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Sample records for isotopic equilibrium method

  1. Modeling equilibrium Fe isotope fractionation

    NASA Astrophysics Data System (ADS)

    Anbar, A.; Jarzecki, A.; Spiro, T.

    2003-04-01

    Research into the stable isotope biogeochemistry of Fe and other transition metals has been driven primarily by analytical innovations which have revealed significant isotope effects in nature and the laboratory. Further development of these new isotope systems requires complementary theoretical research to guide analytical efforts. The results of the first such studies show some discrepancies with experiments. For example, Johnson et al. (2002) report an experimentally-determined 56Fe/54Fe equilibrium fractionation factor between Fe(II) and Fe(III) aquo complexes of ˜1.0025. This effect is ˜50% smaller than predicted theoretically by Schauble et al. (2001). It is important to resolve such discrepancies. Equilibrium isotope fractionation factors can be predicted from vibrational spectroscopic data of isotopically-substituted complexes, or from theoretical predictions of some or all of these frequencies obtained using force field models. The pioneering work of Schauble et al. (2001) utilized a modified Urey-Bradley force field (MUBFF) model. This approach is limiting in at least three ways: First, it is not ab initio, requiring as input some measured vibrational frequencies. Such data are not always available, or may have significant uncertainties. Second, the MUBFF does not include potentially important effects of solvent interaction. Third, because it makes certain assumptions about molecular symmetry, the MUBFF-based approach is not able to model the spectra of mixed-ligand complexes. To address these limitations, we are evaluating the use of density functional theory (DFT) as an ab initio method to predict vibrational frequencies of isotopically-substituted complexes and, hence, equilibrium fractionation factors. In a preliminary examination of the frequency shift upon isotope substitution of the bending and asymmetric stretching modes of the tetrahedral FeCl_42- complex, we find substantial differences between MUBFF and DFT predictions. Results for other Fe

  2. 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.

  3. Experimental determination of equilibrium magnesium isotope fractionation between spinel, forsterite, and magnesite by the three-isotope method at 700 °C and 1 GPa

    NASA Astrophysics Data System (ADS)

    Macris, C. A.; Young, E. D.; Manning, C. E.; Schauble, E. A.

    2011-12-01

    Magnesium isotopes are potentially powerful tools for high-temperature geochemistry if relevant fractionation factors are known. However, experimental data for Mg isotope fractionation are lacking at high temperatures. We performed piston-cylinder experiments at 700 °C and 1 GPa to establish the equilibrium magnesium isotope partitioning between forsterite (Mg2SiO4) and magnesite (MgCO3), and between spinel (MgAl2O4) and magnesite, making use of the well-established advantages of using carbonates as an isotope exchange medium (e.g. Clayton et al., 1989). Our results provide the first experimental calibration of the equilibrium 26Mg/24Mg fractionation between minerals at high temperature. For these experiments we used a high-pressure piston cylinder apparatus and a three-isotope spike technique. The present study extends the applicability of the three-isotope method to experiments involving simple isotope exchange rather than exchange by heterogeneous reaction (Shahar et al., 2008). In these experiments we used magnesite as the exchange medium (and exchange partner) to overcome the sluggish diffusion-limited exchange between spinel and forsterite alone. The carbonate media facilitates chemical and isotopic exchange by promoting annealing and re-crystallization of minerals during the experiment. The combination of a three-isotope method with the use of carbonate as exchange media, used for the first time in this study, allows the experimentalist to determine the partitioning of Mg isotopes between two solid phases without requiring heterogeneous reaction. Results show that at 700 °C and 1 GPa 26ΔFo-Mgs = -0.16 ± 0.13% and 26ΔSp-Mgs = 0.93 ± 0.28%. From these two experimentally-determined equilibrium fractionation values, we can derive the equilibrium fractionation between spinel and forsterite by difference, yielding 26ΔSp-Fo = 1.09 ± 0.31%. This agrees within error with a first- principles estimate of equilibrium magnesium isotope fractionation of 26

  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. 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

  7. 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.

  8. Nuclear Volume Effects in Equilibrium Stable Isotope Fractionations of Hg, Tl and Pb Isotope Systems

    NASA Astrophysics Data System (ADS)

    Yang, S.; Liu, Y.

    2014-12-01

    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. Here we investigate NVEs of Hg, Tl and Pb isotope systems by using quantum chemistry computational methods with careful evaluation on quantum relativistic effects via the Dirac's formalism of full-electron wavefunction. Our results generally agree with previous studies but with noticeable differences in many cases. With the unique NVE driving force, equilibrium 202Hg/198Hg and 205Tl/203Tl isotopes can be fractionated up to 3.94‰ and 2.78‰ at 0℃, respectively, showing potentially large equilibrium isotope fractionations can be expected for future studies of these two isotope systems. Moreover, the NVE causes large mass-independent fractionations (MIF) for odd-mass isotopes (e.g., ∆199NVHg and ∆201NVHg) and small MIFs for even-mass isotopes (e.g., ∆200NVHg). For Pb isotope system, NVEs induce isotope fractionations up to 1.62‰ (207Pb/206Pb) and 4.06‰ (208Pb/206Pb) at 0℃. However, contributions from classical mass-dependent driving force are small, about 0.1-0.5‰ for 207Pb/206Pb and 0.2-0.9‰ for 208Pb/206Pb. We find that Pb4+-bearing species can be significantly enriched heavy isotopes than Pb2+-bearing species. Comparing to Pb0, Pb2+-bearing species even enrich lighter Pb isotopes. A very strange and interesting thing is that the beta value of Pb2+-bearing species can be smaller than the unity (1.000). Similar thing has been found on Tl+-bearing species. This is an impossible and unexplained situation if only based on classical mass-dependent isotope fractionation theory (e.g., Bigeleisen-Mayer equation). The consequence is that the different direction of beta values of Pb2+-bearing species will let the Pb isotope fractionation even larger when they fractionate with Pb4+-bearing species. Moreover, NVEs also cause mass-independent fractionation (MIF) of odd 207Pb

  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. 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

  14. Theoretical estimates of equilibrium chlorine-isotope fractionations

    NASA Astrophysics Data System (ADS)

    Schauble, Edwin A.; Rossman, George R.; Taylor, H. P.

    2003-09-01

    Equilibrium chlorine-isotope ( 37Cl/ 35Cl) fractionations have been determined by using published vibrational spectra and force-field modeling to calculate reduced partition function ratios for Cl-isotope exchange. Ab initio force fields calculated at the HF/6-31G(d) level are used to estimate unknown vibrational frequencies of 37Cl-bearing molecules, whereas crystalline phases are modeled by published lattice-dynamics models. Calculated fractionations are principally controlled by the oxidation state of Cl and its bond partners. Molecular mass (or the absence of C-H bonds) also appears to play a role in determining relative fractionations among simple Cl-bearing organic species. Molecules and complexes with oxidized Cl (i.e., Cl 0, Cl +, etc.) will concentrate 37Cl relative to chlorides (substances with Cl -). At 298 K, ClO 2 (containing Cl 4+) and [ClO 4] - (containing Cl 7+) will concentrate 37Cl relative to chlorides by as much as 27‰ and 73‰, respectively, in rough agreement with earlier calculations. Among chlorides, 37Cl will be concentrated in substances where Cl is bonded to +2 cations (i.e., FeCl 2, MnCl 2, micas, and amphiboles) relative to substances where Cl is bonded to +1 cations (such as NaCl) by ˜2 to 3‰ at 298 K; organic molecules with C-Cl bonds will be even richer in 37Cl (˜5 to 9‰ at 298 K). Precipitation experiments, in combination with our results, provide an estimate for Cl-isotope partitioning in brines and suggest that silicates (to the extent that their Cl atoms are associated with nearest-neighbor +2 cations analogous with FeCl 2 and MnCl 2) will have higher 37Cl/ 35Cl ratios than coexisting brine (by ˜2 to 3‰ at room temperature). Calculated fractionations between HCl and Cl 2, and between brines and such alteration minerals, are in qualitative agreement with both experimental results and systematics observed in natural samples. Our results suggest that Cl-bearing organic molecules will have markedly higher 37Cl/ 35Cl

  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-pyroxene equilibrium iron isotopic fractionation and applications to natural peridotites

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    Eight spinel-group minerals were synthesized by a flux-growth method producing spinels with varying composition and Fe3+/Fetot 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 (β-factors) of these spinels. The mean force constants are strongly dependent on the Fe3+/Fetot 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+/Fetot on the β-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+/Fetot 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. 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.

  18. 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.

  19. 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.

  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. 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.

  2. 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/.

  3. Method of separating boron isotopes

    DOEpatents

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

    1984-01-01

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

  4. 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.

  5. 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.

  6. Low temperature equilibrium isotope fractionation and isotope exchange kinetics between U(IV) and U(VI)

    NASA Astrophysics Data System (ADS)

    Wang, Xiangli; Johnson, Thomas M.; Lundstrom, Craig C.

    2015-06-01

    Measurements of the uranium (U) isotope ratio 238U/235U provide an emerging redox proxy in environmental and paleoredox studies, but many key parameters concerning U isotope fractionation are still poorly constrained. Here we report the equilibrium isotopic fractionation between dissolved U(IV) and dissolved U(VI), and rates of isotope exchange between solid-phase U(IV) and dissolved U(VI). We conducted one experiment at high concentration [35 mM U(IV) and 32 mM U(VI)] and low pH (0.2) in hydrochloric acid media at room temperature to determine the equilibrium isotopic fractionation between dissolved U(IV) and dissolved U(VI). Isotopic equilibrium was reached in about 19 days under such experimental conditions. The equilibrium isotope fractionation was determined to be 1.64 ± 0.16‰, with U(IV) being enriched in 238U relative to U(VI). Applicability of the determined equilibrium fractionation is discussed. We also conducted a set of experiments to determine isotopic exchange rates between dissolved U(VI) and nanouraninite U(IV) under conditions closer to those in natural system, with lower concentrations and neutral pH. The exchange rate was found to conform to the rate law R = k[U(VI)]adsorbed, in which R is the isotopic exchange rate (μM day-1); k is the rate constant determined to be 0.21 day-1; and [U(VI)]adsorbed is the concentration of U(VI) adsorbed to nanouraninite (μM). Our results, combined with consideration of the variables controlling U(VI)-U(IV) contact in natural settings, indicate that the timescale for significant isotope equilibration varies depending on environmental conditions, mostly uranium concentrations. In natural uncontaminated sediments with low uranium concentrations, equilibration is expected to occur on a timescale of hundreds to thousands of years. In contrast, in U-contaminated aquifers with high U concentrations, significant equilibration could occur on timescales of weeks to years.

