    An efficient moving mesh finite difference method is developed for the numerical solution of equilibrium radiation diffusion equations in two dimensions. The method is based on the moving mesh partial differential equation approach and moves the mesh continuously in time using a system of meshing partial differential equations. The mesh adaptation is controlled through a Hessian-based monitor function and the so-called equidistribution and alignment principles. Several challenging issues in the numerical solution are addressed. Particularly, the radiation diffusion coefficient depends on the energy density highly nonlinearly. This nonlinearity is treated using a predictor–corrector and lagged diffusion strategy. Moreover, the nonnegativity of the energy density is maintained using a cutoff method which has been known in literature to retain the accuracy and convergence order of finite difference approximation for parabolic equations. Numerical examples with multi-material, multiple spot concentration situations are presented. Numerical results show that the method works well for radiation diffusion equations and can produce numerical solutions of good accuracy. It is also shown that a two-level mesh movement strategy can significantly improve the efficiency of the computation.

  18. General methods for sensitivity analysis of equilibrium dynamics in patch occupancy models

    USGS Publications Warehouse

    Miller, David A.W.

    2012-01-01

    Sensitivity analysis is a useful tool for the study of ecological models that has many potential applications for patch occupancy modeling. Drawing from the rich foundation of existing methods for Markov chain models, I demonstrate new methods for sensitivity analysis of the equilibrium state dynamics of occupancy models. Estimates from three previous studies are used to illustrate the utility of the sensitivity calculations: a joint occupancy model for a prey species, its predators, and habitat used by both; occurrence dynamics from a well-known metapopulation study of three butterfly species; and Golden Eagle occupancy and reproductive dynamics. I show how to deal efficiently with multistate models and how to calculate sensitivities involving derived state variables and lower-level parameters. In addition, I extend methods to incorporate environmental variation by allowing for spatial and temporal variability in transition probabilities. The approach used here is concise and general and can fully account for environmental variability in transition parameters. The methods can be used to improve inferences in occupancy studies by quantifying the effects of underlying parameters, aiding prediction of future system states, and identifying priorities for sampling effort.

  19. General methods for sensitivity analysis of equilibrium dynamics in patch occupancy models.

    PubMed

    Miller, David A W

    2012-05-01

    Sensitivity analysis is a useful tool for the study of ecological models that has many potential applications for patch occupancy modeling. Drawing from the rich foundation of existing methods for Markov chain models, I demonstrate new methods for sensitivity analysis of the equilibrium state dynamics of occupancy models. Estimates from three previous studies are used to illustrate the utility of the sensitivity calculations: a joint occupancy model for a prey species, its predators, and habitat used by both; occurrence dynamics from a well-known metapopulation study of three butterfly species; and Golden Eagle occupancy and reproductive dynamics. I show how to deal efficiently with multistate models and how to calculate sensitivities involving derived state variables and lower-level parameters. In addition, I extend methods to incorporate environmental variation by allowing for spatial and temporal variability in transition probabilities. The approach used here is concise and general and can fully account for environmental variability in transition parameters. The methods can be used to improve inferences in occupancy studies by quantifying the effects of underlying parameters, aiding prediction of future system states, and identifying priorities for sampling effort. PMID:22764506

  20. Non-Condon equilibrium Fermi's golden rule electronic transition rate constants via the linearized semiclassical method

    NASA Astrophysics Data System (ADS)

    Sun, Xiang; Geva, Eitan

    2016-06-01

    In this paper, we test the accuracy of the linearized semiclassical (LSC) expression for the equilibrium Fermi's golden rule rate constant for electronic transitions in the presence of non-Condon effects. We do so by performing a comparison with the exact quantum-mechanical result for a model where the donor and acceptor potential energy surfaces are parabolic and identical except for shifts in the equilibrium energy and geometry, and the coupling between them is linear in the nuclear coordinates. Since non-Condon effects may or may not give rise to conical intersections, both possibilities are examined by considering: (1) A modified Garg-Onuchic-Ambegaokar model for charge transfer in the condensed phase, where the donor-acceptor coupling is linear in the primary mode coordinate, and for which non-Condon effects do not give rise to a conical intersection; (2) the linear vibronic coupling model for electronic transitions in gas phase molecules, where non-Condon effects give rise to conical intersections. We also present a comprehensive comparison between the linearized semiclassical expression and a progression of more approximate expressions. The comparison is performed over a wide range of frictions and temperatures for model (1) and over a wide range of temperatures for model (2). The linearized semiclassical method is found to reproduce the exact quantum-mechanical result remarkably well for both models over the entire range of parameters under consideration. In contrast, more approximate expressions are observed to deviate considerably from the exact result in some regions of parameter space.

  1. Non-Condon equilibrium Fermi's golden rule electronic transition rate constants via the linearized semiclassical method.

    PubMed

    Sun, Xiang; Geva, Eitan

    2016-06-28

    In this paper, we test the accuracy of the linearized semiclassical (LSC) expression for the equilibrium Fermi's golden rule rate constant for electronic transitions in the presence of non-Condon effects. We do so by performing a comparison with the exact quantum-mechanical result for a model where the donor and acceptor potential energy surfaces are parabolic and identical except for shifts in the equilibrium energy and geometry, and the coupling between them is linear in the nuclear coordinates. Since non-Condon effects may or may not give rise to conical intersections, both possibilities are examined by considering: (1) A modified Garg-Onuchic-Ambegaokar model for charge transfer in the condensed phase, where the donor-acceptor coupling is linear in the primary mode coordinate, and for which non-Condon effects do not give rise to a conical intersection; (2) the linear vibronic coupling model for electronic transitions in gas phase molecules, where non-Condon effects give rise to conical intersections. We also present a comprehensive comparison between the linearized semiclassical expression and a progression of more approximate expressions. The comparison is performed over a wide range of frictions and temperatures for model (1) and over a wide range of temperatures for model (2). The linearized semiclassical method is found to reproduce the exact quantum-mechanical result remarkably well for both models over the entire range of parameters under consideration. In contrast, more approximate expressions are observed to deviate considerably from the exact result in some regions of parameter space. PMID:27369495

  2. A body-force based method to generate supersonic equilibrium turbulent boundary layer profiles

    NASA Astrophysics Data System (ADS)

    Waindim, M.; Gaitonde, D. V.

    2016-01-01

    We further develop a simple counterflow body force-based approach to generate an equilibrium spatially developing turbulent boundary layer suitable for Direct Numerical Simulations (DNS) or Large Eddy Simulations (LES) of viscous-inviscid interactions. The force essentially induces a small separated region in an incoming specified laminar boundary layer. The resulting unstable shear layer then transitions and breaks down to yield the desired unsteady profile. The effects of wall thermal conditions are explored to demonstrate the capability of the method for both fixed wall and adiabatic wall conditions. We then describe an efficient method to select parameters that ensure transition by examining precursor signatures using generalized stability variables. These precursors are shown to be evident in a computational domain spanning only a small region around the trip and can also be detected using 2D simulations. Finally, the method is tested for different Mach numbers ranging from 1.7 to 2.9, with emphasis on flow field surveys, Reynolds stresses, and energy spectra. These results provide guidance on boundary conditions for desired boundary layer thickness at each Mach number. The consequences of using a much lower Reynolds number in computation relative to experiment are evident at the higher Mach number, where a self sustaining turbulent boundary layer is more difficult to obtain.

  3. Equilibrium and dynamic methods when comparing an English text and its Esperanto translation

    NASA Astrophysics Data System (ADS)

    Ausloos, M.

    2008-11-01

    A comparison of two English texts written by Lewis Carroll, one (Alice in Wonderland), also translated into Esperanto, the other (Through the Looking Glass) are discussed in order to observe whether natural and artificial languages significantly differ from each other. One dimensional time series like signals are constructed using only word frequencies (FTS) or word lengths (LTS). The data is studied through (i) a Zipf method for sorting out correlations in the FTS and (ii) a Grassberger-Procaccia (GP) technique based method for finding correlations in LTS. The methods correspond to an equilibrium and a dynamic approach respectively to human texts features. There are quantitative statistical differences between the original English text and its Esperanto translation, but the qualitative differences are very minutes. However different power laws are observed with characteristic exponents for the ranking properties, and the phase space attractor dimensionality. The Zipf exponent can take values much less than unity (∼0.50 or 0.30) depending on how a sentence is defined. This variety in exponents can be conjectured to be an intrinsic measure of the book style or purpose, rather than the language or author vocabulary richness, since a similar exponent is obtained whatever the text. Moreover the attractor dimension r is a simple function of the so called phase space dimension n, i.e., r=nλ, with λ=0.79. Such an exponent could also be conjectured to be a measure of the author style versatility, - here well preserved in the translation.

  4. A one-term extrapolation method for estimating equilibrium constants of aqueous reactions at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Gu, Y.; Gammons, C. H.; Bloom, M. S.

    1994-09-01

    A one-term method for extrapolating equilibrium constants for aqueous reactions is proposed which is based on the observation that the change in free energy of a well-balanced isocoulombic reaction is nearly independent of temperature. The current practice in extrapolating log K values for isocoulombic reactions is to omit the ΔCp term but include a ΔS term (i.e., the two-term extrapolation equation of LINDSAY, 1980). However, we observe that the ΔCp and ΔS terms for many isocoulombic reactions are not only small, but are often opposite in sign, and therefore tend to cancel one another. Thus, inclusion of an entropy term often yields estimates which are less accurate than omission of both terms. The one-term extrapolation technique is tested with literature data for a large number of isocoulombic reactions involving ion-ligand exchange, cation hydrolysis, acid-base neutralization, redox, and selected reactions involving solids. In most cases the extrapolated values are in excellent agreement with the experimental measurements, especially at higher temperatures where they are often more accurate than those obtained using the two-term equation of LINDSAY (1980). The results are also comparable to estimates obtained using the modified HKF model of TANGER and HELGESON (1988) and the density model of ANDERSON et al. (1991). It is also found to produce reasonable estimates for isocoulombic reactions at elevated pressure (up to P = 2 kb) and ionic strength (up to I = 1.0). The principal advantage of the one-term method is that accurate estimates of high temperature equilibrium constants may be obtained using only free energy data for the reaction of interest at one reference temperature. The principal disadvantage is that the accuracies of the estimates are somewhat dependent on the model reaction selected to balance the isocoulombic reaction. Satisfactory results are obtained for reactions that have minimal energetic, electrostatic, structural, and volumetric

  5. VELOCITY SELECTOR METHOD FOR THE SEPARATION OF ISOTOPES

    DOEpatents

    Britten, R.J.

    1957-12-31

    A velocity selector apparatus is described for separating and collecting an enriched fraction of the isotope of a particular element. The invention has the advantage over conventional mass spectrometers in that a magnetic field is not used, doing away with the attendant problems of magnetic field variation. The apparatus separates the isotopes by selectively accelerating the ionized constituents present in a beam of the polyisotopic substance that are of uniform kinetic energy, the acceleration being applied intermittently and at spaced points along the beam and in a direction normal to the direction of the propagation of the uniform energy beam whereby a transverse displacement of the isotopic constituents of different mass is obtained.

  6. Computational Methods for Multi-phase Multi-reaction Thermodynamical Equilibrium Problems

    NASA Astrophysics Data System (ADS)

    Caboussat, A.; Amundson, N. R.; He, J.; Seinfeld, J. H.; Yoo, K.

    2005-05-01

    The computation of phase and chemical equilibria of aqueous organic electrolytes mixtures is of significant interest in atmospheric aerosol modeling. The presence of organic species in solution may substantially influence the phase transitions of the deliquescence and efflorescence of salts with changes in relative humidity. Dissolved electrolytes can have appreciable effects on the solubility of organic components in solution. We present here some computational methods for the prediction of the physical state of atmospheric particles. In the case of inorganic aerosols, an Extended UNIQUAC model is used to compute the excess of Gibbs Free energy. Our method is derived from the minimization of the total Gibbs energy. The computational difficulty is to identify the solid phases existing at the equilibrium. Our algorithm is based on a primal-dual active sets-Newton method for the solution of the Karush-Kuhn-Tucker (KKT) conditions. The inequality constraints are tracked at each iteration so that possible solid salts remain sub-saturated. The corresponding inequality constraint becomes active when the saturation is reached. In the case of organic aerosols, liquid-liquid and liquid-solid equilibria as well as phase stability and separation are considered. The UNIFAC model is used for the calculation of activity coefficients for aqueous organic mixtures. We propose a primal-dual interior-point Newton method to solve the KKT conditions of a relaxed minimization problem. We present numerical results for both inorganic and organic problems to show the ability of our approach, in the prediction of aerosol phases in the atmospheric particles.

  7. Some Developments of the Equilibrium Particle Simulation Method for the Direct Simulation of Compressible Flows

    NASA Technical Reports Server (NTRS)

    Macrossan, M. N.

    1995-01-01

    The direct simulation Monte Carlo (DSMC) method is the established technique for the simulation of rarefied gas flows. In some flows of engineering interest, such as occur for aero-braking spacecraft in the upper atmosphere, DSMC can become prohibitively expensive in CPU time because some regions of the flow, particularly on the windward side of blunt bodies, become collision dominated. As an alternative to using a hybrid DSMC and continuum gas solver (Euler or Navier-Stokes solver) this work is aimed at making the particle simulation method efficient in the high density regions of the flow. A high density, infinite collision rate limit of DSMC, the Equilibrium Particle Simulation method (EPSM) was proposed some 15 years ago. EPSM is developed here for the flow of a gas consisting of many different species of molecules and is shown to be computationally efficient (compared to DSMC) for high collision rate flows. It thus offers great potential as part of a hybrid DSMC/EPSM code which could handle flows in the transition regime between rarefied gas flows and fully continuum flows. As a first step towards this goal a pure EPSM code is described. The next step of combining DSMC and EPSM is not attempted here but should be straightforward. EPSM and DSMC are applied to Taylor-Couette flow with Kn = 0.02 and 0.0133 and S(omega) = 3). Toroidal vortices develop for both methods but some differences are found, as might be expected for the given flow conditions. EPSM appears to be less sensitive to the sequence of random numbers used in the simulation than is DSMC and may also be more dissipative. The question of the origin and the magnitude of the dissipation in EPSM is addressed. It is suggested that this analysis is also relevant to DSMC when the usual accuracy requirements on the cell size and decoupling time step are relaxed in the interests of computational efficiency.

  8. The equilibrium molecular structures of 2-deoxyribose and fructose by the semiexperimental mixed estimation method and coupled-cluster computations.

    PubMed

    Vogt, Natalja; Demaison, Jean; Cocinero, Emilio J; Écija, Patricia; Lesarri, Alberto; Rudolph, Heinz Dieter; Vogt, Jürgen

    2016-06-21

    Fructose and deoxyribose (24 and 19 atoms, respectively) are too large for determining accurate equilibrium structures, either by high-level ab initio methods or by experiments alone. We show in this work that the semiexperimental (SE) mixed estimation (ME) method offers a valuable alternative for equilibrium structure determinations in moderate-sized molecules such as these monosaccharides or other biochemical building blocks. The SE/ME method proceeds by fitting experimental rotational data for a number of isotopologues, which have been corrected with theoretical vibration-rotation interaction parameters (αi), and predicate observations for the structure. The derived SE constants are later supplemented by carefully chosen structural parameters from medium level ab initio calculations, including those for hydrogen atoms. The combined data are then used in a weighted least-squares fit to determine an equilibrium structure (r). We applied the ME method here to fructose and 2-deoxyribose and checked the accuracy of the calculations for 2-deoxyribose against the high level ab initio r structure fully optimized at the CCSD(T) level. We show that the ME method allows determining a complete and reliable equilibrium structure for relatively large molecules, even when experimental rotational information includes a limited number of isotopologues. With a moderate computational cost the ME method could be applied to larger molecules, thereby improving the structural evidence for subtle orbital interactions such as the anomeric effect.

  9. Overview of current methods in sedimentation velocity and sedimentation equilibrium analytical ultracentrifugation.

    PubMed

    Zhao, Huaying; Brautigam, Chad A; Ghirlando, Rodolfo; Schuck, Peter

    2013-02-01

    Modern computational strategies have allowed for the direct modeling of the sedimentation process of heterogeneous mixtures, resulting in sedimentation velocity (SV) size-distribution analyses with significantly improved detection limits and strongly enhanced resolution. These advances have transformed the practice of SV, rendering it the primary method of choice for most existing applications of analytical ultracentrifugation (AUC), such as the study of protein self- and hetero-association, the study of membrane proteins, and applications in biotechnology. New global multisignal modeling and mass conservation approaches in SV and sedimentation equilibrium (SE), in conjunction with the effective-particle framework for interpreting the sedimentation boundary structure of interacting systems, as well as tools for explicit modeling of the reaction/diffusion/sedimentation equations to experimental data, have led to more robust and more powerful strategies for the study of reversible protein interactions and multiprotein complexes. Furthermore, modern mathematical modeling capabilities have allowed for a detailed description of many experimental aspects of the acquired data, thus enabling novel experimental opportunities, with important implications for both sample preparation and data acquisition. The goal of the current unit is to describe the current tools for the study of soluble proteins, detergent-solubilized membrane proteins and their interactions by SV and SE.

  10. A Shrinkage Method for Testing the Hardy-Weinberg Equilibrium in Case-Control Studies

    PubMed Central

    Zang, Yong; Yuan, Ying

    2014-01-01

    Testing for the Hardy-Weinberg equilibrium (HWE) is often used as an initial step for checking the quality of genotyping. When testing the HWE for case-control data, the impact of a potential genetic association between the marker and the disease must be controlled for otherwise the results may be biased. Li and Li (2008) proposed a likelihood ratio test (LRT) that accounts for this potential genetic association and it is more powerful than the commonly used control-only χ2 test. However, the LRT is not efficient when the marker is independent of the disease, and also requires numerical optimization to calculate the test statistic. In this article, we propose a novel shrinkage test for assessing the HWE. The proposed shrinkage test yields higher statistical power than the LRT when the marker is independent of or weakly associated with the disease, and converges to the LRT when the marker is strongly associated with the disease. In addition, the proposed shrinkage test has a closed form and can be easily used to test the HWE for large datasets that result from genome-wide association studies. We compare the performance of the shrinkage test with existing methods using simulation studies, and apply the shrinkage test to a genome-wide association dataset for Alzheimer’s disease. PMID:23934751

  11. Investigation of the Photochemical Method for Uranium Isotope Separation

    DOE R&D Accomplishments Database

    Urey, H. C.

    1943-07-10

    To find a process for successful photochemical separation of isotopes several conditions have to be fulfilled. First, the different isotopes have to show some differences in the spectrum. Secondly, and equally important, this difference must be capable of being exploited in a photochemical process. Parts A and B outline the physical and chemical conditions, and the extent to which one might expect to find them fulfilled. Part C deals with the applicability of the process.

  12. LC-MS determination of bioactive molecules based upon stable isotope-coded derivatization method.

    PubMed

    Toyo'oka, Toshimasa

    2012-10-01

    Liquid chromatography (LC) coupled with mass spectrometry (MS) has been widely used for the analyses of various molecules in many research fields. The electrospray ionization of MS has contributed to the advancement of the LC-MS and LC-MS/MS methods. However, the detection sensitivity is not always sufficient in biological samples, in spite of the highly sensitive ionization method. To increase the sensitivity, chemical derivatization, providing ionization enhancement and avoiding the matrix effect, is effective for various functional groups in the target molecules. However, the accuracy and precision by the determination is sometimes insufficient, especially in complex matrices. In such a case, stable isotope-labeled analogs are often used as the internal standards for the determination of the analytes. When the target compound in samples is limited, a high accuracy and precision is usually obtained by the isotope dilution method. However, the use of individual isotope standards is very difficult for the analyses of multiple molecules in complex matrices. Instead of the use of an isotope analog of the analytes, the differential isotope labeling method based upon chemical derivatization (stable isotope-coded derivatization) (ICD) by both reagents possessing different isotopes is realized. The ICD technique utilizing mass-different isotope tags is known to be an efficient means for metabolite profiling analyses. Thus, the present paper reviews the ICD method reported in the past 10 years. The species of the ICD reagents, their features and the applications to biological specimens are also described in this review.

  13. Reliable Viscosity Calculation from Equilibrium Molecular Dynamics Simulations: A Time Decomposition Method.

    PubMed

    Zhang, Yong; Otani, Akihito; Maginn, Edward J

    2015-08-11

    Equilibrium molecular dynamics is often used in conjunction with a Green-Kubo integral of the pressure tensor autocorrelation function to compute the shear viscosity of fluids. This approach is computationally expensive and is subject to a large amount of variability because the plateau region of the Green-Kubo integral is difficult to identify unambiguously. Here, we propose a time decomposition approach for computing the shear viscosity using the Green-Kubo formalism. Instead of one long trajectory, multiple independent trajectories are run and the Green-Kubo relation is applied to each trajectory. The averaged running integral as a function of time is fit to a double-exponential function with a weighting function derived from the standard deviation of the running integrals. Such a weighting function minimizes the uncertainty of the estimated shear viscosity and provides an objective means of estimating the viscosity. While the formal Green-Kubo integral requires an integration to infinite time, we suggest an integration cutoff time tcut, which can be determined by the relative values of the running integral and the corresponding standard deviation. This approach for computing the shear viscosity can be easily automated and used in computational screening studies where human judgment and intervention in the data analysis are impractical. The method has been applied to the calculation of the shear viscosity of a relatively low-viscosity liquid, ethanol, and relatively high-viscosity ionic liquid, 1-n-butyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([BMIM][Tf2N]), over a range of temperatures. These test cases show that the method is robust and yields reproducible and reliable shear viscosity values. PMID:26574439

  14. A Computational Method for Determining the Equilibrium Composition and Product Temperature in a LH2/LOX Combustor

    NASA Technical Reports Server (NTRS)

    Sozen, Mehmet

    2003-01-01

    In what follows, the model used for combustion of liquid hydrogen (LH2) with liquid oxygen (LOX) using chemical equilibrium assumption, and the novel computational method developed for determining the equilibrium composition and temperature of the combustion products by application of the first and second laws of thermodynamics will be described. The modular FORTRAN code developed as a subroutine that can be incorporated into any flow network code with little effort has been successfully implemented in GFSSP as the preliminary runs indicate. The code provides capability of modeling the heat transfer rate to the coolants for parametric analysis in system design.

  15. 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.

  16. 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.

  17. Simple, rapid method for the preparation of isotopically labeled formaldehyde

    DOEpatents

    Hooker, Jacob Matthew; Schonberger, Matthias; Schieferstein, Hanno; Fowler, Joanna S.

    2011-10-04

    Isotopically labeled formaldehyde (*C.sup..sctn.H.sub.2O) is prepared from labeled methyl iodide (*C.sup..sctn.H.sub.3I) by reaction with an oxygen nucleophile having a pendant leaving group. The mild and efficient reaction conditions result in good yields of *C.sup..sctn.H.sub.2O with little or no *C isotopic dilution. The simple, efficient production of .sup.11CH.sub.2O is described. The use of the .sup.11CH.sub.2O for the formation of positron emission tomography tracer compounds is described. The reaction can be incorporated into automated equipment available to radiochemistry laboratories. The isotopically labeled formaldehyde can be used in a variety of reactions to provide radiotracer compounds for imaging studies as well as for scintillation counting and autoradiography.

  18. Semiexperimental Equilibrium Structures for the Equatorial Conformers of N-Methylpiperidone and Tropinone by the Mixed Estimation Method

    NASA Astrophysics Data System (ADS)

    Demaison, Jean; Craig, Norman C.; Cocinero, Emilio J.; Grabow, Jens-Uwe; Lesarri, Alberto; Rudolph, H. D.

    2012-06-01

    N-methylpiperidone and tropinone, which contain a structural motif found in numerous alkaloids, are too large for determining an accurate equilibrium structure either by ab initio methods or by experiment. However, the ground state rotational constants of the parent species and of all isotopologues with a substituted heavy atom (13C, 15N, 18O) are known from microwave spectroscopy. These constants have been corrected for the rovibrational contribution calculated from an ab initio cubic force field. These semiexperimental equilibrium rotational constants have been supplemented by carefully chosen structural parameters from medium level ab initio calculations. In the mixed estimation method, the two sets of data have been used in a weighted least-squares fit to determine a reliable equilibrium structure for both molecules. This work shows that it is possible to determine reliable equilibrium structures for large molecules (34 degrees of freedom in the case of tropinone). The method could be applied without too much difficulty to still larger molecules. L. Evangelisti, A. Lesarri, M. K. Jahn, E. J. Cocinero, W. Caminati, J.-U. Grabow J. Phys. Chem. A 115, 9545-9551 (2011) E. J. Cocinero, A. Lesarri, P. Écija, J.-U. Grabow, J. A. Fernández, F. Castaño PCCP 12, 6076-6083 (2010)

  19. Nash equilibrium in differential games and the construction of the programmed iteration method

    SciTech Connect

    Averboukh, Yurii V

    2011-05-31

    This work is devoted to the study of nonzero-sum differential games. The set of payoffs in a situation of Nash equilibrium is examined. It is shown that the set of payoffs in a situation of Nash equilibrium coincides with the set of values of consistent functions which are fixed points of the program absorption operator. A condition for functions to be consistent is given in terms of the weak invariance of the graph of the functions under a certain differential inclusion. Bibliography: 18 titles.

  20. A General Method for Automatic Computation of Equilibrium Compositions and Theoretical Rocket Performance of Propellants

    NASA Technical Reports Server (NTRS)

    Gordon, Sanford; Zeleznik, Frank J.; Huff, Vearl N.

    1959-01-01

    A general computer program for chemical equilibrium and rocket performance calculations was written for the IBM 650 computer with 2000 words of drum storage, 60 words of high-speed core storage, indexing registers, and floating point attachments. The program is capable of carrying out combustion and isentropic expansion calculations on a chemical system that may include as many as 10 different chemical elements, 30 reaction products, and 25 pressure ratios. In addition to the equilibrium composition, temperature, and pressure, the program calculates specific impulse, specific impulse in vacuum, characteristic velocity, thrust coefficient, area ratio, molecular weight, Mach number, specific heat, isentropic exponent, enthalpy, entropy, and several thermodynamic first derivatives.

  1. Nash equilibrium in differential games and the construction of the programmed iteration method

    NASA Astrophysics Data System (ADS)

    Averboukh, Yurii V.

    2011-05-01

    This work is devoted to the study of nonzero-sum differential games. The set of payoffs in a situation of Nash equilibrium is examined. It is shown that the set of payoffs in a situation of Nash equilibrium coincides with the set of values of consistent functions which are fixed points of the program absorption operator. A condition for functions to be consistent is given in terms of the weak invariance of the graph of the functions under a certain differential inclusion. Bibliography: 18 titles.

  2. 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.

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

    PubMed

    Reitsema, Laurie J

    2015-01-01

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

  4. Contribution of local thyroxine monodeiodination to intracellular 3,5, 3'-triiodothyronine in several tissues of hyperthyroid rats at isotopic equilibrium

    SciTech Connect

    van Doorn, J.; van der Heide, D.; Roelfsema, F.

    1984-07-01

    The local conversion of T4 as a source of intracellular T3 in several organs of both hypothyroid and euthyroid rats has recently been recognized to be an important phenomenon. In the present study the source and quantity of T3 in various peripheral tissues of hyperthyroid rats were investigated. Athyreotic rats received a continuous iv infusion of T4 over a prolonged period in order to attain hyperthyroid conditions. At the same time, the animals also received a continuous iv infusion of (/sup 125/I)T4 and (/sup 131/I)T3 until isotopic equilibrium was achieved. After the animals were bled and perfused, the source and quantity of T3 in various tissue homogenates and subcellular preparations of liver, kidney, and the anterior pituitary gland were analyzed. In spite of the elevated plasma T3 and T4 levels, the concentration of T3 in the cerebral cortex and cerebellum was within the normal range. The contribution of T3 derived from local T4 to T3 conversion (Lc T3(T4)) was rather low in both parts of the brain when compared with values previously determined for euthyroid rats. Whereas previous studies revealed that Lc T3(T4) contributes significantly to the T3 in the pituitary glands of both hypothyroid and euthyroid rats, this was not the case for the hyperthyroid animals; virtually all T3 was derived from plasma. It was found that the T3 in muscle was derived exclusively from plasma. Both the liver and kidney showed high concentrations of T3. Whereas Lc T3(T4) was the main source of T3 in the liver, it contributed only a minor fraction of the total T3 content in the kidney.

  5. Elucidation of the Cryptic Epimerase Activity of Redox-Inactive Ketoreductase Domains from Modular Polyketide Synthases by Tandem Equilibrium Isotope Exchange

    PubMed Central

    2015-01-01

    Many modular polyketide synthases harbor one or more redox-inactive domains of unknown function that are highly homologous to ketoreductase (KR) domains. A newly developed tandem equilibrium isotope exchange (EIX) assay has now established that such “KR0” domains catalyze the biosynthetically essential epimerization of transient (2R)-2-methyl-3-ketoacyl-ACP intermediates to the corresponding (2S)-2-methyl-3-ketoacyl-ACP diastereomers. Incubation of [2-2H]-(2R,3S)-2-methyl-3-hydroxypentanoyl-SACP ([2-2H]-3b) with the EryKR30 domain from module 3 of the 6-deoxyerythronolide B synthase, and the redox-active, nonepimerizing EryKR6 domain and NADP+ resulted in time- and cofactor-dependent washout of deuterium from 3b, as a result of EryKR30-catalyzed epimerization of transiently generated [2-2H]-2-methyl-3-ketopentanoyl-ACP (4). Similar results were obtained with redox-inactive PicKR30 from module 3 of the picromycin synthase. Four redox-inactive mutants of epimerase-active EryKR1 were engineered by mutagenesis of the NADPH binding site of this enzyme. Tandem EIX established that these EryKR10 mutants retained the intrinsic epimerase activity of the parent EryKR1 domain. These results establish the intrinsic epimerase activity of redox-inactive KR0 domains, rule out any role for the NADPH cofactor in epimerization, and provide a general experimental basis for decoupling the epimerase and reductase activities of a large class of PKS domains. PMID:25004372

  6. A numerical method for retrieving high oxygen isotope temperatures from plutonic igneous rocks: An example from the Laramie Anorthosite Complex, Wyoming, USA

    SciTech Connect

    Farquhar, J.; Chacko, T. . Dept. of Geology); Frost, B.R. )

    1992-01-01

    The Sybille Pit is a late-stage magnetite-ilmenite-plagioclase-bearing differentiate of the Laramie Anorthosite with a wide range of grain sizes and modal mineralogy. This variability makes Sybille an ideal locality in which to study the factors that affect isotopic thermometry in plutonic environments. The authors have developed a numerical model based on isotope exchange trajectories that retrieves close to magmatic temperatures for samples from Sybille. This method is based on the premise that hand sample-scale sub-systems close to exchange with each other at temperatures that exceed those of the constituent minerals. The temperature of hand-sample scale closure is retrieved by back calculating the isotope exchange trajectories to the temperature at which two samples with widely different model compositions are in isotopic equilibrium. Application of these methods to samples from Sybille provides promising results. Whereas conventional isotopic thermometry of individual samples yields a wide range of temperatures ([approximately]600 to > 1000 C) depending on the mineral-pair chosen, application of this numerical model to multiple samples yields temperatures of 1,070 [+-] 100 C which corresponds closely to the inferred solidus for these rocks.

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

    SciTech Connect

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

    1998-01-01

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

  8. Apparatus and method for monitoring of gas having stable isotopes

    DOEpatents

    Clegg, Samuel M; Fessenden-Rahn, Julianna E

    2013-03-05

    Gas having stable isotopes is monitored continuously by using a system that sends a modulated laser beam to the gas and collects and transmits the light not absorbed by the gas to a detector. Gas from geological storage, or from the atmosphere can be monitored continuously without collecting samples and transporting them to a lab.

  9. COMBINING SOURCES IN STABLE ISOTOPE MIXING MODELS: ALTERNATIVE METHODS

    EPA Science Inventory

    Stable isotope mixing models are often used to quantify source contributions to a mixture. Examples include pollution source identification; trophic web studies; analysis of water sources for soils, plants, or water bodies; and many others. A common problem is having too many s...

  10. A time-accurate implicit method for chemical non-equilibrium flows at all speeds

    NASA Technical Reports Server (NTRS)

    Shuen, Jian-Shun

    1992-01-01

    A new time accurate coupled solution procedure for solving the chemical non-equilibrium Navier-Stokes equations over a wide range of Mach numbers is described. The scheme is shown to be very efficient and robust for flows with velocities ranging from M less than or equal to 10(exp -10) to supersonic speeds.

  11. A Simple Method to Calculate the Temperature Dependence of the Gibbs Energy and Chemical Equilibrium Constants

    ERIC Educational Resources Information Center

    Vargas, Francisco M.

    2014-01-01

    The temperature dependence of the Gibbs energy and important quantities such as Henry's law constants, activity coefficients, and chemical equilibrium constants is usually calculated by using the Gibbs-Helmholtz equation. Although, this is a well-known approach and traditionally covered as part of any physical chemistry course, the required…

  12. A method for incorporating equilibrium chemical reactions into multiphase flow models for CO2 storage

    NASA Astrophysics Data System (ADS)

    Saaltink, Maarten W.; Vilarrasa, Victor; De Gaspari, Francesca; Silva, Orlando; Carrera, Jesús; Rötting, Tobias S.

    2013-12-01

    CO2 injection and storage in deep saline aquifers involves many coupled processes, including multiphase flow, heat and mass transport, rock deformation and mineral precipitation and dissolution. Coupling is especially critical in carbonate aquifers, where minerals will tend to dissolve in response to the dissolution of CO2 into the brine. The resulting neutralization will drive further dissolution of both CO2 and calcite. This suggests that large cavities may be formed and that proper simulation may require full coupling of reactive transport and multiphase flow. We show that solving the latter may suffice whenever two requirements are met: (1) all reactions can be assumed to occur in equilibrium and (2) the chemical system can be calculated as a function of the state variables of the multiphase flow model (i.e., liquid and gas pressure, and temperature). We redefine the components of multiphase flow codes (traditionally, water and CO2), so that they are conservative for all reactions of the chemical system. This requires modifying the traditional constitutive relationships of the multiphase flow codes, but yields the concentrations of all species and all reaction rates by simply performing speciation and mass balance calculations at the end of each time step. We applied this method to the H2O-CO2-Na-Cl-CaCO3 system, so as to model CO2 injection into a carbonate aquifer containing brine. Results were very similar to those obtained with traditional formulations, which implies that full coupling of reactive transport and multi-phase flow is not really needed for this kind of systems, but the resulting simplifications may make it advisable even for cases where the above requirements are not met. Regarding the behavior of carbonate rocks, we find that porosity development near the injection well is small because of the low solubility of calcite. Moreover, dissolution concentrates at the front of the advancing CO2 plume because the brine below the plume tends to reach

  13. Comparison of Methods for Characterizing Nonideal Solute Self-Association by Sedimentation Equilibrium

    PubMed Central

    Scott, David J.; Winzor, Donald J.

    2009-01-01

    Abstract We have examined in detail analytical solutions of expressions for sedimentation equilibrium in the analytical ultracentrifuge to describe self-association under nonideal conditions. We find that those containing the radial dependence of total solute concentration that incorporate the Adams-Fujita assumption for composition-dependence of activity coefficients reveal potential shortcomings for characterizing such systems. Similar deficiencies are shown in the use of the NONLIN software incorporating the same assumption about the interrelationship between activity coefficients for monomer and polymer species. These difficulties can be overcome by iterative analyses incorporating expressions for the composition-dependence of activity coefficients predicted by excluded volume considerations. A recommendation is therefore made for the replacement of current software packages by programs that incorporate rigorous statistical-mechanical allowance for thermodynamic nonideality in sedimentation equilibrium distributions reflecting solute self-association. PMID:19651047

  14. Isotope methods for management of shared aquifers in northern Africa.

    PubMed

    Wallin, Bill; Gaye, Cheikh; Gourcy, Laurence; Aggarwal, Pradeep

    2005-01-01

    Access to fresh water is one of the major issues of northern and sub-Saharan Africa. The majority of the fresh water used for drinking and irrigation is obtained from large ground water basins where there is minor contemporary recharge and the aquifers cross national borders. These aquifers include the Nubian Aquifer System shared by Chad, Egypt, Libya, and Sudan; the Iullemeden Aquifer System, extending over Niger, Nigeria, Mali, Benin, and Algeria; and the Northwest Sahara Aquifer System shared by Algeria, Libya, and Tunisia. These resources are subject to increased exploitation and may be severely stressed if not managed properly as witnessed already by declining water levels. In order to make appropriate decisions for the sustainable management of these shared water resources, planners and managers in different countries need an improved knowledge base of hydrological information. Three technical cooperation projects related to aquifer systems will be implemented by the International Atomic Energy Agency, in collaboration with the United Nations Educational, Scientific and Cultural Organization and United Nations Development Programme/Global Environmental Facility. These projects focus on isotope hydrology studies to better quantify ground water recharge and dynamics. The multiple isotope approach combining commonly used isotopes 18O and 2H together with more recently developed techniques (chlorofluorocarbons, 36Cl, noble gases) will be applied to improve the conceptual model to study stratification and ground water flows. Moreover, the isotopes will be an important indicator of changes in the aquifer due to water abstraction, and therefore they will assist in the effort to establish a sustainable ground water management.

  15. Method and apparatus for maintaining equilibrium in a helical axis stellarator

    DOEpatents

    Reiman, Allan; Boozer, Allen

    1987-01-01

    Apparatus for maintaining three-dimensional MHD equilibrium in a plasma contained in a helical axis stellerator includes a resonant coil system, having a configuration such that current therethrough generates a magnetic field cancelling the resonant magnetic field produced by currents driven by the plasma pressure on any given flux surface resonating with the rotational transform of another flux surface in the plasma. Current through the resonant coil system is adjusted as a function of plasma beta.

  16. Method and apparatus for maintaining equilibrium in a helical axis stellarator

    DOEpatents

    Reiman, A.; Boozer, A.

    1984-10-31

    Apparatus for maintaining three-dimensional MHD equilibrium in a plasma contained in a helical axis stellarator includes a resonant coil system, having a configuration such that current therethrough generates a magnetic field cancelling the resonant magnetic field produced by currents driven by the plasma pressure on any given flux surface resonating with the rotational transform of another flux surface in the plasma. Current through the resonant coil system is adjusted as a function of plasma beta.

  17. Stable isotopes and elasmobranchs: tissue types, methods, applications and assumptions.

    PubMed

    Hussey, N E; MacNeil, M A; Olin, J A; McMeans, B C; Kinney, M J; Chapman, D D; Fisk, A T

    2012-04-01

    Stable-isotope analysis (SIA) can act as a powerful ecological tracer with which to examine diet, trophic position and movement, as well as more complex questions pertaining to community dynamics and feeding strategies or behaviour among aquatic organisms. With major advances in the understanding of the methodological approaches and assumptions of SIA through dedicated experimental work in the broader literature coupled with the inherent difficulty of studying typically large, highly mobile marine predators, SIA is increasingly being used to investigate the ecology of elasmobranchs (sharks, skates and rays). Here, the current state of SIA in elasmobranchs is reviewed, focusing on available tissues for analysis, methodological issues relating to the effects of lipid extraction and urea, the experimental dynamics of isotopic incorporation, diet-tissue discrimination factors, estimating trophic position, diet and mixing models and individual specialization and niche-width analyses. These areas are discussed in terms of assumptions made when applying SIA to the study of elasmobranch ecology and the requirement that investigators standardize analytical approaches. Recommendations are made for future SIA experimental work that would improve understanding of stable-isotope dynamics and advance their application in the study of sharks, skates and rays. PMID:22497393

  18. Cryogenic separation of hydrogen isotopes in single-walled carbon and boron-nitride nanotubes: insight into the mechanism of equilibrium quantum sieving in quasi-one-dimensional pores.

    PubMed

    Kowalczyk, Piotr; Gauden, Piotr A; Terzyk, Artur P

    2008-07-17

    Quasi-one-dimensional cylindrical pores of single-walled boron nitride and carbon nanotubes efficiently differentiate adsorbed hydrogen isotopes at 33 K. Extensive path integral Monte Carlo simulations revealed that the mechanisms of quantum sieving for both types of nanotubes are quantitatively similar; however, the stronger and heterogeneous external solid-fluid potential generated from single-walled boron nitride nanotubes enhanced the selectivity of deuterium over hydrogen both at zero coverage and at finite pressures. We showed that this enhancement of the D(2)/H(2) equilibrium selectivity results from larger localization of hydrogen isotopes in the interior space of single-walled boron nitride nanotubes in comparison to that of equivalent single-walled carbon nanotubes. The operating pressures for efficient quantum sieving of hydrogen isotopes are strongly depending on both the type as well as the size of the nanotube. For all investigated nanotubes, we predicted the occurrence of the minima of the D(2)/H(2) equilibrium selectivity at finite pressure. Moreover, we showed that those well-defined minima are gradually shifted upon increasing of the nanotube pore diameter. We related the nonmonotonic shape of the D(2)/H(2) equilibrium selectivity at finite pressures to the variation of the difference between the average kinetic energy computed from single-component adsorption isotherms of H(2) and D(2). In the interior space of both kinds of nanotubes hydrogen isotopes formed solid-like structures (plastic crystals) at 33 K and 10 Pa with densities above the compressed bulk para-hydrogen at 30 K and 30 MPa.

  19. A gas chromatograph/mass spectrometry method for determining isotopic distributions in organic compounds used in the chemical approach to stable isotope separation

    SciTech Connect

    Martinez, A.M.; Spall, W.D.; Smith, B.F.

