Predictive Framework and Experimental Tests of the Kinetic Isotope Effect at Redox-Active Interfaces

NASA Astrophysics Data System (ADS)

Kavner, A.; John, S.; Black, J. R.

2013-12-01

Electrochemical reactions provide a compelling framework to study kinetic isotope effects because redox-related processes are important for a wide variety of geological and environmental processes. In the laboratory, electrochemical reaction rates can be electronically controlled and measured in the laboratory using a potentiostat. This enables variation of redox reactions rates independent of changes in chemistry and, and the resulting isotope compositions of reactants and products can be separated and analyzed. In the past years, a series of experimental studies have demonstrated a large, light, and tunable kinetic isotope effect during electrodeposition of metal Fe, Zn, Li, Cu, and Mo from a variety of solutions (e.g. Black et al., 2009, 2010, 2011). A theoretical framework based on Marcus kinetic theory predicts a voltage-dependent kinetic isotope effect (Kavner et al., 2005, 2008), however while this framework was able to predict the tunable nature of the effect, it was not able to simultaneously predict absolute reaction rates and relative isotope rates. Here we present a more complete development of a statistical mechanical framework for simple interfacial redox reactions, which includes isotopic behavior. The framework is able to predict a kinetic isotope effect as a function of temperature and reaction rate, starting with three input parameters: a single reorganization energy which describes the overall kinetics of the electron transfer reaction, and the equilibrium reduced partition function ratios for heavy and light isotopes in the product and reactant phases. We show the framework, elucidate some of the predictions, and show direct comparisons against isotope fractionation data obtained during laboratory and natural environment redox processes. A. Kavner, A. Shahar, F. Bonet, J. Simon and E. Young (2005) Geochim. Cosmochim. Acta, 69(12), 2971-2979. A. Kavner, S. G. John, S. Sass, and E. A. Boyle (2008), Geochim. Cosmochim. Acta, vol 72, pp. 1731

Kinetic isotope effects and how to describe them

PubMed Central

Karandashev, Konstantin; Xu, Zhen-Hao; Meuwly, Markus; Vaníček, Jiří; Richardson, Jeremy O.

2017-01-01

We review several methods for computing kinetic isotope effects in chemical reactions including semiclassical and quantum instanton theory. These methods describe both the quantization of vibrational modes as well as tunneling and are applied to the ⋅H + H2 and ⋅H + CH4 reactions. The absolute rate constants computed with the semiclassical instanton method both using on-the-fly electronic structure calculations and fitted potential-energy surfaces are also compared directly with exact quantum dynamics results. The error inherent in the instanton approximation is found to be relatively small and similar in magnitude to that introduced by using fitted surfaces. The kinetic isotope effect computed by the quantum instanton is even more accurate, and although it is computationally more expensive, the efficiency can be improved by path-integral acceleration techniques. We also test a simple approach for designing potential-energy surfaces for the example of proton transfer in malonaldehyde. The tunneling splittings are computed, and although they are found to deviate from experimental results, the ratio of the splitting to that of an isotopically substituted form is in much better agreement. We discuss the strengths and limitations of the potential-energy surface and based on our findings suggest ways in which it can be improved. PMID:29282447

Kinetic theory of oxygen isotopic exchange between minerals and water

USGS Publications Warehouse

Criss, R.E.; Gregory, R.T.; Taylor, H.P.

1987-01-01

Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

Kinetic 15N-isotope effects on algal growth

NASA Astrophysics Data System (ADS)

Andriukonis, Eivydas; Gorokhova, Elena

2017-03-01

Stable isotope labeling is a standard technique for tracing material transfer in molecular, ecological and biogeochemical studies. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism metabolism and growth, which is not consistent with current theoretical and empirical knowledge on kinetic isotope effects. Here, we demonstrate profound changes in growth dynamics of the green alga Raphidocelis subcapitata grown in 15N-enriched media. With increasing 15N concentration (0.37 to 50 at%), the lag phase increased, whereas maximal growth rate and total yield decreased; moreover, there was a negative relationship between the growth and the lag phase across the treatments. The latter suggests that a trade-off between growth rate and the ability to adapt to the high 15N environment may exist. Remarkably, the lag-phase response at 3.5 at% 15N was the shortest and deviated from the overall trend, thus providing partial support to the recently proposed Isotopic Resonance hypothesis, which predicts that certain isotopic composition is particularly favorable for living organisms. These findings confirm the occurrence of KIE in isotopically enriched algae and underline the importance of considering these effects when using stable isotope labeling in field and experimental studies.

Carbon kinetic isotope effect in the reaction of CH4 with HO

NASA Technical Reports Server (NTRS)

Davidson, J. A.; Cantrell, C. A.; Tyler, S. C.; Shetter, R. E.; Cicerone, R. J.

1987-01-01

The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

Kinetics of Fe Release from Organic Ligand Complexes: Implications for Fe Isotopes?

NASA Astrophysics Data System (ADS)

Nuester, J.; Liermann, L. J.; Brantley, S. L.

2006-12-01

Although iron is the fourth most abundant element in the earth's surface, its bioavailability is limited by its natural tendency to form insoluble iron (oxyhydr)oxides in terrestrial and marine environments. Paradoxically, iron is an essential nutrient for virtually all living cells, so in order to survive, organisms must develop mechanisms to solubilize iron. To acquire iron, organisms synthesize and release iron-specific chelators called siderophores. These siderophores facilitate the transformation of insoluble crystal-bound iron to organically ligand-bound dissolved iron. The reverse process whereby ferric iron is released from siderophores resulting in the precipitation of iron (oxyhydr)oxides or complexation by other iron chelators is an important but not well studied process in the B-horizon of soils. Fe mobility is documented in soils where Fe is often extracted at the top and precipitated at depth. Both the concentration and isotopic signature of Fe varies with depth due to dissolution, precipitation, sorption, and biological processes. Our study is focused on measurement of isotopic fractionation during this reverse process. In a first approach to understand iron liberation form organic ligands, we mimic this process using a reductive mechanism. We use acetohydroxamic acid (aha), EDTA and desferrioxamine B (DFMB) as test ligands to investigate iron release by sodium ascorbate at varying pH. Our first kinetic measurements showed significant differences in iron release depending on pH and stability of the iron complex. Within one hour all iron is released from aha with a small pH effect in the pH range between 4 and 6. In contrast, the pH has a major influence on the iron release from EDTA and DFMB. Depending on pH, total iron is released from EDTA within 24 hours, while only an incomplete iron release from DFMB could be observed within two weeks. These strong kinetic differences in iron release as a consequence of iron reduction are expected to result in

Kinetic and metabolic isotope effects in coral skeletal carbon isotopes: A re-evaluation using experimental coral bleaching as a case study

NASA Astrophysics Data System (ADS)

Schoepf, Verena; Levas, Stephen J.; Rodrigues, Lisa J.; McBride, Michael O.; Aschaffenburg, Matthew D.; Matsui, Yohei; Warner, Mark E.; Hughes, Adam D.; Grottoli, Andréa G.

2014-12-01

Coral skeletal δ13C can be a paleo-climate proxy for light levels (i.e., cloud cover and seasonality) and for photosynthesis to respiration (P/R) ratios. The usefulness of coral δ13C as a proxy depends on metabolic isotope effects (related to changes in photosynthesis) being the dominant influence on skeletal δ13C. However, it is also influenced by kinetic isotope effects (related to calcification rate) which can overpower metabolic isotope effects and thus compromise the use of coral skeletal δ13C as a proxy. Heikoop et al. (2000) proposed a simple data correction to remove kinetic isotope effects from coral skeletal δ13C, as well as an equation to calculate P/R ratios from coral isotopes. However, despite having been used by other researchers, the data correction has never been directly tested, and isotope-based P/R ratios have never been compared to P/R ratios measured using respirometry. Experimental coral bleaching represents a unique environmental scenario to test this because bleaching produces large physiological responses that influence both metabolic and kinetic isotope effects in corals. Here, we tested the δ13C correction and the P/R calculation using three Pacific and three Caribbean coral species from controlled temperature-induced bleaching experiments where both the stable isotopes and the physiological variables that cause isotopic fractionation (i.e., photosynthesis, respiration, and calcification) were simultaneously measured. We show for the first time that the data correction proposed by Heikoop et al. (2000) does not effectively remove kinetic effects in the coral species studied here, and did not improve the metabolic signal of bleached and non-bleached corals. In addition, isotope-based P/R ratios were in poor agreement with measured P/R ratios, even when the data correction was applied. This suggests that additional factors influence δ13C and δ18O, which are not accounted for by the data correction. We therefore recommend that the

Solvent and α-secondary kinetic isotope effects on β-glucosidase.

PubMed

Xie, Miaomiao; Byers, Larry D

2015-11-01

β-Glucosidase from sweet almond is a retaining, family 1, glycohydrolase. It is known that glycosylation of the enzyme by aryl glucosides occurs with little, if any, acid catalysis. For this reaction both the solvent and α-secondary kinetic isotope effects are 1.0. However, for the deglucosylation reaction (e.g., kcat for 2,4-dinitrophenyl-β-D-glucopyranoside) there is a small solvent deuterium isotope effect of 1.50 (±0.06) and an α-secondary kinetic isotope effect of 1.12 (±0.03). For aryl glucosides, kcat/KM is very sensitive to the pKa of the phenol leaving group [βlg≈-1; Dale et al., Biochemistry25 (1986) 2522-2529]. With alkyl glucosides the βlg is smaller (between -0.2 and -0.3) but still negative. This, coupled with the small solvent isotope effect on the pH-independent second-order rate constant for the glucosylation of the enzyme with 2,2,2-trifluoroethyl-β-glucoside [D2O(kcat/KM)=1.23 (±0.04)] suggests that there is more glycone-aglycone bond fission than aglycone oxygen protonation in the transition state for alkyl glycoside hydrolysis. The kinetics constants for the partitioning (between water and various alcohols) of the glucosyl-enzyme intermediate, coupled with the rate constants for the forward (hydrolysis) reaction provide an estimate of the stability of the glucosyl-enzyme intermediate. This is a relatively stable species with an energy about 2 to 4 kcal/mol higher than that of the ES complex. This article is part of a Special Issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

Heavy atom labeled nucleotides for measurement of kinetic isotope effects.

PubMed

Weissman, Benjamin P; Li, Nan-Sheng; York, Darrin; Harris, Michael; Piccirilli, Joseph A

2015-11-01

Experimental analysis of kinetic isotope effects represents an extremely powerful approach for gaining information about the transition state structure of complex reactions not available through other methodologies. The implementation of this approach to the study of nucleic acid chemistry requires the synthesis of nucleobases and nucleotides enriched for heavy isotopes at specific positions. In this review, we highlight current approaches to the synthesis of nucleic acids enriched site specifically for heavy oxygen and nitrogen and their application in heavy atom isotope effect studies. This article is part of a special issue titled: Enzyme Transition States from Theory and Experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

Kinetic deuterium isotope effects in glucocorticoid receptor activation

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

Aranyi, P.

1984-01-01

Activation and deactivation of the chick thymus glucocorticoid receptor protein was studied in ordinary and heavy water by DNA-cellulose binding of the tritiated triamcinolone acetonide-receptor complex. Activation was significantly slower in heavy water if it was promoted by incubation at elevated temperature in buffers of low ionic strength. In the presence of 300 mM KC1 or after separation from the low molecular weight cytosol constituents, the complex was activated at the same rate in both solvents. Deactivation (time dependent loss of DNA-binding capacity) was much faster in ordinary than in heavy water regardless of gel filtration or the presence ofmore » KC1. A model of receptor activation-deactivation was constructed on the basis of these data that accounts for the observed kinetic deuterium isotope effects and reveals some submolecular details of the process.« less

Observation of the isotope effect in sub-kelvin reactions

NASA Astrophysics Data System (ADS)

Lavert-Ofir, Etay; Shagam, Yuval; Henson, Alon B.; Gersten, Sasha; Kłos, Jacek; Żuchowski, Piotr S.; Narevicius, Julia; Narevicius, Edvardas

2014-04-01

Quantum phenomena in the translational motion of reactants, which are usually negligible at room temperature, can dominate reaction dynamics at low temperatures. In such cold conditions, even the weak centrifugal force is enough to create a potential barrier that keeps reactants separated. However, reactions may still proceed through tunnelling because, at low temperatures, wave-like properties become important. At certain de Broglie wavelengths, the colliding particles can become trapped in long-lived metastable scattering states, leading to sharp increases in the total reaction rate. Here, we show that these metastable states are responsible for a dramatic, order-of-magnitude-strong, quantum kinetic isotope effect by measuring the absolute Penning ionization reaction rates between hydrogen isotopologues and metastable helium down to 0.01 K. We demonstrate that measurements of a single isotope are insufficient to constrain ab initio calculations, making the kinetic isotope effect in the cold regime necessary to remove ambiguity among possible potential energy surfaces.

Mechanistic Analysis of Oxidative C–H Cleavages Using Inter- and Intramolecular Kinetic Isotope Effects

PubMed Central

Jung, Hyung Hoon; Floreancig, Paul E.

2009-01-01

A series of monodeuterated benzylic and allylic ethers were subjected to oxidative carbon–hydrogen bond cleavage to determine the impact of structural variation on intramolecular kinetic isotope effects in DDQ-mediated cyclization reactions. These values are compared to the corresponding intermolecular kinetic isotope effects that were accessed through subjecting mixtures of non-deuterated and dideuterated substrates to the reaction conditions. The results indicate that carbon–hydrogen bond cleavage is rate determining and that a radical cation is most likely a key intermediate in the reaction mechanism. PMID:20640173

An improved pyrite pretreatment protocol for kinetic and isotopic studies

NASA Astrophysics Data System (ADS)

Mirzoyan, Natella; Kamyshny, Alexey; Halevy, Itay

2014-05-01

, and was capable of removing virtually all S0 from the pyrite grains. As pyrite oxidation and dissolution processes are surface-dependent, and even the slightest coating by Fe2+ or sulfide oxidation products can sharply decrease pyrite reactivity, the improved removal of S0 prevents such decreases and allows clearer insights into pyrite reaction mechanisms to be gained from experimental studies. In addition to S0 removal, the suggested method was shown not to introduce any biases in the particle size distribution. The main difference observed between the two protocols is the removal of larger amounts of surface-attached fine particles in the proposed method along with S0. This also removes a potential bias, associated with the surface area of pyrite available for chemical reaction. The suggested pyrite pretreatment protocol is more efficient in removal of S0 contamination from pyrite grains and provides multiple advantages for both kinetic and isotopic investigations of pyrite transformations under various environmental conditions.

Kinetic fractionation of stable nitrogen isotopes during amino acid transamination

NASA Astrophysics Data System (ADS)

Macko, Stephen A.; Estep, Marilyn L. Fogel; Engel, Michael H.; Hare, P. E.

1986-10-01

This study evaluates a kinetic isotope effect involving 15N, during the transamination reactions catalyzed by glutamic oxalacetic transaminase. During the transfer of amino nitrogen from glutamic acid to oxaloacetate to form aspartic acid, 14NH 2 reacted 1.0083 times faster than 14NH 2. In the reverse reaction transferring NH 2 from aspartic acid to α-ketoglutarate, 14NH 2 was incorporated 1.0017 times faster than 15NH 2. Knowledge of the magnitude and sign of these isotope effects will be useful in the interpretation of the distribution of 15N in biological and geochemical systems.

A kinetic model for thermally induced hydrogen and carbon isotope fractionation of individual n-alkanes in crude oil

NASA Astrophysics Data System (ADS)

Tang, Yongchun; Huang, Yongsong; Ellis, Geoffrey S.; Wang, Yi; Kralert, Paul G.; Gillaizeau, Bruno; Ma, Qisheng; Hwang, Rong

2005-09-01

A quantitative kinetic model has been proposed to simulate the large D and 13C isotope enrichments observed in individual n-alkanes (C 13-C 21) during artificial thermal maturation of a North Sea crude oil under anhydrous, closed-system conditions. Under our experimental conditions, average n-alkane δ 13C values increase by ˜4‰ and δD values increase by ˜50‰ at an equivalent vitrinite reflectance value of 1.5%. While the observed 13C-enrichment shows no significant dependence on hydrocarbon chain length, thermally induced D-enrichment increases with increasing n-alkane carbon number. This differential fractionation effect is speculated to be due to the combined effect of the greater extent of thermal cracking of higher molecular weight, n-alkanes compared to lower molecular weight homologues, and the generation of isotopically lighter, lower molecular weight compounds. This carbon-number-linked hydrogen isotopic fractionation behavior could form the basis of a new maturity indicator to quantitatively assess the extent of oil cracking in petroleum reservoirs. Quantum mechanical calculations of the average change in enthalpy (ΔΔH ‡) and entropy (ΔΔS ‡) as a result of isotopic substitution in n-alkanes undergoing homolytic cleavage of C-C bonds lead to predictions of isotopic fractionation that agree quite well with our experimental results. For n-C 20 ( n-icosane), the changes in enthalpy are calculated to be ˜1340 J mol -1 (320 cal mol -1) and 230 J mol -1 (55 cal mol -1) for D-H and 13C- 12C, respectively. Because the enthalpy term associated with hydrogen isotope fractionation is approximately six times greater than that for carbon, variations in δD values for individual long-chain hydrocarbons provide a highly sensitive measure of the extent of thermal alteration experienced by the oil. Extrapolation of the kinetic model to typical geological heating conditions predicts significant enrichment in 13C and D for n-icosane at equivalent vitrinite

Using Beads and Divided Containers to Study Kinetic and Equilibrium Isotope Effects in the Laboratory and in the Classroom

ERIC Educational Resources Information Center

Campbell, Dean J.; Brewer, Emily R.; Martinez, Keri A.; Fitzjarrald, Tamara J.

2017-01-01

The purpose of this laboratory experiment is to study fundamental concepts of kinetics and equilibria and the isotope effects associated with both of these concepts. The concepts of isotopes in introductory and general chemistry courses are typically used within the contexts of atomic weights and radioactivity. Kinetic and equilibrium isotope…

Lattice Boltzmann Simulation of Kinetic Isotope Effect During Snow Crystal Formation

NASA Astrophysics Data System (ADS)

Lu, G.; Depaolo, D. J.; Kang, Q.; Zhang, D.

2007-12-01

The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically-symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over- saturation, determines crystal morphology, there are no quantitative models that relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be direct relationships between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D lattice Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. Crystal growth patterns can be varied between random growth and deterministic growth (along the maximum concentration gradient for example). The input parameters needed are the isotope- dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the condensation coefficient for ice is uncertain. The ratio D/k is a length (order 1 micron) that determines the minimum scale of dendritic growth features

Determination of urea kinetics by isotope dilution with [13C]urea and gas chromatography-isotope ratio mass spectrometry (GC-IRMS) analysis.

PubMed

Kloppenburg, W D; Wolthers, B G; Stellaard, F; Elzinga, H; Tepper, T; de Jong, P E; Huisman, R M

1997-07-01

1. Stable urea isotopes can be used to study urea kinetics in humans. The use of stable urea isotopes for studying urea kinetic parameters in humans on a large scale is hampered by the high costs of the labelled material. We devised a urea dilution for measurement of the distribution volume, production rate and clearance of urea in healthy subjects and renal failure patients using the inexpensive single labelled [13C]urea isotope with subsequent analysis by headspace chromatography-isotope ratio MS (GC-IRMS) of the [13C]urea enrichment. 2. The method involves measurement of the molar percentage excess of [13C]urea in plasma samples taken over a 4 h period after an intravenous bolus injection of [13C]urea. During the sample processing procedure, the plasma samples together with calibration samples containing a known molar percentage excess of [13C]urea are acidified with phosphoric acid to remove endogenous CO2, and are subsequently incubated with urease to convert the urea present in the plasma samples into CO2. The 13C enrichment of the generated CO2 is analysed by means of GC-IRMS. This method allows measurement of the molar percentage excess of [13C]urea to an accuracy of 0.02%. 3. Reproducibility studies showed that the sample processing procedure [within-run coefficient of variation (CV) < 2.8% and between-run CV < 8.8%] and the GC-IRMS analysis (within-day CV < 1.3% and between-day CV < 1.3%) could be repeated with good reproducibility. 4. In clinical urea kinetic studies in a healthy subject and in a renal failure patient without residual renal function, reproducible values of the distribution volume, production rate and clearance of urea were determined using minimal amounts of [13C]urea (25-50 mg). 5. Because only low [13C]urea enrichments are needed in this urea dilution method using GC-IRMS analysis, the costs of urea kinetic studies are reduced considerably, especially in patients with renal failure.

Ab initio study of nitrogen and position-specific oxygen kinetic isotope effects in the NO + O3 reaction

NASA Astrophysics Data System (ADS)

Walters, Wendell W.; Michalski, Greg

2016-12-01

Ab initio calculations have been carried out to investigate nitrogen (k15/k14) and position-specific oxygen (k17/k16O & k18/k16) kinetic isotope effects (KIEs) for the reaction between NO and O3 using CCSD(T)/6-31G(d) and CCSD(T)/6-311G(d) derived frequencies in the complete Bigeleisen equations. Isotopic enrichment factors are calculated to be -6.7‰, -1.3‰, -44.7‰, -14.1‰, and -0.3‰ at 298 K for the reactions involving the 15N16O, 14N18O, 18O16O16O, 16O18O16O, and 16O16O18O isotopologues relative to the 14N16O and 16O3 isotopologues, respectively (CCSD(T)/6-311G(d)). Using our oxygen position-specific KIEs, a kinetic model was constructed using Kintecus, which estimates the overall isotopic enrichment factors associated with unreacted O3 and the oxygen transferred to NO2 to be -19.6‰ and -22.8‰, respectively, (CCSD(T)/6-311G(d)) which tends to be in agreement with previously reported experimental data. While this result may be fortuitous, this agreement suggests that our model is capturing the most important features of the underlying physics of the KIE associated with this reaction (i.e., shifts in zero-point energies). The calculated KIEs will useful in future NOx isotopic modeling studies aimed at understanding the processes responsible for the observed tropospheric isotopic variations of NOx as well as for tropospheric nitrate.

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

PubMed

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

2007-08-28

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

The Power of Integrating Kinetic Isotope Effects into the Formalism of the Michaelis-Menten Equation

PubMed Central

Klinman, Judith P.

2014-01-01

The final arbiter of enzyme mechanism is the ability to establish and test a kinetic mechanism. Isotope effects play a major role in expanding the scope and insight derived from the Michaelis-Menten equation. The integration of isotope effects into the formalism of the Michaelis-Menten equation began in the 1970s and has continued to this day. This review discusses a family of eukaryotic copper proteins that includes dopamine β-monooxygenase, tyramine β-monooxygenase, and peptidylglycine α-amidating enzyme, responsible for the synthesis of the neuro-active compounds, norepinephrine, octopamine and C-terminally carboxamidated peptides, respectively. Highlighted are results that show how combining kinetic isotope effects with initial rate parameters permits an evaluation of: (i) the order of substrate binding to multi-substrate enzymes; (ii) the magnitude of individual rate constants in complex, multi-step reactions; (iii) the identification of chemical intermediates; and (iv) the role of non-classical (tunneling) behavior in C–H activation. PMID:23937475

An Isotopic Exchange Kinetic Model to Assess the Speciation of Metal Available Pool in Soil: The Case of Nickel.

PubMed

Zelano, I O; Sivry, Y; Quantin, C; Gélabert, A; Maury, A; Phalyvong, K; Benedetti, M F

2016-12-06

In this study an innovative approach is proposed to predict the relative contribution of each mineral phase to the total metal availability in soils, which, in other words, could be called the available metal fractionation. Through the use of isotopic exchange kinetics (IEK) performed on typical Ni bearing phases (i.e., two types of serpentines, chlorite, smectite, goethite, and hematite) the isotopic exchange and metal-solid interaction processes are connected, considering both the thermodynamic and kinetic aspects. Results of Ni IEK experiments on mineral phases are fitted with a pseudo-first order kinetic model. For each Ni bearing phase, this allows to (i) determine the number and size of exchangeable pools (E Ni(i) ), (ii) assess their corresponding kinetic constants (k (i) ), and (iii) discuss the mechanism of Ni isotopic exchange at mineral surfaces. It is shown that all the phases investigated, with the only exception of hematite, present at least two distinct reactive pools with significantly different k (i) values. Results suggest also that metal involved in outer-sphere complexes would display isotopic exchange between 100 and 1000 times faster than metal involved in inner-sphere complexes, and that the presence of high and low affinity sites may influence the rate of isotopic exchange up to 1 order of magnitude. Moreover, the method developed represents a tool to predict and estimate Ni mobility and availability in natural soil samples on the basis of soil mineral composition, providing information barely obtained with other techniques.

The influence of kinetics on the oxygen isotope composition of calcium carbonate

NASA Astrophysics Data System (ADS)

Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

2013-08-01

Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

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

NASA Astrophysics Data System (ADS)

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

1989-05-01

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

Kinetic isotope effect in malonaldehyde determined from path integral Monte Carlo simulations.

PubMed

Huang, Jing; Buchowiecki, Marcin; Nagy, Tibor; Vaníček, Jiří; Meuwly, Markus

2014-01-07

The primary H/D kinetic isotope effect on the intramolecular proton transfer in malonaldehyde is determined from quantum instanton path integral Monte Carlo simulations on a fully dimensional and validated potential energy surface for temperatures between 250 and 1500 K. Our calculations, based on thermodynamic integration with respect to the mass of the transferring particle, are significantly accelerated by the direct evaluation of the kinetic isotope effect instead of computing it as a ratio of two rate constants. At room temperature, the KIE from the present simulations is 5.2 ± 0.4. The KIE is found to vary considerably as a function of temperature and the low-T behaviour is dominated by the fact that the free energy derivative in the reactant state increases more rapidly than in the transition state. Detailed analysis of the various contributions to the quantum rate constant together with estimates for rates from conventional transition state theory and from periodic orbit theory suggest that the KIE in malonaldehyde is dominated by zero point energy effects and that tunneling plays a minor role at room temperature.

Stable isotope tracer dilution for quantifying very low-density lipoprotein-triacylglycerol kinetics in man.

PubMed

Sidossis, Labros S; Magkos, Faidon; Mittendorfer, Bettina; Wolfe, Robert R

2004-08-01

A number of approaches have been employed in the past to measure very low-density lipoprotein (VLDL) triacylglycerol (TG) kinetics in humans in vivo, varying in the selection of tracer and mode of administration. All, however, make use of labeled TG precursors and more or less complicated mathematical models to derive the kinetic parameters of interest. The aim of the present study was to develop a conceptually straightforward method, based on the traditional tracer infusion technique, for quantifying VLDL-TG production rates in man using stable isotopes. Our approach involves ingestion of [U-13C3]glycerol to endogenously label the glycerol in VLDL-TG, plasmapheresis, isolation of the newly 13C-labeled VLDL from plasma, and administration within the next 2-3 days via a primed constant autologous reinfusion. This procedure produces enough tracer for a priming dose plus 2-3 h of infusion. In the physiological conditions examined (basal and hyperglycemic states, fat- and carbohydrate-rich diets), with almost 3-fold ranging VLDL-TG pool sizes, a steady state in plasma VLDL-TG glycerol tracer-to-tracee ratio was readily achieved within 2 h. Consequently, calculations are made according to the isotope dilution principle, thus avoiding assumptions implicit in more complicated models. The stable isotope VLDL-TG tracer dilution method offers an alternative and reliable tool for the determination of endogenous VLDL-TG kinetics in man under a variety of metabolic states. Copyright 2003 Elsevier Ltd.

Computational Replication of the Abnormal Secondary Kinetic Isotope Effects in a Hydride Transfer Reaction in Solution with a Motion Assisted H-Tunneling Model

PubMed Central

2015-01-01

We recently reported abnormal secondary deuterium kinetic isotope effects (2° KIEs) for hydride transfer reactions from alcohols to carbocations in acetonitrile (Chem. Comm. 2012, 48, 11337). Experimental 2° KIE values were found to be inflated on the 9-C position in the xanthylium cation but deflated on the β-C position in 2-propanol with respect to the values predicted by the semi-classical transition-state theory. No primary (1°) isotope effect on 2° KIEs was observed. Herein, the KIEs were replicated by the Marcus-like H-tunneling model that requires a longer donor–acceptor distance (DAD) in a lighter isotope transfer process. The 2° KIEs for a range of potential tunneling-ready-states (TRSs) of different DADs were calculated and fitted to the experiments to find the TRS structure. The observed no effect of 1° isotope on 2° KIEs is explained in terms of the less sterically hindered TRS structure so that the change in DAD due to the change in 1° isotope does not significantly affect the reorganization of the 2° isotope and hence the 2° KIE. The effect of 1° isotope on 2° KIEs may be expected to be more pronounced and thus observable in reactions occurring in restrictive environments such as the crowded and relatively rigid active site of enzymes. PMID:24498946

The isotopic effects of electron transfer: an explanation for Fe isotope fractionation in nature

NASA Astrophysics Data System (ADS)

Kavner, A.; Shahar, A.; Bonet, F.; Simon, J. I.; Young, E.

2004-12-01

Recent developments in mass spectrometry techniques have created opportunities to examine the partitioning behavior of stable isotopes of transition metals with a focus on application to iron isotopes. Iron oxidizing and reducing bacteria have been shown to cause isotope fractionations similar in magnitude to those observed in sedimentary environments and it is believed that biological activity is responsible for the most significant Fe isotope fractionation in natural settings. Debate over the use of Fe isotopes as a biological marker resulted from subsequent measurements of fractionations in a variety of abiotic systems. The accumulated evidence, in both biotic and abiotic systems, points to a connection between redox processes and Fe isotope fractionation, however the exact mechanism for isotope fractionation is not yet well understood. Here, we present both a newly-developed theory based on chemical kinetics and preliminary experimental results that quantitatively delineate the relationship between driving force in a charge transfer reaction and resulting Fe isotope fractionation. The theory, based on R. Marcus's chemical kinetics theory for electron transfer (Ann. Rev. Phys. Chem. 15 (1964), 155), predicts that fractionation increases linearly with driving force with a proportionality related to two factors: the difference between isotopic equilibrium exchange of products and reactants, and the reorganization energy along the reaction coordinate. The theoretical predictions were confirmed by measurements of isotopic fractionation associated with electroplating iron metal from a ferrous chloride solution. Isotope fractionation of Fe electroplated under potentiostatic conditions was measured as a function of applied electrochemical potential. As plating voltage was varied from -50 mV to -2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ 56Fe values ranging from -0.106(±0.01) to -2.290(±±0.006)‰ , and corresponding

Kinetic commitment in the catalysis of glutamine synthesis by GS1 from Arabidopsis using 14N/15N and solvent isotope effects.

PubMed

Mauve, Caroline; Giraud, Nicolas; Boex-Fontvieille, Edouard R A; Antheaume, Ingrid; Tea, Illa; Tcherkez, Guillaume

2016-11-01

Glutamine synthetase (GS, EC 6.3.1.2) catalyzes the production of glutamine from glutamate, ammonium and ATP. Although being essential in plants for N assimilation and recycling, kinetic commitments and transition states of the reaction have not been clearly established yet. Here, we examined 12 C/ 13 C, 14 N/ 15 N and H 2 O/D 2 O isotope effects in Arabidopsis GS1 catalysis and compared to the prokaryotic (Escherichia coli) enzyme. A 14 N/ 15 N isotope effect ( 15 V/K ≈ 1.015, with respect to substrate NH 4 + ) was observed in the prokaryotic enzyme, indicating that ammonium utilization (deprotonation and/or amidation) was partially rate-limiting. In the plant enzyme, the isotope effect was inverse ( 15 V/K = 0.965), suggesting that the reaction intermediate is involved in an amidation-deamidation equilibrium favoring 15 N. There was no 12 C/ 13 C kinetic isotope effect ( 13 V/K = 1.000), suggesting that the amidation step of the catalytic cycle involves a transition state with minimal alteration of overall force constants at the C-5 carbon. Surprisingly, the solvent isotope effect was found to be inverse, that is, with a higher turn-over rate in heavy water ( D V ≈ 0.5), showing that restructuration of the active site due to displacement of H 2 O by D 2 O facilitates the processing of intermediates. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Vibrationally-Resolved Kinetic Isotope Effects in the Proton-Transfer Dynamics of Ground-State Tropolone

NASA Astrophysics Data System (ADS)

Chew, Kathryn; Vealey, Zachary; Vaccaro, Patrick

2015-06-01

The vibrational and isotopic dependence of the hindered (tunneling-mediated) proton-transfer reaction taking place in the ground electronic state ( X1{A}1) of monodeuterated tropolone (TrOD) has been explored under ambient (bulk-gas) conditions by applying two-color variants of resonant four-wave mixing (RFWM) spectroscopy in conjunction with polarization-resolved detection schemes designed to alleviate spectral complexity and facilitate rovibrational assignments. Full rotation-tunneling analyses of high-resolution spectral profiles acquired for the fundamental and first-overtone bands of a reaction-promoting O-D\\cdotsO deformation/ring-breathing mode, νb{36}(a1), were performed, thereby extracting refined structural and dynamical information that affords benchmarks for the quantitative interpretation of tunneling-induced signatures found in long-range scans of X1{A}1 vibrational levels residing below Etilde{X}vib = 1700 wn}. Observed kinetic isotope effects, which reflect changes in both reaction kinematics and vibrational displacements, will be discussed, with high-level quantum-chemical calculations serving to elucidate state-resolved propensities for proton transfer in TrOH and TrOD.

Nitrate denitrification with nitrite or nitrous oxide as intermediate products: Stoichiometry, kinetics and dynamics of stable isotope signatures.

PubMed

Vavilin, V A; Rytov, S V

2015-09-01

A kinetic analysis of nitrate denitrification by a single or two species of denitrifying bacteria with glucose or ethanol as a carbon source and nitrite or nitrous oxide as intermediate products was performed using experimental data published earlier (Menyailo and Hungate, 2006; Vidal-Gavilan et al., 2013). Modified Monod kinetics was used in the dynamic biological model. The special equations were added to the common dynamic biological model to describe how isotopic fractionation between N species changes. In contrast to the generally assumed first-order kinetics, in this paper, the traditional Rayleigh equation describing stable nitrogen and oxygen isotope fractionation in nitrate was derived from the dynamic isotopic equations for any type of kinetics. In accordance with the model, in Vidal-Gavilan's experiments, the maximum specific rate of nitrate reduction was proved to be less for ethanol compared to glucose. Conversely, the maximum specific rate of nitrite reduction was proved to be much less for glucose compared to ethanol. Thus, the intermediate nitrite concentration was negligible for the ethanol experiment, while it was significant for the glucose experiment. In Menyailo's and Hungate's experiments, the low value of maximum specific rate of nitrous oxide reduction gives high intermediate value of nitrous oxide concentration. The model showed that the dynamics of nitrogen and oxygen isotope signatures are responding to the biological dynamics. Two microbial species instead of single denitrifying bacteria are proved to be more adequate to describe the total process of nitrate denitrification to dinitrogen. Copyright © 2015 Elsevier Ltd. All rights reserved.

Stable isotope studies of nicotine kinetics and bioavailability

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

Benowitz, N.L.; Jacob, P. 3d.; Denaro, C.

1991-03-01

The stable isotope-labeled compound 3',3'-dideuteronicotine was used to investigate the disposition kinetics of nicotine in smokers, the systemic absorption of nicotine from cigarette smoke, and the bioavailability of nicotine ingested as oral capsules. Blood levels of labeled nicotine could be measured for 9 hours after a 30-minute intravenous infusion. Analysis of disposition kinetics in 10 healthy men revealed a multiexponential decline after the end of an infusion, with an elimination half-life averaging 203 minutes. This half-life was longer than that previously reported, indicating the presence of a shallow elimination phase. Plasma clearance averaged 14.6 ml/min/kg. The average intake of nicotinemore » per cigarette was 2.29 mg. A cigarette smoke-monitoring system that directly measured particulate matter in smoke was evaluated in these subjects. Total particulate matter, number of puffs on the cigarette, total puff volume, and time of puffing correlated with the intake of nicotine from smoking. The oral bioavailability of nicotine averaged 44%. This bioavailability is higher than expected based on the systemic clearance of nicotine and suggests that there may be significant extrahepatic metabolism of nicotine.« less

Linear free energy relationship and deuterium kinetic isotope effect observed on phospho and thiophosphoryl transfer reactions in some organophosphorous compounds

NASA Astrophysics Data System (ADS)

Lumbiny, B. J.; Hui, Z.; Islam, M. A.; Quader, M. A.; Rahman, M.

2014-04-01

Tetracoordinated organophosphorous compounds were synthesized, characterized and nucleophilic substitution reaction were investigated by varying substituents around phosphorous centre or in nucleophile considering its utility in biological and environmental system. The reactivity is expressed in terms of second-order rate constant, k2 and measured conductometrically. Linear Free Energy Relationship (LFER) tools mainly Hammett (ρ), Brönsted (β) LFER coefficients and deuterium kinetic isotope effects (KIEs) being determined for the pyridinolysis of 4 - chlorophenyl 4 - methoxy phenyl chlorophosphate, 1 in acetonitrile at 5.0 °C. The experimental data's were compared with those of structurally similar organophosphorous compounds reported earlier in quest for the mechanistic information. Nice linear correlation being found for Hammett (logk2 vs σx), having negative value of the ρX = -5.85 and Brönsted (logk2 vs pKa(x)) plots having large positive value for βX = 1.18 for 1 can be interpreted as SN2 process with greater extent of bond formation in transition state (TS) of 1. The observed kH/kD values of 1 is 1.00 ± 0.05 and net KIE, 1.32 suggests the primary KIE and indicates frontside nucleophilic attack through the partial deprotonation of pyridine occurs by the hydrogen bonding in the rate-determining step.

Determination of kinetic isotopic fractionation of water during bare soil evaporation

NASA Astrophysics Data System (ADS)

Quade, Maria; Brüggemann, Nicolas; Graf, Alexander; Rothfuss, Youri

2017-04-01

A process-based understanding of the water cycle in the atmosphere is important for improving meteorological and hydrological forecasting models. Usually only net fluxes of evapotranspiration - ET are measured, while land-surface models compute their raw components evaporation -E and transpiration -T. Isotopologues can be used as tracers to partition ET, but this requires knowledge of the isotopic kinetic fractionation factor (αK) which impacts the stable isotopic composition of water pools (e.g., soil and plant waters) during phase change and vapor transport by soil evaporation and plant transpiration. It is defined as a function of the ratio of the transport resistances in air of the less to the most abundant isotopologue. Previous studies determined αK for free evaporating water (Merlivat, 1978) or bare soil evaporation (Braud et al. 2009) at only low temporal resolution. The goal of this study is to provide estimates at higher temporal resolution. We performed a soil evaporation laboratory experiment to determine the αK by applying the Craig and Gordon (1965) model. A 0.7 m high column (0.48 m i.d.) was filled with silt loam (20.1 % sand, 14.9 % loam, 65 % silt) and saturated with water of known isotopic composition. Soil volumetric water content, temperature and the isotopic composition (δ) of the soil water vapor were measured at six different depths. At each depth microporous polypropylene tubing allowed the sampling of soil water vapor and the measurement of its δ in a non-destructive manner with high precision and accuracy as detailed in Rothfuss et al. (2013). In addition, atmospheric water vapor was sampled at seven different heights up to one meter above the surface for isotopic analysis. Results showed that soil and atmospheric δ profiles could be monitored at high temporal and vertical resolutions during the course of the experiment. αK could be calculated by using an inverse modeling approach and the Keeling (1958) plot method at high temporal

Quantification of biodegradation for o-xylene and naphthalene using first order decay models, Michaelis-Menten kinetics and stable carbon isotopes.

PubMed

Blum, Philipp; Hunkeler, Daniel; Weede, Matthias; Beyer, Christof; Grathwohl, Peter; Morasch, Barbara

2009-04-01

At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis-Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d(-1) and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d(-1). Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of k(max)=0.1 microg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d(-1). The stable isotope-based biodegradation rate constant of 0.0027 d(-1) was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d(-1). With MM-kinetics a maximum degradation rate of k(max)=12 microg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor epsilon(field) of -1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.

The reaction of indole with the aminoacrylate intermediate of Salmonella typhimurium tryptophan synthase: observation of a primary kinetic isotope effect with 3-[(2)H]indole.

PubMed

Cash, Michael T; Miles, Edith W; Phillips, Robert S

2004-12-15

The bacterial tryptophan synthase alpha(2)beta(2) complex catalyzes the final reactions in the biosynthesis of L-tryptophan. Indole is produced at the active site of the alpha-subunit and is transferred through a 25-30 A tunnel to the beta-active site, where it reacts with an aminoacrylate intermediate. Lane and Kirschner proposed a two-step nucleophilic addition-tautomerization mechanism for the reaction of indole with the aminoacrylate intermediate, based on the absence of an observed kinetic isotope effect (KIE) when 3-[(2)H]indole reacts with the aminoacrylate intermediate. We have now observed a KIE of 1.4-2.0 in the reaction of 3-[(2)H]indole with the aminoacrylate intermediate in the presence of monovalent cations, but not when an alpha-subunit ligand, disodium alpha-glycerophosphate (Na(2)GP), is present. Rapid-scanning stopped flow kinetic studies were performed of the reaction of indole and 3-[(2)H]indole with tryptophan synthase preincubated with L-serine, following the decay of the aminoacrylate intermediate at 350 nm, the formation of the quinonoid intermediate at 476 nm, and the formation of the L-Trp external aldimine at 423 nm. The addition of Na(2)GP dramatically slows the rate of reaction of indole with the alpha-aminoacrylate intermediate. A primary KIE is not observed in the reaction of 3-[(2)H]indole with the aminoacrylate complex of tryptophan synthase in the presence of Na(2)GP, suggesting binding of indole with tryptophan synthase is rate limiting under these conditions. The reaction of 2-methylindole does not show a KIE, either in the presence of Na(+) or Na(2)GP. These results support the previously proposed mechanism for the beta-reaction of tryptophan synthase, but suggest that the rate limiting step in quinonoid intermediate formation from indole and the aminoacrylate intermediate is deprotonation.