  7. 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.

  8. Stable carbon and hydrogen isotope fractionation of dissolved organic groundwater pollutants by equilibrium sorption

    NASA Astrophysics Data System (ADS)

    Höhener, Patrick; Yu, Xianjing

    2012-03-01

    Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by "heavy divided by light", carbon enrichment factors for equilibrium sorption were derived which ranged from - 0.13 ± 0.04‰ (benzene) to - 0.52 ± 0.19‰ (trichloroethene at 5-15 °C). Hydrogen enrichment factors for sorption of 14 different compounds were between - 2.4 and - 9.2‰. For perdeuterated hydrocarbons the predicted enrichment factors ranged from - 19 ± 5.4‰ (benzene) to - 64 ± 30‰ (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for 13C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants.

  9. 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.

  10. Isotopic equilibrium between mantle peridotite and melt: Evidence from the Corsica ophiolite

    NASA Astrophysics Data System (ADS)

    Rampone, Elisabetta; Hofmann, Albrecht W.; Raczek, Ingrid

    2009-11-01

    A widely used assumption of mantle geochemistry and the theory of partial melting at oceanic settings is the existence of isotopic equilibrium between mantle source and melt. Yet, recent diffusion studies and isotopic investigations of ophiolites, abyssal peridotites and associated MORBs have cast doubts on this assumption, by providing evidence for isotopic disequilibrium between residual peridotites and MORBs. Here we present Sr and Sm-Nd isotope data on mantle peridotites and gabbroic intrusions from the Mt. Maggiore (Alpine Corsica, France) Tethyan ophiolite, which document Nd isotopic homogeneity, implying isotopic equilibrium, on a 1-kilometer scale. The peridotites record multi-stage melt-rock interaction and melt intrusion occurring at different lithospheric depths. Samples studied are residual cpx-poor spinel lherzolites, reactive spinel harzburgites, impregnated plagioclase peridotites and related gabbronoritic veinlets, later gabbroic dykes. Strontium isotopes in peridotites and gabbros are highly variable, due to interaction with sea-water derived fluids, and cannot be used to test melt-residue isotopic equilibrium. In contrast, Nd isotopes are unaffected by sea-water alteration. Peridotites display present-day high 147Sm/ 144Nd (0.49-0.59) and 143Nd/ 144Nd (0.513367-0.513551) ratios, with no appreciable differences between residual and reactive spinel peridotites, and between spinel and plagioclase peridotites. Gabbroic dykes have present-day Nd isotopic compositions typical of MORB ( 143Nd/ 144Nd = 0.513122-0.513138). Internal (plag-whole rock-cpx) Sm-Nd isochrons for olivine gabbro dykes and a gabbronoritic veinlet yield Jurassic ages (162 ± 10 and 159 ± 15 Ma in ol-gabbros, 155 ± 6 Ma in gabbronorite), and initial ɛNd = 8.9-9.7 indicative of a MORB-type source. Sm-Nd isotopic compositions of peridotites conform to the linear array defined by the gabbroic rocks, and yield initial (160 Ma) ɛNd values of 7.6-8.9, again consistent with a MORB

  11. Method for laser induced isotope enrichment

    DOEpatents

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

    2004-09-07

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

  12. Ab initio prediction of equilibrium boron isotope fractionation between minerals and aqueous fluids at high P and T

    NASA Astrophysics Data System (ADS)

    Kowalski, Piotr M.; Wunder, Bernd; Jahn, Sandro

    2013-01-01

    Over the last decade experimental studies have shown a large B isotope fractionation between materials carrying boron incorporated in trigonally and tetrahedrally coordinated sites, but the mechanisms responsible for producing the observed isotopic signatures are poorly known. In order to understand the boron isotope fractionation processes and to obtain a better interpretation of the experimental data and isotopic signatures observed in natural samples, we use first principles calculations based on density functional theory in conjunction with ab initio molecular dynamics and a new pseudofrequency analysis method to investigate the B isotope fractionation between B-bearing minerals (such as tourmaline and micas) and aqueous fluids containing HBO and HBO4- species. We confirm the experimental finding that the isotope fractionation is mainly driven by the coordination of the fractionating boron atoms and have found in addition that the strength of the produced isotopic signature is strongly correlated with the Bsbnd O bond length. We also demonstrate the ability of our computational scheme to predict the isotopic signatures of fluids at extreme pressures by showing the consistency of computed pressure-dependent β factors with the measured pressure shifts of the Bsbnd O vibrational frequencies of HBO and HBO4- in aqueous fluid. The comparison of the predicted with measured fractionation factors between boromuscovite and neutral fluid confirms the existence of the admixture of tetrahedral boron species in neutral fluid at high P and T found experimentally, which also explains the inconsistency between the various measurements on the tourmaline-mica system reported in the literature. Our investigation shows that the calculated equilibrium isotope fractionation factors have an accuracy comparable to the experiments and give unique and valuable insight into the processes governing the isotope fractionation mechanisms on the atomic scale.

  13. 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

  14. 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:

  15. 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…

  16. Extragradient methods for searching for equilibrium points in the parametric problem of equilibrium programming

    NASA Astrophysics Data System (ADS)

    Artem'eva, L. A.

    2014-12-01

    The parametric problem of equilibrium programming is examined. The mathematical programming problem, the search for a saddle-point, the multicriteria search for a Pareto point, etc. are particular cases of this parametric problem. The primal and dual variants of the extragradient method are proposed as a tool for searching for equilibrium points. The convergence of both variants is analyzed.

  17. 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.

  18. A modified graphical method for determination of equilibrium constants

    PubMed Central

    Kilroe-Smith, T. A.

    1966-01-01

    A modification is described of the method of Dixon (1965) for determining equilibrium constants (K) of combinations of the type A+B⇌AB. The method obviates drawing of a tangent to the curve at the origin. PMID:5968534

  19. Isotopic Equilibrium in Mature Oceanic Lithosphere: Insights From Sm-Nd Isotopes on the Corsica (France) Ophiolites

    NASA Astrophysics Data System (ADS)

    Rampone, E.; Hofmann, A. W.; Raczek, I.; Romairone, A.

    2003-12-01

    .6-8.9. Sm/Nd isotopic compositions of the peridotites are therefore consistent with a Jurassic age of melting and melt impregnation, and point to isotopic compositional similarities between depleted peridotites and associated magmatic rocks. In a regional geodynamic context, Sm/Nd isotope data for the Mt.Maggiore gabbro-peridotite association represent the first record of the attainment of a mature oceanic stage of the Ligurian Tethys ocean. Also, the data presented provide striking evidence of the existence of isotopic equilibrium between melts and their mantle residue. References Snow et al. (1994), Nature 371, 57-60. Salters and Dick (2002), Nature 418,68-72.

  20. 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.

  1. 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

  2. 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

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

    PubMed Central

    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 202Hg/198Hg, 205Tl/203Tl, 207Pb/206Pb and 208Pb/206Pb 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 vs. 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, Pb4+-bearing species are found can enrich heavier Pb isotopes than Pb2+-bearing species to a surprising extent, e.g., the enrichment can be up to 4.34‰ in terms of 208Pb/206Pb at room temperature, due to their NVEs are in opposite directions. In contrast, fractionations among Pb2+-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., ) and odd-mass MIFs (i.e., ) are almost the same but with opposite signs. PMID:26224248

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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 185ppm/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 5.2ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5ppm) 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

  10. 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

  11. 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

  12. Equilibrium uranium isotope fractionation by nuclear volume and mass-dependent processes

    NASA Astrophysics Data System (ADS)

    Schauble, E. A.

    2006-12-01

    Uranium serves as a geochemical tracer of oxidation near the Earth's surface, and is also the basis for several isotopic geochronometers. It is thus important to understand possible non-radiogenic and non-radioactive isotopic fractionation of uranium in natural systems. This study presents theoretical estimates of equilibrium uranium isotope fractionations in U-bearing molecules and complexes, calculated using first-principles computational chemistry. Ion-exchange experiments (1,2) have indicated that mass-dependent mechanisms, alone, cannot explain 238U/234U and 238U/^{235}U fractionations, so nuclear volume (i.e., field shift) fractionation effects are also considered in theoretical calculations. The results indicate that equilibrium isotopic fractionation is likely when U4+ and U6+ species equilibrate. Nuclear volume fractionation leads to higher 238U/^{235}U in U4+-bearing species, overwhelming a smaller mass- dependent fractionation in the opposite direction. The calculated net fractionation between U(H2O)_94+ and UO2Cl3(H2O)_2^- is approximately 1 per mil at 20-150°C, in agreement with earlier experiments. These results also reproduce the apparent non mass-dependent signature observed in 238U/234U relative to 238U/^{235}U. In addition to redox reactions, significant fractionation is expected between different U6+-bearing uranyl complexes (e.g., UO2(H2O)_52+, UO2(NO3)_3^-, UO2(CO3)(H2O)3). These results suggest that U-isotope composition could be used as a proxy for the oxidation state and speciation of natural waters, and that U-isotope ratios are not constant in materials formed or equilibrated at low temperatures. More generally, nuclear volume fractionations are expected to partially cancel or reverse mass-dependent fractionations caused by redox transitions among the high oxidation states (≥+2) of lanthanides, actinides, and heavy transition elements. References: 1. Nomura, Higuchi and Fujii, 1996, J. Am. Chem. Soc., v. 118, p. 9127-9130. 2. Bigeleisen