    1990-01-01

    A variety of gas chromatograph/mass spectrometry (GC/MS) methods have been developed to resolve benzene, benzophenone, anthracene, fluorenone, and their respective stable isotope analogs from other components by gas chromatography. The ratio of stable isotope-labeled material to natural isotopic abundance compounds is determined from the mass spectra averaged across the chromatographic peak. Both total ion and selective ion chromatographic approaches were used for relative data and comparison. 9 refs., 11 tabs.

  20. Routine titration of foot-and-mouth disease virus suspensions by analytical ultracentrifugation 2nd communication: sedimentation equilibrium method.

    PubMed

    Strobbe, R; Lacroix, C; Charlier, G; Debecq, J

    1977-01-01

    A routine method for the determination of the virus concentration in FMD virus cultures and vaccines was developed. This method was based on sedimentation equilibrium in the analytical ultraviolet scanning ultracentrifuge. The virus suspension was first clarified. The virions were then sedimented in a preparative ultracentrifuge. The resuspended virions were diluted in a Cesium chloride solution and brought to equilibrium in the density gradient generated in the analytical ultracentrifuge. The optical density of the virus band was measured by the UV scanning system. A calculation procedure was developed to compute the density at the limits and at the maximum of the virus band. The virus concentration expressed as weight, was calculated for the original virus suspension.

  1. On-chip optofluidic single-particle method for rapid microscale equilibrium solubility screening of biologically active substances.

    PubMed

    Svanbäck, Sami; Ehlers, Henrik; Antikainen, Osmo; Yliruusi, Jouko

    2015-01-01

    Solubility is the primary physicochemical property determining the absorption and bioavailability of substances. Here, we present an optofluidic single-particle technique for microscale equilibrium solubility determination, based on on-chip hydrodynamic particle trapping and optical particle size monitoring. The method combines the rapidity, universality, and substance sparing nature of physical analysis, with the accuracy traditionally associated with chemical analysis. Applying the diffusion layer theory, we determined the equilibrium solubility from individual pure substance microparticles of as little as 14 μg in initial mass, in a matter of seconds to minutes. The reduction in time and substance consumption, when compared to the golden standard method, is above 2 orders of magnitude. With a simultaneous improvement above 3-fold in accuracy of the solubility data, the applicability of optofluidics based analytics for small-scale high-throughput quantitative solubility and biological activity screening is demonstrated.

  2. Electrochemical isotope effect and lithium isotope separation.

    PubMed

    Black, Jay R; Umeda, Grant; Dunn, Bruce; McDonough, William F; Kavner, Abby

    2009-07-29

    A large electrochemical isotopic effect is observed upon the electrodeposition of lithium from solutions of propylene carbonate producing isotopically light metal deposits. The magnitude of fractionation is controlled by the applied overpotential and is largest close to equilibrium. Calculated partition function ratios for tetrahedrally coordinated lithium complexes and metallic lithium predict an equilibrium fractionation close to that measured experimentally.

  3. 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.

  4. A Stochastic Method for Estimating the Effect of Isotopic Uncertainties in Spent Nuclear Fuel

    SciTech Connect

    DeHart, M.D.

    2001-08-24

    This report describes a novel approach developed at the Oak Ridge National Laboratory (ORNL) for the estimation of the uncertainty in the prediction of the neutron multiplication factor for spent nuclear fuel. This technique focuses on burnup credit, where credit is taken in criticality safety analysis for the reduced reactivity of fuel irradiated in and discharged from a reactor. Validation methods for burnup credit have attempted to separate the uncertainty associated with isotopic prediction methods from that of criticality eigenvalue calculations. Biases and uncertainties obtained in each step are combined additively. This approach, while conservative, can be excessive because of a physical assumptions employed. This report describes a statistical approach based on Monte Carlo sampling to directly estimate the total uncertainty in eigenvalue calculations resulting from uncertainties in isotopic predictions. The results can also be used to demonstrate the relative conservatism and statistical confidence associated with the method of additively combining uncertainties. This report does not make definitive conclusions on the magnitude of biases and uncertainties associated with isotopic predictions in a burnup credit analysis. These terms will vary depending on system design and the set of isotopic measurements used as a basis for estimating isotopic variances. Instead, the report describes a method that can be applied with a given design and set of isotopic data for estimating design-specific biases and uncertainties.

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

    SciTech Connect

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

    1999-10-20

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

  6. A new method of snowmelt sampling for water stable isotopes

    USGS Publications Warehouse

    Penna, D.; Ahmad, M.; Birks, S. J.; Bouchaou, L.; Brencic, M.; Butt, S.; Holko, L.; Jeelani, G.; Martinez, D. E.; Melikadze, G.; Shanley, J.B.; Sokratov, S. A.; Stadnyk, T.; Sugimoto, A.; Vreca, P.

    2014-01-01

    We modified a passive capillary sampler (PCS) to collect snowmelt water for isotopic analysis. Past applications of PCSs have been to sample soil water, but the novel aspect of this study was the placement of the PCSs at the ground-snowpack interface to collect snowmelt. We deployed arrays of PCSs at 11 sites in ten partner countries on five continents representing a range of climate and snow cover worldwide. The PCS reliably collected snowmelt at all sites and caused negligible evaporative fractionation effects in the samples. PCS is low-cost, easy to install, and collects a representative integrated snowmelt sample throughout the melt season or at the melt event scale. Unlike snow cores, the PCS collects the water that would actually infiltrate the soil; thus, its isotopic composition is appropriate to use for tracing snowmelt water through the hydrologic cycle. The purpose of this Briefing is to show the potential advantages of PCSs and recommend guidelines for constructing and installing them based on our preliminary results from two snowmelt seasons.

  7. Computational methods for reactive transport modeling: An extended law of mass-action, xLMA, method for multiphase equilibrium calculations

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg; Saar, Martin O.

    2016-10-01

    We present an extended law of mass-action (xLMA) method for multiphase equilibrium calculations and apply it in the context of reactive transport modeling. This extended LMA formulation differs from its conventional counterpart in that (i) it is directly derived from the Gibbs energy minimization (GEM) problem (i.e., the fundamental problem that describes the state of equilibrium of a chemical system under constant temperature and pressure); and (ii) it extends the conventional mass-action equations with Lagrange multipliers from the Gibbs energy minimization problem, which can be interpreted as stability indices of the chemical species. Accounting for these multipliers enables the method to determine all stable phases without presuming their types (e.g., aqueous, gaseous) or their presence in the equilibrium state. Therefore, the here proposed xLMA method inherits traits of Gibbs energy minimization algorithms that allow it to naturally detect the phases present in equilibrium, which can be single-component phases (e.g., pure solids or liquids) or non-ideal multi-component phases (e.g., aqueous, melts, gaseous, solid solutions, adsorption, or ion exchange). Moreover, our xLMA method requires no technique that tentatively adds or removes reactions based on phase stability indices (e.g., saturation indices for minerals), since the extended mass-action equations are valid even when their corresponding reactions involve unstable species. We successfully apply the proposed method to a reactive transport modeling problem in which we use PHREEQC and GEMS as alternative backends for the calculation of thermodynamic properties such as equilibrium constants of reactions, standard chemical potentials of species, and activity coefficients. Our tests show that our algorithm is efficient and robust for demanding applications, such as reactive transport modeling, where it converges within 1-3 iterations in most cases. The proposed xLMA method is implemented in Reaktoro, a

  8. The equilibrium CO2 rebreathing method does not affect resting or exercise blood pressure.

    PubMed

    Turner, M J; Tanaka, H; Bassett, D R; Fitton, T R

    1996-07-01

    The equilibrium CO2 rebreathing technique has been widely used for the noninvasive determination of cardiac output. Recently, several investigators have used this technique in conjunction with auscultatory blood pressure measurements to calculate total peripheral resistance. To examine the validity of this approach, we attempted to determine whether the CO2 rebreathing procedure has a significant effect on blood pressure. The participants in the present study were 10 male subjects, 24 +/- 1 yr of age (mean +/- SE). Each subject performed two trials-one with CO2 rebreathing and one without. Both trials consisted of three stages (rest, 25%, and 50% VO2peak), each stage lasting 15 min. During the rebreathing trial, the CO2 rebreathing technique was administered at 10 min into each stage. There were no statistically significant differences in the heart rate, systolic blood pressure, diastolic blood pressure, and mean arterial blood pressure responses between the two trials. These results indicate that the equilibrium CO2 rebreathing technique does not alter auscultatory blood pressures at rest and during exercise up to intensities of 50% VO2peak. PMID:8832548

  9. RAPID FUSION METHOD FOR DETERMINATION OF PLUTONIUM ISOTOPES IN LARGE RICE SAMPLES

    SciTech Connect

    Maxwell, S.

    2013-03-01

    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 that 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.

  10. 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.

  11. Estimating groundwater exchange with lakes: 1. The stable isotope mass balance method

    USGS Publications Warehouse

    Krabbenhoft, David P.; Bowser, Carl J.; Anderson, Mary P.; Valley, John W.

    1990-01-01

    Groundwater inflow and outflow contributions to the hydrologic budget of lakes can be determined using a stable isotope (18O/16O) mass balance method. The stable isotope method provides a way of integrating the spatial and temporal complexities of the flow field around a lake, thereby offering an appealing alternative to the traditional time and labor intensive methods using seepage meters and an extensive piezometer network. In this paper the method is applied to a lake in northern Wisconsin, demonstrating that it can be successfully applied to lakes in the upper midwest where thousands of similar lakes exist. Inflow and outflow rates calculated for the Wisconsin lake using the isotope mass balance method are 29 and 54 cm/yr, respectively, which compare well to estimates, derived independently using a three-dimensional groundwater flow and solute transport model, of 20 and 50 cm/yr. Such a favorable comparison lends confidence to the use of the stable isotope method to estimate groundwater exchange with lakes. In addition, utilization of stable isotopes in studies of groundwater-lake systems lends insight into mixing processes occurring in the unsaturated zone and in the aquifer surrounding the lake and verifies assumed flow paths based on head measurements in piezometers.

  12. System and method of adjusting the equilibrium temperature of an inductively-heated susceptor

    SciTech Connect

    Matsen, Marc R; Negley, Mark A; Geren, William Preston

    2015-02-24

    A system for inductively heating a workpiece may include an induction coil, at least one susceptor face sheet, and a current controller coupled. The induction coil may be configured to conduct an alternating current and generate a magnetic field in response to the alternating current. The susceptor face sheet may be configured to have a workpiece positioned therewith. The susceptor face sheet may be formed of a ferromagnetic alloy having a Curie temperature and being inductively heatable to an equilibrium temperature approaching the Curie temperature in response to the magnetic field. The current controller may be coupled to the induction coil and may be configured to adjust the alternating current in a manner causing a change in at least one heating parameter of the susceptor face sheet.

  13. An equilibrium method for prediction of transverse shear stresses in a thick laminated plate

    NASA Technical Reports Server (NTRS)

    Chaudhuri, R. Z.

    1986-01-01

    First two equations of equilibrium are utilized to compute the transverse shear stress variation through thickness of a thick laminated plate after in-plane stresses have been computed using an assumed quadratic displacement triangular element based on transverse inextensibility and layerwise constant shear angle theory (LCST). Centroid of the triangle is the point of exceptional accuracy for transverse shear stresses. Numerical results indicate close agreement with elasticity theory. An interesting comparison between the present theory and that based on assumed stress hybrid finite element approach suggests that the latter does not satisfy the condition of free normal traction at the edge. Comparison with numerical results obtained by using constant shear angle theory suggests that LCST is close to the elasticity solution while the CST is closer to classical (CLT) solution. It is also demonstrated that the reduced integration gives faster convergence when the present theory is applied to a thin plate.

  14. Influence on isotope effect calculations of the method of obtaining force constants from vibrational data

    SciTech Connect

    Goodson, D.Z.; Sarpal, S.K.; Bopp, P.; Wolfsberg, M.

    1982-01-01

    Reduced isotopic partition function ratios (s/sub 2//s/sub 1/)f are employed in the calculation of isotope effects on thermodynamic equilibrium constrants. The quadratic force constants of the molecular force field are needed to evaluate (s/sub 2//s/sub 1/)f. Often these force constants are directly deduced from observed fundamentals in vibrational spectra and the (s/sub 2//s/sub 1/)f values so obtained are labeled (ANHARM). In a theroretically more valid procedure that is more difficult, one corrects observed fundamentals for anharmonicity on the basis of observed overtone and combination bands and then deduces force constants from these observed harmonic frequencies. The (s/sub 2//s/sub 1/)f values obtained from these force constants are labeled (HARM). (HARM) values and (ANHARM) values are evaluated and the isotope effects calculated with these values are discussed. It is concluded that the consistent use of (ANHARM) values in such calculations is a valid procedure.

  15. 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.

  16. Structural design using equilibrium programming

    NASA Technical Reports Server (NTRS)

    Scotti, Stephen J.

    1992-01-01

    Multiple nonlinear programming methods are combined in the method of equilibrium programming. Equilibrium programming theory has been appied to problems in operations research, and in the present study it is investigated as a framework to solve structural design problems. Several existing formal methods for structural optimization are shown to actually be equilibrium programming methods. Additionally, the equilibrium programming framework is utilized to develop a new structural design method. Selected computational results are presented to demonstrate the methods.

  17. Isobaric molecular dynamics version of the generalized replica exchange method (gREM): Liquid–vapor equilibrium

    SciTech Connect

    Malolepsza, Edyta; Secor, Maxim; Keyes, Tom

    2015-09-23

    A prescription for sampling isobaric generalized ensembles with molecular dynamics is presented and applied to the generalized replica exchange method (gREM), which was designed for simulating first-order phase transitions. The properties of the isobaric gREM ensemble are discussed and a study is presented of the liquid-vapor equilibrium of the guest molecules given for gas hydrate formation with the mW water model. As a result, phase diagrams, critical parameters, and a law of corresponding states are obtained.

  18. Isobaric Molecular Dynamics Version of the Generalized Replica Exchange Method (gREM): Liquid-Vapor Equilibrium.

    PubMed

    Małolepsza, Edyta; Secor, Maxim; Keyes, Tom

    2015-10-22

    A prescription for sampling isobaric generalized ensembles with molecular dynamics is presented and applied to the generalized replica exchange method (gREM), which was designed to simulate first-order phase transitions. The properties of the isobaric gREM ensemble are discussed, and a study is presented for the liquid-vapor equilibrium of the guest molecules given for gas hydrate formation with the mW water model. Phase diagrams, critical parameters, and a law of corresponding states are obtained. PMID:26398582

  19. An Efficient Method to Calculate the Aggregated Isotopic Distribution and Exact Center-Masses

    NASA Astrophysics Data System (ADS)

    Claesen, Jürgen; Dittwald, Piotr; Burzykowski, Tomasz; Valkenborg, Dirk

    2012-04-01

    In this article, we present a computation- and memory-efficient method to calculate the probabilities of occurrence and exact center-masses of the aggregated isotopic distribution of a molecule. The method uses fundamental mathematical properties of polynomials given by the Newton-Girard theorem and Viete's formulae. The calculation is based on the atomic composition of the molecule and the natural abundances of the elemental isotopes in normal terrestrial matter. To evaluate the performance of the proposed method, which we named BRAIN, we compare it with the results obtained from five existing software packages ( IsoPro, Mercury, Emass, NeutronCluster, and IsoDalton) for 10 biomolecules. Additionally, we compare the computed mass centers with the results obtained by calculating, and subsequently aggregating, the fine isotopic distribution for two of the exemplary biomolecules. The algorithm will be made available as a Bioconductor package in R, and is also available upon request.

  20. "Density equilibrium" method for the quantitative and rapid in situ determination of lipid, hydrocarbon, or biopolymer content in microorganisms.

    PubMed

    Eroglu, Ela; Melis, Anastasios

    2009-04-01

    The work provides a simple method, based on a direct density equilibrium measurement, for the rapid in situ estimation of total lipid, hydrocarbon or biopolymer content in a variety of prokaryotic and eukaryotic samples. The method can be readily applied to live microalgae and photosynthetic bacteria, single-celled or colonial microorganisms, as well as cellular fractions and isolated subcellular compartments or components. In this approach, the absolute lipid, hydrocarbon, or biopolymer content of the cells can be readily calculated. This method is especially useful for tracking the oil or polymer content of strains of microalgae and other microorganisms, whose lipid, hydrocarbon or biopolymer content may change with cultivation conditions and/or time, as the case would be in microorganism lipid-induction industrial processes. The method is also useful for the direct in situ measurement of storage polymer accumulation in live cells, such as starch in microalgae and polyhydroxybutyrate, or other polyhydroxyalkanoates, in photosynthetic and non-photosynthetic bacteria. PMID:19031427

  1. Development of an identification method of pressure anisotropy based on equilibrium analysis and magnetics

    SciTech Connect

    Asahi, Y.; Suzuki, Y.; Watanabe, K. Y.; Cooper, W. A.

    2013-02-15

    We evaluate the fluxes measured by the magnetic flux loops installed in LHD by using a three dimensional MHD equilibrium analysis code, ANIMEC, which enable us to directly determine the calibration function between the anisotropic pressure and the measured fluxes for the non-axisymmetric plasmas for the first time. The result indicates that the diamagnetic flux represents a nearly single-valued function of the beta perpendicular with respect to the field, and the saddle loop flux represents a nearly single-valued function of an equally weighted average of the beta values parallel and perpendicular to the field, regardless of the pressure anisotropy or the amount of energetic trapped particles. The values of the beta perpendicular to the field and the equal weighting averaged beta estimated by the single-valued functions (calibration functions) are investigated in order to clarify the magnitude of deviation from those original values, and the range of anisotropy where the beta value evaluated by the magnetic flux measurement is calculated within a 10% error.

  2. 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

  3. Seismic stability analysis of expanded MSW landfills using pseudo-static limit equilibrium method.

    PubMed

    Choudhury, Deepankar; Savoikar, Purnanand

    2011-02-01

    Capacity expansion of existing landfills is the most economical alternative to constructing new landfills where cost of land is prohibitive. From the safety point of view, the stability analyses of existing landfills expanded either vertically and/or laterally are required for different stages of construction, operation and during closure of a landfill. In the present study, a pseudo-static limit equilibrium seismic stability analysis was performed for a typical side-hill type municipal solid waste (MSW) landfill expanded using an engineered berm. Seismic stability analyses were performed for the two critical cases, namely when the failure surface passes below the berm (under berm) and when the failure surface passes over the back slope of the berm (over berm). Close-form solutions were developed for the upper bound and lower bound factor of safety and the yield acceleration of such slopes under both failure conditions. From parametric analyses it was observed that as the height of the berm increased, the factor of safety for both the over-berm failure and the under-berm failure conditions also increased. The average factor of safety and yield acceleration coefficient were found and the under-berm failure condition became critical for a back slope steeper than 1.7H : 1V. The average factor of safety decreased as both horizontal and vertical seismic accelerations increased. Comparisons between the present results and those in the literature for the static case showed good agreement and the present results of the pseudo-static seismic case were found to be of particular importance.

  4. A stable isotope dilution method for measuring bioavailability of organic contaminants

    PubMed Central

    Delgado-Moreno, Laura; Gan, Jay

    2014-01-01

    Methods for determining bioavailability of organic contaminants suffer various operational limitations. We explored the use of stable isotope labeled references in developing an isotope dilution method (IDM) to measure the exchangeable pool (E) of pyrene and bifenthrin as an approximation of their bioavailability in sediments. The exchange of deuterated bifenthrin or pyrene with its native counterpart was completed within 48 h. The derived E was 38–82% for pyrene and 28–59% for bifenthrin. Regression between E and the sum of rapid and slow desorption fractions obtained from sequential desorption showed a slope close to 1.0. The ability of IDM to predict bioavailability was further shown from a strong relationship (r2 > 0.93) between E and bioaccumulation into Chironomus tentans. Given the abundance of stable isotope labeled references and their relatively easy analysis, the IDM has the potential to become a readily adoptable tool for estimating organic contaminants bioaccessibility in various matrices. PMID:23434573

  5. A METHOD FOR THE MEASUREMENT OF SITE-SPECIFIC TAUTOMERIC AND ZWITTERIONIC MICROSPECIES EQUILIBRIUM CONSTANTS

    EPA Science Inventory

    We describe a method for the individual measurement of simultaneously occurring, unimolecular, site-specific "microequilibrium" constants as in, for example, prototropic tautomerism and zwitterionic equilibria. Our method represents an elaboration of that of Nygren et al. (Anal. ...

  6. METHOD FOR THE MEASUREMENT OF SITE-SPECIFIC TAUTOMERIC AND ZWITTERIONIC MICROSPECIES EQUILIBRIUM CONSTANTS

    EPA Science Inventory

    We describe a method for the individual measurement of simultaneously occurring, unimolecular, site-specific “microequilibrium” constants as in, for example, prototropic tautomerism and zwitterionic equilibria. Our method represents an elaboration of that of Nygren et al. (Anal. ...

  7. A benchmark study of molecular structure by experimental and theoretical methods: Equilibrium structure of thymine from microwave rotational constants and coupled-cluster computations

    NASA Astrophysics Data System (ADS)

    Vogt, Natalja; Demaison, Jean; Ksenafontov, Denis N.; Rudolph, Heinz Dieter

    2014-11-01

    Accurate equilibrium, re, structures of thymine have been determined using two different, and to some extent complementary techniques. The composite ab initio Born-Oppenheimer, re(best ab initio), structural parameters are obtained from the all-electron CCSD(T) and MP2 geometry optimizations using Gaussian basis sets up to quadruple-zeta quality. The semi-experimental mixed estimation method, where internal coordinates are fitted concurrently to equilibrium rotational constants and geometry parameters obtained from a high level of electronic structure theory. The equilibrium rotational constants are derived from experimental effective ground-state rotational constants and rovibrational corrections based on a quantum-chemical cubic force field. Equilibrium molecular structures accurate to 0.002 Å and 0.2° have been determined. This work is one of a few accurate equilibrium structure determinations for large molecules. The poor behavior of Kraitchman's equations is discussed.

  8. Trigonometric and hyperbolic functions method for constructing analytic solutions to nonlinear plane magnetohydrodynamics equilibrium equations

    SciTech Connect

    Moawad, S. M.

    2015-02-15

    In this paper, we present a solution method for constructing exact analytic solutions to magnetohydrodynamics (MHD) equations. The method is constructed via all the trigonometric and hyperbolic functions. The method is applied to MHD equilibria with mass flow. Applications to a solar system concerned with the properties of coronal mass ejections that affect the heliosphere are presented. Some examples of the constructed solutions which describe magnetic structures of solar eruptions are investigated. Moreover, the constructed method can be applied to a variety classes of elliptic partial differential equations which arise in plasma physics.

  9. Combined carbonate carbon isotopic and cellular ultrastructural studies of individual benthic foraminifera: Method description

    NASA Astrophysics Data System (ADS)

    Martin, Jonathan B.; Bernhard, Joan M.; Curtis, Jason; Rathburn, Anthony E.

    2010-06-01

    Carbon isotopes of foraminiferal tests provide a widely used proxy for past oceanographic environmental conditions. This proxy can be calibrated using live specimens, which are reliably identified with observations of cell ultrastructure. Observations of ultrastructures can also be used for studies of biological characteristics such as diet and presence of symbionts. Combining biological and isotopic studies on individual foraminifera could provide novel information, but standard isotopic methods destroy ultrastructures by desiccating specimens and observations of ultrastructure require removal of carbonate tests, preventing isotope measurements. The approach described here preserves cellular ultrastructure during isotopic analyses by keeping the foraminifera in an aqueous buffer (Phosphate Buffered Saline (PBS)). The technique was developed and standardized with 36 aliquots of NBS-19 standard of similar weight to foraminiferal tests (5 to 123 μg). Standard errors ranged from ± 0.06 to ± 0.85‰ and were caused by CO2 contaminants dissolved in the PBS. The technique was used to measure δ13C values of 96 foraminifera, 10 of which do not precipitate carbonate tests. Calcareous foraminiferal tests had corrected carbon isotope ratios of -8.5 to +3.2‰. This new technique allows comparisons of isotopic compositions of tests made by foraminifera known to be alive at the time of collection with their biological characteristics such as prey composition and presence or absence of putative symbionts. The approach may be applied to additional biomineralizing organisms such as planktonic foraminifera, pteropods, corals, and coccolithophores to elucidate certain biological controls on their paleoceanographic proxy signatures.

  10. Characterization of the relationship between microbial degradation processes at a hydrocarbon contaminated site using isotopic methods.

    PubMed

    Feisthauer, Stefan; Seidel, Martin; Bombach, Petra; Traube, Sebastian; Knöller, Kay; Wange, Martin; Fachmann, Stefan; Richnow, Hans H

    2012-05-15

    Decisions to employ monitored natural attenuation (MNA) as a remediation strategy at contaminated field sites require a comprehensive characterization of the site-specific biodegradation processes. In the present study, compound-specific carbon and hydrogen isotope analysis (CSIA) was used to investigate intrinsic biodegradation of benzene and ethylbenzene in an aquifer with high levels of aromatic and aliphatic hydrocarbon contamination. Hydrochemical data and isotope fractionation analysis of sulfate and methane was used complementarily to elucidate microbial degradation processes over the course of a three year period, consisting of six sampling campaigns, in the industrial area of Weißandt-Gölzau (Saxony-Anhalt, Germany). Enrichment of (13)C and (2)H isotopes in the residual benzene and ethylbenzene pool downgradient from the pollution sources provided evidence of biodegradation of BTEX compounds at this site, targeting both compounds as the key contaminants of concern. The enrichment of heavy sulfur isotopes accompanied by decreasing sulfate concentrations and the accumulation of isotopically light methane suggested that sulfate-reducing and methanogenic processes are the major contributors to overall biodegradation in this aquifer. Along the contaminant plume, the oxidation of methane with δ(13)C(CH4) values of up to +17.5‰ was detected. This demonstrates that methane formed in the contaminant source can be transported along groundwater flow paths and be oxidized in areas with higher redox potentials, thereby competing directly with the pollutants for electron acceptors. Hydrochemical and isotope data was summarized in a conceptual model to assess whether MNA can be used as viable remediation strategy in Weißandt-Gölzau. The presented results demonstrate the benefits of combining different isotopic methods and hydrochemical approaches to evaluate the fate of organic pollutants in contaminated aquifers.

  11. 2D Quantum Simulation of MOSFET Using the Non Equilibrium Green's Function Method

    NASA Technical Reports Server (NTRS)

    Svizhenko, Alexel; Anantram, M. P.; Govindan, T. R.; Yan, Jerry (Technical Monitor)

    2000-01-01

    The objectives this viewgraph presentation summarizes include: (1) the development of a quantum mechanical simulator for ultra short channel MOSFET simulation, including theory, physical approximations, and computer code; (2) explore physics that is not accessible by semiclassical methods; (3) benchmarking of semiclassical and classical methods; and (4) study other two-dimensional devices and molecular structure, from discretized Hamiltonian to tight-binding Hamiltonian.

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

    USGS Publications Warehouse

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

    2007-01-01

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

  13. Radius evolution of sodium isotopes in mean-field and generator coordinate methods

    NASA Astrophysics Data System (ADS)

    Naulin, F.; Zhang, Jing-Ye; Flocard, H.; Vautherin, D.; Heenen, P. H.; Bonche, P.

    1998-06-01

    Radii of sodium isotopes have been calculated by using the Hartree-Fock-BCS model and the Generator Coordinate Method (GCM) with different forces. It is found that Hartree-Fock-BCS results present a jump in both neutron and proton radii from 22Na to 23Na. However, configuration mixing calculations performed with the GCM result in a smooth increase of the neutron radius and an almost constant proton radius for the sodium isotopes. We analyze and discuss our results in the light of recent experimental data.

  14. RAPID AND PRECISE METHOD FOR MEASURING STABLE CARBON ISOTOPE RATIOS OF DISSOLVED INORGANIC CARBON

    EPA Science Inventory

    We describe a method for rapid preparation, concentration and stable isotopic analysis of dissolved inorganic carbon (d13C-DIC). Liberation of CO2 was accomplished by placing 100 ?l phosphoric acid and 0.9 ml water in an evacuated 1.7-ml gas chromatography (GC) injection vial. Fo...

  15. A simplified method for obtaining high-purity perchlorate from groundwater for isotope analyses.

    SciTech Connect

    vonKiparski, G; Hillegonds, D

    2011-04-04

    Investigations into the occurrence and origin of perchlorate (ClO{sub 4}{sup -}) found in groundwater from across North America have been sparse until recent years, and there is mounting evidence that natural formation mechanisms are important. New opportunities for identifying groundwater perchlorate and its origin have arisen with the utilization of improved detection methods and sampling techniques. Additionally, application of the forensic potential of isotopic measurements has begun to elucidate sources, potential formation mechanisms and natural attenuation processes. Procedures developed appear to be amenable to enable high precision stable isotopic analyses, as well as lower precision AMS analyses of {sup 36}Cl. Immediate work is in analyzing perchlorate isotope standards and developing full analytical accuracy and uncertainty expectations. Field samples have also been collected, and will be analyzed when final qa/qc samples are deemed acceptable.

  16. An economical method for (15)N/(13)C isotopic labeling of proteins expressed in Pichia pastoris.

    PubMed

    Rodriguez, E; Krishna, N R

    2001-07-01

    We report a new and cost-effective approach to prepare (15)N/(13)C labeled proteins for NMR using the Pichia pastoris expression system. Four protocols (P1 to P4) were defined and compared using recombinant Ovine interferon-tau (rOvIFN-tau). Our results demonstrate that in order to get full incorporation of (15)N and (13)C, the isotopes are not totally required during the initial growth phase of P. pastoris culture. The addition of small amounts of (15)N and (13)C compounds 6 h prior to the methanol induction phase is sufficient to obtain 99% incorporation of heavy isotopes into the protein. Our optimized protocol P4 is two-thirds less costly than the classical method using (15)N and (13)C isotopes during the entire growth phase.

  17. General method and thermodynamic tables for computation of equilibrium composition and temperature of chemical reactions

    NASA Technical Reports Server (NTRS)

    Huff, Vearl N; Gordon, Sanford; Morrell, Virginia E

    1951-01-01

    A rapidly convergent successive approximation process is described that simultaneously determines both composition and temperature resulting from a chemical reaction. This method is suitable for use with any set of reactants over the complete range of mixture ratios as long as the products of reaction are ideal gases. An approximate treatment of limited amounts of liquids and solids is also included. This method is particularly suited to problems having a large number of products of reaction and to problems that require determination of such properties as specific heat or velocity of sound of a dissociating mixture. The method presented is applicable to a wide variety of problems that include (1) combustion at constant pressure or volume; and (2) isentropic expansion to an assigned pressure, temperature, or Mach number. Tables of thermodynamic functions needed with this method are included for 42 substances for convenience in numerical computations.

  18. Possible non-equilibrium oxygen isotope effects in mantle nodules, an alternative to the Kyser-O'Neil-Carmichael18O/16O geothermometer

    NASA Astrophysics Data System (ADS)

    Gregory, Robert T.; Taylor, Hugh P.; Kyser, T. Kurtis; O'Neil, James R.; Carmichael, Ian S. E.

    1986-03-01

    Kyser, O'Neil, and Carmichael (1981, 1982) measured the δ 18O values of coexisting minerals from peridotite nodules in alkali basalts and kimberlites, interpreting the nodules as equilibrium assemblages. Using Ca-Mg-Fe element-partition geothermometric data, they proposed an empirical18O/16O geothermometer: T(°C)=1,151-173 Δ-68 Δ 2, where Δ is the per mil pyroxene-olivine fractionation. However, this geothermometer has an unusual “crossover” at 1,150 °C, and in contrast to what might be expected during closed-system equilibrium exchange, the most abundant mineral in the nodules (olivine) shows a much greater range in δ 18O (+4.4 to +7.5) than the much less abundant pyroxene (all 50 pyroxene analyses from spinel peridotites lie within the interval +5.3 to +6.5). On δ 18O-olivine vs. δ 18O-pyroxene diagrams, the mantle nodules exhibit data arrays that cut across the Δ 18O=zero line. These arrays strongly resemble the non-equilibrium quartzfeldspar and feldspar-pyroxene δ 18O arrays that we now know are diagnostic of hydrothermally altered plutonic igneous rocks. Thus, we have re-interpreted the Kyser et al. data as non-equilibrium phenomena, casting doubt on their empirical geothermometer. The peridotite nodules appear to have been open systems that underwent metasomatic exchange with an external, oxygen-bearing fluid (CO2, magma, H2O, etc.); during this event, the relatively inert pyroxenes exchanged at a much slower rate than did the coexisting olivines and spinels, in agreement with available exchange-rate and diffusion measurements on these minerals. This accounts for the correlation between Δ 18O pyroxene-olivine and the whole-rock δ 18O of the peridotites, which is a major difficulty with the equilibrium interpretation.

  19. 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.

  20. Semiclassical field method for the equilibrium Bose gas and application to thermal vortices in two dimensions

    SciTech Connect

    Giorgetti, Luca; Carusotto, Iacopo; Castin, Yvan

    2007-07-15

    We develop a semiclassical field method for the study of the weakly interacting Bose gas at finite temperature which, contrary to the usual classical field model, does not suffer from an ultraviolet cutoff dependence. We apply the method to the study of thermal vortices in spatially homogeneous, two-dimensional systems. We present numerical results for the vortex density and the vortex pair distribution function. Insight in the physics of the system is obtained by comparing the numerical results with the predictions of simple analytical models. In particular, we calculate the activation energy required to form a vortex pair at low temperature.

  1. Effects of preservation methods on stable isotope signatures in bird tissues.

    PubMed

    Bugoni, Leandro; McGill, Rona A R; Furness, Robert W

    2008-08-01

    Increasing use is being made of stable isotopes as indicators of habitat use and trophic ecology of animals. Preservation of tissues can alter stable isotope signatures. We investigated the effects of addition of ethanol and NaCl solution (hereafter 'salt'), and of freezing and drying, on carbon and nitrogen isotopic values in blood of the spectacled petrel Procellaria conspicillata, and compared these with those from simultaneously growing feathers. The mean delta(13)C values of blood preserved in ethanol was significantly higher, and of blood preserved in salt was significantly lower than that of dried or frozen samples. delta(13)C values in ethanol showed high variation according to brand and batch and could account for the differences found in delta(13)C ratios in ethanol-preserved blood samples. Mean delta(13)C and delta(15)N values in growing feathers were higher than in blood, suggesting tissue-specific fractionation. We conclude that different methods of preserving tissues such as blood may bias stable isotope values, and urge researchers to consider this issue. Air drying is proposed as a practical and unbiased method for blood preservation in field situations where freezing is not a practical option, and a mathematical approach is suggested to permit comparison between studies using different preservation methods or tissues. PMID:18642324

  2. A finite element method to compute three-dimensional equilibrium configurations of fluid membranes: Optimal parameterization, variational formulation and applications

    NASA Astrophysics Data System (ADS)

    Rangarajan, Ramsharan; Gao, Huajian

    2015-09-01

    We introduce a finite element method to compute equilibrium configurations of fluid membranes, identified as stationary points of a curvature-dependent bending energy functional under certain geometric constraints. The reparameterization symmetries in the problem pose a challenge in designing parametric finite element methods, and existing methods commonly resort to Lagrange multipliers or penalty parameters. In contrast, we exploit these symmetries by representing solution surfaces as normal offsets of given reference surfaces and entirely bypass the need for artificial constraints. We then resort to a Galerkin finite element method to compute discrete C1 approximations of the normal offset coordinate. The variational framework presented is suitable for computing deformations of three-dimensional membranes subject to a broad range of external interactions. We provide a systematic algorithm for computing large deformations, wherein solutions at subsequent load steps are identified as perturbations of previously computed ones. We discuss the numerical implementation of the method in detail and demonstrate its optimal convergence properties using examples. We discuss applications of the method to studying adhesive interactions of fluid membranes with rigid substrates and to investigate the influence of membrane tension in tether formation.

  3. A New Method of Separating 210Pb from Ra-DEF for a Radioactive Equilibrium Experiment.

    ERIC Educational Resources Information Center

    Wai, C. M.; Lo, J. M.

    1984-01-01

    Background information, procedures, and results are provided for an experiment in which lead-210 is separated from bismuth-210 and polonium-210 by means of solvent extraction of their diethyldithiocarbamate complexes. The method involves a simple extraction procedure which allows complete separation of lead-210 from commercially available…

  4. Development of High Flux Isotope Reactor (HFIR) subcriticality monitoring methods

    SciTech Connect

    Rothrock, R.B.

    1991-01-01

    Use of subcritical source multiplication measurements during refueling has been investigated as a possible replacement for out-of-reactor subcriticality measurements formerly made on fresh HFIR fuel elements at the ORNL Critical Experiment Facility. These measurements have been used in the past for preparation of estimated critical rod positions, and as a partial verification, prior to reactor startup, that the requirements for operational shutdown margin would be met. Results of subcritical count rate data collection during recent HFIR refuelings and supporting calculations are described illustrating the intended measurement method and its expected uncertainty. These results are compared to historical uses of the out-of-reactor core measurements and their accuracy requirements, and a planned in-reactor test is described which will establish the sensitivity of the method and calibrate it for future routine use during HFIR refueling. 2 refs., 1 fig., 2 tabs.

  5. A method to extract soil water for stable isotope analysis

    USGS Publications Warehouse

    Revesz, K.; Woods, P.H.

    1990-01-01

    A method has been developed to extract soil water for determination of deuterium (D) and 18O content. The principle of this method is based on the observation that water and toluene form an azeotropic mixture at 84.1??C, but are completely immiscible at ambient temperature. In a specially designed distillation apparatus, the soil water is distilled at 84.1??C with toluene and is separated quantitatively in the collecting funnel at ambient temperature. Traces of toluene are removed and the sample can be analyzed by mass spectrometry. Kerosene may be substituted for toluene. The accuracy of this technique is ?? 2 and ?? 0.2???, respectively, for ??D and ??18O. Reduced accuracy is obtained at low water contents. ?? 1990.

  6. METHOD OF SEPARATING ISOTOPES OF URANIUM IN A CALUTRON

    DOEpatents

    Jenkins, F.A.

    1958-05-01

    Mass separation devices of the calutron type and the use of uranium hexachloride as a charge material in the calutron ion source are described. The method for using this material in a mass separator includes heating the uranium hexachloride to a temperature in the range of 60 to 100 d C in a vacuum and thereby forming a vapor of the material. The vaporized uranium hexachloride is then ionized in a vapor ionizing device for subsequent mass separation processing.

  7. Finite-Temperature Non-equilibrium Quasicontinuum Method based on Langevin Dynamics

    SciTech Connect

    Marian, J; Venturini, G; Hansen, B; Knap, J; Ortiz, M; Campbell, G

    2009-05-08

    The concurrent bridging of molecular dynamics and continuum thermodynamics presents a number of challenges, mostly associated with energy transmission and changes in the constitutive description of a material across domain boundaries. In this paper, we propose a framework for simulating coarse dynamic systems in the canonical ensemble using the Quasicontinuum method (QC). The equations of motion are expressed in reduced QC coordinates and are strictly derived from dissipative Lagrangian mechanics. The derivation naturally leads to a classical Langevin implementation where the timescale is governed by vibrations emanating from the finest length scale occurring in the computational cell. The equations of motion are integrated explicitly via Newmark's ({beta} = 0; {gamma} = 1/2) method, leading to a robust numerical behavior and energy conservation. In its current form, the method only allows for wave propagations supported by the less compliant of the two meshes across a heterogeneous boundary, which requires the use of overdamped dynamics to avoid spurious heating due to reflected vibrations. We have applied the method to two independent crystallographic systems characterized by different interatomic potentials (Al and Ta) and have measured thermal expansion in order to quantify the vibrational entropy loss due to homogenization. We rationalize the results in terms of system size, mesh coarseness, and nodal cluster diameter within the framework of the quasiharmonic approximation. For Al, we find that the entropy loss introduced by mesh coarsening varies linearly with the element size, and that volumetric effects are not critical in driving the anharmonic behavior of the simulated systems. In Ta, the anomalies of the interatomic potential employed result in negative and zero thermal expansion at low and high temperatures, respectively.

  8. Limitations of SRTM, Logan graphical method, and equilibrium analysis for measuring transient dopamine release with [(11)C]raclopride PET.

    PubMed

    Sullivan, Jenna M; Kim, Su Jin; Cosgrove, Kelly P; Morris, Evan D

    2013-01-01

    Conventional PET methods to estimate [(11)C]raclopride binding potential (BP ND) assume that endogenous dopamine concentration does not change during the scan time. However, this assumption is purposely violated in studies using pharmacological or behavioral stimuli to invoke acute dopamine release. When the assumption of steady-state dopamine is violated, conventional analysis methods may produce biased or even unusable estimates of BP ND. To illustrate this problem, we examined the effect of scan duration on ΔBP ND estimated by three common analysis methods (simplified reference tissue model, Logan graphical reference method, and equilibrium analysis) applied to simulated and experimental single-scan activation studies. The activation - dopamine release - in both the simulated and experimental studies was brief. Simulations showed ΔBP ND to be highly dependent on the window of data used to determine BP ND in the activation state. A similar pattern was seen in the data from human smoking studies. No such pattern of ΔBP ND dependence on the window of data used was apparent in simulations where dopamine was held constant. The dependence of ΔBP ND on the duration of data analyzed illustrates the inability of conventional methods to reliably quantify short-lived increases in endogenous dopamine. PMID:23638336

  9. A rapid method for the determination of radioactive cesium isotopes in water

    USGS Publications Warehouse

    Janzer, V.J.