Kinetics of D/H Isotope Exchange Between H2 and H2O and Potential use of Isotope Geothermometry on Plume Data from Enceladus

NASA Astrophysics Data System (ADS)

Pester, N.; Conrad, M.; Stolper, D.; DePaolo, D.

2018-05-01

Using experimental data, we develop kinetic models that asses the potential to apply H2-H2O isotope geothermometry towards the plume chemistry of Enceladus, such that we might elucidate the T-structure in the liquid ocean beneath the icy shell.

Electrochemically controlled iron isotope fractionation

NASA Astrophysics Data System (ADS)

Black, Jay R.; Young, Edward D.; Kavner, Abby

2010-02-01

Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

Chemical stability of levoglucosan: An isotopic perspective

NASA Astrophysics Data System (ADS)

Sang, X. F.; Gensch, I.; Kammer, B.; Khan, A.; Kleist, E.; Laumer, W.; Schlag, P.; Schmitt, S. H.; Wildt, J.; Zhao, R.; Mungall, E. L.; Abbatt, J. P. D.; Kiendler-Scharr, A.

2016-05-01

The chemical stability of levoglucosan was studied by exploring its isotopic fractionation during the oxidation by hydroxyl radicals. Aqueous solutions as well as mixed (NH4)2SO4-levoglucosan particles were exposed to OH. In both cases, samples experiencing different extents of processing were isotopically analyzed by Thermal Desorption-Gas Chromatography-Isotope Ratio Mass Spectrometry (TD-GC-IRMS). From the dependence of levoglucosan δ13C and concentration on the reaction extent, the kinetic isotope effect (KIE) of the OH oxidation reactions was determined to be 1.00187±0.00027 and 1.00229±0.00018, respectively. Both show good agreement within the uncertainty range. For the heterogeneous oxidation of particulate levoglucosan by gas-phase OH, a reaction rate constant of (2.67±0.03)·10-12 cm3 molecule-1S-1 was derived. The laboratory kinetic data, together with isotopic source and ambient observations, give information on the extent of aerosol chemical processing in the atmosphere.

Redefining the utility of the three-isotope method

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Bao, Huiming

2017-09-01

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

Nuclear quantum effects and kinetic isotope effects in enzyme reactions.

PubMed

Vardi-Kilshtain, Alexandra; Nitoker, Neta; Major, Dan Thomas

2015-09-15

Enzymes are extraordinarily effective catalysts evolved to perform well-defined and highly specific chemical transformations. Studying the nature of rate enhancements and the mechanistic strategies in enzymes is very important, both from a basic scientific point of view, as well as in order to improve rational design of biomimetics. Kinetic isotope effect (KIE) is a very important tool in the study of chemical reactions and has been used extensively in the field of enzymology. Theoretically, the prediction of KIEs in condensed phase environments such as enzymes is challenging due to the need to include nuclear quantum effects (NQEs). Herein we describe recent progress in our group in the development of multi-scale simulation methods for the calculation of NQEs and accurate computation of KIEs. We also describe their application to several enzyme systems. In particular we describe the use of combined quantum mechanics/molecular mechanics (QM/MM) methods in classical and quantum simulations. The development of various novel path-integral methods is reviewed. These methods are tailor suited to enzyme systems, where only a few degrees of freedom involved in the chemistry need to be quantized. The application of the hybrid QM/MM quantum-classical simulation approach to three case studies is presented. The first case involves the proton transfer in alanine racemase. The second case presented involves orotidine 5'-monophosphate decarboxylase where multidimensional free energy simulations together with kinetic isotope effects are combined in the study of the reaction mechanism. Finally, we discuss the proton transfer in nitroalkane oxidase, where the enzyme employs tunneling as a catalytic fine-tuning tool. Copyright © 2015 Elsevier Inc. All rights reserved.

Kinetic stable Cr isotopic fractionation between aqueous Cr(III)-Cl-H2O complexes at 25 °C: Implications for Cr(III) mobility and isotopic variations in modern and ancient natural systems

NASA Astrophysics Data System (ADS)

Babechuk, Michael G.; Kleinhanns, Ilka C.; Reitter, Elmar; Schoenberg, Ronny

2018-02-01

The stable Cr isotope fractionation preserved in natural substances has been attributed predominantly to Cr(III)-Cr(VI) redox transformations. However, non-redox reaction pathways (e.g., ligand-promoted dissolution, ligand exchange, adsorption of Cr(III)) are liable to contribute to isotopic fractionation in natural systems given that soluble Cr(III)-ligands have been directly documented or modeled in several marine, continental, and hydrothermal environments. This study isolates the stable Cr isotope fractionation accompanying Cl-H2O ligand exchange during the transformation of three aqueous species in the Cr(III)-Cl-H2O system, [CrCl2(H2O)4]+aq (abr. CrCl2+ or S1), [CrCl(H2O)5]2+aq (abr. CrCl2+ or S2), and [Cr(H2O)6]3+aq (abr. Cr3+ or S3), at low pH (≤2). In dilute HCl (0.01 to 1 M), Cr3+ is the kinetically favoured species and transformation of CrCl2+ to CrCl2+ to Cr3+ via 2 steps of dechlorination/hydrolyzation begins immediately upon dissolution of a Cr(III)-Cl solid. Individual species are separated with cation exchange chromatography at different stages of transformation and inter- and intra-species (across an elution peak of one species) isotopic fractionation of up to 1 and 2‰ (δ53/52Cr), respectively, is documented. Comparison of peak elution characteristics with Cr-Cl-H-O isotopologue mass abundances suggests mass-dependent sorting of isotopologues alone cannot explain intra-species fractionation, supporting a previously published proposal that preferential adsorption of light Cr isotopes on the resin is driven by vibrational energy effects. The transformation of CrCl2+ to CrCl2+ is faster than CrCl2+ to Cr3+ and the rates of both transformations increase with solution pH. Preferential reaction of light Cr(III) isotopes into product species occurs during each transformation, consistent with closed-system, kinetic fractionation during Cl-H2O ligand exchange. Inter-species fractionation is assessed using time-series experiments beginning from the

Inverse Kinetic and Equilibrium Isotope Effects on Self-Assembly and Supramolecular Chirality of Porphyrin J-Aggregates.

PubMed

Zagami, Roberto; Romeo, Andrea; Castriciano, Maria A; Monsù Scolaro, Luigi

2017-01-01

When mixtures of D 2 O/DCl are used to foster the self-assembly formation of TPPS 4 porphyrin J-aggregates in aqueous solutions, an inverse kinetic isotope effect of 0.4 and an inverse equilibrium isotope effect of 0.6 are clearly detected. Most importantly, the addition of at least 10 % D 2 O causes an inversion in the handedness of the final chiral J-aggregates, thus evidencing an important role of deuterium in driving the enantiomeric excess in the scalemic mixture of such supramolecular assemblies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of the Deuterium Isotope Effect in the Detonation of Aluminum Containing Explosives

DOE PAGES

Tappan, Bryce C.; Bowden, Patrick R.; Manner, Virginia W.; ...

2017-12-04

During or shortly after a detonation in condensed explosives, the reaction rates and the physical mechanism controlling aluminum reaction is poorly understood. We utilize the kinetic isotope effect to probe Al reactions in detonation product gases in aluminized, protonated and deuterated high explosives using high-fidelity detonation velocity and cylinder wall expansion velocity measurements. By observation of the profile of cylinder wall velocity versus time, we are able to determine the timing of aluminum contribution to energy release in product gases and observe the presence or absence of rate changes isotopic substitution. By comparison of the Al oxidation with lithium fluoridemore » (LiF), data indicate that Al oxidation occurs on an extremely fast time scale, with post-detonation kinetic isotope effects observed in carbon containing formulations.« less

Evaluation of the Deuterium Isotope Effect in the Detonation of Aluminum Containing Explosives

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

Tappan, Bryce C.; Bowden, Patrick R.; Manner, Virginia W.

During or shortly after a detonation in condensed explosives, the reaction rates and the physical mechanism controlling aluminum reaction is poorly understood. We utilize the kinetic isotope effect to probe Al reactions in detonation product gases in aluminized, protonated and deuterated high explosives using high-fidelity detonation velocity and cylinder wall expansion velocity measurements. By observation of the profile of cylinder wall velocity versus time, we are able to determine the timing of aluminum contribution to energy release in product gases and observe the presence or absence of rate changes isotopic substitution. By comparison of the Al oxidation with lithium fluoridemore » (LiF), data indicate that Al oxidation occurs on an extremely fast time scale, with post-detonation kinetic isotope effects observed in carbon containing formulations.« less

Kinetic isotope effects reveal early transition state of protein lysine methyltransferase SET8

PubMed Central

Linscott, Joshua A.; Kapilashrami, Kanishk; Wang, Zhen; Senevirathne, Chamara; Bothwell, Ian R.; Blum, Gil; Luo, Minkui

2016-01-01

Protein lysine methyltransferases (PKMTs) catalyze the methylation of protein substrates, and their dysregulation has been linked to many diseases, including cancer. Accumulated evidence suggests that the reaction path of PKMT-catalyzed methylation consists of the formation of a cofactor(cosubstrate)–PKMT–substrate complex, lysine deprotonation through dynamic water channels, and a nucleophilic substitution (SN2) transition state for transmethylation. However, the molecular characters of the proposed process remain to be elucidated experimentally. Here we developed a matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) method and corresponding mathematic matrix to determine precisely the ratios of isotopically methylated peptides. This approach may be generally applicable for examining the kinetic isotope effects (KIEs) of posttranslational modifying enzymes. Protein lysine methyltransferase SET8 is the sole PKMT to monomethylate histone 4 lysine 20 (H4K20) and its function has been implicated in normal cell cycle progression and cancer metastasis. We therefore implemented the MS-based method to measure KIEs and binding isotope effects (BIEs) of the cofactor S-adenosyl-l-methionine (SAM) for SET8-catalyzed H4K20 monomethylation. A primary intrinsic 13C KIE of 1.04, an inverse intrinsic α-secondary CD3 KIE of 0.90, and a small but statistically significant inverse CD3 BIE of 0.96, in combination with computational modeling, revealed that SET8-catalyzed methylation proceeds through an early, asymmetrical SN2 transition state with the C-N and C-S distances of 2.35–2.40 Å and 2.00–2.05 Å, respectively. This transition state is further supported by the KIEs, BIEs, and steady-state kinetics with the SAM analog Se-adenosyl-l-selenomethionine (SeAM) as a cofactor surrogate. The distinct transition states between protein methyltransferases present the opportunity to design selective transition-state analog inhibitors. PMID

Latitudinal change in precipitation and water vapor isotopes over Southern ocean

NASA Astrophysics Data System (ADS)

Rahul, P.

2015-12-01

The evaporation process over ocean is primary source of water vapor in the hydrological cycle. The Global Network of Isotopes in Precipitation (GNIP) dataset of rainwater and water vapor isotopes are predominantly based on continental observations, with very limited observation available from the oceanic area. Stable isotope ratios in precipitation provide valuable means to understand the process of evaporation and transport of water vapor. This is further extended in the study of past changes in climate from the isotopic composition of ice core. In this study we present latitudinal variability of water vapor and rainwater isotopic composition and compared it with factors like physical condition of sea surface water from near equator (1°S) to the polar front (56°S) during the summer time expedition of the year 2013. The water vapor and rainwater isotopes showed a sharp depletion in isotopes while progressively move southward from the tropical regions (i.e. >30°S), which follows the pattern recorded in the surface ocean water isotopic composition. From the tropics to the southern latitudes, the water vapor d18O varied between -11.8‰ to -14.7‰ while dD variation ranges between -77.7‰ to -122.2‰. Using the data we estimated the expected water vapor isotopic composition under kinetic as well as equilibrium process. Our observation suggests that the water vapor isotopic compositions are in equilibrium with the sea water in majority of cases. At one point of observation, where trajectory of air parcel originated from the continental region, we observed a large deviation from the existing trend of latitudinal variability. The deduced rainwater composition adopting equilibrium model showed a consistent pattern with observed values at the tropical region, while role of kinetic process become dominant on progressive shift towards the southern latitudes. We will draw comparison of our observation with other data available in the literature together with isotope

Kinetically Relevant Steps and H2/D2 Isotope Effects in Fischer-Tropsch Synthesis on Fe and Co Catalysts

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

Ojeda, Manuel; Li, Anwu; Nabar, Rahul P.

2010-11-25

H2/D2 isotope effects on Fischer-Tropsch synthesis (FTS) rate and selectivity are examined here by combining measured values on Fe and Co at conditions leading to high C5+ yields with theoretical estimates on model Fe(110) and Co(0001) surfaces with high coverages of chemisorbed CO (CO*). Inverse isotope effects (rH/rD < 1) are observed on Co and Fe catalysts as a result of compensating thermodynamic (H2 dissociation to H*; H* addition to CO* species to form HCO*) and kinetic (H* reaction with HCO*) isotope effects. These isotopic effects and their rigorous mechanistic interpretation confirm the prevalence of H-assisted CO dissociation routes onmore » both Fe and Co catalysts, instead of unassisted pathways that would lead to similar rates with H2 and D2 reactants. The small contributions from unassisted pathways to CO conversion rates on Fe are indeed independent of the dihydrogen isotope, as is also the case for the rates of primary reactions that form CO2 as the sole oxygen rejection route in unassisted CO dissociation paths. Isotopic effects on the selectivity to C5+ and CH4 products are small, and D2 leads to a more paraffinic product than does H2, apparently because it leads to preference for chain termination via hydrogen addition over abstraction. These results are consistent with FTS pathways limited by H-assisted CO dissociation on both Fe and Co and illustrate the importance of thermodynamic contributions to inverse isotope effects for reactions involving quasi-equilibrated H2 dissociation and the subsequent addition of H* in hydrogenation catalysis, as illustrated here by theory and experiment for the specific case of CO hydrogenation.« less

Mechanistic investigations of the hydrolysis of amides, oxoesters and thioesters via kinetic isotope effects and positional isotope exchange.

PubMed

Robins, Lori I; Fogle, Emily J; Marlier, John F

2015-11-01

The hydrolysis of amides, oxoesters and thioesters is an important reaction in both organic chemistry and biochemistry. Kinetic isotope effects (KIEs) are one of the most important physical organic methods for determining the most likely transition state structure and rate-determining step of these reaction mechanisms. This method induces a very small change in reaction rates, which, in turn, results in a minimum disturbance of the natural mechanism. KIE studies were carried out on both the non-enzymatic and the enzyme-catalyzed reactions in an effort to compare both types of mechanisms. In these studies the amides and esters of formic acid were chosen because this molecular structure allowed development of methodology to determine heavy-atom solvent (nucleophile) KIEs. This type of isotope effect is difficult to measure, but is rich in mechanistic information. Results of these investigations point to transition states with varying degrees of tetrahedral character that fit a classical stepwise mechanism. This article is part of a special issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2014 Elsevier B.V. All rights reserved.

Fission fragment mass and total kinetic energy distributions of spontaneously fissioning plutonium isotopes

NASA Astrophysics Data System (ADS)

Pomorski, K.; Nerlo-Pomorska, B.; Bartel, J.; Schmitt, C.

2018-03-01

The fission-fragment mass and total kinetic energy (TKE) distributions are evaluated in a quantum mechanical framework using elongation, mass asymmetry, neck degree of freedom as the relevant collective parameters in the Fourier shape parametrization recently developed by us. The potential energy surfaces (PES) are calculated within the macroscopic-microscopic model based on the Lublin-Strasbourg Drop (LSD), the Yukawa-folded (YF) single-particle potential and a monopole pairing force. The PES are presented and analysed in detail for even-even Plutonium isotopes with A = 236-246. They reveal deep asymmetric valleys. The fission-fragment mass and TKE distributions are obtained from the ground state of a collective Hamiltonian computed within the Born-Oppenheimer approximation, in the WKB approach by introducing a neck-dependent fission probability. The calculated mass and total kinetic energy distributions are found in good agreement with the data.

Predictions and Verification of an Isotope Marine Boundary Layer Model

NASA Astrophysics Data System (ADS)

Feng, X.; Posmentier, E. S.; Sonder, L. J.; Fan, N.

2017-12-01

A one-dimensional (1D), steady state isotope marine boundary layer (IMBL) model is constructed. The model includes meteorologically important features absent in Craig and Gordon type models, namely height-dependent diffusion/mixing and convergence of subsiding external air. Kinetic isotopic fractionation results from this height-dependent diffusion which starts as pure molecular diffusion at the air-water interface and increases linearly with height due to turbulent mixing. The convergence permits dry, isotopically depleted air subsiding adjacent to the model column to mix into ambient air. In δD-δ18O space, the model results fill a quadrilateral, of which three sides represent 1) vapor in equilibrium with various sea surface temperatures (SSTs) (high d18O boundary of quadrilateral); 2) mixture of vapor in equilibrium with seawater and vapor in the subsiding air (lower boundary depleted in both D and 18O); and 3) vapor that has experienced the maximum possible kinetic fractionation (high δD upper boundary). The results can be plotted in d-excess vs. δ18O space, indicating that these processes all cause variations in d-excess of MBL vapor. In particular, due to relatively high d-excess in the descending air, mixing of this air into the MBL causes an increase in d-excess, even without kinetic isotope fractionation. The model is tested by comparison with seven datasets of marine vapor isotopic ratios, with excellent correspondence; >95% of observational data fall within the quadrilateral area predicted by the model. The distribution of observations also highlights the significant influence of vapor from the nearby converging descending air on isotopic variations in the MBL. At least three factors may explain the <5% of observations that fall slightly outside of the predicted region in both δD-δ18O and d-excess - δ18O space: 1) variations in seawater isotopic ratios, 2) variations in isotopic composition of subsiding air, and 3) influence of sea spray. The model

First observation of a mass independent isotopic fractionation in a condensation reaction

NASA Technical Reports Server (NTRS)

Thiemens, M. H.; Nelson, R.; Dong, Q. W.; Nuth, Joseph A., III

1994-01-01

Thiemens and Heidenreich (1983) first demonstrated that a chemically produced mass independent isotopic fractionation process could produce an isotopic composition which is identical to that observed in Allende inclusions. This raised the possibility that the meteoritic components could be produced by chemical, rather than nuclear processes. In order to develop a mechanistic model of the early solar system, it is important that relevant reactions be studied, particularly, those which may occur in the earliest condensation reactions. The isotopic results for isotopic fractionations associated with condensation processes are reported. A large mass independent isotopic fractionation is observed in one of the experiments.

HO + CO reaction rates and H/D kinetic isotope effects: master equation models with ab initio SCTST rate constants.

PubMed

Weston, Ralph E; Nguyen, Thanh Lam; Stanton, John F; Barker, John R

2013-02-07

Ab initio microcanonical rate constants were computed using Semi-Classical Transition State Theory (SCTST) and used in two master equation formulations (1D, depending on active energy with centrifugal corrections, and 2D, depending on total energy and angular momentum) to compute temperature-dependent rate constants for the title reactions using a potential energy surface obtained by sophisticated ab initio calculations. The 2D master equation was used at the P = 0 and P = ∞ limits, while the 1D master equation with centrifugal corrections and an empirical energy transfer parameter could be used over the entire pressure range. Rate constants were computed for 75 K ≤ T ≤ 2500 K and 0 ≤ [He] ≤ 10(23) cm(-3). For all temperatures and pressures important for combustion and for the terrestrial atmosphere, the agreement with the experimental rate constants is very good, but at very high pressures and T ≤ 200 K, the theoretical rate constants are significantly smaller than the experimental values. This effect is possibly due to the presence in the experiments of dimers and prereactive complexes, which were not included in the model calculations. The computed H/D kinetic isotope effects are in acceptable agreement with experimental data, which show considerable scatter. Overall, the agreement between experimental and theoretical H/D kinetic isotope effects is much better than in previous work, and an assumption of non-RRKM behavior does not appear to be needed to reproduce experimental observations.

Effect of amino acids on the precipitation kinetics and Ca isotopic composition of gypsum

NASA Astrophysics Data System (ADS)

Harouaka, Khadouja; Kubicki, James D.; Fantle, Matthew S.

2017-12-01

Stirred gypsum (CaSO4 · 2H2O) precipitation experiments (initial Ωgypsum = 2.4 ± 0.14, duration ≈ 1.0-1.5 h) were conducted in the presence of the amino acids glycine (190 μM), L-alanine (190 μM), D- and L-arginine (45 μM), and L-tyrosine (200 μM) to investigate the effect of simple organic compounds on both the precipitation kinetics and Ca isotopic composition of gypsum. Relative to abiotic controls, glycine, tyrosine, and alanine inhibited precipitation rates by ∼22%, 27%, and 29%, respectively, while L- and D-arginine accelerated crystal growth by ∼8% and 48%, respectively. With the exception of tyrosine, amino acid induced inhibition resulted in fractionation factors (αs-f) associated with precipitation that were no more than 0.3‰ lower than amino acid-free controls. In contrast, the tyrosine and D- and L-arginine experiments had αs-f values associated with precipitation that were similar to the controls. Our experimental results indicate that Ca isotopic fractionation associated with gypsum precipitation is impacted by growth inhibition in the presence of amino acids. Specifically, we propose that the surface-specific binding of amino acids to gypsum can change the equilibrium fractionation factor of the bulk mineral. We investigate the hypothesis that amino acids can influence the growth of gypsum at specific crystal faces via adsorption and that different faces have distinct fractionation factors (αface-fluid). Accordingly, preferential sorption of amino acids at particular faces changes the relative, face-specific mass fluxes of Ca during growth, which influences the bulk isotopic composition of the mineral. Density functional theory (DFT) calculations suggest that the energetic favorability of glycine sorption onto gypsum crystal faces occurs in the order: (1 1 0) > (0 1 0) > (1 2 0) > (0 1 1), while glycine sorption onto the (-1 1 1) face was found to be energetically unfavorable. Face-specific fractionation factors constrained by

Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

PubMed

Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

2015-05-27

The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations.

Fractionation of Fe isotopes by soil microbes and organic acids

USGS Publications Warehouse

Brantley, Susan L.; Liermann, Laura; Bullen, Thomas D.

2001-01-01

Small natural variations in Fe isotopes have been attributed to biological cycling. However, without understanding the mechanism of fractionation, it is impossible to interpret such variations. Here we show that the δ56Fe of Fe dissolved from a silicate soil mineral by siderophore-producing bacteria is as much as 0.8% lighter than bulk Fe in the mineral. A smaller isotopic shift is observed for Fe released abiotically by two chelates, and the magnitude of the shift increases with affinity of the ligand for Fe, consistent with a kinetic isotope effect during hydrolysis of Fe at the mineral surface. Fe dissolved abiotically without chelates shows no isotopic shift. The δ56Fe of the exchange fraction on soil grains is also lighter by ~0.6%-1% than Fe from both hornblende and iron oxyhydroxides. The kinetic isotope effect is therefore preserved in open systems such as soils. when recorded in the rock record, Fe isotopic fractionation could document Fe transport by organic molecules or by microbes where such entities were present in the geologic past.

Multiple stable isotope fronts during non-isothermal fluid flow

NASA Astrophysics Data System (ADS)

Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

2018-02-01

Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may

A Method to Determine 18O Kinetic Isotope Effects in the Hydrolysis of Nucleotide Triphosphates

PubMed Central

Du, Xinlin; Ferguson, Kurt; Sprang, Stephen R.

2007-01-01

A method to determine 18O kinetic isotope effects (KIE) in the hydrolysis of GTP is described that is generally applicable to reactions involving other nucleotide triphosphates. Internal competition, wherein the substrate of the reaction is a mixture of 18O-labeled and unlabeled nucleotides, is employed and the change in relative abundance of the two species in the course of the reaction is used to calculate KIE. The nucleotide labeled with 18O at sites of mechanistic interest also contains 13C at all carbon positions, while the 16O-nucleotide is depleted of 13C. The relative abundance of the labeled and unlabeled substrates or products is reflected in the carbon isotope ratio (13C/12C) in GTP or GDP, which is determined by use of a liquid chromatography-coupled isotope ratio mass spectrometer (LC-coupled IRMS). The LC is coupled to the IRMS by an Isolink™ interface (ThermoFinnigan). Carbon isotope ratios can be determined with accuracy and precision greater than 0.04%, and are consistent over an order of magnitude in sample amount. KIE values for Ras/NF1333-catalyzed hydrolysis of [β18O3,13C]GTP were determined by change in the isotope ratio of GTP or GDP or the ratio of the isotope ratio of GDP to that of GTP. KIE values computed in the three ways agree within 0.1%, although the method using the ratio of isotope ratios of GDP and GTP gives superior precision (< 0.1%). A single KIE measurement can be conducted in 25 minutes with less than 5 μg nucleotide reaction product. PMID:17963711

Steps toward identifying a biogeochemical signal in non-equilibrium methane clumped isotope measurements

NASA Astrophysics Data System (ADS)

Douglas, P. M.; Eiler, J. M.; Sessions, A. L.; Dawson, K.; Walter Anthony, K. M.; Smith, D. A.; Lloyd, M. K.; Yanay, E.

2016-12-01

Microbially produced methane is a globally important greenhouse gas, energy source, and biological substrate. Methane clumped isotope measurements have recently been developed as a new analytical tool for understanding the source of methane in different environments. When methane forms in isotopic equilibrium clumped isotope values are determined by formation temperature, but in many cases microbial methane clumped isotope values deviate strongly from expected equilibrium values. Indeed, we observe a very wide range of clumped isotope values in microbial methane, which are likely strongly influenced by kinetic isotope effects, but thus far the biological and environmental parameters controlling this variability are not understood. We will present data from both culture experiments and natural environments to explore patterns of variability in non-equilibrium clumped isotope values on temporal and spatial scales. In methanogen batch cultures sampled at different time points along a growth curve we observe significant variability in clumped isotope values, with values decreasing from early to late exponential growth. Clumped isotope values then increase during stationary growth. This result is consistent with previous work suggesting that differences in the reversibility of methanogenesis related to metabolic rates control non-equilibrium clumped isotope values. Within single lakes in Alaska and Sweden we observe substantial variability in clumped isotope values on the order of 5‰. Lower clumped isotope values are associated with larger 2H isotopic fractionation between water and methane, which is also consistent with a kinetic isotope effect determined by the reversibility of methanogenesis. Finally, we analyzed a time-series clumped isotope compositions of methane emitted from two seeps in an Alaskan lake over several months. Temporal variability in these seeps is on the order of 2‰, which is much less than the observed spatial variability within the lake

Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

NASA Astrophysics Data System (ADS)

Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

2015-04-01

Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

The C-13/C-12 kinetic isotope effect for soil oxidation of methane at ambient atmospheric concentrations

NASA Technical Reports Server (NTRS)

King, Stagg L.; Quay, Paul D.; Lansdown, John M.

1989-01-01

During a survey of the Alaskan North Slope to estimate the isotopic composition and fluxes of methane (CH4) from the tundra, two sites were encountered that showed net methane consumption within flux chambers. Methane concentrations decreased from ambient (1.78 ppmv) by up to 50 percent, and the delta C-13 increased by up to 10 percent in the two chamber deployments showing CH4 consumption. CH4 consumption rates were measured to be 1.2 and 0.6 mg CH4/sq m per day; the corresponding carbon kinetic isotope effects (k13/k12) were 0.974 and 0.984, respectively.

Evaluating the skills of isotope-enabled general circulation models against in situ atmospheric water vapor isotope observations

NASA Astrophysics Data System (ADS)

Steen-Larsen, H. C.; Risi, C.; Werner, M.; Yoshimura, K.; Masson-Delmotte, V.

2017-01-01

The skills of isotope-enabled general circulation models are evaluated against atmospheric water vapor isotopes. We have combined in situ observations of surface water vapor isotopes spanning multiple field seasons (2010, 2011, and 2012) from the top of the Greenland Ice Sheet (NEEM site: 77.45°N, 51.05°W, 2484 m above sea level) with observations from the marine boundary layer of the North Atlantic and Arctic Ocean (Bermuda Islands 32.26°N, 64.88°W, year: 2012; south coast of Iceland 63.83°N, 21.47°W, year: 2012; South Greenland 61.21°N, 47.17°W, year: 2012; Svalbard 78.92°N, 11.92°E, year: 2014). This allows us to benchmark the ability to simulate the daily water vapor isotope variations from five different simulations using isotope-enabled general circulation models. Our model-data comparison documents clear isotope biases both on top of the Greenland Ice Sheet (1-11‰ for δ18O and 4-19‰ for d-excess depending on model and season) and in the marine boundary layer (maximum differences for the following: Bermuda δ18O = 1‰, d-excess = 3‰; South coast of Iceland δ18O = 2‰, d-excess = 5‰; South Greenland δ18O = 4‰, d-excess = 7‰; Svalbard δ18O = 2‰, d-excess = 7‰). We find that the simulated isotope biases are not just explained by simulated biases in temperature and humidity. Instead, we argue that these isotope biases are related to a poor simulation of the spatial structure of the marine boundary layer water vapor isotopic composition. Furthermore, we specifically show that the marine boundary layer water vapor isotopes of the Baffin Bay region show strong influence on the water vapor isotopes at the NEEM deep ice core-drilling site in northwest Greenland. Our evaluation of the simulations using isotope-enabled general circulation models also documents wide intermodel spatial variability in the Arctic. This stresses the importance of a coordinated water vapor isotope-monitoring network in order to discriminate amongst these model

Cross-Course Collaboration in the Undergraduate Chemistry Curriculum: Primary Kinetic Isotope Effect in the Hypochlorite Oxidation of 1-Phenylethanol in the Physical Chemistry Laboratory

ERIC Educational Resources Information Center

Noll, Robert J.; Fitch, Richard W.; Kjonaas, Richard A.; Wyatt, Richard A.

2017-01-01

A kinetic isotope effect (KIE) experiment is described for the physical chemistry laboratory. Students conduct a hypochlorite (household bleach) oxidation of an equimolar mixture of 1-phenylethanol and 1-deuterio-1-phenylethanol to acetophenone. The reaction occurs in a biphasic reaction mixture and follows first-order kinetics with respect to…

Dual isotope notch observer for isotope identification, assay and imaging with mono-energetic gamma-ray sources

DOEpatents

Barty, Christopher P.J.

2013-02-05

A dual isotope notch observer for isotope identification, assay and imaging with mono-energetic gamma-ray sources includes a detector arrangement consists of three detectors downstream from the object under observation. The latter detector, which operates as a beam monitor, is an integrating detector that monitors the total beam power arriving at its surface. The first detector and the middle detector each include an integrating detector surrounding a foil. The foils of these two detectors are made of the same atomic material, but each foil is a different isotope, e.g., the first foil may comprise U235 and second foil may comprise U238. The integrating detectors surrounding these pieces of foil measure the total power scattered from the foil and can be similar in composition to the final beam monitor. Non-resonant photons will, after calibration, scatter equally from both foils.

Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

NASA Astrophysics Data System (ADS)

Wiegel, Aaron A.; Cole, Amanda S.; Hoag, Katherine J.; Atlas, Elliot L.; Schauffler, Sue M.; Boering, Kristie A.

2013-10-01

We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the 17O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O(1D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

Soil solution phosphorus turnover: derivation, interpretation, and insights from a global compilation of isotope exchange kinetic studies

NASA Astrophysics Data System (ADS)

Helfenstein, Julian; Jegminat, Jannes; McLaren, Timothy I.; Frossard, Emmanuel

2018-01-01

The exchange rate of inorganic phosphorus (P) between the soil solution and solid phase, also known as soil solution P turnover, is essential for describing the kinetics of bioavailable P. While soil solution P turnover (Km) can be determined by tracing radioisotopes in a soil-solution system, few studies have done so. We believe that this is due to a lack of understanding on how to derive Km from isotopic exchange kinetic (IEK) experiments, a common form of radioisotope dilution study. Here, we provide a derivation of calculating Km using parameters obtained from IEK experiments. We then calculated Km for 217 soils from published IEK experiments in terrestrial ecosystems, and also that of 18 long-term P fertilizer field experiments. Analysis of the global compilation data set revealed a negative relationship between concentrations of soil solution P and Km. Furthermore, Km buffered isotopically exchangeable P in soils with low concentrations of soil solution P. This finding was supported by an analysis of long-term P fertilizer field experiments, which revealed a negative relationship between Km and phosphate-buffering capacity. Our study highlights the importance of calculating Km for understanding the kinetics of P between the soil solid and solution phases where it is bioavailable. We argue that our derivation can also be used to calculate soil solution turnover of other environmentally relevant and strongly sorbing elements that can be traced with radioisotopes, such as zinc, cadmium, nickel, arsenic, and uranium.

Determination of the mechanism of demethylenation of (methylenedioxy)phenyl compounds by cytochrome P450 using deuterium isotope effects

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

Fukuto, J.M.; Kumagai, Y.; Cho, A.K.

1991-09-01

The mechanism of demethylenation of (methylenedioxy)benzene (MDB), (methylenedioxy)amphetamine (MDA), and (methylenedioxy)methamphetamine (MDMA) by purified rabbit liver cytochrome P450IIB4 has been investigated by using deuterium isotope effects. A comparison of the magnitude and direction of the observed kinetic isotope effects indicates that the three compounds are demethylenated by different mechanisms. The different mechanisms of demethylenation have been proposed on the basis of comparisons of the observed biochemical isotope effects with the isotope effects from purely chemical systems.

Light Nuclei and Isotope Abundances in Cosmic Rays. Results from AMS-01

NASA Astrophysics Data System (ADS)

Tomassetti, N.

2011-06-01

Observations of the chemical and isotopic composition of light cosmic-ray nuclei can be used to constrain the propagation models. Nearly 200,000 light nuclei (Z > 2) have been observed by AMS-01 during the 10-day flight STS-91 in June 1998. Using these data, we have measured Li, Be, B and C in the kinetic energy range 0.35 - 45 GeV/nucleon. In this proceeding, our charge and isotopic composition results are presented and discussed.

Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride-Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations.

PubMed

Derakhshani-Molayousefi, Mortaza; Kashefolgheta, Sadra; Eilers, James E; Lu, Yun

2016-06-30

We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride-transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD) than in H-tunneling. To examine the isotopic DAD difference explanation, in this paper, following an activated motion-assisted H-tunneling model that requires a shorter DAD in a heavier isotope transfer process, we computed the 2° KIEs at various H/D positions at different DADs (2.9 Å to 3.5 Å) for the hydride-transfer reactions from 2-propanol to the xanthylium and thioxanthylium ions (Xn(+) and TXn(+)) and their 9-phenyl substituted derivatives (Ph(T)Xn(+)). The calculated 2° KIEs match the experiments and the calculated DAD effect on the 2° KIEs fits the observed 1° isotope effect on the 2° KIEs. These support the motion-assisted H-tunneling model and the isotopically different TRS conformations. Furthermore, it was found that the TRS of the sterically hindered Ph(T)Xn(+) system does not possess a longer DAD than that of the (T)Xn(+) system. This predicts a no larger 1° KIE in the former system than in the latter. The observed 1° KIE order is, however, contrary to the prediction. This implicates the stronger DAD-compression vibrations coupled to the bulky Ph(T)Xn(+) reaction coordinate.

Synthetic use of the primary kinetic isotope effect in hydrogen atom transfer 2: generation of captodatively stabilised radicals.

PubMed

Wood, Mark E; Bissiriou, Sabine; Lowe, Christopher; Windeatt, Kim M

2013-04-28

Using C-3 di-deuterated morpholin-2-ones bearing N-2-iodobenzyl and N-3-bromobut-3-enyl radical generating groups, only products derived from the more stabilised C-3, rather than the less stabilised C-5 translocated radicals, were formed after intramolecular 1,5-hydrogen atom transfer, suggesting that any kinetic isotope effect present was not sufficient to offset captodative stabilisation.

Zinc isotope ratio imaging of rat brain thin sections from stable isotope tracer studies by LA-MC-ICP-MS.

PubMed

Urgast, Dagmar S; Hill, Sarah; Kwun, In-Sook; Beattie, John H; Goenaga-Infante, Heidi; Feldmann, Jörg

2012-10-01

Zinc stable isotope tracers (⁶⁷Zn and ⁷⁰Zn) were injected into rats at two different time points to investigate the feasibility of using tracers to study zinc kinetics at the microscale within distinct tissue features. Laser ablation coupled to multi-collector ICP-MS was used to analyse average isotope ratios in liver thin sections and to generate bio-images showing zinc isotope ratio distribution in brain thin sections. Average isotope ratios of all samples from treated animals were found to be statistically different (P < 0.05) from samples from untreated control animals. Furthermore, differing isotope ratios in physiological features of the brain, namely hippocampus, amygdala, cortex and hypothalamus, were identified. This indicates that these regions differ in their zinc metabolism kinetics. While cortex and hypothalamus contain more tracer two days after injection than 14 days after injection, the opposite is true for hippocampus and amygdala. This study showed that stable isotope tracer experiments can be combined with laser ablation MC-ICP-MS to measure trace element kinetics in tissues at a microscale level.

Clumped isotope effects during OH and Cl oxidation of methane

NASA Astrophysics Data System (ADS)

Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan A.; Wang, David T.; Johnson, Matthew S.; Ono, Shuhei

2017-01-01

A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH was produced from the reaction of O(1D) (from O3 photolysis) with H2O, and Cl was from photolysis of Cl2. Samples were taken from the reaction cell and analyzed for methane (12CH4, 12CH3D, 13CH4, 13CH3D) isotopologue ratios using tunable infrared laser direct absorption spectroscopy. Measured kinetic isotope effects for singly substituted species were consistent with previous experimental studies. For doubly substituted methane, 13CH3D, the observed kinetic isotope effects closely follow the product of the kinetic isotope effects for the 13C and deuterium substituted species (i.e., 13,2KIE = 13KIE × 2KIE). The deviation from this relationship is 0.3‰ ± 1.2‰ and 3.5‰ ± 0.7‰ for OH and Cl oxidation, respectively. This is consistent with model calculations performed using quantum chemistry and transition state theory. The OH and Cl reactions enrich the residual methane in the clumped isotopologue in open system reactions. In a closed system, however, this effect is overtaken by the large D/H isotope effect, which causes the residual methane to become anti-clumped relative to the initial methane. Based on these results, we demonstrate that oxidation of methane by OH, the predominant oxidant for tropospheric methane, will only have a minor (∼0.3‰) impact on the clumped isotope signature (Δ13CH3D, measured as a deviation from a stochastic distribution of isotopes) of tropospheric methane. This paper shows that Δ13CH3D will provide constraints on methane source strengths, and predicts that Δ12CH2D2 can provide information on methane sink strengths.

Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

PubMed

Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

2016-06-01

The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental

Integration of kinetic isotope effect analyses to elucidate ribonuclease mechanism.

PubMed

Harris, Michael E; Piccirilli, Joseph A; York, Darrin M

2015-11-01

The well-studied mechanism of ribonuclease A is believed to involve concerted general acid-base catalysis by two histidine residues, His12 and His119. The basic features of this mechanism are often cited to explain rate enhancement by both protein and RNA enzymes that catalyze RNA 2'-O-transphosphorylation. Recent kinetic isotope effect analyses and computational studies are providing a more chemically detailed description of the mechanism of RNase A and the rate limiting transition state. Overall, the results support an asynchronous mechanism for both solution and ribonuclease catalyzed reactions in which breakdown of a transient dianoinic phosphorane intermediate by 5'OP bond cleavage is rate limiting. Relative to non-enzymatic reactions catalyzed by specific base, a smaller KIE on the 5'O leaving group and a less negative βLG are observed for RNase A catalysis. Quantum mechanical calculations consistent with these data support a model in which electrostatic and H-bonding interactions with the non-bridging oxygens and proton transfer from His119 render departure of the 5'O less advanced and stabilize charge buildup in the transition state. Both experiment and computation indicate advanced 2'OP bond formation in the rate limiting transition state. However, this feature makes it difficult to resolve the chemical steps involved in 2'O activation. Thus, modeling the transition state for RNase A catalysis underscores those elements of its chemical mechanism that are well resolved, as well as highlighting those where ambiguity remains. This article is part of a Special Issue entitled: Enzyme Transition States from Theory and Experiment. Published by Elsevier B.V.

Further Insight into the Reaction FeO+ + H2 Yields Fe+ + H2O: Temperature Dependent Kinetics, Isotope Effects, and Statistical Modeling (Postprint)

DTIC Science & Technology

2014-07-31

a laminar flow tube via a Venturi inlet, where ∼104 to 105 collisions with a He buffer gas act to thermalize the ions and carry them downstream...ISOTOPE EFFECTS , AND STATISTICAL MODELING (POSTPRINT) Shaun G. Ard, et al. 31 July 2014 Journal Article AIR FORCE RESEARCH LABORATORY Space Vehicles...Kinetics, Isotope Effects , and Statistical Modeling (Postprint) 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 61102F 6

Nitrogen isotope effects induced by anammox bacteria

PubMed Central

Brunner, Benjamin; Contreras, Sergio; Lehmann, Moritz F.; Matantseva, Olga; Rollog, Mark; Kalvelage, Tim; Klockgether, Gabriele; Lavik, Gaute; Jetten, Mike S. M.; Kartal, Boran; Kuypers, Marcel M. M.

2013-01-01

Nitrogen (N) isotope ratios (15N/14N) provide integrative constraints on the N inventory of the modern ocean. Anaerobic ammonium oxidation (anammox), which converts ammonium and nitrite to dinitrogen gas (N2) and nitrate, is an important fixed N sink in marine ecosystems. We studied the so far unknown N isotope effects of anammox in batch culture experiments. Anammox preferentially removes 14N from the ammonium pool with an isotope effect of +23.5‰ to +29.1‰, depending on factors controlling reversibility. The N isotope effects during the conversion of nitrite to N2 and nitrate are (i) inverse kinetic N isotope fractionation associated with the oxidation of nitrite to nitrate (−31.1 ± 3.9‰), (ii) normal kinetic N isotope fractionation during the reduction of nitrite to N2 (+16.0 ± 4.5‰), and (iii) an equilibrium N isotope effect between nitrate and nitrite (−60.5 ± 1.0‰), induced when anammox is exposed to environmental stress, leading to the superposition of N isotope exchange effects upon kinetic N isotope fractionation. Our findings indicate that anammox may be responsible for the unresolved large N isotope offsets between nitrate and nitrite in oceanic oxygen minimum zones. Irrespective of the extent of N isotope exchange between nitrate and nitrite, N removed from the combined nitrite and nitrate (NOx) pool is depleted in 15N relative to NOx. This net N isotope effect by anammox is superimposed on the N isotope fractionation by the co-occurring reduction of nitrate to nitrite in suboxic waters, possibly enhancing the overall N isotope effect for N loss from oxygen minimum zones. PMID:24191043

Ion kinetic scale in the solar wind observed.