  13. Using equilibrium isotope effects to detect intramolecular OH/OH hydrogen bonds: structural and solvent effects.

    PubMed

    Vasquez, Thomas E; Bergset, Jon M; Fierman, Matthew B; Nelson, Alshakim; Roth, Joshua; Khan, Saeed I; O'Leary, Daniel J

    2002-03-27

    A comparative (1)H NMR study of partially deuterated 1,3- and 1,4-diols has demonstrated that intramolecular hydrogen bonds of different geometry can give rise to equilibrium isotope shifts of opposite sign in hydrogen-bond-accepting solvents such as DMSO-d(6), acetone-d(6), and THF-d(8). The sign inversion is interpreted in terms of the ability of solvent molecules to form competitive intermolecular hydrogen bonds with the diol and in terms of the limiting chemical shifts for the interior and exterior hydroxyl groups. Deuterium is shown to prefer the intermolecular solvent hydrogen bond by 10.9 +/- 0.5 cal/mol for 1,4-diol 3 dissolved in DMSO-d(6) at room temperature. Pyridine-d(5) is shown to be capable of amplifying positive (downfield) isotope shifts measured in DMSO-d(6), in some cases by as much as a factor of 3. Its use is demonstrated for the assignment of the syn or anti relative configuration of 2,4-pentanediol and for the amplification of isotope shifts used to detect intramolecular hydrogen bonds in alpha- and beta-cyclodextrin. Studies in apolar solvents such as CD(2)Cl(2) and benzene-d(6) reveal that the isotope shift is negative (upfield) for all hydrogen bond geometries studied. Larger isotope shifts are measured in benzene-d(6), and a rationale for this amplification is presented. The use of apolar solvents is particularly useful for assigning the syn or anti configuration of 2,4-pentanediol. PMID:11902884

  14. Antarctic seawater temperature evaluation based on stable isotope measurements on Adamussium colbecki shells: kinetic effects vs. isotopic equilibrium

    NASA Astrophysics Data System (ADS)

    Trevisiol, A.; Bergamasco, A.; Montagna, P.; Sprovieri, M.; Taviani, M.

    2013-10-01

    A year-long controlled growth experiment of 60 specimens of the Antarctic bivalve Adamussium colbecki was conducted in Terra Nova Bay (Ross Sea) to evaluate its reliability as a suitable archive of water mass properties. Nine shells were sub-sampled for stable oxygen and carbon isotope analysis to study the inter and intra specimen variations. Slow-growing A. colbecki precipitate their calcitic shells close to the expected oxygen and carbon isotopic equilibrium, whereas the fast-growing individuals are strongly influenced by biogenetic and kinetic effects. The equation of Kim and O'Neil (1997) is considered a fair approximation for the δ18O-temperature relationship in slow-growing individuals. The reconstructed temperature is closer to the mean experimental summer temperature than the annual one. This fact is interpreted as reflecting a possible winter decrease of shell growth, the salinity variation and the corrections for negative temperature on calibrating the δ18O-temperature relationship. Our results support the hypothesis that A. colbecki might represent a good archive for encoding Antarctic Shelf water summer temperature information. Further improvements in adopting A. colbecki as a paleotemperature archive will require the evaluation of the seasonal variability in shell growth rate through culturing slow-growing A. colbecki individuals at near-freezing temperatures to calibrate a species-specific δ18O-temperature equation.

  15. Equilibrium structures of heterocyclic molecules with large principal axis rotations upon isotopic substitution.

    PubMed

    Demaison, Jean; Császár, Attila G; Margulès, Laurent D; Rudolph, Heinz Dieter

    2011-12-01

    Equilibrium structures, r(e), of the heterocyclic molecules oxirane, furazan, furan, ethylene ozonide, and 1,3,4-oxadiazole have been determined using three different, somewhat complementary techniques: a completely experimental technique (r(m)), a semiexperimental technique (r(e)(SE), whereby equilibrium rotational constants are derived from experimental effective ground-state rotational constants and corrections based principally on an ab initio cubic force field), and an ab initio technique (r(e)(BO), whereby geometry optimizations are usually performed at the coupled cluster level of theory including single and double excitations augmented by a perturbational estimate of the effects of connected triple excitations [CCSD(T)] using quadruple-ζ Gaussian basis sets). All these molecules are asymmetric tops with the moment of inertia I(c) much larger than the other two moments of inertia, I(a) and I(b). Molecules of this shape experience a large rotation of the principal axis system upon certain isotopic substitutions. For such isotopologues it is difficult to obtain a good structural fit to the semiexperimental moments of inertia I(a) and I(b), which may significantly reduce the accuracy of the r(e)(SE) structural parameters. The origin of this difficulty is explained. For the heavy-atom skeleton of these molecules it was possible to determine a rather accurate empirical mass-dependent structure without a priori knowledge of the equilibrium structure. PMID:22032750

  16. 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.

  17. 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.

  18. 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

  19. 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

  20. 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., Jr.; 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

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. Experimental determination of equilibrium magnesium isotope fractionation between spinel, forsterite, and magnesite from 600 °C to 800 °C

    NASA Astrophysics Data System (ADS)

    Macris, C. A.; Young, E. D.; Manning, C. E.

    2012-12-01

    Magnesium isotopes are potentially powerful tools for high-temperature geochemistry if relevant fractionation factors are known. However, experimental data for Mg isotope fractionation are lacking at high temperatures. We performed piston-cylinder experiments at 600, 700, and 800 °C at 1 GPa to establish the equilibrium magnesium isotope partitioning between forsterite (Mg2SiO4) and magnesite (MgCO3) and between spinel (MgAl2O4) and magnesite, making use of the well-established advantages of using carbonates as an isotope exchange medium (e.g. Clayton et al., 1989). In these experiments we implemented the three-isotope method with forsterite and magnesite, and with spinel and magnesite, at three different temperatures in high-pressure piston cylinder apparatus for varying lengths of time. The present study extends the applicability of the three-isotope method to experiments involving simple isotope exchange rather than exchange by heterogeneous reaction (Shahar et al., 2008). We used magnesite as the exchange medium (and exchange partner) to overcome the sluggish diffusion-limited exchange between spinel and forsterite alone. The carbonate medium evidently facilitates chemical and isotopic exchange by promoting annealing and re-crystallization of minerals during the experiment. Results are as follows: 600 °C and 1 GPa 26ΔSp-Mgs = 1.73 ± 0.38‰ and 26ΔFo-Mgs = 0.44 ± 0.10‰; 700 °C 26ΔSp-Mgs = 1.10 ± 0.27‰ and 26ΔFo-Mgs = -0.13 ± 0.13‰; 800 °C 26ΔSp-Mgs = 0.90 ± 0.28‰ and 26ΔFo-Mgs = 0.04 ± 0.04‰. From these experimentally determined equilibrium fractionation values, we derive the temperature-dependent equilibrium fractionation between spinel and forsterite by difference, yielding 26ΔSp-Fo = 1.29 ± 0.39‰, 26ΔSp-Fo = 1.22 ± 0.30‰, and 26ΔSp-Fo = 0.86 ± 0.29‰ for 600, 700, and 800 °C respectively. These results agree within error with first- principles estimates of equilibrium magnesium isotope fractionation between spinel and

  13. 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)

  14. 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.

  15. 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.

  16. 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.

  17. Method for production of an isotopically enriched compound

    DOEpatents

    Watrous, Matthew G.

    2012-12-11

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

  18. 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.

  19. Wide reflective equilibrium as a method of justification in bioethics.

    PubMed

    Nichols, Peter

    2012-10-01

    Carson Strong has recently argued that wide reflective equilibrium (WRE) is an unacceptable method of justification in bioethics. In its place, Strong recommends a methodology in which certain foundational moral judgments play a central role in the justification of moral beliefs, and coherence plays a limited justificatory role in that the rest of our judgments are made to cohere with these foundational judgments. In this paper, I argue that Strong's chief criticisms of WRE are unsuccessful and that his proposed alternative is in fact just another version of WRE. In the course of doing so, I specify which theses are central to WRE and which are not, and thus, provide a response to an additional objection, advanced by Peter Singer, that WRE is vacuous. I conclude by arguing that there may be better prospects for advancing the debate regarding methodology in bioethics if we focus on restricted epistemic and methodological theses rather than broad approaches, such as WRE, that come in many different varieties. PMID:22752538

  20. 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.

  1. Modeling of Non-equilibrium Processes in Oil Trunk Pipeline Using Godunov Type Method

    NASA Astrophysics Data System (ADS)

    Sumskoi, S. I.; Sverchkov, A. M.

    The Article presents the numerical method of solving the system of one-dimensional non-stationary equations describing oil movement in the oil pipeline. The method is aimed at modeling the non-equilibrium and transitional processes in the oil pipelines in the normal and emergency modes. This new developed method can be applied for relaxation non-equilibrium flow case, that can't be modeling using another methods. Also this method is aimed at modeling the non-equilibrium and transitional processes in the liquefied hydrocarbon pipelines in the normal and emergency modes. Phase non-equilibrium flow is considered for boiling liquids transporting pipeline.

  2. 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

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. Ethanol isotope method (EIM) for uncovering illegal wine.

    PubMed

    Smajlović, I; Sparks, K L; Sparks, J P; Čukalović, I Leskošek; Jović, S

    2013-01-01

    Isotopic methods have proven to be a powerful analytical tool for the determination of origin and authenticity of wine. In addition, measuring the stable isotope ratio provides useful information for the detection of many illegal practices in the production of wine. The determinations of the stable isotope composition of compounds are based on measuring the relative ratios using isotope ratio mass spectrometry. This article describes a new isotopic method for measuring the δD value of non-exchangeable hydrogen stable isotopes in ethanol for investigating adulteration practices in wine making. With this new method, we are able to determine the addition of water and sugar in wine with higher accuracy, repeatability and reliability. PMID:22462798

  9. 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.

  10. Equilibrium oxygen isotope behavior of sulfate in marine sediments: A new paradigm

    NASA Astrophysics Data System (ADS)

    Blake, R.; Boettcher, M.; Surkov, A.; Ferdelman, T.; Jorgensen, B.