    1973-01-01

    Radioactive cesium in water is concentrated by ion-exchange on finely divided ammonium hexacyanocobalt ferrate (NCFC), and then determined by beta counting. No carrier is added, and the method can be used to determine beta-emitting cesium isotopes at the 10-pCi/l level using a 100-ml sample. Five samples can be prepared for counting, in approximately 3 hours, and the method is applicable to fresh and saline waters.

  10. Model for determining vapor equilibrium rates in the hanging drop method for protein crystal growth

    NASA Technical Reports Server (NTRS)

    Baird, James K.; Frieden, Richard W.; Meehan, E. J., Jr.; Twigg, Pamela J.; Howard, Sandra B.; Fowlis, William A.

    1987-01-01

    An engineering analysis of the rate of evaporation of solvent in the hanging drop method of protein crystal growth is presented. Results are applied to 18 drop and well arrangements commonly encountered in the laboratory. The chemical nature of the salt, drop size and shape, drop concentration, well size, well concentration, and temperature are taken into account. The rate of evaporation increases with temperature, drop size, and the salt concentration difference between the drop and the well. The evaporation in this model possesses no unique half-life. Once the salt in the drop achieves 80 percent of its final concentration, further evaporation suffers from the law of diminishing returns.

  11. A numerical method for generating rapidly rotating bipolytropic structures in equilibrium

    NASA Astrophysics Data System (ADS)

    Kadam, Kundan; Motl, Patrick M.; Frank, Juhan; Clayton, Geoffrey C.; Marcello, Dominic C.

    2016-10-01

    We demonstrate that rapidly rotating bipolytropic (composite polytropic) stars and toroidal discs can be obtained using Hachisu's self-consistent field technique. The core and the envelope in such a structure can have different polytropic indices and also different average molecular weights. The models converge for high T/|W| cases, where T is the kinetic energy and W is the gravitational energy of the system. The agreement between our numerical solutions with known analytical as well as previously calculated numerical results is excellent. We show that the uniform rotation lowers the maximum core mass fraction or the Schönberg-Chandrasekhar limit for a bipolytropic sequence. We also discuss the applications of this method to magnetic braking in low-mass stars with convective envelopes.

  12. When stable-stage equilibrium is unlikely: integrating transient population dynamics improves asymptotic methods

    PubMed Central

    Tremblay, Raymond L.; Raventos, Josep; Ackerman, James D.

    2015-01-01

    Background and Aims Evaluation of population projection matrices (PPMs) that are focused on asymptotically based properties of populations is a commonly used approach to evaluate projected dynamics of managed populations. Recently, a set of tools for evaluating the properties of transient dynamics has been expanded to evaluate PPMs and to consider the dynamics of populations prior to attaining the stable-stage distribution, a state that may never be achieved in disturbed or otherwise ephemeral habitats or persistently small populations. This study re-evaluates data for a tropical orchid and examines the value of including such analyses in an integrative approach. Methods Six small populations of Lepanthes rubripetala were used as a model system and the R software package popdemo was used to produce estimates of the indices for the asymptotic growth rate (lambda), sensitivities, reactivity, first-time step attenuation, maximum amplification, maximum attenuation, maximal inertia and maximal attenuation. The response in lambda to perturbations of demographic parameters using transfer functions and multiple perturbations on growth, stasis and fecundity were also determined. The results were compared with previously published asymptotic indices. Key Results It was found that combining asymptotic and transient dynamics expands the understanding of possible population changes. Comparison of the predicted density from reactivity and first-time step attenuation with the observed change in population size in two orchid populations showed that the observed density was within the predicted range. However, transfer function analysis suggests that the traditional approach of measuring perturbation of growth rates and persistence (inertia) may be misleading and is likely to result in erroneous management decisions. Conclusions Based on the results, an integrative approach is recommended using traditional PPMs (asymptotic processes) with an evaluation of the diversity of dynamics

  13. Spectral-Lagrangian methods for collisional models of non-equilibrium statistical states

    SciTech Connect

    Gamba, Irene M. Tharkabhushanam, Sri Harsha

    2009-04-01

    We propose a new spectral Lagrangian based deterministic solver for the non-linear Boltzmann transport equation (BTE) in d-dimensions for variable hard sphere (VHS) collision kernels with conservative or non-conservative binary interactions. The method is based on symmetries of the Fourier transform of the collision integral, where the complexity in its computation is reduced to a separate integral over the unit sphere S{sup d-1}. The conservation of moments is enforced by Lagrangian constraints. The resulting scheme, implemented in free space, is very versatile and adjusts in a very simple manner to several cases that involve energy dissipation due to local micro-reversibility (inelastic interactions) or elastic models of slowing down process. Our simulations are benchmarked with available exact self-similar solutions, exact moment equations and analytical estimates for the homogeneous Boltzmann equation, both for elastic and inelastic VHS interactions. Benchmarking of the simulations involves the selection of a time self-similar rescaling of the numerical distribution function which is performed using the continuous spectrum of the equation for Maxwell molecules as studied first in Bobylev et al. [A.V. Bobylev, C. Cercignani, G. Toscani, Proof of an asymptotic property of self-similar solutions of the Boltzmann equation for granular materials, Journal of Statistical Physics 111 (2003) 403-417] and generalized to a wide range of related models in Bobylev et al. [A.V. Bobylev, C. Cercignani, I.M. Gamba, On the self-similar asymptotics for generalized non-linear kinetic Maxwell models, Communication in Mathematical Physics, in press. URL: ()]. The method also produces accurate results in the case of inelastic diffusive Boltzmann equations for hard spheres (inelastic collisions under thermal bath), where overpopulated non-Gaussian exponential tails have been conjectured in computations by stochastic methods [T.V. Noije, M. Ernst

  14. A new method for calibrating a boron isotope paleo-pH proxy using massive Porites corals

    NASA Astrophysics Data System (ADS)

    Kubota, Kaoru; Yokoyama, Yusuke; Ishikawa, Tsuyoshi; Suzuki, Atsushi

    2015-09-01

    The boron isotope ratio (δ11B) of marine biogenic carbonates can reconstruct pH and pCO2 of seawater, and potentially CO2 concentration in the atmosphere. To date, δ11B-pHSW calibration has been proposed via culturing experiments, where calcifying organisms are cultured under artificially acidified seawater. However, in scleractinian corals, reconstructed pH values using culture-based calibrations do not agree well with actual observations of seawater CO2 chemistry. Thus, another approach is needed to establish a more reliable calibration method. In this study, we established field-based calibrations for Chichijima and Tahiti, both located in subtropical gyres where surface seawater is close to CO2 equilibrium. We suggest a new approach to calibration of δ11B-pH in which the long-term δ11B variation of massive Porites corals is compared with the decreasing pH trend (i.e., ocean acidification) that has occurred since the Industrial Revolution. This calibration will offer a new avenue for studying seawater CO2 chemistry using coral δ11B in diverse settings, such as upwelling regions, coral reefs, and coastal areas.

  15. Ammonia volatilization from artificial dung and urine patches measured by the equilibrium concentration technique (JTI method)

    NASA Astrophysics Data System (ADS)

    Saarijärvi, K.; Mattila, P. K.; Virkajärvi, P.

    The aim of this study was to investigate the dynamics of ammonia (NH 3) volatilization from intensively managed pastures on a soil type typical of the dairy production area in Finland and to clarify the effect of rainfall on NH 3 volatilization. The study included two experiments. In Experiment 1 the total amount of NH 3-N emitted was calculated based on the annual surface coverage of dung (4%) and urine (17%). The application rate of total N in the simulated dung and urine patches was approximately 47 g N m -2 and 113 g N m -2, respectively. In Experiment 1 the general level of NH 3 emissions from the urine patches was high and the peak volatilization rate was 0.54 g NH 3-N m -2 h -1. As expected, emissions from the dung pats were clearly lower with a maximum rate of 0.10 g NH 3-N m -2 h -1. The total emission calculated for the whole pasture area (stocking rate four cows ha -1 y -1, urine coverage 17% and dung coverage 4%) was 16.1 kg NH 3-N ha -1. Approximately 96% of the total emission originated from urine. In Experiment 2 we measured the emissions from urine only and the treatments on the urine patches were: (1) no irrigation, (2) 5+5 mm and (3) 20 mm irrigation. The peak emission rates were 0.13, 0.09 and 0.04 g NH 3-N m -2 h -1 and the total emissions were 6.9, 3.0 and 1.7 kg NH 3-N ha -1, for treatments (1), (2) and (3), respectively. In both measurements over 80% of the total emission occurred during the first 48 h and there was a clear diurnal rhythm. Increasing rainfall markedly decreased NH 3 emission. Volatilization was highest with dry and warm soil. The JTI method appeared to be suitable for measuring NH 3 volatilization in this kind of experiment. According to our results, the importance of pastures as a source of NH 3 emission in Finland is minor.

  16. Method and apparatus for noble gas atom detection with isotopic selectivity

    DOEpatents

    Hurst, G. Samuel; Payne, Marvin G.; Chen, Chung-Hsuan; Parks, James E.

    1984-01-01

    Apparatus and methods of operation are described for determining, with isotopic selectivity, the number of noble gas atoms in a sample. The analysis is conducted within an evacuated chamber which can be isolated by a valve from a vacuum pumping system capable of producing a pressure of 10.sup.-8 Torr. Provision is made to pass pulses of laser beams through the chamber, these pulses having wavelengths appropriate for the resonance ionization of atoms of the noble gas under analysis. A mass filter within the chamber selects ions of a specific isotope of the noble gas, and means are provided to accelerate these selected ions sufficiently for implantation into a target. Specific types of targets are discussed. An electron measuring device produces a signal relatable to the number of ions implanted into the target and thus to the number of atoms of the selected isotope of the noble gas removed from the gas sample. The measurement can be continued until a substantial fraction, or all, of the atoms in the sample have been counted. Furthermore, additional embodiments of the apparatus are described for bunching the atoms of a noble gas for more rapid analysis, and for changing the target for repetitive cycling of the gas in the chamber. The number of repetitions of the cyclic steps depend upon the concentration of the isotope of interest, the separative efficiency of the mass filter, etc. The cycles are continued until a desired selectivity is achieved. Also described are components and a method of operation for a pre-enrichment operation for use when an introduction of a total sample would elevate the pressure within the chamber to levels in excess of those for operation of the mass filter, specifically a quadrupole mass filter. Specific examples of three noble gas isotope analyses are described.

  17. 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

  18. Isotopic Dilution GC/MS Method for Methionine Determination in Biological Media

    NASA Astrophysics Data System (ADS)

    Horj, Elena; Iordache, Andreea; Culea, Monica

    2011-10-01

    The isotopic dilution mass spectrometry technique is the method of choice for sensitive and accurate determination of analytes in biological samples. The aim of this work was to establish a sensitive analytical method for the determination of methionine in different biological media. Quantitation of methionine from the resultant tracer spectrum requires deconvolution of the enrichment of the isotopomers. Deconvolution of the ion abundance ratios to yield tracer-to-tracee ratio for the isotopomer was done using Brauman's least squares approach. Comparison with regression curve calculation method is presented. The method was applied for amino-acids determination in beef, pork and fish meat.

  19. DoE optimization of a mercury isotope ratio determination method for environmental studies.

    PubMed

    Berni, Alex; Baschieri, Carlo; Covelli, Stefano; Emili, Andrea; Marchetti, Andrea; Manzini, Daniela; Berto, Daniela; Rampazzo, Federico

    2016-05-15

    By using the experimental design (DoE) technique, we optimized an analytical method for the determination of mercury isotope ratios by means of cold-vapor multicollector ICP-MS (CV-MC-ICP-MS) to provide absolute Hg isotopic ratio measurements with a suitable internal precision. By running 32 experiments, the influence of mercury and thallium internal standard concentrations, total measuring time and sample flow rate was evaluated. Method was optimized varying Hg concentration between 2 and 20 ng g(-1). The model finds out some correlations within the parameters affect the measurements precision and predicts suitable sample measurement precisions for Hg concentrations from 5 ng g(-1) Hg upwards. The method was successfully applied to samples of Manila clams (Ruditapes philippinarum) coming from the Marano and Grado lagoon (NE Italy), a coastal environment affected by long term mercury contamination mainly due to mining activity. Results show different extents of both mass dependent fractionation (MDF) and mass independent fractionation (MIF) phenomena in clams according to their size and sampling sites in the lagoon. The method is fit for determinations on real samples, allowing for the use of Hg isotopic ratios to study mercury biogeochemical cycles in complex ecosystems. PMID:26992509

  20. Reverse isotope dilution method for determining benzene and metabolites in tissues

    SciTech Connect

    Bechtold, W.E.; Sabourin, P.J.; Henderson, R.F.

    1988-07-01

    A method utilizing reverse isotope dilution for the analysis of benzene and its organic soluble metabolites in tissues of rats and mice is presented. Tissues from rats and mice that had been exposed to radiolabeled benzene were extracted with ethyl acetate containing known, excess quantities of unlabeled benzene and metabolites. Butylated hydroxytoluene was added as an antioxidant. The ethyl acetate extracts were analyzed with semipreparative reversed-phase HPLC. Isolated peaks were collected and analyzed for radioactivity (by liquid scintillation spectrometry) and for mass (by UV absorption). The total amount of each compound present was calculated from the mass dilution of the radiolabeled isotope. This method has the advantages of high sensitivity, because of the high specific activity of benzene, and relative stability of the analyses, because of the addition of large amounts of unlabeled carrier analogue.

  1. Method for correcting for isotope burn-in effects in fission neutron dosimeters

    DOEpatents

    Gold, Raymond; McElroy, William N.

    1988-01-01

    A method is described for correcting for effect of isotope burn-in in fission neutron dosimeters. Two quantities are measured in order to quantify the "burn-in" contribution, namely P.sub.Z',A', the amount of (Z', A') isotope that is burned-in, and F.sub.Z', A', the fissions per unit volume produced in the (Z', A') isotope. To measure P.sub.Z', A', two solid state track recorder fission deposits are prepared from the very same material that comprises the fission neutron dosimeter, and the mass and mass density are measured. One of these deposits is exposed along with the fission neutron dosimeter, whereas the second deposit is subsequently used for observation of background. P.sub.Z', A' is then determined by conducting a second irradiation, wherein both the irradiated and unirradiated fission deposits are used in solid state track recorder dosimeters for observation of the absolute number of fissions per unit volume. The difference between the latter determines P.sub.Z', A' since the thermal neutron cross section is known. F.sub.Z', A' is obtained by using a fission neutron dosimeter for this specific isotope, which is exposed along with the original threshold fission neutron dosimeter to experience the same neutron flux-time history at the same location. In order to determine the fissions per unit volume produced in the isotope (Z', A') as it ingrows during the irradiation, B.sub.Z', A', from these observations, the neutron field must generally be either time independent or a separable function of time t and neutron energy E.

  2. Coupled quantum-scattering modeling of thermoelectric performance of nanostructured materials using the non-equilibrium Green's function method

    NASA Astrophysics Data System (ADS)

    Bulusu, Anuradha

    Semi-classical transport models based on Boltzmann and Fermi-Dirac statistics have been very effective identifying the pertinent physical parameters responsible for thermoelectric performance in bulk materials. Reliance on Boltzmann-based models has produced a culture of "smaller is better" research, where the reduction in size is expected to produce limitless increase in performance. Experimental observations especially in the case of thermoelectric performance of nanoscale devices have not exhibited this behavior. The semi-classical Boltzmann models are based on the relaxation-time approximation and cannot model strong non-equilibrium transport. In addition, wave effects in these models are included through correction terms that cannot suitably capture their influence on transport. A coupled quantum-scattering model to study thermoelectric performance of nanoscale structures is proposed through the nonequilibrium Green's function method. The model includes all the pertinent physics of the wave nature of electrons while coupling election-phonon scattering effects. The NEGF method is used to study the performance of silicon nano-films and nanowires as well as strained quantum well Si/Ge/Si superlattices as a function of doping, effective mass and in the case of superlattices, substrate strain and superlattice geometry. Results suggest that the power factor of nanostructured materials is dominated by the electrical conductivity which in turn is strongly influenced by quantum confinement effects and electron-phonon scattering effects. No significant improvement in the Seebeck coefficient is observed due to the decrease in dimensionality of the structure. The NEGF method can be used as a tool to design structure with optimized values of doping, effective mass, substrate strain and superlattice geometry taking into consideration the effects of electron confinement and scattering. The method developed in this research can be used as a framework to guide further studies

  3. Integral Method for the Assessment of U-RANS Effectiveness in Non-Equilibrium Flows and Heat Transfer

    NASA Astrophysics Data System (ADS)

    Pond, Ian; Edabi, Alireza; Dubief, Yves; White, Christopher

    2015-11-01

    Reynolds Average Navier Stokes (RANS) modeling has established itself as a critical design tool in many engineering applications, thanks to its superior computational efficiency. The drawbacks of RANS models are well known, but not necessarily well understood: poor prediction of transition, non equilibrium flows, mixing and heat transfer, to name the ones relevant to our study. In the present study, we use a DNS of a reciprocating channel flow driven by an oscillating pressure gradient to test several low- and high-Reynolds RANS models. Temperature is introduced as a passive scalar to study heat transfer modeling. Low-Reynolds models manage to capture the overall physics of wall shear and heat flux well, yet with some phase discrepancies, whereas high Reynolds models fail. Under the microscope of the integral method for wall shear and wall heat flux, the qualitative agreement appears more serendipitous than driven by the ability of the models to capture the correct physics. The integral method is shown to be more insightful in the benchmarking of RANS models than the typical comparisons of statistical quantities. The authors acknowledges the support of NSF and DOE under grant NSF/DOE 1258697 (VT) and 1258702 (NH).

  4. CF-IRMS method to measure the isotopic composition of very small/stratospheric water samples

    NASA Astrophysics Data System (ADS)

    Franz, P.; Roeckmann, T.

    2003-04-01

    Measurements of the isotopic composition of stratospheric water vapor are believed to provide further insight about sources of stratospheric water vapor, i.e. transport from the troposphere and in situ formation, and thus about the stratospheric water budget. Including the 17O signature in addition to the usually targeted 18O and D data is interesting, since water formed in the stratosphere may inherit a fraction of the oxygen isotope anomaly present in ozone in its photochemical production. Whereas several methods are being developed for in situ measurements with optical techniques, we attempt to obtain stratospheric water samples and analyze them in the laboratory with a novel high precision continuous-flow isotope ratio monitoring technique. The laboratory extraction and measurement parts have been setup and will be presented. For the measurement of the stable oxygen isotopes, the sample is injected into a heated tube filled with CoF_3, where water is chemically converted to oxygen. The O_2 sample is then injected into a multi-cup isotope ratio mass spectrometer, where δ17O and δ18O are determined. Due to the extremely small sample size requirement for continuous-flow isotope ratio mass spectrometry, many measurements can be made on the same sample. This is realized by flushing the sample out of its container with purified helium into a sample loop trap, and successively injecting many aliquots. Non-linearity effects and instrumental fractionation can then be taken into account by fitting an entire measurement series onto a mathematical model. At present, measurement errors are about 0.8 0/00 for δ17O and 0.5 0/00 for δ18O. Alternatively, a high temperature furnace (alumina tube filled with Ni-wires) can be used for the conversion to hydrogen gas. Carbon molecules can be deposited on the Ni by flushing the furnace with CH_4, hence allowing the later pyrolysis of water to H_2 and CO. Due to the somewhat more complicated analysis of H_2, this method has not

  5. Evaluation of Isotope 32P Method to Mark Culex pipiens (Diptera: Culicidae) in a Laboratory

    PubMed Central

    Zhang, Chongxing; Shi, Guihong; Zhao, Yuqiang; Yan, Dongmei; Li, Huaiju; Liu, Hongmei; Wiwatanaratanabutr, Itsanun; Gong, Maoqing

    2016-01-01

    Background: The aim of the current study was to develop a marking technique as an internal marker to mark post blood meal mosquitoes by using stable phosphate isotope 32P and determine the optimal concentration of it. Methods: An isotonic physiological saline solution, containing different concentration of radioactive isotope 32P-labeled disodium phosphate (Na2H32PO4) was injected into rabbits via the jugular vein in the laboratory. Emerged Cx. pipiens were marked after feeding on rabbit. At the same time, the labeled conditions of emerged Cx. pipiens were also measured by placing feces of No. 6 rabbit into containers with mosquito larvae and pupae inside. Results: According to the label condition of Cx. pipiens after taking blood and the effect of different dosage Na2H32PO4 on rabbit health, the optimal concentration of radioactive isotope was determined, that is, 0.1211 mCi/kg. By placing feces of No. 6 rabbit into containers with mosquito larvae and pupae inside, the emerged mosquitoes were also labeled. Therefore, feeding mosquitoes on the animal injected with radioactive Na2H32PO4 was more practical for detecting and tracing mosquitoes. Conclusion: The method was less time-consuming, more sensitive and safer. This marking method will facilitate post-bloodmeal studies of mosquitoes and other blood-sucking insects. PMID:27308279

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

    PubMed

    Elyahyaoui, A; Zarki, R; Chiadli, A

    2003-01-01

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

  7. RAPID SEPARATION METHOD FOR 237NP AND PU ISOTOPES IN LARGE SOIL SAMPLES

    SciTech Connect

    Maxwell, S.; Culligan, B.; Noyes, G.

    2010-07-26

    A new rapid method for the determination of {sup 237}Np and Pu isotopes in soil and sediment samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used for large soil samples. The new soil method utilizes an acid leaching method, iron/titanium hydroxide precipitation, a lanthanum fluoride soil matrix removal step, and a rapid column separation process with TEVA Resin. The large soil matrix is removed easily and rapidly using this two simple precipitations with high chemical recoveries and effective removal of interferences. Vacuum box technology and rapid flow rates are used to reduce analytical time.

  8. Improved method for isotopic and quantitative analysis of dissolved inorganic carbon in natural water samples.

    PubMed

    Assayag, Nelly; Rivé, Karine; Ader, Magali; Jézéquel, Didier; Agrinier, Pierre

    2006-01-01

    We present here an improved and reliable method for measuring the concentration of dissolved inorganic carbon (DIC) and its isotope composition (delta(13)C(DIC)) in natural water samples. Our apparatus, a gas chromatograph coupled to an isotope ratio mass spectrometer (GCIRMS), runs in a quasi-automated mode and is able to analyze about 50 water samples per day. The whole procedure (sample preparation, CO(2(g))-CO(2(aq)) equilibration time and GCIRMS analysis) requires 2 days. It consists of injecting an aliquot of water into a H(3)PO(4)-loaded and He-flushed 12 mL glass tube. The H(3)PO(4) reacts with the water and converts the DIC into aqueous and gaseous CO(2). After a CO(2(g))-CO(2(aq)) equilibration time of between 15 and 24 h, a portion of the headspace gas (mainly CO(2)+He) is introduced into the GCIRMS, to measure the carbon isotope ratio of the released CO(2(g)), from which the delta(13)C(DIC) is determined via a calibration procedure. For standard solutions with DIC concentrations ranging from 1 to 25 mmol . L(-1) and solution volume of 1 mL (high DIC concentration samples) or 5 mL (low DIC concentration samples), delta(13)C(DIC) values are determined with a precision (1sigma) better than 0.1 per thousand. Compared with previously published headspace equilibration methods, the major improvement presented here is the development of a calibration procedure which takes the carbon isotope fractionation associated with the CO(2(g))-CO(2(aq)) partition into account: the set of standard solutions and samples has to be prepared and analyzed with the same 'gas/liquid' and 'H(3)PO(4)/water' volume ratios. A set of natural water samples (lake, river and hydrothermal springs) was analyzed to demonstrate the utility of this new method. PMID:16810706

  9. Physical and Mathematical Methods for Removing Organic Interference from Optical Isotope Measurements

    NASA Astrophysics Data System (ADS)

    Hsiao, G.; Chappellet-Volini, L.; Vu, D.

    2012-12-01

    Portable high precision isotope analyzers using CRDS technology have greatly increased the use of stable isotopes in hydrological, oceanographic, and ecological studies over the past five years. However studies of some water samples yielded incorrect isotopic values indicating some form of spectroscopic interference. Subsequent work has shown that waters derived from some plants containing interfering alcohols but meteoric waters are not affected. The initial approach to handling such samples was to use spectroscopic anomalies to identify and flag affected samples for later analysis by non-optical methods. This presentation will examine the approaches developed within the past year to allow for accurate analysis of such samples by optical methods. The first approach uses an advanced spectroscopic model to identify and quantify alcohols present in the sample. The alcohol signal is incorporated into the overall fit of the measure spectra to calculate the concentration of the individual isotopes. It was found that the δ18O value could be calculated with high accuracy, the result for the δ2H value was sufficient for many applications. The second approach uses physical treatment of the sample to break down the organic molecules into non-interfering species. The liquid sample is injected into a flash vaporizer then the vapor travels through a cartridge for physical treatment prior to analysis by CRDS. Inside the cartridge the organic molecules undergo oxidation at high temperature in the air carrier gas when exposed to the catalyst. This approach is highly effective for ethanol solutions as high as 5% as well as for the complex mixtures of alcohols found in plants. Comparison of the results of both of these methods will be compared with tertiary techniques such as IRMS where possible.

  10. Evaluating gull diets: A comparison of conventional methods and stable isotope analysis

    USGS Publications Warehouse

    Weiser, E.L.; Powell, A.N.

    2011-01-01

    Samples such as regurgitated pellets and food remains have traditionally been used in studies of bird diets, but these can produce biased estimates depending on the digestibility of different foods. Stable isotope analysis has been developed as a method for assessing bird diets that is not biased by digestibility. These two methods may provide complementary or conflicting information on diets of birds, but are rarely compared directly. We analyzed carbon and nitrogen stable isotope ratios of feathers of Glaucous Gull (Larus hyperboreus) chicks from eight breeding colonies in northern Alaska, and used a Bayesian mixing model to generate a probability distribution for the contribution of each food group to diets. We compared these model results with probability distributions from conventional diet samples (pellets and food remains) from the same colonies and time periods. Relative to the stable isotope estimates, conventional analysis often overestimated the contributions of birds and small mammals to gull diets and often underestimated the contributions of fish and zooplankton. Both methods gave similar estimates for the contributions of scavenged caribou, miscellaneous marine foods, and garbage to diets. Pellets and food remains therefore may be useful for assessing the importance of garbage relative to certain other foods in diets of gulls and similar birds, but are clearly inappropriate for estimating the potential impact of gulls on birds, small mammals, or fish. However, conventional samples provide more species-level information than stable isotope analysis, so a combined approach would be most useful for diet analysis and assessing a predator's impact on particular prey groups. ?? 2011 Association of Field Ornithologists.

  11. Effect of cohesion and fill amplification on seismic stability of municipal solid waste landfills using limit equilibrium method.

    PubMed

    Savoikar, Purnanand; Choudhury, Deepankar

    2010-12-01

    Municipal solid waste (MSW) landfills in seismic zones are subjected to the seismic forces both in the horizontal and vertical directions. The stability of landfills against these seismic forces was evaluated by computing the factor of safety of landfills with different modes of failure among which failures of landfills due to translation are very common. Conventionally, the seismic stability of landfill is evaluated by using pseudo-static limit equilibrium method. In the present study, seismic stability of landfills is evaluated by both the conventional pseudo-static and modern pseudo-dynamic method. The pseudo-dynamic method is superior as it takes into account the effect of duration and frequency of earthquake motion and corresponding body waves in addition to the variation of earthquake accelerations along depth and time. In the present study, the effects of cohesion and fill amplification on seismic stability of landfill are also taken into account. It was noticed that, neglecting cohesion of fill material as well as liner material, results in a lower factor of safety and, hence, a very conservative/uneconomic design. Also, fill amplification is found to reduce the factor of safety values computed only by using the pseudo-dynamic method, showing its advantage. Generalized expressions are developed for factor of safety and yield acceleration against translational failure, which can be used for evaluating the seismic stability of MSW landfills. Comparisons of results under static condition with existing, similar methodology show a very good agreement. However, the present study seems to provide unique results for the seismic case. PMID:19837709

  12. Effect of cohesion and fill amplification on seismic stability of municipal solid waste landfills using limit equilibrium method.

    PubMed

    Savoikar, Purnanand; Choudhury, Deepankar

    2010-12-01

    Municipal solid waste (MSW) landfills in seismic zones are subjected to the seismic forces both in the horizontal and vertical directions. The stability of landfills against these seismic forces was evaluated by computing the factor of safety of landfills with different modes of failure among which failures of landfills due to translation are very common. Conventionally, the seismic stability of landfill is evaluated by using pseudo-static limit equilibrium method. In the present study, seismic stability of landfills is evaluated by both the conventional pseudo-static and modern pseudo-dynamic method. The pseudo-dynamic method is superior as it takes into account the effect of duration and frequency of earthquake motion and corresponding body waves in addition to the variation of earthquake accelerations along depth and time. In the present study, the effects of cohesion and fill amplification on seismic stability of landfill are also taken into account. It was noticed that, neglecting cohesion of fill material as well as liner material, results in a lower factor of safety and, hence, a very conservative/uneconomic design. Also, fill amplification is found to reduce the factor of safety values computed only by using the pseudo-dynamic method, showing its advantage. Generalized expressions are developed for factor of safety and yield acceleration against translational failure, which can be used for evaluating the seismic stability of MSW landfills. Comparisons of results under static condition with existing, similar methodology show a very good agreement. However, the present study seems to provide unique results for the seismic case.

  13. Nonlinear Boltzmann equation for the homogeneous isotropic case: Some improvements to deterministic methods and applications to relaxation towards local equilibrium

    NASA Astrophysics Data System (ADS)

    Asinari, P.

    2011-03-01

    Boltzmann equation is one the most powerful paradigms for explaining transport phenomena in fluids. Since early fifties, it received a lot of attention due to aerodynamic requirements for high altitude vehicles, vacuum technology requirements and nowadays, micro-electro-mechanical systems (MEMs). Because of the intrinsic mathematical complexity of the problem, Boltzmann himself started his work by considering first the case when the distribution function does not depend on space (homogeneous case), but only on time and the magnitude of the molecular velocity (isotropic collisional integral). The interest with regards to the homogeneous isotropic Boltzmann equation goes beyond simple dilute gases. In the so-called econophysics, a Boltzmann type model is sometimes introduced for studying the distribution of wealth in a simple market. Another recent application of the homogeneous isotropic Boltzmann equation is given by opinion formation modeling in quantitative sociology, also called socio-dynamics or sociophysics. The present work [1] aims to improve the deterministic method for solving homogenous isotropic Boltzmann equation proposed by Aristov [2] by two ideas: (a) the homogeneous isotropic problem is reformulated first in terms of particle kinetic energy (this allows one to ensure exact particle number and energy conservation during microscopic collisions) and (b) a DVM-like correction (where DVM stands for Discrete Velocity Model) is adopted for improving the relaxation rates (this allows one to satisfy exactly the conservation laws at macroscopic level, which is particularly important for describing the late dynamics in the relaxation towards the equilibrium).

  14. A validated method for the quantitation of 1,1-difluoroethane using a gas in equilibrium method of calibration.

    PubMed

    Avella, Joseph; Lehrer, Michael; Zito, S William

    2008-10-01

    1,1-Difluoroethane (DFE), also known as Freon 152A, is a member of a class of compounds known as halogenated hydrocarbons. A number of these compounds have gained notoriety because of their ability to induce rapid onset of intoxication after inhalation exposure. Abuse of DFE has necessitated development of methods for its detection and quantitation in postmortem and human performance specimens. Furthermore, methodologies applicable to research studies are required as there have been limited toxicokinetic and toxicodynamic reports published on DFE. This paper describes a method for the quantitation of DFE using a gas chromatography-flame-ionization headspace technique that employs solventless standards for calibration. Two calibration curves using 0.5 mL whole blood calibrators which ranged from A: 0.225-1.350 to B: 9.0-180.0 mg/L were developed. These were evaluated for linearity (0.9992 and 0.9995), limit of detection of 0.018 mg/L, limit of quantitation of 0.099 mg/L (recovery 111.9%, CV 9.92%), and upper limit of linearity of 27,000.0 mg/L. Combined curve recovery results of a 98.0 mg/L DFE control that was prepared using an alternate technique was 102.2% with CV of 3.09%. No matrix interference was observed in DFE enriched blood, urine or brain specimens nor did analysis of variance detect any significant differences (alpha = 0.01) in the area under the curve of blood, urine or brain specimens at three identical DFE concentrations. The method is suitable for use in forensic laboratories because validation was performed on instrumentation routinely used in forensic labs and due to the ease with which the calibration range can be adjusted. Perhaps more importantly it is also useful for research oriented studies because the removal of solvent from standard preparation eliminates the possibility for solvent induced changes to the gas/liquid partitioning of DFE or chromatographic interference due to the presence of solvent in specimens. PMID:19007521

  15. Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea).

    PubMed

    Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

    2015-01-01

    Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ15N, δ13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ13C and δ15N and C/N atomic values. Chemical preservatives caused δ13C enrichment as great as 1.5‰, and δ15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ15N depletion up to 1.8‰. Freezing depleted δ13C and δ15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets.

  16. Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea)

    PubMed Central

    Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

    2015-01-01

    Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ15N, δ13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ13C and δ15N and C/N atomic values. Chemical preservatives caused δ13C enrichment as great as 1.5‰, and δ15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ15N depletion up to 1.8‰. Freezing depleted δ13C and δ15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets. PMID:26390400

  17. Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea).

    PubMed

    Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

    2015-01-01

    Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ15N, δ13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ13C and δ15N and C/N atomic values. Chemical preservatives caused δ13C enrichment as great as 1.5‰, and δ15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ15N depletion up to 1.8‰. Freezing depleted δ13C and δ15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets. PMID:26390400

  18. Isotope geochemistry. Biological signatures in clumped isotopes of O₂.

    PubMed

    Yeung, Laurence Y; Ash, Jeanine L; Young, Edward D

    2015-04-24

    The abundances of molecules containing more than one rare isotope have been applied broadly to determine formation temperatures of natural materials. These applications of "clumped" isotopes rely on the assumption that isotope-exchange equilibrium is reached, or at least approached, during the formation of those materials. In a closed-system terrarium experiment, we demonstrate that biological oxygen (O2) cycling drives the clumped-isotope composition of O2 away from isotopic equilibrium. Our model of the system suggests that unique biological signatures are present in clumped isotopes of O2—and not formation temperatures. Photosynthetic O2 is depleted in (18)O(18)O and (17)O(18)O relative to a stochastic distribution of isotopes, unlike at equilibrium, where heavy-isotope pairs are enriched. Similar signatures may be widespread in nature, offering new tracers of biological and geochemical cycling.

  19. Isotope geochemistry. Biological signatures in clumped isotopes of O₂.

    PubMed

    Yeung, Laurence Y; Ash, Jeanine L; Young, Edward D

    2015-04-24

    The abundances of molecules containing more than one rare isotope have been applied broadly to determine formation temperatures of natural materials. These applications of "clumped" isotopes rely on the assumption that isotope-exchange equilibrium is reached, or at least approached, during the formation of those materials. In a closed-system terrarium experiment, we demonstrate that biological oxygen (O2) cycling drives the clumped-isotope composition of O2 away from isotopic equilibrium. Our model of the system suggests that unique biological signatures are present in clumped isotopes of O2—and not formation temperatures. Photosynthetic O2 is depleted in (18)O(18)O and (17)O(18)O relative to a stochastic distribution of isotopes, unlike at equilibrium, where heavy-isotope pairs are enriched. Similar signatures may be widespread in nature, offering new tracers of biological and geochemical cycling. PMID:25908819

  20. Estimating the Isotope Ratio of Ecosystem Respiration Using the Keeling Plot and the Flux Ratio Method

    NASA Astrophysics Data System (ADS)

    Zhang, J.; Griffis, T. J.; Baker, J. M.

    2004-12-01

    Stable carbon isotope analyses have been used in identifying global carbon sources and sinks and in partitioning ecosystem CO2 exchange into component fluxes. The isotope ratio of ecosystem respiration (δ 13Cr) is a critical parameter in applying stable isotope techniques to carbon cycle problems. The commonly used Keeling plot method in estimating δ 13Cr has limitations related to: 1) insufficient range of CO2 mixing ratio; 2) high sensitivity to curve-fitting techniques; and 3) extrapolation of CO2 mixing ratio beyond observations. In this study, the Keeling plot method was examined and compared with the flux ratio approach using continuous measurements of the mixing ratios of 12CO2 and 13CO2 over an extensive corn canopy during the 2003 growing season. The seasonal variation of δ 13Cr estimated from both methods harmonized with the ecosystem phenology. The δ 13Cr started to increase (became more positive) from mid June and peaked in early August, followed by a decrease into October. The Keeling plot method agreed well with the flux ratio method in the seasonal pattern of δ 13Cr, but tended to give lower values (more negative). The discrepancy between the two approaches was significant in July and August (about 5 per mil) and relatively small in June and September (about 1 to 2 per mil). We examined this discrepancy with respect to wind direction/advection and measurement footprints. In addition, our analysis of high-frequency data (every two minutes) using the flux ratio method indicates that δ 13Cr may vary significantly at short time-scales (e.g., hourly), which could have significant implications for flux partitioning studies.

  1. Detection of Human Sewage in Urban Stormwater Using DNA Based Methods and Stable Isotope Analysis

    NASA Astrophysics Data System (ADS)

    McLellan, S. L.; Malet, N.; Sauer, E.; Mueller-Spitz, S.; Borchardt, M.

    2008-12-01

    related to the mixed organic matter sources in polluted stormwater runoff, and that this signal will distinct from untreated sanitary sewage. Stable isotope signatures of stormwater and untreated sewage were determined and compared with the rivers. Isotopic values of stormwater was delta 15N = 1.1 ± 2 %; delta 13C = -25.5 ± 3 % and sewage was delta 15N = -1.9 ± 0.2 %; delta 13C = -23.6 ± 0.3. Suspended particular organic matter (SPOM) of Milwaukee River showed depleted delta 13C (-28.6 ± 1.6 %) and enriched delta 15N (7.7 ± 1.9 %) values. SPOM of the KK River exhibited the most depleted delta 15N (0.2 ± 1.6 %) and enriched delta 13C (-24.8 ± 1.8 %) isotopic values. Menomonee River SPOM showed intermediate isotopic values. The delta 13C values of each river and the estuary enriched significantly throughout the summer storm periods. The isotope signals in the KK and Menomonee were indicative of stormwater runoff and sewage contamination. These results suggest that unrecognized sewage inputs are chronically present and may be delivered through urban stormwater systems. DNA based methods combined with isotope analysis may provide a useful tool for urban watershed assessments and to identify sewage inputs. Delineating the relative contribution of stormwater and sewage to overall degraded water quality might give the first indication of the impact of these sources on the Michigan Lake waters.

  2. Stable isotope analysis of plant-derived nitrate - novel method for discrimination between organically and conventionally grown vegetables.

    PubMed

    Mihailova, A; Pedentchouk, N; Kelly, S D

    2014-07-01

    The lack of reliable markers for the discrimination between organic and conventional products makes the organic food market susceptible to attempted fraud. Robust analytical methodologies for organic food authentication are urgently needed. In this study a new approach, compound-specific nitrogen and oxygen isotope analysis of plant-derived nitrate, has been applied alongside bulk nitrogen isotope analysis for discrimination between organically and conventionally greenhouse-grown lettuce and retail potatoes and tomatoes. The method revealed significant differences between conventional and organic fertilisation. An intra-plant isotopic variation as well as significant impact of the fertiliser application rate on the nitrogen and oxygen isotope values of plant-derived nitrate has been observed. Nitrogen and oxygen isotope analysis of nitrate has a potential for differentiation between organic and conventional crops. Further analysis is needed to improve our understanding of the scope of application and robustness of this compound-specific approach. PMID:24518338

  3. Stable isotope analysis of plant-derived nitrate - novel method for discrimination between organically and conventionally grown vegetables.

    PubMed

    Mihailova, A; Pedentchouk, N; Kelly, S D

    2014-07-01

    The lack of reliable markers for the discrimination between organic and conventional products makes the organic food market susceptible to attempted fraud. Robust analytical methodologies for organic food authentication are urgently needed. In this study a new approach, compound-specific nitrogen and oxygen isotope analysis of plant-derived nitrate, has been applied alongside bulk nitrogen isotope analysis for discrimination between organically and conventionally greenhouse-grown lettuce and retail potatoes and tomatoes. The method revealed significant differences between conventional and organic fertilisation. An intra-plant isotopic variation as well as significant impact of the fertiliser application rate on the nitrogen and oxygen isotope values of plant-derived nitrate has been observed. Nitrogen and oxygen isotope analysis of nitrate has a potential for differentiation between organic and conventional crops. Further analysis is needed to improve our understanding of the scope of application and robustness of this compound-specific approach.

  4. Use of ramping and equilibrium water vapor sorption methods to determine the critical relative humidity at which the glassy to rubbery transition occurs in polydextrose.