PubMed

Śafránková, Jana; Němeček, Zdeněk; Přech, Lubomír; Zastenker, Georgy N

2013-01-11

This Letter shows the first results from the solar wind monitor onboard the Spektr-R spacecraft which measures plasma moments with a time resolution of 31 ms. This high-time resolution allows us to make direct observations of solar wind turbulence below ion kinetic length scales. We present examples of the frequency spectra of the density, velocity, and thermal velocity. Our study reveals that although these parameters exhibit the same behavior at the magnetohydrodynamic scale, their spectra are remarkably different at the kinetic scale.

Using in-situ observations of atmospheric water vapor isotopes to benchmark and isotope-enabled General Circulation Models and improve ice core paleo-climate reconstruction

NASA Astrophysics Data System (ADS)

Steen-Larsen, Hans Christian; Sveinbjörnsdottir, Arny; Masson-Delmotte, Valerie; Werner, Martin; Risi, Camille; Yoshimura, Kei

2016-04-01

We have since 2010 carried out in-situ continuous water vapor isotope observations on top of the Greenland Ice Sheet (3 seasons at NEEM), in Svalbard (1 year), in Iceland (4 years), in Bermuda (4 years). The expansive dataset containing high accuracy and precision measurements of δ18O, δD, and the d-excess allow us to validate and benchmark the treatment of the atmospheric hydrological cycle's processes in General Circulation Models using simulations nudged to reanalysis products. Recent findings from both Antarctica and Greenland have documented strong interaction between the snow surface isotopes and the near surface atmospheric water vapor isotopes on diurnal to synoptic time scales. In fact, it has been shown that the snow surface isotopes take up the synoptic driven atmospheric water vapor isotopic signal in-between precipitation events, erasing the precipitation isotope signal in the surface snow. This highlights the importance of using General or Regional Climate Models, which accurately are able to simulate the atmospheric water vapor isotopic composition, to understand and interpret the ice core isotope signal. With this in mind we have used three isotope-enabled General Circulation Models (isoGSM, ECHAM5-wiso, and LMDZiso) nudged to reanalysis products. We have compared the simulations of daily mean isotope values directly with our in-situ observations. This has allowed us to characterize the variability of the isotopic composition in the models and compared it to our observations. We have specifically focused on the d-excess in order to characterize why both the mean and the variability is significantly lower than our observations. We argue that using water vapor isotopes to benchmark General Circulation Models offers an excellent tool for improving the treatment and parameterization of the atmospheric hydrological cycle. Recent studies have documented a very large inter-model dispersion in the treatment of the Arctic water cycle under a future global

Probing Reversible Chemistry in Coenzyme B12-Dependent Ethanolamine Ammonia Lyase with Kinetic Isotope Effects

PubMed Central

Jones, Alex R; Rentergent, Julius; Scrutton, Nigel S; Hay, Sam

2015-01-01

Coenzyme B12-dependent enzymes such as ethanolamine ammonia lyase have remarkable catalytic power and some unique properties that enable detailed analysis of the reaction chemistry and associated dynamics. By selectively deuterating the substrate (ethanolamine) and/or the β-carbon of the 5′-deoxyadenosyl moiety of the intrinsic coenzyme B12, it was possible to experimentally probe both the forward and reverse hydrogen atom transfers between the 5′-deoxyadenosyl radical and substrate during single-turnover stopped-flow measurements. These data are interpreted within the context of a kinetic model where the 5′-deoxyadenosyl radical intermediate may be quasi-stable and rearrangement of the substrate radical is essentially irreversible. Global fitting of these data allows estimation of the intrinsic rate constants associated with CoC homolysis and initial H-abstraction steps. In contrast to previous stopped-flow studies, the apparent kinetic isotope effects are found to be relatively small. PMID:25950663

Mathematical treatment of isotopologue and isotopomer speciation and fractionation in biochemical kinetics

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

Maggi, F.M.; Riley, W.J.

2009-11-01

We present a mathematical treatment of the kinetic equations that describe isotopologue and isotopomer speciation and fractionation during enzyme-catalyzed biochemical reactions. These equations, presented here with the name GEBIK (general equations for biochemical isotope kinetics) and GEBIF (general equations for biochemical isotope fractionation), take into account microbial biomass and enzyme dynamics, reaction stoichiometry, isotope substitution number, and isotope location within each isotopologue and isotopomer. In addition to solving the complete GEBIK and GEBIF, we also present and discuss two approximations to the full solutions under the assumption of biomass-free and enzyme steady-state, and under the quasi-steady-state assumption as applied tomore » the complexation rate. The complete and approximate approaches are applied to observations of biological denitrification in soils. Our analysis highlights that the full GEBIK and GEBIF provide a more accurate description of concentrations and isotopic compositions of substrates and products throughout the reaction than do the approximate forms. We demonstrate that the isotopic effects of a biochemical reaction depend, in the most general case, on substrate and complex concentrations and, therefore, the fractionation factor is a function of time. We also demonstrate that inverse isotopic effects can occur for values of the fractionation factor smaller than 1, and that reactions that do not discriminate isotopes do not necessarily imply a fractionation factor equal to 1.« less

Influence of water on clumped-isotope bond reordering kinetics in calcite

NASA Astrophysics Data System (ADS)

Brenner, Dana C.; Passey, Benjamin H.; Stolper, Daniel A.

2018-03-01

Oxygen self-diffusion in calcite and many other minerals is considerably faster under wet conditions relative to dry conditions. Here we investigate whether this "water effect" also holds true for solid-state isotope exchange reactions that alter the abundance of carbonate groups with multiple rare isotopes ('clumped' isotope groups) via the process of solid-state bond reordering. We present clumped-isotope reordering rates for optical calcite heated under wet, high-pressure (100 MPa) conditions. We observe only modest increases in reordering rates under such conditions compared with rates for the same material reacted in dry CO2 under low-pressure conditions. Activation energies under wet, high-pressure conditions are indistinguishable from those for dry, low-pressure conditions, while rate constants are resolvably higher (up to ∼3 times) for wet, high-pressure relative to dry, low-pressure conditions in most of our interpretations of experimental results. This contrasts with the water effect for oxygen self-diffusion in calcite, which is associated with lower activation energies, and diffusion coefficients that are ≥103 times higher compared with dry (pure CO2) conditions in the temperature range of this study (385-450 °C). The water effect for clumped-isotopes leads to calculated apparent equilibrium temperatures ("blocking temperatures") for typical geological cooling rates that are only a few degrees higher than those for dry conditions, while O self-diffusion blocking temperatures in calcite grains are ∼150-200 °C lower in wet conditions compared with dry conditions. Since clumped-isotope reordering is a distributed process that occurs throughout the mineral volume, our clumped-isotope results support the suggestion of Labotka et al. (2011) that the water effect in calcite does not involve major changes in bulk (volume) diffusivity, but rather is primarily a surface phenomenon that facilitates oxygen exchange between the calcite surface and external

Combinatorial effects on clumped isotopes and their significance in biogeochemistry

NASA Astrophysics Data System (ADS)

Yeung, Laurence Y.

2016-01-01

The arrangement of isotopes within a collection of molecules records their physical and chemical histories. Clumped-isotope analysis interrogates these arrangements, i.e., how often rare isotopes are bound together, which in many cases can be explained by equilibrium and/or kinetic isotope fractionation. However, purely combinatorial effects, rooted in the statistics of pairing atoms in a closed system, are also relevant, and not well understood. Here, I show that combinatorial isotope effects are most important when two identical atoms are neighbors on the same molecule (e.g., O2, N2, and D-D clumping in CH4). When the two halves of an atom pair are either assembled with different isotopic preferences or drawn from different reservoirs, combinatorial effects cause depletions in clumped-isotope abundance that are most likely between zero and -1‰, although they could potentially be -10‰ or larger for D-D pairs. These depletions are of similar magnitude, but of opposite sign, to low-temperature equilibrium clumped-isotope effects for many small molecules. Enzymatic isotope-pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect, although it is not limited to biological reactions. Chemical-kinetic isotope effects, which are related to a bond-forming transition state, arise independently and express second-order combinatorial effects related to the abundance of the rare isotope. Heteronuclear moeties (e.g., Csbnd O and Csbnd H), are insensitive to direct combinatorial influences, but secondary combinatorial influences are evident. In general, both combinatorial and chemical-kinetic factors are important for calculating and interpreting clumped-isotope signatures of kinetically controlled reactions. I apply this analytical framework to isotope-pairing reactions relevant to geochemical oxygen, carbon, and nitrogen cycling that may be influenced by combinatorial

Hydrogen Donor-Acceptor Fluctuations from Kinetic Isotope Effects: A Phenomenological Model

PubMed Central

Roston, Daniel; Cheatum, Christopher M.; Kohen, Amnon

2012-01-01

Kinetic isotope effects (KIEs) and their temperature dependence can probe the structural and dynamic nature of enzyme-catalyzed proton or hydride transfers. The molecular interpretation of their temperature dependence requires expensive and specialized QM/MM calculations to provide a quantitative molecular understanding. Currently available phenomenological models use a non-adiabatic assumption that is not appropriate for most hydride and proton-transfer reactions, while others require more parameters than the experimental data justify. Here we propose a phenomenological interpretation of KIEs based on a simple method to quantitatively link the size and temperature dependence of KIEs to a conformational distribution of the catalyzed reaction. The present model assumes adiabatic hydrogen tunneling, and by fitting experimental KIE data, the model yields a population distribution for fluctuations of the distance between donor and acceptor atoms. Fits to data from a variety of proton and hydride transfers catalyzed by enzymes and their mutants, as well as non-enzymatic reactions, reveal that steeply temperature-dependent KIEs indicate the presence of at least two distinct conformational populations, each with different kinetic behaviors. We present the results of these calculations for several published cases and discuss how the predictions of the calculations might be experimentally tested. The current analysis does not replace molecular quantum mechanics/molecular mechanics (QM/MM) investigations, but it provides a fast and accessible way to quantitatively interpret KIEs in the context of a Marcus-like model. PMID:22857146

Deuterium isotope effects in polymerization of benzene under pressure

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

Cai, Weizhao; Dunuwille, Mihindra; He, Jiangang

The enormous versatility in the properties of carbon materials depends on the content of the sp 2 and sp 3 covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C 6H 6 and C 6D 6 up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures showmore » the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C 6D 6 shed light on the mechanism of polymerization of benzene. Lastly, we find that C 6D 6-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp 3 hydrogen contents. Significant isotopic shift (≥7 GPa) in persistence of Bragg reflections of C 6D 6 is observed.« less

Deuterium isotope effects in polymerization of benzene under pressure

DOE PAGES

Cai, Weizhao; Dunuwille, Mihindra; He, Jiangang; ...

2017-04-10

The enormous versatility in the properties of carbon materials depends on the content of the sp 2 and sp 3 covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C 6H 6 and C 6D 6 up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures showmore » the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C 6D 6 shed light on the mechanism of polymerization of benzene. Lastly, we find that C 6D 6-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp 3 hydrogen contents. Significant isotopic shift (≥7 GPa) in persistence of Bragg reflections of C 6D 6 is observed.« less

Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects

USGS Publications Warehouse

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

2004-01-01

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr-(VI) and Cr(VI) adsorbed onto ??-Al2O3 and goethite is less than 0.04???. (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO42- was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in ??53 Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

Isotope effect of mercury diffusion in air

PubMed Central

Koster van Groos, Paul G.; Esser, Bradley K.; Williams, Ross W.; Hunt, James R.

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature. PMID:24364380

Isotope effect of mercury diffusion in air.

PubMed

Koster van Groos, Paul G; Esser, Bradley K; Williams, Ross W; Hunt, James R

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature.

Carbonic Anhydrase, Calcification Dynamics and Stable Isotope Vital Effects: Deep Sea Corals and Beyond

NASA Astrophysics Data System (ADS)

Chen, S.; Gagnon, A. C.; Adkins, J. F.

2017-12-01

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed "vital effects". A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ18O and δ13C in a range of values that are depleted from equilibrium. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO2(aq)-HCO3- inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO3- inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ18O-δ13C correlation. With this model, we are not only able to fit deep sea coral data, but also explain the stable isotope vital effects of other calcifying organisms. This fully kinetic model of stable isotope vital effects and the underlying calcification dynamics may also help us better understand mechanisms of other paleoceanographic tracers in biogenic carbonates, including boron isotopes and trace metal proxies.

Methane clumped isotopes: Progress and potential for a new isotopic tracer

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

Douglas, Peter M. J.; Stolper, Daniel A.; Eiler, John M.

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding hydrocarbon systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a potentially valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here wemore » present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. We review different processes affecting methane clumped isotope compositions, describe the relationships between conventional isotope and clumped isotope data, and summarize the types of information that this measurement can provide in different Earth and planetary environments.« less

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects.

PubMed

Lemke, Sonja; Handle, Philip H; Plaga, Lucie J; Stern, Josef N; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

2017-07-21

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects

NASA Astrophysics Data System (ADS)

Lemke, Sonja; Handle, Philip H.; Plaga, Lucie J.; Stern, Josef N.; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W.; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

2017-07-01

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

Observations of Carbon Isotopic Fractionation in Interstellar Formaldehyde

NASA Technical Reports Server (NTRS)

Wirstrom, E. S.; Charnley, S. B.; Geppert, W. D.; Persson, C. M.

2012-01-01

Primitive Solar System materials (e.g. chondrites. IDPs, the Stardust sample) show large variations in isotopic composition of the major volatiles (H, C, N, and O ) even within samples, witnessing to various degrees of processing in the protosolar nebula. For ex ample. the very pronounced D enhancements observed in IDPs [I] . are only generated in the cold. dense component of the interstellar medium (ISM), or protoplanetary disks, through ion-molecule reactions in the presence of interstellar dust. If this isotopic anomaly has an interstellar origin, this leaves open the possibility for preservation of other isotopic signatures throughout the form ation of the Solar System. The most common form of carbon in the ISM is CO molecules, and there are two potential sources of C-13 fractionation in this reservoir: low temperature chemistry and selective photodissociation. While gas-phase chemistry in cold interstellar clouds preferentially incorporates C-13 into CO [2], the effect of self-shielding in the presence of UV radiation instead leads to a relative enhancement of the more abundant isotopologue, 12CO. Solar System organic material exhibit rather small fluctuations in delta C-13 as compared to delta N-15 and delta D [3][1], the reason for which is still unclear. However, the fact that both C-13 depleted and enhanced material exists could indicate an interstellar origin where the two fractionation processes have both played a part. Formaldehyde (H2CO) is observed in the gas-phase in a wide range of interstellar environments, as well as in cometary comae. It is proposed as an important reactant in the formation of more complex organic molecules in the heated environments around young stars, and formaldehyde polymers have been suggested as the common origin of chondritic insoluable organic matter (IOM) and cometary refractory organic solids [4]. The relatively high gas-phase abundance of H2CO observed in molecular clouds (10(exp- 9) - 10(exp- 8) relative to H2) makes

The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

NASA Astrophysics Data System (ADS)

Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

2014-04-01

Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

Modeling stable isotope transport in metamorphic and hydrothermal systems

NASA Astrophysics Data System (ADS)

Baumgartner, L. P.; Mueller, T.; Skora, S.; Begue, F.

2007-12-01

Stable isotopes are powerful tools for deciphering the fluid flow histories of metamorphic terrains. The nature of fluid flow, fluid sources, and fluid fluxes can be delineated in well constrained studies. Continuum mechanics models for stable isotope fluid-rock exchange were developed and used over the last three decades in an attempt to accurately interpret the signatures left behind by fluid flow in the earths crust. The efforts have been hampered by the realization that the exchange of many stable isotopes, e.g. oxygen and carbon, by intracrystalline diffusion, hence without re-organization of the crystal lattice, appears to be too slow to achieve significant exchange. This should lead to relatively flat isotopic exchange profiles on hand-, outcrop, or aureole scale. Nevertheless, isotopic fronts are typically sharp (sub mm to cm scale), when measured in the field. This has lead to the suggestion that these sharp fronts correspond to the sides of infiltration fronts, implying the data to have been collected at a high angle to the infiltration direction. Nevertheless, the fact that the oxygen and carbon fronts are located at the same place is not explained by this. A review of published carbon and oxygen data reveals that many contact aureoles show linear trends in oxygen-carbon isotope ratio diagrams for carbonate sample suits. This implies that the fluid composition infiltrating the aureoles had essentially an X(CO2) of 0.5. This is in contrast to skarn mineralogy developed, which requires a water-rich fluid, in agreement with the general notion that igneous fluids are water-rich. These and other observations indicate that the mass transport equation used for stable isotope exchange needs to be improved to model appropriately the actual isotope kinetics during fluid-rock exchange. Detailed isotope studies on systems where net transport reactions are driven by mass transport have led us to identify different exchange mechanisms, including: a) the stable isotope

Carbon Kinetic Isotope Effects in the Oxidation of Atmospheric Alkane and Aromatic Hydrocarbons by Hydroxyl Radicals

NASA Astrophysics Data System (ADS)

Anderson, R. S.; Thompson, A. E.; Rudolph, J.; Huang, L.

2001-12-01

To interpret measurements of stable carbon isotope ratios of ambient NMHC, we need to understand the isotopic composition of the emissions, and the isotope fractionation associated with the removal of NMHC from the atmosphere. Oxidation by OH-radicals is by far the most important atmospheric process for removal of NMHC. In this presentation measurements of the kinetic isotope effects (KIEs) for the reactions of hydroxyl radicals with several C5-C8 alkanes, including cyclic, branched and straight-chain alkanes, as well as C6-C9 aromatics are presented. All KIEs are positive: compounds containing only 12C atoms react faster than 13C labelled compounds. KIEs for light n-alkanes are typically between 1.5-4‰ and are larger than mass dependent collision frequencies, deviating from the collision frequency as carbon number increases. For n-alkanes there is no statistically significant difference between the KIEs of structural isomers. KIEs for the reactions of light alkenes and aromatics with OH-radicals are considerably higher than for alkane reactions, ranging from 3-18‰ . The KIEs for the aromatic reactions can be described by a 33.3+/-2.0‰ fractionation for the addition of an OH-radical to the aromatic ring and an inverse dependency on the number of carbon atoms, added to the mass dependent collision frequency. There are indications for minor structure specific effects, however the deviations from the idealised inverse carbon number dependence is relatively small and the limited number of studied alkyl benzenes does not yet allow the identification of systematic dependencies.

The NO+O3 reaction: a triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly.

PubMed

Savarino, J; Bhattacharya, S K; Morin, S; Baroni, M; Doussin, J-F

2008-05-21

Atmospheric nitrate shows a large oxygen isotope anomaly (Delta 17 O), characterized by an excess enrichment of 17 O over 18 O, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NOx=NO+NO2). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NO(x), greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO+O3. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8+/-5)%(+/-2 sigma) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O3 to NO2, which is described by the linear relationship Delta 17 O(NO2)=A x Delta 17 O(O3)+B, with A=1.18+/-0.07(+/-1 sigma) and B=(6.6+/-1.5)[per thousand](+/-1 sigma). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.

Path Integral Simulation of the H/D Kinetic Isotope Effect in Monoamine Oxidase B Catalyzed Decomposition of Dopamine.

PubMed

Mavri, Janez; Matute, Ricardo A; Chu, Zhen T; Vianello, Robert

2016-04-14

Brain monoamines regulate many centrally mediated body functions, and can cause adverse symptoms when they are out of balance. A starting point to address challenges raised by the increasing burden of brain diseases is to understand, at atomistic level, the catalytic mechanism of an essential amine metabolic enzyme-monoamine oxidase B (MAO B). Recently, we demonstrated that the rate-limiting step of MAO B catalyzed conversion of amines into imines represents the hydride anion transfer from the substrate α-CH2 group to the N5 atom of the flavin cofactor moiety. In this article we simulated for MAO B catalyzed dopamine decomposition the effects of nuclear tunneling by the calculation of the H/D kinetic isotope effect. We applied path integral quantization of the nuclear motion for the methylene group and the N5 atom of the flavin moiety in conjunction with the QM/MM treatment on the empirical valence bond (EVB) level for the rest of the enzyme. The calculated H/D kinetic isotope effect of 12.8 ± 0.3 is in a reasonable agreement with the available experimental data for closely related biogenic amines, which gives strong support for the proposed hydride mechanism. The results are discussed in the context of tunneling in enzyme centers and advent of deuterated drugs into clinical practice.

Carbon kinetic isotope effects in the gas-phase reactions of aromatic hydrocarbons with the OH radical at 296 +/- 4 K

NASA Astrophysics Data System (ADS)

Anderson, Rebecca S.; Iannone, Richard; Thompson, Alexandra E.; Rudolph, Jochen; Huang, Lin

2004-08-01

The carbon kinetic isotope effects (KIEs) of the room temperature reactions of benzene and several light alkyl benzenes with OH radicals were studied in a reaction chamber at ambient pressure using gas chromatography coupled with online combustion and isotope ratio mass spectrometry (GCC-IRMS). The KIEs are reported in per mil according to $\\varepsilon$ (‰) = (KIE - 1) × 1000, where KIE = k12/k13. The following average KIEs were obtained, (all in ‰): benzene 7.53 +/- 0.50; toluene 5.95 +/- 0.28; ethylbenzene 4.34 +/- 0.28; o-xylene 4.27 +/- 0.05, p-xylene 4.83 +/- 0.81; o-ethyltoluene 4.71 +/- 0.12 and 1,2,4-trimethylbenzene 3.18 +/- 0.09. Our KIE value for benzene + OH agrees with the only reported value known to us [Rudolph et al., 2000]. It is shown that measurements of the stable carbon isotope ratios of light aromatic compounds should be extremely useful to study atmospheric processing by the OH radical.

Sulfur Isotope Effects of Dissimilatory Sulfite Reductase

PubMed Central

Leavitt, William D.; Bradley, Alexander S.; Santos, André A.; Pereira, Inês A. C.; Johnston, David T.

2015-01-01

The precise interpretation of environmental sulfur isotope records requires a quantitative understanding of the biochemical controls on sulfur isotope fractionation by the principle isotope-fractionating process within the S cycle, microbial sulfate reduction (MSR). Here we provide the only direct observation of the major (34S/32S) and minor (33S/32S, 36S/32S) sulfur isotope fractionations imparted by a central enzyme in the energy metabolism of sulfate reducers, dissimilatory sulfite reductase (DsrAB). Results from in vitro sulfite reduction experiments allow us to calculate the in vitro DsrAB isotope effect in 34S/32S (hereafter, 34εDsrAB) to be 15.3 ± 2‰, 2σ. The accompanying minor isotope effect in 33S, described as 33λDsrAB, is calculated to be 0.5150 ± 0.0012, 2σ. These observations facilitate a rigorous evaluation of the isotopic fractionation associated with the dissimilatory MSR pathway, as well as of the environmental variables that govern the overall magnitude of fractionation by natural communities of sulfate reducers. The isotope effect induced by DsrAB upon sulfite reduction is a factor of 0.3–0.6 times prior indirect estimates, which have ranged from 25 to 53‰ in 34εDsrAB. The minor isotope fractionation observed from DsrAB is consistent with a kinetic or equilibrium effect. Our in vitro constraints on the magnitude of 34εDsrAB is similar to the median value of experimental observations compiled from all known published work, where 34εr−p = 16.1‰ (r–p indicates reactant vs. product, n = 648). This value closely matches those of MSR operating at high sulfate reduction rates in both laboratory chemostat experiments (34εSO4−H2S =  17.3 ± 1.5‰, 2σ) and in modern marine sediments (34εSO4−H2S =  17.3 ± 3.8‰). Targeting the direct isotopic consequences of a specific enzymatic processes is a fundamental step toward a biochemical foundation for reinterpreting the biogeochemical and geobiological sulfur isotope records in

Magnesium Isotopic Evidence for Widespread Microbial Dolomite Precipitation in the Geological Record.

NASA Astrophysics Data System (ADS)

Carder, E. A.; Galy, A.; McKenzie, J. A.; Vasconcelos, C.; Elderfield, H.

2005-12-01

The enigma surrounding the `Dolomite Problem' is the relative abundance of dolomite in the geological record versus its very rare occurrence on the surface of the modern Earth despite a particularly favourable modern seawater chemistry. Recent studies of modern dolomite from hypersaline coastal lagoons in Brazil and Pleistocene dolomite from ODP cores collected during ODP Leg 201 on the Peru Margin suggest microbial mediation is an important factor [1]. Indeed, cultures of sulfate-reducing bacteria isolated from the lagoons mediate dolomite precipitation in the laboratory [2, 3]. In this study we report magnesium isotopic analyses of these modern microbial associated dolomites and ancient dolomites of a range of geological ages and environments. The application of stable magnesium isotopes to study dolomite formation and the nature of the processes involved represents a new frontier in isotope geochemistry. Highly accurate determination of the magnesium isotopic composition allows us to distinguish between kinetic and equilibrium isotope fractionation on the basis of the excess of 25Mg. A significant kinetic isotope fractionation is observed in laboratory cultures and surfical microbial mats from the Brazilian lagoons. Older dolomites (<3000 yrs.) taken from cores recovered from the lagoon are much closer to equilibrium. We interpret our data as evidencing an initial microbial mediated nucleation of dolomite that is a kinetic process and a subsequent inorganic addition of dolomite overprinting an equilibrium signature. This is in agreement with a previous major element and crystallographic study of the Brazilian dolomites [1]. The ancient dolomites analysed range in age from Neoproterozoic to Pleistocene and come from diverse geological environments including submarine diagenetic zones, platform carbonates and lagoonal environments. Magnesium isotopic analysis shows evidence of a varying component of kinetic fractionation, smaller than the kinetic end member as

How to explain Si isotopes of chert?

NASA Astrophysics Data System (ADS)

Liu, Y.

2016-12-01

The variations of d30Si values in diagenetic chert and chert- associated BIFs over time can be used to reconstruct the environmental conditions of the early Earth, and become a hot topic in the Si isotope society. However, there are several different views of explaining the variation of d30Si values over time. Moreover, there are disputes in explaining the distribution of Si isotope in several main reservoirs in surface systems. Those disagreements are caused by lacking key Si isotope fractionation factors associated with the formation processes of chert and its altered products. There are many unexplained observations about Si isotope distributions in Earth's surface systems (Opfergelt and Delmelle, 2012). For example, the deduced Si isotope equilibrium fractionation factors by Rayleigh model at ambient temperature between clay and the solution D30Siclay-solution = -1.5 ‰ and -2.05 ‰ (Hughes et al., 2013) obviously disagree with common sense, which dictates that stiffer chemical bonds will enrich heavier isotopes, i.e., the precipitated minerals will preferentially incorporate heavy isotopes relative to aqueous H4SiO4 due to their shorter Si-O bonds. Another similar case is the fractionation between quartz and solution. Most field observations suggested that solution will be enriched with heavier Si isotope compared to quartz, conflicting to the fact that quartz is the one with much shorter Si-O bonds than aqueous H4SiO4 (ca. 1.610Å vs. 1.639Å). Here we provide equilibrium and kinetic Si isotope fractionation factors associated with the formation of amorphous quartz and other secondary minerals in polymerization, co-precipitation and adsorption processes. The adsorption processes of silica gel to Fe-hydroxides have been carefully examined. The Si isotope fractionations due to the formation of mono-dentate to quadru-dentate adsorbed Fe-Si complexes have been calculated. These data can explain well the experimental observations (e.g., Zheng et al., 2016) and

Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

DOE PAGES

Luo, Weifang; Cowgill, Donald F.

2015-07-22

Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H 2 + PdD and D 2 + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H 2/atm cm 2 s is found for H 2 + PdD atmore » 298 K, 1.4 times higher than that for D 2 + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.« less

Kinetic isotopic fractionation during diffusion of ionic species in water

NASA Astrophysics Data System (ADS)

Richter, Frank M.; Mendybaev, Ruslan A.; Christensen, John N.; Hutcheon, Ian D.; Williams, Ross W.; Sturchio, Neil C.; Beloso, Abelardo D.

2006-01-01

Experiments specifically designed to measure the ratio of the diffusivities of ions dissolved in water were used to determine DLi/DK,D/D,D/D,D/D,andD/D. The measured ratio of the diffusion coefficients for Li and K in water (D Li/D K = 0.6) is in good agreement with published data, providing evidence that the experimental design being used resolves the relative mobility of ions with adequate precision to also be used for determining the fractionation of isotopes by diffusion in water. In the case of Li, we found measurable isotopic fractionation associated with the diffusion of dissolved LiCl (D/D=0.99772±0.00026). This difference in the diffusion coefficient of 7Li compared to 6Li is significantly less than that reported in an earlier study, a difference we attribute to the fact that in the earlier study Li diffused through a membrane separating the water reservoirs. Our experiments involving Mg diffusing in water found no measurable isotopic fractionation (D/D=1.00003±0.00006). Cl isotopes were fractionated during diffusion in water (D/D=0.99857±0.00080) whether or not the co-diffuser (Li or Mg) was isotopically fractionated. The isotopic fractionation associated with the diffusion of ions in water is much smaller than values we found previously for the isotopic fractionation of Li and Ca isotopes by diffusion in molten silicate liquids. A major distinction between water and silicate liquids is that water surrounds dissolved ions with hydration shells, which very likely play an important but still poorly understood role in limiting the isotopic fractionation associated with diffusion.

Rare earth element transport in the western North Atlantic inferred from Nd isotopic observations

NASA Technical Reports Server (NTRS)

Piepgras, D. J.; Wasserburg, G. J.

1987-01-01

The relationship between the Nd isotopic composition in the Atlantic waters and the origin and circulation of the water masses was investigated. Samples were collected in the western North Atlantic between 7 and 54 deg N. The isotopic composition (Nd-143/Nd-144 ratios) showed extensive vertical structure at all locations. In regions where a thermocline was well-developed, large isotopic shifts were observed across the base of the thermocline, while regions without a thermocline were characterized by much more gradual shifts in isotopic composition with depth. The data reveal an excellent correlation between the Nd isotopic distribution in the western North Atlantic water column and the distribution of water masses identified from temperature and salinity measurements.

Extremely elevated room-temperature kinetic isotope effects quantify the critical role of barrier width in enzymatic C-H activation.

PubMed

Hu, Shenshen; Sharma, Sudhir C; Scouras, Alexander D; Soudackov, Alexander V; Carr, Cody A Marcus; Hammes-Schiffer, Sharon; Alber, Tom; Klinman, Judith P

2014-06-11

The enzyme soybean lipoxygenase (SLO) has served as a prototype for hydrogen-tunneling reactions, as a result of its unusual kinetic isotope effects (KIEs) and their temperature dependencies. Using a synergy of kinetic, structural, and theoretical studies, we show how the interplay between donor-acceptor distance and active-site flexibility leads to catalytic behavior previously predicted by quantum tunneling theory. Modification of the size of two hydrophobic residues by site-specific mutagenesis in SLO reduces the reaction rate 10(4)-fold and is accompanied by an enormous and unprecedented room-temperature KIE. Fitting of the kinetic data to a non-adiabatic model implicates an expansion of the active site that cannot be compensated by donor-acceptor distance sampling. A 1.7 Å resolution X-ray structure of the double mutant further indicates an unaltered backbone conformation, almost identical side-chain conformations, and a significantly enlarged active-site cavity. These findings show the compelling property of room-temperature hydrogen tunneling within a biological context and demonstrate the very high sensitivity of such tunneling to barrier width.

Observation and modelling of stable isotopes in precipitation for midlatitude weather systems in Melbourne, Australia

NASA Astrophysics Data System (ADS)

Barras, Vaughan; Simmonds, Ian

2010-05-01

The application of stable water isotopes as tracers of moisture throughout the hydrological cycle is often hindered by the relatively coarse temporal and spatial resolution of observational data. Intensive observation periods (IOPs) of isotopes in precipitation have been valuable in this regard enabling the quantification of the effects of vapour recycling, convection, cloud top height and droplet reevaporation (Dansgaard, 1953; Miyake et al., 1968; Gedzelman and Lawrence, 1982; 1990; Pionke and DeWalle, 1992; Risi et al., 2008; 2009) and have been used as a basis to develop isotope models of varying complexity (Lee and Fung, 2008; Bony et al., 2008). This study took a unified approach combining observation and modelling of stable isotopes in precipitation in an investigation of three key circulation types that typically bring rainfall to southeastern Australia. The observational component of this study involved the establishment of the Melbourne University Network of Isotopes in Precipitation (MUNIP). MUNIP was devised to sample rainwater simultaneously at a number of collection sites across greater Melbourne to record the spatial and temporal isotopic variability of precipitation during the passage of particular events. Samples were collected at half-hourly intervals for three specific rain events referred to as (1) mixed-frontal, (2) convective, and (3) stratiform. It was found that the isotopic content for each event varied over both high and low frequencies due to influences from local changes in rain intensity and large scale rainout respectively. Of particular note was a positive relationship between deuterium excess and rainfall amount under convective conditions. This association was less well defined for stratiform rainfall. As a supplement to the data coverage of the observations, the events were simulated using a version of NCAR CAM3 running with an isotope hydrology scheme. This was done by periodically nudging the model dynamics with data from the

Arctic Ocean Cyclostratigraphy: An Alternative to Marine Oxygen Isotope curves as measures of Cryospheric and Sea-Level History

NASA Astrophysics Data System (ADS)

Cronin, T. M.; Marzen, R.; O'Regan, M.; Dwyer, G. S.

2016-12-01

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed "vital effects". A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ18O and δ13C in a range of values that are depleted from equilibrium. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO2(aq)-HCO3- inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO3- inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ18O-δ13C correlation. With this model, we are not only able to fit deep sea coral data, but also explain the stable isotope vital effects of other calcifying organisms. This fully kinetic model of stable isotope vital effects and the underlying calcification dynamics may also help us better understand mechanisms of other paleoceanographic tracers in biogenic carbonates, including boron isotopes and trace metal proxies.

Transient-state kinetic approach to mechanisms of enzymatic catalysis.

PubMed

Fisher, Harvey F

2005-03-01

Transient-state kinetics by its inherent nature can potentially provide more directly observed detailed resolution of discrete events in the mechanistic time courses of enzyme-catalyzed reactions than its more widely used steady-state counterpart. The use of the transient-state approach, however, has been severely limited by the lack of any theoretically sound and applicable basis of interpreting the virtual cornucopia of time and signal-dependent phenomena that it provides. This Account describes the basic kinetic behavior of the transient state, critically examines some currently used analytic methods, discusses the application of a new and more soundly based "resolved component transient-state time-course method" to the L-glutamate-dehydrogenase reaction, and establishes new approaches for the analysis of both single- and multiple-step substituted transient-state kinetic isotope effects.

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

PubMed

Tea, Illa; Tcherkez, Guillaume

2017-01-01

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

Kinetic control on Zn isotope signatures recorded in marine diatoms

NASA Astrophysics Data System (ADS)

Köbberich, Michael; Vance, Derek

2017-08-01

Marine diatoms dominate the oceanic cycle of the essential micronutrient zinc (Zn). The stable isotopes of zinc and other metals are increasingly used to understand trace metal micronutrient cycling in the oceans. One clear feature of the early isotope data is the heavy Zn isotope signature of the average oceanic dissolved pool relative to the inputs, potentially driven by uptake of light isotopes into phytoplankton cells and export to sediments. However, despite the fact that diatoms strip Zn from surface waters across the Antarctic polar front in the Southern Ocean, the local upper ocean is not isotopically heavy. Here we use culturing experiments to quantify the extent of Zn isotope fractionation by diatoms and to elucidate the mechanisms driving it. We have cultured two different open-ocean diatom species (T. oceanica and Chaetoceros sp.) in a series of experiments at constant medium Zn concentration but at bioavailable medium Fe ranging from limiting to replete. We find that T. oceanica can maintain high growth rates and Zn uptake rates over the full range of bioavailable iron (Fe) investigated, and that the Zn taken up has a δ66Zn that is unfractionated relative to that of the bioavailable free Zn in the medium. The studied representative of the genus Chaetoceros, on the other hand, shows more significantly reduced Zn uptake rates at low Fe and records more variable biomass δ66Zn signatures, of up to 0.85‰ heavier than the medium. We interpret the preferential uptake of heavy isotopes at extremely low Zn uptake rates as potentially due to either of the following two mechanisms. First, the release of extracellular polymeric substances (EPS), at low Fe levels, may preferentially scavenge heavy Zn isotopes. Second, the Zn uptake rate may be slow enough to establish pseudo-equilibrium conditions at the transporter site, with heavy Zn isotopes forming more stable surface complexes. Thus we find that, in our experiments, Fe-limitation exerts a key control that

New constraints on kinetic isotope effects during CO2(aq) hydration and hydroxylation: Revisiting theoretical and experimental data

NASA Astrophysics Data System (ADS)

Sade, Ziv; Halevy, Itay

2017-10-01

CO2 (de)hydration (i.e., CO2 hydration/HCO3- dehydration) and (de)hydroxylation (i.e., CO2 hydroxylation/HCO3- dehydroxylation) are key reactions in the dissolved inorganic carbon (DIC) system. Kinetic isotope effects (KIEs) during these reactions are likely to be expressed in the DIC and recorded in carbonate minerals formed during CO2 degassing or dissolution of gaseous CO2. Thus, a better understanding of KIEs during CO2 (de)hydration and (de)hydroxylation would improve interpretations of disequilibrium compositions in carbonate minerals. To date, the literature lacks direct experimental constraints on most of the oxygen KIEs associated with these reactions. In addition, theoretical estimates describe oxygen KIEs during separate individual reactions. The KIEs of the related reverse reactions were neither derived directly nor calculated from a link to the equilibrium fractionation. Consequently, KIE estimates of experimental and theoretical studies have been difficult to compare. Here we revisit experimental and theoretical data to provide new constraints on oxygen KIEs during CO2 (de)hydration and (de)hydroxylation. For this purpose, we provide a clearer definition of the KIEs and relate them both to isotopic rate constants and equilibrium fractionations. Such relations are well founded in studies of single isotope source/sink reactions, but they have not been established for reactions that involve dual isotopic sources/sinks, such as CO2 (de)hydration and (de)hydroxylation. We apply the new quantitative constraints on the KIEs to investigate fractionations during simultaneous CaCO3 precipitation and HCO3- dehydration far from equilibrium.

Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

NASA Astrophysics Data System (ADS)

Xie, Xueshu; Zubarev, Roman A.

2015-03-01

Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p << 10-15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas.

Evaluating rainfall kinetic energy - intensity relationships with observed disdrometric data

NASA Astrophysics Data System (ADS)

Angulo-Martinez, Marta; Begueria, Santiago; Latorre, Borja

2016-04-01

Rainfall kinetic energy is required for determining erosivity, the ability of rainfall to detach soil particles and initiate erosion. Its determination relay on the use of disdrometers, i.e. devices capable of measuring the drop size distribution and velocity of falling raindrops. In the absence of such devices, rainfall kinetic energy is usually estimated with empirical expressions relating rainfall energy and intensity. We evaluated the performance of 14 rainfall energy equations in estimating one-minute rainfall energy and event total energy, in comparison with observed data from 821 rainfall episodes (more than 100 thousand one-minute observations) by means of an optical disdrometer. In addition, two sources of bias when using such relationships were evaluated: i) the influence of using theoretical terminal raindrop fall velocities instead of measured values; and ii) the influence of time aggregation (rainfall intensity data every 5-, 10-, 15-, 30-, and 60-minutes). Empirical relationships did a relatively good job when complete events were considered (R2 > 0.82), but offered poorer results for within-event (one-minute resolution) variation. Also, systematic biases where large for many equations. When raindrop size distribution was known, estimating the terminal fall velocities by empirical laws produced good results even at fine time resolution. The influence of time aggregation was very high in the estimated kinetic energy, although linear scaling may allow empirical correction. This results stress the importance of considering all these effects when rainfall energy needs to be estimated from more standard precipitation records. , and recommends the use of disdrometer data to locally determine rainfall kinetic energy.

A surprisingly complex aqueous chemistry of the simplest amino acid. A pulse radiolysis and theoretical study on H/D kinetic isotope effects in the reaction of glycine anions with hydroxyl radicals.

PubMed

Stefanić, I; Ljubić, I; Bonifacić, M; Sabljić, A; Asmus, K-D; Armstrong, D A

2009-04-07

A pulse radiolysis study was carried out of the reaction rate constants and kinetic isotope effects of hydroxyl-radical-induced H/D abstraction from the most-simple alpha-amino acid glycine in its anionic form in water. The rate constants and yields of three predominantly formed radical products, glycyl (NH2-*CH-CO2-), aminomethyl (NH2-*CH2), and aminyl (*NH-CH2-CO2-) radicals, as well as of their partially or fully deuterated analogs, were found to be of comparable magnitude. The primary, secondary, and primary/secondary H/D kinetic isotope effects on the rate constants were determined with respect to each of the three radicals. The unusual variety of products for such an elementary reaction between two small and simple species indicates a complex mechanism with several reactions taking place simultaneously. Thus, a theoretical modeling of the reaction mechanism and kinetics in the gas- and aqueous phase was performed by using the unrestricted density functional theory with the BB1K functional (employing the polarizable continuum model for the aqueous phase), unrestricted coupled cluster UCCSD(T) method, and improved canonical variational theory. Several hydrogen-bonded prereaction complexes and transition states were detected. In particular, the calculations pointed to a significant mechanistic role of the three-electron two-orbital (sigma/sigma* N therefore O) hemibonded prereaction complexes in the aqueous phase. A good agreement with the experimental rate constants and kinetic isotope effects was achieved by downshifting the calculated reaction barriers by 3 kcal mol(-1) and damping the NH(D) stretching frequency by a factor of 0.86.

Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets

NASA Technical Reports Server (NTRS)

Boering, Kristie A.; Connell, Peter; Rotman, Douglas

2004-01-01

We investigated the isotopic fractionation of CH4 and hydrogen (H2) in the stratosphere by incorporating isotope-specific rate coefficients into the Lawrence Livermore National Laboratory (LLNL) 2D model and comparing the model results with new observations from the NASA ER-2 aircraft (funded through a separate task under the Upper Atmosphere Research Program). The model results reveal that fractionation which occurs in the stratosphere has a significant influence on isotope compositions in the free troposphere, an important point which had previously been ignored, unrecognized or unquantified for many long-lived trace gases, including CH4 and H2 which we have focused our efforts on to date. Our analyses of the model results and new isotope observations have also been used to test how well the kinetic isotope effects are known, at least to within the uncertainties in model chemistry and transport. Overall, these results represent an important step forward in our understanding of isotope fractionation in the atmosphere and demonstrate that stratospheric isotope fractionation cannot be ignored in modeling studies which use isotope observations in the troposphere to infer the global budgets of CH4 (an important greenhouse gas) and of H2 (a gas whose atmospheric budget must be better quantified, particularly before a large human perturbation from fuel cell use is realized). Our analyses of model results and observations from the NASA ER-2 aircraft are briefly summarized separately below for CH4, H2, and H2O and for the contribution of these modeling studies to date to our understanding of isotope fractionation for N2O, CO2, and O3 as well.

Trajectory Calculations for Bergman Cyclization Predict H/D Kinetic Isotope Effects Due to Nonstatistical Dynamics in the Product.

PubMed

Doubleday, Charles; Boguslav, Mayla; Howell, Caronae; Korotkin, Scott D; Shaked, David

2016-06-22

An unusual H/D kinetic isotope effect (KIE) is described, in which isotopic selectivity arises primarily from nonstatistical dynamics in the product. In DFT-based quasiclassical trajectories of Bergman cyclization of (Z)-3-hexen-1,5-diyne (1) at 470 K, the new CC bond retains its energy, and 28% of nascent p-benzyne recrosses back to the enediyne on a vibrational time scale. The competing process of intramolecular vibrational redistribution (IVR) in p-benzyne is too slow to prevent this. Deuteration increases the rate of IVR, which decreases the fraction of recrossing and increases the yield of statistical (trapable) p-benzyne, 2. Trapable yields for three isotopomers of 2 range from 72% to 86%. The resulting KIEs for Bergman cyclization differ substantially from KIEs predicted by transition state theory, which suggests that IVR in this reaction can be studied by conventional KIEs. Leakage of vibrational zero point energy (ZPE) into the reaction coordinate was probed by trajectories in which initial ZPE in the CH/CD stretching modes was reduced by 25%. This did not change the predicted KIEs.

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

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

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

2015-07-01

The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Femore » isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II) aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II) aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II) aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous solutions, but presents a

Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles

NASA Astrophysics Data System (ADS)

Kuga, Maïa; Carrasco, Nathalie; Marty, Bernard; Marrocchi, Yves; Bernard, Sylvain; Rigaudier, Thomas; Fleury, Benjamin; Tissandier, Laurent

2014-05-01

The formation of organic compounds is generally assumed to result from abiotic processes in the Solar System, with the exception of biogenic organics on Earth. Nitrogen-bearing organics are of particular interest, notably for prebiotic perspectives but also for overall comprehension of organic formation in the young Solar System and in planetary atmospheres. We have investigated abiotic synthesis of organics upon plasma discharge, with special attention to N isotope fractionation. Organic aerosols were synthesized from N2-CH4 and N2-CO gaseous mixtures using low-pressure plasma discharge experiments, aimed at simulating chemistry occurring in Titan's atmosphere and in the protosolar nebula, respectively. The nitrogen content, the N speciation and the N isotopic composition were analyzed in the resulting organic aerosols. Nitrogen is efficiently incorporated into the synthesized solids, independently of the oxidation degree, of the N2 content of the starting gas mixture, and of the nitrogen speciation in the aerosols. The aerosols are depleted in 15N by 15-25‰ relative to the initial N2 gas, whatever the experimental setup is. Such an isotopic fractionation is attributed to mass-dependent kinetic effect(s). Nitrogen isotope fractionation upon electric discharge cannot account for the large N isotope variations observed among Solar System objects and reservoirs. Extreme N isotope signatures in the Solar System are more likely the result of self-shielding during N2 photodissociation, exotic effect during photodissociation of N2 and/or low temperature ion-molecule isotope exchange. Kinetic N isotope fractionation may play a significant role in the Titan's atmosphere. On the Titan's night side, 15N-depletion resulting from electron driven reactions may counterbalance photo-induced 15N enrichments occurring on the day's side. We also suggest that the low δ15N values of Archaean organic matter (Beaumont and Robert, 1999) are partly the result of abiotic synthesis of

Measurement of Enzyme Isotope Effects.

PubMed

Kholodar, Svetlana A; Ghosh, Ananda K; Kohen, Amnon

2017-01-01

Enzyme isotope effects, or the kinetic effects of "heavy" enzymes, refer to the effect of isotopically labeled protein residues on the enzyme's activity or physical properties. These effects are increasingly employed in the examination of the possible contributions of protein dynamics to enzyme catalysis. One hypothesis assumed that isotopic substitution of all 12 C, 14 N, and nonexchangeable 1 H by 13 C, 15 N, and 2 H, would slow down protein picosecond to femtosecond dynamics without any effect on the system's electrostatics following the Born-Oppenheimer approximation. It was suggested that reduced reaction rates reported for several "heavy" enzymes accords with that hypothesis. However, numerous deviations from the predictions of that hypothesis were also reported. Current studies also attempt to test the role of individual residues by site-specific labeling or by labeling a pattern of residues on activity. It appears that in several systems the protein's fast dynamics are indeed reduced in "heavy" enzymes in a way that reduces the probability of barrier crossing of its chemical step. Other observations, however, indicated that slower protein dynamics are electrostatically altered in isotopically labeled enzymes. Interestingly, these effects appear to be system dependent, thus it might be premature to suggest a general role of "heavy" enzymes' effect on catalysis. © 2017 Elsevier Inc. All rights reserved.

Human neutrophil kinetics: modeling of stable isotope labeling data supports short blood neutrophil half-lives.

PubMed

Lahoz-Beneytez, Julio; Elemans, Marjet; Zhang, Yan; Ahmed, Raya; Salam, Arafa; Block, Michael; Niederalt, Christoph; Asquith, Becca; Macallan, Derek

2016-06-30

Human neutrophils have traditionally been thought to have a short half-life in blood; estimates vary from 4 to 18 hours. This dogma was recently challenged by stable isotope labeling studies with heavy water, which yielded estimates in excess of 3 days. To investigate this disparity, we generated new stable isotope labeling data in healthy adult subjects using both heavy water (n = 4) and deuterium-labeled glucose (n = 9), a compound with more rapid labeling kinetics. To interpret results, we developed a novel mechanistic model and applied it to previously published (n = 5) and newly generated data. We initially constrained the ratio of the blood neutrophil pool to the marrow precursor pool (ratio = 0.26; from published values). Analysis of heavy water data sets yielded turnover rates consistent with a short blood half-life, but parameters, particularly marrow transit time, were poorly defined. Analysis of glucose-labeling data yielded more precise estimates of half-life (0.79 ± 0.25 days; 19 hours) and marrow transit time (5.80 ± 0.42 days). Substitution of this marrow transit time in the heavy water analysis gave a better-defined blood half-life of 0.77 ± 0.14 days (18.5 hours), close to glucose-derived values. Allowing the ratio of blood neutrophils to mitotic neutrophil precursors (R) to vary yielded a best-fit value of 0.19. Reanalysis of the previously published model and data also revealed the origin of their long estimates for neutrophil half-life: an implicit assumption that R is very large, which is physiologically untenable. We conclude that stable isotope labeling in healthy humans is consistent with a blood neutrophil half-life of less than 1 day. © 2016 by The American Society of Hematology.

Observations of Nitrogen Isotope Fractionation in Prestellar Cores

NASA Technical Reports Server (NTRS)

Milam, Stefanie N.; Charnley, Steven B.

2011-01-01

Isotopically fractionated material is found in many solar system objects, including meteorites and comets [1]. It is considered, in some cases, to trace interstellar material that was incorporated into the solar system without undergoing significant processing, thus preserving the fractionation. In interstellar molecular clouds, ion-molecule chemistry continually cycles nitrogen between the two main reservoirs - Nand N2 - leading to only minor N-15 enrichments [2]. Charnley and Rodgers [3,4] showed that depletion of CO removes oxygen from the gas and weakens this cycle such that significant N-15 fractionation can occur for N2 and other N-bearing species in such cores. Observations are being conducted at millimeter and submillimeter wavelengths employing various facilities in order to both spatially and spectrally, resolve emission from these cores. A preliminary study to obtain the N-14/N-15 ratio in nitriles was conducted at the Arizona Radio Observatory's 12m telescope on Kitt Peak, AZ. Spectra were obtained at high resolution (0.08 km/s) in order to resolve dynamic properties of each source as well as to resolve hyperfine structure present in certain isotopologues. This study included four dark cloud cores, observed to have varying levels of molecular depletion: Ll521E, Ll498, Ll544, and Ll521F. Previous studies of the N-14/N-15 ratio towards Ll544 were obtained with N2H(+) and NH3 yielding ratios of 446 and greater than 700, respectively [5,6]. The discrepancy observed in these two measurements suggests a strong chemical dependence on the fractionation of nitrogen. Ratios (C,N, and D) obtained from isotopologues for a particular molecule are likely tracing the same chemical heritage and are directly comparable within a given source. Results and comparisons between the protostellar evolutionary state and isomer isotope fractionation as well as between other N-bearing species will be presented.

Tunneling effects in the kinetics of helium and hydrogen isotopes desorption from single-walled carbon nanotube bundles

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

Danilchenko, B. A., E-mail: danil@iop.kiev.ua; Yaskovets, I. I.; Uvarova, I. Y.

2014-04-28

The kinetics of desorption both helium isotopes and molecules of hydrogen and deuterium from open-ended or γ-irradiated single-walled carbon nanotube bundles was investigated in temperature range of 10–300 K. The gases desorption rates obey the Arrhenius law at high temperatures, deviate from it with temperature reduction and become constant at low temperatures. These results indicate the quantum nature of gas outflow from carbon nanotube bundles. We had deduced the crossover temperature below which the quantum corrections to the effective activation energy of desorption become significant. This temperature follows linear dependence against the inverse mass of gas molecule and is consistent withmore » theoretical prediction.« less

Silicon Isotopic Fractionation of CAI-like Vacuum Evaporation Residues

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

Knight, K; Kita, N; Mendybaev, R

2009-06-18

Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquidsmore » (Richter et al., 2002, 2007a). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, {alpha}{sub Si}, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that {alpha}{sub Si} = 0.98985 {+-} 0.00044 (2{sigma}) for {sup 29}Si/{sup 28}Si with no resolvable variation with temperature over the temperature range of the experiments, 1600-1900 C. This value is different from what has been reported for evaporation of liquid Mg{sub 2}SiO{sub 4} (Davis et al., 1990) and of a melt with CI chondritic proportions of the major elements (Wang et al., 2001). There appears to be some compositional control on {alpha}{sub Si}, whereas no compositional effects have been reported for {alpha}{sub Mg}. We use the values of {alpha}Si and {alpha}Mg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites

Silicon isotope fractionations in pure Si and Fe-Si systems and their geological implications

NASA Astrophysics Data System (ADS)

Zheng, X. Y.; Beard, B. L.; Reddy, T. R.; Roden, E. E.; Johnson, C.

2016-12-01

Amorphous Si or Si-bearing materials are ubiquitous in nature, and are likely precursors to various rock types, such as cherts and banded iron formations (BIFs). Si isotope exchange kinetics and fractionation factors between these materials and aqueous Si, however, are poorly constrained, preventing a mechanistic or quantitative understanding of geological δ30Si records. A series of laboratory experiments were conducted to provide better estimates on Si isotope exchange kinetics and fractionation factors. Equilibrium Si isotope fractionation factors between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aq) in artificial Archean seawater (AAS), determined by a three-isotope method with a 29Si tracer, are -2.3‰ where Fe2+ is absent from the solution, and -3.2‰ where Fe2+ is present in the solution[1]. Aqueous Fe2+ catalyzes Si isotope exchange, and causes larger Si isotope fractionation due to incorporation into the solid that may have changed Si bonding. In contrast, our preliminary results show that Δ30Sigel-aq between pure Si gel and aqueous Si at equilibrium is -0.13‰. Ongoing experiments are intended to approach the isotope equilibrium from multiple directions to resolve potential kinetic effects, and to explore temperature dependence. Nonetheless, the contrast in Δ30Sigel-aq between Fe-Si and pure Si systems highlights a significant impact of Fe on Si isotope fractionations. These results have important implications for Si isotopes in Precambrian cherts and BIFs, as well as in weathering systems in general. Silicon isotope fractionation was also studied in experiments that involved dissimilatory iron reduction of Fe(III)-Si gel by Desulfuromonas acetoxidans in AAS[2], and was found to become larger with progression of Fe reduction. A Δ30Sigel-aq of -3.5‰ was observed at 32% reduction of Fe3+. This result explains lower δ30Si values in magnetite-associated quartz that those in hematite-associated quartz in some BIFs. The large Si isotope fractionation

Magnesium isotopic evidence for chemical disequilibrium among cumulus minerals in layered mafic intrusion

NASA Astrophysics Data System (ADS)

Chen, Lie-Meng; Teng, Fang-Zhen; Song, Xie-Yan; Hu, Rui-Zhong; Yu, Song-Yue; Zhu, Dan; Kang, Jian

2018-04-01

Magnesium isotopic compositions of olivine, clinopyroxene, and ilmenite from the Baima intrusion, SW China, for the first time, are investigated to constrain the magnitude and mechanisms of Mg isotope fractionation among cumulus minerals in layered mafic intrusions and to evaluate their geological implications. Olivine and clinopyroxene have limited Mg isotope variations, with δ26Mg ranging from -0.33 to +0.05‰ and from -0.29 to -0.13‰, respectively, similar to those of mantle xenolithic peridotites. By contrast, ilmenites display extremely large Mg isotopic variation, with δ26Mg ranging from -0.50 to +1.90‰. The large inter-mineral fractionations of Mg isotopes between ilmenite and silicates may reflect both equilibrium and kinetic processes. A few ilmenites have lighter Mg isotopic compositions than coexisting silicates and contain high MgO contents without compositional zoning, indicating equilibrium fractionation. The implication is that the light Mg isotopic compositions of lunar high-Ti basalts may result from an isotopically light source enriched in cumulate ilmenites. On the other hand, most ilmenites have heavy Mg isotopic compositions, coupled with high MgO concentration and chemical zoning, which can be quantitatively modeled by kinetic Mg isotope fractionations induced by subsolidus Mg-Fe exchange between ilmenite and ferromagnesian silicates during the cooling of the Baima intrusion. The extensive occurrence of kinetic Mg isotope fractionation in ilmenites implies the possibility of widespread compositional disequilibrium among igneous minerals in magma chambers. Consequently, disequilibrium effects need to be considered in studies of basaltic magma evolution, magma chamber processes, and magmatic Fe-Ti oxide ore genesis.

Stable isotopes of transition and post-transition metals as tracers in environmental studies

USGS Publications Warehouse

Bullen, Thomas D.; Baskaran, Mark

2011-01-01

The transition and post-transition metals, which include the elements in Groups 3–12 of the Periodic Table, have a broad range of geological and biological roles as well as industrial applications and thus are widespread in the environment. Interdisciplinary research over the past decade has resulted in a broad understanding of the isotope systematics of this important group of elements and revealed largely unexpected variability in isotope composition for natural materials. Significant kinetic and equilibrium isotope fractionation has been observed for redox sensitive metals such as iron, chromium, copper, molybdenum and mercury, and for metals that are not redox sensitive in nature such as cadmium and zinc. In the environmental sciences, the isotopes are increasingly being used to understand important issues such as tracing of metal contaminant sources and fates, unraveling metal redox cycles, deciphering metal nutrient pathways and cycles, and developing isotope biosignatures that can indicate the role of biological activity in ancient and modern planetary systems.

Observations of the Li, Be, and B Isotopes and Constraints on Cosmic-ray Propagation

NASA Technical Reports Server (NTRS)

deNolfo, G. A.; Moskalenko, I. V.; Binns, W. R.; Christian, E. R.; Cummings, A. C.; Davis, A. J.; George, J. S.; Hink, P. L.; Israel, M. H.; Leske, R. A.;

Quantitative production of compound I from a cytochrome P450 enzyme at low temperatures. Kinetics, activation parameters, and kinetic isotope effects for oxidation of benzyl alcohol.

PubMed

Wang, Qin; Sheng, Xin; Horner, John H; Newcomb, Martin

2009-08-05

Cytochrome P450 enzymes are commonly thought to oxidize substrates via an iron(IV)-oxo porphyrin radical cation transient termed Compound I, but kinetic studies of P450 Compounds I are essentially nonexistent. We report production of Compound I from cytochrome P450 119 (CYP119) in high conversion from the corresponding Compound II species at low temperatures in buffer mixtures containing 50% glycerol by photolysis with 365 nm light from a pulsed lamp. Compound I was studied as a reagent in oxidations of benzyl alcohol and its benzylic mono- and dideuterio isotopomers. Pseudo-first-order rate constants obtained at -50 degrees C with concentrations of substrates between 1.0 and 6.0 mM displayed saturation kinetics that gave binding constants for the substrate in the Compound I species (K(bind)) and first-order rate constants for the oxidation reactions (k(ox)). Representative results are K(bind) = 214 M(-1) and k(ox) = 0.48 s(-1) for oxidation of benzyl alcohol. For the dideuterated substrate C(6)H(5)CD(2)OH, kinetics were studied between -50 and -25 degrees C, and a van't Hoff plot for complexation and an Arrhenius plot for the oxidation reaction were constructed. The H/D kinetic isotope effects (KIEs) at -50 degrees C were resolved into a large primary KIE (P = 11.9) and a small, inverse secondary KIE (S = 0.96). Comparison of values extrapolated to 22 degrees C of both the rate constant for oxidation of C(6)H(5)CD(2)OH and the KIE for the nondeuterated and dideuterated substrates to values obtained previously in laser flash photolysis experiments suggested that tunneling could be a significant component of the total rate constant at -50 degrees C.

AMS Observations of Light Cosmic Ray Isotopes and Implications for their Production in the Galaxy

NASA Astrophysics Data System (ADS)

Tomassetti, Nicola

2012-08-01

Observations of light isotopes in cosmic rays provide information on their origin and propagation in the Galaxy. Using the data collected by AMS-01 in the STS-91 space mission, we report our final results on the isotopic composition of hydrogen and helium between 200 MeV and 1.4 GeV per nucleon. These measurements are in good agreement with the previous data and set new standards of precision. We discuss the role of isotopic composition data in modeling the cosmic ray production, acceleration and diffusive transport in the Galaxy.

The kinetics and mechanism of the organo-iridium catalysed racemisation of amines.

PubMed

Stirling, Matthew J; Mwansa, Joseph M; Sweeney, Gemma; Blacker, A John; Page, Michael I

2016-08-07

The dimeric iodo-iridium complex [IrCp*I2]2 (Cp* = pentamethylcyclopentadiene) is an efficient catalyst for the racemisation of secondary and tertiary amines at ambient and higher temperatures with a low catalyst loading. The racemisation occurs with pseudo-first-order kinetics and the corresponding four rate constants were obtained by monitoring the time dependence of the concentrations of the (R) and (S) enantiomers starting with either pure (R) or (S) and show a first-order dependence on catalyst concentration. Low temperature (1)H NMR data is consistent with the formation of a 1 : 1 complex with the amine coordinated to the iridium and with both iodide anions still bound to the metal-ion, but at the higher temperatures used for kinetic studies binding is weak and so no saturation zero-order kinetics are observed. A cross-over experiment with isotopically labelled amines demonstrates the intermediate formation of an imine which can dissociate from the iridium complex. Replacing the iodides in the catalyst by other ligands or having an amide substituent in Cp* results in a much less effective catalysts for the racemisation of amines. The rate constants for a deuterated amine yield a significant primary kinetic isotope effect kH/kD = 3.24 indicating that hydride transfer is involved in the rate-limiting step.

Evaporation and Accompanying Isotopic Fractionation of Sulfur from FE-S Melt During Shock Wave Heating

NASA Technical Reports Server (NTRS)

Tachibana, S.; Huss, G. R.; Miura, H.; Nakamoto, T.

2004-01-01

Chondrules probably formed by melting and subsequent cooling of solid precursors. Evaporation during chondrule melting may have resulted in depletion of volatile elements in chondrules. It is known that kinetic evaporation, especially evaporation from a melt, often leads to enrichment of heavy isotopes in an evaporation residue. However, no evidence for a large degree of heavy-isotope enrichment has been reported in chondrules for K, Mg, Si, and Fe (as FeO). The lack of isotopic fractionation has also been found for sulfur in troilites (FeS) within Bishunpur (LL3.1) and Semarkona (LL3.0) chondrules by an ion microprobe study. The largest fractionation, found in only one grain, was 2.7 +/- 1.4 %/amu, while all other troilite grains showed isotopic fractionations of <1 %/amu. The suppressed isotopic fractionation has been interpreted as results of (i) rapid heating of precursors at temperatures below the silicate solidus and (ii) diffusion-controlled evaporation through a surrounding silicate melt at temperatures above the silicate solidus. The kinetic evaporation model suggests that a rapid heating rate of >10(exp 4)-10(exp 6) K/h for a temperature range of 1000-1300 C is required to explain observed isotopic fractionations. Such a rapid heating rate seems to be difficult to be achieved in the X-wind model, but can be achieved in shock wave heating models. In this study, we have applied the sulfur evaporation model to the shock wave heating conditions of to evaluate evaporation of sulfur and accompanying isotopic fractionation during shock wave heating at temperatures below the silicate solidus.

Observation of the 162Dy-164Dy Isotope Shift for the 0 → 16 717.79 cm-1 Optical Transition.

PubMed

Nardin Barreta, Luiz Felipe; Victor, Alessandro Rogério; Bueno, Patrícia; Dos Santos, Jhonatha Ricardo; da Silveira, Carlos Alberto Barbosa; Neri, José Wilson; Neto, Jonas Jakutis; Sbampato, Maria Esther; Destro, Marcelo Geraldo

2017-08-01

In this work, we report a newly observed isotope shift between 162 Dy and 164 Dy isotopes for the 0 → 16 717.79 cm -1 (598.003 nm) optical transition. We compared the newly observed results against two other lines (597.452 nm and 598.859 nm), which we measured in this work, and were already reported in the literature. The newly observed 162-164 Dy isotope shift, shows at least a 20% larger isotope shift than the isotope shifts for the other two lines investigated. The larger 162-164 isotope shift observed for the 598.003 nm line could lead to an increased isotope selectivity for atomic vapor laser isotope separation (AVLIS). Hence, this line could be a good choice for application in AVLIS. Experimental data available in the literature for the 597.452 nm and 598.859 nm lines, enabled us to perform simulations of spectra for both lines, in order to confirm the accuracy of our experimental measurements.

Structural and Kinetic Isotope Effect Studies of Nicotinamidase (Pnc1) from Saccharomyces cerevisiae

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

Smith, Brian C.; Anderson, Mark A.; Hoadley, Kelly A.

2012-05-08

Nicotinamidases catalyze the hydrolysis of nicotinamide to nicotinic acid and ammonia. Nicotinamidases are absent in mammals but function in NAD{sup +} salvage in many bacteria, yeast, plants, protozoa, and metazoans. We have performed structural and kinetic investigations of the nicotinamidase from Saccharomyces cerevisiae (Pnc1). Steady-state product inhibitor analysis revealed an irreversible reaction in which ammonia is the first product released, followed by nicotinic acid. A series of nicotinamide analogues acting as inhibitors or substrates were examined, revealing that the nicotinamide carbonyl oxygen and ring nitrogen are critical for binding and reactivity. X-ray structural analysis revealed a covalent adduct between nicotinaldehydemore » and Cys167 of Pnc1 and coordination of the nicotinamide ring nitrogen to the active-site zinc ion. Using this structure as a guide, the function of several residues was probed via mutagenesis and primary {sup 15}N and {sup 13}C kinetic isotope effects (KIEs) on V/K for amide bond hydrolysis. The KIE values of almost all variants were increased, indicating that C-N bond cleavage is at least partially rate limiting; however, a decreased KIE for D51N was indicative of a stronger commitment to catalysis. In addition, KIE values using slower alternate substrates indicated that C-N bond cleavage is at least partially rate limiting with nicotinamide to highly rate limiting with thionicotinamide. A detailed mechanism involving nucleophilic attack of Cys167, followed by elimination of ammonia and then hydrolysis to liberate nicotinic acid, is discussed. These results will aid in the design of mechanism-based inhibitors to target pathogens that rely on nicotinamidase activity.« less

Catalytic-site design for inverse heavy-enzyme isotope effects in human purine nucleoside phosphorylase

PubMed Central

Harijan, Rajesh K.; Zoi, Ioanna; Antoniou, Dimitri; Schwartz, Steven D.; Schramm, Vern L.

2017-01-01

Heavy-enzyme isotope effects (15N-, 13C-, and 2H-labeled protein) explore mass-dependent vibrational modes linked to catalysis. Transition path-sampling (TPS) calculations have predicted femtosecond dynamic coupling at the catalytic site of human purine nucleoside phosphorylase (PNP). Coupling is observed in heavy PNPs, where slowed barrier crossing caused a normal heavy-enzyme isotope effect (kchem light/kchem heavy > 1.0). We used TPS to design mutant F159Y PNP, predicted to improve barrier crossing for heavy F159Y PNP, an attempt to generate a rare inverse heavy-enzyme isotope effect (kchem light/kchem heavy < 1.0). Steady-state kinetic comparison of light and heavy native PNPs to light and heavy F159Y PNPs revealed similar kinetic properties. Pre–steady-state chemistry was slowed 32-fold in F159Y PNP. Pre–steady-state chemistry compared heavy and light native and F159Y PNPs and found a normal heavy-enzyme isotope effect of 1.31 for native PNP and an inverse effect of 0.75 for F159Y PNP. Increased isotopic mass in F159Y PNP causes more efficient transition state formation. Independent validation of the inverse isotope effect for heavy F159Y PNP came from commitment to catalysis experiments. Most heavy enzymes demonstrate normal heavy-enzyme isotope effects, and F159Y PNP is a rare example of an inverse effect. Crystal structures and TPS dynamics of native and F159Y PNPs explore the catalytic-site geometry associated with these catalytic changes. Experimental validation of TPS predictions for barrier crossing establishes the connection of rapid protein dynamics and vibrational coupling to enzymatic transition state passage. PMID:28584087

Experimental investigation of nitrogen isotopic effects associated with ammonia degassing at 0-70 °C

NASA Astrophysics Data System (ADS)

Deng, Yuying; Li, Yingzhou; Li, Long

2018-04-01

Ammonia degassing is a common process in natural alkaline waters and in the atmosphere. To quantitatively assess the nitrogen cycle in these systems, the essential parameter of nitrogen isotope fractionation factors associated with ammonia degassing is required, but still not constrained yet. In this study, we carried out laboratory experiments to examine the nitrogen isotope behavior during ammonia degassing in alkaline conditions. The experiments started with ammonium sulfate solution with excess sodium hydroxide. The reaction can be described as: NH4+ + OH- (excess) → NH3·nH2O → NH3 (g)↑. Two sets of experiments, one with ammonia degassing under static conditions and the other with ammonia degassing by bubbling of N2 gas, were carried out at 2, 21, 50, and 70 °C. The results indicate that kinetic isotopic effects are dominated during efficient degassing of ammonia in the bubbling experiments, which yielded kinetic nitrogen isotope fractionation factors αNH3(g)-NH3(aq) of 0.9898 at 2 °C, 0.9918 at 21 °C, 0.9935 at 50 °C and 0.9948 at 70 °C. These values show a good relationship with temperature as 103lnαNH3(g)-NH3(aq) = 14.6 - 6.8 × 1000/T. In contrast, isotopic effects during less efficient degassing of ammonia in the static experiments are more complicated. The results do not match either kinetic isotope fractionation or equilibrium isotope fractionation but sit between these two. The most likely cause is that back dissolution of the degassed ammonia occurred in these experiments and consequently shifted kinetic isotope fractionation toward equilibrium isotope fractionation. Our experimental results highlight complicated isotopic effects may occur in natural environments, and need to be fully considered in the interpretation of field data.

Nucleosynthetic Heterogeneity Controls Vanadium Isotope Variations in Bulk Chondrites

NASA Technical Reports Server (NTRS)

Nielsen, S. G.; Righter, K.; Wu, F.; Owens, J. D.; Prytulak, J.; Burton, K.; Parkinson, I.; Davis, D.

2018-01-01

The vanadium (V) isotope composition of early solar system materials have been hypothesized to be sensitive to high energy irradiation that originated from the young Sun. Vanadium has two isotopes with masses 50 and 51 that have (51)V/(50)V ratio of approximately 410. High energy irradiation produces (50)V from various target isotopes of Ti, Cr and Fe, which would result in light V isotope compositions (expressed as delta (51)V in per mille = 1000 x (((51)V/(50)V(sub sample)/(51)V/(50)V(sub AlfaAesar)) - 1)) relative to a presumably chondritic starting composition. Recently published V isotope data for calcium aluminium inclusions (CAIs) has revealed some very negative values relative to chondrites (by almost -4 per mille) that were indeed interpreted to reflect irradiation processes despite the fact that the studied CAIs all exhibited significant initial abundances of (10)Be, while only a few CAIs displayed light V isotope compositions. It is difficult to relate V isotope variations directly to a singular process because V only possesses two isotopes. Therefore, V isotope variations can principally be produced both mass dependent and independent processes. Mass dependent kinetic stable isotope fractionation is common in CAIs for refractory elements due to partial condensation/evaporation processes. The element strontium (Sr) has an almost identical condensation temperature to V and studies of stable Sr isotope compositions in CAIs reveal both heavy and light values relative to chondrites of several permil. These variations are similar in magnitude to those reported for V isotopes in CAIs, which suggests it is possible that some of the V isotope variation in CAIs could be due to kinetic stable isotope fractionation during condensation/evaporation processes.

Kinetic Isotope Effects as a Probe of Hydrogen Transfers to and from Common Enzymatic Cofactors

PubMed Central

Roston, Daniel; Islam, Zahidul; Kohen, Amnon

2013-01-01

Enzymes use a number of common cofactors as sources of hydrogen to drive biological processes, but the physics of the hydrogen transfers to and from these cofactors is not fully understood. Researchers study the mechanistically important contributions from quantum tunneling and enzyme dynamics and connect those processes to the catalytic power of enzymes that use these cofactors. Here we describe some progress that has been made in studying these reactions, particularly through the use of kinetic isotope effects (KIEs). We first discuss the general theoretical framework necessary to interpret experimental KIEs, and then describe practical uses for KIEs in the context of two case studies. The first example is alcohol dehydrogenase, which uses a nicotinamide cofactor to catalyze a hydride transfer, and the second example is thymidylate synthase, which uses a folate cofactor to catalyze both a hydride and a proton transfer. PMID:24161942

Deuterium and oxygen-18 isotope effects on nucleophilic displacement by water

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

Lee, J.

1981-01-01

Kinetic deuterium isotope effects (k/sub H/sub 2/O//k/sub D/sub 2/O/) have been measured for nucleophilic attack by water at primary alkyl carbon (S-methylthiophenium ion (MeTh+), methyl trifluoromethane-sulfonate (MeOTf), methyl and ethyl perchlorate (MeOClO/sub 3/, EtOClO/sub 3/)) in aprotic solvents (acetonitrile (MeCN) and tetrahydrothiophene-1, 1-dioxide (TMSO/sub 2/; solfolane)) and L/sub 2/O. In L/sub 2/O solvent k/sub H/sub 2/O//k/sub D/sub 2/O/ is significantly greater than unity while it is reduced to near unity in aprotic solvents. The oxygen-18 isotope effect has also been observed to be 1.002 +- 0.004 for the reaction of MeTh/sup +/ with dilute H/sub 2/O in TMSO/sub 2/ atmore » 35/sup 0/C. For the reaction of MeTh/sup +/ and MeOClO/sub 3/ in aprotic solvents the chemical reaction kinetics are discussed.« less

Isotope effects accompanying evaporation of water from leaky containers.

PubMed

Rozanski, Kazimierz; Chmura, Lukasz

2008-03-01

Laboratory experiments aimed at quantifying isotope effects associated with partial evaporation of water from leaky containers have been performed under three different settings: (i) evaporation into dry atmosphere, performed in a dynamic mode, (ii) evaporation into dry atmosphere, performed in a static mode, and (iii) evaporation into free laboratory atmosphere. The results demonstrate that evaporative enrichment of water stored in leaky containers can be properly described in the framework of the Craig-Gordon evaporation model. The key parameter controlling the degree of isotope enrichment is the remaining fraction of water in the leaking containers. Other factors such as temperature, relative humidity, or extent of kinetic fractionation play only minor roles. Satisfactory agreement between observed and predicted isotope enrichments for both (18)O and (2)H in experiments for the case of evaporation into dry atmosphere could be obtained only when molecular diffusivity ratios of isotope water molecules as suggested recently by Cappa et al. [J. Geophys. Res., 108, 4525-4535, (2003).] were adopted. However, the observed and modelled isotope enrichments for (2)H and (18)O could be reconciled also for the ratios of molecular diffusivities obtained by Merlivat [J. Chem. Phys., 69, 2864-2871 (1978).], if non-negligible transport resistance in the viscous liquid sub-layer adjacent to the evaporating surface is considered. The evaporation experiments revealed that the loss of mass of water stored in leaky containers in the order of 1%, will lead to an increase of the heavy isotope content in this water by ca. 0.35 and 1.1 per thousand, for delta (18)O and delta (2)H, respectively.

Ground Based Observation of Isotopic Oxygen in the Martian Atmosphere Using Infrared Heterodyne Spectroscopy

NASA Technical Reports Server (NTRS)

Smith, R. L.; Kostiuk, T.; Livengood, T. A.; Fast, K. E.; Hewagama, T.; Delgado, J. D.; Sonnabend, G.

2010-01-01

Infrared heterodyne spectra of isotopic CO2 in the Martian atmosphere were obtained using the Goddard Heterodyne Instrument for Planetary Wind and Composition, HIPWAC, which was interfaced with the 3-meter telescope at the NASA Infrared Telescope Facility- Spectra were colle cted at a resolution of lambda/delta lambda=10(exp 7). Absorption fea tures of the CO2 isotopologues have been identified from which isotop ic ratios of oxygen have been determined. The isotopic ratios O-17/O -16 and O-18/O-16 in the Martian atmosphere can be related to Martian atmospheric evolution and can be compared to isotopic ratios of oxyg en in the Earth's atmosphere. Isotopic carbon and oxygen are importa nt constraints on any theory for the erosion of the Martian primordia l atmosphere and the interaction between the atmosphere and surface o r subsurface chemical reservoirs. This investigation explored the pr esent abundance of the stable isotopes of oxygen in Mars' atmospheric carbon dioxide by measuring rovibrational line absorption in isotop ic species of CO2 using groundbased infrared heterodyne spectroscopy in the vicinity of the 9.6 micron and 10.6 micron CO2 lasing bands. T he target transitions during this observation were O-18 C-12 O-16 as well as O-178 C-12 O-16 and O-16 C-113 O-16 at higher resolving power of lambda/delta lambda=10(exp 7) and with high signal-to-noise ratio (longer integration time) in order to fully characterize the absorpt ion line profiles. The fully-resolved lineshape of both the strong n ormal-isotope and the weak isotopic CO2 lines were measured simultane ously in a single spectrum.

Hybrid quantum and classical methods for computing kinetic isotope effects of chemical reactions in solutions and in enzymes.

PubMed

Gao, Jiali; Major, Dan T; Fan, Yao; Lin, Yen-Lin; Ma, Shuhua; Wong, Kin-Yiu

2008-01-01

A method for incorporating quantum mechanics into enzyme kinetics modeling is presented. Three aspects are emphasized: 1) combined quantum mechanical and molecular mechanical methods are used to represent the potential energy surface for modeling bond forming and breaking processes, 2) instantaneous normal mode analyses are used to incorporate quantum vibrational free energies to the classical potential of mean force, and 3) multidimensional tunneling methods are used to estimate quantum effects on the reaction coordinate motion. Centroid path integral simulations are described to make quantum corrections to the classical potential of mean force. In this method, the nuclear quantum vibrational and tunneling contributions are not separable. An integrated centroid path integral-free energy perturbation and umbrella sampling (PI-FEP/UM) method along with a bisection sampling procedure was summarized, which provides an accurate, easily convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. In the ensemble-averaged variational transition state theory with multidimensional tunneling (EA-VTST/MT), these three aspects of quantum mechanical effects can be individually treated, providing useful insights into the mechanism of enzymatic reactions. These methods are illustrated by applications to a model process in the gas phase, the decarboxylation reaction of N-methyl picolinate in water, and the proton abstraction and reprotonation process catalyzed by alanine racemase. These examples show that the incorporation of quantum mechanical effects is essential for enzyme kinetics simulations.

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

Evaluating Volatility-controlled Isotope Fractionation During Planet Formation: Kinetics versus Equilibrium

NASA Astrophysics Data System (ADS)

Young, E. D.

2017-12-01

Recent advances in our ability to measure stable isotope ratios of light, rock-forming elements, including those for Zn, K, Fe, Si, and Mg, among others, has resulted in an emerging hypothesis that collisions among rocky planetesimals, planetary embryos, and/or proto-planets caused losses of moderately volatile elements (e.g., K) and "common" or moderately refractory elements (e.g., Mg and Si). The primary evidence is in the form of heavy isotope enrichments in rock-forming elements relative to the chondrite groups that are thought to be representative of planetary precursors. Equilibrium volatility-controlled isotope fractionation for planetesimal magma oceans might have occurred for bodies larger than 0.1% of an Earth mass (½ the mass of Pluto) as these bodies had sufficient gravity to overpower the escape velocities of hot gas at 2000K. Both Jean's escape and viscous drag hydrodynamic escape can obviate the escape velocity limit but will fractionate by mass, not by volatility. Equilibrium vapor/melt fractionation is qualitatively consistent with the greater disparity in 29Si/28Si between Earth and chondrites than in 25Mg/24Mg. However, losses of large masses of vapor are required to record the fractionation in the melts. We consider that if Earth was derived from E chondrite-like materials, the bulk composition of the Earth, assuming refractory Ca was retained, requires > 60% loss of Mg. This is a lot of vapor loss for a process relying on at least intermittent equilibrium, although it comports with the isotopic lever-rule requirements. Paradoxically, the alternative of evaporative loss of rock-forming elements requires less total mass loss. For example, the calculated Mg and Si isotopic compositions of residues resulting from evaporation of chondritic melts can fit the Mg and Si isotopic compositions of Earth, Mars, and angrites with varying background pressures and with total mass losses of near 5% or less. These mass losses are closer to, and even lower than

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

NASA Astrophysics Data System (ADS)

Kavner, Abby; Bonet, François; Shahar, Anat; Simon, Justin; Young, Edward

2005-06-01

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from -0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ 56Fe values (relative to IRMM-14) ranging from -0.18(±0.02) to -2.290(±0.006) ‰, and corresponding δ 57Fe values of -0.247(±0.014) and -3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus's theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.

Zinc Isotopic Compositions of Spinel Peridotites

NASA Astrophysics Data System (ADS)

Chen, S.; Huang, F.

2015-12-01

Zn isotope geochemistry has shown great potential in exploring planetary differentiation and volatilization history [1,2,3,4]. However, the zinc isotopic composition of the mantle and its fractionation mechanism in high-temperature processes are still unclear. In order to understand Zn isotope composition of the mantle, here we measured Zn isotope data for mantle rocks and minerals, including coexisting olivine, orthopyroxene (Opx), clinopyroxene (Cpx) and spinel from peridotite xenoliths in the Hannuoba (China), Vitim (Siberia), Tariat (central Mongolia), and Dariganga (SE Mongolia). As an accessary mineral, spinels in our study have high Zn contents (500-1400 ppm), accounting for 18%-40% of the total Zn budget in peridotites. Spinels have higher δ66Zn ranging from 0.17 to 0.30‰ than other mantle minerals. For most samples, the δ66Zn of olivines vary from -0.03‰ to 0.19‰, indistinguishable to the value of the coexisting Opx (0.05‰ to 0.20‰). However, we also observed large fractionation between these two minerals, which may reflect disequilibrium fractionation due to kinetic processes. Finally, δ66Zn for peridotites are 0.12-0.21‰, slightly lighter than that of basalts (~0.25±0.05‰), revealing that Zn isotopes can be slightly fractionated during mantle melting. [1] Luck et al., (2005) Geochimica Cosmo Acta, 69, 5351-5363. [2] Paniello et al., (2012) Nature, 490, 376-379. [3] Chen et al., (2013) Meteoritics Planet Sci, 48, 2441-2450. [4] Day and Moynier, (2014) Phil. Transac. of the Royal Society B, 372, 20130259

Quantum instanton calculation of rate constant for CH4 + OH → CH3 + H2O reaction: Torsional anharmonicity and kinetic isotope effect

NASA Astrophysics Data System (ADS)

Wang, Wenji; Zhao, Yi

2012-12-01

Thermal rate constants for the title reaction are calculated by using the quantum instanton approximation within the full dimensional Cartesian coordinates. The results reveal that the quantum effect is remarkable for the reaction at both low and high temperatures, and the obtained rates are in good agreement with experimental measurements at high temperatures. Compared to the harmonic approximation, the torsional anharmonic effect of the internal rotation has a little influence on the rates at low temperatures, however, it enhances the rate by about 20% at 1000 K. In addition, the free energy barriers for the isotopic reactions and the temperature dependence of kinetic isotope effects are also investigated. Generally speaking, for the title reaction, the replacement of OH with OD will reduce the free energy barrier, while substituting D for H (connected to C) will increase the free energy barrier.