    2006-05-01

    We have determined the oxygen (18O/16O) and sulfur (34S/32S) isotope ratios of porewater sulfate to depths of over 400 mbsf in sediments from open-ocean and upwelling sites in the Eastern Equatorial Pacific ocean. Sulfate δ18O ranges from near-normal seawater values (9.5 permil) at organic-poor open-ocean sites, to approximately 30 permil at sites with higher organic matter content and higher associated microbial activity. Depth-correlative trends of δ18O, δ34S, alkalinity, methane, ammonium and the presence of sulfide, indicate significant oxidation of sedimentary organic matter by sulfate-reducing microbial populations as well as anaerobic oxidation of methane. δ18O ?SO4 values at low-activity sites reveal the presence of significant microbial sulfur-cycling activity despite relatively flat sulfate concentration and δ34S profiles. This activity may include contributions from several processes including: enzyme-catalyzed equilibration between oxygen in sulfate and water superimposed upon microbial sulfate reduction, sulfide oxidation, and bacterial disproportionation of sulfur intermediates. Positive correlation between water and sulfate δ18O values supports sulfate-water O isotope exchange as the dominant process controlling porewater sulfate δ18O values. Results of this study indicate that coupled measurements of S and O isotope ratios of porewater sulfate are essential for interpreting microbial sulfur cycling in marine sediments.

  11. 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

  12. 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.

  13. INSTRUMENTS AND METHODS OF INVESTIGATION: Isotope engineering

    NASA Astrophysics Data System (ADS)

    Plekhanov, Vladimir G.

    2000-11-01

    Major applications of the novel and extremely promising technology of isotope engineering are reviewed which, along with basic research, also include — by no means exhaustively — optical fibers, optoelectronics, tunable solid-state lasers, neutron transmutation doping, and information storage.

  14. 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.

  15. 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.

  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. 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.

  18. 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.

  19. An iterative method for the solution of the statistical and radiative equilibrium equations in expanding atmospheres

    NASA Astrophysics Data System (ADS)

    Hillier, D. J.

    1990-05-01

    A method for the solution of the statistical equilibrium, and radiative equilibrium equations in spherical atmospheres is presented. The iterative scheme uses a tridiagonal (or pentadiagonal) Newton-Raphson operator, and is based on the complete linearization method of Auer and Mihalas (1969) but requires less memory, and imposes no limit on the number of transitions that can be treated. The method is also related to iterative techniques that use approximate diagonal lambda operators but it has a vastly superior convergence rate. Calculations of WN and WC model atmospheres illustrate the excellent rate of convergence.

  20. 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.

  1. 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…

  2. 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.

  3. Ab-initio structure, energy and stable Fe isotope equilibrium fractionation of some geochemically relevant H-O-Fe complexes

    NASA Astrophysics Data System (ADS)

    Ottonello, Giulio; Zuccolini, Marino Vetuschi

    2009-11-01

    The hexa-aqua complexes [Fe(H 2O) 6-m-n(OH) n] (2-n)+n = 0 → 3, m = 0 → 6 - n; [Fe(H 2O) 6-m-n(OH) n] (3-n)+n = 0 → 4, m = 0 → 6 - n were investigated by ab-initio methods with the aim of determining their ground-state geometries, total energies and vibrational properties by treating their inner solvation shell as part of their gaseous precursor (or " hybrid approach"). After a gas-phase energy optimization within the Density Functional Theory (DFT), the molecules were surrounded by a dielectric representing the Reaction Field through an implicit Polarized Continuum Model (PCM). The exploration of several structural ligand arrangements allowed us to quantify the relative stabilities of the various ionic species and the role of the various forms of energy (solute-solvent electronic interaction, cavitation, dispersion, repulsion, liberation free energy) that contribute to stabilize the aqueous complexes. A comparison with experimental thermochemistries showed that ab-initio gas-phase + solvation energies are quite consistent with experimental evidence and allow the depiction of the most stable form in solution and the eventual configurational disorder of water/hydroxyl species around central cations. A vibrational analysis performed on the 54Fe, 56Fe, 57Fe and 58Fe isotopomers indicated important separative effects systematically affected by the extent of deprotonation. The role of the system's redox state (fO 2) and acidity (pH) on the isotopic imprinting of the aqueous species in solution was investigated by coupling the separative effects with speciation calculations. The observed systematics provided a tool of general utility in the interpretation of the iron isotopic signature of natural waters. Applications to the interpretation of isotopic fractionation in solution dictated by redox equilibria and to the significance of the Fe-isotopic imprinting of Banded Iron Formations are given. With "gaseous precursor" it is intended here the isolated gaseous

  4. 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.

  5. 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

  6. 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.

  7. 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)

  8. 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

  9. [Equilibrium surface charge distribution in phospholipid vesicles. I. Method of calculation].

    PubMed

    Tenchov, B G; Raĭchev, B D

    1977-01-01

    This paper presents a method of calculation of the surface charge equilibrium distribution between the two surfaces of a spherically closed phospholipid bilayer suspended in aqueous electrolyte solution. The net surface charge is supposed to be provided by the ionized polar groups of the phospholipid molecules. Its equilibrium distribution is found by minimization of the free electrostatic energy. The procedure of minimization utilizes the solution of the Poisson-Boltzmann equation which describes the double electric layers of the membrane and an expression for the membrane potential derived under the assumption of absence of charges in the membrane phase. An analytical solution of the problem in the range of validity of the linearized Poisson-Boltzman equation is obtained. It is shown that in this case an equilibrium transmembrane potential exists, and the surface charge density is greater at the outer surface of the vesicle. PMID:588604

  10. 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.

  11. 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

  12. 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

  13. Quantum chemical study of the Fe(III)-desferrioxamine B siderophore complex—Electronic structure, vibrational frequencies, and equilibrium Fe-isotope fractionation

    NASA Astrophysics Data System (ADS)

    Domagal-Goldman, S. D.; Paul, K. W.; Sparks, D. L.; Kubicki, J. D.

    2009-01-01

    This study presents molecular orbital/density functional theory (MO/DFT) calculations of the electronic structure, vibrational frequencies, and equilibrium isotope fractionation factors for iron desferrioxamine B (Fe-DFO-B) complexes in aqueous solution. In general, there was good agreement between the predicted properties of Fe(III)-DFO-B and previously published experimental and theoretical results. The predicted fractionation factor for equilibrium between Fe(III)-DFO-B and Fe(III)-catecholate at 22 °C, 0.68 ± 0.25‰, was in good agreement with a previously measured isotopic difference between bacterial cells and solution during the bacterial-mediated dissolution of hornblende [Brantley S. L., Liermann L. and Bullen T. D. (2001) Fractionation of Fe isotopes by soil microbes and organic acids. Geology29, 535-538]. Conceptually, this agreement is consistent with the notion that Fe is first removed from mineral surfaces via complexation with small organic acids (e.g., oxalate), subsequently sequestered by DFO-B in solution, and ultimately delivered to bacterial cells by Fe(III)-DFO-B complexes. The ability of DFO-B to discriminate between Fe(III) and Fe(II)/Al(III) was investigated with Natural Bond Orbital (NBO) analysis and geometry calculations of each metal-DFO-B complex. The results indicated that higher affinity for Fe(III) is not strictly a function of bond length but also the degree of Fe-O covalent bonding.

  14. A Hybrid Method for Flows in Local Chemical Equilibrium and Nonequilibrium

    NASA Astrophysics Data System (ADS)

    Currier, Nicholas G.

    The primary objective of this work is to develop a more efficient chemically active compressible Euler equation solver. Currently, a choice between the physical accuracy of a finite-rate solver or the computational efficiency of an equilibrium flow solver must be made. The number of species modeled continues to increase with available computational resources. A method of further leveraging the increase in computational power is desired. The hybrid chemistry scheme proposed here attempts to maintain the accuracy of finite-rate schemes while retaining some of the cost savings associated with equilibrium chemistry solvers. The method given uses a full finite-rate flux in regions where chemistry is slow compared to the advection rate and an equilibrium chemistry scheme in regions where the chemistry outpaces the fluid transport. Control volume switching is based on a locally defined Damkohler number. This method could be extremely useful for full reaction path modeling or the tracking of a very large number of species. The cost of symmetric Gauss-Seidel iterations grows like the number of species plus four, quantity squared. Thus, eliminating the increased cost of solving for a large number of unknowns in regions where it is unjustified can be very useful. Tenasi, a University of Tennessee SimCenter research code, is used as a base for the new solver. The hybrid method is implemented and tested with an explicit solution technique in one dimension. In combination with a five species air chemistry model, a high-temperature shock tube is used as a verification test case. Results are compared with those from pure equilibrium, full finite-rate, perfect gas Euler, and exact perfect gas Riemann solvers. Timings are also given, suggesting the cost savings that would be possible should the hybrid method be extended using implicit algorithms.

  15. Development of a non-equilibrium quantum transport calculation method based on constrained density functional

    NASA Astrophysics Data System (ADS)

    Kim, Han Seul; Kim, Yong-Hoon

    2015-03-01

    We report on the development of a novel first-principles method for the calculation of non-equilibrium quantum transport process. Within the scheme, non-equilibrium situation and quantum transport within the open-boundary condition are described by the region-dependent Δ self-consistent field method and matrix Green's function theory, respectively. We will discuss our solutions to the technical difficulties in describing bias-dependent electron transport at complicated nanointerfaces and present several application examples. Global Frontier Program (2013M3A6B1078881), Basic Science Research Grant (2012R1A1A2044793), EDISON Program (No. 2012M3C1A6035684), and 2013 Global Ph.D fellowship program of the National Research Foundation. KISTI Supercomputing Center (KSC-2014-C3-021).

  16. 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.

  17. 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.

  18. A New Method of Assessing the Extent of Topographic Equilibrium at Different Spatial Scales

    NASA Astrophysics Data System (ADS)

    Walcott, R.