    PubMed

    Li, Qingruisi E; Schmidt, Shelly J

    2011-01-01

    Recent research has demonstrated that the critical relative humidity (RHc) values, obtained using automatic water vapor sorption instruments, can be used to detect the glassy to rubbery transition. However, reported time dependency of these RHc values suggests that additional research be carried out using equilibrium water vapor sorption methods. Thus, the objectives of this study were to: (1) determine the RHc for amorphous polydextrose at various temperatures using both instrumental (Dynamic Vapor Sorption [DVS] ramping and equilibrium) and saturated salt slurry methods, and (2) compare the RHc values obtained via sorption methods to the glass transition temperature (Tg) values obtained via differential scanning calorimetry (DSC). When plotted as a "glass curve" on a state diagram, the RHc values (plotted as a function of temperature) were found to be similar to the Tg values (plotted as a function of relative humidity). Of the 3 sorption methods employed, at 25 °C, the saturated salt slurry exhibited the lowest RHc value (34.3%), followed by the DVS equilibrium method (41.7%), and the DVS ramping method (49.9%). The RHc DVS equilibrium method was closest to the calculated DSC Tg onset RHc value (41.6% at 25 °C). These water sorption methods show promise as practical tools for predicting the quality and stability attributes of amorphous materials by being able to routinely determine the location of the glassy to rubbery transition. Future research applying these sorption methods to more complex amorphous food systems is suggested. Practical Application: Despite its extreme usefulness, the Tg, a key element of the Food Polymer Science approach, remains a challenging parameter to routinely measure in amorphous food materials. Recent research has demonstrated that the RHc values can be used to detect the glassy to rubbery transition. However, reported time dependency of these RHc values suggests that additional research be carried out using equilibrium water vapor

  5. A rapid method for the sampling of atmospheric water vapour for isotopic analysis.

    PubMed

    Peters, Leon I; Yakir, Dan

    2010-01-01

    Analysis of the stable isotopic composition of atmospheric moisture is widely applied in the environmental sciences. Traditional methods for obtaining isotopic compositional data from ambient moisture have required complicated sampling procedures, expensive and sophisticated distillation lines, hazardous consumables, and lengthy treatments prior to analysis. Newer laser-based techniques are expensive and usually not suitable for large-scale field campaigns, especially in cases where access to mains power is not feasible or high spatial coverage is required. Here we outline the construction and usage of a novel vapour-sampling system based on a battery-operated Stirling cycle cooler, which is simple to operate, does not require any consumables, or post-collection distillation, and is light-weight and highly portable. We demonstrate the ability of this system to reproduce delta(18)O isotopic compositions of ambient water vapour, with samples taken simultaneously by a traditional cryogenic collection technique. Samples were collected over 1 h directly into autosampler vials and were analysed by mass spectrometry after pyrolysis of 1 microL aliquots to CO. This yielded an average error of < +/-0.5 per thousand, approximately equal to the signal-to-noise ratio of traditional approaches. This new system provides a rapid and reliable alternative to conventional cryogenic techniques, particularly in cases requiring high sample throughput or where access to distillation lines, slurry maintenance or mains power is not feasible. PMID:19960497

  6. A New, Rapid, Precise and Sensitive Method for Chlorine Stable Isotope Analysis of Chlorinated Aliphatic Hydrocarbons

    NASA Astrophysics Data System (ADS)

    van Acker, M. R.; Shahar, A.; Young, E. D.; Coleman, M. L.

    2005-12-01

    Chlorinated aliphatic hydrocarbons (CAH) are recognized common groundwater contaminants. Because of their physico-chemical properties, their lifespan in groundwater is in the order of decades (Pankow and Cherry, 1996). Stable isotopes can play a role in determining the rate and extent of CAH attenuation (Slater, 2003). The use of chlorine has been hampered by the current time consuming and insensitive analytical methods. We present a new analytical procedure to measure chlorine stable isotope values using a gas chromatograph coupled to a multi-collector inductively coupled mass spectrometer (GC-MC-ICP-MS). The GC has a Porapack Q packed column. The carrier gas was helium and the temperature was constant at 160°C. The GC was coupled to the MC-ICP-MS by heated stainless steel tubing. Our high resolution spectra showed that 37Cl is free of its main interference 36Ar-H over a range of 0.004 amu. Two pure CAH, trichloroethene (TCE) and tetrachloroethene (PCE), were used for zero enrichment (sample relative to itself) and standard-sample difference measurements. Integrations and background corrections of transient signals were performed using Microsoft Excel after import of the raw data from the MC-ICPMS acquisition software. Zero enrichment tests with TCE and PCE yielded δ37Cl of -0.04±0.16‰ and -0.03±0.17‰, respectively, results for sample injections of 0.12 to 0.02 microliters. Accuracy was tested by injecting 0.24 microliters of a 50/50 mixture of TCE and PCE of known isotopic compositions as the difference between the two solvents was of paramount interest. The δ37Cl(TCE) value of PCE was -1.99±0.16‰. A highly satisfactory comparison with the conventional method is shown by published values for TCE and PCE, -2.04±0.12‰ and -0.30±0.14‰, respectively (Jendrzejewski et al., 2001), giving a δ37Cl(TCE) value for PCE of -2.34±0.18‰. These tests of the GC-MC-ICP-MS method showed that we can obtain reproducible and accurate Cl isotope values using an

  7. A new method for stable carbon isotope analysis of chlorofluorocarbons in contaminated groundwater

    NASA Astrophysics Data System (ADS)

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2015-04-01

    Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been widely used as refrigerants, propellants, solvents, foaming agents and are important intermediates in the production of anesthetics and other fluorinated compounds. Due to their ozone depletion potential, production was banned for most uses under the Montreal Protocol (1987) and its amendments and atmospheric mixing ratios have started to decrease. In addition to the atmosphere, CFCs and HCFCs have been detected in groundwater, and emissions from various sources such as landfill sites are still ongoing. Previous studies have shown that both abiotic and biotic transformation of CFCs may occur under certain conditions. To investigate degradation that may take place in soils and groundwaters, a purge and trap method (P&T) has been developed to measure the stable carbon isotopic composition of CFCs and HCFCs extracted from waters. A set of pure phase working standards (HCFC-22, CFC-11, CFC-113) has been prepared offline and characterized by sealed tube combustion dual inlet mass spectrometry. Comparison between isotopic standards and CFCs extracted by our method demonstrates the sample P&T extraction steps do not induce significant δ13C fractionation (lt;0.5 per mill). Standards characterized by continuous flow CSIA (compound specific isotope analysis) after extraction agree with offline characterized values. Evaporation experiments were carried out to investigate any isotope effects due to volatile loss that might occur either due to sampling methods or sample handling in the lab. Monitoring δ13C values during progressive evaporation showed small isotopic fractionation associated with evaporation. Enrichment factors, obtained from Rayleigh plots, showed inverse isotope fractionation i.e depletion in 13C in the remaining compound. Notably, this effect is in the opposite direction to the fractionation (13C enrichment) that is likely to be associated with abiotic or biotic transformation effects

  8. The effect of carbonic anhydrase on the kinetics and equilibrium of the oxygen isotope exchange in the CO2-H2O system: Implications for δ18O vital effects in biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Uchikawa, Joji; Zeebe, Richard E.

    2012-10-01

    Interpretations of the primary paleoceanographic information recorded in stable oxygen isotope values (δ18O) of biogenic CaCO3 can be obscured by disequilibrium effects. CaCO3 is often depleted in 18O relative to the δ18O values expected for precipitation in thermodynamic equilibrium with ambient seawater as a result of vital effects. Vital effects in δ18O have been explained in terms of the influence of fluid pH on the overall δ18O of the sum of dissolved inorganic carbon (DIC) species (often referred to as "pH model") and in terms of 18O depletion as a result of the kinetic effects associated with CO2 hydration (CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+) and CO2 hydroxylation (CO2 + OH- ↔ HCO3-) in the calcification sites (so-called "kinetic model"). This study addresses the potential role of an enzyme, carbonic anhydrase (CA), that catalyzes inter-conversion of CO2 and HCO3- in relation to the underlying mechanism of vital effects. We performed quantitative inorganic carbonate precipitation experiments in order to examine the changes in 18O equilibration rate as a function of CA concentration. Experiments were performed at pH 8.3 and 8.9. These pH values are comparable to the average surface ocean pH and elevated pH levels observed in the calcification sites of some coral and foraminiferal species, respectively. The rate of uncatalyzed 18O exchange in the CO2-H2O system is governed by the pH-dependent DIC speciation and the kinetic rate constant for CO2 hydration and hydroxylation, which can be summarized by a simple mathematical expression. The results from control experiments (no CA addition) are in agreement with this expression. The results from control experiments also suggest that the most recently published kinetic rate constant for CO2 hydroxylation has been overestimated. When CA is present, the 18O equilibration process is greatly enhanced at both pH levels due to the catalysis of CO2 hydration by the enzyme. For example, the time required for 18O

  9. Physicochemical properties of MoO sub 3 -TiO sub 2 prepared by an equilibrium adsorption method

    SciTech Connect

    Kim, Du Soung; Kurusu, Yasuhiko; Segawa, Kohichi ); Wachs, I.E.; Hardcastle, F.D. )

    1989-12-01

    The adsorption phenomena of molybdena species onto titania surfaces and the surface properties of the catalysts have been studied by using an equilibrium adsorption method. {sup 95}Mo NMR and UV spectroscopic studies show that the aqueous molybdena species vary as a function of the pH of the impregnating solution. For acidic pH values, polymeric species, Mo{sub 7}O{sub 24}{sup 6{minus}} ions, are present, while in the basic solutions it is the monomeric MoO{sub 4}{sup 2{minus}} ions that are present. The adsorbed amounts of molybdate anion are strongly dependent on the pH of the impregnating solution and increase as an inverse function of the pH. XRD, Raman, and XPS data of the calcined samples show that monolayer coverage of molybdenum oxide is established at pH 3.98 (6.6 wt%). The Raman studies reveal that the molybdenum oxide monolayer is composed of distorted octahedra. At more acidic pH regions, pH < 3.98, crystalline MoO{sub 3} is formed above monolayer coverage. The result of catalytic oxidation of methanol show that the catalysts up to monolayer coverage of surface molybdate species possess higher turnover numbers than the catalysts possessing more than monolayer coverage (presence of crystalline MoO{sub 3}). The primary methanol oxidation product is dimethoxymethane at low conversions; methyl formate is next in abundance. The selectivity for dimethyl ether, which occurred as a side reaction on the acidic sites of catalysts, increases as the Mo loading increases.

  10. Rapid fusion method for the determination of refractory thorium and uranium isotopes in soil samples

    SciTech Connect

    Maxwell, Sherrod L.; Hutchison, Jay B.; McAlister, Daniel R.

    2015-02-14

    Recently, approximately 80% of participating laboratories failed to accurately determine uranium isotopes in soil samples in the U.S Department of Energy Mixed Analyte Performance Evaluation Program (MAPEP) Session 30, due to incomplete dissolution of refractory particles in the samples. Failing laboratories employed acid dissolution methods, including hydrofluoric acid, to recover uranium from the soil matrix. The failures illustrate the importance of rugged soil dissolution methods for the accurate measurement of analytes in the sample matrix. A new rapid fusion method has been developed by the Savannah River National Laboratory (SRNL) to prepare 1-2 g soil sample aliquots very quickly, with total dissolution of refractory particles. Soil samples are fused with sodium hydroxide at 600 ºC in zirconium crucibles to enable complete dissolution of the sample. Uranium and thorium are separated on stacked TEVA and TRU extraction chromatographic resin cartridges, prior to isotopic measurements by alpha spectrometry on cerium fluoride microprecipitation sources. Plutonium can also be separated and measured using this method. Batches of 12 samples can be prepared for measurement in <5 hours.

  11. Rapid fusion method for the determination of refractory thorium and uranium isotopes in soil samples

    DOE PAGES

    Maxwell, Sherrod L.; Hutchison, Jay B.; McAlister, Daniel R.

    2015-02-14

    Recently, approximately 80% of participating laboratories failed to accurately determine uranium isotopes in soil samples in the U.S Department of Energy Mixed Analyte Performance Evaluation Program (MAPEP) Session 30, due to incomplete dissolution of refractory particles in the samples. Failing laboratories employed acid dissolution methods, including hydrofluoric acid, to recover uranium from the soil matrix. The failures illustrate the importance of rugged soil dissolution methods for the accurate measurement of analytes in the sample matrix. A new rapid fusion method has been developed by the Savannah River National Laboratory (SRNL) to prepare 1-2 g soil sample aliquots very quickly, withmore » total dissolution of refractory particles. Soil samples are fused with sodium hydroxide at 600 ºC in zirconium crucibles to enable complete dissolution of the sample. Uranium and thorium are separated on stacked TEVA and TRU extraction chromatographic resin cartridges, prior to isotopic measurements by alpha spectrometry on cerium fluoride microprecipitation sources. Plutonium can also be separated and measured using this method. Batches of 12 samples can be prepared for measurement in <5 hours.« less

  12. Determination of U, Pu and Am isotopes in Irish Sea sediment by a combination of AMS and radiometric methods.

    PubMed

    Srncik, M; Hrnecek, E; Steier, P; Wallner, G

    2011-04-01

    Samples from a marine sediment core from the Irish Sea (54.416 N, 3.563 W) were analyzed for the isotopic composition of uranium, plutonium and americium by a combination of radiometric methods and AMS. The radiochemical procedure consisted of a Pu separation step by anion exchange, subsequent U separation by extraction chromatography using UTEVA® and finally Am separation with TRU® Resin. Additionally to radiometric determination of these isotopes by alpha spectrometry, the separated samples were also used for the determination of (236)U/(238)U and plutonium isotope ratios by Accelerator Mass Spectrometry (AMS) at the VERA facility. PMID:21316820

  13. Installations for separation of hydrogen isotopes by the method of chemical isotopic exchange in the `water-hydrogen` system

    SciTech Connect

    Andreev, B.M.; Sakharovsky, Y.A.; Rozenkevich, M.B.; Magomedbekov, E.P.; Park, Y.S.; Uborskiy, V.V.; Trenin, V.D.; Alekseev, I.A.; Fedorchenko, O.A.; Karpov, S.P.; Konoplev, K.A.

    1995-10-01

    The paper presents the results of more than a year of running a pilot setup for separation of hydrogen isotopes using catalytic isotopic exchange between hydrogen and liquid water. The setup is 5 m high, has the inner diameter of 28 mm, and is equipped with upper and lower reflux devices. The experimental values of HETP vary from 15 cm at T=333 K to 38 cm at T=293 K. The setup is capable of upgrading diluted heavy water with 85-90% deuterium content up to [D{sub 2}O] > 99.95 at.%, yielding daily 4 kg of the product. We also report on the progress in constructing a similar setup for eliminating tritium and an industrial setup, for which the one reported is a prototype. 10 refs., 1 fig., 3 tabs.

  14. Method and apparatus for storing hydrogen isotopes. [stored as uranium hydride in a block of copper

    DOEpatents

    McMullen, J.W.; Wheeler, M.G.; Cullingford, H.S.; Sherman, R.H.

    1982-08-10

    An improved method and apparatus for storing isotopes of hydrogen (especially tritium) are provided. The hydrogen gas is stored as hydrides of material (for example uranium) within boreholes in a block of copper. The mass of the block is critically important to the operation, as is the selection of copper, because no cooling pipes are used. Because no cooling pipes are used, there can be no failure due to cooling pipes. And because copper is used instead of stainless steel, a significantly higher temperature can be reached before the eutectic formation of uranium with copper occurs, (the eutectic of uranium with the iron in stainless steel forms at a significantly lower temperature).

  15. Rapid Method for the Determination of the Stable Oxygen Isotope Ratio of Water in Alcoholic Beverages.

    PubMed

    Wang, Daobing; Zhong, Qiding; Li, Guohui; Huang, Zhanbin

    2015-10-28

    This paper demonstrates the first successful application of an online pyrolysis technique for the direct determination of oxygen isotope ratios (δ(18)O) of water in alcoholic beverages. Similar water concentrations in each sample were achieved by adjustment with absolute ethyl alcohol, and then a fixed GC split ratio can be used. All of the organic ingredients were successfully separated from the analyte on a CP-PoraBond Q column and subsequently vented out, whereas water molecules were transferred into the reaction furnace and converted to CO. With the system presented, 15-30 μL of raw sample was diluted and can be analyzed repeatedly; the analytical precision was better than 0.4‰ (n = 5) in all cases, and more than 50 injections can be made per day. No apparent memory effect was observed even if water samples were injected using the same syringe; a strong correlation (R(2) = 0.9998) was found between the water δ(18)O of measured sample and that of working standards. There was no significant difference (p > 0.05) between the mean δ(18)O value and that obtained by the traditional method (CO2-water equilibration/isotope ratio mass spectrometry) and the newly developed method in this study. The advantages of this new method are its rapidity and straightforwardness, and less test portion is required.

  16. Adaptation of the doubly labeled water method for subjects consuming isotopically enriched water.

    PubMed

    Gretebeck, R J; Schoeller, D A; Socki, R A; Davis-Street, J; Gibson, E K; Schulz, L O; Lane, H W

    1997-02-01

    The use of doubly labeled water (DLW) to measure energy expenditure is subject to error if the background abundance of the oxygen and hydrogen isotope tracers changes during the test period. This study evaluated the accuracy and precision of different methods by which such background isotope changes can be corrected, including a modified method that allows prediction of the baseline that would be achieved if subjects were to consume water from a given source indefinitely. Subjects in this study were eight women (4 test subjects and 4 control subjects) who consumed for 28 days water enriched to resemble drinking water aboard the United States space shuttle. Test subjects and control subjects were given a DLW dose on days 1 and 15, respectively. The change to an enriched water source produced a bias in expenditure calculations that exceeded 2.9 MJ/day (35%), relative to calculations from intake-balance. The proposed correction based on the predicted final abundance of 18O and deuterium after equilibration to the new water source eliminated this bias, as did the traditional use of a control group. This new modified correction method is advantageous under field conditions when subject numbers are limited.

  17. Comparison of methods for separating small quantities of hydrogen isotopes from an inert gas

    SciTech Connect

    Willms, R.S.; Tuggle, D.; Birdsell, S.; Parkinson, J.; Price, B.; Lohmeir, D.

    1998-03-01

    It is frequent within tritium processing systems that a small amount of hydrogen isotopes (Q{sub 2}) must be separated from an inert gas such as He, Ar and N{sub 2}. Thus, a study of presently available technologies for effecting such a separation was performed. A base case and seven technology alternatives were identified and a simple design of each was prepared. These technologies included oxidation-adsorption-metal bed reduction, oxidation-adsorption-palladium membrane reactor, cryogenic adsorption, cryogenic trapping, cryogenic distillation, hollow fiber membranes, gettering and permeators. It was found that all but the last two methods were unattractive for recovering Q{sub 2} from N{sub 2}. Reasons for technology rejection included (1) the method unnecessarily turns the hydrogen isotopes into water, resulting in a cumbersome and more hazardous operation, (2) the method would not work without further processing, and (3) while the method would work, it would only do so in an impractical way. On the other hand, getters and permeators were found to be attractive methods for this application. Both of these methods would perform the separation in a straightforward, essentially zero-waste, single step operation. The only drawback for permeators was that limited low-partial Q{sub 2} pressure data is available. The drawbacks for getters are their susceptibility to irreversible and exothermic reaction with common species such as oxygen and water, and the lack of long-term operation of such beds. More research is envisioned for both of these methods to mature these attractive technologies.

  18. Isotope separation

    DOEpatents

    Bartlett, Rodney J.; Morrey, John R.

    1978-01-01

    A method and apparatus is described for separating gas molecules containing one isotope of an element from gas molecules containing other isotopes of the same element in which all of the molecules of the gas are at the same electronic state in their ground state. Gas molecules in a gas stream containing one of the isotopes are selectively excited to a different electronic state while leaving the other gas molecules in their original ground state. Gas molecules containing one of the isotopes are then deflected from the other gas molecules in the stream and thus physically separated.

  19. An improved method of ion exchange for nitrogen isotope analysis of water nitrate.

    PubMed

    Xing, Meng; Liu, Weiguo

    2011-02-01

    Nitrate nitrogen and oxygen isotopes have been widely used to trace the nitrogen biogeochemical cycle by identifying NO(3)(-) sources. An improved method of anion exchange was developed to measure δ(15)N-NO(3)(-) in fresh water by continuous-flow elemental analyzer/isotope ratio mass spectrometry (EA-IRMS). We used a custom-built exchange resin column, a peristaltic pump and the oven-drying method in our experiments. Consequently, the amount of Ag(2)O used as a neutralizer was reduced, time was saved, and operation became simpler than before. Meanwhile, analytical precision remained identical to previous studies. KNO(3) solutions were prepared at 0.2, 5 and 25 mg-N L(-1) from KNO(3) standard salt (δ(15)N=+6.27‰), and the average δ(15)N values of the solutions after having been absorbed on and subsequently stripped from anion columns were +6.62±0.22‰ (n=6), +6.38±0.09‰ (n=6), and +6.26±0.07‰ (n=6), respectively. In addition, the "natural" water sample δ(15)N-NO(3)(-) showed consistency in comparison to standards, and the mean standard deviation by the different approaches was 0.08‰. Accordingly, by these improvements the anion exchange resin technique is demonstrated to be more suitable for measuring δ(15)N in NO(3)(-) than original techniques. PMID:21237315

  20. An isotope-dilution standard GC/MS/MS method for steroid hormones in water

    USGS Publications Warehouse

    Foreman, William T.; Gray, James L.; ReVello, Rhiannon C.; Lindley, Chris E.; Losche, Scott A.

    2013-01-01

    An isotope-dilution quantification method was developed for 20 natural and synthetic steroid hormones and additional compounds in filtered and unfiltered water. Deuterium- or carbon-13-labeled isotope-dilution standards (IDSs) are added to the water sample, which is passed through an octadecylsilyl solid-phase extraction (SPE) disk. Following extract cleanup using Florisil SPE, method compounds are converted to trimethylsilyl derivatives and analyzed by gas chromatography with tandem mass spectrometry. Validation matrices included reagent water, wastewater-affected surface water, and primary (no biological treatment) and secondary wastewater effluent. Overall method recovery for all analytes in these matrices averaged 100%; with overall relative standard deviation of 28%. Mean recoveries of the 20 individual analytes for spiked reagent-water samples prepared along with field samples analyzed in 2009–2010 ranged from 84–104%, with relative standard deviations of 6–36%. Detection levels estimated using ASTM International’s D6091–07 procedure range from 0.4 to 4 ng/L for 17 analytes. Higher censoring levels of 100 ng/L for bisphenol A and 200 ng/L for cholesterol and 3-beta-coprostanol are used to prevent bias and false positives associated with the presence of these analytes in blanks. Absolute method recoveries of the IDSs provide sample-specific performance information and guide data reporting. Careful selection of labeled compounds for use as IDSs is important because both inexact IDS-analyte matches and deuterium label loss affect an IDS’s ability to emulate analyte performance. Six IDS compounds initially tested and applied in this method exhibited deuterium loss and are not used in the final method.

  1. Clumped isotope thermometry and catagenesis

    NASA Astrophysics Data System (ADS)

    Eiler, J. M.; Clog, M. D.; Dallas, B.; Douglas, P. M.; Piasecki, A.; Sessions, A. L.; Stolper, D. A.

    2014-12-01

    Clumped- and site-specific isotopic compositions of organic compounds can constrain their formation temperatures, sources, and chemical reaction histories. The large number of isotopologues of organic molecules may allow for the isotopic composition of a single compound to illuminate many processes. For example, it is possible that clumping or site specific effects in different parts of the same molecule will differ in blocking temperature, such that a molecule's full isotopic structure could simultaneously constrain conditions of biosynthesis, catagenic 'cracking', and storage in the crust. Recent innovations in high-resolution mass spectrometry and methods of IR and NMR spectroscopy make it possible to explore these questions. Methane is the first organic molecule to have its clumped isotope geochemistry analyzed in a variety of natural environments and controlled experiments. Methane generated through catagenic cracking of kerogen and other organic matter forms in equilibrium with respect to isotopic clumping, and preserves that state through later storage or migration, up to temperatures of ~250 ˚C. This kinetic behavior permits a variety of useful geological applications. But it is unexpected because the bulk stable isotope composition of thermogenic methane is thought to reflect kinetic isotope effects on irreversible reactions. Our observations imply a new interpretation of the chemical physics of catagenic methane formation. Additional instrument and methods developments are currently extending the measurement of isotopic clumping and position specific effects to larger alkanes, other hydrocarbon compounds, and amino acids. These measurements will ultimately expand our capacity to understand the formational conditions and fates of organic molecules in high- and low-temperature environments through geological time.

  2. Double isotopic method using dansyl chloride for the determination of GABA in rat C6 astrocytoma cell cultures

    SciTech Connect

    Kohl, R.L.; Quay, W.B.; Perez-Polo, J.R.

    1986-01-01

    Methods are described for the quantitative measurement of GABA in culture. The method can be adapted to any amino acid or dansyl-chloride-reactive species. The sensitivity and selectivity of the procedure result from the double isotopic design in which (/sup 14/C)-labeled internal standard was added to the samples before reaction with (3M)-labeled dansyl chloride. Values obtained by ion-exchange amino acid analysis of cultures agree closely with the values obtained by the double isotopic method. This method is sensitive enough to measure GABA intracellularly and the condition medium.

  3. Sampling and analytical methods of stable isotopes and dissolved inorganic carbon from CO2 injection sites

    NASA Astrophysics Data System (ADS)

    van Geldern, Robert; Myrttinen, Anssi; Becker, Veith; Barth, Johannes A. C.

    2010-05-01

    The isotopic composition (δ13C) of dissolved inorganic carbon (DIC), in combination with DIC concentration measurements, can be used to quantify geochemical trapping of CO2 in water. This is of great importance in monitoring the fate of CO2 in the subsurface in CO2 injection projects. When CO2 mixes with water, a shift in the δ13C values, as well as an increase in DIC concentrations is observed in the CO2-H2O system. However, when using standard on-site titration methods, it is often challenging to determining accurate in-situ DIC concentrations. This may be due to CO2 degassing and CO2-exchange between the sample and the atmosphere during titration, causing a change in the pH value or due to other unfavourable conditions such as turbid water samples or limited availability of fluid samples. A way to resolve this problem is by simultaneously determining the DIC concentration and carbon isotopic composition using a standard continuous flow Isotope Ratio Mass Spectrometry (CF-IRMS) setup with a Gasbench II coupled to Delta plusXP mass spectrometer. During sampling, in order to avoid atmospheric contact, water samples taken from the borehole-fluid-sampler should be directly transferred into a suitable container, such as a gasbag. Also, to avoid isotope fractionation due to biological activity in the sample, it is recommended to stabilize the gasbags prior to sampling with HgCl2 for the subsequent stable isotope analysis. The DIC concentration of the samples can be determined from the area of the sample peaks in a chromatogram from a CF-IRMS analysis, since it is directly proportional to the CO2 generated by the reaction of the water with H3PO4. A set of standards with known DIC concentrations should be prepared by mixing NaHCO3 with DIC free water. Since the DIC concentrations of samples taken from CO2 injection sites are expected to be exceptionally high due to the additional high amounts of added CO2, the DIC concentration range of the standards should be set high

  4. Integrated use of soil physical and water isotope methods for ecohydrological characterization of desertified areas

    NASA Astrophysics Data System (ADS)

    Külls, Christoph; Nunes, Alice; Köbel-Batista, Melanie; Branquinho, Cristina; Bianconi, Nadja; Costantini, Eduardo

    2014-05-01

    marked decrease in water permeability at 0.04, 0.20, or 0.40 m depth. Soil isotope profiles indicated that percolation beneath the root zone and groundwater recharge ranges from 21.7 mm/y to 29.7 mm/y. The recharge rate was positively related to mean annual rainfall and soil organic matter, and interestingly, increased with aridity and desertification. The difference between mean annual rainfall and percolation was positively related to plant cover and in inverse proportion to the aridity index. Our results highlight the importance of combining different methods of site characterization by soil physics, soil water isotopes and soil water chemistry (chloride) with vegetation data, providing a more specific analysis of ecohydrological conditions and their relation to ecosystem functioning and recovery potential. The field protocol applied can provide relevant information for guiding restoration strategies. Costantini, E. A. C., Urbano, F., Aramini, G., Barbetti, R., Bellino, F., Bocci, M., & Tascone, F. (2009). Rationale and methods for compiling an atlas of desertification in Italy. Land Degradation & Development, 20(3), 261-276. Garvelmann, J., Külls, C., & Weiler, M. (2012). A porewater-based stable isotope approach for the investigation of subsurface hydrological processes. Hydrology and Earth System Sciences, 16(2), 631-640.

  5. Equilibrium Shaping

    NASA Astrophysics Data System (ADS)

    Izzo, Dario; Petazzi, Lorenzo

    2006-08-01

    We present a satellite path planning technique able to make identical spacecraft aquire a given configuration. The technique exploits a behaviour-based approach to achieve an autonomous and distributed control over the relative geometry making use of limited sensorial information. A desired velocity is defined for each satellite as a sum of different contributions coming from generic high level behaviours: forcing the final desired configuration the behaviours are further defined by an inverse dynamic calculation dubbed Equilibrium Shaping. We show how considering only three different kind of behaviours it is possible to acquire a number of interesting formations and we set down the theoretical framework to find the entire set. We find that allowing a limited amount of communication the technique may be used also to form complex lattice structures. Several control feedbacks able to track the desired velocities are introduced and discussed. Our results suggest that sliding mode control is particularly appropriate in connection with the developed technique.

  6. A simple method for rapid, high-precision isotope measurements of small samples with MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Kamenov, G. D.; Mueller, P. A.; Gilli, A.; Coyner, S. J.; Nielsen, S. H.

    2006-12-01

    A key factor for accurate and precise isotopic measurements is optimal signal to noise ratio, which makes analyses of very small samples challenging due to the small number of available analyte ions. If, however, the analysis time can be drastically reduced, then very small samples (e.g., 1ng) can be analyzed by placing the analyte ions in small volumes (e.g., 0.1ml). This will result in 10ppb sample solution and will give acceptable signal to noise ratio on Faraday detectors on modern MC-ICP-MS instruments. The signal from a 0.1ml solution, however, will last no more than a minute and very few ratios will be acquired with traditional isotope measurement protocols. In a series of experiments with standard reference materials and samples we established that high-precision isotopic ratio measurements can be obtained in much shorter times compared to traditional methods for isotopic analyses using TIMS and MC-ICP-MS. The protocol utilizes the Nu Plasma TRA (time-resolved analysis) software operating with a 0.2 second acquisition time (i.e., 300 isotopic ratios/minute). Using a low- flow nebulizer, only 0.1-0.2 ml of sample solution is required for 1-2 minutes signal duration. Consequently, placing the available analytical ions in small volume leads to higher signal to noise ratio that results in precise isotopic analyses, regardless of the very short acquisition times employed during the experiments. This technique can be applied for analyses of virtually any isotope system, as we demonstrate with examples for Sr, Nd, and Pb isotopic measurements. In addition to high-precision isotopic analyses of very small samples on Faraday detectors, another advantage of this protocol is enhanced lab productivity because overall analysis time is significantly reduced.

  7. A Robust and Fully-Automated Chromatographic Method for the Quantitative Purification of Ca and Sr for Isotopic Analysis

    NASA Astrophysics Data System (ADS)

    Smith, H. B.; Kim, H.; Romaniello, S. J.; Field, P.; Anbar, A. D.

    2014-12-01

    High throughput methods for sample purification are required to effectively exploit new opportunities in the study of non-traditional stable isotopes. Many geochemical isotopic studies would benefit from larger data sets, but these are often impractical with manual drip chromatography techniques, which can be time-consuming and demand the attention of skilled laboratory staff. Here we present a new, fully-automated single-column method suitable for the purification of both Ca and Sr for stable and radiogenic isotopic analysis. The method can accommodate a wide variety of sample types, including carbonates, bones, and teeth; silicate rocks and sediments; fresh and marine waters; and biological samples such as blood and urine. Protocols for these isotopic analyses are being developed for use on the new prepFAST-MCTM system from Elemental Scientific (ESI). The system is highly adaptable and processes up to 24-60 samples per day by reusing a single chromatographic column. Efficient column cleaning between samples and an all Teflon flow path ensures that sample carryover is maintained at the level of background laboratory blanks typical for manual drip chromatography. This method is part of a family of new fully-automated chromatographic methods being developed to address many different isotopic systems including B, Ca, Fe, Cu, Zn, Sr, Cd, Pb, and U. These methods are designed to be rugged and transferrable, and to allow the preparation of large, diverse sample sets via a highly repeatable process with minimal effort.

  8. Enhanced Method for Molybdenum Separation and Isotopic Determination in Geological Samples and Uranium-Rich Materials

    NASA Astrophysics Data System (ADS)

    Migeon, V.; Bourdon, B.; Pili, E.

    2014-12-01

    Molybdenum (Mo) shares analogous geochemical properties with uranium. Mo ispresent as a minor or a trace element in uranium ores under two main oxidation states: +IVand +VI. Mo has seven stable isotopes (92, 94, 95, 96, 97, 98 and 100). In natural systems,Mo and Mo isotopes were shown to fractionate during redox reactions. Because Morepresents an impurity difficult to separate in the nuclear fuel cycle, it has the potential to beused as an indicator of the origins of uranium concentrates, in the framework of nuclearforensics. This work focuses on developing an enhanced separation method for Mo from auranium-rich matrix (uranium ore, uranium concentrate) in order to analyze the massfractionation induced by processes typical of the nuclear fuel cycle. Purification of Mo forisotope ratio measurements is performed with a three-step separation on ion-exchange resins,with yields between 45 and 82%. Matrix and isobaric interferences (Zr, Ru) were reduced ingeological and uranium standards, such as U/Mo ≤ 2*10-4, Zr/Mo ≤ 1*10-3, Ru/Mo ≤ 6*10-4and Fe/Mo ≤ 4*10-3. Mo isotopic compositions were measured on a Neptune Plus MC-ICPMSequipped with Jet cones, for a concentration of 30 ng/ml. The achieved sensitivity is~1200-1800 V/ppm with interferences below 10 mV and an overall reproducibility of 0.02 ‰on the δ98Mo values. A double spike, with 97Mo and 100Mo, was added to the samples beforethe purification. It allows for correction of the chemical and instrumental mass fractionations,without requiring a quantitative yield. For igneous rocks, δ98Mo values range between -0.55and -0.03 ‰, relative to the NIST-SRM 3134 molybdenum standard. Fractionation amonguranium ore concentrates is higher, with δ98Mo ranging between 0.02 and -2.84 ‰.

  9. Equilibrium Fermi's Golden Rule Charge Transfer Rate Constants in the Condensed Phase: The Linearized Semiclassical Method vs Classical Marcus Theory.

    PubMed

    Sun, Xiang; Geva, Eitan

    2016-05-19

    In this article, we present a comprehensive comparison between the linearized semiclassical expression for the equilibrium Fermi's golden rule rate constant and the progression of more approximate expressions that lead to the classical Marcus expression. We do so within the context of the canonical Marcus model, where the donor and acceptor potential energy surface are parabolic and identical except for a shift in both the free energies and equilibrium geometries, and within the Condon region. The comparison is performed for two different spectral densities and over a wide range of frictions and temperatures, thereby providing a clear test for the validity, or lack thereof, of the more approximate expressions. We also comment on the computational cost and scaling associated with numerically calculating the linearized semiclassical expression for the rate constant and its dependence on the spectral density, temperature, and friction.

  10. Methods for the separation of rhenium, osmium and molybdenum applicable to isotope geochemistry

    USGS Publications Warehouse

    Morgan, J.W.; Golightly, D.W.; Dorrzapf, A.F.

    1991-01-01

    Effective methods are described for the chemical separation of rhenium, osmium and molybdenum. The methods are based on distillation and anion-exchange chromatography, and have been the basis for rhenium-osmium isotope studies of ore deposits and meteorites. Successful anion-exchange separation of osmium requires both recognition and careful control of the osmium species in solution; thus, distillation of osmium tetroxide from a mixture of sulfuric acid and hydrogen peroxide is preferred to anion-exchange. Distribution coefficients measured for perrhenate in sulfuric acid media are sufficiently high (Kd > 500) for rhenium to be directly loaded onto an ion-exchange column from a distillation residue and subsequently eluted with nitric acid. Polymerization of molybdenum species during elution is prevented by use of a solution that is 1M in hydrochloric acid and 1M in sodium chloride. ?? 1991.

  11. Extraction of gadolinium from high flux isotope reactor control plates. [Alternative method

    SciTech Connect

    Kohring, M.W.

    1987-04-01

    Gadolinium-153 is an important radioisotope used in the diagnosis of various bone disorders. Recent medical and technical developments in the detection and cure of osteoporosis, a bone disease affecting an estimated 50 million people, have greatly increased the demand for this isotope. The Oak Ridge National Laboratory (ORNL) has produced /sup 153/Gd since 1980 primarily through the irradiation of a natural europium-oxide powder followed by the chemical separation of the gadolinium fraction from the europium material. Due to the higher demand for /sup 153/Gd, an alternative production method to supplement this process has been investigated. This process involves the extraction of gadolinium from the europium-bearing region of highly radioactive, spent control plates used at the High Flux Isotope Reactor (HFIR) with a subsequent re-irradiation of the extracted material for the production of the /sup 153/Gd. Based on the results of experimental and calculational analyses, up to 25 grams of valuable gadolinium (greater than or equal to60% enriched in /sup 152/Gd) resides in the europium-bearing region of the HFIR control components of which 70% is recoverable. At a specific activity yield of 40 curies of /sup 153/Gd for each gram of gadolinium re-irradiated, 700 one-curie sources can be produced from each control plate assayed.

  12. METHOD FOR REMOVAL OF LIGHT ISOTOPE PRODUCT FROM LIQUID THERMAL DIFFUSION UNITS

    DOEpatents

    Hoffman, J.D.; Ballou, J.K.

    1957-11-19

    A method and apparatus are described for removing the lighter isotope of a gaseous-liquid product from a number of diffusion columns of a liquid thermal diffusion system in two stages by the use of freeze valves. The subject liquid flows from the diffusion columns into a heated sloping capsule where the liquid is vaporized by the action of steam in a heated jacket surrounding the capsule. When the capsule is filled the gas flows into a collector. Flow between the various stages is controlled by freeze valves which are opened and closed by the passage of gas and cool water respectively through coils surrounding portions of the pipes through which the process liquid is passed. The use of the dual stage remover-collector and the freeze valves is an improvement on the thermal diffusion separation process whereby the fraction containing the lighter isotope many be removed from the tops of the diffusion columns without intercolumn flow, or prior stage flow while the contents of the capsule is removed to the final receiver.

  13. A facile method for controlling the reaction equilibrium of sphingolipid ceramide N-deacylase for lyso-glycosphingolipid production[S

    PubMed Central

    Huang, Feng-Tao; Han, Yun-Bin; Feng, Yan; Yang, Guang-Yu

    2015-01-01

    Lyso-glycosphingolipids (lyso-GSLs), the N-deacylated forms of glycosphingolipids (GSLs), are important synthetic intermediates for the preparation of GSL analogs. Although lyso-GSLs can be produced by hydrolyzing natural GSLs using sphingolipid ceramide N-deacylase (SCDase), the yield for this reaction is usually low because SCDase also catalyzes the reverse reaction, ultimately establishing an equilibrium between hydrolysis and synthesis. In the present study, we developed an efficient method for controlling the reaction equilibrium by introducing divalent metal cation and detergent in the enzymatic reaction system. In the presence of both Ca2+ and taurodeoxycholate hydrate, the generated fatty acids were precipitated by the formation of insoluble stearate salts and pushing the reaction equilibrium toward hydrolysis. The yield of GM1 hydrolysis can be achieved as high as 96%, with an improvement up to 45% compared with the nonoptimized condition. In preparative scale, 75 mg of lyso-GM1 was obtained from 100 mg of GM1 with a 90% yield, which is the highest reported yield to date. The method can also be used for the efficient hydrolysis of a variety of GSLs and sphingomyelin. Thus, this method should serve as a facile, easily scalable, and general tool for lyso-GSL production to facilitate further GSL research. PMID:26130766

  14. Phonon coherence in isotopic silicon superlattices

    SciTech Connect

    Frieling, R.; Radek, M.; Eon, S.; Bracht, H.; Wolf, D. E.

    2014-09-29

    Recent experimental and theoretical investigations have confirmed that a reduction in thermal conductivity of silicon is achieved by isotopic silicon superlattices. In the present study, non-equilibrium molecular dynamics simulations are performed to identify the isotope doping and isotope layer ordering with minimum thermal conductivity. Furthermore, the impact of isotopic intermixing at the superlattice interfaces on phonon transport is investigated. Our results reveal that the coherence of phonons in isotopic Si superlattices is prevented if interfacial mixing of isotopes is considered.

  15. A method for in situ monitoring of the isotope composition of tree xylem water using laser spectroscopy.

    PubMed

    Volkmann, Till H M; Kühnhammer, Kathrin; Herbstritt, Barbara; Gessler, Arthur; Weiler, Markus

    2016-09-01

    Field studies analyzing the stable isotope composition of xylem water are providing important information on ecosystem water relations. However, the capacity of stable isotopes to characterize the functioning of plants in their environment has not been fully explored because of methodological constraints on the extent and resolution at which samples could be collected and analysed. Here, we introduce an in situ method offering the potential to continuously monitor the stable isotope composition of tree xylem water via its vapour phase using a commercial laser-based isotope analyser and compact microporous probes installed into the xylem. Our technique enables efficient high-frequency measurement with intervals of only a few minutes per sample while eliminating the need for costly and cumbersome destructive collection of plant material and laboratory-based processing. We present field observations of xylem water hydrogen and oxygen isotope compositions obtained over several days including a labelled irrigation event and compare them against results from concurrent destructive sampling with cryogenic distillation and mass spectrometric analysis. The data demonstrate that temporal changes as well as spatial patterns of integration in xylem water isotope composition can be resolved through direct measurement. The new technique can therefore present a valuable tool to study the hydraulic architecture and water utilization of trees.