Experimental and theoretical kinetics for the H2O+ + H2/D2 → H3O+/H2DO+ + H/D reactions: observation of the rotational effect in the temperature dependence.

PubMed

Ard, Shaun G; Li, Anyang; Martinez, Oscar; Shuman, Nicholas S; Viggiano, Albert A; Guo, Hua

2014-12-11

Thermal rate coefficients for the title reactions computed using a quasi-classical trajectory method on an accurate global potential energy surface fitted to ∼81,000 high-level ab initio points are compared with experimental values measured between 100 and 600 K using a variable temperature selected ion flow tube instrument. Excellent agreement is found across the entire temperature range, showing a subtle, but unusual temperature dependence of the rate coefficients. For both reactions the temperature dependence has a maximum around 350 K, which is a result of H2O(+) rotations increasing the reactivity, while kinetic energy is decreasing the reactivity. A strong isotope effect is found, although the calculations slightly overestimate the kinetic isotope effect. The good experiment-theory agreement not only validates the accuracy of the potential energy surface but also provides more accurate kinetic data over a large temperature range.

Influences of large-scale convection and moisture source on monthly precipitation isotope ratios observed in Thailand, Southeast Asia

NASA Astrophysics Data System (ADS)

Wei, Zhongwang; Lee, Xuhui; Liu, Zhongfang; Seeboonruang, Uma; Koike, Masahiro; Yoshimura, Kei

2018-04-01

Many paleoclimatic records in Southeast Asia rely on rainfall isotope ratios as proxies for past hydroclimatic variability. However, the physical processes controlling modern rainfall isotopic behaviors in the region is poorly constrained. Here, we combined isotopic measurements at six sites across Thailand with an isotope-incorporated atmospheric circulation model (IsoGSM) and the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to investigate the factors that govern the variability of precipitation isotope ratios in this region. Results show that rainfall isotope ratios are both correlated with local rainfall amount and regional outgoing longwave radiation, suggesting that rainfall isotope ratios in this region are controlled not only by local rain amount (amount effect) but also by large-scale convection. As a transition zone between the Indian monsoon and the western North Pacific monsoon, the spatial difference of observed precipitation isotope among different sites are associated with moisture source. These results highlight the importance of regional processes in determining rainfall isotope ratios in the tropics and provide constraints on the interpretation of paleo-precipitation isotope records in the context of regional climate dynamics.

Coupled extremely light Ca and Fe isotopes in peridotites

NASA Astrophysics Data System (ADS)

Zhao, Xinmiao; Zhang, Zhaofeng; Huang, Shichun; Liu, Yufei; Li, Xin; Zhang, Hongfu

2017-07-01

Large metal stable isotopic variations have been observed in both extraterrestrial and terrestrial samples. For example, Ca exhibits large mass-dependent isotopic variation in terrestrial igneous rocks and mantle minerals (on the order of ∼2‰ variation in 44Ca/40Ca). A thorough assessment and understanding of such isotopic variations in peridotites provides important constraints on the evolution and compositon of the Earth's mantle. In order to better understand the Ca and Fe isotopic variations in terrestrial silicate rocks, we report Ca isotopic compositions in a set of peridotitic xenoliths from North China Craton (NCC), which have been studied for Fe isotopes. These NCC peridotites have large Ca and Fe isotopic variations, with δ44/40Ca ranging from -0.08 to 0.92 (delta value relative to SRM915a) and δ57/54Fe (delta value relative to IRMM-014) ranging from -0.61 to 0.16, and these isotopic variations are correlated with large Mg# (100 × Mg/(Mg + Fe) molar ratio) variation, ranging from 80 to 90. Importantly, NCC Fe-rich peridotites have the lowest 44Ca/40Ca and 57Fe/54Fe ratios in all terrestrial silicate rocks. In contrast, although ureilites, mantle rocks from a now broken differentiated asteroid(s), have large Mg# variation, from 70 to 92, they have very limited δ57Fe/54Fe variation (0.03-0.21, delta value relative to IRMM-014). Our model calculations show that the coupled extremely light Ca-Fe isotopic signatures in NCC Fe-rich peridotites most likely reflect kinetic isotopic fractionation during melt-peridotite reaction on a timescale of several to 104 years. In addition, our new data and compiled literature data show a possible compositional effect on the inter-mineral Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene pairs.

Calcium and Oxygen Isotopic Composition of Calcium Carbonates

NASA Astrophysics Data System (ADS)

Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

2016-04-01

Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40

Pressure-dependent boron isotopic fractionation observed by column chromatography

NASA Astrophysics Data System (ADS)

Musashi, M.; Oi, T.; Matsuo, M.; Nomura, M.

2007-12-01

Boron isotopic fractionation factor ( S ) between boron taken up in strongly basic anion exchange resin and boron in aqueous solution was determined by breakthrough column chromatography at 5 and 17 MPa at 25°C, using 0.1 mmol/L boric acid solution as feed solution. The S values obtained were 1.018 and 1.012, respectively, which were smaller than the value reported by using the same chromatographic method at atmospheric pressure at 25°C with the boron concentration of 10 mmol/L, but were larger than the values at the same condition with much higher concentration of 100 and 501 mmol/L, indicating that borate-polymerization reducing the isotopic fractionation was negligible. However, calculations based on the theory of isotope distribution between two phases estimated that 21% (5MPa) and 47% (17MPa) of boron taken up in the resin phase was in the three-coordinated B(OH)3-form, instead of in the four-coordinated B(OH)4--form, at high pressures even with the very diluted solution. We discussed this discrepancy by introducing (1) hydration or (2) a partial molar volume difference between isotopic molecules. It was inferred that borate ions were partially dehydrated upon transfer from the solution phase to the resin phase at high pressures, which resulted in smaller S values compared with those at the atmospheric pressure. Alternatively, it was likely that the S value decreased with increasing pressure, because the difference of the partial isotopic molar volumes between 10B(OH)3 and 11B(OH)3 was larger than that between 10B(OH)4- and 11B(OH)4-. If either will be the case, the influence of a pressure upon the isotope effect may not be negligible for boron isotopic exchange equilibrium. This knowledge is crucial for the principle of the boron isotopic pH-metry reconstructing a chemical variation at the paleo-deep oceanic environment where the early life may have been evolved.

Shifts in rotifer life history in response to stable isotope enrichment: testing theories of isotope effects on organismal growth

PubMed Central

2017-01-01

In ecology, stable isotope labelling is commonly used for tracing material transfer in trophic interactions, nutrient budgets and biogeochemical processes. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism growth and metabolism. This assumption is, however, challenged by theoretical considerations and experimental studies on kinetic isotope effects in vivo. Here, I demonstrate profound changes in life histories of the rotifer Brachionus plicatilis fed 15N-enriched algae (0.4–5.0 at%); i.e. at the enrichment levels commonly used in ecological studies. These findings support theoretically predicted effects of heavy isotope enrichment on growth, metabolism and ageing in biological systems and underline the importance of accounting for such effects when using stable isotope labelling in experimental studies. PMID:28405367

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

PubMed Central

Sharma, Sudhir C.; Klinman, Judith P.

2009-01-01

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

Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

NASA Technical Reports Server (NTRS)

Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

1983-01-01

In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

A combined radio- and stable-isotopic study of a California coastal aquifer system

USGS Publications Warehouse

Swarzenski, Peter W.; Baskaran, Mark; Rosenbauer, Robert J.; Edwards, Brian D.; Land, Michael

2013-01-01

Stable and radioactive tracers were utilized in concert to characterize geochemical processes in a complex coastal groundwater system and to provide constraints on the kinetics of rock/water interactions. Groundwater samples from wells within the Dominguez Gap region of Los Angeles County, California were analyzed for a suite of major cations (Na+, K+, Mg2+, Ca2+) and anions (Cl−, SO42−), silica, alkalinity, select trace elements (Ba, B, Sr), dissolved oxygen, stable isotopes of hydrogen (δD), oxygen (δ18O), dissolved inorganic carbon (δ13CDIC), and radioactive isotopes (3H, 222Rn and 223,224,226,228Ra). In the study area, groundwater may consist of a complex mixture of native groundwater, intruded seawater, non-native injected water, and oil-field brine water. In some wells, Cl− concentrations attained seawater-like values and in conjunction with isotopically heavier δ18O values, these tracers provide information on the extent of seawater intrusion and/or mixing with oil-field brines. Groundwater 3H above 1 tritium unit (TU) was observed only in a few select wells close to the Dominguez Gap area and most other well groundwater was aged pre-1952. Based on an initial 14C value for the study site of 90 percent modern carbon (pmc), groundwater age estimates likely extend beyond 20 kyr before present and confirm deep circulation of some native groundwater through multiple aquifers. Enriched values of groundwater δ13CDIC in the absence of SO42− imply enhanced anaerobic microbial methanogenesis. While secular equilibrium was observed for 234U/238U (activity ratios ~1) in host matrices, strong isotopic fractionation in these groundwater samples can be used to obtain information of adsorption/desorption kinetics. Calculated Ra residence times are short, and the associated desorption rate constant is about three orders of magnitude slower than that of the adsorption rate constant. Combined stable- and radio-isotopic results provide unique insights into aquifer

New observations and insights into the morphology and growth kinetics of hydrate films.

PubMed

Li, Sheng-Li; Sun, Chang-Yu; Liu, Bei; Li, Zhi-Yun; Chen, Guang-Jin; Sum, Amadeu K

2014-02-19

The kinetics of film growth of hydrates of methane, ethane, and methane-ethane mixtures were studied by exposing a single gas bubble to water. The morphologies, lateral growth rates, and thicknesses of the hydrate films were measured for various gas compositions and degrees of subcooling. A variety of hydrate film textures was revealed. The kinetics of two-dimensional film growth was inferred from the lateral growth rate and initial thickness of the hydrate film. A clear relationship between the morphology and film growth kinetics was observed. The shape of the hydrate crystals was found to favour heat or mass transfer and favour further growth of the hydrate film. The quantitative results on the kinetics of film growth showed that for a given degree of subcooling, the initial film thicknesses of the double hydrates were larger than that of pure methane or ethane hydrate, whereas the thickest hydrate film and the lowest lateral growth rate occurred when the methane mole fraction was approximately 0.6.

New Observations and Insights into the Morphology and Growth Kinetics of Hydrate Films

PubMed Central

Li, Sheng-Li; Sun, Chang-Yu; Liu, Bei; Li, Zhi-Yun; Chen, Guang-Jin; Sum, Amadeu K.

2014-01-01

The kinetics of film growth of hydrates of methane, ethane, and methane-ethane mixtures were studied by exposing a single gas bubble to water. The morphologies, lateral growth rates, and thicknesses of the hydrate films were measured for various gas compositions and degrees of subcooling. A variety of hydrate film textures was revealed. The kinetics of two-dimensional film growth was inferred from the lateral growth rate and initial thickness of the hydrate film. A clear relationship between the morphology and film growth kinetics was observed. The shape of the hydrate crystals was found to favour heat or mass transfer and favour further growth of the hydrate film. The quantitative results on the kinetics of film growth showed that for a given degree of subcooling, the initial film thicknesses of the double hydrates were larger than that of pure methane or ethane hydrate, whereas the thickest hydrate film and the lowest lateral growth rate occurred when the methane mole fraction was approximately 0.6. PMID:24549241

Observational Constraints on Modeling Growth and Evaporation Kinetics of Isoprene SOA

NASA Astrophysics Data System (ADS)

Zaveri, R. A.; Shilling, J. E.; Zelenyuk, A.; Liu, J.; Wilson, J. M.; Laskin, A.; Wang, B.; Fast, J. D.; Easter, R. C.; Wang, J.; Kuang, C.; Thornton, J. A.; Setyan, A.; Zhang, Q.; Onasch, T. B.; Worsnop, D. R.

2014-12-01

Isoprene is thought to be a major contributor to the global secondary organic aerosol (SOA) budget, and therefore has the potential to exert a significant influence on earth's climate via aerosol direct and indirect radiative effects. Both aerosol optical and cloud condensation nuclei properties are quite sensitive to aerosol number size distribution, as opposed to the total aerosol mass concentration. Recent studies suggest that SOA particles can be highly viscous, which can affect the kinetics of SOA partitioning and size distribution evolution when the condensing organic vapors are semi-volatile. In this study, we examine the growth kinetics of SOA formed from isoprene photooxidation in the presence of pre-existing Aitken and accumulation mode aerosols in: (a) the ambient atmosphere during the CARES field campaign, and (b) the environmental chamber at PNNL. Each growth episode is analyzed and interpreted with the updated MOSAIC aerosol box model, which performs kinetic gas-particle partitioning of SOA and takes into account diffusion and chemical reaction within the particle phase. The model is initialized with the observed aerosol size distribution and composition at the beginning of the experiment, and the total amount of SOA formed in the model at any given time is constrained by the observed total amount of SOA formed. The variable model parameters include the number of condensing organic species, their gas-phase formation rates, their effective volatilities, and their bulk diffusivities in the Aitken and accumulation modes. The objective of the constrained modeling exercise is then to determine which model configuration is able to best reproduce the observed size distribution evolution, thus providing valuable insights into the possible mechanism of SOA formation. We also examine the evaporation kinetics of size-selected particles formed in the environmental chamber to provide additional constraints on the effective volatility and bulk diffusivity of the

Arrhenius curves of hydrogen transfers: tunnel effects, isotope effects and effects of pre-equilibria

PubMed Central

Limbach, Hans-Heinrich; Miguel Lopez, Juan; Kohen, Amnon

2006-01-01

In this paper, the Arrhenius curves of selected hydrogen-transfer reactions for which kinetic data are available in a large temperature range are reviewed. The curves are discussed in terms of the one-dimensional Bell–Limbach tunnelling model. The main parameters of this model are the barrier heights of the isotopic reactions, barrier width of the H-reaction, tunnelling masses, pre-exponential factor and minimum energy for tunnelling to occur. The model allows one to compare different reactions in a simple way and prepare the kinetic data for more-dimensional treatments. The first type of reactions is concerned with reactions where the geometries of the reacting molecules are well established and the kinetic data of the isotopic reactions are available in a large temperature range. Here, it is possible to study the relation between kinetic isotope effects (KIEs) and chemical structure. Examples are the tautomerism of porphyrin, the porphyrin anion and related compounds exhibiting intramolecular hydrogen bonds of medium strength. We observe pre-exponential factors of the order of kT/h≅1013 s−1 corresponding to vanishing activation entropies in terms of transition state theory. This result is important for the second type of reactions discussed in this paper, referring mostly to liquid solutions. Here, the reacting molecular configurations may be involved in equilibria with non- or less-reactive forms. Several cases are discussed, where the less-reactive forms dominate at low or at high temperature, leading to unusual Arrhenius curves. These cases include examples from small molecule solution chemistry like the base-catalysed intramolecular H-transfer in diaryltriazene, 2-(2′-hydroxyphenyl)-benzoxazole, 2-hydroxy-phenoxyl radicals, as well as in the case of an enzymatic system, thermophilic alcohol dehydrogenase. In the latter case, temperature-dependent KIEs are interpreted in terms of a transition between two regimes with different temperature

Arrhenius curves of hydrogen transfers: tunnel effects, isotope effects and effects of pre-equilibria.

PubMed

Limbach, Hans-Heinrich; Miguel Lopez, Juan; Kohen, Amnon

2006-08-29

In this paper, the Arrhenius curves of selected hydrogen-transfer reactions for which kinetic data are available in a large temperature range are reviewed. The curves are discussed in terms of the one-dimensional Bell-Limbach tunnelling model. The main parameters of this model are the barrier heights of the isotopic reactions, barrier width of the H-reaction, tunnelling masses, pre-exponential factor and minimum energy for tunnelling to occur. The model allows one to compare different reactions in a simple way and prepare the kinetic data for more-dimensional treatments. The first type of reactions is concerned with reactions where the geometries of the reacting molecules are well established and the kinetic data of the isotopic reactions are available in a large temperature range. Here, it is possible to study the relation between kinetic isotope effects (KIEs) and chemical structure. Examples are the tautomerism of porphyrin, the porphyrin anion and related compounds exhibiting intramolecular hydrogen bonds of medium strength. We observe pre-exponential factors of the order of kT/h congruent with 10(13) s-1 corresponding to vanishing activation entropies in terms of transition state theory. This result is important for the second type of reactions discussed in this paper, referring mostly to liquid solutions. Here, the reacting molecular configurations may be involved in equilibria with non- or less-reactive forms. Several cases are discussed, where the less-reactive forms dominate at low or at high temperature, leading to unusual Arrhenius curves. These cases include examples from small molecule solution chemistry like the base-catalysed intramolecular H-transfer in diaryltriazene, 2-(2'-hydroxyphenyl)-benzoxazole, 2-hydroxy-phenoxyl radicals, as well as in the case of an enzymatic system, thermophilic alcohol dehydrogenase. In the latter case, temperature-dependent KIEs are interpreted in terms of a transition between two regimes with different temperature

Dynamical and many-body correlation effects in the kinetic energy spectra of isotopes produced in nuclear multifragmentation

NASA Astrophysics Data System (ADS)

Souza, S. R.; Donangelo, R.; Lynch, W. G.; Tsang, M. B.

2018-03-01

The properties of the kinetic energy spectra of light isotopes produced in the breakup of a nuclear source and during the de-excitation of its products are examined. The initial stage, at which the hot fragments are created, is modeled by the statistical multifragmentation model, whereas the Weisskopf-Ewing evaporation treatment is adopted to describe the subsequent fragment de-excitation, as they follow their classical trajectories dictated by the Coulomb repulsion among them. The energy spectra obtained are compared to available experimental data. The influence of the fusion cross section entering into the evaporation treatment is investigated and its influence on the qualitative aspects of the energy spectra turns out to be small. Although these aspects can be fairly well described by the model, the underlying physics associated with the quantitative discrepancies remains to be understood.

Reaction rates and kinetic isotope effects of H{sub 2} + OH → H{sub 2}O + H

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

Meisner, Jan; Kästner, Johannes, E-mail: kaestner@theochem.uni-stuttgart.de

2016-05-07

We calculated reaction rate constants including atom tunneling of the reaction of dihydrogen with the hydroxy radical down to a temperature of 50 K. Instanton theory and canonical variational theory with microcanonical optimized multidimensional tunneling were applied using a fitted potential energy surface [J. Chen et al., J. Chem. Phys. 138, 154301 (2013)]. All possible protium/deuterium isotopologues were considered. Atom tunneling increases at about 250 K (200 K for deuterium transfer). Even at 50 K the rate constants of all isotopologues remain in the interval 4 ⋅ 10{sup −20} to 4 ⋅ 10{sup −17} cm{sup 3} s{sup −1}, demonstrating thatmore » even deuterated versions of the title reaction are possibly relevant to astrochemical processes in molecular clouds. The transferred hydrogen atom dominates the kinetic isotope effect at all temperatures.« less

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

NASA Astrophysics Data System (ADS)

Yeung, L.

2015-12-01

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

Partitioning evapotranspiration fluxes with water stable isotopic measurements: from the lab to the field

NASA Astrophysics Data System (ADS)

Quade, M. E.; Brueggemann, N.; Graf, A.; Rothfuss, Y.

2017-12-01

Water stable isotopes are powerful tools for partitioning net into raw water fluxes such as evapotranspiration (ET) into soil evaporation (E) and plant transpiration (T). The isotopic methodology for ET partitioning is based on the fact that E and T have distinct water stable isotopic compositions, which in turn relies on the fact that each flux is differently affected by isotopic kinetic effects. An important work to be performed in parallel to field measurements is to better characterize these kinetic effects in the laboratory under controlled conditions. A soil evaporation laboratory experiment was conducted to retrieve characteristic values of the kinetic fractionation factor (αK) under varying soil and atmospheric water conditions. For this we used a combined soil and atmosphere column to monitor the soil and atmospheric water isotopic composition profiles at a high temporal and vertical resolution in a nondestructive manner by combining micro-porous membranes and laser spectroscopy. αK was calculated by using a well-known isotopic evaporation model in an inverse mode with the isotopic composition of E as one input variable, which was determined using a micro-Keeling regression plot. Knowledge on αK was further used in the field (Selhausen, North Rhine-Westphalia, Germany) to partition ET of catch crops and sugar beet (Beta vulgaris) during one growing season. Soil and atmospheric water isotopic profiles were measured automatically across depths and heights following a similar modus operandi as in the laboratory experiment. Additionally, a newly developed continuously moving elevator was used to obtain water vapor isotopic composition profiles with a high vertical resolution between soil surface, plant canopy and atmosphere. Finally, soil and plant samples were collected destructively to provide a comparison with the traditional isotopic methods. Our results illustrate the changing proportions of T and E along the growing season and demonstrate the

An exceptional kinetic quantum sieving separation effect of hydrogen isotopes on commercially available carbon molecular sieves.

PubMed

Xing, Yanlong; Cai, Jinjun; Li, Liangjun; Yang, Menglong; Zhao, Xuebo

2014-08-14

The quantum sieving effect of H2/D2 at 77 K on commercially available carbon molecular sieves (1.5GN-H and 3KT-172) was studied. An exceptional reverse kinetic quantum effect is observed on 1.5GN-H where D2 diffuses much faster than H2 with a ratio of up to 5.83 at low pressure, and the difference is still very evident even as the pressure increases up to 1 bar. D2 also diffuses faster than H2 on 3KT-172 with a ratio of up to 1.86. However, the reverse kinetic sieving disappears in a polymer-based carbon (PC). The present kinetic quantum sieving effect of H2 and D2 at 77 K on 1.5GN-H is the highest to date.

Calcium Isotope Geochemistry: Research Horizons and Nanoscale Fractionation Processes

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

Yang, W; Simon, J I; DePaolo, D J

Interest in studies of calcium isotope variations in nature continues to increase. Investigations span human biology, plants and soils, oceanography and paleoclimate, early solar system processes, aqueous geochemistry, and silicate liquid structure. Variations in the 44Ca/40Ca ratio are generally small, about 5 {per_thousand}, but gradual small improvements in analytical capability now yield 0.05 to 0.1 {per_thousand} resolution. The field is still plagued by a lack of universal standards for isotope ratios and data representation, but these are secondary issues. Traditional isotopic systems have been based in equilibrium thermodynamics, which can explain the magnitude and sign of observed mass-dependent fractionation behavior.more » For Ca isotopes this is not the case. There is still no reliable way to estimate the equilibrium free energy associated with isotopic exchange between most phases of interest. Experiments are difficult to interpret because it is almost impossible to precipitate minerals from aqueous solution at equilibrium at low temperature. Some studies suggest that, for example, there is no equilibrium isotopic fractionation between calcite and dissolved aqueous Ca. There is good evidence that most Ca isotopic fractionation is caused by kinetic effects. The details of the controlling processes are still missing, and without this mechanistic understanding it is difficult to fully understand the implications of natural isotopic variations. Recent work on dissolved Ca, calcite, and sulfates in both laboratory and natural settings is shedding light on where the fractionation may arise. There is emerging evidence for mass dependent fractionation associated with aqueous diffusion, but probably the primary source of the effects is in the details of precipitation of minerals from solution. This makes the fractionation potentially dependent on a number of factors, including solution composition and mineral growth rate. The next challenge is to develop

Combined simulation of carbon and water isotopes in a global ocean model

NASA Astrophysics Data System (ADS)

Paul, André; Krandick, Annegret; Gebbie, Jake; Marchal, Olivier; Dutkiewicz, Stephanie; Losch, Martin; Kurahashi-Nakamura, Takasumi; Tharammal, Thejna

2013-04-01

Carbon and water isotopes are included as passive tracers in the MIT general circulation model (MITgcm). The implementation of the carbon isotopes is based on the existing MITgcm carbon cycle component and involves the fractionation processes during photosynthesis and air-sea gas exchange. Special care is given to the use of a real freshwater flux boundary condition in conjunction with the nonlinear free surface of the ocean model. The isotopic content of precipitation and water vapor is obtained from an atmospheric GCM (the NCAR CAM3) and mapped onto the MITgcm grid system, but the kinetic fractionation during evaporation is treated explicitly in the ocean model. In a number of simulations, we test the sensitivity of the carbon isotope distributions to the formulation of fractionation during photosynthesis and compare the results to modern observations of δ13C and Δ14C from GEOSECS, WOCE and CLIVAR. Similarly, we compare the resulting distribution of oxygen isotopes to modern δ18O data from the NASA GISS Global Seawater Oxygen-18 Database. The overall agreement is good, but there are discrepancies in the carbon isotope composition of the surface water and the oxygen isotope composition of the intermediate and deep waters. The combined simulation of carbon and water isotopes in a global ocean model will provide a framework for studying present and past states of ocean circulation such as postulated from deep-sea sediment records.

Nitrogen Isotopic Ratio in Jupiter's Atmosphere from Observations by Composite Infrared Spectrometer (CIRS) on the Cassini Spacecraft

NASA Technical Reports Server (NTRS)

Abbas, M. M.; LeClair, A.; Owen, T.; Conrath, B. J.; Flasar, F. M.; Kunde, V. G.; Nixon, C. A..; Achterberg, R. K.; Bjoraker, G.; Jennings, D. J.

2003-01-01

The Composite Infrared Spectrometer (CIRS) on the Cassini spacecraft made infrared observations of Jupiter's atmosphere during the flyby in December 2000 to January 2001. The unique database in the 600-1400/cm region with 0.53 and 2.8/cm spectral resolutions obtained from the observations permits retrieval of global maps of the thermal structure and composition of Jupiter's atmosphere including the distributions of (14)NH3 and (15)NH3. Analysis of Jupiter's ammonia distributions from three isolated (15)NH3 spectral lines in eight latitudes is presented for evaluation of the nitrogen isotopic ratio. The nitrogen isotopic ratio (14)N/(15)N (or (15)N/(14)N) in Jupiter's atmosphere in this analysis is calculated to be: 448 +/- 62 ((2.23 +/- 0.31) x 10(exp -3)). This value of the ratio determined from CIRS data is found to be in very close agreement with the value previously obtained from the measurements by the Galileo Probe Mass Spectrometer. Some possible mechanisms to account for the variation of Jupiter's observed isotopic ratio relative to various astrophysical environments are discussed.

A comparison of observed and numerically predicted eddy kinetic energy budgets for a developing extratropical cyclone

NASA Technical Reports Server (NTRS)

Dare, P. M.; Smith, P. J.

1983-01-01

The eddy kinetic energy budget is calculated for a 48-hour forecast of an intense occluding winter cyclone associated with a strong well-developed jet stream. The model output consists of the initialized (1200 GMT January 9, 1975) and the 12, 24, 36, and 48 hour forecast fields from the Drexel/NCAR Limited Area Mesoscale Prediction System (LAMPS) model. The LAMPS forecast compares well with observations for the first 24 hours, but then overdevelops the low-level cyclone while inadequately developing the upper-air wave and jet. Eddy kinetic energy was found to be concentrated in the upper-troposphere with maxima flanking the primary trough. The increases in kinetic energy were found to be due to an excess of the primary source term of kinetic energy content, which is the horizontal flux of eddy kinetic energy over the primary sinks, and the generation and dissipation of eddy kinetic energy.

Theoretical studies for the rates and kinetic isotope effects of the excited-state double proton transfer in the 1:1 7-azaindole:H2O complex using variational transition state theory including multidimensional tunneling.

PubMed

Duong, My Phu Thi; Kim, Yongho

2010-03-18

Variational transition state theory calculations including multidimensional tunneling (VTST/MT) for excited-state tautomerization in the 1:1 7-azaindole:H(2)O complex were performed. Electronic structures and energies for reactant, product, transition state, and potential energy curves along the reaction coordinate were computed at the CASSCF(10,9)/6-31G(d,p) level of theory. The potential energies were corrected by second-order multireference perturbation theory to take the dynamic electron correlation into consideration. The final potential energy curves along the reaction coordinate were generated at the MRPT2//CASSCF(10,9)/6-31G(d,p) level. Two protons in the excited-state tautomerization are transferred concertedly, albeit asynchronously. The position of the variational transition state is very different from the conventional transition state, and is highly dependent on isotopic substitution. Rate constants were calculated using VTST/MT, and were on the order of 10(-6) s(-1) at room temperature. The HH/DD kinetic isotope effects are consistent with experimental observations; consideration of both tunneling and variational effects was essential to predict the experimental values correctly.

Stable isotope analysis at the molecular level: A new approach for determining the origins of amino acids in the Murchison meteorite

NASA Technical Reports Server (NTRS)

Engel, M. H.; Macko, S. A.; Qian, Y.; Silfer, J. A.

1995-01-01

A combined gas chromatography/isotope ratio mass spectrometry (GC/IRMS) method has been developed that permits the direct stable carbon isotope analysis of N(O)-trifluoroacetyl-isopropyl esters of individual amino acids and their respective enantiomers at nanomole abundances. Calculation of the original delta C-13 values of the amino acids is accomplished via a correction for the carbon introduced during the derivatization process. Previous GC/IRMS analyses of individual amino acids in the non-hydrolyzed water extract of an interior sample of a Murchison meteorite stone revealed an enrichment in C-13 relative to terrestrial organic matter, in agreement with previous findings for bulk extracts. The range of amino acid delta C-13 values (+5 to +30 per mill, PDB) suggests possible kinetic effects during synthesis. In this study, an apparent kinetic isotope effect was also observed for the amino acid products of a spark discharge experiment. These preliminary resutls are supportive of a similar mechanism for the abiotic synthesis of amino acids in the Murchison meteorite.

Observations of Isotope Fractionation in Prestellar Cores: Interstellar Origin of Meteoritic Hot Spot?

NASA Technical Reports Server (NTRS)

Milam, S. N.; Charnley, S. B.

2011-01-01

Isotopically fractionated material is found in many solar system objects, including meteorites and comets. It is thought, in some cases, to trace interstellar material that was incorporated into the solar system without undergoing significant processing. Here, we show the results of models and observations of the nitrogen and carbon fractionation in proto-stellar cores.

Safety of stable isotope use.

PubMed

Koletzko, B; Sauerwald, T; Demmelmair, H

1997-08-01

The increased employment of stable isotope tracers for diagnostic and research purposes frequently raises questions on potential risks associated with their use, which is of particular importance in the paediatric age group. Biological effects and the potential of adverse events has been evaluated in a large number of animal and, in part, also human studies. Possible differences in physical, chemical and biochemical behaviour resulting in kinetic and thermodynamic isotope effects between stable isotopes of the same element are related to the relative differences in atomic weight. Deuterium (2H), which differs markedly in mass from the predominant hydrogen isotope 1H, may induce serious side-effects at high concentrations in body fluids. The threshold dose for the occurrence of side-effects lies well above the usual tracer dosages for clinical use. In contrast to deuterium, heavier stable isotopes such as 13C, 15N or 18O that differ relatively little in mass from the predominant isotopes such as 12C, does not show any adverse biological effects even at highest enrichments. The doses of stable isotope tracer substances that are used for clinical diagnostic and research purposes appear safe and without any adverse effects. Stable isotope tracers should only be used in children if the trace is safe at the doses applied, and tracer is chemically pure and stable. In the case of intravenous application, the tracer preparation must also be sterile and pyrogen free.

Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

NASA Astrophysics Data System (ADS)

Boshers, D.; Granger, J.; Bohlke, J. K.

2016-12-01

Measurements of the naturally occurring nitrogen and oxygen stable isotope ratios of nitrate (NO3-), δ15N and δ18O, can be used to determine the source, dispersal, and fate of natural and contaminant NO3- in aquatic environments. To this end, it is necessary to know the extent to which NO3- isotopologues are modified by biological reactions, as heavy and light isotopes have different reaction rates. The purpose of this study was to determine the influence of the δ18O of ambient water on the isotope composition of NO3- produced during nitrification, the biological oxidation of ammonium (NH4+) to nitrite (NO2-) and then NO3-, which is poorly constrained in freshwater systems. To determine the δ18O of NO3- produced by nitrification in freshwater, we collected water from a stream in New England, which we amended with NH4+ and with increments of 18O-enriched water, to monitor the isotope composition of NO3- produced by a natural consortium of nitrifiers. Added NH4+ was completely oxidized to NO3- over 26 days. The final δ18O of nitrified NO3- revealed sensitivity to the δ18O of water mediated by (a) isotopic equilibration between water and NO2- and (b) kinetic isotope fractionation during O-atom incorporation from water into NO2- and NO3-. Our results concur with nitrifying culture experiments that have demonstrated analogous sensitivity of the δ18O of nitrified NO3- to equilibrium and kinetic O isotope effects (Buchwald et al. 2012), as well as show that these dynamics need to be considered to interpret NO3- isotope distribution in freshwater environments.

In Situ Observation of Intermittent Dissipation at Kinetic Scales in the Earth's Magnetosheath

NASA Astrophysics Data System (ADS)

Chasapis, Alexandros; Matthaeus, W. H.; Parashar, T. N.; Wan, M.; Haggerty, C. C.; Pollock, C. J.; Giles, B. L.; Paterson, W. R.; Dorelli, J.; Gershman, D. J.; Torbert, R. B.; Russell, C. T.; Lindqvist, P.-A.; Khotyaintsev, Y.; Moore, T. E.; Ergun, R. E.; Burch, J. L.

2018-03-01

We present a study of signatures of energy dissipation at kinetic scales in plasma turbulence based on observations by the Magnetospheric Multiscale mission (MMS) in the Earth’s magnetosheath. Using several intervals, and taking advantage of the high-resolution instrumentation on board MMS, we compute and discuss several statistical measures of coherent structures and heating associated with electrons, at previously unattainable scales in space and time. We use the multi-spacecraft Partial Variance of Increments (PVI) technique to study the intermittent structure of the magnetic field. Furthermore, we examine a measure of dissipation and its behavior with respect to the PVI as well as the current density. Additionally, we analyze the evolution of the anisotropic electron temperature and non-Maxwellian features of the particle distribution function. From these diagnostics emerges strong statistical evidence that electrons are preferentially heated in subproton-scale regions of strong electric current density, and this heating is preferentially in the parallel direction relative to the local magnetic field. Accordingly, the conversion of magnetic energy into electron kinetic energy occurs more strongly in regions of stronger current density, a finding consistent with several kinetic plasma simulation studies and hinted at by prior studies using lower resolution Cluster observations.

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

DOE PAGES

Loyd, S. J.; Sample, J.; Tripati, R. E.; ...

2016-07-22

Here, 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, mixingmore » 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.« less

Abiologic silicon isotope fractionation between aqueous Si and Fe(III)-Si gel in simulated Archean seawater: Implications for Si isotope records in Precambrian sedimentary rocks

NASA Astrophysics Data System (ADS)

Zheng, Xin-Yuan; Beard, Brian L.; Reddy, Thiruchelvi R.; Roden, Eric E.; Johnson, Clark M.

2016-08-01

Precambrian Si-rich sedimentary rocks, including cherts and banded iron formations (BIFs), record a >7‰ spread in 30Si/28Si ratios (δ30Si values), yet interpretation of this large variability has been hindered by the paucity of data on Si isotope exchange kinetics and equilibrium fractionation factors in systems that are pertinent to Precambrian marine conditions. Using the three-isotope method and an enriched 29Si tracer, a series of experiments were conducted to constrain Si isotope exchange kinetics and fractionation factors between amorphous Fe(III)-Si gel, a likely precursor to Precambrian jaspers and BIFs, and aqueous Si in artificial Archean seawater under anoxic conditions. Experiments were conducted at room temperature, and in the presence and absence of aqueous Fe(II) (Fe(II)aq). Results of this study demonstrate that Si solubility is significantly lower for Fe-Si gel than that of amorphous Si, indicating that seawater Si concentrations in the Precambrian may have been lower than previous estimates. The experiments reached ∼70-90% Si isotope exchange after a period of 53-126 days, and the highest extents of exchange were obtained where Fe(II)aq was present, suggesting that Fe(II)-Fe(III) electron-transfer and atom-exchange reactions catalyze Si isotope exchange through breakage of Fe-Si bonds. All experiments except one showed little change in the instantaneous solid-aqueous Si isotope fractionation factor with time, allowing extraction of equilibrium Si isotope fractionation factors through extrapolation to 100% isotope exchange. The equilibrium 30Si/28Si fractionation between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -2.30 ± 0.25‰ (2σ) in the absence of Fe(II)aq. In the case where Fe(II)aq was present, which resulted in addition of ∼10% Fe(II) in the final solid, creating a mixed Fe(II)-Fe(III) Si gel, the equilibrium fractionation between Fe(II)-Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -3.23 ± 0.37‰ (2�

Western US Seismic Observations Viewed Through Lead Isotope Maps

NASA Astrophysics Data System (ADS)

Bouchet, R. A.; Blichert-Toft, J.; Levander, A.; Reid, M. R.; Albarede, F.

2013-12-01

To shed light on the nature and history of the different geological units identified by the seismic models that have come from USArray in the western US, we compiled literature Pb isotope compositions of ores (n=1200), K-feldspars from granites (n=400), and felsic plutonic rocks (n=1300), data that for most part were not in the NAVDAT database. We complemented this compilation by analyzing the Pb isotope compositions of K-feldspars (76) and whole-rocks (6) of felsic xenoliths and felsic plutonic rocks from the Colorado Plateau (CP). The raw Pb isotope abundances for the complete data set were converted into three independent, geologically informative parameters in the form of the model age T (time of last U/Pb fractionation) and the two chemical ratios 238U/204Pb (μ) and 232Th/238U (κ). These parameters were then imaged on isotopic maps of the western US using 0.5°×0.5° grid-cell averaging for μ and κ and a 0.5°×0.5° grid-cell maximum after removing the 2.5% highest values (outliers) for T. Comparing these chemical maps to seismic maps of tomographic anomalies [1] and Moho and LAB depths determined from receiver functions [2] leads to the following observations: (i) Pb model ages: they match geological ages mostly where the continental mantle is cold and the Moho is deep. Elsewhere, Pb model ages are younger than geological ages. We interpret this feature as the chronological expression of a delayed cooling of deep crustal layers below the closure temperature (˜550-700°C) of Pb in K-feldspar, the major host of this element in the crust [3] or of age resetting by orogenic activity. (ii) While U/Pb (μ) does not vary systematically with other geochemical or seismic data, high Th/U (κ) values are usually observed where Vp/Vs is also high, as in the Snake River basin and central Colorado. High kappa values also form a 'ridge' trending south from northwestern Utah through the Basin and Range into the Mojave-Yavapai block. High-κ areas may reflect the

Determination of nitrogen-15 isotope fractionation in tropine: evaluation of extraction protocols for isotope ratio measurement by isotope ratio mass spectrometry.

PubMed

Molinié, Roland; Kwiecień, Renata A; Silvestre, Virginie; Robins, Richard J

2009-12-01

N-Demethylation of tropine is an important step in the degradation of this compound and related metabolites. With the purpose of understanding the reaction mechanism(s) involved, it is desirable to measure the 15N kinetic isotope effects (KIEs), which can be accessed through the 15N isotope shift (Deltadelta15N) during the reaction. To measure the isotope fractionation in 15N during tropine degradation necessitates the extraction of the residual substrate from dilute aqueous solution without introducing artefactual isotope fractionation. Three protocols have been compared for the extraction and measurement of the 15N/14N ratio of tropine from aqueous medium, involving liquid-liquid phase partitioning or silica-C18 solid-phase extraction. Quantification was by gas chromatography (GC) on the recovered organic phase and delta15N values were obtained by isotope ratio measurement mass spectrometry (irm-MS). Although all the protocols used can provide satisfactory data and both irm-EA-MS and irm-GC-MS can be used to obtain the delta15N values, the most convenient method is liquid-liquid extraction from a reduced aqueous volume combined with irm-GC-MS. The protocols are applied to the measurement of 15N isotope shifts during growth of a Pseudomonas strain that uses tropane alkaloids as sole source of carbon and nitrogen. The accuracy of the determination of the 15N/14N ratio is sufficient to be used for the determination of 15N-KIEs. Copyright 2009 John Wiley & Sons, Ltd.

Martian Cryogenic Carbonate Formation: Stable Isotope Variations Observed in Laboratory Studies

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K. Jr.

2014-01-01

The history of water on Mars is tied to the formation of carbonates through atmospheric CO2 and its control of the climate history of the planet. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms easily from freezing solutions when carbon dioxide degasses quickly from Ca-bicarbonate-rich water, a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lake beds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. A series of laboratory experiments were conducted that simulated cryogenic carbonate formation on Mars in order to understand their isotopic systematics. The results indicate that carbonates grown under martian conditions show variable enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Climatic and environmental controls on speleothem oxygen-isotope values

NASA Astrophysics Data System (ADS)

Lachniet, Matthew S.

2009-03-01

Variations in speleothem oxygen-isotope values ( δ18O) result from a complicated interplay of environmental controls and processes in the ocean, atmosphere, soil zone, epikarst, and cave system. As such, the controls on speleothem δ18O values are extremely complex. An understanding of the processes that control equilibrium and kinetic fractionation of oxygen isotopes in water and carbonate species is essential for the proper interpretation of speleothem δ18O as paleoclimate and paleoenvironmental proxies, and is best complemented by study of site-specific cave processes such as infiltration, flow routing, drip seasonality and saturation state, and cave microclimate, among others. This review is a process-based summary of the multiple controls on δ18O in the atmosphere, soil, epikarst, and speleothem calcite, illustrated with case studies. Primary controls of δ18O in the atmosphere include temperature and relative humidity through their role in the multiple isotope "effects". Variability and modifications of water δ18O values in the soil and epikarst zones are dominated by evaporation, mixing, and infiltration of source waters. The isotopically effective recharge into a cave system consists of those waters that participate in precipitation of CaCO 3, resulting in calcite deposition rates which may be biased to time periods with optimal dripwater saturation state. Recent modeling, experimental, and observational data yield insight into the significance of kinetic fractionation between dissolved carbonate phases and solid CaCO 3, and have implications for the 'Hendy' test. To assist interpretation of speleothem δ18O time series, quantitative and semi-quantitative δ18O-climate calibrations are discussed with an emphasis on some of the difficulties inherent in using modern spatial and temporal isotope gradients to interpret speleothems as paleoclimate proxy records. Finally, several case studies of globally significant speleothem paleoclimate records are

Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

NASA Technical Reports Server (NTRS)

Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.