    2013-12-01

    The Earth's surface represents the current resultant state of the interaction between forces working to lower topography and those working to resist this, or to raise topography. A diversity of processes generate these forces and in some cases coupled feedbacks allow a dynamic equilibrium to emerge at certain spatial and temporal scales. Dynamic equilibrium is typically expressed by distinctive geometries (e.g., regular catchment shapes, first order geometry of an orogen, constant thickness of a soil horizon over space). However, the presence of stochastic surface and tectonic processes also means that regular geometries are rarely observed at all scales. Determining the scale and temporal range over which topography can be considered to be in equilibrium can be difficult and expensive, requiring a large range of spatially distributed data, and/or data that spans significant time periods. Here we present a new morphometric method that focuses on the product of erosive competition between catchments, that is the geometry of drainage divide intersections. We use this method to show that stable areas, with minimal tectonic disturbance and homogeneous rock types have distinctive drainage divide geometry (e.g. Eastern USA) which differs from the geometry of drainage divide intersections in other environments (e.g. tectonically active regions such as the South Island of New Zealand). With a few caveats, this method could be used to predict areas prone to drainage divide migration and river network reconfiguration.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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).

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Towards bulk thermodynamics via non-equilibrium methods: gaseous methane as a case study.

    PubMed

    Zerbetto, Mirco; Frezzato, Diego

    2015-01-21

    We illustrate how the Jarzynski equality (JE), which is the progenitor of non-equilibrium methods aimed at constructing free energy landscapes for molecular-sized fluctuating systems subjected to steered transformations, can be applied to derive equations of state for bulk systems. The key-step consists of physically framing the computational strategy of "total energy morphing", recently presented by us as an efficient implementation of the JE [M. Zerbetto, A. Piserchia, D. Frezzato, J. Comput. Chem., 2014, 35, 1865-1881], in terms of build-up of the real thermodynamic state of a bulk material from the corresponding ideal state, in which the particles are non-interacting. In this context, the JE machinery yields the excess free energy versus suitably chosen controlled state variables, whose thermodynamic derivatives eventually lead to the equation of state. As an explanatory case study, we apply the methodology to derive the equation of state of gaseous methane by constructing the Helmholtz free energy versus the particle density (at fixed temperature) and then evaluating the thermodynamic derivative with respect to the volume. In our intent, this "old-style" work on gaseous methane should open the way for the investigation of thermodynamics of extended systems via non-equilibrium methods. PMID:25475171

  10. INSTRUMENTS AND METHODS OF INVESTIGATION: Plasma isotope separation based on ion cyclotron resonance

    NASA Astrophysics Data System (ADS)

    Dolgolenko, Dmitrii A.; Muromkin, Yurii A.

    2009-04-01

    Experiments that have been conducted in the USA, France, and Russia to investigate isotopically selective ion cyclotron resonance (ICR) as a tool for plasma isotope separation are analyzed. Because this method runs into difficulties at low values of the relative isotope mass difference ΔM/M, for some elements (for gadolinium, as an example) isotope separation still remains a problem. There are ways to solve it, however, as experimental results and theoretical calculations suggest.

  11. A Modal Expansion Equilibrium Cycle Perturbation Method for Optimizing High Burnup Fast Reactors

    NASA Astrophysics Data System (ADS)

    Touran, Nicholas W.

    This dissertation develops a simulation tool capable of optimizing advanced nuclear reactors considering the multiobjective nature of their design. An Enhanced Equilibrium Cycle (EEC) method based on the classic equilibrium method is developed to evaluate the response of the equilibrium cycle to changes in the core design. Advances are made in the consideration of burnup-dependent cross sections and dynamic fuel performance (fission gas release, fuel growth, and bond squeeze-out) to allow accuracy in high-burnup reactors such as the Traveling Wave Reactor. EEC is accelerated for design changes near a reference state through a new modal expansion perturbation method that expands arbitrary flux perturbations on a basis of λ-eigenmodes. A code is developed to solve the 3-D, multigroup diffusion equation with an Arnoldi-based solver that determines hundreds of the reference flux harmonics and later uses these harmonics to determine expansion coefficients required to approximate the perturbed flux. The harmonics are only required for the reference state, and many substantial and localized perturbations from this state are shown to be well-approximated with efficient expressions after the reference calculation is performed. The modal expansion method is coupled to EEC to produce the later-in-time response of each design perturbation. Because the code determines the perturbed flux explicitly, a wide variety of core performance metrics may be monitored by working within a recently-developed data management system called the ARMI. Through ARMI, the response of each design perturbation may be evaluated not only for the flux and reactivity, but also for reactivity coefficients, thermal hydraulics parameters, economics, and transient performance. Considering the parameters available, an automated optimization framework is designed and implemented. A non-parametric surrogate model using the Alternating Conditional Expectation (ACE) algorithm is trained with many design

  12. 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).

  13. 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.

  14. A comparison of Coulombic interaction methods in non-equilibrium studies of heat transfer in water

    NASA Astrophysics Data System (ADS)

    Muscatello, Jordan; Bresme, Fernando

    2011-12-01

    We investigate the impact of the treatment of electrostatic interactions on the heat conduction of liquid water. With this purpose, we report a series of non-equilibrium molecular dynamics computer simulations of the Modified Central Force Model of water. We consider both the Ewald summation approach, which includes the full range of the electrostatic interactions, and the Wolf method, which uses a cutoff to truncate the long range contributions. It is shown that the relaxation of the temperature profiles towards the stationary state solution and the equation of state of the liquid are not affected by the treatment of the electrostatic interactions. However, the truncation of the interactions results in lower internal energy fluxes as well as lower thermal conductivities. We also find that the anomalous increase of the thermal conductivity of water with temperature is reproduced by the different methods considered in this work, showing that this physical behavior is independent of the treatment of the long range electrostatic interactions.

  15. 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.

  16. A model-based method for the prediction of the isotopic distribution of peptides.

    PubMed

    Valkenborg, Dirk; Jansen, Ivy; Burzykowski, Tomasz

    2008-05-01

    The process of monoisotopic mass determination, i.e., nomination of the correct peak of an isotopically resolved group of peptide peaks as a monoisotopic peak, requires prior information about the isotopic distribution of the peptide. This points immediately to the difficulty of monoisotopic mass determination, whereas a single mass spectrum does not contain information about the atomic composition of a peptide and therefore the isotopic distribution of the peptide remains unknown. To solve this problem a technique is required, which is able to estimate the isotopic distribution given the information of a single mass spectrum. Senko et al. calculated the average isotopic distribution for any mass peptide via the multinomial expansion (Yergey 1983), using a scaled version of the average amino acid Averagine (Senko et al. 1995). Another method, introduced by Breen et al., approximates the result of the multinomial expansion by a Poisson model (Breen et al. 2000). Although both methods perform well, they have their specific limitations. In this manuscript, we propose an alternative method for the prediction of the isotopic distribution based on a model for consecutive ratios of peaks from the isotopic distribution, similar in spirit to the approach introduced by Gay et al. (1999). The presented method is computationally simple and accurate in predicting the expected isotopic distribution. Further, we extend our method to estimate the isotopic distribution of sulphur-containing peptides. This is important because the naturally occurring isotopes of sulphur have an impact on the isotopic distribution of a peptide. PMID:18325782

  17. 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.

  18. 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.

  19. Phases, periphases, and interphases equilibrium by molecular modeling. I. Mass equilibrium by the semianalytical stochastic perturbations method and application to a solution between (120) gypsum faces

    NASA Astrophysics Data System (ADS)

    Pedesseau, Laurent; Jouanna, Paul

    2004-12-01

    The SASP (semianalytical stochastic perturbations) method is an original mixed macro-nano-approach dedicated to the mass equilibrium of multispecies phases, periphases, and interphases. This general method, applied here to the reflexive relation Ck⇔μk between the concentrations Ck and the chemical potentials μk of k species within a fluid in equilibrium, leads to the distribution of the particles at the atomic scale. The macroaspects of the method, based on analytical Taylor's developments of chemical potentials, are intimately mixed with the nanoaspects of molecular mechanics computations on stochastically perturbed states. This numerical approach, directly linked to definitions, is universal by comparison with current approaches, DLVO Derjaguin-Landau-Verwey-Overbeek, grand canonical Monte Carlo, etc., without any restriction on the number of species, concentrations, or boundary conditions. The determination of the relation Ck⇔μk implies in fact two problems: a direct problem Ck⇒μk and an inverse problem μk⇒Ck. Validation of the method is demonstrated in case studies A and B which treat, respectively, a direct problem and an inverse problem within a free saturated gypsum solution. The flexibility of the method is illustrated in case study C dealing with an inverse problem within a solution interphase, confined between two (120) gypsum faces, remaining in connection with a reference solution. This last inverse problem leads to the mass equilibrium of ions and water molecules within a 3 Å thick gypsum interface. The major unexpected observation is the repulsion of SO42- ions towards the reference solution and the attraction of Ca2+ ions from the reference solution, the concentration being 50 times higher within the interphase as compared to the free solution. The SASP method is today the unique approach able to tackle the simulation of the number and distribution of ions plus water molecules in such extreme confined conditions. This result is of prime

  20. Equilibrium Iron Isotope Fractionation Factors of Minerals: Reevaluation from the Data of Nuclear Inelastic Resonant X-ray Scattering and Mossbauer Spectroscopy

    SciTech Connect

    Polyakov, Dr. V. B.; Clayton, R. N.; Horita, Juske; Mineev, S. D.