  16. A method for in situ monitoring of the isotope composition of tree xylem water using laser spectroscopy.

    PubMed

    Volkmann, Till H M; Kühnhammer, Kathrin; Herbstritt, Barbara; Gessler, Arthur; Weiler, Markus

    2016-09-01

    Field studies analyzing the stable isotope composition of xylem water are providing important information on ecosystem water relations. However, the capacity of stable isotopes to characterize the functioning of plants in their environment has not been fully explored because of methodological constraints on the extent and resolution at which samples could be collected and analysed. Here, we introduce an in situ method offering the potential to continuously monitor the stable isotope composition of tree xylem water via its vapour phase using a commercial laser-based isotope analyser and compact microporous probes installed into the xylem. Our technique enables efficient high-frequency measurement with intervals of only a few minutes per sample while eliminating the need for costly and cumbersome destructive collection of plant material and laboratory-based processing. We present field observations of xylem water hydrogen and oxygen isotope compositions obtained over several days including a labelled irrigation event and compare them against results from concurrent destructive sampling with cryogenic distillation and mass spectrometric analysis. The data demonstrate that temporal changes as well as spatial patterns of integration in xylem water isotope composition can be resolved through direct measurement. The new technique can therefore present a valuable tool to study the hydraulic architecture and water utilization of trees. PMID:27260852

  17. Method for the identification and elimination of contamination during carbon isotopic analyses of extraterrestrial samples

    SciTech Connect

    Swart, P.K.; Grady, M.M.; Pillinger, C.T.

    1983-06-30

    A stepped combustion method for the elimination of carbon-containing contamination and weathering products from meteorite and lunar samples is presented. Samples of the Allende CV3 chondrite, the Sharps and Weston ordinary chondrite falls, one ordinary and five Antarctic finds, and lunar soils from Apollo 11 were oxidized in pure O2 at increasing temperatures, from 200 to 1200 C in 100-C, 30-min steps and C yield and delta-(C-13) were measured after each step. It is found that some C contamination is present in all samples and can adversely affect C-isotopic-abundance measurements. Except for C1 and C2 carbonaceous chondrites, C combustion below 425 + or - 25 C is limited to the terrestrial contaminants, demonstrating the usefulness of stepped combustion in removing them. Graphs and tables of the results are presented and discussed. 34 references.

  18. Methods for the stable isotopic analysis of chlorine in chlorate and perchlorate compounds.

    PubMed

    Ader, M; Coleman, M L; Doyle, S P; Stroud, M; Wakelin, D

    2001-10-15

    Chlorate and perchlorate compounds, used as herbicides, solid fuel propellants, and explosives, are increasingly recognized as pollutants in groundwater. Stable isotope characterization would permit both environmental monitoring of extent of remediation and forensic characterization. Stoichiometric reduction to chloride (greater than 98% yield), by Fe(II) for chlorate and alkaline fusion-decomposition for perchlorate, allows analysis by standard methods to give highly reproducible and accurate delta37Cl results (0.05/1000, 2 x standard error). Analysis of various compounds from different suppliers yielded delta37Cl values for chlorate samples near to +0.2/1000 (SMOC), but one has within-sample heterogeneity of 0.5/1000, possibly due to crystallization processes during manufacture. Results for perchlorate samples also are generally near +0.2/1000, but one is +2.3/1000 (SMOC). The initial results suggest that both forensic and environmental applications might be feasible.

  19. Radiometric method for determining concentration of naturally occurring isotopes and device therefor

    SciTech Connect

    Yakubovich, S.L.; Gerling, V.E.; Golubnichy, V.V.; Kotsen, M.E.; Stepanov, J.N.

    1984-10-09

    The proposed method essentially consists in that a sample of a substance is placed between two scintillators in immediate contact therewith whereupon said sample is hermetically sealed. Arranged in close proximity to each scintillator is a photomultiplier tube recording ionizing ..cap alpha..- and b-radiation. A selector is utilized to select pulses corresponding to ..cap alpha..- and b-particles, and delayed coincidence circuits of a recording element separate and record b-..cap alpha.. and ..cap alpha..-..cap alpha.. cascade pairs of delayed coincidences of RaC, ThC, and AcA radionuclides. Flows are measured twice at a predetermined time interval to account for emanation build-up tendency and concentration of isotopes of radium is determined from a formula.

  20. Methods for the stable isotopic analysis of chlorine in chlorate and perchlorate compounds.

    PubMed

    Ader, M; Coleman, M L; Doyle, S P; Stroud, M; Wakelin, D

    2001-10-15

    Chlorate and perchlorate compounds, used as herbicides, solid fuel propellants, and explosives, are increasingly recognized as pollutants in groundwater. Stable isotope characterization would permit both environmental monitoring of extent of remediation and forensic characterization. Stoichiometric reduction to chloride (greater than 98% yield), by Fe(II) for chlorate and alkaline fusion-decomposition for perchlorate, allows analysis by standard methods to give highly reproducible and accurate delta37Cl results (0.05/1000, 2 x standard error). Analysis of various compounds from different suppliers yielded delta37Cl values for chlorate samples near to +0.2/1000 (SMOC), but one has within-sample heterogeneity of 0.5/1000, possibly due to crystallization processes during manufacture. Results for perchlorate samples also are generally near +0.2/1000, but one is +2.3/1000 (SMOC). The initial results suggest that both forensic and environmental applications might be feasible. PMID:11681470

  1. Sensitivity analysis and stability charts for uniform slopes computed via the MLD methods in the frame of the limit equilibrium theory

    NASA Astrophysics Data System (ADS)

    Ausilia Paparo, Maria; Tinti, Stefano

    2013-04-01

    Stability charts represent a graphical solution to derive the safety factor (F) without incurring the difficulties of mathematical and numerical methods for the analysis of slope stability, widely used in the engineering field: employed in a preliminary phase of analysis, the consultation of charts allows one to determine the approximate equilibrium conditions. The first to develop this method is Taylor (1948) who made them of common use: his stability charts are the relationships between the height and the inclination of a schematic slope, for particular types of failure surface (toe circle, circle slope, and midpoint circle) and for different values of friction angle. Thereafter the charts have become more detailed and complete (Janbu, 1968), thanks to the continuous introduction of new methods, like the limit equilibrium method (LEM), the limit analysis method and the finite element method (FEM). The aim of this work is to compare sets of stability charts found in literature (Michalowski, 1997; 2002; Li et alii, 2009; Steward et alii, 2011; Zhang et alii, 2011) with new charts obtained with the results obtained by means of the method of minimum lithostatic deviation (MLD) introduced by Tinti and Manucci (2006 and 2008) for 2D problems: the slope is a homogenous body and we analyze different cases, by varying the geometry (e.g. the slope angle and height), the geotechnical parameters (such as cohesion and angle of friction), the pore pressure and the external loads (as seismic or hydrostatic loadings) treated as quasi-static forcing.

  2. Isotopic Geochronology by Means of a Dynamic Simulation Model --- Part I. Uranium Series Method

    NASA Astrophysics Data System (ADS)

    Hung, C.

    2004-12-01

    This paper presents the hydrodynamic implications of traditional approaches to dating minerals and rocks by the U-Pb method, the development of an alternative dynamic simulation model, and the comparison of these two models. The proposed alternative model simulates dynamic mass transport and radioactive decay of the decay-chain members in a crystalline mineral deposit and in the surrounding host rocks. In conjunction with the results of mass spectrometer measurements, the simulation results can be used for geochronological dating of minerals and rocks. Because of the dynamic simulation approach, this model can avoid imposing two crude assumptions that are normally required by the traditional modeling approach. They are: (1) mineral deposits are confined in a closed system and (2) the decay chain is in secular equilibrium at the time of dating. Currently, these crude assumptions still remain controversial amongst geochronological scientists. The proposed simulation model is verified for the cases of diffusion and radioactive decay. Comparison of the simulation results and analytical solutions for the radioactive decay and the 3-D diffusion cases indicates that they are in excellent agreement. Eight scenarios are analyzed to demonstrate the effects of preexisting daughter nuclides, closed system assumptions, and secular equilibrium assumptions. By selecting the most conservative-values as model input parameters, all eight scenarios are analyzed. The results indicate that (1) analysis with preexisting daughter nuclides is always greater than those without, (2) closed system assumptions may considerably overestimate the age of minerals and rocks, and (3) secular equilibrium assumptions will result in an underestimation of the age of minerals and rocks. The results of an existing radiometric dating study conducted for the Alder Creek rhyolite by Getty and Depaolo are compared with the dynamic simulation model using the same mass spectrometer data. The results indicate

  3. Multiple ion counting ICPMS double spike method for precise U isotopic analysis at ultra-trace levels

    NASA Astrophysics Data System (ADS)

    Snow, Jonathan E.; Friedrich, Jon M.

    2005-04-01

    Of the various methods for the measurement of the isotopic composition of U in solids and solutions, few offer both sensitivity and precision. In recent years, the use of ICPMS technology for this determination has become increasingly prevalent. Here we describe a method for the determination of the 235U/238U ratio in very small quantities (<=350 pg) with an accuracy of better than 3[per mille sign]. We measured several terrestrial standard materials and repeated analyses of the U960 isotopic composition standard. We used a 233U/236U double spike, with multiple ion counting on an unmodified Nu Instruments multicollector ICPMS and a non-standard detector configuration that allows an approximately 20-fold sensitivity gain over the best conventional techniques. This technique shows promise for the detection of isotopic tracers in the environment (for example anthropogenic 238U) at very extreme dilutions, or in cases where the total amount of analyte is necessarily limited.

  4. 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)

  5. 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.

  6. A field and laboratory method for monitoring the concentration and isotopic composition of soil CO2.

    PubMed

    Breecker, Dan; Sharp, Zachary D

    2008-01-01

    The stable isotope composition of nmol size gas samples can be determined accurately and precisely using continuous flow isotope ratio mass spectrometry (IRMS). We have developed a technique that exploits this capability in order to measure delta13C and delta18O values and, simultaneously, the concentration of CO2 in sub-mL volume soil air samples. A sampling strategy designed for monitoring CO2 profiles at particular locations of interest is also described. This combined field and laboratory technique provides several advantages over those previously reported: (1) the small sample size required allows soil air to be sampled at a high spatial resolution, (2) the field setup minimizes sampling times and does not require powered equipment, (3) the analytical method avoids the introduction of air (including O2) into the mass spectrometer thereby extending filament life, and (4) pCO2, delta13C and delta18O are determined simultaneously. The reproducibility of measurements of CO2 in synthetic tank air using this technique is: +/-0.08 per thousand (delta13C), +/-0.10 per thousand (delta18O), and +/-0.7% (pCO2) at 5550 ppm. The reproducibility for CO2 in soil air is estimated as: +/-0.06 per thousand (delta13C), +/-0.06 per thousand (delta18O), and +/-1.6% (pCO2). Monitoring soil CO2 using this technique is applicable to studies concerning soil respiration and ecosystem gas exchange, the effect of elevated atmospheric CO2 (e.g. free air carbon dioxide enrichment) on soil processes, soil water budgets including partitioning evaporation from transpiration, pedogenesis and weathering, diffuse solid-earth degassing, and the calibration of speleothem and pedogenic carbonate delta13C values as paleoenvironmental proxies.

  7. LC/MS Method for the Determination of Stable Isotope Labeled Promethazine in Human Plasma

    NASA Technical Reports Server (NTRS)

    Zuwei, Wang; Boyd, Jason; Berens, Kurt L.; Putcha, Lakshmi

    2004-01-01

    Promethazine (PMZ) is taken by astronauts orally (PO), intramuscularly (IM) or rectally (PR) for space motion sickness. LC/MS method was developed with off-line solid phase extraction to measure plasma concentrations of PMZ given as stable isotope-labeled (SIL) formulations by the three different routes of administration simultaneously. Samples (0.5ml) were loaded on to Waters Oasis HLB co-polymer cartridges and eluted with 1.0 mL methanol. HPLC separation of the eluted sample was performed using an Agilent Zorbax SB-CN column (50 x 2.1 mm) at a flow rate of 0.2 mL/min for 6 min. Acetonitrile/ ammonium acetate (30 mM) in water (3:2, v/v), pH 5.6 plus or minus 0.1, was used as the mobile phase for separation. Concentrations of PMZ, PMZ-d4 and PMZ-d7 and chlorpromazine (internal standard) were determined using a Micromass ZMD single quadrupole mass spectrometer with Electrospray Ionization (ESI). ESI mass spectra were acquired in positive ion mode with selected ion monitoring of [M+ H]dot plus. The method is rapid, reproducible and the assay specific parameters are listed in a table. A novel, sensitive and specific method for the measurement of PMZ and SIL PMZ in human plasma is reported.

  8. A novel method for the quantification of quinic acid in food using stable isotope dilution analysis.

    PubMed

    Erk, Thomas; Bergmann, Hannah; Richling, Elke

    2009-01-01

    Organic acids play an important role in the flavor and taste of plant-derived foods. Quinic acid (QA) is one of the major acids. In the past, several methods like HPLC/UV, GC, and capillary electrophoresis were used for identification and quantification of QA. For the first time, a novel, sensitive, and selective method for the quantification of QA in food using stable isotope dilution analysis with HPLC/MS/MS has been established. Uniformly labeled 13C-QA was used as a standard to reduce sample preparations and to overcome matrix and ionization effects. The method was used to determine the QA content of red wines, instant coffees, and cloudy apple juices. QA contents of instant coffees were 64.4 and 63.6 g/kg powder. The concentrations in red wines were 24.0 and 25.1 mg/L, and 1493.3 and 1705.2 mg/L in cloudy apple juices.

  9. Fe, Zn, and Cd stable isotopes from the eastern tropical South Pacific from GEOTRACES cruise GP16 - Methods and data

    NASA Astrophysics Data System (ADS)

    Helgoe, J. M.; Townsend, E.; John, S.

    2014-12-01

    A new method has been developed for the rapid analysis of metal concentrations and stable isotope ratios using a prepFAST automated sample processing robot. Although concentrations and isotopes are processed separately, similar methods are used for both. Initially all seawater is acidified to pH 2. Then Nobias resin with EDTA/IDA functional groups is added to either 10mL of sample for concentrations or ~1L samples for isotopes. Fe binds to the resin at low pH, and the pH is subsequently raised to allow Zn and Cd to bind. For concentration analyses, all subsequent chemistry is automated on the prepFAST including removal of seawater, rinsing of resin, and elution of resin into acid. For isotope samples these extraction techniques are performed manually, but the subsequent purification of Fe, Zn, and Cd by anion exchange chromatography is automated using the prepFAST. With these new methods, samples from the US GEOTRACES cruise GP16, in the eastern tropical South Pacific, are being analyzed. High concentrations of dissolved Fe are observed near the continental shelf and near submarine hydrothermal vents. Interestingly, isotope data show that dissolved Fe near the continental shelf generally has a δ56Fe close to 0 ‰. This δ56 Fe signature is suggestive of a non-reductive dissolution source for Fe, as Fe(II) released by reductive dissolution is typically closer to -2 ‰. Preliminary data show nutrient-type profiles for Zn and Cd, with Zn matching Si and Cd having a similar distribution to P. An increase in dissolved Zn near hydrothermal vents suggests a possible hydrothermal zinc source to the deep ocean. Continuing analysis of isotope data will reveal more about the source and biogeochemical cycling of these three chemically and biologically important trace metals throughout the eastern tropical Pacific Ocean.

  10. Comparative evaluation of quantitative glomerular filtration rate measured by isotopic and nonisotopic methods

    SciTech Connect

    Balachandran, S.; Toguri, A.G.; Petrusick, T.W.; Abbott, L.C.

    1981-04-01

    Good correlation of glomerular filtration rate measured isotopically from plasma disappearance of Tc-99m-DTPA was shown with inulin clearance, creatinine clearance, and graded radionuclide imaging. The isotopic GFR is a simple, urineless technique not requiring continuous infusion that enables one to perform simultaneous renal imaging with one radiotracer.

  11. Comparative evaluation of quantitative glomerular filtration rate measured by isotopic and nonisotopic methods

    SciTech Connect

    Balachandran, S.; Toguri, A.G.; Petrusick, T.W.; Abbott, L.C.

    1981-04-01

    Good correlation of glomerular filtration rate (GFR) measured isotopically from plasma disappearance of Tc-99m-DTPA (Sn) was shown with inulin clearance, creatinine clearance, and graded radionuclide imaging. The isotopic GFR is a simple, urineless technique not requiring continuous infusion that enables one to perform simultaneous renal imaging with one radiotracer.

  12. 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.

  13. Equilibrium CO bond lengths

    NASA Astrophysics Data System (ADS)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  14. Comparing three methods of NEE-flux partitioning from the same grassland ecosystem: the 13C, 18O isotope approach and using simulated Ecosystem respiration

    NASA Astrophysics Data System (ADS)

    Siegwolf, R.; Bantelmann, E.; Saurer, M.; Eugster, W.; Buchmann, N.

    2007-12-01

    As a change in the global climate occurs with increasing temperatures, the Carbon exchange processes of terrestrial ecosystems will change as well. However, it is difficult to quantify the degree to what ecosystem respiration will change relative to the CO2 uptake by photosynthesis. To estimate the carbon sequestration potential of terrestrial vegetation cover it is essential to know both fluxes: ecosystem respiration and the carbon uptake by the vegetation cover. Therefore the net ecosystem exchange of CO2 (NEE) was measured with the eddy covariance method and separated into assimilation and respiration flux. We applied three different approaches, 1) the conventional method, applying the nighttime relationship between soil temperature and NEE for calculating the respiration flux during the day, 2) the use of stable carbon and 3) oxygen isotopes. We compared the results of the three partitioning exercises for a temperate grassland ecosystem in the pre-Alps of Switzerland for four days in June 2004. The assimilation flux derived with the conventional NEE partitioning approach, was best represented at low PAR and low temperatures, in the morning between 5 and 9 am. With increasing temperature and PAR the assimilation for the whole canopy was underestimated. For partitioning NEE via 18O approach, correlations of temperature and radiation with assimilation and respiration flux were significantly higher for the partitioning approach with 18O than for the 13C NEE partitioning. A sensitivity analysis showed the importance of an accurate determination of the equilibrium term θ between CO2 and leaf water δ18O for the NEE partitioning with 18O. For using 13C to partition NEE, the correct magnitude of the 13C fractionation and for the respiration term is essential. The analysis of the data showed that for low light and low morning temperatures the conventional method delivers reasonably good results. When the temperatures exceeded 21°C the isotope approach provided the

  15. Online induction heating for determination of isotope composition of woody stem water with laser spectrometry: A methods assessment

    USGS Publications Warehouse

    Lazarus, Brynne E.; Germino, Matthew; Vander Veen, Jessica L.

    2016-01-01

    Application of stable isotopes of water to studies of plant–soil interactions often requires a substantial preparatory step of extracting water from samples without fractionating isotopes. Online heating is an emerging approach for this need, but is relatively untested and major questions of how to best deliver standards and assess interference by organics have not been evaluated. We examined these issues in our application of measuring woody stem xylem of sagebrush using a Picarro laser spectrometer with online induction heating. We determined (1) effects of cryogenic compared to induction-heating extraction, (2) effects of delivery of standards on filter media compared to on woody stem sections, and (3) spectral interference from organic compounds for these approaches (and developed a technique to do so). Our results suggest that matching sample and standard media improves accuracy, but that isotopic values differ with the extraction method in ways that are not due to spectral interference from organics.

  16. Torque equilibrium attitude control for Skylab reentry

    NASA Technical Reports Server (NTRS)

    Glaese, J. R.; Kennel, H. F.

    1979-01-01

    All the available torque equilibrium attitudes (most were useless from the standpoint of lack of electrical power) and the equilibrium seeking method are presented, as well as the actual successful application during the 3 weeks prior to Skylab reentry.

  17. The molecular yo-yo method: Live jump detection improves throughput of single-molecule force spectroscopy for out-of-equilibrium transitions

    NASA Astrophysics Data System (ADS)

    Mack, A. H.; Schlingman, D. J.; Kamenetska, M.; Collins, R.; Regan, L.; Mochrie, S. G. J.

    2013-08-01

    By monitoring multiple molecular transitions, force-clamp, and trap-position-clamp methods have led to precise determinations of the free energies and free energy landscapes for molecular states populated in equilibrium at the same or similar forces. Here, we present a powerful new elaboration of the force-clamp and force-jump methods, applicable to transitions far from equilibrium. Specifically, we have implemented a live jump detection and force-clamp algorithm that intelligently adjusts and maintains the force on a single molecule in response to the measured state of that molecule. We are able to collect hundreds of individual molecular transitions at different forces, many times faster than previously, permitting us to accurately determine force-dependent lifetime distributions and reaction rates. Application of our method to unwinding and rewinding the nucleosome inner turn, using optical tweezers reveals experimental lifetime distributions that comprise a statistically meaningful number of transitions, and that are accurately single exponential. These measurements significantly reduce the error in the previously measured rates, and demonstrate the existence of a single, dominant free energy barrier at each force studied. A key benefit of the molecular yo-yo method for nucleosomes is that it reduces as far as possible the time spent in the tangentially bound state, which minimizes the loss of nucleosomes by dissociation.

  18. Source apportionment of methane using a triple isotope approach - Method development and application in the Baltic Sea

    NASA Astrophysics Data System (ADS)

    Steinbach, Julia; Holmstrand, Henry; Semiletov, Igor; Shakhova, Natalia; Shcherbakova, Kseniia; Kosmach, Denis; Sapart, Célia J.; Gustafsson, Örjan

    2015-04-01

    We present a method for measurements of the stable and radiocarbon isotope systems of methane in seawater and sediments. The triple isotope characterization of methane is useful in distinguishing different sources and for improving our understanding of biogeochemical processes affecting methane in the water column. D14C-CH4 is an especially powerful addition to stable isotope analyses in distinguishing between thermogenic and biogenic origins of the methane. Such measurements require large sample sizes, due to low natural abundance of the radiocarbon in CH4. Our system for sample collection, methane extraction and purification builds on the approach by Kessler and Reeburgh (Limn. & Ocean. Meth., 2005). An in-field system extracts methane from 30 -120 l water or 1-2 l sediment (depending on the in-situ methane concentration) by purging the samples with Helium to transfer the dissolved methane to the headspace and circulating it through cryogenically cooled absorbent traps where methane is collected. The in-field preparation eliminates the risks of storage and transport of large seawater quantities and subsequent leakage of sample gas as well as ongoing microbial processes and chemical reactions that may alter the sample composition. In the subsequent shore-based treatment, a laboratory system is used to purify and combust the collected CH4 to AMS-amenable CO2. Subsamples from the methane traps are analyzed for stable isotopes and compared to stable isotope measurements directly measured from small water samples taken in parallel, to correct for any potential fractionation occurring during this process. The system has been successfully tested and used on several shorter shipboard expeditions in the Baltic Sea and on a long summer expedition across the Arctic Ocean. Here we present the details of the method and testing, as well as first triple isotope field data from two cruises to the Landsort Deep area in the Central Baltic Sea.

  19. Development and validation of a liquid chromatography isotope dilution mass spectrometry method for the reliable quantification of alkylphenols in environmental water samples by isotope pattern deconvolution.

    PubMed

    Fabregat-Cabello, Neus; Sancho, Juan V; Vidal, Andreu; González, Florenci V; Roig-Navarro, Antoni Francesc

    2014-02-01

    We present here a new measurement method for the rapid extraction and accurate quantification of technical nonylphenol (NP) and 4-t-octylphenol (OP) in complex matrix water samples by UHPLC-ESI-MS/MS. The extraction of both compounds is achieved in 30min by means of hollow fiber liquid phase microextraction (HF-LPME) using 1-octanol as acceptor phase, which provides an enrichment (preconcentration) factor of 800. On the other hand we have developed a quantification method based on isotope dilution mass spectrometry (IDMS) and singly (13)C1-labeled compounds. To this end the minimal labeled (13)C1-4-(3,6-dimethyl-3-heptyl)-phenol and (13)C1-t-octylphenol isomers were synthesized, which coelute with the natural compounds and allows the compensation of the matrix effect. The quantification was carried out by using isotope pattern deconvolution (IPD), which permits to obtain the concentration of both compounds without the need to build any calibration graph, reducing the total analysis time. The combination of both extraction and determination techniques have allowed to validate for the first time a HF-LPME methodology at the required levels by legislation achieving limits of quantification of 0.1ngmL(-1) and recoveries within 97-109%. Due to the low cost of HF-LPME and total time consumption, this methodology is ready for implementation in routine analytical laboratories. PMID:24423386

  20. A routine high-precision method for Lu-Hf isotope geochemistry and chronology

    USGS Publications Warehouse

    Patchett, P.J.; Tatsumoto, M.

    1981-01-01

    A method for chemical separation of Lu and Hf from rock, meteorite and mineral samples is described, together with a much improved mass spectrometric running technique for Hf. This allows (i) geo- and cosmochronology using the176Lu???176Hf+??- decay scheme, and (ii) geochemical studies of planetary processes in the earth and moon. Chemical yields for the three-stage ion-exchange column procedure average 90% for Hf. Chemical blanks are <0.2 ng for Lu and Hf. From 1 ??g of Hf, a total ion current of 0.5??10-11 Ampere can be maintained for 3-5 h, yielding 0.01-0.03% precision on the ratio176Hf/177Hf. Normalisation to179Hf/177Hf=0.7325 is used. Extensive results for the Johnson Matthey Hf standard JMC 475 are presented, and this sample is urged as an international mass spectrometric standard; suitable aliquots, prepared from a single batch of JMC 475, are available from Denver. Lu-Hf analyses of the standard rocks BCR-1 and JB-1 are given. The potential of the Lu-Hf method in isotope geochemistry is assessed. ?? 1980 Springer-Verlag.

  1. Pantothenic acid quantification: method comparison of a stable isotope dilution assay and a microbiological assay.

    PubMed

    Rychlik, Michael; Roth-Maier, Dora

    2005-05-01

    Different foods and feedstuffs were analyzed for pantothenic acid (PA) by the recently developed stable isotope dilution assay (SIDA) and by the standard method, a microbiological assay (MA). The SIDA involved the use of [13C3, 15N]-pantothenic acid as the internal standard and detection by liquid chromatography-tandem mass spectrometry. The analysis of identical extracts minimized systematic bias due to equal extraction yields and enabled an ideal comparison between both methods. For the samples derived from plants a good accordance between the MA and the SIDA of total PA was found, whereas for the products of animal origin, higher contents were measured by MA than by SIDA. From the results of treatments by pantetheinase and phosphatase on the one hand and papain and diastase on the other, it was concluded that MA is able to measure a significant amount of bound PA. Furthermore, the data imply that microbial enzymes were able to cleave PA conjugates more effectively than pantetheinase and phosphatase treatment. PMID:16028638

  2. 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.

  3. Present limitations and future prospects of stable isotope methods for nitrate source identification in surface- and groundwater.

    PubMed

    Xue, Dongmei; Botte, Jorin; De Baets, Bernard; Accoe, Frederik; Nestler, Angelika; Taylor, Philip; Van Cleemput, Oswald; Berglund, Michael; Boeckx, Pascal

    2009-03-01

    Nitrate (NO3(-)) contamination of surface- and groundwater is an environmental problem in many regions of the world with intensive agriculture and high population densities. Knowledge of the sources of NO3(-) contamination in water is important for better management of water quality. Stable nitrogen (delta15N) and oxygen (delta18O) isotope data of NO3(-) have been frequently used to identify NO3(-) sources in water. This review summarizes typical delta15N- and delta18O-NO3(-) ranges of known NO3(-) sources, interprets constraints and future outlooks to quantify NO3(-) sources, and describes three analytical techniques ("ion-exchange method", "bacterial denitrification method", and "cadmium reduction method") for delta15N- and delta18)O-NO3(-) determination. Isotopic data can provide evidence for the presence of dominant NO3(-) sources. However, quantification, including uncertainty assessment, is lacking when multiple NO3(-) sources are present. Moreover, fractionation processes are often ignored, but may largely constrain the accuracy of NO3(-) source identification. These problems can be overcome if (1) NO3(-) isotopic data are combined with co-migrating discriminators of NO3(-) sources (e.g. (11)B), which are not affected by transformation processes, (2) contributions of different NO3(-) sources can be quantified via linear mixing models (e.g. SIAR), and (3) precise, accurate and high throughput isotope analytical techniques become available.

  4. Quantifying the ion atmosphere of unfolded, single-stranded nucleic acids using equilibrium dialysis and single-molecule methods

    PubMed Central

    Jacobson, David R.; Saleh, Omar A.

    2016-01-01

    To form secondary structure, nucleic acids (NAs) must overcome electrostatic strand–strand repulsion, which is moderated by the surrounding atmosphere of screening ions. The free energy of NA folding therefore depends on the interactions of this ion atmosphere with both the folded and unfolded states. We quantify such interactions using the preferential ion interaction coefficient or ion excess: the number of ions present near the NA in excess of the bulk concentration. The ion excess of the folded, double-helical state has been extensively studied; however, much less is known about the salt-dependent ion excess of the unfolded, single-stranded state. We measure this quantity using three complementary approaches: a direct approach of Donnan equilibrium dialysis read out by atomic emission spectroscopy and two indirect approaches involving either single-molecule force spectroscopy or existing thermal denaturation data. The results of these three approaches, each involving an independent experimental technique, are in good agreement. Even though the single-stranded NAs are flexible polymers that are expected to adopt random-coil configurations, we find that their ion atmosphere is quantitatively described by rod-like models that neglect large-scale conformational freedom, an effect that we explain in terms of the competition between the relevant structural and electrostatic length scales. PMID:27036864

  5. An upwind, kinetic flux-vector splitting method for flows in chemical and thermal non-equilibrium

    NASA Technical Reports Server (NTRS)

    Eppard, W. M.; Grossman, B.

    1993-01-01

    We have developed new upwind kinetic difference schemes for flows with non-equilibrium thermodynamics and chemistry. These schemes are derived from the Boltzmann equation with the resulting Euler schemes developed as moments of the discretized Boltzmann scheme with a locally Maxwellian velocity distribution. Splitting the velocity distribution at the Boltzmann level is seen to result in a flux-split Euler scheme and is called Kinetic Flux Vector Splitting (KFVS). Extensions to flows with finite-rate chemistry and vibrational relaxation is accomplished utilizing nonequilibrium kinetic theory. Computational examples are presented comparing KFVS with the schemes of Van Leer and Roe for a quasi-one-dimensional flow through a supersonic diffuser, inviscid flow through two-dimensional inlet, and viscous flow over a cone at zero angle-of-attack. Calculations are also shown for the transonic flow over a bump in a channel and the transonic flow over an NACA 0012 airfoil. The results show that even though the KFVS scheme is a Riemann solver at the kinetic level, its behavior at the Euler level is more similar to the existing flux-vector splitting algorithms than to the flux-difference splitting scheme of Roe.

  6. The equilibrium shape of fluid-fluid interfaces: Derivation and a new numerical method for Young’s and Young-Laplace equations

    SciTech Connect

    Soligno, Giuseppe; Roij, René van; Dijkstra, Marjolein

    2014-12-28

    Many physical problems require explicit knowledge of the equilibrium shape of the interface between two fluid phases. Here, we present a new numerical method which is simply implementable and easily adaptable for a wide range of problems involving capillary deformations of fluid-fluid interfaces. We apply a simulated annealing algorithm to find the interface shape that minimizes the thermodynamic potential of the system. First, for completeness, we provide an analytical proof that minimizing this potential is equivalent to solving the Young-Laplace equation and the Young law. Then, we illustrate our numerical method showing two-dimensional results for fluid-fluid menisci between vertical or inclined walls and curved surfaces, capillary interactions between vertical walls, equilibrium shapes of sessile heavy droplets on a flat horizontal solid surface, and of droplets pending from flat or curved solid surfaces. Finally, we show illustrative three-dimensional results to point out the applicability of the method to micro- or nano-particles adsorbed at a fluid-fluid interface.

  7. The equilibrium shape of fluid-fluid interfaces: derivation and a new numerical method for Young's and Young-Laplace equations.

    PubMed

    Soligno, Giuseppe; Dijkstra, Marjolein; van Roij, René

    2014-12-28

    Many physical problems require explicit knowledge of the equilibrium shape of the interface between two fluid phases. Here, we present a new numerical method which is simply implementable and easily adaptable for a wide range of problems involving capillary deformations of fluid-fluid interfaces. We apply a simulated annealing algorithm to find the interface shape that minimizes the thermodynamic potential of the system. First, for completeness, we provide an analytical proof that minimizing this potential is equivalent to solving the Young-Laplace equation and the Young law. Then, we illustrate our numerical method showing two-dimensional results for fluid-fluid menisci between vertical or inclined walls and curved surfaces, capillary interactions between vertical walls, equilibrium shapes of sessile heavy droplets on a flat horizontal solid surface, and of droplets pending from flat or curved solid surfaces. Finally, we show illustrative three-dimensional results to point out the applicability of the method to micro- or nano-particles adsorbed at a fluid-fluid interface.

  8. The equilibrium shape of fluid-fluid interfaces: derivation and a new numerical method for Young's and Young-Laplace equations.

    PubMed

    Soligno, Giuseppe; Dijkstra, Marjolein; van Roij, René

    2014-12-28

    Many physical problems require explicit knowledge of the equilibrium shape of the interface between two fluid phases. Here, we present a new numerical method which is simply implementable and easily adaptable for a wide range of problems involving capillary deformations of fluid-fluid interfaces. We apply a simulated annealing algorithm to find the interface shape that minimizes the thermodynamic potential of the system. First, for completeness, we provide an analytical proof that minimizing this potential is equivalent to solving the Young-Laplace equation and the Young law. Then, we illustrate our numerical method showing two-dimensional results for fluid-fluid menisci between vertical or inclined walls and curved surfaces, capillary interactions between vertical walls, equilibrium shapes of sessile heavy droplets on a flat horizontal solid surface, and of droplets pending from flat or curved solid surfaces. Finally, we show illustrative three-dimensional results to point out the applicability of the method to micro- or nano-particles adsorbed at a fluid-fluid interface. PMID:25554170

  9. A New Method for Evaluating the Carbon Isotope Characteristics of Carbonate Formed Under Cryogenic Conditions Analogous to Mars

    NASA Technical Reports Server (NTRS)

    Niles, P. B.; Socki, R. A.; Hredzak, P. L.

    2007-01-01

    soil or dust. This study demonstrates an innovative new method for measuring the isotopic composition of gas evolved from the freezing of carbonate solutions in real time, which allows for a much clearer view of the chemical processes involved. This method now sets the stage for detailed analysis of the chemical and isotopic mechanisms that produce cryogenic carbonates.

  10. 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

  11. Organic Tank Safety Project: development of a method to measure the equilibrium water content of Hanford organic tank wastes and demonstration of method on actual waste

    SciTech Connect

    Scheele, R.D.; Bredt, P.R.; Sell, R.L.

    1996-09-01

    Some of Hanford`s underground waste storage tanks contain Organic- bearing high level wastes that are high priority safety issues because of potentially hazardous chemical reactions of organics with inorganic oxidants in these wastes such as nitrates and nitrites. To ensure continued safe storage of these wastes, Westinghouse Hanford Company has placed affected tanks on the Organic Watch List and manages them under special rules. Because water content has been identified as the most efficient agent for preventing a propagating reaction and is an integral part of the criteria developed to ensure continued safe storage of Hanford`s organic-bearing radioactive tank wastes, as part of the Organic Tank Safety Program the Pacific Northwest National Laboratory developed and demonstrated a simple and easily implemented procedure to determine the equilibrium water content of these potentially reactive wastes exposed to the range of water vapor pressures that might be experienced during the wastes` future storage. This work focused on the equilibrium water content and did not investigate the various factors such as @ ventilation, tank surface area, and waste porosity that control the rate that the waste would come into equilibrium, with either the average Hanford water partial pressure 5.5 torr or other possible water partial pressures.

  12. Open tube combustion method of organic samples for stable carbon isotope analysis.

    PubMed

    Velivetskaya, Tatiana A; Ignatyev, Alexander V; Reize, Marina V; Kiyashko, Serguei I

    2007-01-01

    A simple and effective method for the conversion of organic carbon into carbon dioxide for analysis of stable carbon isotopes (delta(13)C) in samples of various organic substances, soils, sedimentary rocks, oils and volatile organic liquids is presented. The conversion of organic carbon of the samples is carried out in a quartz reactor connected to a vacuum line for CO(2) freezing and purification. A solid organic sample mixed with CuO is placed at the reactor bottom and the reactor is subsequently filled with granular CuO. One end of the CuO column is preheated to 850 degrees C while the other end of the column in contact with the sample is kept at ambient temperature. Heating of the sample (850 degrees C) and the remainder of the column is then performed. The preheated part of the column provides efficient conversion of carbon into CO(2). The reactor for the conversion of volatile liquid organic compounds is filled with granular CuO. The column of CuO is heated to 850 degrees C. Samples of volatile liquids are introduced into the reactor through a septum using a microsyringe. Complete conversion takes 10 min for solid samples and 3 min for volatile liquids. The precision of the delta(13)C analysis for solid and volatile liquid organic substances is +/-0.1 per thousand and +/-0.04 per thousand, respectively.

  13. A comparison of force fields and calculation methods for vibration intervals of isotopic H3(+) molecules

    NASA Astrophysics Data System (ADS)

    Carney, G. D.; Adler-Golden, S. M.; Lesseski, D. C.

    1986-04-01

    This paper reports (1) improved values for low-lying vibration intervals of H3(+), H2D(+), D2H(+), and D3(+) calculated using the variational method and Simons-Parr-Finlan (1973) representations of the Carney-Porter (1976) and Dykstra-Swope (1979) ab initio H3(+) potential energy surfaces, (2) quartic normal coordinate force fields for isotopic H3(+) molecules, (3) comparisons of variational and second-order perturbation theory, and (4) convergence properties of the Lai-Hagstrom internal coordinate vibrational Hamiltonian. Standard deviations between experimental and ab initio fundamental vibration intervals of H3(+), H2D(+), D2H(+), and D3(+) for these potential surfaces are 6.9 (Carney-Porter) and 1.2/cm (Dykstra-Swope). The standard deviations between perturbation theory and exact variational fundamentals are 5 and 10/cm for the respective surfaces. The internal coordinate Hamiltonian is found to be less efficient than the previously employed 't' coordinate Hamiltonian for these molecules, except in the case of H2D(+).

  14. Open tube combustion method of organic samples for stable carbon isotope analysis.

    PubMed

    Velivetskaya, Tatiana A; Ignatyev, Alexander V; Reize, Marina V; Kiyashko, Serguei I

    2007-01-01

    A simple and effective method for the conversion of organic carbon into carbon dioxide for analysis of stable carbon isotopes (delta(13)C) in samples of various organic substances, soils, sedimentary rocks, oils and volatile organic liquids is presented. The conversion of organic carbon of the samples is carried out in a quartz reactor connected to a vacuum line for CO(2) freezing and purification. A solid organic sample mixed with CuO is placed at the reactor bottom and the reactor is subsequently filled with granular CuO. One end of the CuO column is preheated to 850 degrees C while the other end of the column in contact with the sample is kept at ambient temperature. Heating of the sample (850 degrees C) and the remainder of the column is then performed. The preheated part of the column provides efficient conversion of carbon into CO(2). The reactor for the conversion of volatile liquid organic compounds is filled with granular CuO. The column of CuO is heated to 850 degrees C. Samples of volatile liquids are introduced into the reactor through a septum using a microsyringe. Complete conversion takes 10 min for solid samples and 3 min for volatile liquids. The precision of the delta(13)C analysis for solid and volatile liquid organic substances is +/-0.1 per thousand and +/-0.04 per thousand, respectively. PMID:17610237

  15. Improved curve fits for the thermodynamic properties of equilibrium air suitable for numerical computation using time-dependent or shock-capturing methods, part 1

    NASA Technical Reports Server (NTRS)

    Tannehill, J. C.; Mugge, P. H.

    1974-01-01

    Simplified curve fits for the thermodynamic properties of equilibrium air were devised for use in either the time-dependent or shock-capturing computational methods. For the time-dependent method, curve fits were developed for p = p(e, rho), a = a(e, rho), and T = T(e, rho). For the shock-capturing method, curve fits were developed for h = h(p, rho) and T = T(p, rho). The ranges of validity for these curves fits were for temperatures up to 25,000 K and densities from 10 to the minus 7th power to 10 to the 3d power amagats. These approximate curve fits are considered particularly useful when employed on advanced computers such as the Burroughs ILLIAC 4 or the CDC STAR.

  16. Artifactual responses of mesophyll conductance to CO2 and irradiance estimated with the variable J and online isotope discrimination methods

    SciTech Connect

    Gu, Lianhong; Sun, Ying

    2013-01-01

    Studies with the variable J method have reported that mesophyll conductance (gm) rapidly decreases with increasing intercellular CO2 partial pressures (Ci) or decreasing irradiance. Similar responses have been suggested with the online isotope discrimination method, although with less consistency. Here we show that even when the true gm is constant, the variable J method can produce an artifactual dependence of gm on Ci or irradiance similar to those reported in previous studies for any of the following factors: day respiration and chloroplastic CO2 photocompensation point are estimated with Laisk method; Ci or electron transport rate is positively biased; net photosynthetic rate is negatively biased; insufficient NADPH is assumed while insufficient ATP limits RuBP regeneration. The isotopic method produces similar artifacts if fractionation of carboxylation or Ci are positively biased or 13 negatively biased. A nonzero chloroplastic resistance to CO2 movement results in a qualitatively different dependence of gm on Ci or irradiance and this dependence is only sensitive at low Ci. We thus cannot rule out the possibility that previously reported dependence of gm on Ci or irradiance is a methodological artifact. Recommendations are made to take advantage of sensitivities of the variable J and isotopic methods for estimating gm.