2004-01-01

Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

Isotope Fractionation by Diffusion in Liquids (Final Technical Report)

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

Richter, Frank

The overall objective of the DOE-funded research by grant DE-FG02-01ER15254 was document and quantify kinetic isotope fractionations during chemical and thermal (i.e., Soret) diffusion in liquids (silicate melts and water) and in the later years to include alloys and major minerals such as olivine and pyroxene. The research involved both laboratory experiments and applications to natural settings. The key idea is that major element zoning on natural geologic materials is common and can arise for either changes in melt composition during cooling and crystallization or from diffusion. The isotope effects associated with diffusion that we have documented are the keymore » for determining whether or not the zoning observed in a natural system was the result of diffusion. Only in those cases were the zoning is demonstrably due to diffusion can use independently measured rates of diffusion to constrain the thermal evolution of the system.« less

Isotopic excesses of proton-rich nuclei related to space weathering observed in a gas-rich meteorite Kapoeta

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

Hidaka, Hiroshi; Yoneda, Shigekazu, E-mail: hidaka@hiroshima-u.ac.jp, E-mail: s-yoneda@kahaku.go.jp

2014-05-10

The idea that solar system materials were irradiated by solar cosmic rays from the early Sun has long been suggested, but is still questionable. In this study, Sr, Ba, Ce, Nd, Sm, and Gd isotopic compositions of sequential acid leachates from the Kapoeta meteorite (howardite) were determined to find systematic and correlated variations in their isotopic abundances of proton-rich nuclei, leading to an understanding of the irradiation condition by cosmic rays. Significantly large excesses of proton-rich isotopes (p-isotopes), {sup 84}Sr, {sup 130}Ba, {sup 132}Ba, {sup 136}Ce, {sup 138}Ce, and {sup 144}Sm, were observed, particularly in the first chemical separate, whichmore » possibly leached out of the very shallow layer within a few μm from the surface of regolith grains in the sample. The results reveal the production of p-isotopes through the interaction of solar cosmic rays with the superficial region of the regolith grains before the formation of the Kapoeta meteorite parent body, suggesting strong activity in the early Sun.« less

Observation of narrow isotopic optical magnetic resonances in individual emission spectral lines of neon

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

Saprykin, E G; Sorokin, V A; Shalagin, A M

Narrow resonances are observed in the course of recording the individual emission lines of the glow discharge in the mixture of isotopes {sup 20}Ne and {sup 22}Ne, depending on the strength of the longitudinal magnetic field. The position of resonances in the magnetic scale corresponds to the compensation of the isotopic shift for certain spectral lines due to the Zeeman effect. It is found that the contrast of the resonances is higher for the transitions between the highly excited energy levels, and the resonances themselves are formed in the zone of longitudinal spatial nonuniformity of the magnetic field. (laser applicationsmore » and other topics in quantum electronics)« less

Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

NASA Astrophysics Data System (ADS)

Keppler, Frank; Bahlmann, Enno; Greule, Markus; Schöler, Heinz Friedrich; Wittmer, Julian; Zetzsch, Cornelius

2018-05-01

Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be -264±45 and -280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of -205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

Observations of nitrogen isotope fractionation in deeply embedded protostars

NASA Astrophysics Data System (ADS)

Wampfler, S. F.; Jørgensen, J. K.; Bizzarro, M.; Bisschop, S. E.

2014-12-01

Context. The terrestrial planets, comets, and meteorites are significantly enriched in 15N compared to the Sun and Jupiter. While the solar and jovian nitrogen isotope ratio is believed to represent the composition of the protosolar nebula, a still unidentified process has caused 15N-enrichment in the solids. Several mechanisms have been proposed to explain the variations, including chemical fractionation. However, observational results that constrain the fractionation models are scarce. While there is evidence of 15N-enrichment in prestellar cores, it is unclear how the signature evolves into the protostellar phases. Aims: The aim of this study is to measure the 14N/15N ratio around three nearby, embedded low- to intermediate-mass protostars. Methods: Isotopologues of HCN and HNC were used to probe the 14N/15N ratio. A selection of J = 3-2 and 4-3 transitions of H13CN, HC15N, HN13C, and H15NC was observed with the Atacama Pathfinder EXperiment telescope (APEX). The 14N/15N ratios were derived from the integrated intensities assuming a standard 12C/13C ratio. The assumption of optically thin emission was verified using radiative transfer modeling and hyperfine structure fitting. Results: Two sources, IRAS 16293A and R CrA IRS7B, show 15N-enrichment by a factor of ~1.5-2.5 in both HCN and HNC with respect to the solar composition. IRAS 16293A falls in the range of typical prestellar core values. Solar composition cannot be excluded for the third source, OMC-3 MMS6. Furthermore, there are indications of a trend toward increasing 14N/15N ratios with increasing outer envelope temperature. Conclusions: The enhanced 15N abundances in HCN and HNC found in two Class 0 sources (14N /15N ~ 160-290) and the tentative trend toward a temperature-dependent 14N/15N ratio are consistent with the chemical fractionation scenario, but 14N/15N ratios from additional tracers are indispensable for testing the models. Spatially resolved observations are needed to distinguish between

Nitrogen isotope fractionation during archaeal ammonia oxidation: Coupled estimates from isotopic measurements of ammonium and nitrite

NASA Astrophysics Data System (ADS)

Mooshammer, Maria; Stieglmeier, Michaela; Bayer, Barbara; Jochum, Lara; Melcher, Michael; Wanek, Wolfgang

2014-05-01

Ammonia-oxidizing archaea (AOA) are ubiquitous in marine and terrestrial environments and knowledge about the nitrogen (N) isotope effect associated with their ammonia oxidation activity will allow a better understanding of natural abundance isotope ratios, and therefore N transformation processes, in the environment. Here we examine the kinetic isotope effect for ammonia oxidation in a pure soil AOA culture (Ca. Nitrososphaera viennensis) and a marine AOA enrichment culture. We estimated the isotope effect from both isotopic signatures of ammonium and nitrite over the course of ammonia oxidation. Estimates of the isotope effect based on the change in the isotopic signature of ammonium give valuable insight, because these estimates are not subject to the same concerns (e.g., accumulation of an intermediate) as estimates based on isotopic measurements of nitrite. Our results show that both the pure soil AOA culture and a marine AOA enrichment culture have similar but substantial isotope effect during ammonia consumption (31-34 per mill; based on ammonium) and nitrite production (43-45 per mill; based on nitrite). The 15N fractionation factors of both cultures tested fell in the upper range of the reported isotope effects for archaeal and bacterial ammonia oxidation (10-41 per mill) or were even higher than those. The isotope fractionation for nitrite production was significantly larger than for ammonium consumption, indicating that (1) some intermediate (e.g., hydroxylamine) of ammonia oxidation accumulates, allowing for a second 15N fractionation step to be expressed, (2) a fraction of ammonia oxidized is lost via gaseous N forms (e.g., NO or N2O), which is 15N-enriched or (3) a fraction of ammonium is assimilated into AOA biomass, biomass becoming 15N-enriched. The significance of these mechanisms will be explored in more detail for the soil AOA culture, based on isotope modeling and isotopic measurements of biomass and N2O.

Triple oxygen isotope composition of leaf waters in Mpala, central Kenya

NASA Astrophysics Data System (ADS)

Li, Shuning; Levin, Naomi E.; Soderberg, Keir; Dennis, Kate J.; Caylor, Kelly K.

2017-06-01

Variations in triple oxygen isotopes have been used in studies of atmospheric photochemistry, global productivity and increasingly in studies of hydroclimate. Understanding the distribution of triple oxygen isotopes in plant waters is critical to studying the fluxes of oxygen isotopes between the atmosphere and hydrosphere, in which plants play an important role. In this paper we report triple oxygen isotope data for stem and leaf waters from Mpala, Kenya and explore how Δ17 O, the deviation from an expected relationship between 17O /16O and 18O /16O ratios, in plant waters vary with respect to relative humidity and deuterium excess (d-excess). We observe significant variation in Δ17 O among waters in leaves and stems from a single plant (up to 0.16‰ range in Δ17 O in leaf water in a plant over the course of a signal day), which correlates to changes in relative humidity. A steady state model for evaporation in leaf water reproduces the majority of variation in Δ17 O and d-excess we observed in leaf waters, except for samples that were collected in the morning, when relative humidity is high and the degree of fractionation in the system is minimal. The data and the steady state model indicate that the slope, λtransp, that links δ17 O and δ18 O values of stem and leaf waters and characterizes the fractionation during transpiration, is strongly influenced by the isotopic composition of ambient vapor when relative humidity is high. We observe a strong, positive relationship between d-excess and Δ17 O, with a slope 2.2 ± 0.2 per meg ‰-1, which is consistent with the observed relationship in tropical rainfall and in water in an evaporating open pan. The strong linear relationship between d-excess and Δ17 O should be typical for any process involving evaporation or any other fractionation that is governed by kinetic effects.

Mass Dependency of Isotope Fractionation of Gases Under Thermal Gradient and Its Possible Implications for Planetary Atmosphere Escaping Process

NASA Technical Reports Server (NTRS)

Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard

2014-01-01

Physical processes that unmix elements/isotopes of gas molecules involve phase changes, diffusion (chemical or thermal), effusion and gravitational settling. Some of those play significant roles for the evolution of chemical and isotopic compositions of gases in planetary bodies which lead to better understanding of surface paleoclimatic conditions, e.g. gas bubbles in Antarctic ice, and planetary evolution, e.g. the solar-wind erosion induced gas escaping from exosphere on terrestrial planets.. A mass dependent relationship is always expected for the kinetic isotope fractionations during these simple physical processes, according to the kinetic theory of gases by Chapman, Enskog and others [3-5]. For O-bearing (O16, -O17, -O18) molecules the alpha O-17/ alpha O-18 is expected at 0.5 to 0.515, and for S-bearing (S32,-S33. -S34, -S36) molecules, the alpha S-33/ alpha S-34 is expected at 0.5 to 0.508, where alpha is the isotope fractionation factor associated with unmixing processes. Thus, one isotope pair is generally proxied to yield all the information for the physical history of the gases. However, we recently] reported the violation of mass law for isotope fractionation among isotope pairs of multiple isotope system during gas diffusion or convection under thermal gradient (Thermal Gradient Induced Non-Mass Dependent effect, TGI-NMD). The mechanism(s) that is responsible to such striking observation remains unanswered. In our past studies, we investigated polyatomic molecules, O2 and SF6, and we suggested that nuclear spin effect could be responsible to the observed NMD effect in a way of changing diffusion coefficients of certain molecules, owing to the fact of negligible delta S-36 anomaly for SF6.. On the other hand, our results also showed that for both diffusion and convection under thermal gradient, this NMD effect is increased by lower gas pressure, bigger temperature gradient and lower average temperature, which indicate that the nuclear spin effect may

Theoretical, observational, and isotopic estimates of the lifetime of the solar nebula

NASA Technical Reports Server (NTRS)

Podosek, Frank A.; Cassen, Patrick

1994-01-01

There are a variety of isotopic data for meteorites which suggest that the protostellar nebula existed and was involved in making planetary materials for some 10(exp 7) yr or more. Many cosmochemists, however, advocate alternative interpretations of such data in order to comply with a perceived constraint, from theoretical considerations, that the nebula existed only for a much shorter time, usually stated as less than or equal to 10(exp 6) yr. In this paper, we review evidence relevant to solar nebula duration which is available through three different disciplines: theoretical modeling of star formation, isotopic data from meteorites, and astronomical observations of T Tauri stars. Theoretical models based on observations of present star-forming regions indicate that stars like the Sun form by dynamical gravitational collapse of dense cores of cold molcular clouds in the interstellar clouds in the interstellar medium. The collapse to a star and disk occurs rapidly, on a time scale of the order 10(exp 5) yr. Disks evolve by dissipating energy while redistributing angular momentum, but it is difficult to predict the rate of evolution, particularly for low mass (compared to the star) disks which nonetheless still contain enough material to account for the observed planetary system. There is no compelling evidence, from available theories of disk structure and evolution, that the solar nebula must have evolved rapidly and could not have persisted for more than 1 Ma. In considering chronoloically relevant isotopic data for meteorites, we focus on three methodologies: absolute ages by U-Pb/Pb-Pb, and relative ages by short-lived radionuclides (especially Al-26) and by evolution of Sr-87/Sr-86. Two kinds of meteoritic materials-refractory inclusions such as CAIs and differential meteorites (eucrites and augrites) -- appear to have experienced potentially dateable nebular events. In both cases, the most straightforward interpretations of the available data indicate

Theoretical, observational, and isotopic estimates of the lifetime of the solar nebula

NASA Technical Reports Server (NTRS)

Podosek, Frank A.; Cassen, Patrick

1994-01-01

There are a variety of isotopic data for meteorites which suggest that the protostellar nebula existed and was involved in making planetary materials for some 10(exp 7) yr or more. Many cosmochemists, however, advocate alternative interpretations of such data in order to comply with a perceived constraint, from theoretical considerations, that the nebula existed only for a much shorter time, usually stated as less than or = 10(exp 6) yr. In this paper, we review evidence relevant to solar nebula duration which is available through three different disciplines: theoretical modelling of star formation, isotopic data from meteorites, and astronomical observations of T Tauri stars. Theoretical models based on observations of present star-forming regions indicate that stars like the Sun form by dynamical gravitational collapse of dense cores of cold molecular clouds in the interstellar medium. The collapse to a star and disk occurs rapidly on a time scale of the order 10(exp 5) yr. Disks evolve by dissipating energy while redistributing angular momentum, but it is difficult to predict the rate of evolution, particularly for low mass (compared to the star) disks which nonetheless still contain enough material to account for the observed planetary system. There is no compelling evidence, from available theories of disk structure and evolution, that the solar nebula must have evolved rapidly and could not have persisted for more than 1 Ma. In considering chronologically relevant isotopic data for meteorites, we focus on three methodologies: absolute ages by U-Pb/Pb-Pb, and relative ages by short-lived radionuclides (especially Al-26) and by evolution of Sr-87/Sr-86. Two kinds of meteoritic materials-refractory inclusions such as CAIs and differentiated meteorites (eucrites and angrites) - appear to have experience potentially dateable nebular events. In both case, the most straightforward interpretations of the available data indicate nebular events spanning several Ma. We

Noncovalent Hydrogen Isotope Effects

NASA Astrophysics Data System (ADS)

Buchachenko, A. L.; Breslavskaya, N. N.

2018-02-01

Zero-point energies (ZPE) and isotope effects, induced by intermolecular, noncovalent vibrations, are computed and tested by experimental data. The ZPE differences of H- and D-complexes of water with hydrogen, methane, and water molecules are about 100-300 cal/mol; they result to isotope effects IE of 1.20-1.70. Semi-ionic bonds between metal ions and water ligands in M(H2O) 6 2+ complexes are much stronger; their ZPEs are about 12-14 kcal/mol per molecule and result to IE of 1.9-2.1 at 300 K. Protonated (deuterated) water and biwater exhibit the largest ZPE differences and isotope effects; the latter are 25-28 and 12-13 for water and biwater, respectively. Noncovalent IEs contribute markedly into the experimentally measured effects and explain many anomalous and even magic properties of the effects, such as the dependence of IE on the solvents and on the presence of the third substances, enormously large isotope effects at the mild conditions, the difference between IEs measured in the reactions of individual protiated and deuterated compounds and those measured in their mixture. Noncovalent IEs are not negligible and should be taken into account to make correct and substantiated conclusions on the reaction mechanisms. The kinetic equations are derived for the total isotope effects, which include noncovalent IEs as additive factors.

Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6 reaction and kinetics study of rate constants and kinetic isotope effects.

PubMed

Rangel, Cipriano; Espinosa-Garcia, Joaquin

2018-02-07

activation energy and the kinetics isotope effects reproduce the experimental information.

Quantum path integral simulation of isotope effects in the melting temperature of ice Ih.

PubMed

Ramírez, R; Herrero, C P

2010-10-14

The isotope effect in the melting temperature of ice Ih has been studied by free energy calculations within the path integral formulation of statistical mechanics. Free energy differences between isotopes are related to the dependence of their kinetic energy on the isotope mass. The water simulations were performed by using the q-TIP4P/F model, a point charge empirical potential that includes molecular flexibility and anharmonicity in the OH stretch of the water molecule. The reported melting temperature at ambient pressure of this model (T=251 K) increases by 6.5±0.5 and 8.2±0.5 K upon isotopic substitution of hydrogen by deuterium and tritium, respectively. These temperature shifts are larger than the experimental ones (3.8 and 4.5 K, respectively). In the classical limit, the melting temperature is nearly the same as that for tritiated ice. This unexpected behavior is rationalized by the coupling between intermolecular interactions and molecular flexibility. This coupling makes the kinetic energy of the OH stretching modes larger in the liquid than in the solid phase. However, the opposite behavior is found for intramolecular modes, which display larger kinetic energy in ice than in liquid water.

E2 transition probabilities for decays of isomers observed in neutron-rich odd Sn isotopes

DOE PAGES

Iskra, Ł. W.; Broda, R.; Janssens, R. V.F.; ...

2015-01-01

High-spin states were investigated with gamma coincidence techniques in neutron-rich Sn isotopes produced in fission processes following ⁴⁸Ca + ²⁰⁸Pb, ⁴⁸Ca + ²³⁸U, and ⁶⁴Ni + ²³⁸U reactions. By exploiting delayed and cross-coincidence techniques, level schemes have been delineated in odd ¹¹⁹⁻¹²⁵Sn isotopes. Particular attention was paid to the occurrence of 19/2⁺ and 23/2⁺ isomeric states for which the available information has now been significantly extended. Reduced transition probabilities, B(E2), extracted from the measured half-lives and the established details of the isomeric decays exhibit a striking regularity. This behavior was compared with the previously observed regularity of the B(E2) amplitudesmore » for the seniority ν = 2 and 3, 10⁺ and 27/2⁻ isomers in even- and odd-Sn isotopes, respectively.« less

Compound-Specific Carbon and Hydrogen Isotope Analysis - Field Evidence of MTBE Bioremediation

NASA Astrophysics Data System (ADS)

Kuder, T.; Kolhatkar, R. V.; Philp, P.; Wilson, J. T.; Landmeyer, J. E.; Allen, J.

2002-12-01

Compound-specific stable isotope analysis allows opportunity to determine the isotopic ratios of individual contaminants. The technique has been applied to confirm biodegradation in studies of chlorinated solvents and recently BTEX, MTBE and TBA. Chemical reactions (including bio- and inorganic degradation) tend to favor molecules with the lighter isotopic species (e.g., 12C, 1H), resulting with enrichment of the unreacted substrate in the heavier isotopic species (13C, D), referred to as kinetic isotopic fractionation, so that the extent of fractionation may be used as a proxy for biodegradation. Processes such as volatilization, sorption etc., result in minimal degree of fractionation and do not interfere with the isotopic signal due to biodegradation. The results presented here show the first successful applications of compound-specific isotope analysis to understanding MTBE biodegradation in the field, at both aerobic and anaerobic sites. Observed fractionations suggest that two different biodegradation pathways may be involved. At a number of anaerobic locations major fractionation effects were observed for both C and H; enrichment factors Ÿnfor both elements were approaching or exceeding -10. A laboratory microcosm study using an enrichment culture yielded similar results (C data only). A characteristic feature of these sites was the presence of high concentrations of TBA. Conversely, at a number of sites, the C composition remained stable with little fractionation and stayed within the analytical precision range or changed minimally, while H displayed significant fractionation in excess of 60 per mil. Moderate agreement of the data with Rayleigh fractionation model was observed, suggesting that biodegradation effect was distorted by variability at the source or the plume was not homogeneous. The enrichment factor calculated for these data is similar to the one Ÿnpublished for aerobic microcosm of MTBE-degrading culture from Vandenberg AFB by Gray et al

Comparing Stable Water Isotope Variation in Atmospheric Moisture Observed over Coastal Water and Forests

NASA Astrophysics Data System (ADS)

Lai, C. T.; Rambo, J. P.; Welp, L. R.; Bible, K.; Hollinger, D. Y.

2014-12-01

Stable oxygen (δ18O) and hydrogen (δD) isotopologues of atmospheric moisture are strongly influenced by large-scale synoptic weather cycles, surface evapotranspiration and boundary layer mixing. Atmospheric water isotope variation has been shown to empirically relate to relative humidity (Rh) of near surface moisture, and to a less degree, air temperature. Continuous δ18O and δD measurements are becoming more available, providing new opportunities to investigate processes that control isotope variability. This study shows the comparison of δ18O and δD measured at a continental location and over coastal waters for 3 seasons (spring to fall, 2014). The surface moisture isotope measurements were made using two LGR spectroscopy water vapor isotope analyzers (Los Gatos Research Inc.), one operated in an old-growth coniferous forest at Wind River field station, WA (45.8205°N, 121.9519°W), and another sampling marine air over seawater at the Scripps Pier in San Diego, CA (32.8654°N, 117.2536°W), USA. Isotope variations were measured at 1Hz and data were reported as hourly averages with an overall accuracy of ±0.1‰ for δ18O, ±0.5‰ for δ2H. Day-to-day variations in δ18O and δD are shown strongly influenced by synoptic weather events at both locations. Boundary layer mixing between surface moisture and the dry air entrained from the free troposphere exerts a midday maximum and a consistent diel pattern in deuterium excess (dx). At the forest site, surface moisture also interacts with leaf water through transpiration during the day and re-equilibration at night. The latter occurs by retro-diffusion of atmospheric H2O molecules into leaf intercellular space, which becomes intensified as Rh increaes after nightfall, and continues until sunrise, to counter-balance the evaporative isotopic enrichment in leaf water on a daily basis. These vegetation effects lead to negative dx values consistently observed at nighttime in this continental location that were not

Solvent isotope-induced equilibrium perturbation for isocitrate lyase.

PubMed

Quartararo, Christine E; Hadi, Timin; Cahill, Sean M; Blanchard, John S

2013-12-23

Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacterium's life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage ((D₂O)V = 2.0 ± 0.1, and (D₂O)[V/K(isocitrate)] = 2.2 ± 0.3) arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of the succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate, and succinate prepared in D₂O would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by ¹H NMR spectroscopy shows a clear equilibrium perturbation in D₂O. The final equilibrium isotopic composition of reactants in D₂O revealed dideuterated succinate, protiated glyoxylate, and monodeuterated isocitrate, with the transient appearance and disappearance of monodeuterated succinate. A model for the equilibrium perturbation of substrate species and their time-dependent isotopic composition is presented.

Solvent Isotope-induced Equilibrium Perturbation for Isocitrate Lyase

PubMed Central

Quartararo, Christine E.; Hadi, Timin; Cahill, Sean M.; Blanchard, John S.

2014-01-01

Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacteria’s life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage of D2OV = 2.0 ± 0.1 and D2O[V/Kisocitrate] = 2.2 ± 0.3 arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate and succinate prepared in D2O, would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of NMR spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by 1H NMR spectroscopy shows a clear equilibrium perturbation in D2O. The final equilibrium isotopic composition of reactants in D2O revealed di-deuterated succinate, protiated glyoxylate, and mono-deuterated isocitrate, with the transient appearance and disappearance of mono-deuterated succinate. A model for the equilibrium perturbation of substrate species, and their time-dependent isotopic composition is presented. PMID:24261638

Isotopic exchange of hydrogen in aromatic amino acids

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

Pshenichnikova, A.B.; Karnaukhova, E.N.; Mitsner, B.I.

The kinetics of the isotopic replacement of hydrogen in the aromatic amino acids L-tryptophan, L-tyrosine, and L-phenylalanine in solutions of deuterochloric and deuterosulfuric acids in deuterium oxide were investigated by PMR spectroscopy. The reactions were shown to be of first orders with respect both to the concentration of the substrate and to the activity of the deuterium ion. The isotopic effects of hydrogen and the values of the activation energy of H-D exchange in different positions of the aromatic ring in tryptophan and tyrosine were determined. The effect of properties of the medium on the rate of the isotopic exchangemore » of hydrogen is discussed. 17 refs., 2 figs., 2 tabs.« less

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.

Direct observation of spatially heterogeneous single-layer graphene oxide reduction kinetics.

PubMed

McDonald, Matthew P; Eltom, Ahmed; Vietmeyer, Felix; Thapa, Janak; Morozov, Yurii V; Sokolov, Denis A; Hodak, Jose H; Vinodgopal, Kizhanipuram; Kamat, Prashant V; Kuno, Masaru

2013-01-01

Graphene oxide (GO) is an important precursor in the production of chemically derived graphene. During reduction, GO's electrical conductivity and band gap change gradually. Doping and chemical functionalization are also possible, illustrating GO's immense potential in creating functional devices through control of its local hybridization. Here we show that laser-induced photolysis controllably reduces individual single-layer GO sheets. The reaction can be followed in real time through sizable decreases in GO's photoluminescence efficiency along with spectral blueshifts. As-produced reduced graphene oxide (rGO) sheets undergo additional photolysis, characterized by dramatic emission enhancements and spectral redshifts. Both GO's reduction and subsequent conversion to photobrightened rGO are captured through movies of their photoluminescence kinetics. Rate maps illustrate sizable spatial and temporal heterogeneities in sp(2) domain growth and reveal how reduction "flows" across GO and rGO sheets. The observed heterogeneous reduction kinetics provides mechanistic insight into GO's conversion to chemically derived graphene and highlights opportunities for overcoming its dynamic, chemical disorder.

Conversion and origin of normal and abnormal temperature dependences of kinetic isotope effect in hydride transfer reactions.

PubMed

Zhu, Xiao-Qing; Li, Xiu-Tao; Han, Su-Hui; Mei, Lian-Rui

2012-05-18

The effects of substituents on the temperature dependences of kinetic isotope effect (KIE) for the reactions of the hydride transfer from the substituted 5-methyl-6-phenyl-5,6-dihydrophenanthridine (G-PDH) to thioxanthylium (TX(+)) in acetonitrile were examined, and the results show that the temperature dependences of KIE for the hydride transfer reactions can be converted by adjusting the nature of the substituents in the molecule of the hydride donor. In general, electron-withdrawing groups can make the KIE to have normal temperature dependence, but electron-donating groups can make the KIE to have abnormal temperature dependence. Thermodynamic analysis on the possible pathways of the hydride transfer from G-PDH to TX(+) in acetonitrile suggests that the transfers of the hydride anion in the reactions are all carried out by the concerted one-step mechanism whether the substituent is an electron-withdrawing group or an electron-donating group. But the examination of Hammett-type free energy analysis on the hydride transfer reactions supports that the concerted one-step hydride transfer is not due to an elementary chemical reaction. The experimental values of KIE at different temperatures for the hydride transfer reactions were modeled by using a kinetic equation formed according to a multistage mechanism of the hydride transfer including a returnable charge-transfer complex as the reaction intermediate; the real mechanism of the hydride transfer and the root that why the temperature dependences of KIE can be converted as the nature of the substituents are changed were discovered.

Observations of geomagnetically trapped light isotopes by NINA

NASA Astrophysics Data System (ADS)

Bakaldin, A.; Galper, A.; Koldashov, S.; Korotkov, M.; Leonov, A.; Mikhailov, V.; Murashov, A.; Voronov, S.; Bidoli, V.; Casolino, M.; De Pascale, M.; Furano, G.; Iannucci, A.; Morselli, A.; Picozza, P.; Sparvoli, R.; Boezio, M.; Bonvicini, V.; Cirami, R.; Vacci, A.; Zampa, N.; Ambriola, M.; Bellotti, R.; sCafagna, F.; Ciacio, F.; Circella, M.; De Marzo, C.; Adriani, O.; Papini, P.; Spillantini, P.; Straulino, S.; Vannuccini, E.; Bartalucci, S.; Ricci, M.; Castellini, G.; Wizard-NINA Collaboration

2001-08-01

The detector NINA aboard the satellite Resurs-01N4 detected hydrogen and helium isotopes geomagnetically trapped, while crossing the South Atlantic Anomaly. Deuterium and tritium at L-shell<1.2 were unambiguously recognized. The 3 He and 4 He power-law spectra, reconstructed at L-shell=1.2 and B<0.22 G, have indices equal to 2.30±0.08 in the energy range 12-50 MeV/n, and 3.4±0.2 in 10-40 MeV/n respectively. The measured 3 He/4 He ratio bring to the conclusion that the main source of radiation belt light isotopes is the interaction of trapped protons with residual atmospheric helium.

Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

NASA Technical Reports Server (NTRS)

Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

1986-01-01

The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

Carbon and hydrogen isotope fractionation during aerobic biodegradation of quinoline and 3-methylquinoline.

PubMed

Cui, Mingchao; Zhang, Wenbing; Fang, Jun; Liang, Qianqiong; Liu, Dongxuan

2017-08-01

Compound-specific isotope analysis has been used extensively to investigate the biodegradation of various organic pollutants. To date, little isotope fractionation information is available for the biodegradation of quinolinic compounds. In this study, we report on the carbon and hydrogen isotope fractionation during quinoline and 3-methylquinoline aerobic microbial degradation by a Comamonas sp. strain Q10. Degradation of quinoline and 3-methylquinoline was accompanied by isotope fractionation. Large hydrogen and small carbon isotope fractionation was observed for quinoline while minor carbon and hydrogen isotope fractionation effects occurred for 3-methylquinoline. Bulk carbon and hydrogen enrichment factors (ε bulk ) for quinoline biodegradation were -1.2 ± 0.1 and -38 ± 1‰, respectively, while -0.7 ± 0.1 and -5 ± 1‰ for 3-methylquinoline, respectively. This reveals a potential advantage for employing quinoline as the model compound and hydrogen isotope analysis for assessing aerobic biodegradation of quinolinic compounds. The apparent kinetic isotope effects (AKIE C ) values of carbon were 1.008 ± 0.0005 for quinoline and 1.0048 ± 0.0005 for 3-methylquinoline while AKIE H values of hydrogen of 1.264 ± 0.011 for quinoline and 1.0356 ± 0.0103 for 3-methylquinoline were obtained. The combined evaluation of carbon and hydrogen isotope fractionation yields Λ values (Λ = Δδ 2 H/Δδ 13 C ≈ εH bulk /εC bulk ) of 29 ± 2 for quinoline and 8 ± 2 for 3-methylquinoline. The results indicate that the substrate specificity may have a significant influence on the isotope fractionation for the biodegradation of quinolinic compounds. The substrate-specific isotope enrichment factors would be important for assessing the behavior and fate of quinolinic compounds in the environment.

Observation of new neutron-rich Mn, Fe, Co, Ni, and Cu isotopes in the vicinity of 78Ni

NASA Astrophysics Data System (ADS)

Sumikama, T.; Nishimura, S.; Baba, H.; Browne, F.; Doornenbal, P.; Fukuda, N.; Franchoo, S.; Gey, G.; Inabe, N.; Isobe, T.; John, P. R.; Jung, H. S.; Kameda, D.; Kubo, T.; Li, Z.; Lorusso, G.; Matea, I.; Matsui, K.; Morfouace, P.; Mengoni, D.; Napoli, D. R.; Niikura, M.; Nishibata, H.; Odahara, A.; Sahin, E.; Sakurai, H.; Söderström, P.-A.; Stefan, G. I.; Suzuki, D.; Suzuki, H.; Takeda, H.; Taniuchi, R.; Taprogge, J.; Vajta, Zs.; Watanabe, H.; Werner, V.; Wu, J.; Xu, Z. Y.; Yagi, A.; Yoshinaga, K.

2017-05-01

Neutron-rich nuclei in the vicinity of 78Ni were produced using a 238U beam at the RIKEN Radioactive Isotope Beam Factory. The particle-identification plot for the in-flight fission fragments highlights the first observation of eight new isotopes: 73Mn, 76Fe, Co,7877, 80,81,82Ni, and 83Cu. Although the β -decay half-lives of 77Co and 80Ni were recently reported by Xu et al. [Phys. Rev. Lett. 113, 032505 (2014)], 10.1103/PhysRevLett.113.032505 using data from the same experiment, the current work provides the first direct, quantitative evidence for the existence of these isotopes. The experimental production cross sections are reproduced in a satisfactory manner by theoretical predictions. An odd-even staggering of the cross sections was observed, and the effect appears to become more pronounced for the most exotic nuclei that were investigated. The staggering effect was interpreted as an increase of the neutron-evaporation probability for odd-N isotopes, owing to the decrease of the neutron-separation energy, Sn. The predicted cross section for 80Ni is significantly overestimated, which may be related to a weak binding of the neutron pair above the N =50 shell closure.

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr

Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds

PubMed Central

Lamb, Kara D.; Clouser, Benjamin W.; Bolot, Maximilien; Sarkozy, Laszlo; Ebert, Volker; Saathoff, Harald; Möhler, Ottmar; Moyer, Elisabeth J.

2017-01-01

The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (−40 °C), conditions necessary to form cirrus clouds in the Earth’s atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122–127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H2O equilibrium fractionation between vapor and ice (αeq) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of αeq, and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice–vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems. PMID:28495968

Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds.

PubMed

Lamb, Kara D; Clouser, Benjamin W; Bolot, Maximilien; Sarkozy, Laszlo; Ebert, Volker; Saathoff, Harald; Möhler, Ottmar; Moyer, Elisabeth J

2017-05-30

The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (-40 °C), conditions necessary to form cirrus clouds in the Earth's atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122-127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H 2 O equilibrium fractionation between vapor and ice ([Formula: see text]) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of [Formula: see text], and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice-vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems.

Carbon isotope effects associated with autotrophic acetogenesis

NASA Technical Reports Server (NTRS)

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

1989-01-01

The carbon kinetic isotope effects associated with synthesis of acetate from CO2 and H2 during autotrophic growth of Acetobacterium woodii at 30 degrees C have been measured by isotopic analyses of CO2, methyl-carbon, and total acetate. Closed systems allowing construction of complete mass balances at varying stages of growth were utilized, and the effects of the partitioning of carbon between CO2 and HCO3- were taken account. For the overall reaction, total carbonate --> total acetate, isotope effects measured in replicate experiments ranged from -59.0 +/- 0.9% to -57.2 +/- 2.3%. Taking into account all measurements, the weighted mean and standard deviation are -58.6 +/- 0.7%. There is no evidence for intramolecular ordering in the acetate. The carbon isotopic composition of sedimentary acetate, otherwise expected to be near that of sedimentary organic carbon, is likely to be depleted in environments in which autotrophic acetogenesis is occurring.

Identifying and Characterizing Kinetic Instabilities using Solar Wind Observations of Non-Maxwellian Plasmas

NASA Astrophysics Data System (ADS)

Klein, K. G.

2016-12-01

Weakly collisional plasmas, of the type typically observed in the solar wind, are commonly in a state other than local thermodynamic equilibrium. This deviation from a Maxwellian velocity distribution can be characterized by pressure anisotropies, disjoint beams streaming at differing speeds, leptokurtic distributions at large energies, and other non-thermal features. As these features may be artifacts of dynamic processes, including the the acceleration and expansion of the solar wind, and as the free energy contained in these features can drive kinetic micro-instabilities, accurate measurement and modeling of these features is essential for characterizing the solar wind. After a review of these features, a technique is presented for the efficient calculation of kinetic instabilities associated with a general, non-Maxwellian plasma. As a proof of principle, this technique is applied to bi-Maxwellian systems for which kinetic instability thresholds are known, focusing on parameter scans including beams and drifting heavy minor ions. The application of this technique to fits of velocity distribution functions from current, forthcoming, and proposed missions including WIND, DSCOVR, Solar Probe Plus, and THOR, as well as the underlying measured distribution functions, is discussed. Particular attention is paid to the effects of instrument pointing and integration time, as well as potential deviation between instabilities associated with the Maxwellian fits and those associated with the observed, potentially non-Maxwellian, velocity distribution. Such application may further illuminate the role instabilities play in the evolution of the solar wind.

Wave-Particle Energy Exchange Directly Observed in a Kinetic Alfven-Branch Wave

NASA Technical Reports Server (NTRS)

Gershman, Daniel J.; F-Vinas, Adolfo; Dorelli, John C.; Boardsen, Scott A. (Inventor); Avanov, Levon A.; Bellan, Paul M.; Schwartz, Steven J.; Lavraud, Benoit; Coffey, Victoria N.; Chandler, Michael O.;

FE and MG Isotopic Analyses of Isotopically Unusual Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Messenger, S.; Ito, M.; Rahman, Z.

2011-01-01

Interstellar and circumstellar silicate grains are thought to be Mg-rich and Fe-poor, based on astronomical observations and equilibrium condensation models of silicate dust formation in stellar outflows. On the other hand, presolar silicates isolated from meteorites have surprisingly high Fe contents and few Mg-rich grains are observed. The high Fe contents in meteoritic presolar silicates may indicate they formed by a non-equilibrium condensation process. Alternatively, the Fe in the stardust grains could have been acquired during parent body alteration. The origin of Fe in presolar silicates may be deduced from its isotopic composition. Thus far, Fe isotopic measurements of presolar silicates are limited to the Fe-54/Fe-56 ratios of 14 grains. Only two slight anomalies (albeit solar within error) were observed. However, these measurements suffered from contamination of Fe from the adjacent meteorite matrix, which diluted any isotopic anomalies. We have isolated four presolar silicates having unusual O isotopic compositions by focused ion beam (FIB) milling and obtained their undiluted Mg and Fe isotopic compositions. These compositions help to identify the grains stellar sources and to determine the source of Fe in the grains.

Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

NASA Astrophysics Data System (ADS)

Meshoulam, Alexander; Ellis, Geoffrey S.; Said Ahmad, Ward; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

2016-09-01

The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n-hexadecane (n-C16) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H2S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H2S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4‰ for H2S and as much as 22.2‰ for BT. The fractionations decrease as the H2S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H2S and sulfate (∼17‰). Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4 dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and

Isotope fractionation associated with the direct photolysis of 4-chloroaniline.

PubMed

Ratti, Marco; Canonica, Silvio; McNeill, Kristopher; Erickson, Paul R; Bolotin, Jakov; Hofstetter, Thomas B

2015-04-07

Compound-specific isotope analysis is a useful approach to track transformations of many organic soil and water pollutants. Applications of CSIA to characterize photochemical processes, however, have hardly been explored. In this work, we systematically studied C and N isotope fractionation associated with the direct photolysis of 4-Cl-aniline used as a model compound for organic micropollutants that are known to degrade via photochemical processes. Laboratory experiments were carried out at an irradiation wavelength of 254 nm over the pH range 2.0 to 9.0 as well as in the presence of Cs(+) as a quencher of excited singlet 4-Cl-aniline at pH 7.0 and 9.0. We observed considerable variation of C and N isotope enrichment factors, ϵC and ϵN, between -1.2 ± 0.2‰ to -2.7 ± 0.2‰ for C and -0.6 ± 0.2‰ to -9.1 ± 1.6‰ for N, respectively, which could not be explained by the speciation of 4-Cl-aniline alone. In the presence of 1 M Cs(+), we found a marked increase of apparent (13)C-kinetic isotope effects ((13)C-AKIE) and decrease of 4-Cl-aniline fluorescence lifetimes. Our data suggest that variations of C and N isotope fractionation originate from heterolytic dechlorination of excited triplet and singlet states of 4-Cl-aniline. Linear correlations of (13)C-AKIE vs (15)N-AKIE were distinctly different for these two reaction pathways and may be explored further for the identification of photolytic aromatic dechlorination reactions.

Stable δ15N and δ13C isotope ratios in aquatic ecosystems

PubMed Central

Wada, Eitaro

2009-01-01

In the past 20 years, rapid progress in stable isotope (SI) studies has allowed scientists to observe natural ecosystems from entirely new perspectives. This report addresses the fundamental concepts underlying the use of the SI ratio. The unique characteristics of the SI ratio make it an interdisciplinary parameter that acts as a chemical fingerprint of biogenic substances and provides a key to the world of isotopomers. Variations in SI ratios of biogenic substances depend on the isotopic compositions of reactants, the pathways and kinetic modes of reaction dynamics, and the physicochemical conditions. In fact, every biogenic material has its own isotopic composition, its “dynamic SI fingerprint”, which is governed by its function and position in the material flow. For example, the relative SI ratio in biota is determined by dietary lifestyle, e.g., the modes of drinking, eating, and excreting, and appears highly regular due to the physicochemical differences of isotopomers. Our primary goal here is to elucidate the general principals of isotope partitioning in major biophilic elements in molecules, biogenic materials, and ecosystems (Wada, E. et al., 1995). To this end, the nitrogen and carbon SI distribution ratios (δ15N and δ13C, respectively) are used to examine materials cycling, food web structures, and their variability in various kinds of watershed-including aquatic ecosystems to elucidate an “isotopically ordered world”. PMID:19282646

Comparison of Meteorological Data and Stable Isotope Time Series from an Indonesian Stalagmite

NASA Astrophysics Data System (ADS)

Watanabe, Y.; Matsuoka, H.; Sakai, S.; Ueda, J.; Yamada, M.; Ohsawa, S.; Kiguchi, M.; Satomura, T.; Nakai, S.; Brahmantyo, B.; Maryunani, K. A.; Tagami, T.; Takemura, K.; Yoden, S.

2007-12-01

In the last decade, geochemical records in stalagmites have been widely recognized as a powerful tool for the elucidation of paleoclimate/environment of the terrestrial areas. The previous data are mainly reported from middle latitude. However, this study aims at reconstructing past climate variations in the Asian equatorial regions by using oxygen and carbon isotope ratios recorded in Indonesian stalagmites. Especially, we focused on the comparison of meteorological data and stable isotope time series from an Indonesia stalagmite, in order to check whether the geochemistry of stalagmite is influenced by local precipitation. We performed geological surveys in Buniayu limestone caves, Sukabumi, West Java, Indonesia, and collected a series of stalagmites/stalactites and drip water samples. A stalagmite sample was observed using thin sections to identify banding. Moreover, to construct the age model of the stalagmite, we also measured both (1) the number of bands and (2) uranium series disequilibrium ages using the MC-ICP-MS. These data suggest that each layer is annual banding dominantly. Oxygen and carbon isotope ratios were analyzed on the stalagmite for annual time scales. The carbon isotope ratio has a clear correlation with oxygen isotope ratios. Furthermore, the proxy data was compared with meteorological data set in the past 80 years, showing a good correlation between the temporal variation of oxygen/carbon isotope ratios and annual precipitation. These lines of evidence suggest that the isotopic variation is predominantly caused by kinetic mass fractionation driven by the degassing of carbon dioxide in the cave.