    2007-01-01

    We have critically reevaluated equilibrium iron isotope fractionation factors for oxide and sulfide minerals using recently acquired data obtained by Moessbauer spectroscopy and inelastic nuclear resonant X-ray scattering (INRXS) synchrotron radiation. Good agreement was observed in the iron {beta}-factors of metallic iron ({alpha}-Fe) and hematite calculated using both Moessbauer- and INRXS-derived data, which supports the validity and reliability of the calculations. Based on this excellent agreement, we suggest the use of the present data on the iron {beta}-factors of hematite as a reference. The previous Moessbauer-derived iron {beta}-factor for magnetite has been modified significantly based on the Fe-sublattice density of states obtained from the INRXS experiments. This resolves the disagreement between naturally observed iron isotope fractionation factors for mineral pairs involving magnetite and those obtained from the calculated {beta}-factors. The correctness of iron {beta}-factor for pyrite has been corroborated by the good agreement with experimental data of sulfur isotope geothermometers of pyrite-galena and pyrite-sphalerite. A good correlation between the potential energy of the cation site, the oxidation state of iron and the iron {beta}-factor value has been established. Specifically, ferric compounds, which have a higher potential energy of iron than ferrous compounds, have higher {beta}-factors. A similar dependence of b-factors on the oxidation state and potential energy could be extended to other transition metals. Extremely low values of INRXS-derived iron {beta}-factors for troilite and Fe{sub 3}S significantly widen the range of iron b-factors for covalently bonded compounds.

  1. Generalized non-equilibrium vertex correction method in coherent medium theory for quantum transport simulation of disordered nanoelectronics

    NASA Astrophysics Data System (ADS)

    Yan, Jiawei; Ke, Youqi

    In realistic nanoelectronics, disordered impurities/defects are inevitable and play important roles in electron transport. However, due to the lack of effective quantum transport method, the important effects of disorders remain poorly understood. Here, we report a generalized non-equilibrium vertex correction (NVC) method with coherent potential approximation to treat the disorder effects in quantum transport simulation. With this generalized NVC method, any averaged product of two single-particle Green's functions can be obtained by solving a set of simple linear equations. As a result, the averaged non-equilibrium density matrix and various important transport properties, including averaged current, disordered induced current fluctuation and the averaged shot noise, can all be efficiently computed in a unified scheme. Moreover, a generalized form of conditionally averaged non-equilibrium Green's function is derived to incorporate with density functional theory to enable first-principles simulation. We prove the non-equilibrium coherent potential equals the non-equilibrium vertex correction. Our approach provides a unified, efficient and self-consistent method for simulating non-equilibrium quantum transport through disorder nanoelectronics. Shanghaitech start-up fund.

  2. 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

  3. 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.

  4. 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%).

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

    DOEpatents

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

    2013-07-02

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

  6. 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.

  7. 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.

  8. 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.

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

    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.

    2013-07-01

    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. In most of the snow pits, nitrate loss (either by physical release or UV photolysis of nitrate) is observed and fractionation constants associated are calculated. Nitrate collected from snow pits on the plateau (snow accumulation rate below 50 kg m-2 a-1) displays average 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 fractionation constants of (-16±14) ‰, (-0.2±1.5) ‰ and (+3.1±5.8) ‰, for δ15N, Δ17O and δ18O, respectively. Our observations corroborate that photolysis (associated with a 15N / 14N fractionation constant of the order of -48 ‰ according to Frey et al. (2009) 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. Atmospheric nitrate deposition may lead to fractionation of the nitrogen isotopes and explain the almost constant shift of the order of 25 ‰ between the δ15N values in the atmospheric and skin layer nitrate at DC. Asymptotic δ15N(NO3-) values calculated for each snow pit are found to be correlated with the inverse of the snow accumulation rate (ln(δ15N as. + 1) = (5.76±0.47) ċ (kg m-2 a-1/ A) + (0.01±0.02)), confirming the strong relationship between the snow accumulation rate and the degree of isotopic

  10. 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.

  11. 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

  12. 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.

  13. A comparison of the toluene distillation and vacuum/heat methods for extracting soil water for stable isotopic analysis

    NASA Astrophysics Data System (ADS)

    Ingraham, Neil L.; Shadel, Craig

    1992-12-01

    not enough to affect the remaining unbound introduced soil water. Pretreatment of the soil to equilibrate the heat-labile water to the test water produced good results for the toluene distillation but not the vacuum/heat extraction method. Vapors collected over the soils also show stable isotopic variations related to soilwater content. These vapors also appear to be in closer equilibrium with the free water, as extracted by the toluene method, than with the originally introduced water; thus, the soil vapors do not appear to be isotopically affected by the heat-labile water. The toluene method appears to be better for extracting soil water for stable isotopic analysis because it allows more precise temperature control and excludes the extraction of heat-labile water which is isotopically fractionated. The bound nature of this heat-labile water limits association with the hydrologically active soil water; thus, the exclusion of this water from the soil water attained by toluene distillation may be advantageous. However, the azeotropic nature of toluene distillation affords no benefit and the extraction procedure must continue to completion.

  14. An isotopic exchange method for the characterization of the irreversibility of pesticide sorption-desorption in soil.

    PubMed

    Celis, R; Koskinen, W C

    1999-02-01

    An isotopic exchange method is presented that characterizes the irreversibility of pesticide sorption-desorption by soil observed in batch equilibration experiments. The isotopic exchange of (12)C- and (14)C-labeled triadimefon [(1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1, 2,4-triazol-1-yl)-2-butanone] and imidacloprid-guanidine [1-[(6-chloro-3-pyridinyl)methyl]-4,5-dihydro-1H-imidazol-2-amine] in Hanford sandy loam soil indicated that these systems can be described by a two-compartment model in which about 90% of sorption occurs on reversible, easily desorbable sites, whereas 10% of the sorbed molecules are irreversibly sorbed on soil and do not participate in the sorption-desorption equilibrium. This model closely predicted the hysteresis observed in the desorption isotherms from batch equilibration experiments. The isotopic exchange of triadimefon and imidacloprid-guanidine in Drummer silty clay loam soil indicated that there was a fraction of the sorbed (14)C-labeled pesticide that was resistant to desorption, which increased as pesticide concentration decreased and was higher for triadimefon than for imidacloprid-guanidine. In contrast, the batch equilibration method resulted in ill-defined desorption isotherms for the Drummer soil, which made accurate desorption characterization problematic. PMID:10563969

  15. 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.

  16. 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.

  17. 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.

  18. 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. PMID:27212641

  19. 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

  20. Isotopes Separation Method using Physical Vapor Deposition Technique

    NASA Astrophysics Data System (ADS)

    Javed Akhtar, S. M.; Saleem, M.; Mahmood, Nasir

    2010-02-01

    An isotope separation technique using effusive emission of vapors from the heated molybdenum boat is presented. The technique is applied for the separation of the lithium isotopes. Lithium fluoride with natural isotopic abundance was chosen for evaporation and it was achieved by resistive heating of the molybdenum boat with an exit orifice in the center that provides a point source emission. Glass substrates were placed in a semi-circle around the source of evaporation at different positions of peripheral region to deposit the evaporated material. A non-commercial laboratory developed linear Time of Flight (TOF) mass spectrometer was used for isotopic abundance measurements of lithium in the deposited thin films. The dependence of the size of exit orifice on the separation is also studied for the three exit orifices with diameters of 0.3, 0.6 and 1.0 mm. The separation factors of the isotopes as a function of different peripheral locations are calculated and presented. The abundance of the 6Li isotope has been increased up to 16% on the peripheral positions.

  1. 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

  2. Supplementing environmental isotopes with time series methods to date groundwater

    NASA Astrophysics Data System (ADS)

    Farlin, Julien

    2015-04-01

    A popular method to estimate the transit time of groundwater is to fit the predictions of a lumped parameter model (LPM) to environmental isotope measurements. The fitting, or inverse modeling, procedure consists in rejecting all parameters (or parameter combinations for more complex LPMs) that exceeds a given error threshold. In many usual cases where this does not lead to a single acceptable solution, additional and independent data can prove useful to further eliminate some of the remaining solutions. In the case study presented here, groundwater transit times have been estimated by combining tritium, temperature, and discharge measurements. Tritium measurements from a series of contact springs draining the Luxembourg Sandstone aquifer were used to estimate the two parameters of an exponential piston flow model. The piston flow parameter gives the transit time of tritium through the thick unsaturated zone of the aquifer, while the exponential component corresponds to its mean transit time in the saturated zone. Due to the limited extent of the tritium time series and the fact that tritium activity has nearly returned to its background concentration, the solution of the inverse modeling was not unique. The discharge measurements were then used to reduce the number of retained parameter combinations by estimating independently from tritium the transit time through the unsaturated and saturated zones. The former was calculated from the time lag between a time series of net annual recharge over ten years and the fluctuations in discharge over that same period, while the latter was calculated from the discharge recession during the dry season. Although both methods necessitate relatively long time series of at least a few years, they reduce dramatically the range of estimated transit times. Another possibility is to use the temperature signal measured in spring water. The amplitude damping and its shift relatively to air temperature (which we used as proxy for the

  3. Reducing the matrix effects in chemical analysis: fusion of isotope dilution and standard addition methods

    NASA Astrophysics Data System (ADS)

    Pagliano, Enea; Meija, Juris

    2016-04-01

    The combination of isotope dilution and mass spectrometry has become an ubiquitous tool of chemical analysis. Often perceived as one of the most accurate methods of chemical analysis, it is not without shortcomings. Current isotope dilution equations are not capable of fully addressing one of the key problems encountered in chemical analysis: the possible effect of sample matrix on measured isotope ratios. The method of standard addition does compensate for the effect of sample matrix by making sure that all measured solutions have identical composition. While it is impossible to attain such condition in traditional isotope dilution, we present equations which allow for matrix-matching between all measured solutions by fusion of isotope dilution and standard addition methods.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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)

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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...

  15. 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.

  16. 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…

  17. METHOD TO QUANTIFY THE CARBON CYCLE OF FOREST BIOMES IN THE FORMER SOVIET UNION (EQUILIBRIUM ANALYSIS)

    EPA Science Inventory

    Human activities have caused a measurable increase in the atmospheric concentration of CO2 which is predicted to cause the earth's temperatures to rise and accelerate rates of plant respiration and the decay of organic matter, disrupting the equilibrium of the terrestrial carbon ...

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Viscosity-projection method for a family of general equilibrium problems and asymptotically strict pseudocontractions in the intermediate sense.