  17. Determination of (241)Pu by the method of disturbed radioactive equilibrium using 2πα-counting and precision gamma-spectrometry.

    PubMed

    Alekseev, I; Kuzmina, T

    2016-04-01

    A simple technique is proposed for the determination of the content of (241)Pu, which is based on disturbance of radioactive equilibrium in the genetically related (237)U←(241)Pu→(241)Am decay chain of radionuclides, with the subsequent use of 2πα-counting and precision gamma-spectroscopy for monitoring the process of restoration of that equilibrium. It has been shown that the data on dynamics of accumulation of the daughter (241)Am, which were obtained from the results of measurements of α- and γ-spectra of the samples, correspond to the estimates calculated for the chain of two genetically related radionuclides, the differences in the estimates of (241)Pu radioactivity not exceeding 2%. Combining the different methods of registration (2πα-counting, semiconductor alpha- and gamma-spectrometry) enables the proposed method to be efficiently applied both for calibration of (241)Pu-sources (from several hundreds of kBq and higher) and for radioisotopic analysis of plutonium mixtures. In doing so, there is a deep purification of (241)Pu from its daughter decay products required due to unavailability of commercial detectors that could make it possible, based only on analysis of alpha-spectra, to conduct quantitative analysis of the content of (238)Pu and (241)Am. PMID:26868275

  18. Determination of (241)Pu by the method of disturbed radioactive equilibrium using 2πα-counting and precision gamma-spectrometry.

    PubMed

    Alekseev, I; Kuzmina, T

    2016-04-01

    A simple technique is proposed for the determination of the content of (241)Pu, which is based on disturbance of radioactive equilibrium in the genetically related (237)U←(241)Pu→(241)Am decay chain of radionuclides, with the subsequent use of 2πα-counting and precision gamma-spectroscopy for monitoring the process of restoration of that equilibrium. It has been shown that the data on dynamics of accumulation of the daughter (241)Am, which were obtained from the results of measurements of α- and γ-spectra of the samples, correspond to the estimates calculated for the chain of two genetically related radionuclides, the differences in the estimates of (241)Pu radioactivity not exceeding 2%. Combining the different methods of registration (2πα-counting, semiconductor alpha- and gamma-spectrometry) enables the proposed method to be efficiently applied both for calibration of (241)Pu-sources (from several hundreds of kBq and higher) and for radioisotopic analysis of plutonium mixtures. In doing so, there is a deep purification of (241)Pu from its daughter decay products required due to unavailability of commercial detectors that could make it possible, based only on analysis of alpha-spectra, to conduct quantitative analysis of the content of (238)Pu and (241)Am.

  19. Modification of a method-of-characteristics solute-transport model to incorporate decay and equilibrium-controlled sorption or ion exchange

    USGS Publications Warehouse

    Goode, D.J.; Konikow, L.F.

    1989-01-01

    The U.S. Geological Survey computer model of two-dimensional solute transport and dispersion in ground water (Konikow and Bredehoeft, 1978) has been modified to incorporate the following types of chemical reactions: (1) first-order irreversible rate-reaction, such as radioactive decay; (2) reversible equilibrium-controlled sorption with linear, Freundlich, or Langmuir isotherms; and (3) reversible equilibrium-controlled ion exchange for monovalent or divalent ions. Numerical procedures are developed to incorporate these processes in the general solution scheme that uses method-of- characteristics with particle tracking for advection and finite-difference methods for dispersion. The first type of reaction is accounted for by an exponential decay term applied directly to the particle concentration. The second and third types of reactions are incorporated through a retardation factor, which is a function of concentration for nonlinear cases. The model is evaluated and verified by comparison with analytical solutions for linear sorption and decay, and by comparison with other numerical solutions for nonlinear sorption and ion exchange.

  20. Evaluation of the three-phase equilibrium method for measuring temperature dependence of internally consistent partition coefficients (KOW, KOA, and KAW) for volatile methylsiloxanes and trimethylsilanol

    PubMed Central

    Xu, Shihe; Kropscott, Bruce

    2014-01-01

    Partitioning equilibria and their temperature dependence of chemicals between different environmental media are important in determining the fate, transport, and distribution of contaminants. Unfortunately, internally consistent air/water (KAW), 1-octanol/air (KOA), and 1-octanol/water (KOW) partition coefficients, as well as information on their temperature dependence, are scarce for organosilicon compounds because of the reactivity of these compounds in water and octanol and their extreme partition coefficients. A newly published 3-phase equilibrium method was evaluated for simultaneous determination of the temperature dependence of KAW, KOA, and KOW of 5 volatile methylsiloxanes (VMS) and trimethylsilanol (TMS) in a temperature range from 4 °C to 35 °C. The measured partition coefficients at the different temperatures for any given compound, and the enthalpy and entropy changes for the corresponding partition processes, were all internally consistent, suggesting that the 3-phase equilibrium method is suitable for this type of measurement. Compared with common environmental contaminants reported in the literature, VMS have enthalpy and entropy relationships similar to those of alkanes for air/water partitioning and similar to those of polyfluorinated compounds for octanol/air partitioning, but more like those for benzoates and phenolic compounds for octanol/water partitioning. The temperature dependence of the partition coefficients of TMS is different from those of VMS and is more like that of alcohols, phenols, and sulfonamides. Environ Toxicol Chem 2014;33:2702–2710. © 2014 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. PMID:25242335

  1. Discovery of the krypton isotopes

    SciTech Connect

    Heim, M.; Fritsch, A.; Schuh, A.; Shore, A.; Thoennessen, M.

    2010-07-15

    Thirty-two krypton isotopes have been observed so far and the discovery of these isotopes is discussed here. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.

  2. Thermochemical parameters of minerals from oxygen-buffered hydrothermal equilibrium data: Method, application to annite and almandine

    USGS Publications Warehouse

    Zen, E.-A.

    1973-01-01

    Reversed univariant hydrothermal phase-equilibrium reactions, in which a redox reaction occurs and is controlled by oxygen buffers, can be used to extract thermochemical data on minerals. The dominant gaseous species present, even for relatively oxidizing buffers such as the QFM buffer, are H2O and H2; the main problem is to calculate the chemical potentials of these components in a binary mixture. The mixing of these two species in the gas phase was assumed by Eugster and Wones (1962) to be ideal; this assumption allows calculation of the chemical potentials of the two components in a binary gas mixture, using data in the literature. A simple-mixture model of nonideal mixing, such as that proposed by Shaw (1967), can also be combined with the equations of state for oxygen buffers to permit derivation of the chemical potentials of the two components. The two mixing models yield closely comparable results for the more oxidizing buffers such as the QFM buffer. For reducing buffers such as IQF, the nonideal-mixing correction can be significant and the Shaw model is better. The procedure of calculation of mineralogical thermochemical data, in reactions where hydrogen and H2O simultaneously appear, is applied to the experimental data on annite, given by Wones et al. (1971), and on almandine, given by Hsu (1968). For annite the results are: Standard entropy of formation from the elements, Sf0 (298, 1)=-283.35??2.2 gb/gf, S0 (298, 1) =+92.5 gb/gf. Gf0 (298, 1)=-1148.2??6 kcal, and Hf0 (298, 1)=-1232.7??7 kcal. For almandine, the calculation takes into account the mutual solution of FeAl2O4 (Hc) in magnetite and of Fe3O4 (Mt) in hercynite and the temperature dependence of this solid solution, as given by Turnock and Eugster (1962); the calculations assume a regular-solution model for this binary spinel system. The standard entropy of formation of almandine, Sf,A0 (298, 1) is -272.33??3 gb/gf. The third law entropy, S0 (298, 1) is +68.3??3 gb/gf, a value much less than the

  3. New treatment method for boron in aqueous solutions using Mg-Al layered double hydroxide: Kinetics and equilibrium studies.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2015-08-15

    Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg - Al LDHs) and with Cl(-) (Cl · Mg - Al LDHs) were found to take up boron from aqueous solutions. Boron was removed by anion exchange of B(OH)4(-) in solution with NO3(-) and Cl(-) intercalated in the interlayer of the LDH. Using three times the stoichiometric quantity of NO3 · Mg-Al LDH, the residual concentration of B decreased from 100 to 1.9 mg L(-1) in 120 min. Using five times the stoichiometric quantity of Cl · Mg - Al LDH, the residual concentration of B decreased from 100 to 5.6 mg L(-1) in 120 min. It must be emphasized that, in both cases, the residual concentration of B was less than the effluent standards in Japan (10 mg L(-1)). The rate-determining step of B removal by the NO3 · Mg - Al and Cl · Mg - Al LDHs was found to be chemical adsorption involving anion exchange of B(OH)4(-) with intercalated NO3(-) and Cl(-). The removal of B was well described by a pseudo second-order kinetic equation. The adsorption of B by NO3 · Mg - Al LDH and Cl · Mg - Al LDH followed a Langmuir-type adsorption. The values of the maximum adsorption and the equilibrium adsorption constant were 3.6 mmol g(-1) and 1.7, respectively, for NO3 · Mg - Al LDH, and 3.8 mmol g(-1) and 0.7, respectively, for Cl · Mg-Al LDH. The B(OH)4(-) in B(OH)4 · Mg - Al LDH produced by removal of B was found to undergo anion exchange with NO3(-) and Cl(-) in solution. The NO3 · Mg - Al and Cl · Mg - Al LDHs obtained after this regeneration treatment were able to remove B from aqueous solutions, indicating the possibility of recycling NO3 · Mg - Al and Cl · Mg - Al LDHs for B removal. PMID:25827268

  4. New treatment method for boron in aqueous solutions using Mg-Al layered double hydroxide: Kinetics and equilibrium studies.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2015-08-15

    Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg - Al LDHs) and with Cl(-) (Cl · Mg - Al LDHs) were found to take up boron from aqueous solutions. Boron was removed by anion exchange of B(OH)4(-) in solution with NO3(-) and Cl(-) intercalated in the interlayer of the LDH. Using three times the stoichiometric quantity of NO3 · Mg-Al LDH, the residual concentration of B decreased from 100 to 1.9 mg L(-1) in 120 min. Using five times the stoichiometric quantity of Cl · Mg - Al LDH, the residual concentration of B decreased from 100 to 5.6 mg L(-1) in 120 min. It must be emphasized that, in both cases, the residual concentration of B was less than the effluent standards in Japan (10 mg L(-1)). The rate-determining step of B removal by the NO3 · Mg - Al and Cl · Mg - Al LDHs was found to be chemical adsorption involving anion exchange of B(OH)4(-) with intercalated NO3(-) and Cl(-). The removal of B was well described by a pseudo second-order kinetic equation. The adsorption of B by NO3 · Mg - Al LDH and Cl · Mg - Al LDH followed a Langmuir-type adsorption. The values of the maximum adsorption and the equilibrium adsorption constant were 3.6 mmol g(-1) and 1.7, respectively, for NO3 · Mg - Al LDH, and 3.8 mmol g(-1) and 0.7, respectively, for Cl · Mg-Al LDH. The B(OH)4(-) in B(OH)4 · Mg - Al LDH produced by removal of B was found to undergo anion exchange with NO3(-) and Cl(-) in solution. The NO3 · Mg - Al and Cl · Mg - Al LDHs obtained after this regeneration treatment were able to remove B from aqueous solutions, indicating the possibility of recycling NO3 · Mg - Al and Cl · Mg - Al LDHs for B removal.

  5. Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters

    NASA Technical Reports Server (NTRS)

    Bauer, J. E.; Haddad, R. I.; Des Marais, D. J.

    1991-01-01

    A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO2 evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1-5 micromoles of carbon and has an associated blank of 0.1-0.2 micromole of carbon. Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO2 as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3%. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The delta 13C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC. The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average delta 13C = -12.4%). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and delta 13C of pore-water DOC was nearly 8% lighter at 1.5-2.0-cm depth than in the mat surface layer (0-0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and delta 13C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters

  6. Determining origin in a migratory marine vertebrate: a novel method to integrate stable isotopes and satellite tracking

    USGS Publications Warehouse

    Vander Zanden, Hannah B.; Tucker, Anton D.; Hart, Kristen M.; Lamont, Margaret M.; Fujisaki, Ikuko; Addison, David S.; Mansfield, Katherine L.; Phillips, Katrina F.; Wunder, Michael B.; Bowen, Gabriel J.; Pajuelo, Mariela; Bolten, Alan B.; Bjorndal, Karen A.

    2015-01-01

    Stable isotope analysis is a useful tool to track animal movements in both terrestrial and marine environments. These intrinsic markers are assimilated through the diet and may exhibit spatial gradients as a result of biogeochemical processes at the base of the food web. In the marine environment, maps to predict the spatial distribution of stable isotopes are limited, and thus determining geographic origin has been reliant upon integrating satellite telemetry and stable isotope data. Migratory sea turtles regularly move between foraging and reproductive areas. Whereas most nesting populations can be easily accessed and regularly monitored, little is known about the demographic trends in foraging populations. The purpose of the present study was to examine migration patterns of loggerhead nesting aggregations in the Gulf of Mexico (GoM), where sea turtles have been historically understudied. Two methods of geographic assignment using stable isotope values in known-origin samples from satellite telemetry were compared: 1) a nominal approach through discriminant analysis and 2) a novel continuous-surface approach using bivariate carbon and nitrogen isoscapes (isotopic landscapes) developed for this study. Tissue samples for stable isotope analysis were obtained from 60 satellite-tracked individuals at five nesting beaches within the GoM. Both methodological approaches for assignment resulted in high accuracy of foraging area determination, though each has advantages and disadvantages. The nominal approach is more appropriate when defined boundaries are necessary, but up to 42% of the individuals could not be considered in this approach. All individuals can be included in the continuous-surface approach, and individual results can be aggregated to identify geographic hotspots of foraging area use, though the accuracy rate was lower than nominal assignment. The methodological validation provides a foundation for future sea turtle studies in the region to inexpensively

  7. New online method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

    NASA Astrophysics Data System (ADS)

    Affolter, S.; Fleitmann, D.; Leuenberger, M.

    2014-07-01

    A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us simultaneously to measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the online water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δ D robustness. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water, resulting in an artificial water background with well-known δ D and δ18O values. The speleothem sample is placed in a copper tube, attached to the line, and after system stabilisation it is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements, a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain &delta D; and δ18O isotopic compositions of measured water aliquots. Precision is better than 1.5 ‰ for δ D and 0.4 ‰ for δ18O for water measurements for an extended range (-210 to 0 ‰ for δ D and -27 to 0 ‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to the isotope ratio mass

  8. New on-line method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

    NASA Astrophysics Data System (ADS)

    Affolter, S.; Fleitmann, D.; Leuenberger, M.

    2014-01-01

    A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us to simultaneously measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the on-line water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δD reliability. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water resulting in an artificial water background with well-known δD and δ18O values. The speleothem sample is placed into a copper tube, attached to the line and after system stabilisation is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain δD and δ18O isotopic composition of measured water aliquots. Precision is better than 1.5‰ for δD and 0.4‰ for δ18O for water measurement for an extended range (-210 to 0‰ for δD and -27 to 0‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to Isotope Ratio Mass Spectrometry (IRMS) technique.

  9. Determining origin in a migratory marine vertebrate: a novel method to integrate stable isotopes and satellite tracking.

    PubMed

    Zanden, Hannah B Vander; Tucker, Anton D; Hart, Kristen M; Lamont, Margaret M; Fuisaki, Ikuko; Addison, David; Mansfield, Katherine L; Phillips, Katrina F; Wunder, Michael B; Bowen, Gabriel J; Pajuelo, Mariela; Bolten, Alan B; Bjorndal, Karen A

    2015-03-01

    Stable isotope analysis is a useful tool to track animal movements in both terrestrial and marine environments. These intrinsic markers are assimilated through the diet and may exhibit spatial gradients as a result of biogeochemical processes at the base of the food web. In the marine environment, maps to predict the spatial distribution of stable isotopes are limited, and thus determining geographic origin has been reliant upon integrating satellite telemetry and stable isotope data. Migratory sea turtles regularly move between foraging and reproductive areas. Whereas most nesting populations can be easily accessed and regularly monitored, little is known about the demographic trends in foraging populations. The purpose of the present study was to examine migration patterns of loggerhead nesting aggregations in the Gulf of Mexico (GoM), where sea turtles have been historically understudied. Two methods of geographic assignment using stable isotope values in known-origin samples from satellite telemetry were compared: (1) a nominal approach through discriminant analysis and (2) a novel continuous-surface approach using bivariate carbon and nitrogen isoscapes (isotopic landscapes) developed for this study. Tissue samples for stable isotope analysis were obtained from 60 satellite-tracked individuals at five nesting beaches within the GoM. Both methodological approaches for assignment resulted in high accuracy of foraging area determination, though each has advantages and disadvantages. The nominal approach is more appropriate when defined boundaries are necessary, but up to 42% of the individuals could not be considered in this approach. All individuals can be included in the continuous-surface approach, and individual results can be aggregated to identify geographic hotspots of foraging area use, though the accuracy rate was lower than nominal assignment. The methodological validation provides a foundation for future sea turtle studies in the region to

  10. Improved methods for achieving the equilibrium number of phases in mixtures suitable for use in battery electrodes e. g. , for lithiating FeS/sub 2/

    DOEpatents

    Guidotti, R.A.

    1986-06-10

    A method is disclosed for preparing lithiated, particulate FeS/sub 2/ useful as a catholyte material in a lithium thermal battery, whereby the latter's voltage regulation properties are improved. The method comprises admixing FeS/sub 2/ and an amount of a lithium-containing compound, whereby the resultant total composition falls in an invariant region of the metallurgical phase diagram of its constituent components. Said lithium-containing compound and FeS/sub 2/ are admixed together with a solid electrolyte compatible with said catholyte, and the mixture is heated at a temperature above the melting point of said electrolyte and at which said mixture reaches its thermodynamic equilibrium number of phases.

  11. Bird migration and avian influenza: a comparison of hydrogen stable isotopes and satellite tracking methods

    USGS Publications Warehouse

    Bridge, Eli S.; Kelly, Jeffrey F.; Xiao, Xiangming; Takekawa, John Y.; Hill, Nichola J.; Yamage, Mat; Haque, Enam Ul; Islam, Mohammad Anwarul; Mundkur, Taej; Yavuz, Kiraz Erciyas; Leader, Paul; Leung, Connie Y.H.; Smith, Bena; Spragens, Kyle A.; Vandegrift, Kurt J.; Hosseini, Parviez R.; Saif, Samia; Mohsanin, Samiul; Mikolon, Andrea; Islam, Ausrafal; George, Acty; Sivananinthaperumal, Balachandran; Daszak, Peter; Newman, Scott H.

    2014-01-01

    Satellite-based tracking of migratory waterfowl is an important tool for understanding the potential role of wild birds in the long-distance transmission of highly pathogenic avian influenza. However, employing this technique on a continental scale is prohibitively expensive. This study explores the utility of stable isotope ratios in feathers in examining both the distances traveled by migratory birds and variation in migration behavior. We compared the satellite-derived movement data of 22 ducks from 8 species captured at wintering areas in Bangladesh, Turkey, and Hong Kong with deuterium ratios (δD) in the feathers of these and other individuals captured at the same locations. We derived likely molting locations from the satellite tracking data and generated expected isotope ratios based on an interpolated map of δD in rainwater. Although δD was correlated with the distance between wintering and molting locations, surprisingly, measured δD values were not correlated with either expected values or latitudes of molting sites. However, population-level parameters derived from the satellite-tracking data, such as mean distance between wintering and molting locations and variation in migration distance, were reflected by means and variation of the stable isotope values. Our findings call into question the relevance of the rainfall isotope map for Asia for linking feather isotopes to molting locations, and underscore the need for extensive ground truthing in the form of feather-based isoscapes. Nevertheless, stable isotopes from feathers could inform disease models by characterizing the degree to which regional breeding populations interact at common wintering locations. Feather isotopes also could aid in surveying wintering locations to determine where high-resolution tracking techniques (e.g. satellite tracking) could most effectively be employed. Moreover, intrinsic markers such as stable isotopes offer the only means of inferring movement information from

  12. Bird Migration and Avian Influenza: A Comparison of Hydrogen Stable Isotopes and Satellite Tracking Methods.

    PubMed

    Bridge, Eli S; Kelly, Jeffrey F; Xiao, Xiangming; Takekawa, John Y; Hill, Nichola J; Yamage, Mat; Haque, Enam Ul; Islam, Mohammad Anwarul; Mundkur, Taej; Yavuz, Kiraz Erciyas; Leader, Paul; Leung, Connie Y H; Smith, Bena; Spragens, Kyle A; Vandegrift, Kurt; Hosseini, Parviez R; Saif, Samia; Mohsanin, Samiul; Mikolon, Andrea; Islam, Ausrafal; George, Acty; Sivananinthaperumal, Balachandran; Daszak, Peter; Newman, Scott H

    2014-10-01

    Satellite-based tracking of migratory waterfowl is an important tool for understanding the potential role of wild birds in the long-distance transmission of highly pathogenic avian influenza. However, employing this technique on a continental scale is prohibitively expensive. This study explores the utility of stable isotope ratios in feathers in examining both the distances traveled by migratory birds and variation in migration behavior. We compared the satellite-derived movement data of 22 ducks from 8 species captured at wintering areas in Bangladesh, Turkey, and Hong Kong with deuterium ratios (δD) of these and other individuals captured at the same locations. We derived likely molting locations from the satellite tracking data and generated expected isotope ratios based on an interpolated map of δD in rainwater. Although δD was correlated with the distance between wintering and molting locations, surprisingly, measured δD values were not correlated with either expected values or latitudes of molting sites. However, population-level parameters derived from the satellite-tracking data, such as mean distance between wintering and molting locations and variation in migration distance, were reflected by means and variation of the stable isotope values. Our findings call into question the relevance of the rainfall isotope map for Asia for linking feather isotopes to molting locations, and underscore the need for extensive ground truthing in the form of feather-based isoscapes. Nevertheless, stable isotopes from feathers could inform disease models by characterizing the degree to which regional breeding populations interact at common wintering locations. Feather isotopes also could aid in surveying wintering locations to determine where high-resolution tracking techniques (e.g. satellite tracking) could most effectively be employed. Moreover, intrinsic markers such as stable isotopes offer the only means of inferring movement information from birds that have died

  13. Bird Migration and Avian Influenza: A Comparison of Hydrogen Stable Isotopes and Satellite Tracking Methods.

    PubMed

    Bridge, Eli S; Kelly, Jeffrey F; Xiao, Xiangming; Takekawa, John Y; Hill, Nichola J; Yamage, Mat; Haque, Enam Ul; Islam, Mohammad Anwarul; Mundkur, Taej; Yavuz, Kiraz Erciyas; Leader, Paul; Leung, Connie Y H; Smith, Bena; Spragens, Kyle A; Vandegrift, Kurt; Hosseini, Parviez R; Saif, Samia; Mohsanin, Samiul; Mikolon, Andrea; Islam, Ausrafal; George, Acty; Sivananinthaperumal, Balachandran; Daszak, Peter; Newman, Scott H

    2014-10-01

    Satellite-based tracking of migratory waterfowl is an important tool for understanding the potential role of wild birds in the long-distance transmission of highly pathogenic avian influenza. However, employing this technique on a continental scale is prohibitively expensive. This study explores the utility of stable isotope ratios in feathers in examining both the distances traveled by migratory birds and variation in migration behavior. We compared the satellite-derived movement data of 22 ducks from 8 species captured at wintering areas in Bangladesh, Turkey, and Hong Kong with deuterium ratios (δD) of these and other individuals captured at the same locations. We derived likely molting locations from the satellite tracking data and generated expected isotope ratios based on an interpolated map of δD in rainwater. Although δD was correlated with the distance between wintering and molting locations, surprisingly, measured δD values were not correlated with either expected values or latitudes of molting sites. However, population-level parameters derived from the satellite-tracking data, such as mean distance between wintering and molting locations and variation in migration distance, were reflected by means and variation of the stable isotope values. Our findings call into question the relevance of the rainfall isotope map for Asia for linking feather isotopes to molting locations, and underscore the need for extensive ground truthing in the form of feather-based isoscapes. Nevertheless, stable isotopes from feathers could inform disease models by characterizing the degree to which regional breeding populations interact at common wintering locations. Feather isotopes also could aid in surveying wintering locations to determine where high-resolution tracking techniques (e.g. satellite tracking) could most effectively be employed. Moreover, intrinsic markers such as stable isotopes offer the only means of inferring movement information from birds that have died

  14. Bird Migration and Avian Influenza: A Comparison of Hydrogen Stable Isotopes and Satellite Tracking Methods

    PubMed Central

    Kelly, Jeffrey F.; Xiao, Xiangming; Takekawa, John Y.; Hill, Nichola J.; Yamage, Mat; Haque, Enam Ul; Islam, Mohammad Anwarul; Mundkur, Taej; Yavuz, Kiraz Erciyas; Leader, Paul; Leung, Connie Y. H.; Smith, Bena; Spragens, Kyle A.; Vandegrift, Kurt; Hosseini, Parviez R.; Saif, Samia; Mohsanin, Samiul; Mikolon, Andrea; Islam, Ausrafal; George, Acty; Sivananinthaperumal, Balachandran; Daszak, Peter; Newman, Scott H.

    2014-01-01

    Satellite-based tracking of migratory waterfowl is an important tool for understanding the potential role of wild birds in the long-distance transmission of highly pathogenic avian influenza. However, employing this technique on a continental scale is prohibitively expensive. This study explores the utility of stable isotope ratios in feathers in examining both the distances traveled by migratory birds and variation in migration behavior. We compared the satellite-derived movement data of 22 ducks from 8 species captured at wintering areas in Bangladesh, Turkey, and Hong Kong with deuterium ratios (δD) of these and other individuals captured at the same locations. We derived likely molting locations from the satellite tracking data and generated expected isotope ratios based on an interpolated map of δD in rainwater. Although δD was correlated with the distance between wintering and molting locations, surprisingly, measured δD values were not correlated with either expected values or latitudes of molting sites. However, population-level parameters derived from the satellite-tracking data, such as mean distance between wintering and molting locations and variation in migration distance, were reflected by means and variation of the stable isotope values. Our findings call into question the relevance of the rainfall isotope map for Asia for linking feather isotopes to molting locations, and underscore the need for extensive ground truthing in the form of feather-based isoscapes. Nevertheless, stable isotopes from feathers could inform disease models by characterizing the degree to which regional breeding populations interact at common wintering locations. Feather isotopes also could aid in surveying wintering locations to determine where high-resolution tracking techniques (e.g. satellite tracking) could most effectively be employed. Moreover, intrinsic markers such as stable isotopes offer the only means of inferring movement information from birds that have died

  15. Uniform deposition of uranium hexafluoride (UF6): Standardized mass deposits and controlled isotopic ratios using a thermal fluorination method.

    PubMed

    McNamara, Bruce K; O'Hara, Matthew J; Casella, Andrew M; Carter, Jennifer C; Addleman, R Shane; MacFarlan, Paul J

    2016-07-01

    We report a convenient method for the generation of volatile uranium hexafluoride (UF6) from solid uranium oxides and other U compounds, followed by uniform deposition of low levels of UF6 onto sampling coupons. Under laminar flow conditions, UF6 is shown to interact with surfaces within a fixed reactor geometry to a highly predictable degree. We demonstrate the preparation of U deposits that range between approximately 0.01 and 500ngcm(-2). The data suggest the method can be extended to creating depositions at the sub-picogramcm(-2) level. The isotopic composition of the deposits can be customized by selection of the U source materials and we demonstrate a layering technique whereby two U solids, each with a different isotopic composition, are employed to form successive layers of UF6 on a surface. The result is an ultra-thin deposit that bears an isotopic signature that is a composite of the two U sources. The reported deposition method has direct application to the development of unique analytical standards for nuclear safeguards and forensics. Further, the method allows access to very low atomic or molecular coverages of surfaces.

  16. Uniform deposition of uranium hexafluoride (UF6): Standardized mass deposits and controlled isotopic ratios using a thermal fluorination method.

    PubMed

    McNamara, Bruce K; O'Hara, Matthew J; Casella, Andrew M; Carter, Jennifer C; Addleman, R Shane; MacFarlan, Paul J

    2016-07-01

    We report a convenient method for the generation of volatile uranium hexafluoride (UF6) from solid uranium oxides and other U compounds, followed by uniform deposition of low levels of UF6 onto sampling coupons. Under laminar flow conditions, UF6 is shown to interact with surfaces within a fixed reactor geometry to a highly predictable degree. We demonstrate the preparation of U deposits that range between approximately 0.01 and 500ngcm(-2). The data suggest the method can be extended to creating depositions at the sub-picogramcm(-2) level. The isotopic composition of the deposits can be customized by selection of the U source materials and we demonstrate a layering technique whereby two U solids, each with a different isotopic composition, are employed to form successive layers of UF6 on a surface. The result is an ultra-thin deposit that bears an isotopic signature that is a composite of the two U sources. The reported deposition method has direct application to the development of unique analytical standards for nuclear safeguards and forensics. Further, the method allows access to very low atomic or molecular coverages of surfaces. PMID:27154668

  17. METHOD FOR PRODUCING ISOTOPIC METHANES FROM LITHIUM CARBONATE AND LITHIUM HYDRIDE

    DOEpatents

    Frazer, J.W.

    1959-10-27

    A process is descrlbed for the production of methane and for the production of methane containing isotopes of hydrogen and/or carbon. Finely divided lithium hydrlde and litldum carbonate reactants are mixed in intimate contact and subsequently compacted under pressures of from 5000 to 60,000 psl. The compacted lithium hydride and lithium carbenate reactunts are dispised in a gas collecting apparatus. Subsequently, the compact is heated to a temperature in the range 350 to 400 deg C whereupon a solid-solid reaction takes place and gaseous methane is evolved. The evolved methane is contaminated with gaseous hydrogen and a very small amount of CO/sub 2/; however, the desired methane product is separated from sald impurities by well known chemical processes, e.g., condensation in a cold trap. The product methane contalns isotopes of carbon and hydrogen, the Isotopic composition being determined by the carbon isotopes originally present In the lithium carbonate and the hydrogen isotopes originally present in the lithium hydride.

  18. Gluconeogenesis from labeled carbon: estimating isotope dilution

    SciTech Connect

    Kelleher, J.K.

    1986-03-01

    To estimate the rate of gluconeogenesis from steady-state incorporation of labeled 3-carbon precursors into glucose, isotope dilution must be considered so that the rate of labeling of glucose can be quantitatively converted to the rate of gluconeogenesis. An expression for the value of this isotope dilution can be derived using mathematical techniques and a model of the tricarboxylic acid (TCA) cycle. The present investigation employs a more complex model than that used in previous studies. This model includes the following pathways that may affect the correction for isotope dilution: 1) flux of 3-carbon precursor to the oxaloacetate pool via acetyl-CoA and the TCA cycle; 2) flux of 4- or 5-carbon compounds into the TCA cycle; 3) reversible flux between oxaloacetate (OAA) and pyruvate and between OAA and fumarate; 4) incomplete equilibrium between OAA pools; and 5) isotope dilution of 3-carbon tracers between the experimentally measured pool and the precursor for the TCA-cycle OAA pool. Experimental tests are outlined which investigators can use to determine whether these pathways are significant in a specific steady-state system. The study indicated that flux through these five pathways can significantly affect the correction for isotope dilution. To correct for the effects of these pathways an alternative method for calculating isotope dilution is proposed using citrate to relate the specific activities of acetyl-CoA and OAA.

  19. A novel in situ method for sampling urban soil dust: particle size distribution, trace metal concentrations, and stable lead isotopes.

    PubMed

    Bi, Xiangyang; Liang, Siyuan; Li, Xiangdong

    2013-06-01

    In this study, a novel in situ sampling method was utilized to investigate the concentrations of trace metals and Pb isotope compositions among different particle size fractions in soil dust, bulk surface soil, and corresponding road dust samples collected within an urban environment. The aim of the current study was to evaluate the feasibility of using soil dust samples to determine trace metal contamination and potential risks in urban areas in comparison with related bulk surface soil and road dust. The results of total metal loadings and Pb isotope ratios revealed that soil dust is more sensitive than bulk surface soil to anthropogenic contamination in urban areas. The new in situ method is effective at collecting different particle size fractions of soil dust from the surface of urban soils, and that soil dust is a critical indicator of anthropogenic contamination and potential human exposure in urban settings.

  20. Edge equilibrium code for tokamaks

    SciTech Connect

    Li, Xujing; Drozdov, Vladimir V.

    2014-01-15

    The edge equilibrium code (EEC) described in this paper is developed for simulations of the near edge plasma using the finite element method. It solves the Grad-Shafranov equation in toroidal coordinate and uses adaptive grids aligned with magnetic field lines. Hermite finite elements are chosen for the numerical scheme. A fast Newton scheme which is the same as implemented in the equilibrium and stability code (ESC) is applied here to adjust the grids.

  1. DNA-based stable isotope probing coupled with cultivation methods implicates Methylophaga in hydrocarbon degradation

    PubMed Central

    Mishamandani, Sara; Gutierrez, Tony; Aitken, Michael D.

    2014-01-01

    Marine hydrocarbon-degrading bacteria perform a fundamental role in the oxidation and ultimate removal of crude oil and its petrochemical derivatives in coastal and open ocean environments. Those with an almost exclusive ability to utilize hydrocarbons as a sole carbon and energy source have been found confined to just a few genera. Here we used stable isotope probing (SIP), a valuable tool to link the phylogeny and function of targeted microbial groups, to investigate hydrocarbon-degrading bacteria in coastal North Carolina sea water (Beaufort Inlet, USA) with uniformly labeled [13C]n-hexadecane. The dominant sequences in clone libraries constructed from 13C-enriched bacterial DNA (from n-hexadecane enrichments) were identified to belong to the genus Alcanivorax, with ≤98% sequence identity to the closest type strain—thus representing a putative novel phylogenetic taxon within this genus. Unexpectedly, we also identified 13C-enriched sequences in heavy DNA fractions that were affiliated to the genus Methylophaga. This is a contentious group since, though some of its members have been proposed to degrade hydrocarbons, substantive evidence has not previously confirmed this. We used quantitative PCR primers targeting the 16S rRNA gene of the SIP-identified Alcanivorax and Methylophaga to determine their abundance in incubations amended with unlabeled n-hexadecane. Both showed substantial increases in gene copy number during the experiments. Subsequently, we isolated a strain representing the SIP-identified Methylophaga sequences (99.9% 16S rRNA gene sequence identity) and used it to show, for the first time, direct evidence of hydrocarbon degradation by a cultured Methylophaga sp. This study demonstrates the value of coupling SIP with cultivation methods to identify and expand on the known diversity of hydrocarbon-degrading bacteria in the marine environment. PMID:24578702

  2. Inadequacy, Impurity and Infidelity; Modifying the Modified Brendel Alpha-Cellulose Extraction Method for Resinous Woods in Stable Isotope Dendroclimatology

    NASA Astrophysics Data System (ADS)

    Brookman, T. H.; Whittaker, T. E.; King, P. L.; Horton, T. W.

    2011-12-01

    Stable isotope dendroclimatology is a burgeoning field in palaeoclimate science due to its unique potential to contribute (sub)annually resolved climate records, over millennial timescales, to the terrestrial palaeoclimate record. Until recently the time intensive methods precluded long-term climate reconstructions. Advances in continuous-flow mass spectrometry and isolation methods for α-cellulose (ideal for palaeoclimate studies as, unlike other wood components, it retains its initial isotopic composition) have made long-term, calendar dated palaeoclimate reconstructions a viable proposition. The Modified Brendel (mBrendel) α-cellulose extraction method is a fast, cost-effective way of preparing whole-wood samples for stable oxygen and carbon isotope analysis. However, resinous woods often yield incompletely processed α-cellulose using the standard mBrendel approach. As climate signals may be recorded by small (<1%) isotopic shifts it is important to investigate if incomplete processing affects the accuracy and precision of tree-ring isotopic records. In an effort to address this methodological issue, we investigated three highly resinous woods: kauri (Agathis australis), ponderosa pine (Pinus ponderosa) and huon pine (Lagarastrobus franklinii). Samples of each species were treated with 16 iterations of the mBrendel, varying reaction temperature, time and reagent volumes. Products were investigated using microscopic and bulk transmission Fourier Transform infrared spectroscopy (FITR) to reveal variations in the level of processing; poorly-digested fibres display a peak at 1520cm-1 suggesting residual lignin and a peak at ~1600cm-1 in some samples suggests retained resin. Despite the different levels of purity, replicate analyses of samples processed by high temperature digestion yielded consistent δ18O within and between experiments. All α-cellulose samples were 5-7% enriched compared to the whole-wood, suggesting that even incomplete processing at high

  3. Isotopic evidence for lateral flow and diffusive transport, but not sublimation, in a sloped seasonal snowpack, Idaho, USA

    NASA Astrophysics Data System (ADS)

    Evans, Samantha L.; Flores, Alejandro N.; Heilig, Achim; Kohn, Matthew J.; Marshall, Hans-Peter; McNamara, James P.

    2016-04-01

    Oxygen and hydrogen isotopes in snow were measured in weekly profiles during the growth and decline of a sloped subalpine snowpack, southern Idaho, 2011-2012. Isotopic steps (10‰, δ18O; 80‰, δD) were preserved relative to physical markers throughout the season, albeit with some diffusive smoothing. Melting stripped off upper layers without shifting isotopes within the snowpack. Meltwater is in isotopic equilibrium with snow at the top but not with snow at each respective collection height. Transport of meltwater occurred primarily along pipes and lateral flow paths allowing the snowpack to melt initially in reverse stratigraphic order. Isotope diffusivities are ~2 orders of magnitude faster than estimated from experiments but can be explained by higher temperature and porosity. A better understanding of how snowmelt isotopes change during meltout improves hydrograph separation methods, whereas constraints on isotope diffusivities under warm conditions improve models of ice core records in low-latitude settings.

  4. Measurement of dinitrogen fixation by Biological soil crust (BSC) from the Sahelian zone: an isotopic method.

    NASA Astrophysics Data System (ADS)

    Ehrhardt, F.; Alavoine, G.; Bertrand, I.

    2012-04-01

    Amongst the described ecological roles of Biological Soil Crust, N fixation is of importance for soil fertility, especially in arid and semi-arid ecosystems with low inputs. In BSC, the quantification of N fixation fluxes using an indirect method is widespread, usually with the Acetylene Reduction Assay (ARA) which consists in measuring the nitrogenase activity through the process of acetylene reduction into ethylene. A converting factor, still discussed in the literature and greatly depending of the constitutive organisms of the BSC, is the tool used to convert the amount of reduced ethylene into quantitative fixed Nitrogen. The aim of this poster is to describe an isotopic direct method to quantify the atmospheric dinitrogen fixation fluxes in BSC, while minimizing the variability due to manipulations. Nine different BSC from the Sahelian zone were selected and placed in an incubation room at 28° C in dark and light conditions during three days, while moisture equivalent to pF=2 was regularly adjusted using the gravimetric method with needles and deionized water, in order to activate and reach a dynamic stability of their metabolisms. Subsequently, each crust was placed into a gas-tight glass vial for incubation with a reconstituted 15N2 enriched atmosphere (31.61 % atom 15N, while the proportion of each main gas present in the air was conserved, i.e. 78% N2, 21% O2 and 0.04% CO2). Principal difficulties are to guarantee the airtighness of the system, to avoid crust desiccation and to keep the crust metabolically active under stable conditions for six hours. Several tests were performed to determine the optimum time for 15N2 incubation. Three replicated control samples per crust were also stabilized for three days and then dried at 105° C, without any incubation with 15N2 enriched atmosphere. Total N and 15N were then measured in the grounded (80μm) and dried (105° C) crust, using a Flash EA elemental analyzer (Eurovector, Milan, Italy) coupled to a Delta

  5. Application of speciated isotope dilution mass spectrometry to evaluate extraction methods for determining mercury speciation in soils and sediments.

    PubMed

    Rahman, G M Mizanur; Kingston, H M Skip

    2004-07-01

    Extraction techniques commonly used to extract methylmercury or mercury species from various matrixes have been evaluated regarding their potential to transform inorganic mercury to methylmercury, or vice versa, during sample preparation steps by applying speciated isotope dilution mass spectrometry. Two of the five tested methods were highly prone to form inorganic mercury from methylmercury. Some published methods converted methylmercury to inorganic mercury approximately 100% (including the spiked CH(3)(201)Hg(+)). In other methods, as much as 45% of methylmercury was converted to inorganic mercury during extraction. The methods evaluated included cold acid extraction and sonication. Other methods, such as the proposed EPA RCRA Draft Method 3200, microwave-assisted extraction, and another sonication-based methods induced very little or no methylmercury transformation to inorganic mercury. Among these three methods, the proposed Draft EPA Method 3200 was found to be the most efficient.

  6. Equilibrium state of anatase to rutile transformation for nano-structured Titanium Dioxide powder using polymer template method.

    NASA Astrophysics Data System (ADS)

    Dam, Tapabrata; Jena, Sidhartha S.; Pradhan, Dillip K.