Sedimentary denitrification: Isotope fractionation and its impact on water column nitrate isotopes

NASA Astrophysics Data System (ADS)

Dähnke, K.; Thamdrup, B.

2012-04-01

The global marine nitrogen cycle is constrained by one major source and two processes that act as nitrogen sinks: nitrogen fixation on the one side and denitrification or anammox on the other. These processes with their respective isotope effecst set the marine nitrate 15N-isotope value to a relatively constant average of 5 per mil. This value can be used to better assess the magnitude of these source and sink terms, but the underlying assumption at present is that sedimentary denitrification, a process responsible for approximately one third of global nitrogen removal, has little to no isotope effect on the water column. We tested this hypothesis in sediment incubations, measuring net denitrification and nitrogen and oxygen stable isotope fractionation in surface sediments from the coastal Baltic Sea (Boknis Eck, Northern Germany). We found tremendously high denitrification rates, and regardless of current paradigms assuming little fractionation during sediment denitrification, we measured fractionation factors of 19 per mil for nitrogen and 11 per mil for oxygen in nitrate. These results potentially challenge the current view of fractionation during sedimentary denitrification and imply that nitrogen budget calculation may need to consider this variability. Furthermore, the ratio of fractionation factors for nitrogen and oxygen is distinct from the 1 : 1 ratio otherwise found in marine systems, and suggests that isotope kinetics of sedimentary denitrification might be entirely different from water column denitrification. Acknowledgements: This work was funded by the German Research Foundation (DFG) and in parts by the Danish National Research Foundation.

Stable isotope tracing of anaerobic methane oxidation in the gassy sediments of Eckernfoerde Bay, German Baltic Sea

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

Martens, C.S.; Albert, D.B.; Alperin, M.J.

Methane concentrations in the pore waters of Eckernfoerde Bay in the German Baltic Sea generally reach gas bubble saturation values within the upper meter of the sediment column. The depth at which saturation occurs is controlled by a balance between rates of methane production, consumption (oxidation), and transport. The relative importance of anaerobic methane oxidation (AMO) in controlling dissolved and gas bubble methane distributions in the bay's sediments is indirectly revealed through methane concentration versus depth profiles, depth variations in the stable C and H isotope composition of methane, and the C isotope composition of total dissolved inorganic carbon ({Sigma}CO{submore » 2}). Direct radiotracer measurements indicate that AMO rates of over 15 mM/yr are focused at the base of the sulfate reduction zone. Diagenetic equations that describe the depth destructions of the {delta}{sup 13}C and {delta}D values of methane reproduce isotopic shifts observed throughout the methane oxidation zone and are best fit with kinetic isotope fractionation factors of 1.012 {+-} 0.001 and 1.120 {plus{underscore}minus} 0.020 respectively.« less

Zinc isotope fractionation during adsorption onto Mn oxyhydroxide at low and high ionic strength

NASA Astrophysics Data System (ADS)

Bryan, Allison L.; Dong, Shuofei; Wilkes, Elise B.; Wasylenki, Laura E.

2015-05-01

Marine ferromanganese sediments represent one of the largest sinks from global seawater for Zn, a critical trace metal nutrient. These sediments are variably enriched in heavier isotopes of Zn relative to deep seawater, and some are among the heaviest natural samples analyzed to date. New experimental results demonstrate that adsorption of Zn to poorly crystalline Mn oxyhydroxide results in preferential association of heavier isotopes with the sorbent phase. At low ionic strength our experimental system displayed a short-lived kinetic isotope effect, with light isotopes adsorbed to birnessite (Δ66/64Znadsorbed-dissolved ∼ -0.2‰). After 100 h the sense of fractionation was opposite, such that heavier isotopes were preferentially adsorbed at steady state, but the magnitude of Δ66/64Znadsorbed-dissolved was indistinguishable from zero (+0.05 ± 0.08‰). At high ionic strength, we observed preferential sorption of heavy isotopes, with a strong negative correlation between Δ66/64Znadsorbed-dissolved and the percentage of Zn on the birnessite. Values of Δ66/64Znadsorbed-dissolved ranged from nearly +3‰ at low surface loading to +0.16‰ at high surface loading. Based on previous EXAFS work we infer that Zn adsorbs first as tetrahedral, inner-sphere complexes at low surface loading, with preferential incorporation of heavier isotopes relative to the octahedral Zn species predominating in solution. As surface loading increases, so does the proportion of Zn adsorbing as octahedral complexes, thus diminishing the magnitude of fractionation between the dissolved and adsorbed pools of Zn. The magnitude of fractionation at high ionic strength is also governed by aqueous speciation of Zn in synthetic seawater; a substantial fraction of Zn ions reside in chloro complexes, which preferentially incorporate light Zn isotopes, and this drives the adsorbed pool to be heavier relative to the bulk solution than it was at low ionic strength. Our results explain the observation

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

NASA Astrophysics Data System (ADS)

Kiczka, Mirjam; Wiederhold, Jan G.; Frommer, Jakob; Voegelin, Andreas; Kraemer, Stephan M.; Bourdon, Bernard; Kretzschmar, Ruben

2011-10-01

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ 56Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ 56Fe. For all soils the lightest isotopic composition was observed in a 1 M NH 2OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral

Kinetic investigation of human 5-lipoxygenase with arachidonic acid.

PubMed

Mittal, Monica; Kumar, Ramakrishnan B; Balagunaseelan, Navisraj; Hamberg, Mats; Jegerschöld, Caroline; Rådmark, Olof; Haeggström, Jesper Z; Rinaldo-Matthis, Agnes

2016-08-01

Human 5-lipoxygenase (5-LOX) is responsible for the formation of leukotriene (LT)A4, a pivotal intermediate in the biosynthesis of the leukotrienes, a family of proinflammatory lipid mediators. 5-LOX has thus gained attention as a potential drug target. However, details of the kinetic mechanism of 5-LOX are still obscure. In this Letter, we investigated the kinetic isotope effect (KIE) of 5-LOX with its physiological substrate, arachidonic acid (AA). The observed KIE is 20±4 on kcat and 17±2 on kcat/KM at 25°C indicating a non-classical reaction mechanism. The observed rates show slight temperature dependence at ambient temperatures ranging from 4 to 35°C. Also, we observed low Arrhenius prefactor ratio (AH/AD=0.21) and a small change in activation energy (Ea(D)-Ea(H)=3.6J/mol) which suggests that 5-LOX catalysis involves tunneling as a mechanism of H-transfer. The measured KIE for 5-LOX involves a change in regioselectivity in response to deuteration at position C7, resulting in H-abstraction form C10 and formation of 8-HETE. The viscosity experiments influence the (H)kcat, but not (D)kcat. However the overall kcat/KM is not affected for labeled or unlabeled AA, suggesting that either the product release or conformational rearrangement might be involved in dictating kinetics of 5-LOX at saturating conditions. Investigation of available crystal structures suggests the role of active site residues (F421, Q363 and L368) in regulating the donor-acceptor distances, thus affecting H-transfer as well as regiospecificity. In summary, our study shows that that the H-abstraction is the rate limiting step for 5-LOX and that the observed KIE of 5-LOX is masked by a change in regioselectivity. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reassessing the stable isotope composition assigned to methane flux from natural wetlands in isotope-constrained budgets

NASA Astrophysics Data System (ADS)

Hornibrook, Edward; Maxfield, Peter; Gauci, Vincent; Stott, Andrew

2013-04-01

Stable isotope ratios in CH4 preserve information about its origin and history, and are commonly used to constrain global CH4 budgets. Wetlands are key contributors to the atmospheric burden of CH4 and typically are assigned a stable carbon isotope composition of ~-60 permil in isotope-weighted stable isotope models despite the considerable range of δ13C(CH4) values (~ -100 to -40 permil) known to occur in these diverse ecosystems. Kinetic isotope effects (KIEs) associated with the metabolism of CH4-producing microorganisms generate much of the natural variation but highly negative and positive δ13C(CH4) values generally result from secondary processes (e.g., diffusive transport or oxidation by soil methanotrophs). Despite these complexities, consistent patterns exist in the isotope composition of wetland CH4 that can be linked conclusively to trophic status and consequently, natural succession or human perturbations that impact nutrient levels. Another challenge for accurate representation of wetlands in carbon cycle models is parameterisation of sporadic CH4 emission events. Abrupt release of large volumes of CH4-rich bubbles in short periods of time can account for a significant proportion of the annual CH4 flux from a wetland but such events are difficult to detect using conventional methods. New infrared spectroscopy techniques capable of high temporal resolution measurements of CH4 concentration and stable isotope composition can readily quantify short-lived CH4 pulses. Moreover, the isotope data can be used conclusively to determine shifts in the mode of CH4 transport and provide the potential to link initiation of abrupt emission events to forcing by internal or external factors.

Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass

NASA Astrophysics Data System (ADS)

Fleming, Donald G.; Arseneau, Donald J.; Sukhorukov, Oleksandr; Brewer, Jess H.; Mielke, Steven L.; Truhlar, Donald G.; Schatz, George C.; Garrett, Bruce C.; Peterson, Kirk A.

2011-11-01

The neutral muonic helium atom 4Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of 4Heμ with molecular hydrogen, 4Heμ + H2 → 4HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, kHeμ, are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for kHeμ are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for kHeμ on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H2 and Mu + H2 reactions in a novel study of kinetic isotope effects for the H + H2 reactions over a factor of 36.1 in isotopic mass of the atomic reactant.

Variations in stable hydrogen and oxygen isotopes in atmospheric water vapor in the marine boundary layer across a wide latitude range.

PubMed

Liu, Jingfeng; Xiao, Cunde; Ding, Minghu; Ren, Jiawen

2014-11-01

The newly-developed cavity ring-down laser absorption spectroscopy analyzer with special calibration protocols has enabled the direct measurement of atmospheric vapor isotopes at high spatial and temporal resolution. This paper presents real-time hydrogen and oxygen stable isotope data for atmospheric water vapor above the sea surface, over a wide range of latitudes spanning from 38°N to 69°S. Our results showed relatively higher values of δ(18)O and δ(2)H in the subtropical regions than those in the tropical and high latitude regions, and also a notable decreasing trend in the Antarctic coastal region. By combining the hydrogen and oxygen isotope data with meteoric water line and backward trajectory model analysis, we explored the kinetic fractionation caused by subsiding air masses and related saturated vapor pressure in the subtropics, and the evaporation-driven kinetic fractionation in the Antarctic region. Simultaneous observations of meteorological and marine variables were used to interpret the isotopic composition characteristics and influential factors, indicating that d-excess is negatively correlated with humidity across a wide range of latitudes and weather conditions worldwide. Coincident with previous studies, d-excess is also positively correlated with sea surface temperature and air temperature (Tair), with greater sensitivity to Tair. Thus, atmospheric vapor isotopes measured with high accuracy and good spatial-temporal resolution could act as informative tracers for exploring the water cycle at different regional scales. Such monitoring efforts should be undertaken over a longer time period and in different regions of the world. Copyright © 2014. Published by Elsevier B.V.

Explicit integration with GPU acceleration for large kinetic networks

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

Brock, Benjamin; Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37830; Belt, Andrew

2015-12-01

We demonstrate the first implementation of recently-developed fast explicit kinetic integration algorithms on modern graphics processing unit (GPU) accelerators. Taking as a generic test case a Type Ia supernova explosion with an extremely stiff thermonuclear network having 150 isotopic species and 1604 reactions coupled to hydrodynamics using operator splitting, we demonstrate the capability to solve of order 100 realistic kinetic networks in parallel in the same time that standard implicit methods can solve a single such network on a CPU. This orders-of-magnitude decrease in computation time for solving systems of realistic kinetic networks implies that important coupled, multiphysics problems inmore » various scientific and technical fields that were intractable, or could be simulated only with highly schematic kinetic networks, are now computationally feasible.« less

Explicit integration with GPU acceleration for large kinetic networks

DOE PAGES

Brock, Benjamin; Belt, Andrew; Billings, Jay Jay; ...

2015-09-15

In this study, we demonstrate the first implementation of recently-developed fast explicit kinetic integration algorithms on modern graphics processing unit (GPU) accelerators. Taking as a generic test case a Type Ia supernova explosion with an extremely stiff thermonuclear network having 150 isotopic species and 1604 reactions coupled to hydrodynamics using operator splitting, we demonstrate the capability to solve of order 100 realistic kinetic networks in parallel in the same time that standard implicit methods can solve a single such network on a CPU. In addition, this orders-of-magnitude decrease in computation time for solving systems of realistic kinetic networks implies thatmore » important coupled, multiphysics problems in various scientific and technical fields that were intractable, or could be simulated only with highly schematic kinetic networks, are now computationally feasible.« less

Stable isotopes evidence of recycled subduction fluids in the hydrothermal/volcanic activity across Nicaragua and Costa Rica

NASA Astrophysics Data System (ADS)

Ramírez-Leiva, A.; Sánchez-Murillo, R.; Martínez-Cruz, M.; Calderón, H.; Esquivel-Hernández, G.; Delgado, V.; Birkel, C.; Gazel, E.; Alvarado, G. E.; Soulsby, C.

2017-10-01

The Central America volcanic front provides a unique opportunity to study hydrothermal inputs and their interaction and mixing with modern meteoric waters. The objectives of this study were to: a) characterize the isotopic composition (δ18O, δ2H, d-excess, and lc-excess) of hydrothermal/volcanic systems, b) analyze the influence of kinetic fractionation and meteoric water inputs in the isotopic composition of hydrothermal waters, and c) estimate the 'andesitic water' contribution (recycled subduction fluids) within the volcanic front of Nicaragua and Costa Rica. Hydrothermal evaporation lines are described as: δ2H = 4.7·δ18O - 13.0 (Costa Rica) and δ2H = 2.7·δ18O - 31.6 (Nicaragua). These regressions are significantly (p < 0.001) deviated from their respective meteoric water lines: δ2H = 7.6·δ18O + 7.4 (Costa Rica) and δ2H = 7.4·δ18O + 5.2 (Nicaragua). The greater rainfall inputs in Costa Rica with respect to Nicaragua, resulted in the attenuation of the evaporative effect as observed in the strong bimodal distribution of the hydrothermal waters, which can be divided in fluids: a) isotopically-close to meteoric conditions and b) isotopically-altered by the interaction with recycled subduction fluids and kinetic fractionation. The latter is clearly depicted in the significantly (p < 0.001) low d-excess and lc-excess median values between Costa Rica (+ 5.10‰, - 5.25‰) and Nicaragua (- 2.42‰, - 10.65‰), respectively. Poor correlations between δ18O/δ2H and the elevation gradient emphasize that the contribution of recycled subduction fluids and subsequent surface kinetic fractionation are the main drivers of the isotopic departure from the orographic distillation trend captured in the rainfall isoscapes. End-member mixing calculations resulted in a significant difference (p < 0.001) between the mean 'andesitic water' contribution to the hydrothermal systems of 15.3 ± 10.8 (%, ± 1σ) (Nicaragua) and 19.7 ± 10.3 (%, ± 1σ) (Costa Rica). The

Mechanistic deductions from kinetic isotope effects and pH studies of pyridoxal phosphate dependent carbon-carbon lyases: Erwinia herbicola and Citrobacter freundii tyrosine phenol-lyase

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

Kiick, D.M.; Phillips, R.S.

1988-09-20

The pH dependence of the kinetic parameters and primary deuterium isotope effects have been determined for tyrosine phenol-lyase from both Erwinia herbicola and Citrobacter freundii. The primary deuterium isotope effects indicate that proton abstraction from the 2-position of the substrate is partially rate-limiting for both enzymes. The C. freundii enzyme primary deuterium isotope effects (DV = 3.5 and D(V/Ktyr) = 2.5) are pH independent, indicating that tyrosine is not sticky (i.e., does not dissociate slower than it reacts to give products). Since Vmax for both tyrosine and the alternate substrate S-methyl-L-cysteine is also pH independent, substrate binds only to themore » correctly protonated form of the enzyme. For the E. herbicola enzyme, both Vmax and V/K for tyrosine or S-methyl-L-cysteine are pH dependent, as well as both DV and D(V/Ktyr). Thus, while both the protonated and unprotonated enzyme can bind substrate, and may be interconverted directly, only the unprotonated Michaelis complex is catalytically competent. At pH 9.5, DV = 2.5 and D(V/Ktyr) = 1.5. However, at pH 6.4 the isotope effect on both parameters is equal to 4.1. From these data, the forward commitment factor (cf = 5.2) and catalytic ratio (cvf = 1.1) for tyrosine and S-methyl-L-cysteine (cf = 2.2, cvf = 24) are calculated. Also, the Michaelis complex partition ratio (cf/cvf) for substrate and products is calculated to be 4.7 for tyrosine and 0.1 for S-methyl-L-cysteine.« less

Determining Oxygen Isotopic Fractionation between the ferrous sulfate, melanterite, and aqueous sulfate

NASA Astrophysics Data System (ADS)

Shulaker, D. Z.; Kohl, I.; Coleman, M. L.

2011-12-01

, evaporation rates and fractionation were larger than at 25 deg C. Because no Rayleigh fractionation was observed, this system was not in equilibrium, and was most likely dominated by kinetics. Because of the unexpected results, further research will be conducted on the oxygen isotope fractionation of melanterite.

Activation Thermodynamics and H/D Kinetic Isotope Effect of the Hox to HredH+ Transition in [FeFe] Hydrogenase.

PubMed

Ratzloff, Michael W; Wilker, Molly B; Mulder, David W; Lubner, Carolyn E; Hamby, Hayden; Brown, Katherine A; Dukovic, Gordana; King, Paul W

2017-09-20

Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The H ox →H red H + reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol -1 and a ∼2.5-fold kinetic isotope effect. Overall, these results support electron injection from CdSe into CaI involving F-clusters, and that the H ox →H red H + step of catalytic proton reduction in CaI proceeds by a proton-dependent process.

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

PubMed

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

2014-05-20

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

Cadmium isotope fractionation during adsorption to Mn-oxyhydroxide

NASA Astrophysics Data System (ADS)

Wasylenki, L. E.; Swihart, J. W.

2013-12-01

fractionation might manifest as an open system Rayleigh trend, with isotope signatures along the flow path reflecting the extent to which adsorption attenuates mobility of Cd. In simplified synthetic seawater (I=0.7m), the magnitude of fractionation decreases slightly with increasing proportion of Cd adsorbed, suggesting a kinetic or Rayleigh effect (irreversible sorption). A time series (1-192 hours) shows that the fractionation decreases from 0.3‰ to 0.2‰ over the course of 8 days. A longer experiment is underway to determine whether our study supports the observation of Horner et al. that Cd partitioned between deepwater and ferromanganese crusts is isotopically homogeneous [2]. The difference in Cd isotope behavior between low and high ionic strength conditions is likely due to different speciation of Cd in solution; chloro- complexes dominate Cd speciation in artificial seawater, while Cd2+ dominates at low ionic strength. [1] Price & Morel (1990) Nature 344, 658. [2] Horner et al (2010) G-cubed doi:10.1029/2009GC002987. [3] Lacan et al. (2006) Geochim. Cosmochim. Acta. 70, 5104. [4] Berna et al. (2010) Env. Sci. & Tech. 44, 1043.

Oxygen isotope fractionation in the CaCO3-DIC-H2O system

NASA Astrophysics Data System (ADS)

Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

2017-10-01

The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading

Deuterium kinetic isotope effects on the dissociation of a protein-fatty acid complex in the gas phase.

PubMed

Liu, Lan; Michelsen, Klaus; Kitova, Elena N; Schnier, Paul D; Brown, Alex; Klassen, John S

2012-04-04

Deuterium kinetic isotope effects (KIEs) are reported for the first time for the dissociation of a protein-ligand complex in the gas phase. Temperature-dependent rate constants were measured for the loss of neutral ligand from the deprotonated ions of the 1:1 complex of bovine β-lactoglobulin (Lg) and palmitic acid (PA), (Lg + PA)(n-) → Lg(n-) + PA, at the 6- and 7- charge states. At 25 °C, partial or complete deuteration of the acyl chain of PA results in a measurable inverse KIE for both charge states. The magnitude of the KIEs is temperature dependent, and Arrhenius analysis of the rate constants reveals that deuteration of PA results in a decrease in activation energy. In contrast, there is no measurable deuterium KIE for the dissociation of the (Lg + PA) complex in aqueous solution at pH 8. Deuterium KIEs were calculated using conventional transition-state theory with an assumption of a late dissociative transition state (TS), in which the ligand is free of the binding pocket. The vibrational frequencies of deuterated and non-deuterated PA in the gas phase and in various solvents (n-hexane, 1-chlorohexane, acetone, and water) were established computationally. The KIEs calculated from the corresponding differences in zero-point energies account qualitatively for the observation of an inverse KIE but do not account for the magnitude of the KIEs nor their temperature dependence. It is proposed that the dissociation of the (Lg + PA) complex in aqueous solution also proceeds through a late TS in which the acyl chain is extensively hydrated such that there is no significant differential change in the vibrational frequencies along the reaction coordinate and, consequently, no significant KIE.

Analysis of the site-specific carbon isotope composition of propane by gas source isotope ratio mass spectrometer

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Neto, E. V. Santos; Eiler, John M.

2016-09-01

Site-specific isotope ratio measurements potentially provide valuable information about the formation and degradation of complex molecules-information that is lost in conventional bulk isotopic measurements. Here we discuss the background and possible applications of such measurements, and present a technique for studying the site-specific carbon isotope composition of propane at natural abundance based on mass spectrometric analysis of the intact propane molecule and its fragment ions. We demonstrate the feasibility of this approach through measurements of mixtures of natural propane and propane synthesized with site-specific 13C enrichment, and we document the limits of precision of our technique. We show that mass balance calculations of the bulk δ13C of propane based on our site-specific measurements is generally consistent with independent constraints on bulk δ13C. We further demonstrate the accuracy of the technique, and illustrate one of its simpler applications by documenting the site-specific carbon isotope signature associated with gas phase diffusion of propane, confirming that our measurements conform to the predictions of the kinetic theory of gases. This method can be applied to propane samples of moderate size (tens of micromoles) isolated from natural gases. Thus, it provides a means of studying the site-specific stable isotope systematics of propane at natural isotope abundances on sample sizes that are readily recovered from many natural environments. This method may also serve as a model for future techniques that apply high-resolution mass spectrometry to study the site-specific isotopic distributions of larger organic molecules, with potential applications to biosynthesis, forensics and other geochemical subjects.

Diffusion of multi-isotopic chemical species in molten silicates

NASA Astrophysics Data System (ADS)

Watkins, James M.; Liang, Yan; Richter, Frank; Ryerson, Frederick J.; DePaolo, Donald J.

2014-08-01

Diffusion experiments in a simplified Na2O-CaO-SiO2 liquid system are used to develop a general formulation for the fractionation of Ca isotopes during liquid-phase diffusion. Although chemical diffusion is a well-studied process, the mathematical description of the effects of diffusion on the separate isotopes of a chemical element is surprisingly underdeveloped and uncertain. Kinetic theory predicts a mass dependence on isotopic mobility, but it is unknown how this translates into a mass dependence on effective binary diffusion coefficients, or more generally, the chemical diffusion coefficients that are housed in a multicomponent diffusion matrix. Our experiments are designed to measure Ca mobility, effective binary diffusion coefficients, the multicomponent diffusion matrix, and the effects of chemical diffusion on Ca isotopes in a liquid of single composition. We carried out two chemical diffusion experiments and one self-diffusion experiment, all at 1250 °C and 0.7 GPa and using a bulk composition for which other information is available from the literature. The self-diffusion experiment is used to determine the mobility of Ca in the absence of diffusive fluxes of other liquid components. The chemical diffusion experiments are designed to determine the effect on Ca isotope fractionation of changing the counter-diffusing component from fast-diffusing Na2O to slow-diffusing SiO2. When Na2O is the main counter-diffusing species, CaO diffusion is fast and larger Ca isotopic effects are generated. When SiO2 is the main counter-diffusing species, CaO diffusion is slow and smaller Ca isotopic effects are observed. In both experiments, the liquid is initially isotopically homogeneous, and during the experiment Ca isotopes become fractionated by diffusion. The results are used as a test of a new general expression for the diffusion of isotopes in a multicomponent liquid system that accounts for both self diffusion and the effects of counter-diffusing species. Our

DeuteRater: a tool for quantifying peptide isotope precision and kinetic proteomics.

PubMed

Naylor, Bradley C; Porter, Michael T; Wilson, Elise; Herring, Adam; Lofthouse, Spencer; Hannemann, Austin; Piccolo, Stephen R; Rockwood, Alan L; Price, John C

2017-05-15

Using mass spectrometry to measure the concentration and turnover of the individual proteins in a proteome, enables the calculation of individual synthesis and degradation rates for each protein. Software to analyze concentration is readily available, but software to analyze turnover is lacking. Data analysis workflows typically don't access the full breadth of information about instrument precision and accuracy that is present in each peptide isotopic envelope measurement. This method utilizes both isotope distribution and changes in neutromer spacing, which benefits the analysis of both concentration and turnover. We have developed a data analysis tool, DeuteRater, to measure protein turnover from metabolic D 2 O labeling. DeuteRater uses theoretical predictions for label-dependent change in isotope abundance and inter-peak (neutromer) spacing within the isotope envelope to calculate protein turnover rate. We have also used these metrics to evaluate the accuracy and precision of peptide measurements and thereby determined the optimal data acquisition parameters of different instruments, as well as the effect of data processing steps. We show that these combined measurements can be used to remove noise and increase confidence in the protein turnover measurement for each protein. Source code and ReadMe for Python 2 and 3 versions of DeuteRater are available at https://github.com/JC-Price/DeuteRater . Data is at https://chorusproject.org/pages/index.html project number 1147. Critical Intermediate calculation files provided as Tables S3 and S4. Software has only been tested on Windows machines. jcprice@chem.byu.edu. Supplementary data are available at Bioinformatics online. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com

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

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

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

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

O and C stable isotopes in cryogenic cave calcite (CCC) - possible proxy for past climate changes

NASA Astrophysics Data System (ADS)

-Andreea, Badaluta Carmen; Ersek, Vasile; Piotrowska, Natalia; Persoiu, Aurel

2017-04-01

Perennial ice deposits in caves host various proxies of past climate variability, most notable, the isotopic composition of ice, which has been shown to reflect, generally, the temperature outside the cave during the formation of ice (usually, autumn though spring). This ice forms by the freezing of water, water that contains large amounts of dissolved calcium carbonate. The freezing is accompanied by degassing of CO2, and precipitation of cryogenic cave calcite (CCC) under strong kinetic conditions. These kinetic processes could lead to the alteration of the original putative climatic signal carried by the isotopic composition of CCC. Here, we present a possibly climatic explanation of the isotopic composition of CCC from a 1000 years old cave ice deposit from Scărișoara Ice Cave (SIC) in Romania, Eastern Europe. In a 7 m core from the Great Hall of SIC we have analyzed the isotopic composition of the water (oxygen and hydrogen) and CCC (oxygen and carbon) from individual ice layers in the core, as well as that of precipitation , outside the cave. The isotopic composition of precipitation from the cave area varies between -3.6 ‰ for δˡ⁸O and -22 ‰ for δ2H in summer, and -17.8 ‰ for δˡ⁸O and -22 ‰ for δ2H in winter, with mean values of -9.1 ‰ for δˡ⁸O and -62 ‰ for δ2H. A positive correlation between air temperature and the isotopic composition of precipitation, as well as drip water in the cave has been found. The mean values in the ice core during the past 1000 years are -10.3‰ for δ18O and -71 ‰ for δ2H. The water isotopic values in the ice core show low values up to 900 AD, higher values between 900 and 1300 AD (Medieval Warm Period, MWP), and again lower values after 1300 AD (Little Ice Age, LIA), reaching their minimum after 1800 AD. The isotopic composition of CCC shows slightly higher values in the MWP and lower in LIA, possibly suggesting a climatic influence. Modern observations are too short to be able to calibrate this

An observationally-driven kinetic approach to coronal heating

NASA Astrophysics Data System (ADS)

Moraitis, K.; Toutountzi, A.; Isliker, H.; Georgoulis, M.; Vlahos, L.; Chintzoglou, G.

2016-11-01

Aims: Coronal heating through the explosive release of magnetic energy remains an open problem in solar physics. Recent hydrodynamical models attempt an investigation by placing swarms of "nanoflares" at random sites and times in modeled one-dimensional coronal loops. We investigate the problem in three dimensions, using extrapolated coronal magnetic fields of observed solar active regions. Methods: We applied a nonlinear force-free field extrapolation above an observed photospheric magnetogram of NOAA active region (AR) 11 158. We then determined the locations, energy contents, and volumes of "unstable" areas, namely areas prone to releasing magnetic energy due to locally accumulated electric current density. Statistical distributions of these volumes and their fractal dimension are inferred, investigating also their dependence on spatial resolution. Further adopting a simple resistivity model, we inferred the properties of the fractally distributed electric fields in these volumes. Next, we monitored the evolution of 105 particles (electrons and ions) obeying an initial Maxwellian distribution with a temperature of 10 eV, by following their trajectories and energization when subjected to the resulting electric fields. For computational convenience, the length element of the magnetic-field extrapolation is 1 arcsec, or 725 km, much coarser than the particles' collisional mean free path in the low corona (0.1-1 km). Results: The presence of collisions traps the bulk of the plasma around the unstable volumes, or current sheets (UCS), with only a tail of the distribution gaining substantial energy. Assuming that the distance between UCS is similar to the collisional mean free path we find that the low active-region corona is heated to 100-200 eV, corresponding to temperatures exceeding 2 MK, within tens of seconds for electrons and thousands of seconds for ions. Conclusions: Fractally distributed, nanoflare-triggening fragmented UCS in the active-region corona can

Investigating inner-sphere reorganization via secondary kinetic isotope effects in the C-H cleavage reaction catalyzed by soybean lipoxygenase: tunneling in the substrate backbone as well as the transferred hydrogen.

PubMed

Meyer, Matthew P; Klinman, Judith P

2011-01-26

This work describes the application of NMR to the measurement of secondary deuterium (2° (2)H) and carbon-13 ((13)C) kinetic isotope effects (KIEs) at positions 9-13 within the substrate linoleic acid (LA) of soybean lipoxygenase-1. The KIEs have been measured using LA labeled with either protium (11,11-h2-LA) or deuterium (11,11-d2-LA) at the reactive C11 position, which has been previously shown to yield a primary deuterium isotope effect of ca. 80. The conditions of measurement yield the intrinsic 2° (2)H and (13)C KIEs on k(cat)/K(m) directly for 11,11-d2-LA, whereas the values for the 2° (2)H KIEs for 11,11-h2-LA are obtained after correction for a kinetic commitment. The pattern of the resulting 2° (2)H and (13)C isotope effects reveals values that lie far above those predicted from changes in local force constants. Additionally, many of the experimental values cannot be modeled by electronic effects, torsional strain, or the simple inclusion of a tunneling correction to the rate. Although previous studies have shown the importance of extensive tunneling for cleavage of the primary hydrogen at C11 of LA, the present findings can only be interpreted by extending the conclusion of nonclassical behavior to the secondary hydrogens and carbons that flank the position undergoing C-H bond cleavage. A quantum mechanical method introduced by Buhks et al. [J. Phys. Chem. 1981, 85, 3763] to model the inner-sphere reorganization that accompanies electron transfer has been shown to be able to reproduce the scale of the 2° (2)H KIEs.

Experimental high temperature carbon isotope fractionation involving graphite

NASA Astrophysics Data System (ADS)

Kueter, N.; Schmidt, M. W.; Lilley, M. D.; Bernasconi, S. M.

2016-12-01

Graphite/carbonate carbon isotope fractionation was mainly investigated at 400- 800°C and is based on empirical calibrations, theoretical calculations and few experiments [1,2]. Own work on COH-fluid/graphite isotope fractionation shows that in experiments up to 1000oC a fluid phase is always enriched in 13C compared to coexisting graphitic carbon. The eventual kinetic isotope effect in these experiments is best displayed by the graphitic carbon being at least 3 ‰ lighter than methane. Only few experiments done in the graphite/carbonate pair dealt with higher temperatures reaching 1400°C, indicating a fractionation of up to 2 ‰ at temperatures of the Earth's mantle [2-4]. To better understand carbon isotope fractionation in crustal systems and still overcome kinetic effects, we study the graphite/carbonatite pair with piston cylinder experiments in the Na2CO3-CaCO3-CaO-COH system. Tartaric acid (C4H6O6) supplies reduced carbon, time series are performed at 10 kbar, 1300-1800°C. Initial experiments at 1300°C produce well-ordered, micron-sized graphite flakes growing attached to the capsule walls while the Na-Ca-carbonatite-melt quenches to dendritic textures. No gaseous phase was observed. Conditions well above the liquidus of the Na2CO3-CaCO3-binary lead to dissolution of the H2O from tartaric acid decomposition in the melt, any CO2-component is bound by the excess CaO to CaCO3melt while in the relatively oxidizing capsule environment any CH4-component reacts with CO2 to carbon and H2O. The graphite and the carbonatite quench are measured for their δ13C composition using a GasBench II (carbonate-dissolution in phosphoric acid) and TC/EA (residual graphite combusted in oxygen atmosphere) system coupled to a Thermo Fischer IRMS. Our results expand from the graphite-carbonate system to graphite-fluid system when adding available fluid-carbonate fractionation factors, but are also directly applicable to diamond synthesis as graphite is often found as a

Secondary. cap alpha. -deuterium kinetic isotope effects in solvolyses of ferrocenylmethyl acetate and benzoate in ethanol

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

Sutic, D.; Asperger, S.; Borcic, S.

1982-12-17

Secondary ..cap alpha..-deuterium kinetic isotope effects (KIE) in solvolyses of ferrocenyldideuteriomethyl acetate and benzoate were determined in 96% (v/v) ethanol, at 25/sup 0/C, as k/sub H//k/sub D/ = 1.24 and 1.26, respectively. The KIEs were also determined in the presence of 0.1 mol dm/sup -3/ lithium perchlorate: the k/sub H//k/ sub D/ values were 1.23 and 1.22 for acetate and benzoate complexes, respectively. The maximum KIE for the C-O bond cleavage of a primary substrate is as large as, or larger than, that of secondary derivatives, which is estimated to be 1.23 per deuterium. The measured KIE of about 12%more » per D therefore represents a strongly reduced effect relative to its maximum. The solvolyses exhibit ''a special salt effect''. This effect indicates the presence of solvent-separated ion pairs and the return to tight pairs. As the maximum KIE is expected in solvolyses involving transformation of one type of ion pair into another, the strongly reduced ..cap alpha..-D KIE supports the structure involving direct participation of electrons that in the ground state are localized at the iron atom. The alkyl-oxygen cleavage is accompanied by 10-15% acyl-oxygen cleavage.« less

Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

USGS Publications Warehouse

Xia, Xinyu; Ellis, Geoffrey S.; Ma, Qisheng; Tang, Yongchun

2014-01-01

The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C2–5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C2–5 hydrocarbons becoming more enriched in 13C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ13C2+ values (>−10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3

Stable isotopes in water vapor and rainwater over Indian sector of Southern Ocean and estimation of fraction of recycled moisture.

PubMed

Rahul, P; Prasanna, K; Ghosh, Prosenjit; Anilkumar, N; Yoshimura, Kei

2018-05-15

Stable Hydrogen and Oxygen isotopic composition of water vapor, rainwater and surface seawater show a distinct trend across the latitude over the Southern Indian Ocean. Our observations on isotopic composition of surface seawater, water vapor and rainwater across a transect covering the tropical Indian Ocean to the regions of the Southern Ocean showed a strong latitudinal dependency; characterized by the zonal process of evaporation and precipitation. The sampling points were spread across diverse zones of SST, wind speed and rainfall regimes. The observed physical parameters such as sea surface temperature, wind speed and relative humidity over the oceanic regions were used in a box model calculation across the latitudes to predict the isotopic composition of water vapor under equilibrium and kinetic conditions, and compared with results from isotope enabled global spectral model. Further, we obtained the average fraction of recycled moisture across the oceanic transect latitudes as 13.4 ± 7.7%. The values of recycled fraction were maximum at the vicinity of the Inter Tropical Convergence Zone (ITCZ), while the minimum values were recorded over the region of subsidence and evaporation, at the Northern and Southern latitudes of the ITCZ. These estimates are consistent with the earlier reported recyling values.

Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface.

PubMed

Li, Jun; Guo, Hua

2018-03-15

Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

Triple Oxygen and Clumped Isotopes in Synthetic and Natural Carbonates: Implications for Paleoclimate and Paleohydrology Studies

NASA Astrophysics Data System (ADS)

Laskar, A. H.; Rangarajan, R.; Liang, M. C.

2016-12-01

Conventional oxygen isotope (δ18O) has widely been used for paleoclimate studies. However, multiple influencing factors such as temperature, precipitation and kinetic effects during carbonate precipitation complicate the interpretation of δ18O data sometimes. Triple oxygen isotope (Δ17O) in carbonates could be sensitive to kinetic effect occur during its precipitation in water. Carbonates may also record the Δ17O signature of the parent waters, providing a basis in the natural carbonates for identifying kinetic processes such as rapid degassing at lower relative humidity inside a cave during speleothem deposition. Clumped isotopes (Δ47) in carbonates give the formation temperatures of the carbonates if precipitated under isotopic equilibrium. The first goal of the study is to explore the applicability of Δ17O for paleohydrolocial studies. The second is to reconstruct paleotemperature with suitable natural carbonates using Δ47values. This is a rare paleoclimate study utilizing two sophisticated new tools. CO2 produced from carbonates by acid digestion was used for both Δ47 and Δ17O analysis. Purified CO2 samples were directly introduced into the Mass spectrometer (MAT 253) for clumped isotope analysis [1] and CO2-O2 exchange method in presence of platinum for Δ17O analysis [2,3]. We measured Δ47 and Δ17O values in synthetic carbonates precipitated at different temperatures (10-90 oC) and Δ17O values in the water from which the carbonate precipitated. We observed consistent Δ47 values in the carbonates while Δ17O were found to vary. Probably a proper slope (between δ18O and δ17O) selection for carbonates would give consistent results. We also measured Δ47 and Δ17O in modern and well dated speleothems from Chinese and Indian caves to study the paleohydrology and paleotemperature. Δ47 and Δ17O were also measured in modern natural carbonate depositions such as corals, foraminifer and marbles to explore their potentials for paleoclimate studies

In Vivo Mass-independent Fractionation of Mercury Isotopes in Fish

NASA Astrophysics Data System (ADS)

Das, R.; Odom, L. A.

2008-12-01

Recent experimental work and analyses of natural samples have revealed both mass-dependent and mass- independent isotope fractionation effects in mercury. These findings portend new avenues toward understanding the global mercury cycle. It has been shown experimentally that photo reduction of Hg+2 and methylmercury in water with concomitant release of the reduced, gaseous species Hg° results in the residual methylmercury possessing a mass-independent isotope effect. This effect is a relative enrichment of isotopes 199Hg and 201Hg over the even mass number isotopes when compared to the mercury standard NIST SRM3133. Large mass independent fractionation (MIF) effects (Δ199Hg values of a few ‰) have been found in mercury in fish and interpreted as isotope effects inherited from the water. To evaluate the possibility that MIF might be produced within the fish, we have analyzed 38 samples that include zooplankton and twelve different species of fish from a single lake collected over a 2-month time period for mercury isotopic compositions. Trophic levels of the same fish specimens had previously been determined from stomach contents and nitrogen isotopes. Zooplankton in the lake contain mercury with Δ199Hg and Δ201Hg values of +0.43 (±0.07) and +0.44 (±0.07) respectively. Among the fish species there is a striking correspondence between trophic level and Δ199Hg and Δ201Hg values for primary, secondary, and tertiary consumers. The Δ199Hg values ranges over ~1‰ from ~+0.4 in zooplankton, juvenile bluegill and several other small fishes to Δ199Hg = + 1.36 for the Florida gar that is the top predator fish in the lake. These observations indicate that the MIF effect, rather than being an artifact of the water column is produced in vivo. Partial separation of 199Hg and 201Hg from isotopes of even neutron number can be achieved by the magnetic isotope effect in reactions involving sufficiently long-lived intermediate free radicals, where nuclear - electron

Gas Dynamics and Kinetics in the Cometary Coma: Theory and Observations

NASA Technical Reports Server (NTRS)

Combi, Michael R.; Harris, Walter M.; Smyth, William H.

2005-01-01

Our ability to describe the physical state of the expanding coma affects fundamental areas of cometary study both directly and indirectly. In order to convert measured abundances of gas species in the coma to gas production rates, models for the distribution and kinematics of gas species in the coma are required. Conversely, many different types of observations, together with laboratory data and theory, are still required to determine coma model attributes and parameters. Accurate relative and absolute gas production rates and their variations with time and from comet to comet are crucial to our basic understanding of the composition and structure of cometary nuclei and their place in the solar system. We review the gas dynamics and kinetics of cometary comae from both theoretical and observational perspectives, which are important for understanding the wide variety of physical conditions that are encountered.

Iron Isotopes in Meteorites

NASA Astrophysics Data System (ADS)

Kehm, K.; Alexander, C. M.; Hauri, E. H.