    PubMed

    Wen, Dao-Jun

    2013-01-01

    In this paper, a Meir-Keeler contraction is introduced to propose a viscosity-projection approximation method for finding a common element of the set of solutions of a family of general equilibrium problems and the set of fixed points of asymptotically strict pseudocontractions in the intermediate sense. Strong convergence of the viscosity iterative sequences is obtained under some suitable conditions. Results presented in this paper extend and unify the previously known results announced by many other authors. PMID:24285937

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Equilibrium strategy-based optimization method for the coal-water conflict: A perspective from China.

    PubMed

    Xu, Jiuping; Lv, Chengwei; Zhang, Mengxiang; Yao, Liming; Zeng, Ziqiang

    2015-09-01

    Environmental water problems have become increasingly severe, with the coal-water conflict becoming one of the most difficult issues in large scale coal mining regions. In this paper, a bi-level optimization model based on the Stackelberg-Nash equilibrium strategy with fuzzy coefficients is developed to deal with environmental water problems in large scale coal fields, in which both the groundwater quality and quantity are considered. Using the proposed model, and fully considering the relationship between the authority and the collieries and also the equilibrium between economic development and environmental protection, an environmental protection based mining quotas competition mechanism is established. To deal with the inherent uncertainties, the model is defuzzified using a possibility measure, and a solution approach based on the Karush-Kuhn-Tucker condition is designed to search for the solutions. A case study is presented to demonstrate the practicality and efficiency of the model, and different constraint violation risk levels and related results are also obtained. The results showed that under the environmental protection based mining quotas competition mechanism, collieries attempt to conduct environmentally friendly exploitation to seek greater mining quotas. This demonstrates the practicality and efficiency in the proposed model of reducing the coal-water conflict. Finally, a comprehensive discussion is provided and some propositions is given as a foundation for the proposed management recommendations. PMID:26144559

  13. Magnetic measurement based methods in determination of plasma equilibrium parameters in Damavand tokamak

    NASA Astrophysics Data System (ADS)

    Noori, E.; Sadeghi, Y.; Mehdian, H.

    2016-06-01

    Determination of plasma equilibrium parameters such as poloidal beta (βp) with half of plasma internal inductance (li) known as Shafranov parameter (asymmetry factor) (βp+𝔡li2) and edge safety factor plays very important role in primary equilibrium and stability analysis and control of tokamak plasma. In this study, the well known Shafranov semi-empirical model, based on external magnetic measurements is used to extract Shafranov parameter and effective edge safety factor in low-β operating regime of Damavand tokamak. The well known integral representation of βp+𝔡li2 was modified for non-circular tokamaks with ellipse-like cross section. After calibration of magnetic pick-up coils, Shafranov parameter was estimated with respect to the first and second Fourier harmonic of radial and poloidal components of magnetic field. The results were compared with approximate, semi-analytical determination of Shafranov parameter which is based on analytical solution of Grad-Shafranov equation (GSE). Founding evolution of Shafranov parameter, effective edge safety factor was obtained in terms of Shafranov parameter and compared with semi-empirical description. It was found that between the ramp-up and ramp-down domain of the plasma current, the result from Shafranov model is approximately in good agreement with the semi-analytical and semi-empirical benchmarks and the integral model provides more reliable trace of the Shafranov parameter in out of ramp domains of the discharge.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  15. 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.

  16. 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.

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

    DOEpatents

    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.

  18. 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.

  19. A hybrid smoothed extended finite element/level set method for modeling equilibrium shapes of nano-inhomogeneities

    NASA Astrophysics Data System (ADS)

    Zhao, Xujun; Bordas, Stéphane P. A.; Qu, Jianmin

    2013-12-01

    Interfacial energy plays an important role in equilibrium morphologies of nanosized microstructures of solid materials due to the high interface-to-volume ratio, and can no longer be neglected as it does in conventional mechanics analysis. When designing nanodevices and to understand the behavior of materials at the nano-scale, this interfacial energy must therefore be taken into account. The present work develops an effective numerical approach by means of a hybrid smoothed extended finite element/level set method to model nanoscale inhomogeneities with interfacial energy effect, in which the finite element mesh can be completely independent of the interface geometry. The Gurtin-Murdoch surface elasticity model is used to account for the interface stress effect and the Wachspress interpolants are used for the first time to construct the shape functions in the smoothed extended finite element method. Selected numerical results are presented to study the accuracy and efficiency of the proposed method as well as the equilibrium shapes of misfit particles in elastic solids. The presented results compare very well with those obtained from theoretical solutions and experimental observations, and the computational efficiency of the method is shown to be superior to that of its most advanced competitor.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. In vitro interaction study of retinoic acid isomers with telmisartan and amlodipine by equilibrium dialysis method using UV spectroscopy

    NASA Astrophysics Data System (ADS)

    Varghese, Susheel John; Johny, Sojimol K.; Paul, David; Ravi, Thengungal Kochupappy

    2011-07-01

    The in vitro protein binding of retinoic acid isomers (isotretinoin and tretinoin) and the antihypertensive drugs (amlodipine and telmisartan) was studied by equilibrium dialysis method. In this study, free fraction of drugs and the % of binding of drugs in the mixture to bovine serum albumin (BSA) were calculated. The influence of retinoic acid isomers on the % of protein binding of telmisartan and amlodipine at physiological pH (7.4) and temperature (37 ± 0.5 °C) was also evaluated. The in vitro displacement interaction study of drugs telmisartan and amlodipine on retinoic acid isomers and also interaction of retinoic acid isomers on telmisartan and amlodipine were carried out.

  5. Hydrogen Isotope Behavior in Type 316 Stainless Steel Sorbed by Various Methods

    SciTech Connect

    Oya, Y.; Onishi, Y.; Okuno, K.; Kawano, T.; Asakura, Y.; Uda, T.; Tanaka, S.

    2005-07-15

    Typical materials for components, type 316 stainless steel (316-SS), were chosen as a sample and hydrogen isotope was charged by various methods, water adsorption, electrolysis and ion irradiation to elucidate hydrogen isotope behavior on/in SS. The chemical states of SS surface were studied by XPS and the hydrogen isotope retention and its desorption behavior were analyzed by TDS. Two types of surface finish, namely non-pretreated sample and pretreated sample by polish and annealing were prepared. It was found that the oxy-hydroxide and hydroxide were formed on the surface layer. The hydrogen isotope desorption stages consisted of three stages, namely the desorption stages from oxy-hydroxide, hydroxide and bulk hydrogen. A large amount of deuterium was trapped by the oxy-hydroxide layer for the non-pretreated sample with electrolysis. The hydrogen isotope trapping by this layer would have a large influence on the hydrogen isotope retention. The surface finish would be one of the effective improvement for decreasing its retention on SS.

  6. 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.

  7. A robust and efficient numerical method for multiphase equilibrium calculations: Application to CO2-brine-rock systems at high temperatures, pressures and salinities

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Blunt, Martin J.; LaForce, Tara C.

    2013-12-01

    We present a robust and efficient method for calculating chemical equilibria of general multiphase systems. The method is based on a stoichiometric approach, which uses Newton's method to solve a system of mass-action equations coupled with a system of equilibrium constraints. A stabilisation procedure is developed to promote convergence of the calculation when a presupposed phase in the chemical system is absent in the equilibrium state. The formulation of the chemical equilibrium problem is developed by presuming no specific details of the involved phases and species. As a consequence, the method is flexible and general enough so that the calculation can be customised with a combination of thermodynamic models that are appropriate for the problem of interest. Finally, we show the use of the method to solve relevant geochemical equilibrium problems for modelling carbon storage in highly saline aquifers.

  8. Computational Efficiency and Accuracy of the Two Forms of the Rate-Controlled Constrained-Equilibrium Method

    NASA Astrophysics Data System (ADS)

    Hadi, Fatemeh; Sheikhi, Reza

    2015-11-01

    In this study, the Rate-Controlled Constrained-Equilibrium (RCCE) method in constraint potential and constraint forms have been investigated in terms of accuracy and numerical performance. The RCCE originates from the observation that chemical systems evolve based on different time scales, dividing reactions into rate-controlling and fast reactions. Each group of rate-controlling reactions imposes a slowly changing constraint on the allowed states of the system. The fast reactions relax the system to the associated constrained-equilibrium state on a time scale shorter than that of constraints. The two RCCE formulations are equivalent mathematically; however, they involve different numerical procedures and thus show different computational performance. In this work, the RCCE method is applied to study methane oxygen combustion in an adiabatic, isobaric stirred reactor. The RCCE results are compared with those obtained by direct integration of detailed chemical kinetics. Both methods are shown to provide very accurate representation of the kinetics. It is also evidenced that while the constraint form involves less numerical stiffness, the constraint potential implementation results in more overall saving in computation time.

  9. 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. ...

  10. 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. ...

  11. 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

  12. 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.

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

    NASA Astrophysics Data System (ADS)

    Moawad, S. M.

    2015-02-01

    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.

  14. 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.

  15. Isotopic quantum effects in liquid methanol.

    PubMed

    Ludwig, Ralf

    2005-07-11

    Density functional calculations (B3 LYP/6-31+G*) on molecular clusters and a quantum cluster equilibrium (QCE) model were used to calculate thermodynamic and structural properties of four isotopically labeled methanol species. The method allowed the reproduction of the characteristic differences in boiling points and heats of vaporization. Structural changes were also detected and related to recent experimental findings. It was shown that isotopic effects clearly have a quantum-mechanical origin. PMID:15991271

  16. 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...