    2016-02-01

    In this work we report the novel synthesis procedure of phase-pure nano-structured titania in anatase phase using polyacrylamide gel based polymer template method. The evolution of rutile phased titania with increasing temperature has also been investigated. The synthesized nano-materials are characterized using X-ray diffraction, Brunauer - Emmett - Teller surface analysis technique and Scanning electron microscopy. We have used dual phase Rietveld refinement method to analyse the X-Ray diffraction data to get clear picture of crystallographic information of the prepared samples.

  7. New method for the measurement of osmium isotopes applied to a New Zealand Cretaceous/Tertiary boundary shale

    USGS Publications Warehouse

    Lichte, F.E.; Wilson, S.M.; Brooks, R.R.; Reeves, R.D.; Holzbecher, J.; Ryan, D.E.

    1986-01-01

    The determination of osmium content and isotopic abundances in geological materials has received increasing attention in recent years following the proposal of Alvarez et al.1 that mass extinctions at the end of the Cretaceous period were caused by the impact of a large (???10km) meteorite which left anomalously high iridium levels as a geochemical signature in the boundary shales. Here we report a new and simple method for measuring osmium in geological materials, involving fusion of the sample with sodium peroxide, distillation of the osmium as the tetroxide using perchloric acid, extraction into chloroform, and absorption of the chloroform extract onto graphite powder before instrumental neutron activation analysis. In a variant of this technique, the chloroform extract is back-extracted into an aqueous phase and the osmium isotopes are determined by plasma-source mass spectrometry (ICPMS). We have used this method on the Woodside Creek (New Zealand) Cretaceous/Tertiary boundary clay and have obtained the first osmium content (6g ng g-1) for this material. The 187Os/186Os ratio is 1.12??0.16, showing a typical non-crustal signature. This combined distillation-extraction- ICPMS method will prove to be useful for measuring osmium isotopes in other geological materials. ?? 1986 Nature Publishing Group.

  8. Linear Algebra Aspects in the Equilibrium-Based Implementation of Finite/Boundary Element Methods for FGMs

    NASA Astrophysics Data System (ADS)

    Dumont, Ney Augusto

    2008-02-01

    The paper briefly outlines the conventional and three variational implementations of the boundary element method, pointing out the conceptual imbrications of their constituent matrices. The nature of fundamental solutions is investigated in terms of the resulting matrix spectral properties, as applied to multiply-connected domains, reentering corners and FGMs.

  9. A Method of Determining the Equilibrium Performance and the Stability of an Engine Equipped with an Exhaust Turbosupercharger

    NASA Technical Reports Server (NTRS)

    Rea, James Buchanan

    1941-01-01

    The performance of an exhaust turbine driving a supercharger is investigated by means of a sample calculation based on reasonable assumptions for the purpose of determining whether the assumed installation is stable with respect to changes in the mass of gas handled, boost pressure, etc. The arrangement was found to be stable throughout the entire range of operation. The method developed can be generally applied.

  10. Methods for achieving the equilibrium number of phases in mixtures suitable for use in battery electrodes, e.g., for lithiating FeS.sub.2

    DOEpatents

    Guidotti, Ronald A.

    1988-01-01

    In a method for preparing lithiated, particulate FeS.sub.2 useful as a catholyte material in a lithium thermal battery, whereby the latter's voltage regulation properties are improved, comprising admixing FeS.sub.2 and an amount of a lithium-containing compound whereby the resultant total composition falls in an invariant region of the metallurgical phase diagram of its constituent components, an improvement comprises admixing said lithium-containing compound and FeS.sub.2 together with a solid electrolyte compatible with said catholyte, and heating the mixture at a temperature above the melting point of said electrolyte and at which said mixture reaches its thermodynamic equilibrium number of phases.

  11. Method optimization for non-equilibrium solid phase microextraction sampling of HAPs for GC/MS analysis

    NASA Astrophysics Data System (ADS)

    Zawadowicz, M. A.; Del Negro, L. A.

    2010-12-01

    Hazardous air pollutants (HAPs) are usually present in the atmosphere at pptv-level, requiring measurements with high sensitivity and minimal contamination. Commonly used evacuated canister methods require an overhead in space, money and time that often is prohibitive to primarily-undergraduate institutions. This study optimized an analytical method based on solid-phase microextraction (SPME) of ambient gaseous matrix, which is a cost-effective technique of selective VOC extraction, accessible to an unskilled undergraduate. Several approaches to SPME extraction and sample analysis were characterized and several extraction parameters optimized. Extraction time, temperature and laminar air flow velocity around the fiber were optimized to give highest signal and efficiency. Direct, dynamic extraction of benzene from a moving air stream produced better precision (±10%) than sampling of stagnant air collected in a polymeric bag (±24%). Using a low-polarity chromatographic column in place of a standard (5%-Phenyl)-methylpolysiloxane phase decreased the benzene detection limit from 2 ppbv to 100 pptv. The developed method is simple and fast, requiring 15-20 minutes per extraction and analysis. It will be field-validated and used as a field laboratory component of various undergraduate Chemistry and Environmental Studies courses.

  12. Development of a Tunable Laser Spectroscopic Method for Determining Multiple Sulfur Isotope Composition of Nanomoles of SO2

    NASA Astrophysics Data System (ADS)

    Guo, W.; Christensen, L. E.

    2013-12-01

    Multiple sulfur isotope (32S, 33S, 34S, 36S) analyses of geological material provide important constraints on the sulfur cycles on Earth [1] and other planetary bodies, e.g., Mars [2]. However, most current multiple sulfur isotope measurements are performed on magnetic sector isotope ratio mass spectrometers (IRMS) and thus require relatively large sample size (usually about several micromoles of sulfur, except the MC-ICPMS and SIMS methods) and time-consuming sample preparation procedures. More importantly, these IRMS methods demand relatively sophisticated instrumentation, and are not ideal for field measurements or flight missions. In contrast, laser spectroscopic methods provide opportunities for significantly reducing the sample size requirement and enabling real-time monitoring in the field, and have been proven to be of great importance in the isotopic measurements of many molecules in nature, e.g. CO2, H2O, N2O, CH4. Based on a prototype built for measuring δ34S of SO2 [3], we're developing a new tunable laser spectrometer (TLS) for simultaneously determining the δ34S and Δ33S of nanomoles of pure SO2. We have identified a new spectral window (<1 cm-1 wide) suitable for measuring 32SO2, 33SO2, 34SO2 simultaneously. Ongoing work focuses on increasing the optical path length of the analysis cell and determining the optimal analytical conditions, with the goal of achieving ≤0.5‰ precision in both δ34S and Δ33S over 30 seconds of analysis duration of ~20 nmol of pure SO2. Progress of these developments and comparison with conventional IRMS methods will be presented at the meeting. As a case study, we will also present preliminary TLS results from laboratory low pressure SO2 UV photolysis experiments where δ34S and Δ33S of the residual SO2 are expected to decrease as the photolysis proceeds [4]. Future developments of this method will involve the coupling of a sample introduction system to enable multiple sulfur isotope analysis of samples other than

  13. Continuous flow stable isotope methods for study of δ13C fractionation during halomethane production and degradation

    USGS Publications Warehouse

    Kalin, Robert M.; Hamilton, John T.G.; Harper, David B.; Miller, Laurence G.; Lamb, Clare; Kennedy, James T.; Downey, Angela; McCauley, Sean; Goldstein, Allen H.

    2001-01-01

    Gas chromatography/mass spectrometry/isotope ratio mass spectrometry (GC/MS/IRMS) methods for δ13C measurement of the halomethanes CH3Cl, CH3Br, CH3I and methanethiol (CH3SH) during studies of their biological production, biological degradation, and abiotic reactions are presented. Optimisation of gas chromatographic parameters allowed the identification and quantification of CO2, O2, CH3Cl, CH3Br, CH3I and CH3SH from a single sample, and also the concurrent measurement of δ13C for each of the halomethanes and methanethiol. Precision of δ13C measurements for halomethane standards decreased (±0.3, ±0.5 and ±1.3‰) with increasing mass (CH3Cl, CH3Br, CH3I, respectively). Given that carbon isotope effects during biological production, biological degradation and some chemical (abiotic) reactions can be as much as 100‰, stable isotope analysis offers a precise method to study the global sources and sinks of these halogenated compounds that are of considerable importance to our understanding of stratospheric ozone destruction. 

  14. Method for the isolation of citric acid and malic acid in Japanese apricot liqueur for carbon stable isotope analysis.

    PubMed

    Akamatsu, Fumikazu; Hashiguchi, Tomokazu; Hisatsune, Yuri; Oe, Takaaki; Kawao, Takafumi; Fujii, Tsutomu

    2017-02-15

    A method for detecting the undeclared addition of acidic ingredients is required to control the authenticity of Japanese apricot liqueur. We developed an analytical procedure that minimizes carbon isotope discrimination for measurement of the δ(13)C values of citric and malic acid isolated from Japanese apricot liqueur. Our results demonstrated that freeze-drying is preferable to nitrogen spray-drying, because it does not significantly affect the δ(13)C values of citric acid and results in smaller isotope discrimination for malic acid. Both 0.1% formic acid and 0.2% phosphoric acid are acceptable HPLC mobile phases for the isolation of citric and malic acid, although the δ(13)C values of malic acid exhibited relatively large variation compared with citric acid following isolation using either mobile phase. The developed procedure allows precise δ(13)C measurements of citric and malic acid isolated from Japanese apricot liqueur. PMID:27664615

  15. Method for the isolation of citric acid and malic acid in Japanese apricot liqueur for carbon stable isotope analysis.

    PubMed

    Akamatsu, Fumikazu; Hashiguchi, Tomokazu; Hisatsune, Yuri; Oe, Takaaki; Kawao, Takafumi; Fujii, Tsutomu

    2017-02-15

    A method for detecting the undeclared addition of acidic ingredients is required to control the authenticity of Japanese apricot liqueur. We developed an analytical procedure that minimizes carbon isotope discrimination for measurement of the δ(13)C values of citric and malic acid isolated from Japanese apricot liqueur. Our results demonstrated that freeze-drying is preferable to nitrogen spray-drying, because it does not significantly affect the δ(13)C values of citric acid and results in smaller isotope discrimination for malic acid. Both 0.1% formic acid and 0.2% phosphoric acid are acceptable HPLC mobile phases for the isolation of citric and malic acid, although the δ(13)C values of malic acid exhibited relatively large variation compared with citric acid following isolation using either mobile phase. The developed procedure allows precise δ(13)C measurements of citric and malic acid isolated from Japanese apricot liqueur.

  16. Theoretical investigations of uranium isotope fractionation caused by nuclear volume effects

    NASA Astrophysics Data System (ADS)

    Yang, S.

    2015-12-01

    Because the half-life times of uranium isotopes are all very long, e.g., 4.5Ga for 238U and 0.7Ga for 235U, people actually treat uranium isotope system as a stable one in many young geologic systems (e.g., Bopp et al., 2010; Basu et al., 2014). There is an increasing trend of using U isotope method to study surface geochemistry problems. For example, people start to use U isotopes as a new tracer to determine the change of redox conditions (Holmden et al., 2015; Wang et al., 2015). However, there are only a few equilibrium U isotope fractionation factors available right now. The new enterprise of U isotope method requires a much expanded data-base of equilibrium U isotope fractionation factor. Many evidences showed that heavy isotope systems could be significantly fractionated as the consequence of the nuclear volume effect (NVE) or so-called nuclear field shift effect,which is a driving force of mass-independent fractionation induced by differences in nuclear size and nuclear shape of isotopes. Here we theoretically estimate the magnitude of equilibrium isotope fractionation factors of U-bearing gaseous and solid compounds caused by NVE via density functional theory (DFT) quantum chemistry methods with careful evaluation on quantum relativistic effects. Our calculation results show the NVE drives 238U/235U fractionations can be up to -4.43‰ between U(VI) and U(IV) species, or can be up to -1.68‰ between U(IV) and U(III) species, at room temperature. The U4+-bearing species or phases tend to enrich heavier isotopes (i.e., 238U) relative to the oxidized phases (U6+-bearing), and enrich lighter isotopes (i.e., 235U) relative to the reduced U(III) phases (U3+-bearing), which generally agree with the recent experimental results (Wang et al., 2015). Our results provide a base for broad applications of equilibrium U isotope fractionation in surface environments.

  17. 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

  18. Deformation around Neutron-Rich Cr Isotopes in Axially Symmetric Skyrme-Hatree-Fock-Bogoliubov Method

    NASA Astrophysics Data System (ADS)

    Oba, H.; Matsuo, M.

    2008-07-01

    We analyse the deformation mechanism in neutron-rich Cr, Fe and Ti isotopes with N = 32-44 using a Skyrme-Hartree-Fock-Bogoliubov mean-field code employing a two-dimensional mesh representation in the cylindrical coordinate system. Evaluating the quadrupole deformation energy systematically, we show that the Skyrme parameter set SkM* gives a quadrupole instability around the neutron numbers N ˜ 38-42 in Cr isotopes, where the deformation energy curve suggests a transitional behavior with a shallow minimum extending to a large prolate deformation. The roles of a deformed N = 38 gap and the position of the neutron g_{9/2} orbit are analysed in detail.

  19. Sources of groundwater nitrate revealed using residence time and isotope methods

    SciTech Connect

    Moore, K B; Ekwurzel, B; Esser, B K; Hudson, G B; Moran, J E

    2004-10-07

    Nitrate concentrations approaching and greater than the maximum contaminant level (MCL) are impairing the viability of many groundwater basins as drinking water sources. Nitrate isotope data are effective in determining contaminant sources, especially when combined with other isotopic tracers such as stable isotopes of water and tritium-helium ages to give insight into the routes and timing of nitrate inputs to the flow system. This combination of techniques is demonstrated in Livermore, CA, where it is determined that low nitrate reclaimed wastewater predominates in the northwest, while two flowpaths with distinct nitrate sources originate in the southeast. Along the eastern flowpath, {delta}{sup 15}N values greater than 10{per_thousand} indicate that animal waste is the primary source. Diminishing concentrations over time suggest that contamination results from historical land use practices. The other flowpath begins in an area where rapid recharge, primarily of low-nitrate imported water (identified by stable isotopes of water and a tritium-helium residence time of less than 1 year), mobilizes a significant local nitrate source, bringing groundwater concentrations up to 53 mg NO{sub 3} L{sup -1}. In this area, artificial recharge of imported water via local arroyos increases the flux of nitrate to the regional aquifer. The low {delta}{sup 15}N value (3.1{per_thousand}) in this location implicates synthetic fertilizer. In addition to these anthropogenic sources, natural nitrate background levels between 15 and 20 mg NO{sub 3} L{sup -1} are found in deep wells with residence times greater than 50 years.

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

    SciTech Connect

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

    2007-11-01

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

  1. 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

  2. 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

  3. Effects of preservation methods of muscle tissue from upper-trophic level reef fishes on stable isotope values (δ13C and δ15N)

    PubMed Central

    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 δ13C and δ15N 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 δ15N values in nearly all comparisons. Ethanol also had strong effects on the δ13C 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

  4. Capture and isotopic exchange method for water and hydrogen isotopes on zeolite catalysts up to technical scale for pre-study of processing highly tritiated water

    SciTech Connect

    Michling, R.; Braun, A.; Cristescu, I.; Dittrich, H.; Gramlich, N.; Lohr, N.; Glugla, M.; Shu, W.; Willms, S.

    2015-03-15

    Highly tritiated water (HTW) may be generated at ITER by various processes and, due to the excessive radio toxicity, the self-radiolysis and the exceedingly corrosive property of HTW, a potential hazard is associated with its storage and process. Therefore, the capture and exchange method for HTW utilizing Molecular Sieve Beds (MSB) was investigated in view of adsorption capacity, isotopic exchange performance and process parameters. For the MSB, different types of zeolite were selected. All zeolite materials were additionally coated with platinum. The following work comprised the selection of the most efficient zeolite candidate based on detailed parametric studies during the H{sub 2}/D{sub 2}O laboratory scale exchange experiments (about 25 g zeolite per bed) at the Tritium Laboratory Karlsruhe (TLK). For the zeolite, characterization analytical techniques such as Infrared Spectroscopy, Thermogravimetry and online mass spectrometry were implemented. Followed by further investigation of the selected zeolite catalyst under full technical operation, a MSB (about 22 kg zeolite) was processed with hydrogen flow rates up to 60 mol*h{sup -1} and deuterated water loads up to 1.6 kg in view of later ITER processing of arising HTW. (authors)

  5. Modeling nuclear volume isotope effects in crystals.

    PubMed

    Schauble, Edwin A

    2013-10-29

    Mass-independent isotope fractionations driven by differences in volumes and shapes of nuclei (the field shift effect) are known in several elements and are likely to be found in more. All-electron relativistic electronic structure calculations can predict this effect but at present are computationally intensive and limited to modeling small gas phase molecules and clusters. Density functional theory, using the projector augmented wave method (DFT-PAW), has advantages in greater speed and compatibility with a three-dimensional periodic boundary condition while preserving information about the effects of chemistry on electron densities within nuclei. These electron density variations determine the volume component of the field shift effect. In this study, DFT-PAW calculations are calibrated against all-electron, relativistic Dirac-Hartree-Fock, and coupled-cluster with single, double (triple) excitation methods for estimating nuclear volume isotope effects. DFT-PAW calculations accurately reproduce changes in electron densities within nuclei in typical molecules, when PAW datasets constructed with finite nuclei are used. Nuclear volume contributions to vapor-crystal isotope fractionation are calculated for elemental cadmium and mercury, showing good agreement with experiments. The nuclear-volume component of mercury and cadmium isotope fractionations between atomic vapor and montroydite (HgO), cinnabar (HgS), calomel (Hg2Cl2), monteponite (CdO), and the CdS polymorphs hawleyite and greenockite are calculated, indicating preferential incorporation of neutron-rich isotopes in more oxidized, ionically bonded phases. Finally, field shift energies are related to Mössbauer isomer shifts, and equilibrium mass-independent fractionations for several tin-bearing crystals are calculated from (119)Sn spectra. Isomer shift data should simplify calculations of mass-independent isotope fractionations in other elements with Mössbauer isotopes, such as platinum and uranium.

  6. Modeling nuclear volume isotope effects in crystals

    PubMed Central

    Schauble, Edwin A.

    2013-01-01

    Mass-independent isotope fractionations driven by differences in volumes and shapes of nuclei (the field shift effect) are known in several elements and are likely to be found in more. All-electron relativistic electronic structure calculations can predict this effect but at present are computationally intensive and limited to modeling small gas phase molecules and clusters. Density functional theory, using the projector augmented wave method (DFT-PAW), has advantages in greater speed and compatibility with a three-dimensional periodic boundary condition while preserving information about the effects of chemistry on electron densities within nuclei. These electron density variations determine the volume component of the field shift effect. In this study, DFT-PAW calculations are calibrated against all-electron, relativistic Dirac–Hartree–Fock, and coupled-cluster with single, double (triple) excitation methods for estimating nuclear volume isotope effects. DFT-PAW calculations accurately reproduce changes in electron densities within nuclei in typical molecules, when PAW datasets constructed with finite nuclei are used. Nuclear volume contributions to vapor–crystal isotope fractionation are calculated for elemental cadmium and mercury, showing good agreement with experiments. The nuclear-volume component of mercury and cadmium isotope fractionations between atomic vapor and montroydite (HgO), cinnabar (HgS), calomel (Hg2Cl2), monteponite (CdO), and the CdS polymorphs hawleyite and greenockite are calculated, indicating preferential incorporation of neutron-rich isotopes in more oxidized, ionically bonded phases. Finally, field shift energies are related to Mössbauer isomer shifts, and equilibrium mass-independent fractionations for several tin-bearing crystals are calculated from 119Sn spectra. Isomer shift data should simplify calculations of mass-independent isotope fractionations in other elements with Mössbauer isotopes, such as platinum and uranium

  7. Modeling nuclear volume isotope effects in crystals

    NASA Astrophysics Data System (ADS)

    Schauble, Edwin A.

    2013-10-01

    Mass-independent isotope fractionations driven by differences in volumes and shapes of nuclei (the field shift effect) are known in several elements and are likely to be found in more. All-electron relativistic electronic structure calculations can predict this effect but at present are computationally intensive and limited to modeling small gas phase molecules and clusters. Density functional theory, using the projector augmented wave method (DFT-PAW), has advantages in greater speed and compatibility with a three-dimensional periodic boundary condition while preserving information about the effects of chemistry on electron densities within nuclei. These electron density variations determine the volume component of the field shift effect. In this study, DFT-PAW calculations are calibrated against all-electron, relativistic Dirac-Hartree-Fock, and coupled-cluster with single, double (triple) excitation methods for estimating nuclear volume isotope effects. DFT-PAW calculations accurately reproduce changes in electron densities within nuclei in typical molecules, when PAW datasets constructed with finite nuclei are used. Nuclear volume contributions to vapor-crystal isotope fractionation are calculated for elemental cadmium and mercury, showing good agreement with experiments. The nuclear-volume component of mercury and cadmium isotope fractionations between atomic vapor and montroydite (HgO), cinnabar (HgS), calomel (Hg2Cl2), monteponite (CdO), and the CdS polymorphs hawleyite and greenockite are calculated, indicating preferential incorporation of neutron-rich isotopes in more oxidized, ionically bonded phases. Finally, field shift energies are related to Mössbauer isomer shifts, and equilibrium mass-independent fractionations for several tin-bearing crystals are calculated from 119Sn spectra. Isomer shift data should simplify calculations of mass-independent isotope fractionations in other elements with Mössbauer isotopes, such as platinum and uranium.

  8. Lifetimes in neutron-rich Nd isotopes measured by Doppler profile method

    SciTech Connect

    Ahmad, I.; Lister, C.J.; Morss, L.R.

    1995-08-01

    Lifetimes of the rotational levels in neutron-rich even-even Nd isotopes were deduced from the analysis of the Doppler broadened line shapes. The experiment was performed at Daresbury with the Eurogam array, which at that time consisted of 45 Compton-suppressed Ge detectors and 5 Low-Energy Photon Spectrometers. The source was in the form of a 7-mm pellet which was prepared by mixing 5-mg; {sup 248}Cm and 65-mg KCl and pressing it under high pressure. Events for which three or more detectors fired were used to construct a cubic data array whose axes represented the {gamma}-ray energies and the contents of each channel the number of events with that particular combination of {gamma}-ray energies. From this cubic array, one-dimensional spectra were generated by placing gates on peaks on the other two axes. Gamma-ray spectra of even-even Nd isotopes were obtained by gating on the transitions in the complimentary Kr fragments. The gamma peaks de-exciting states with I {>=} 12 h were found to be broader than the instrumental line width due to the Doppler effect. The line shapes of they-ray peaks were fitted separately with a simple model for the feeding of the states and assuming a rotational band with constant intrinsic quadruple moment and these are shown in Fig. I-27. The quadrupole moments thus determined were found to be in good agreement with the quadrupole moments measured previously for lower spin states. Because of the success of this technique for the Nd isotopes, we intend to apply this technique to the new larger data set collected with the Eurogam II array. The results of this study were published.

  9. METHOD OF AND APPARATUS FOR WITHDRAWING LIGHT ISOTOPIC PRODUCT FROM A LIQUID THERMAL DIFFUSION PLANT

    DOEpatents

    Dole, M.

    1959-09-22

    An improved process and apparatus are described for removing enriched product from the columns of a thermal diffusion plant for separation of isotopes. In the removal cycle, light product at the top cf the diffusion columns is circulated through the column tops and a shipping cylinder connected thereto unttl the concertation of enriched product in the cylinder reaches the desired point. During the removal, circulation through the bottoms is blocked bv freezing. in the diffusion cycle, the bottom portion is unfrozen, fresh feed is distributed to the bottoms of the columns, ard heavy product is withdrawn from the bottoms, while the tops of the columns are blocked by freezing.

  10. A method to quantitatively trap volatilized organoselenides for stable selenium isotope analysis.

    PubMed

    Schilling, Kathrin; Wilcke, Wolfgang

    2011-01-01

    If volatile organoselenides are to be analyzed for their stable Se isotope composition to elucidate sources and formation processes, organoselenides need to be trapped quantitatively to avoid artificial Se isotope fractionation. We developed an efficient trap of organoselenides to be used in microcosms designed to determine the Se isotope fractionation by microbial transformation of inorganic Se to volatile organoselenides. The recoveries of volatilized dimethyldiselenide (DMDSe) from aqueous standard solutions by activated charcoal and alkaline peroxide solution with subsequent freeze-drying and purification via a cation exchange resin were tested. Microcosm experiments with the Se-methylating fungus in a growth medium were conducted, and tightness of the microcosm was assessed by comparing mass balances of total Se of the fungus, medium, and trapped organoselenides with the supplied Se mass. At the end of the experiment, we calculated δSe values of the whole microcosm and compared them with the δSe value of supplied Se(IV) and Se(VI). Our results demonstrated that activated charcoal cannot be used for quantitative trapping of organoselenides because generally <64% of the outgassed DMDSe were recovered. The mean recovery of Se volatilized from an aqueous DMDSe standard trapped in alkaline peroxide, in contrast, was 96 ± 11% (SD) after 2 h ( = 4). The mass balances of total Se in microcosm experiments with alkaline peroxide traps run for 11 to 15 d were 96 ± 15 and 102 ± 2.4% for Se(IV) and Se(VI) ( = 3), respectively. The mass-weighted mean δSe values for the Se(IV) and Se(VI) batch experiments were -0.31 ± 0.05‰ ( = 3) and -0.76 ± 0.07‰ ( = 3), compared with -0.20 ± 0.10‰ and -0.69 ± 0.10‰ in the supplied Se oxyanions, respectively. We conclude that the alkaline peroxide trap can reliably be used to determine the Se isotope composition of organoselenides. PMID:21546688

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

    PubMed

    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 (13)C-acetate, (15)N-ammonium, and (33)S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope ((13)C/(12)C, (15)N/(14)N, and (33)S/(32)S) 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.

  12. 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

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

    PubMed

    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 (13)C-acetate, (15)N-ammonium, and (33)S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope ((13)C/(12)C, (15)N/(14)N, and (33)S/(32)S) 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

  14. Equilibrium cycle pin by pin transport depletion calculations with DeCART

    SciTech Connect

    Kochunas, B.; Downar, T.; Taiwo, T.

    2012-07-01

    As the Advanced Fuel Cycle Initiative (AFCI) program has matured it has become more important to utilize more advanced simulation methods. The work reported here was performed as part of the AFCI fellowship program to develop and demonstrate the capability of performing high fidelity equilibrium cycle calculations. As part of the work here, a new multi-cycle analysis capability was implemented in the DeCART code which included modifying the depletion modules to perform nuclide decay calculations, implementing an assembly shuffling pattern description, and modifying iteration schemes. During the work, stability issues were uncovered with respect to converging simultaneously the neutron flux, isotopics, and fluid density and temperature distributions in 3-D. Relaxation factors were implemented which considerably improved the stability of the convergence. To demonstrate the capability two core designs were utilized, a reference UOX core and a CORAIL core. Full core equilibrium cycle calculations were performed on both cores and the discharge isotopics were compared. From this comparison it was noted that the improved modeling capability was not drastically different in its prediction of the discharge isotopics when compared to 2-D single assembly or 2-D core models. For fissile isotopes such as U-235, Pu-239, and Pu-241 the relative differences were 1.91%, 1.88%, and 0.59%), respectively. While this difference may not seem large it translates to mass differences on the order of tens of grams per assembly, which may be significant for the purposes of accounting of special nuclear material. (authors)

  15. 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

    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

  16. 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

  17. Use of the semi-equilibrium dialysis method in studying the thermodynamics of solubilization of org nic compounds in surfactant micelles. system n-hexadecylpyridinium chloride-phenol-water

    SciTech Connect

    Smith, G,A.; Christian, S.D.; Scamehorn, J.F.; Tucker, E.E.

    1986-06-01

    The semi-equilibrium dialysis method has been used to infer solubilization equilibrium constants or, alternatively, activity coefficients of solutes solubilized into micelles of aqueous surfactant solutions. Methods are described for inferring the concentrationa of monomers of the organic solute and of the surfactant on both sides of the dialysis membrane, under conditions where the organic solute is in equilibrium with both the high-concentration (retentate) and low-concentration (permeate) solutions. By using a form of the Gibbs-Duhem equation, activity coefficients of both phenol (the solubilizate) and n-hexadecylpyridinium chloride (the surfactant) are obtained for aqueous solutions at 25 /sup 0/C throughout a wide range of relative compositions of surfactant and solubilizate within the micelle. The apparent solubilization constant, K = (solubilized phenol)/((monomeric phenol) (micellar surfactant)), is found to decrease significantly as the mole fraction of phenol in the micelle increases.

  18. Adsorption and isotopic fractionation of Xe

    NASA Technical Reports Server (NTRS)

    Bernatowicz, T. J.; Podosek, F. A.

    1986-01-01

    A theoretical description of the mechanisms of isotopic fractionation arising during adsorption of noble gases in a Henry's Law pressure regime is given. Experimental data on the isotopic composition of Xe adsorbed on activated charcoal in the temperature range 220 K to 350 K are presented. Both theoretical considerations and the experimental data indicate that equilibrium adsorption does not significantly alter the isotopic structure of adsorbed structure of adsorbed noble gases. Therefore, if adsorption is responsible for the elemental noble gas pattern in meteorites and the earth, the heavy noble gas isotopic fractionation between them must have been produced prior to and by a different process than equilibrium adsorption.

  19. Kinetic and equilibrium studies for the adsorption process of cadmium(II) and copper(II) onto Pseudomonas aeruginosa using square wave anodic stripping voltammetry method.

    PubMed

    Kong, Bo; Tang, Biyu; Liu, Xiaoying; Zeng, Xiandong; Duan, Haiyan; Luo, Shenglian; Wei, Wanzhi

    2009-08-15

    A novel method for the simultaneous determination of cadmium(II) and copper(II) during the adsorption process onto Pseudomonas aeruginosa was developed. The concentration of the free metal ions was successfully detected by square wave anodic stripping voltammetry (SWASV) on the mercaptoethane sulfonate (MES) modified gold electrode, while the P. aeruginosa was efficiently avoided approaching to the electrode surface by the MES monolayer. And the anodic stripping peaks of Cd(2+) and Cu(2+) appear at -0.13 and 0.34V respectively, at the concentration range of 5-50 microM, the peak currents of SWASV present linear relationships with the concentrations of cadmium and copper respectively. As the determination of Cd(2+) and Cu(2+) was in real time and without pretreatment, the kinetic characteristics of the adsorption process were studied and all the corresponding regression parameters were obtained by fitting the electrochemical experimental data to the pseudo-second-order kinetic model. Moreover, Langmuir and Freundlich models well described the biosorption isotherms. And there were some differences in the amount of metal ion adsorbed at equilibrium (q(e)) and other kinetics parameters when the two ions coexisted were compared with the unaccompanied condition, which were also discussed in this paper. The proposed electrode system provides excellent platform for the simultaneous determination of trace metals in complex biosorption process.

  20. Accounting for pore water pressure and confined aquifers in assessing the stability of slopes: a Limit Equilibrium analysis carried out through the Minimum Lithostatic Deviation method

    NASA Astrophysics Data System (ADS)

    Ausilia Paparo, Maria; Tinti, Stefano

    2015-04-01

    The model we introduce is an implementation of the Minimum Lithostatic Deviation (MLD) method, developed by Tinti and Manucci (Tinti and Manucci 2006; 2008), that makes use of the limit equilibrium (LE) theory to estimate the stability of a slope. The main purpose here is to analyse the role of a confined aquifer on the value of the Safety Factor (F), the parameter that in the LE is used to determine if a slope is stable or unstable. The classical LE methods treat unconfined aquifers by including the water pore pressure in the Mohr-Coulomb failure formula: since the water decreases the friction shear strength, the soil above the sliding surface turns out to be more prone to instability. In case of a confined aquifer, however, due to a presence of impermeable layers, the water is not free to flow into the matrix of the overlying soil. We consider here the assumption of a permeable soil sliding over an impermeable layer, which is an occurrence that is found in several known landslide cases (e.g. Person, 2008; Strout and Tjeltja, 2008; Morgan et al., 2010 for offshore slides; and Palladino and Peck, 1972; Miller and Sias, 1998; Jiao et al. 2005; Paparo et al., 2013 for slopes in proximity of artificial or natural water basins) where clay beds form the potential sliding surface: the water, confined below, pushes along these layers and acts on the sliding body as an external bottom load. We modify the MLD method equations in order to take into account the load due to a confined aquifer and apply the new model to the Vajont case, where many have hypothesised the contribution of a confined aquifer to the failure. Our calculations show that the rain load i) infiltrating directly into the soil body and ii) penetrating into the confined aquifer below the clay layers, in addition with the lowering of the reservoir level, were key factors of destabilization of the Mt Toc flank and caused the disastrous landslide.

  1. Shape characteristics of equilibrium and non-equilibrium fractal clusters.

    PubMed

    Mansfield, Marc L; Douglas, Jack F

    2013-07-28

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

  2. Shape characteristics of equilibrium and non-equilibrium fractal clusters.

    PubMed

    Mansfield, Marc L; Douglas, Jack F

    2013-07-28

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

  3. Shape characteristics of equilibrium and non-equilibrium fractal clusters

    NASA Astrophysics Data System (ADS)

    Mansfield, Marc L.; Douglas, Jack F.

    2013-07-01

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

  4. Ion-exchange method in the collection of nitrate from freshwater ecosystems for nitrogen and oxygen isotope analysis: a review.

    PubMed

    Li, Wen-Bing; Song, Yao-Bin; Xu, Hong-Ke; Chen, Ling-Yun; Dai, Wen-Hong; Dong, Ming

    2015-07-01

    Nitrate (NO3(-)) contamination of freshwater is considered one of the most prevalent global environmental problems. Dual stable isotopic compositions (δ(15)N and δ(18)O) of NO3(-) can provide helpful information and have been well documented as being a powerful tool to track the source of NO3(-) in freshwater ecosystems. The ion-exchange method is a reliable and precise technique for measuring the δ(15)N and δ(18)O of NO3(-) and has been widely employed to collect NO3(-) from freshwater ecosystems. This review summarizes and presents the principles, affecting factors and corresponding significant improvements of the ion-exchange method. Finally, potential improvements and perspectives for the applicability of this method are also discussed, as are suggestions for further research and development drawn from the overall conclusions.

  5. Calcium isotopic composition of mantle peridotites

    NASA Astrophysics Data System (ADS)

    Huang, F.; Kang, J.; Zhang, Z.

    2015-12-01

    Ca isotopes are useful to decipher mantle evolution and the genetic relationship between the Earth and chondrites. It has been observed that Ca isotopes can be fractionated at high temperature [1-2]. However, Ca isotopic composition of the mantle peridotites and fractionation mechanism are still poorly constrained. Here, we report Ca isotope composition of 12 co-existing pyroxene pairs in 10 lherzolites, 1 harzburgite, and 1 wehrlite xenoliths collected from Hainan Island (South Eastern China). Ca isotope data were measured on a Triton-TIMS using the double spike method at the Guangzhou Institute of Geochemistry, CAS. The long-term external error is 0.12‰ (2SD) based on repeated analyses of NIST SRM 915a and geostandards. δ44Ca of clinopyroxenes except that from the wehrlite ranges from 0.85‰ to 1.14‰, while opx yields a wide range from 0.98‰ up to 2.16‰. Co-existing pyroxene pairs show large ∆44Caopx-cpx (defined as δ44Caopx-δ44Cacpx) ranging from 0 to 1.23‰, reflecting equilibrium fractionation controlled by variable Ca contents in the opx. Notably, clinopyroxene of wehrlite shows extremely high δ44Ca (3.22‰). δ44Ca of the bulk lherzolites and harzburgites range from 0.86‰ to 1.14‰. This can be explained by extracting melts with slightly light Ca isotopic compositions. Finally, the high δ44Ca of the wehrlite (3.22‰) may reflect metasomatism by melt which has preferentially lost light Ca isotopes due to chemical diffusion during upwelling through the melt channel. [1] Amini et al (2009) GGR 33; [2] Huang et al (2010) EPSL 292.

  6. A new method for collection of nitrate from fresh water and the analysis of nitrogen and oxygen isotope ratios

    USGS Publications Warehouse

    Silva, S.R.; Kendall, C.; Wilkison, D.H.; Ziegler, A.C.; Chang, Cecily C.Y.; Avanzino, R.J.

    2000-01-01

    A new method for concentrating nitrate from fresh waters for ??15N and ??18O analysis has been developed and field-tested for four years. The benefits of the method are: (1) elimination of the need to transport large volumes of water to the laboratory for processing; (2) elimination of the need for hazardous preservatives; and (3) the ability to concentrate nitrate from fresh waters. Nitrate is collected by, passing the water-sample through pre-filled, disposable, anion exchanging resin columns in the field. The columns are subsequently transported to the laboratory where the nitrate is extracted, converted to AgNO3 and analyzed for its isotope composition. Nitrate is eluted from the anion exchange columns with 15 ml of 3 M HCl. The nitrate-bearing acid eluant is neutralized with Ag2O, filtered to remove the AgCl precipitate, then freeze-dried to obtain solid AgNO3, which is then combusted to N2 in sealed quartz tubes for ?? 15N analysis. For ?? 18O analysis, aliquots of the neutralized eluant are processed further to remove non-nitrate oxygen-bearing anions and dissolved organic matter. Barium chloride is added to precipitate sulfate and phosphate; the solution is then filtered, passed through a cation exchange column to remove excess Ba2+, re-neutralized with Ag2O, filtered, agitated with activated carbon to remove dissolved organic matter and freeze-dried. The resulting AgNO3 is combusted with graphite in a closed tube to produce CO2, which is cryogenically purified and analyzed for its oxygen isotope composition. The 1?? analytical precisions for ??15N and ??18O are ?? 0.05%o and ??0.5???, respectively, for solutions of KNO3 standard processed through the entire column procedure. High concentrations of anions in solution can interfere with nitrate adsorption on the anion exchange resins, which may result in isotope fractionation of nitrogen and oxygen (fractionation experiments were conducted for nitrogen only; however, fractionation for oxygen is expected

  7. A new method for collection of nitrate from fresh water and the analysis of nitrogen and oxygen isotope ratios

    NASA Astrophysics Data System (ADS)

    Silva, S. R.; Kendall, C.; Wilkison, D. H.; Ziegler, A. C.; Chang, C. C. Y.; Avanzino, R. J.

    2000-02-01

    A new method for concentrating nitrate from fresh waters for δ15N and δ18O analysis has been developed and field-tested for four years. The benefits of the method are: (1) elimination of the need to transport large volumes of water to the laboratory for processing; (2) elimination of the need for hazardous preservatives; and (3) the ability to concentrate nitrate from fresh waters. Nitrate is collected by, passing the water-sample through pre-filled, disposable, anion exchanging resin columns in the field. The columns are subsequently transported to the laboratory where the nitrate is extracted, converted to AgNO 3 and analyzed for its isotope composition. Nitrate is eluted from the anion exchange columns with 15 ml of 3 M HCl. The nitrate-bearing acid eluant is neutralized with Ag 2O, filtered to remove the AgCl precipitate, then freeze-dried to obtain solid AgNO 3, which is then combusted to N 2 in sealed quartz tubes for δ15N analysis. For δ18O analysis, aliquots of the neutralized eluant are processed further to remove non-nitrate oxygen-bearing anions and dissolved organic matter. Barium chloride is added to precipitate sulfate and phosphate; the solution is then filtered, passed through a cation exchange column to remove excess Ba 2+, re-neutralized with Ag 2O, filtered, agitated with activated carbon to remove dissolved organic matter and freeze-dried. The resulting AgNO 3 is combusted with graphite in a closed tube to produce CO 2, which is cryogenically purified and analyzed for its oxygen isotope composition. The 1 σ analytical precisions for δ15N and δ18O are ±0.05‰ and ±0.5‰, respectively, for solutions of KNO 3 standard processed through the entire column procedure. High concentrations of anions in solution can interfere with nitrate adsorption on the anion exchange resins, which may result in isotope fractionation of nitrogen and oxygen (fractionation experiments were conducted for nitrogen only; however, fractionation for oxygen is

  8. Lead isotope ratios for bullets, a descriptive approach for investigative purposes and a new method for sampling of bullet lead.

    PubMed

    Sjåstad, Knut-Endre; Simonsen, Siri Lene; Andersen, Tom H

    2014-11-01

    To establish a link between a bullet fired from a suspected firearm, investigation of striation marks are one of the corner stones in the forensic laboratory. Nevertheless, on some occasions, the bullet may be deformed to such extent that traditional investigation of striation marks will be impossible. Fragments of lead can be investigated by lead isotope ratio determination in order to distinguish between bullets with different origin. This approach initially seems reasonable, since the abundance of lead isotopes varies significantly in nature. To make a method valid for forensic purposes, it is important to have a fundamental understanding of the variation within a box of lead bullets and the expected variation between boxes. Studies of variability within and between boxes of ammunition are imperative to perform any type of forensic interpretation, both in an investigative and evaluative context. This work presents an extensive study of variability within and between boxes of ammunition by use of multicollector inductive coupled mass spectrometry. As a first approximation to classify bullets to any given source, a simple and robust graphical method is presented. In addition, an easy-to-use sampling procedure of lead is presented.