  17. Partition Equilibrium

    NASA Astrophysics Data System (ADS)

    Feldman, Michal; Tennenholtz, Moshe

    We introduce partition equilibrium and study its existence in resource selection games (RSG). In partition equilibrium the agents are partitioned into coalitions, and only deviations by the prescribed coalitions are considered. This is in difference to the classical concept of strong equilibrium according to which any subset of the agents may deviate. In resource selection games, each agent selects a resource from a set of resources, and its payoff is an increasing (or non-decreasing) function of the number of agents selecting its resource. While it has been shown that strong equilibrium exists in resource selection games, these games do not possess super-strong equilibrium, in which a fruitful deviation benefits at least one deviator without hurting any other deviator, even in the case of two identical resources with increasing cost functions. Similarly, strong equilibrium does not exist for that restricted two identical resources setting when the game is played repeatedly. We prove that for any given partition there exists a super-strong equilibrium for resource selection games of identical resources with increasing cost functions; we also show similar existence results for a variety of other classes of resource selection games. For the case of repeated games we identify partitions that guarantee the existence of strong equilibrium. Together, our work introduces a natural concept, which turns out to lead to positive and applicable results in one of the basic domains studied in the literature.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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…

  5. Equilibrium properties of quantum water clusters by the variational Gaussian wavepacket method.

    PubMed

    Frantsuzov, Pavel A; Mandelshtam, Vladimir A

    2008-03-01

    The variational Gaussian wavepacket (VGW) method in combination with the replica-exchange Monte Carlo is applied to calculations of the heat capacities of quantum water clusters, (H(2)O)(8) and (H(2)O)(10). The VGW method is most conveniently formulated in Cartesian coordinates. These in turn require the use of a flexible (i.e., unconstrained) water potential. When the latter is fitted as a linear combination of Gaussians, all the terms involved in the numerical solution of the VGW equations of motion are analytic. When a flexible water model is used, a large difference in the timescales of the inter- and intramolecular degrees of freedom generally makes the system very difficult to simulate numerically. Yet, given this difficulty, we demonstrate that our methodology is still practical. We compare the computed heat capacities to those for the corresponding classical systems. As expected, the quantum effects shift the melting temperatures toward the lower values. PMID:18331090

  6. General Retarded Contact Self-energies in and beyond the Non-equilibrium Green's Functions Method

    NASA Astrophysics Data System (ADS)

    Kubis, Tillmann; He, Yu; Andrawis, Robert; Klimeck, Gerhard

    2016-03-01

    Retarded contact self-energies in the framework of nonequilibrium Green's functions allow to model the impact of lead structures on the device without explicitly including the leads in the actual device calculation. Most of the contact self-energy algorithms are limited to homogeneous or periodic, semi-infinite lead structures. In this work, the complex absorbing potential method is extended to solve retarded contact self-energies for arbitrary lead structures, including irregular and randomly disordered leads. This method is verified for regular leads against common approaches and on physically equivalent, but numerically different irregular leads. Transmission results on randomly alloyed In0.5Ga0.5As structures show the importance of disorder in the leads. The concept of retarded contact self-energies is expanded to model passivation of atomically resolved surfaces without explicitly increasing the device's Hamiltonian.

  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. Helical equilibrium

    SciTech Connect

    Yoshikawa, S.

    1981-08-01

    A straight, helical plasma equilibrium equation is solved numerically for a plasma with a helical magnetic axis. As is expected, by a suitable choice of the plasma boundary, the vacuum configuration is made line ..integral.. dl/B stable. As the plasma pressure increases, the line ..integral.. dl/B criterion will improve (again as expected). There is apparently no limit on the plasma ..beta.. from the equilibrium consideration. Thus helical-axis stellarator ..beta.. will presumably be limited by MHD stability ..beta.., and not by equilibrium ..beta...

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  11. 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

  12. 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.

  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. 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.

  15. 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

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-11-01

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

  18. New online method for water isotope analysis of fluid inclusions in speleothems

    NASA Astrophysics Data System (ADS)

    Affolter, Stéphane; Leuenberger, Markus; Fleitmann, Dominik

    2013-04-01

    Speleothems are increasingly becoming key archives for paleoclimate reconstruction. The fluid inclusions contained in these speleothems represent natural repositories of cave drip waters. The hydrogen (δD) and oxygen (δ18O) isotopic composition of fluid inclusions can yield direct information on the isotopic composition of paleoprecipitation, which can then be combined with isotopic analyses of speleothem calcite to either directly calculate paleotemperatures or to reveal changes in the source of moisture. To liberate speleothem fluid inclusion water and to measure its isotopic composition, a new method was developed. It consists of a simple hydraulic crushing device similar to the one used to extract noble gases from fluid inclusions. Prior to crushing, the sample tube is conditioned by heating and flushing with nitrogen in order to release adsorbed water. Thereafter, the speleothem sample (approximately 1g of calcite) is crushed and the released water from fluid inclusions is transferred by a nitrogen gas stream to a laser spectrometer using a wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) technology that allows us to simultaneously monitor hydrogen and oxygen isotopes. The main task we would like to address with this method is a comparison between the isotope signals of the fluid inclusion and calcite to reduce uncertainties associated with the interpretation of calcite δ18O values in speleothems in Switzerland and Turkey. Currently, we are mainly focussing on a stalagmite (M6) from Milandre cave, Jura, Switzerland. We installed a high precision drip logger, which continuously counts the number of water drops per time unit using an acoustic technique. This way we can monitor the drip water rate at the sampling site and collect drip water, which was originally dripping and precipitating on the M6 stalagmite. In parallel, we collected rainfall water at the MeteoSwiss station "Le Mormont" located close to the cave. Thus we are able to compare δD and

  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 20ngg(-1). The model finds out some correlations within the parameters affect the measurements precision and predicts suitable sample measurement precisions for Hg concentrations from 5ngg(-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. Treatment methods for the determination of delta2H and delta18O of hair keratin by continuous-flow isotope-ratio mass spectrometry.

    PubMed

    Bowen, Gabriel J; Chesson, Lesley; Nielson, Kristine; Cerling, Thure E; Ehleringer, James R

    2005-01-01

    The structural proteins that comprise approximately 90% of animal hair have the potential to record environmentally and physiologically determined variation in delta2H and delta18O values of body water. Broad, systematic, geospatial variation in stable hydrogen and oxygen isotopes of environmental water and the capacity for rapid, precise measurement via methods such as high-temperature conversion elemental analyzer/isotope ratio mass spectrometry (TC/EA-IRMS) make these isotope systems particularly well suited for applications requiring the geolocation of hair samples. In order for such applications to be successful, however, methods must exist for the accurate determination of hair delta2H and delta18O values reflecting the primary products of biosynthesis. Here, we present the results of experiments designed to examine two potential inaccuracies affecting delta2H and delta18O measurements of hair: the contribution of non-biologic hydrogen and oxygen to samples in the form of sorbed molecular water, and the exchange of hydroxyl-bound hydrogen between hair keratin and ambient water vapor. We show that rapid sorption of molecular water from the atmosphere can have a substantial effect on measured delta2H and delta18O values of hair (comprising approximately 7.7% of the measured isotopic signal for H and up to approximately 10.6% for O), but that this contribution can be effectively removed through vacuum-drying of samples for 6 days. Hydrogen exchange between hair keratin and ambient vapor is also rapid (reaching equilibrium within 3-4 days), with 9-16% of the total hydrogen available for exchange at room temperature. Based on the results of these experiments, we outline a recommended sample treatment procedure for routine measurement of delta2H and delta18O in mammal hair. PMID:16047316

  1. Evolution of the South African mantle — A case study of garnet peridotites from the Finsch diamond mine (Kaapvaal craton); part 1: Inter-mineral trace element and isotopic equilibrium

    NASA Astrophysics Data System (ADS)

    Lazarov, Marina; Brey, Gerhard P.; Weyer, Stefan

    2012-12-01

    A thorough assessment of inter-mineral equilibrium is essential for the understanding of trace element partitioning and also for the interpretation of isotopic data. Here we investigated high temperature (~ 1200 °C and 6 GPa) garnet peridotite xenoliths from the Kaapvaal craton (Finsch mine, South Africa), with exceptionally well equilibrated mineral major element compositions, for their trace element and isotopic inter-mineral equilibrium. Trace element compositions for all major mineral phases, i.e. olivine, orthopyroxene (opx), clinopyroxene (cpx) and garnet, were analysed by laser ablation inductively coupled plasma mass spectrometry (ICP-MS). Garnet, cpx and opx of selected samples were analysed for their Sm-Nd and Lu-Hf isotope compositions by multi collector ICP-MS. Most important mineral characteristics include: a) olivines from most samples are enriched in high-field-strength elements relative to other incompatible trace elements. Their lithium content correlates negatively with Mg#, indicating a depletion signature; b) all other minerals are depleted in heavy and middle rare earth elements (H- and M-REE) and enriched in light REE and large ion lithophile elements. This implies a complex history of depletion and metasomatic overprint for the Finsch cratonic mantle; c) orthopyroxene has similarly shaped trace element patterns as cpx, with one to two orders of magnitude lower abundances; and d) both, garnet and cpx, display variable, mostly positive ɛHf coupled with moderate variations in ɛNd. Trace element partitioning between garnet/cpx, cpx/opx and garnet/opx, displays only a weak pressure and temperature dependency. However, equilibrium partitioning of most trace elements between garnet and cpx shows a strong compositional dependency, i.e. on the Cr- (and Ca-) content of the garnets. Garnet-cpx partition coefficients follow a second grade polynomial correlation with Cr2O3 of garnet, whereby high chromium garnets (Cr2O3 > 6 wt.%) have generally higher

  2. Isotopically sensitive branching and its effect on the observed intramolecular isotope effects in cytochrome P-450 catalyzed reactions: a new method for the estimation of intrinsic isotope effects

    SciTech Connect

    Jones, J.P.; Korzekwa, K.R.; Rettie, A.E.; Trager, W.F.

    1986-10-29

    Two selectively deuterated n-octanes (octane-1-/sup 2/H/sub 3/ and octane-1,2,3-/sup 2/H/sub 7/) were synthesized and subjected to hydroxylation by phenobarbital-induced rat liver microsomes and purified cytochrome P-450b. The results of these experiments provide evidence which clarifies the interplay between a branched reaction pathway and the equilibration of an enzyme-substrate complex, in determining the magnitude of an observed isotope effect. An equation is derived that allows limits to placed on the intrinsic isotope effect. The equation is based on the observed isotope effect and the regioselectivity of a branch reaction pathway, catalyzed by an enzyme that forms two products via a single enzyme-substrate complex. The intrinsic isotope effect for the formation of 1-octanol was determined by this equation to lie between 9.5 and 9.8.

  3. 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.

  4. 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).

  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. 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.

  7. 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

  8. 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.

  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. 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