  9. Keeling plots for hummingbirds: a method to estimate carbon isotope ratios of respired CO(2) in small vertebrates.

    PubMed

    Carleton, Scott A; Wolf, Blair O; del Rio, Carlos Martinez

    2004-09-01

    The carbon isotope composition of an animal's breath reveals the composition of the nutrients that it catabolizes for energy. Here we describe the use of Keeling plots, a method widely applied in ecosystem ecology, to measure the delta(13)C of respired CO(2) of small vertebrates. We measured the delta(13)C of Rufous Hummingbirds ( Selasphorus rufus) in the laboratory and of Mourning ( Zenaida macroura) and White-winged ( Z. asiatica) Doves in the field. In the laboratory, when hummingbirds were fed a sucrose based C3 diet, the delta(13)C of respired CO(2) was not significantly different from that of their diet (delta(13)C(C3 diet)). The delta(13)C of respired CO(2) for C3 fasted birds was slightly, albeit significantly, depleted in delta(13)C relative to delta(13)C(C3 diet). Six hours after birds were shifted to a sucrose based C4 diet, the isotopic composition of their breath revealed that birds were catabolizing a mixture of nutrients derived from both the C3 and the C4 diet. In the field, the delta(13)C of respired CO(2) from Mourning and White-winged Doves reflected that of their diets: the CAM saguaro cactus ( Carnegeia gigantea) and C3 seeds, respectively. Keeling plots are an easy, effective and inexpensive method to measure delta(13)C of respired CO(2) in the lab and the field. PMID:15309607

  10. Keeling plots for hummingbirds: a method to estimate carbon isotope ratios of respired CO(2) in small vertebrates.

    PubMed

    Carleton, Scott A; Wolf, Blair O; del Rio, Carlos Martinez

    2004-09-01

    The carbon isotope composition of an animal's breath reveals the composition of the nutrients that it catabolizes for energy. Here we describe the use of Keeling plots, a method widely applied in ecosystem ecology, to measure the delta(13)C of respired CO(2) of small vertebrates. We measured the delta(13)C of Rufous Hummingbirds ( Selasphorus rufus) in the laboratory and of Mourning ( Zenaida macroura) and White-winged ( Z. asiatica) Doves in the field. In the laboratory, when hummingbirds were fed a sucrose based C3 diet, the delta(13)C of respired CO(2) was not significantly different from that of their diet (delta(13)C(C3 diet)). The delta(13)C of respired CO(2) for C3 fasted birds was slightly, albeit significantly, depleted in delta(13)C relative to delta(13)C(C3 diet). Six hours after birds were shifted to a sucrose based C4 diet, the isotopic composition of their breath revealed that birds were catabolizing a mixture of nutrients derived from both the C3 and the C4 diet. In the field, the delta(13)C of respired CO(2) from Mourning and White-winged Doves reflected that of their diets: the CAM saguaro cactus ( Carnegeia gigantea) and C3 seeds, respectively. Keeling plots are an easy, effective and inexpensive method to measure delta(13)C of respired CO(2) in the lab and the field.

  11. Equilibrium sampling by reweighting nonequilibrium simulation trajectories.

    PubMed

    Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

    2016-03-01

    Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems. PMID:27078486

  12. Equilibrium sampling by reweighting nonequilibrium simulation trajectories.

    PubMed

    Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

    2016-03-01

    Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems.

  13. Equilibrium sampling by reweighting nonequilibrium simulation trajectories

    NASA Astrophysics Data System (ADS)

    Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

    2016-03-01

    Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems.

  14. Detecting isotopic ratio outliers

    SciTech Connect

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

    1985-01-01

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

  15. Utilization of the limit equilibrium and finite element methods for the stability analysis of the slope debris: An example of the Kalebasi District (NE Turkey)

    NASA Astrophysics Data System (ADS)

    Alemdag, Selcuk; Kaya, Ayberk; Karadag, Mustafa; Gurocak, Zulfu; Bulut, Fikri

    2015-06-01

    The stability of the slope debris in residential area of the Kalebasi District (Ozkurtun-Gumushane) was investigated using the Limit Equilibrium (LE) and Finite Element Shear-Strength Reduction (FE-SSR) methods. Along the survey lines, four trial pits were dug and fourteen boreholes having a total length of 345 m were drilled. Also, seismic refraction studies were conducted along the five lines. According to the field studies, thickness of the slope debris covering the 98 ha of the study area varies between 1 and 36 m. To determine the physical and shear strength properties of the slope debris, undisturbed samples were taken from the trial pits. As a result of the laboratory tests, soil categories of the debris were found to be as Clayey Sand (SC), Silty Sand (SM) and Low Plasticity Clay (CL). The deformation-controlled shear box tests were carried out to determine the shear strength parameters of the slope debris. According to these tests it was found that the peak cohesion and peak friction angle varies between 2.63-16.35 kN/m2 and 20-27°, respectively. Stability analyses were performed using the obtained data from field and laboratory investigations in the Slide v5.0 and Phase2 v6.0 software programs and results were compared. In LE stability analyses, the factor of safety (FOS) of survey lines were found to be as 1.44, 1.80, 1.96, and 1.72; however for the FE-SSR method they were determined as 1.39, 1.72, 1.59, and 1.58, respectively.

  16. Method for detecting and correcting for isotope burn-in during long-term neutron dosimetry exposure

    DOEpatents

    Ruddy, Francis H.

    1988-01-01

    A method is described for detecting and correcting for isotope burn-in during-long term neutron dosimetry exposure. In one embodiment, duplicate pairs of solid state track recorder fissionable deposits are used, including a first, fissionable deposit of lower mass to quantify the number of fissions occuring during the exposure, and a second deposit of higher mass to quantify the number of atoms of for instance .sup.239 Pu by alpha counting. In a second embodiment, only one solid state track recorder fissionable deposit is used and the resulting higher track densities are counted with a scanning electron microscope. This method is also applicable to other burn-in interferences, e.g., .sup.233 U in .sup.232 Th or .sup.238 Pu in .sup.237 Np.

  17. Getting Freshman in Equilibrium.

    ERIC Educational Resources Information Center

    Journal of Chemical Education, 1983

    1983-01-01

    Various aspects of chemical equilibrium were discussed in six papers presented at the Seventh Biennial Conference on Chemical Education (Stillwater, Oklahoma 1982). These include student problems in understanding hydrolysis, helping students discover/uncover topics, equilibrium demonstrations, instructional strategies, and flaws to kinetic…

  18. Method for ultra-trace cesium isotope ratio measurements from environmental samples using thermal ionization mass spectrometry

    SciTech Connect

    Snow, Mathew S.; Snyder, Darin C.; Mann, Nick R.; White, Byron M.

    2015-05-01

    135Cs/137Cs isotope ratios can provide the age, origin and history of environmental Cs contamination. Relatively high precision 135Cs/137Cs isotope ratio measurements from samples containing femtogram quantities of 137Cs are needed to accurately track contamination resuspension and redistribution following environmental 137Cs releases; however, mass spectrometric analyses of environmental samples are limited by the large quantities of ionization inhibitors and isobaric interferences which are present at relatively high concentrations in the environment. We report a new approach for Cs purification from environmental samples. An initial ammonium molybdophosphate-polyacrylonitrile (AMP-PAN) column provides a robust method for extracting Cs under a wide variety of sample matrices and mass loads. Cation exchange separations using a second AMP-PAN column result in more than two orders of magnitude greater Cs/Rb separation factors than commercially available strong cation exchangers. Coupling an AMP-PAN cation exchanging step to a microcation column (AG50W resin) enables consistent 2-4% (2σ) measurement errors for samples containing 3-6,000 fg 137Cs, representing the highest precision 135Cs/137Cs ratio measurements currently reported for soil samples at the femtogram level.

  19. A facile method for expression and purification of (15)N isotope-labeled human Alzheimer's β-amyloid peptides from E. coli for NMR-based structural analysis.

    PubMed

    Sharma, Sudhir C; Armand, Tara; Ball, K Aurelia; Chen, Anna; Pelton, Jeffrey G; Wemmer, David E; Head-Gordon, Teresa

    2015-12-01

    Alzheimer's disease (AD) is a progressive neurodegenerative disease affecting millions of people worldwide. AD is characterized by the presence of extracellular plaques composed of aggregated/oligomerized β-amyloid peptides with Aβ42 peptide representing a major isoform in the senile plaques. Given the pathological significance of Aβ42 in the progression of AD, there is considerable interest in understanding the structural ensembles for soluble monomer and oligomeric forms of Aβ42. This report describes an efficient method to express and purify high quality (15)N isotope-labeled Aβ42 for structural studies by NMR. The protocol involves utilization of an auto induction system with (15)N isotope labeled medium, for high-level expression of Aβ42 as a fusion with IFABP. After the over-expression of the (15)N isotope-labeled IFABP-Aβ42 fusion protein in the inclusion bodies, pure (15)N isotope-labeled Aβ42 peptide is obtained following a purification method that is streamlined and improved from the method originally developed for the isolation of unlabeled Aβ42 peptide (Garai et al., 2009). We obtain a final yield of ∼ 6 mg/L culture for (15)N isotope-labeled Aβ42 peptide. Mass spectrometry and (1)H-(15)N HSQC spectra of monomeric Aβ42 peptide validate the uniform incorporation of the isotopic label. The method described here is equally applicable for the uniform isotope labeling with (15)N and (13)C in Aβ42 peptide as well as its other variants including any Aβ42 peptide mutants.

  20. Hybrid quantum and classical methods for computing kinetic isotope effects of chemical reactions in solutions and in enzymes.

    PubMed

    Gao, Jiali; Major, Dan T; Fan, Yao; Lin, Yen-Lin; Ma, Shuhua; Wong, Kin-Yiu

    2008-01-01

    A method for incorporating quantum mechanics into enzyme kinetics modeling is presented. Three aspects are emphasized: 1) combined quantum mechanical and molecular mechanical methods are used to represent the potential energy surface for modeling bond forming and breaking processes, 2) instantaneous normal mode analyses are used to incorporate quantum vibrational free energies to the classical potential of mean force, and 3) multidimensional tunneling methods are used to estimate quantum effects on the reaction coordinate motion. Centroid path integral simulations are described to make quantum corrections to the classical potential of mean force. In this method, the nuclear quantum vibrational and tunneling contributions are not separable. An integrated centroid path integral-free energy perturbation and umbrella sampling (PI-FEP/UM) method along with a bisection sampling procedure was summarized, which provides an accurate, easily convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. In the ensemble-averaged variational transition state theory with multidimensional tunneling (EA-VTST/MT), these three aspects of quantum mechanical effects can be individually treated, providing useful insights into the mechanism of enzymatic reactions. These methods are illustrated by applications to a model process in the gas phase, the decarboxylation reaction of N-methyl picolinate in water, and the proton abstraction and reprotonation process catalyzed by alanine racemase. These examples show that the incorporation of quantum mechanical effects is essential for enzyme kinetics simulations.

  1. 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.

  2. Magnetospheric equilibrium with anisotropic pressure

    SciTech Connect

    Cheng, C.Z.

    1991-07-01

    Self-consistent magnetospheric equilibrium with anisotropic pressure is obtained by employing an iterative metric method for solving the inverse equilibrium equation in an optimal flux coordinate system. A method of determining plasma parallel and perpendicular pressures from either analytic particle distribution or particle distribution measured along the satellite's path is presented. The numerical results of axisymmetric magnetospheric equilibrium including the effects of finite beta, pressure anisotropy, and boundary conditions are presented for a bi-Maxwellian particle distribution. For the isotropic pressure cases, the finite beta effect produces an outward expansion of the constant magnetic flux surfaces in relation to the dipole field lines, and along the magnetic field the toroidal ring current is maximum at the magnetic equator. The effect of pressure anisotropy is found to further expand the flux surfaces outward. Along the magnetic field lines the westward ring current can be peak away from the equator due to an eastward current contribution resulting from pressure anisotropy. As pressure anisotropy increases, the peak westward current can become more singular. The outer boundary flux surface has significant effect on the magnetospheric equilibrium. For the outer flux boundary resembling dayside compressed flux surface due to solar wind pressure, the deformation of the magnetic field can be quite different from that for the outer flux boundary resembling the tail-like surface. 23 refs., 17 figs.

  3. A stable isotope dilution LC-ESI-MS/MS method for the quantification of pyridoxal-5'-phosphate in whole blood.

    PubMed

    van Zelst, Bertrand D; de Jonge, Robert

    2012-08-15

    Vitamin B6 is a cofactor in numerous biologic processes that include gluconeogenesis, neurotransmitter synthesis and amino acid metabolism. The aim of this study was to develop a method to measure the concentration of the biologically active form of vitamin B6 (pyridoxal-5'-phosphate, PLP) in whole blood with stable isotope dilution LC-ESI-MS/MS and compare this new procedure with an established HPLC method based on derivatization of pyridoxal-5'-phosphate. 50 μl of stable isotope (PLP-d3) was added to 250 μl of sample, followed by deproteinization with 10% trichloroacetic acid. After centrifugation, 20 μl of the supernatant was injected into the LC-ESI-MS/MS. Reversed phase chromatography was performed on a UPLC system, using a Waters™ Symmetry C18 column, with a gradient of 0.1% formic acid in methanol. PLP was measured on a tandem MS with a mass transition of 247.8>149.8 in the positive ion mode with a collision energy of 14 eV. The chromatographic run lasted 4 min. The method was linear from 4 to 8000 nmol/l. The intra-day and inter-day precision ranged between 1.7-2.8% and 3.0-4.1%, respectively. The mean absolute matrix-effect was 99.3% [97-102%]. The relative matrix-effect was 98.8%. The mean recovery was 98% [89-103%]. The lower limit of quantification was 4 nmol/l. The comparison of the LC-ESI-MS/MS method with our current HPLC method yielded the following equation: LC-ESI-MS/MS=1.11 [confidence interval, CI: 1.03-1.20] × HPLC+4.6 [CI: -1.3 to 11.0] (r²=0.94). This LC-ESI-MS/MS based method is characterized by simple sample processing and a short run time. The comparison with the current HPLC method is excellent although a significant proportional bias was detected. To conclude, the LC-ESI-MS/MS method is an appropriate method to determine PLP in whole blood.

  4. Stable isotopes of authigenic minerals in variably-saturated fractured tuff

    SciTech Connect

    Weber, D.S.; Evans, D.D.

    1988-11-01

    Identifying stable isotope variation and mineralogical changes in fractured rock may help establish the history of climatic and geomorphological processes that might affect the isolation properties of a waste repository site. This study examines the use of the stable isotope ratios of oxygen ({sup 18}O/{sup 16}O) and carbon ({sup 13}C/{sup 12}C) in authigenic minerals as hydrogeochemical tools tracing low-temperature rock-water interaction in variably-saturated fractured stuff. Isotopic compositions of fracture-filling and rock matrix minerals in the Apache Leap tuff, near Superior, Arizona were concordant with geothermal temperatures and in equilibrium with water isotopically similar to present-day meteoric water and groundwater. Oxygen and carbon isotope ratios of fracture-filling, in unsaturated fractured tuff, displayed an isotopic gradient believed to result from near-surface isotopic enrichment due to evaporation rather than the effects of rock-water interaction. Oxygen isotope ratios of rock matrix opal samples exhibited an isotopic gradient believed to result from, leaching and reprecipitation of silica at depth. Methods and results can be used to further define primary flowpaths and the movement of water in variably-saturated fractured rock. 71 refs., 23 figs., 3 tabs.

  5. Oxygen isotopes as a tracer of phosphate sources and cycling in aquatic systems (Invited)

    NASA Astrophysics Data System (ADS)

    Young, M. B.; Kendall, C.; Paytan, A.

    2013-12-01

    The oxygen isotopic composition of phosphate can provide valuable information about sources and processes affecting phosphorus as it moves through hydrologic systems. Applications of this technique in soil and water have become more common in recent years due to improvements in extraction methods and instrument capabilities, and studies in multiple aquatic environments have demonstrated that some phosphorus sources may have distinct isotopic compositions within a given system. Under normal environmental conditions, the oxygen-phosphorus bonds in dissolved inorganic phosphate (DIP) can only be broken by enzymatic activity. Biological cycling of DIP will bring the phosphate oxygen into a temperature-dependent equilibrium with the surrounding water, overprinting any existing isotopic source signals. However, studies conducted in a wide range of estuarine, freshwater, and groundwater systems have found that the phosphate oxygen is often out of biological equilibrium with the water, suggesting that it is common for at least a partial isotopic source signal to be retained in aquatic systems. Oxygen isotope analysis on various potential phosphate sources such as synthetic and organic fertilizers, animal waste, detergents, and septic/wastewater treatment plant effluents show that these sources span a wide range of isotopic compositions, and although there is considerable overlap between the source groups, sources may be isotopically distinct within a given study area. Recent soil studies have shown that isotopic analysis of phosphate oxygen is also useful for understanding microbial cycling across different phosphorus pools, and may provide insights into controls on phosphorus leaching. Combining stable isotope information from soil and water studies will greatly improve our understanding of complex phosphate cycling, and the increasing use of this isotopic technique across different environments will provide new information regarding anthropogenic phosphate inputs and

  6. Nuclear Volume-Dependent Fractionation of Uranium Isotopes

    NASA Astrophysics Data System (ADS)

    Weyer, S.; Schauble, E. A.; Anbar, A. D.

    2007-12-01

    Chemical reactions can fractionate isotopes because the magnitudes of equilibrium and rate constants are subtly sensitive to nuclear mass. Geoscientists have exploited this fact to learn about modern environmental processes and past environmental conditions by precisely measuring variations in the isotope compositions of a wide range of elements in natural materials. Here we present evidence from natural terrestrial samples that processes related to ¡°nuclear volume¡± rather than ¡°nuclear mass¡± significantly fractionate the isotope composition of the heaviest primordial element ¨C uranium. The isotopic composition of U in nature is generally assumed to be invariant. Here, we report variations of the 238U/235U isotope ratio in natural samples (basalts, granites, seawater, corals, black shales, suboxic sediments, ferro-manganese crusts/nodules and BIFs), which span a range of δ238U values of ~ 1.3 ‰, exceeding by far the analytical precision of our method (¡Ö 0.06‰, 2SD, based on replicate measurements of individual samples). The largest isotope variations found in our survey are between oxidized and reduced depositional environments, with seawater and suboxic sediments falling in between. U isotopes were analyzed with MC-ICP-MS. A mixed 236U-233U isotopic tracer (double spike) was used to correct for isotope fractionation during sample purification and instrumental mass bias. Sediments formed in oxic environments, such as manganese crusts from the Atlantic and Pacific oceans, display δ238U of -0.54 to -0.62 ‰, slightly lighter than that of seawater (-0.41 ‰). However, sediments from reducing environments, such as black shales from the Black Sea (unit I and unit II) and the Cariaco basin, display heavy U isotope compositions with δ238U of up to +0.43 ‰ (0.84 ‰ heavier than seawater). Uranium enrichment in these sediments probably occurred during the reduction of soluble U(VI) (from seawater) to insoluble U(IV). Intriguingly, isotope

  7. Comparative evaluation of Logan and relative-equilibrium graphical methods for parametric imaging of dynamic [18F]FDDNP PET determinations

    PubMed Central

    Wong, Koon-Pong; Kepe, Vladimir; Dahlbom, Magnus; Satyamurthy, Nagichettiar; Small, Gary W.; Barrio, Jorge R.; Huang, Sung-Cheng

    2013-01-01

    Logan graphical analysis with cerebellum as reference region has been widely used for the estimation of the distribution volume ratio (DVR) of [18F]FDDNP as a measure of amyloid burden and tau deposition in human brain because of its simplicity and computational ease. However, spurious parametric DVR images may be produced with shorter scanning times and when the noise level is high. In this work, we have characterized a relative-equilibrium-based (RE) graphical method against the Logan analysis for parametric imaging and region-of-interest (ROI) analysis. Methods Dynamic [18F]FDDNP PET scans were performed on 9 control subjects and 12 patients diagnosed with Alzheimer’s disease. Using the cerebellum as reference input, regional DVR estimates were derived using both the Logan analysis and the RE plot approach. Effects on DVR estimates obtained at voxel and ROI levels by both graphical approaches using data in different time windows were investigated and compared with the standard values derived using the Logan analysis on a voxel-by-voxel basis for the time window of 35–125 min used in previous studies. Results Larger bias and variability were observed for DVR estimates obtained by the Logan graphical analysis at the voxel level when short time windows (85–125 and 45–65 min) were used, because of high noise levels in voxel-wise parametric imaging. However, when the Logan graphical analysis was applied at the ROI level over those short time windows, the DVR estimates did not differ significantly from the standard values derived using the Logan analysis on the voxel level for the time window of 35–125 min, and their bias and variability were remarkably lower. Conversely, the RE plot approach was more robust in providing DVR estimates with less bias and variability even when short time windows were used. The DVR estimates obtained at voxel and ROI levels were consistent. No significant differences were observed in DVR estimates obtained by the RE plot

  8. A preliminary report on methods of determining the age of Colorado plateau carnotite

    USGS Publications Warehouse

    Stieff, Lorin Rollins; Girhard, M.N.; Stern, T.W.

    1950-01-01

    Four methods of dating Colorado Plateau carnotite have been examined and evaluated: mineralogic methods, radioactive-equilibrium methods, lead-uranium-ratio methods, and lead-isotope methods. The data on 12 high-grade samples, from a suite of 50 representative carnotite ores, are presented.

  9. Chemical Principles Revisited: Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Mickey, Charles D.

    1980-01-01

    Describes: (1) Law of Mass Action; (2) equilibrium constant and ideal behavior; (3) general form of the equilibrium constant; (4) forward and reverse reactions; (5) factors influencing equilibrium; (6) Le Chatelier's principle; (7) effects of temperature, changing concentration, and pressure on equilibrium; and (8) catalysts and equilibrium. (JN)

  10. A Method for Analyzing A+2 Isotope Patterns for Use in Undergraduate Organic Courses

    ERIC Educational Resources Information Center

    Gross, Ray A.

    2007-01-01

    A novel ratio method is developed and automated for finding the bromine-chlorine-sulfur stoichiometry in the molecular formula of an unknown. This method is also useful in spectrometric analysis or beginning organic chemistry.

  11. Carbonate clumped isotope bond reordering and geospeedometry

    NASA Astrophysics Data System (ADS)

    Passey, Benjamin H.; Henkes, Gregory A.

    2012-10-01

    Carbonate clumped isotope thermometry is based on the preference of 13C and 18O to form bonds with each other. At elevated temperatures such bond ordering is susceptible to resetting by diffusion of C and O through the solid mineral lattice. This type of bond reordering has the potential to obscure primary paleoclimate information, but could also provide a basis for reconstructing shallow crustal temperatures and cooling rates. We determined Arrhenius parameters for solid-state reordering of C-O bonds in two different calcites through a series of laboratory heating experiments. We find that the calcites have different susceptibilities to solid-state reordering. Reaction progress follows a first order rate law in both calcites, but only after an initial period of non-first order reaction that we suggest relates to annealing of nonequilibrium defects when the calcites are first heated to experimental temperature. We show that the apparent equilibrium temperature equations (or "closure temperature" equations) for carbonate clumped isotope reordering are analogous Dodson's equations for first order loss of daughter isotopes. For each calcite, the sensitivity of apparent equilibrium temperature to cooling rate is sufficiently high for inference of cooling rates within a factor of ˜5 or better for cooling rates ranging from tens of degrees per day to a few degrees per million years. However, because the calcites have different susceptibilities to reordering, each calcite defines its own cooling rate-apparent equilibrium temperature relationship. The cooling rates of Carrara marble inferred from carbonate clumped isotope geospeedometry are 10-6-10-3 degrees per annum and are in broad agreement with rates inferred from thermochronometric methods. Cooling rates for 13C-depleted calcites from the late Neoproterozoic Doushantou cap carbonates in south China are on the order of 102-104 degrees per annum, consistent with rapid cooling following formation of these calcites by a

  12. 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.

  13. 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.

  14. Stable carbon and hydrogen isotope analysis of methyl tert-butyl ether and tert-amyl methyl ether by purge and trap-gas chromatography-isotope ratio mass spectrometry: method evaluation and application.

    PubMed

    Kujawinski, Dorothea M; Stephan, Manuel; Jochmann, Maik A; Krajenke, Karen; Haas, Joe; Schmidt, Torsten C

    2010-01-01

    In order to monitor the behaviour of contaminants in the aqueous environment effective enrichment techniques often have to be employed due to their low concentrations. In this work a robust and sensitive purge and trap-gas chromatography-isotope ratio mass spectrometry method for carbon and hydrogen isotope analysis of fuel oxygenates in water is presented. The method evaluation included the determination of method detection limits, accuracy and reproducibility of deltaD and delta(13)C values. Lowest concentrations at which reliable delta(13)C values could be determined were 5 microg L(-1) and 28 microg L(-1) for TAME and MTBE, respectively. Stable deltaD values for MTBE and TAME could be achieved for concentrations as low as 25 and 50 microg L(-1). Good long-term reproducibility of delta(13)C and deltaD values was obtained for all target compounds. But deltaD values varying more than 5 per thousand were observed using different thermal conversion tubes. Thus, a correction of deltaD values in the analysis of groundwater samples was necessary to guarantee comparability of the results. The applicability of this method was shown by the analysis of groundwater samples from a gasoline contaminated site. By two dimensional isotope analysis two locations within this site were identified at which anaerobic and aerobic degradation of methyl tert-butyl ether occurred.

  15. Response reactions: equilibrium coupling.

    PubMed

    Hoffmann, Eufrozina A; Nagypal, Istvan

    2006-06-01

    It is pointed out and illustrated in the present paper that if a homogeneous multiple equilibrium system containing k components and q species is composed of the reactants actually taken and their reactions contain only k + 1 species, then we have a unique representation with (q - k) stoichiometrically independent reactions (SIRs). We define these as coupling reactions. All the other possible combinations with k + 1 species are the coupled reactions that are in equilibrium when the (q - k) SIRs are in equilibrium. The response of the equilibrium state for perturbation is determined by the coupling and coupled equilibria. Depending on the circumstances and the actual thermodynamic data, the effect of coupled equilibria may overtake the effect of the coupling ones, leading to phenomena that are in apparent contradiction with Le Chatelier's principle. PMID:16722770

  16. Isotopic Biogeochemistry

    NASA Technical Reports Server (NTRS)

    Hayes, J. M.

    1985-01-01

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

  17. Computing Equilibrium Chemical Compositions

    NASA Technical Reports Server (NTRS)

    Mcbride, Bonnie J.; Gordon, Sanford

    1995-01-01

    Chemical Equilibrium With Transport Properties, 1993 (CET93) computer program provides data on chemical-equilibrium compositions. Aids calculation of thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93/PC is version of CET93 specifically designed to run within 640K memory limit of MS-DOS operating system. CET93/PC written in FORTRAN.

  18. 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.

  19. Achieving comparability with IFCC reference method for the measurement of hemoglobin A1c by use of an improved isotope-dilution mass spectrometry method.

    PubMed

    Liu, Hong; Wong, Lingkai; Yong, Sharon; Liu, Qinde; Lee, Tong Kooi

    2015-10-01

    The development of reference measurement methods for hemoglobin A1c (HbA1c) is important for quality assurance in diabetes management. The IFCC reference method using purified proteins as calibration standards is the recommended accuracy-based reference method for the standardization of HbA1c measurement. We developed a highly precise and accurate liquid chromatography-isotope-dilution tandem mass spectrometry (LC-IDMS/MS) procedure, which can serve as an alternative accuracy-based method for HbA1c measurement. In this method, enzymatic proteolysis was applied to sample preparation, followed by LC-IDMS/MS measurement of hemoglobin A0 (HbA0) and HbA1c, using two "signature" hexapeptides for calibration. The concentrations of the signature hexapeptide calibration solutions were, in turn, determined using a hydrolysis method with HCl, followed by LC-IDMS/MS measurement using amino acid solutions as calibration standards. These solutions were gravimetrically prepared from pure amino acid certified reference materials (CRMs). The developed LC-IDMS/MS method was used in participation in an IFCC ring trial for reference laboratories (RELA 2013 and 2014) for HbA1c, where our results were compared with those using the IFCC reference method. The deviations were found to be 0.4-1.7 mmol mol(-1) [or 0.04-0.16% in National Glygohemoglobin Standardization Program (NGSP) units], revealing good comparability with the IFCC reference method. The relative expanded uncertainty of the LC-IDMS/MS was in the range of 2.6% to 2.8% (1.6% to 2.2% after converting to NGSP units). With excellent method precision, good comparability with the IFCC reference method, and a small measurement uncertainty, the developed LC-IDMS/MS method may be used as an alternative accuracy-based reference method for HbA1c measurement.

  20. An evaluation of materials and methods for vapour measurement of the isotopic composition of pore water in deep, unsaturated zones.

    PubMed

    Pratt, Dyan L; Lu, Mengna; Lee Barbour, S; Jim Hendry, M

    2016-01-01

    The development of in situ vapour sampling methods to measure δ(2)H and δ(18)O in pore water of deep, unsaturated soil profiles, including mine tailings and waste rock, is required to improve our ability to track water migration through these deposits. To develop appropriate field sampling methods, a laboratory study was first undertaken to evaluate potential materials and sampling methods to collect and analyse vapour samples from unsaturated mine waste. Field methods were developed based on these findings and tested at two mine sites using either on-site analyses with a portable isotope laser spectrometer or sample collection and storage prior to laboratory analyses. The field sites included a series of deep (>50 m) multiport profiles within a coal waste rock dump and open wells installed in a sand tailings dyke at an oil sands mine. Laboratory results show that memory effects in sample bags and tubing require 3-5 pore volumes of vapour flushing prior to sample collection and sample storage times are limited to 24 h. Field sampling highlighted a number of challenges including the need to correct for sample humidity and in situ temperature. Best results were obtained when a portable laser spectrometer was used to measure vapour samples in situ. PMID:27002493

  1. Recoil distance transmission method: Measurement of interaction cross sections of excited states with fast rare-isotope beams

    NASA Astrophysics Data System (ADS)

    Kobayashi, N.; Whitmore, K.; Iwasaki, H.

    2016-09-01

    The possible appearance of nuclear halos in ground and excited states close to the particle-decay threshold is of great importance in the investigation of nuclear structure and few-body correlations at the limit of stability. In order to obtain direct evidence of the halo structure manifested in nuclear excited states, we have considered a new method to measure the interaction cross sections of excited states. The combination of the transmission method and the recoil distance Doppler-shift method with a plunger device enables us to measure the number of interactions of the excited states in a target. Formulae to determine the interaction cross section are derived, and key issues to realize measurements are discussed. Dominant sources of errors are uncertainties in the excited-state lifetimes and γ-ray yields. We examine prototype experiments and perform simulations to study the impact of each uncertainty on the final result. This method provides a novel opportunity to perform cross section measurements on the excited states of rare isotopes.

  2. An Investigation Into the Molecular and Isotopic Composition of Diatom Frustule-Bound Organic Matter: Method Development for New Proxies

    NASA Astrophysics Data System (ADS)

    Bridoux, M. C.; Ingalls, A. E.

    2009-12-01

    Diatoms are single cell phytoplankton that are ubiquitous in marine ecosystems and are responsible for up to 40% of the carbon fixed annually in the ocean. Their intricately nanopatterned siliceous frustules are formed under the control of template organic molecules, some of which are incorporated into the frustule during growth. Several diatom frustule-based paleoproxies have been developed to exploit these microfossils because they are from a known phytoplankton source that is relatively unaltered from diagenesis. Among these proxies, diatom frustule-bound organic matter (OM) is recognized as a potentially important material for use in paleoreconstructions of past productivity (13C/12C), nutrient utilization (15N/14N) as well as to determine the radiocarbon age of sedimentary frustules (Δ14C). Despite numerous advances, diatom frustule-bound OM remains poorly characterized. Here we focus on the chemical characterization of diatom frustule-bound OM with the goal of developing molecular and compound-specific isotope methods to better reconstruct the past environments of diatom rich regions such as the Southern Ocean and the North Pacific. To do this, we 1) chemically cleaned diatom frustules, 2) dissolve them in HF to release organic compounds embedded in the frustules and 3) unambiguously characterized this organic matter by ion pairing reversed phase liquid chromatography coupled to diode array, electrospray ionization - ion trap mass spectrometry (ESI/IT-MSn) and accurate mass quadrupole time of flight mass spectrometry (Q-TOF). These analyses reveal the presence of low molecular weight, UV light absorbing compounds called mycosporine-like amino acids (MAAs) and a series of long chain polyamines (LCPAs) consisting of N-methylated derivatives of polypropyleneimine units attached to putrescine. LCPAs are known to direct silicification, while MAAs are thought to provide sunscreen to many marine organisms. The presence of these specific biomarkers in sediment

  3. On the Equilibrium States of Interconnected Bubbles or Balloons.

    ERIC Educational Resources Information Center

    Weinhaus, F.; Barker, W.

    1978-01-01

    Describes the equilibrium states of a system composed of two interconnected, air-filled spherical membranes of different sizes. The equilibrium configurations are determined by the method of minimization of the availability of the system at constant temperature. (GA)

  4. Experimental methods for extracting seawater thorium isotopes from sediments as a proxy for dissolved dust inputs to the ocean.

    NASA Astrophysics Data System (ADS)

    Noble, T. L.; Robinson, L. F.; McManus, J. F.

    2006-12-01

    Dust fertilisation of the ocean could have a significant impact on atmospheric CO2, primarily by stimulating productivity. But this mechanism is hard to test due to the challenges associated with reconstructing the dissolved fraction of dust to the ocean in the past. We have developed a method that uses thorium adsorbed from seawater onto the surface of settling marine particles to record these dissolved detrital inputs and applied it to a suite of core top sediments samples from a diverse range of oceanographic and sedimentary settings. All U and Th isotopes were analyzed by ICP mass spectrometry. Dissolved 232Th in seawater is derived exclusively from continental material. By contrast 230Th is produced in situ from the radiogenic decay of 234U in the water column so it can be used to account for sedimentary processes that would otherwise bias the 232Th record. We tested eight methods for isolating scavenged (seawater) thorium. These methods included acid leaches and complexing agents. Progressively stronger acid leaches gave higher 232Th yields, but with no significant change in the 232Th/230Th ratio for nine out of ten sites. In addition there is no relationship between the percent dissolution of the sediment and the amount of 232Th recovery. A red clay sample from the deep Atlantic presented the greatest difficulty in isolating the adsorbed from lattice-bound Th signal. There was only one case where the ratio was significantly higher when treated with the strongest acid, presumably indicative of some detrital dissolution during the procedure. Our results demonstrate that six methods are successful at isolating scavenged from lattice bound Th. The ten core top sediments, from the Pacific, Indian, Atlantic, and Southern Oceans have 232Th/230Th ratios that range from 2000 to 16000, and are close to the values predicted by modern water column measurements and present day dust loading. For example, a north south transect across the Southern Ocean shows a progressive

  5. Dual-isotope method for determination of human zinc absorption: the use of a test meal of turkey meat

    SciTech Connect

    Flanagan, P.R.; Cluett, J.; Chamberlain, M.J.; Valberg, L.S.

    1985-01-01

    The percentage of /sup 65/Zn taken up (absorbed) from extrinsically labeled turkey meat was calculated from the amounts of /sup 65/Zn and a nonabsorbed /sup 51/Cr marker present in the body or in a single stool specimen after 1-2 d. /sup 51/CrCl/sub 3/ proved to be a suitable marker for unabsorbed /sup 65/Zn and so the early determination of /sup 65/Zn absorption was possible. With stool counting, /sup 65/Zn absorption data from first stool samples after 1-2 d were accurate as judged by correlation with the amount of /sup 65/Zn in the body 7-10 d later (retention); results from subsequent stools gave lower absorption values due to the early excretion of some absorbed /sup 65/Zn. The dual-isotope method gave reproducible results when four successive tests of zinc absorption were carried out in a group of six subjects. The average (mean +/- SD) /sup 65/Zn absorption from turkey meals containing 31 mumol (2 mg) and 46 mumol (3 mg) of zinc was 39 +/- 8% and 29 +/- 6%, respectively, measured by stool counting; /sup 65/Zn absorption and retention correlated well in both studies. A series of different beverages was given in place of water with the turkey meal. Orange juice significantly reduced /sup 65/Zn absorption and milk also showed this tendency, but tea, whiskey, wine or beer had no significant effect on the absorption of /sup 65/Zn from the turkey meal. In groups of subjects the mean ratio of /sup 65/Zn absorption from extrinsically labeled turkey meat on two occasions (1.06) was not significantly different from that of the absorption of extrinsic to intrinsic /sup 65/Zn labels (1.16). The dual-isotope technique with either stool or body counting is suitable for the rapid determination of /sup 65/Zn absorption from extrinsically labeled turkey within 2 d.

  6. Thermodynamic equilibrium at heterogeneous pressure

    NASA Astrophysics Data System (ADS)

    Vrijmoed, J. C.; Podladchikov, Y. Y.

    2015-07-01

    Recent advances in metamorphic petrology point out the importance of grain-scale pressure variations in high-temperature metamorphic rocks. Pressure derived from chemical zonation using unconventional geobarometry based on equal chemical potentials fits mechanically feasible pressure variations. Here, a thermodynamic equilibrium method is presented that predicts chemical zoning as a result of pressure variations by Gibbs energy minimization. Equilibrium thermodynamic prediction of the chemical zoning in the case of pressure heterogeneity is done by constrained Gibbs minimization using linear programming techniques. In addition to constraining the system composition, a certain proportion of the system is constrained at a specified pressure. Input pressure variations need to be discretized, and each discrete pressure defines an additional constraint for the minimization. The Gibbs minimization method provides identical results to a geobarometry approach based on chemical potentials, thus validating the inferred pressure gradient. The thermodynamic consistency of the calculation is supported by the similar result obtained from two different approaches. In addition, the method can be used for multi-component, multi-phase systems of which several applications are given. A good fit to natural observations in multi-phase, multi-component systems demonstrates the possibility to explain phase assemblages and zoning by spatial pressure variations at equilibrium as an alternative to pressure variation in time due to disequilibrium.

  7. A novel method of carbon dioxide clumped isotope analysis with tunable infra-red laser direct absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Prokhorov, Ivan; Kluge, Tobias; Janssen, Christof

    2016-04-01

    Precise clumped isotopes analysis of carbon dioxide opens up new horizons of atmospheric and biogeochemical research. Recent advances in laser and spectroscopic techniques provides us necessary instrumentation to access extremely low sub-permill variations of multiply-substituted isotopologues. We present an advanced analysis method of carbon dioxide clumped isotopes using direct absorption spectroscopy. Our assessments predict the ultimate precision of the new method on the sub-permill level comparable to state of the art mass spectrometry. Among the most auspicious intrinsic properties of this method we highlight genuine Δ16O13C18O and Δ16O13C18O measurements without isobaric interference, measurement cycle duration of several minutes versus hours for mass spectrometric analysis, reduced sample size of ˜ 10 μmol and high flexibility, allowing us to perform in-situ measurements. The pilot version of the instrument is being developed in an international collaboration framework between Heidelberg University, Germany and Pierre and Marie Curie University, Paris, France. It employs two continuous interband quantum cascade lasers tuned at 4.439 μm and 4.329 μm to measure doubly ( 16O13C18O, 16O13C17O) and singly ( 16O12C16O, 16O13C16O, 16O12C17O, 16O12C18O) substituted isotopologues, respectively. Two identical Herriot cells are filled with dry pure CO2 sample and reference gas at working pressure of 1 ‑ 10 mbar. Cells provide optical path lengths of ˜ 17 m for the laser tuned at doubly substituted isotopologues lines and use a single pass for the laser tuned at the stronger lines of singly substituted isotopologues. Light outside of the gas cells is coupled into optical fiber to avoid absorption by ambient air CO2. Simulations predict sub-permill precision at working pressure of 1 mbar and room temperature stabilised at the ±10 mK level. Our prime target is to apply the proposed method for continuous in-situ analysis of CO2. We are foreseeing potential

  8. A novel method of carbon dioxide clumped isotope analysis with tunable infra-red laser direct absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Prokhorov, Ivan; Kluge, Tobias; Janssen, Christof

    2016-04-01

    Precise clumped isotopes analysis of carbon dioxide opens up new horizons of atmospheric and biogeochemical research. Recent advances in laser and spectroscopic techniques provides us necessary instrumentation to access extremely low sub-permill variations of multiply-substituted isotopologues. We present an advanced analysis method of carbon dioxide clumped isotopes using direct absorption spectroscopy. Our assessments predict the ultimate precision of the new method on the sub-permill level comparable to state of the art mass spectrometry. Among the most auspicious intrinsic properties of this method we highlight genuine Δ16O13C18O and Δ16O13C18O measurements without isobaric interference, measurement cycle duration of several minutes versus hours for mass spectrometric analysis, reduced sample size of ˜ 10 μmol and high flexibility, allowing us to perform in-situ measurements. The pilot version of the instrument is being developed in an international collaboration framework between Heidelberg University, Germany and Pierre and Marie Curie University, Paris, France. It employs two continuous interband quantum cascade lasers tuned at 4.439 μm and 4.329 μm to measure doubly ( 16O13C18O, 16O13C17O) and singly ( 16O12C16O, 16O13C16O, 16O12C17O, 16O12C18O) substituted isotopologues, respectively. Two identical Herriot cells are filled with dry pure CO2 sample and reference gas at working pressure of 1 - 10 mbar. Cells provide optical path lengths of ˜ 17 m for the laser tuned at doubly substituted isotopologues lines and use a single pass for the laser tuned at the stronger lines of singly substituted isotopologues. Light outside of the gas cells is coupled into optical fiber to avoid absorption by ambient air CO2. Simulations predict sub-permill precision at working pressure of 1 mbar and room temperature stabilised at the ±10 mK level. Our prime target is to apply the proposed method for continuous in-situ analysis of CO2. We are foreseeing potential

  9. Isotope ratio mass spectrometric <