2001-12-01

The recent identification of naturally occurring isotopic mass fractionation of the transition met-als on the Earth has prompted a search for similar variability in meteorites. Studies of Cu, Zn, and Fe, for example, have revealed per-mil level and larger mass fractionations between different bulk meteorites. Such variations can result from temperature-sensitive isotope exchange reactions and kinetic processes, and therefore may reflect conditions in the solar nebula and on meteorite parent bodies. Recent advances in ICP-MS have permitted isotope studies of transition metals and other elements with similarly small isotopic mass dispersions. Among the transition metals, Fe is perhaps the most difficult to analyze by ICP-MS because plasma sources are copious producers of argide molecules that interfere with the measurement of iron isotopes. However, the stable isotope behavior of Fe is of special interest because it is a non-refractory major element in meteorites, present in a variety of mineral associations and redox states. Considerable effort has gone into overcoming the inherent analytical difficulties of measuring Fe using ICP-MS. We recently reported on a technique that achieves argide reduction by operating the plasma source in so-called 'cold' mode. In this presentation, we report results from this ongoing work. To date, analyses of nine different meteorites, and eight individual Tieschitz (H3) chondrules have been completed, along with a number of measurements of the Hawaiian basalt sample Kil1919. All of the bulk meteorite compositions, which include both chondrites and irons, have identical 56Fe/54Fe to within ~ 0.14 per mil (2 sigma), and are indistinguishable from the composition of the terrestrial basalt. The Tieschitz chondrules, on the other hand, tend to have isotopically light compositions. This could reflect formation from fractionated starting material. Alternatively, Fe condensation, under non-equilibrium conditions can enrich light isotopes

Carbonate “clumped” isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

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

Kimball, Justine; Eagle, Robert; Dunbar, Robert

Here, deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C 18O 16O 2 inmore » carbonate minerals, analyzed in CO 2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ 47 values. We analyzed Δ 47 in live-collected aragonitic scleractinian ( Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ 47 values were compared to in situ temperatures, and the relationship between Δ 47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ 47–temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ 47–temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO 2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these

Carbonate “clumped” isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

DOE PAGES

Kimball, Justine; Eagle, Robert; Dunbar, Robert

2016-12-12

Here, deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C 18O 16O 2 inmore » carbonate minerals, analyzed in CO 2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ 47 values. We analyzed Δ 47 in live-collected aragonitic scleractinian ( Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ 47 values were compared to in situ temperatures, and the relationship between Δ 47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ 47–temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ 47–temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO 2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these

Constraining the global bromomethane budget from carbon stable isotopes

NASA Astrophysics Data System (ADS)

Bahlmann, Enno; Wittmer, Julian; Greule, Markus; Zetzsch, Cornelius; Seifert, Richard; Keppler, Frank

2016-04-01

Despite intense research in the last two decades, the global bromomethane (CH3Br) budget remains unbalanced with the known sinks exceeding the known sources by about 25%. The reaction with OH is the largest sink for CH3Br. We have determined the kinetic isotope effects for the reactions of CH3Br with the OH and Cl radical in order to better constrain the global CH3Br budget from an isotopic perspective. The isotope fractionation experiments were performed at 20±1°C in a 3500 L Teflon smog-chamber with initial CH3Br mixing ratios of about 2 and 10 ppm and perflourohexane (25 ppb) as internal standard. Atomic chlorine (Cl) was generated via photolysis of molecular chlorine (Cl2) using a solar simulator with an actinic flux comparable to that of the sun in mid-summer in Germany. OH radicals were generated via the photolysis of ozone (O3) at 253.7 nm in the presence of water vapor (RH = 70%).The mixing ratios of CH3Br, and perflourohexane were monitored by GC-MS with a time resolution of 15 minutes throughout the experiments. From each experiment 10 to 15 sub samples were taken in regular time intervals for subsequent carbon isotope ratio determinations by GC-IRMS performed at two independent laboratories in parallel. We found a kinetic isotope effect (KIE) of 17.6±3.3‰ for the reaction of CH3Br with OH and a KIE of 9.8±1.4 ‰ for the reaction with Cl*. We used these fractionation factors along with new data on the isotopic composition of CH3Br in the troposphere (-34±7‰) and the surface ocean (-26±7‰) along with reported source signatures, to constrain the unknown source from an isotopic perspective. The largest uncertainty in estimating the isotopic composition of the unknown source arises from the soil sink. Microbial degradation in soils is the second largest sink and assigned with a large fractionation factors of about 50‰. However, field experiments revealed substantially smaller apparent fractionation factors ranging from 11 to 22‰. In addition

Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

NASA Astrophysics Data System (ADS)

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

2015-04-01

Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

Advances in laser ablation MC-ICPMS isotopic analysis of rock materials

NASA Astrophysics Data System (ADS)

Young, E. D.

2007-12-01

Laser ablation multiple-collector inductively coupled plasma-source mass spectrometry (LA-MC-ICPMS) is a rapid method for obtaining high-precision isotope ratio measurements in geological samples. The method has been used with success for measuring isotope ratios of numerous elements, including Pb, Hf, Mg, Si, and Fe in terrestrial and extraterrestrial samples. It fills the gap between the highest precision obtainable with acid digestion together with MC-ICPMS and thermal ionization mass spectrometry (TIMS) and the maximum spatial resolution afforded by secondary ion mass spectrometry (SIMS). Matrix effects have been shown to be negligible for Pb isotopic analysis by LA-MC-ICPMS (Simon et al., 2007). Glass standards NBS 610, 612, and 614 have Pb/matrix ratios spanning two orders of magnitude. Our sample-standard bracketing laser ablation technique gives accurate and precise 208Pb/206Pb and 207Pb/206Pb for these glasses. The accuracy is superior to that obtained when using Tl to correct for mass fractionation. Accuracy and precision (± 0.2 ‰) for Pb in feldspars is comparable to that for double-spike TIMS. Data like these have been used to distinguish distinct sources of magmas in the Long Valley silicic magma system. LA-MC-ICPMS analyses of Mg isotope ratios in calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrite meteorites have revealed a wealth of new information about the history of these objects. A byproduct of this work has been recognition of the importance of different mass fractionation laws among three isotopes of a given element. Kinetic and equilibrium processes define distinct fractionation laws. Reservoir effects can further modify these laws. The result is that the linear coefficient β that relates the logarithms of the ratios n2/n1 and n3/n1 (ni refers to the number of atoms of isotope i) of isotopes with masses m3 > m2 > m1 is not unique. Rather, it is process dependent. In the case of Mg, this coefficient ranges from 0.521 for

Global scale observations of atmospheric molecular hydrogen and its stable isotopic composition

NASA Astrophysics Data System (ADS)

Batenburg, A. M.

2012-09-01

With average mixing ratios (χ) around 550 ppb (nmole/mole), molecular hydrogen (H2) is the most abundant reduced gas in our atmosphere after methane (CH4), but considerably less studied. H2 is also a promising energy carrier that might replace fossil fuels in vehicles with great sustainability advantages, but there may be environmental side effects. Large-scale leakage of H2 into the atmosphere might affect the atmosphere’s oxidative capacity and stratospheric ozone chemistry. To assess these risks, a better understanding of the atmospheric H2 cycle is needed. Stable isotopic composition measurements can be used to constrain the source and sink terms in the budgets of atmospheric trace gases, as the different processes affect the stable isotopic composition of the gases in different ways. For H2, the effects are particularly large, due to the large relative mass difference between the isotopes (H and D). The largest source, hydrocarbon oxidation, yields D-enriched H2, whereas the smaller combustion-related sources and the minor microbial sources yield D-depleted and extremely D-depleted H2, respectively. Both sink processes, uptake in soils and reaction with hydroxyl radicals (OH), have a D-enriching effect, but the effect is much stronger for OH. Despite its usefulness, few environmental observations of H2 isotopic composition (δD(H2)) are available. We present three new χ(H2) and δD(H2) datasets to fill this gap. First, we present one- to five-year long time series from six globally distributed, predominantly background stations. As expected, average χ(H2) and δD(H2) values were larger in the southern hemisphere (SH) than in the northern hemisphere (NH). The minimum in δD(H2) was found at the NH midlatitude stations, likely a result of fossil fuel combustion. At the three NH coastal and island stations, seasonal δD(H2)-cycles were observed, which were five to six months out-of-phase with the χ(H2)-cycles. No δD(H2)-cycles were observed at the other

An Isotopic Labelling Strategy to Study Cytochrome P450 Oxidations of Terpenes.

PubMed

Rinkel, Jan; Litzenburger, Martin; Bernhardt, Rita; Dickschat, Jeroen Sidney

2018-04-26

The cytochrome P450 monooxygenase CYP267B1 from Sorangium cellulosum was applied for enzymatic oxidation of the sesquiterpene alcohols T-muurolol and isodauc-8-en-11-ol. Various isotopically labelled geranyl and farnesyl diphosphates were used for product identification from micro-scale reactions, for determination of the absolute configurations of unknown compounds, to follow the stereochemical course of a cytochrome P450-catalysed hydroxylation step, and to investigate kinetic isotope effects. Overall, this study demonstrates that isotopically labelled terpene precursors are highly useful to follow cytochrome P450 dependent oxidations of terpenes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observations of hydrogen and helium isotopes in solar cosmic rays. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Hurford, G. J.

1974-01-01

The isotopic composition of hydrogen and helium in solar cosmic rays provides a means of studying solar flare particle acceleration mechanisms since the enhanced relative abundance of rare isotopes, such as H-2, H-3, and He-3, is due to their production by inelastic nuclear collisions in the solar atmosphere during the flare. Electron isotope spectrometer on an IMP spacecraft was used to measure this isotopic composition. The response of the dE/dx-E particle telescope is discussed, and alpha particle channeling in thin detectors is identified as an important background source affecting measurement of low values of (He-3/He-4). The flare-averaged results obtained for the period October, 1972 November, 1973 are given.

Noninvasive in situ observation of the crystallization kinetics of biological macromolecules by confocal laser scanning microscopy.

PubMed

Mühlig, P; Klupsch, Th; Kaulmann, U; Hilgenfeld, R

2003-04-01

High-resolution confocal laser scanning microscopy (CLSM) is a powerful tool for in situ observation and analysis of protein crystal growth kinetics. Because the resolution of CLSM is not diffraction-limited by the object, it is possible to visualize, under certain conditions, objects in molecular dimensions. A modified batch technique is applied which allows the growth kinetics of sufficiently small crystallites fixed at the lower side of a cover glass, within a hanging drop, to be studied in reflected light near the total reflection angle. A gap, or cavity, filled with solution is formed between the cover glass and the upper crystal face, which acts to fix small crystallites by hydrodynamic friction forces. The cavity height enables the propagation of molecular steps across the upper crystal face without constraint, so that the propagation velocity and geometrical parameters can be measured by CLSM. The layer growth kinetics of monoclinic crystallites of a long-acting insulin derivative (Insulin Glargine) is investigated. For a twofold supersaturation of the solution, the growth is governed by 2D nucleation at the edges of the crystallites followed by a spreading of molecular steps. The layer growth kinetics are well fitted by the simple cubic kinetic lattice model. We find that only about one of a thousand solute (protein) molecules which push a kink place due to their Brownian motion becomes really incorporated into the growing crystal.

Dual-isotope PET using positron-gamma emitters.

PubMed

Andreyev, A; Celler, A

2011-07-21

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

Kinetic fractionation processes recorded in the stalagmites of some limestone caves in Korea

NASA Astrophysics Data System (ADS)

Woo, K. S.; Jo, K.; Edwards, L. R.; Cheng, H.; Wang, Y.; Yoon, H.

2006-12-01

Stable isotope data (oxygen and carbon) of carbonate minerals (mostly calcite, but sometimes aragonite) in stalagmites have been the most commonly and widely used proxies for paleoclimatic research. This is based upon the assumption that carbonate minerals precipitated in isotopic equilibrium with dripping waters from stalactites, thus should reflect paleoclimatic variations. The state of equilibrium, so called "Hendy Test", has been commonly used. Hendy (1971) showed that during kinetic fractionation both oxygen and carbon isotopes behaves in a similar way due to faster degassing rate of cabon dioxide, resulting in the enrichment of both isotopes. The stalagmites from three limestone caves (Gwaneum, Eden and Daeya Caves) in Korea were investigated to understand the effects of kinetic fractionation during their growth. The stalagmites are mostly composed of columnar calcites, but contains the layers of cave coral that is composed of fibrous calcite. The cave coral layers should have grown when the supply rate of dripping water decreased significantly. Stable isotope pattern in three stalagmites do not show the same pattern of disequilibrium process. The cave corals in the Eden stalagmite show the enriched carbon and oxygen isotope values (15 and 5 per mil, respectively) that has the same bimodal pattern as suggested by Hendy (1971). However, the cave corals in the Gwaneum stalagmites show the enriched carbon, but depleted oxygen isotope values (3 and 1 per mil, respectively). Also, the calcite layer precipitated in disequilibrium in the Daeya stalagmite show more enriched carbon isotope values by up to 6 per mil, but show more or less the same oxygen isotopic values, compared to the columnar calcite which was precipitated in equilibrium. Therefore, caution should be made to determine the state of equilibrium precipitation of carbonate minerals in stalagmites. The "Hendy Test" may not be the only solution because other types of speleothems can be formed in

A large column analog experiment of stable isotope variations during reactive transport: I. A comprehensive model of sulfur cycling and δ34S fractionation

NASA Astrophysics Data System (ADS)

Druhan, Jennifer L.; Steefel, Carl I.; Conrad, Mark E.; DePaolo, Donald J.

2014-01-01

This study demonstrates a mechanistic incorporation of the stable isotopes of sulfur within the CrunchFlow reactive transport code to model the range of microbially-mediated redox processes affecting kinetic isotope fractionation. Previous numerical models of microbially mediated sulfate reduction using Monod-type rate expressions have lacked rigorous coupling of individual sulfur isotopologue rates, with the result that they cannot accurately simulate sulfur isotope fractionation over a wide range of substrate concentrations using a constant fractionation factor. Here, we derive a modified version of the dual-Monod or Michaelis-Menten formulation (Maggi and Riley, 2009, 2010) that successfully captures the behavior of the 32S and 34S isotopes over a broad range from high sulfate and organic carbon availability to substrate limitation using a constant fractionation factor. The new model developments are used to simulate a large-scale column study designed to replicate field scale conditions of an organic carbon (acetate) amended biostimulation experiment at the Old Rifle site in western Colorado. Results demonstrate an initial period of iron reduction that transitions to sulfate reduction, in agreement with field-scale behavior observed at the Old Rifle site. At the height of sulfate reduction, effluent sulfate concentrations decreased to 0.5 mM from an influent value of 8.8 mM over the 100 cm flow path, and thus were enriched in sulfate δ34S from 6.3‰ to 39.5‰. The reactive transport model accurately reproduced the measured enrichment in δ34S of both the reactant (sulfate) and product (sulfide) species of the reduction reaction using a single fractionation factor of 0.987 obtained independently from field-scale measurements. The model also accurately simulated the accumulation and δ34S signature of solid phase elemental sulfur over the duration of the experiment, providing a new tool to predict the isotopic signatures associated with reduced mineral pools

Oxygen isotope anomaly observed in water vapor from Alert, Canada and the implication for the stratosphere

PubMed Central

Lin, Ying; Clayton, Robert N.; Huang, Lin; Nakamura, Noboru; Lyons, James R.

2013-01-01

To identify the possible anomalous oxygen isotope signature in stratospheric water predicted by model studies, 25 water vapor samples were collected in 2003−2005 at Alert station, Canada (82°30′N), where there is downward transport of stratospheric air to the polar troposphere, and were analyzed for δ17O and δ18O relative to Chicago local precipitation (CLP). The latter was chosen as a reference because the relatively large evaporative moisture source should erase any possible oxygen isotope anomaly from the stratosphere. A mass-dependent fractionation coefficient for meteoric waters, λMDF(H2O) = 0.529 ± 0.003 [2σ standard error (SE)], was determined from 27 CLP samples collected in 2003−2005. An oxygen isotopic anomaly of Δ17O = 76 ± 16 ppm (2σ SE) was found in water vapor samples from Alert relative to CLP. We propose that the positive oxygen isotope anomalies observed at Alert originated from stratospheric ozone, were transferred to water in the stratosphere, and subsequently mixed with tropospheric water at high latitudes as the stratospheric air descended into the troposphere. On the basis of this ground signal, the average Δ17O in stratospheric water vapor predicted by a steady-state box model is ∼40‰. Seven ice core samples (1930−1991) from Dasuopu glacier (Himalayas, China) and Standard Light Antarctic Precipitation did not show an obvious oxygen isotope anomaly, and Vienna Standard Mean Ocean Water exhibited a negative Δ17O relative to CLP. Six Alert snow samples collected in March 2011 and measured at Laboratoire des Sciences du Climat et de l'Environnement, Gif sur Yvette, France, had 17Oexcess of 45 ± 5 ppm (2σ SE) relative to Vienna Standard Mean Ocean Water. PMID:24009339

Iron isotope evidence for the origin of the Moon through partial vaporisation

NASA Astrophysics Data System (ADS)

Poitrasson, F.; Halliday, A. N.; Lee, D. C.; Levasseur, S.; Teutsch, N.

2003-04-01

The currently favoured scenario of the origin of the Moon through a Giant Impact, in which a body approaching the size of Mars hit the proto-Earth and yielded ejecta leading to the Moon remains hypothetical. This theory predicts extremely high temperatures, sufficient to induce planetary-scale vaporisation. We have thus measured the Fe isotope composition of the Earth, Moon and meteorites thought to come from Mars and asteroid Vesta to see if this highly energetic process left an imprint. Our analytical method involves Fe purification through anionic exchange chromatography and iron isotope measurement by MC-ICP-MS. Repeat analyses of standards define 57Fe/54Fe reproducibility of 0.09 per mil (2SD). Meteorites from Mars and Vesta, give δ57Fe/54Fe values indistinguishable to the international IRMM-14 Fe isotopic standard. In contrast, ten lunar samples, spanning a large range in composition give a mean 0.2 per mil heavier than IRMM-14. Mantle-derived terrestrial samples yield a mean δ57Fe/54Fe intermediate between the Moon and Mars. Student's t-tests show that the terrestrial mean is significantly different from the averages of Mars, Vesta and the Moon at a confidence level of more than 99%. These new Fe isotope measurements, combined with previous oxygen isotope data rule out alternative theories of the origin of the Moon through co-accretion, capture or fission from the proto-Earth. In contrast, vaporisation of bodies in space can generate kinetic isotope fractionation, leaving residues with a relatively heavier isotope signature. Hence, the Earth, and especially the Moon, can represent such heavy residues having lost part of their light iron through vaporisation. Only the Giant Impact can account for the energy required to partially melt and vaporise major portion of the Earth and the impactor. Rayleigh kinetic isotope calculations suggest that the Moon lost up to 1% of its iron, whereas the Earth lost up to 0.5% during partial vaporisation.

A Critical Look at the Combined Use of Sulfur and Oxygen Isotopes to Study Microbial Metabolisms in Methane-Rich Environments

PubMed Central

Antler, Gilad; Pellerin, André

2018-01-01

Separating the contributions of anaerobic oxidation of methane and organoclastic sulfate reduction in the overall sedimentary sulfur cycle of marine sediments has benefited from advances in isotope biogeochemistry. Particularly, the coupling of sulfur and oxygen isotopes measured in the residual sulfate pool (δ18OSO4 vs. δ34SSO4). Yet, some important questions remain. Recent works have observed patterns that are inconsistent with previous interpretations. We differentiate the contributions of oxygen and sulfur isotopes to separating the anaerobic oxidation of methane and organoclastic sulfate reduction into three phases; first evidence from conventional high methane vs. low methane sites suggests a clear relationship between oxygen and sulfur isotopes in porewater and the metabolic process taking place. Second, evidence from pure cultures and organic matter rich sites with low levels of methane suggest the signatures of both processes overlap and cannot be differentiated. Third, we take a critical look at the use of oxygen and sulfur isotopes to differentiate metabolic processes (anaerobic oxidation of methane vs. organoclastic sulfate reduction). We identify that it is essential to develop a better understanding of the oxygen kinetic isotope effect, the degree of isotope exchange with sulfur intermediates as well as establishing their relationships with the cell-specific metabolic rates if we are to develop this proxy into a reliable tool to study the sulfur cycle in marine sediments and the geological record. PMID:29681890

Preservation of carbonate clumped isotopes in sedimentary paleoclimate archives

NASA Astrophysics Data System (ADS)

Henkes, G. A.; Passey, B. H.; Grossman, E. L.; Shenton, B.; Perez-Huerta, A.

2014-12-01

Carbonate clumped isotope thermometry is increasingly used to reconstruct paleotemperatures of ancient terrestrial environments. One promising application is elucidating paleoelevation from carbonate archives such as paleosols, lacustrine marls, and fossil freshwater shells. Unlike conventional stable isotope approaches (e.g., mineral δ18O or δD), clumped isotope thermometry is independent of the isotopic composition of the precipitating waters and can therefore be used to reconstruct elevation by both the temperature-altitude relationship and the rainfall δ18O-altitude relationship. However, interpretation of clumped isotope data is not without its own complications. Like conventional stable isotopes, clumped isotope paleotemperatures can be effectively reset to warmer values by dissolution/reprecipitation-type diagenesis during sedimentary burial. It is also known that carbonate clumped isotope bonds (i.e., 13C-18O) are susceptible to 'reordering' in the solid mineral lattice at warmer burial temperatures, with laboratory studies of natural carbonates indicating activation of this phenomenon at temperatures as low as 100 °C over geologic timescales. A challenge in applying carbonate clumped isotope thermometry to natural samples is now evaluating terrestrial archives with respect to both types of alteration: 'open-system' alteration and 'closed-system' bond reordering. In this talk we will review our experimental efforts to constrain the kinetics of clumped isotope reordering, with relevance to low-temperature carbonates like fossil shells and early diagenetic minerals, and present new laboratory data that further inform our theoretical framework for the mechanism(s) of 13C-18O bond reordering. Together with traditional analytical and petrographic screening for recrystallization, empirical and laboratory studies of carbonate clumped isotope reordering represent the next steps in evaluating isotopic records of paleoclimate, paleobiology, and paleoelevation

Utilizing Stable Isotopes and Isotopic Anomalies to Study Early Solar System Formation Processes

NASA Technical Reports Server (NTRS)

Simon, Justin

2017-01-01

Chondritic meteorites contain a diversity of particle components, i.e., chondrules and calcium-, aluminum-rich refractory inclusions (CAIs), that have survived since the formation of the Solar System. The chemical and isotopic compositions of these materials provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of the processes and reservoirs in which solids formed in the solar nebula, an important step leading to the accretion of planetesimals. Isotopic anomalies associated with nucleosynthetic processes are observed in these discrete materials, and can be compared to astronomical observations and astrophysical formation models of stars and more recently proplyds. The existence and size of these isotopic anomalies are typically thought to reflect a significant state of isotopic heterogeneity in the earliest Solar System, likely left over from molecular cloud heterogeneities on the grain scale, but some could also be due to late stellar injection. The homogenization of these isotopic anomalies towards planetary values can be used to track the efficiency and timescales of disk wide mixing,

Calcium Isotopes in Foraminifera Shells: Evaluation for Paleo-temperature Reconstruction

NASA Astrophysics Data System (ADS)

Paytan, A.; Revello, C. A.; Bullen, T. D.

2002-12-01

The Ca stable isotope ratio of foraminifera shells has been suggested as a potential paleo-temperature proxy and has recently been applied in several studies to reconstruct glacial interglacial fluctuations in seawater temperatures. The major advantage of using Ca isotopes for paleo-temperature reconstruction is the relatively long residence time of Ca in the ocean. Thus, no spatial or temporal change in the Ca isotopic composition of seawater is expected over time scales much shorter than a million years. Moreover, since Ca is a major constituent of carbonate, and an isotopic ratio rather than an element concentration or element-element ratio (e.g. Mg/Ca, Sr/Ca) is measured, the Ca isotope proxy is much less likely to be affected by post depositional diagenetic alteration. However, preliminary results indicate that kinetic effects might largely control the Ca isotope fractionation involved in calcite shell formation. Before this new and exciting proxy can be utilized routinely, a better understanding of the parameters controlling Ca isotope fractionation in carbonate minerals in general and in foraminifera and other carbonate-secreting organisms is required. We have measured the Ca stable isotope ratio of several foraminifera species from core top sediments from two well-studied sites to determine the inter-species and within-species variability in Ca isotopes. We assess the effects of water temperature, calcification rate, and vital effects on the Ca stable isotope ratio of modern foraminifera and evaluate the potential of this proxy for paleo-temperature reconstruction.

Observations of kinetic scale magnetic holes in terrestrial space

NASA Astrophysics Data System (ADS)

Shutao, Y.; Shi, Q.; Wang, X.; Zong, Q.; Tian, A.; Yao, Z.; Hamrin, M.; Pitkänen, T.; Pu, Z.; Xiao, C.; Fu, S.; Zhang, H.; Giles, B. L.; Russell, C. T.; Guo, R.; Sun, W. J.; Li, W.; Zhou, X.; De Spiegeleer, A.

2017-12-01

Plasma is a macroscopically neutral system. It contains a mass of interacting ionized particles. Because of the much higher mass ratio between ions and electrons, plasma is a complicated multiple characteristic scales system with complicated properties. Thus it is necessary to carefully choose different models corresponding to the relevant scale when analyzing magnetic holes (MHs). Although there are many studies for the magnetohydrodynamics (MHD) scale MHs, few of them are for kinetic scale MHs (KSMHs). In this study, several multi-point spacecraft techniques are used to determine the propagating velocity of plasma sheet KSMHs. Based on the electronmagnetohydrodynamics (EMHD) theory, the width, depth and propagating velocity of electron solitary wave are calculated and compared to the observations. Furthermore, we report a series of the KSMHs in the magnetosheath whereby we use measurements from the Magnetospheric Multiscale (MMS) mission. The KSMHs have been observed with a scale of 10-20 ρe (electron gyroradii) and lasted 0.1-0.3 s. Distinctive electron dynamics features are observed. We find that at the 90° pitch angle, the flux of electrons with energy 34-66 eV decreased, while for electrons of energy 109-1024 eV increased inside the KSMHs. We also find the electron flow vortex perpendicular to the magnetic field, a feature self-consistent with the magnetic depression. The calculated current density is mainly contributed by the electron diamagnetic drift. Test particle is used to simulate the electron acceleration of the KSMHs.

Equilibrium isotopic fractionation of copper during oxidation/reduction, aqueous complexation and ore-forming processes: Predictions from hybrid density functional theory

NASA Astrophysics Data System (ADS)

Sherman, David M.

2013-10-01

Copper exists as two isotopes: 65Cu (∼30.85%) and 63Cu (∼69.15%). The isotopic composition of copper in secondary minerals, surface waters and oxic groundwaters is 1-12‰ heavier than that of copper in primary sulfides. Changes in oxidation state and complexation should yield substantial isotopic fractionation between copper species but it is unclear to what extent the observed Cu isotopic variations reflect equilibrium fractionation. Here, I calculate the reduced partition function ratios for chalcopyrite (CuFeS2), cuprite (Cu2O), tenorite (CuO) and aqueous Cu+, Cu+2 complexes using periodic and molecular hybrid density functional theory to predict the equilibrium isotopic fractionation of Cu resulting from oxidation of Cu+ to Cu+2 and by complexation of dissolved Cu. Among the various copper(II) complexes in aqueous environments, there is a significant (1.3‰) range in the reduced partition function ratios. Oxidation and congruent dissolution of chalcopyrite (CuFeS2) to dissolved Cu+2 (as Cu(H2O)5+2) yields 65-63δ(Cu+2-CuFeS2) = 3.1‰ at 25 °C; however, chalcopyrite oxidation/dissolution is incongruent so that the observed isotopic fractionation will be less. Secondary precipitation of cuprite (Cu2O) would yield further enrichment of dissolved 65Cu since 65-63δ(Cu+2-Cu2O) is 1.2‰ at 25 °C. However, precipitation of tenorite (CuO) will favor the heavy isotope by +1.0‰ making dissolved Cu isotopically lighter. These are upper-limit estimates for equilibrium fractionation. Therefore, the extremely large (9‰) fractionations between dissolved Cu+2 (or Cu+2 minerals) and primary Cu+ sulfides observed in supergene environments must reflect Rayleigh (open-system) or kinetic fractionation. Finally the previously proposed (Asael et al., 2009) use of δ65Cu in chalcopyrite to estimate the oxidation state of fluids that transported Cu in stratiform sediment-hosted copper deposits is refined.

Interpretation of orbital scale variability in mid-latitude speleothem δ18O: Significance of growth rate controlled kinetic fractionation effects

NASA Astrophysics Data System (ADS)

Stoll, Heather; Mendez-Vicente, Ana; Gonzalez-Lemos, Saul; Moreno, Ana; Cacho, Isabel; Cheng, Hai; Edwards, R. Lawrence

2015-11-01

Oxygen isotopes have been the most widely used climate indicator in stalagmites, applied to reconstruct past changes in rainfall δ18O and cave temperature. However, the δ18O signal in speleothems may also be influenced by variable kinetic fractionation effects, here conceived broadly as fractionation effects not arising from temperature variation. The regional reproducibility of speleothem δ18O signals has been proposed as a way to distinguish the δ18O variations arising directly from changes rainfall δ18O and cave temperature, from variations due to kinetic effects which may nonetheless be influenced by climate. Here, we compare isotopic records from 5 coeval stalagmites from two proximal caves in NW Spain covering the interval 140 to 70 ka, which experienced the same primary variations in temperature and rainfall δ18O, but exhibit a large range in growth rates and temporal trends in growth rate. Stalagmites growing at faster rates near 50 μm/yr have oxygen isotopic ratios over 1‰ more negative than coeval stalagmites with very slow (5 μm/yr) growth rates. Because growth rate variations also occur over time within any given stalagmite, the measured oxygen isotopic time series for a given stalagmite includes both climatic and kinetic components. Removal of the kinetic component of variation in each stalagmite, based on the dependence of the kinetic component on growth rate, is effective at distilling a common temporal evolution of among the oxygen isotopic records of the multiple stalagmites. However, this approach is limited by the quality of the age model. For time periods characterized by very slow growth and long durations between dates, the presence of crypto-hiatus may result in average growth rates which underestimate the instantaneous speleothem deposition rates and which therefore underestimate the magnitude of kinetic effects. The stacked growth rate-corrected speleothem δ18O is influenced by orbital scale variation in the cave temperature and

Isotopic Analysis and Evolved Gases

NASA Technical Reports Server (NTRS)

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

1996-01-01

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

Carbon isotopes in mollusk shell carbonates

NASA Astrophysics Data System (ADS)

McConnaughey, Ted A.; Gillikin, David Paul

2008-10-01

Mollusk shells contain many isotopic clues about calcification physiology and environmental conditions at the time of shell formation. In this review, we use both published and unpublished data to discuss carbon isotopes in both bivalve and gastropod shell carbonates. Land snails construct their shells mainly from respired CO2, and shell δ13C reflects the local mix of C3 and C4 plants consumed. Shell δ13C is typically >10‰ heavier than diet, probably because respiratory gas exchange discards CO2, and retains the isotopically heavier HCO3 -. Respired CO2 contributes less to the shells of aquatic mollusks, because CO2/O2 ratios are usually higher in water than in air, leading to more replacement of respired CO2 by environmental CO2. Fluid exchange with the environment also brings additional dissolved inorganic carbon (DIC) into the calcification site. Shell δ13C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell δ13C retains clues about processes such as ecosystem metabolism and estuarine mixing. Ca2+ ATPase-based models of calcification physiology developed for corals and algae likely apply to mollusks, too, but lower pH and carbonic anhydrase at the calcification site probably suppress kinetic isotope effects. Carbon isotopes in biogenic carbonates are clearly complex, but cautious interpretation can provide a wealth of information, especially after vital effects are better understood.

Isotope Geochemistry for Comparative Planetology of Exoplanets

NASA Technical Reports Server (NTRS)

Mandt, K. E.; Atreya, S.; Luspay-Kuti, A.; Mousis, O.; Simon, A.; Hofstadter, M. D.

2017-01-01

Isotope geochemistry has played a critical role in understanding processes at work in and the history of solar system bodies. Application of these techniques to exoplanets would be revolutionary and would allow comparative planetology with the formation and evolution of exoplanet systems. The roadmap for comparative planetology of the origins and workings of exoplanets involves isotopic geochemistry efforts in three areas: (1) technology development to expand observations of the isotopic composition of solar system bodies and expand observations to isotopic composition of exoplanet atmospheres; (2) theoretical modeling of how isotopes fractionate and the role they play in evolution of exoplanetary systems, atmospheres, surfaces and interiors; and (3) laboratory studies to constrain isotopic fractionation due to processes at work throughout the solar system.

Combined C and Cl isotope effects indicate differences between corrinoids and enzyme (Sulfurospirillum multivorans PceA) in reductive dehalogenation of tetrachloroethene, but not trichloroethene.

PubMed

Renpenning, Julian; Keller, Sebastian; Cretnik, Stefan; Shouakar-Stash, Orfan; Elsner, Martin; Schubert, Torsten; Nijenhuis, Ivonne

2014-10-21

The role of the corrinoid cofactor in reductive dehalogenation catalysis by tetrachloroethene reductive dehalogenase (PceA) of Sulfurospirillum multivorans was investigated using isotope analysis of carbon and chlorine. Crude extracts containing PceA--harboring either a native norpseudo-B12 or the alternative nor-B12 cofactor--were applied for dehalogenation of tetrachloroethene (PCE) or trichloroethene (TCE), and compared to abiotic dehalogenation with the respective purified corrinoids (norpseudovitamin B12 and norvitamin B12), as well as several commercially available cobalamins and cobinamide. Dehalogenation of TCE resulted in a similar extent of C and Cl isotope fractionation, and in similar dual-element isotope slopes (εC/εCl) of 5.0-5.3 for PceA enzyme and 3.7-4.5 for the corrinoids. Both observations support an identical reaction mechanism. For PCE, in contrast, observed C and Cl isotope fractionation was smaller in enzymatic dehalogenation, and dual-element isotope slopes (2.2-2.8) were distinctly different compared to dehalogenation mediated by corrinoids (4.6-7.0). Remarkably, εC/εCl of PCE depended in addition on the corrinoid type: εC/εCl values of 4.6 and 5.0 for vitamin B12 and norvitamin B12 were significantly different compared to values of 6.9 and 7.0 for norpseudovitamin B12 and dicyanocobinamide. Our results therefore suggest mechanistic and/or kinetic differences in catalytic PCE dehalogenation by enzymes and different corrinoids, whereas such differences were not observed for TCE.

Kinetic analysis of lead metabolism in healthy humans

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

Rabinowitz, M.B.; Wetherill, G.W.; Kopple, J.D.

The steady state kinetics of lead metabolism were studied in five healthy men with stable isotope tracers. Subjects lived in a metabolic unit and ate constant low lead diets. Their intake was supplemented each day with 79 to 204 ..mu..g of enriched lead-204 as nitrate which was ingested with meals for 1 to 124 days. The concentration and isotopic composition of lead was determined serially in blood, urine, feces, and diet and less commonly in hair, nails, sweat, bone, and alimentary tract secretions by isotopic dilution, mass spectrometric analysis. The data suggest a three-compartmental model for lead metabolism. The firstmore » compartment encompasses blood and is 1.5 to 2.2 times larger than the blood mass. It contains approximately 1.7 to 2.0 mg of lead and has a mean life of 35 days. This pool is in direct communication with ingested lead, urinary lead, and pools two and three. The second compartment is largely composed of soft tissue, contains about 0.3 to 0.9 mg of lead, and has a mean life of approximately 40 days. This pool gives rise to lead in hair, nails, sweat, and salivary, gastric, pancreatic, and biliary secretions. Pool three resides primarily in the skeleton, contains the vast quantity of body lead, and has a very slow mean life. Bones appear to differ in their rates of lead turnover. Within the relatively small changes in blood lead observed in the present study, the transfer coefficients between the pools remained constant.« less

Stable mercury isotope ratios as tracers for Hg cycling at the inoperative New Idria Hg mine, California

NASA Astrophysics Data System (ADS)

Wiederhold, J. G.; Jew, A. D.; Brown, G. E.; Bourdon, B.; Kretzschmar, R.

2010-12-01

The seven stable isotopes of Hg are fractionated in the environment as a result of mass-dependent (MDF) and mass-independent (MIF) fractionation processes that can be studied in parallel by analyzing the ratios of even and odd mass Hg isotopes. MDF and MIF Hg isotope signatures of natural samples may provide a new tool to trace sources and transformations in environmental Hg cycling. However, the mechanisms controlling the extent of kinetic and equilibrium Hg isotope fractionations are still only partially understood. Thus, development of this promising tracer requires experimental calibration of relevant fractionation factors as well as assessment of natural variations of Hg isotope ratios under different environmental conditions. The inoperative Hg mine in New Idria (California, USA) represents an ideal case study to explore Hg isotope fractionation during Hg transformation and transport processes. More than a century of Hg mining and on-site thermal refining to obtain elemental Hg until 1972 produced large volumes of contaminated mine wastes which now represent sources of Hg pollution for the surrounding ecosystems. Here, we present Hg isotope data from various materials collected at New Idria using Cold-Vapor-MC-ICPMS with a long-term δ202Hg reproducibility of ±0.1‰ (2SD). Uncalcined mine waste samples were isotopically similar to NIST-3133 and did not exhibit any MIF signatures. In contrast, calcine samples, which represent the residue of the thermal ore processing at 700°C, had significantly heavier δ202Hg values of up to +1.5‰. In addition, we observed small negative MIF anomalies of the odd-mass Hg isotopes in the calcine samples, which could be caused either by nuclear volume fractionation or a magnetic isotope effect during or after the roasting process. The mass-dependent enrichment of heavy Hg isotopes in the calcine materials indicates that light Hg isotopes were preferentially removed during the roasting process, in agreement with a previous

The plumbotectonic model for Pb isotopic systematics among major terrestrial reservoirs - A case for bi-directional transport

NASA Astrophysics Data System (ADS)

Zartman, Robert E.; Haines, Sara M.

1988-06-01

Version IV of plumbotectonics expands and refines the original model of DOE and ZARTMAN (1979) and ZARTMAN and DOE (1981) for explaining Pb (Sr, and Nd) isotopic systematics among major terrestrial reservoirs. A case for bi-directional transport among reservoirs is based on the observed isotopic compositions for different tectonic settings, and finds a rationale in the kinetics of plate tectonics. Chemical fractionation and radioactive decay create isotopic differences during periods of isolation of one reservoir from another, whereas dynamic processes allowing mixing between reservoirs tend to reduce these differences. Observed isotopic characteristics reflect a balance between these opposing tendencies and provide constraints on the extent and timing of fractionation and mixing processes. Plumbotectonics does not require interaction with a lower mantle or core reservoir over most of the Earth's lifetime, and, in fact, achieves a material balance consistent with no such exchange of material. Important evidence of the amount and timing of crustal recycling, and of the residence times of mantle heterogeneities lies in the coupled 207Pb /204Pb- 206 Pb 204Pb systematics. We believe that examination of the published data base fully supports our contention of significant bi-directional transport of material among terrestrial reservoirs. Plumbotectonics allows us to explore many aspects of reservoir interaction, and to identify parameters that provide meaningful constraints on mantle-crust differentiation. We put forth a compromise fit to many of the model variables in version IV, which can serve as a reference for future work.

Theoretical analysis of the unusual temperature dependence of the kinetic isotope effect in quinol oxidation.

PubMed

Ludlow, Michelle K; Soudackov, Alexander V; Hammes-Schiffer, Sharon

2009-05-27

In this paper we present theoretical calculations on model biomimetic systems for quinol oxidation. In these model systems, an excited-state [Ru(bpy)(2)(pbim)](+) complex (bpy = 2,2'-dipyridyl, pbim = 2-(2-pyridyl)benzimidazolate) oxidizes a ubiquinol or plastoquinol analogue in acetonitrile. The charge transfer reaction occurs via a proton-coupled electron transfer (PCET) mechanism, in which an electron is transferred from the quinol to the Ru and a proton is transferred from the quinol to the pbim(-) ligand. The experimentally measured average kinetic isotope effects (KIEs) at 296 K are 1.87 and 3.45 for the ubiquinol and plastoquinol analogues, respectively, and the KIE decreases with temperature for plastoquinol but increases with temperature for ubiquinol. The present calculations provide a possible explanation for the differences in magnitudes and temperature dependences of the KIEs for the two systems and, in particular, an explanation for the unusual inverse temperature dependence of the KIE for the ubiquinol analogue. These calculations are based on a general theoretical formulation for PCET reactions that includes quantum mechanical effects of the electrons and transferring proton, as well as the solvent reorganization and proton donor-acceptor motion. The physical properties of the system that enable the inverse temperature dependence of the KIE are a stiff hydrogen bond, which corresponds to a high-frequency proton donor-acceptor motion, and small inner-sphere and solvent reorganization energies. The inverse temperature dependence of the KIE may be observed if the 0/0 pair of reactant/product vibronic states is in the inverted Marcus region, while the 0/1 pair of reactant/product vibronic states is in the normal Marcus region and is the dominant contributor to the overall rate. In this case, the free energy barrier for the dominant transition is lower for deuterium than for hydrogen because of the smaller splittings between the vibronic energy levels

In vivo kinetic approach reveals slow SOD1 turnover in the CNS

PubMed Central

Crisp, Matthew J.; Mawuenyega, Kwasi G.; Patterson, Bruce W.; Reddy, Naveen C.; Chott, Robert; Self, Wade K.; Weihl, Conrad C.; Jockel-Balsarotti, Jennifer; Varadhachary, Arun S.; Bucelli, Robert C.; Yarasheski, Kevin E.; Bateman, Randall J.; Miller, Timothy M.

2015-01-01

Therapeutic strategies that target disease-associated transcripts are being developed for a variety of neurodegenerative syndromes. Protein levels change as a function of their half-life, a property that critically influences the timing and application of therapeutics. In addition, both protein kinetics and concentration may play important roles in neurodegeneration; therefore, it is essential to understand in vivo protein kinetics, including half-life. Here, we applied a stable isotope-labeling technique in combination with mass spectrometric detection and determined the in vivo kinetics of superoxide dismutase 1 (SOD1), mutation of which causes amyotrophic lateral sclerosis. Application of this method to human SOD1-expressing rats demonstrated that SOD1 is a long-lived protein, with a similar half-life in both the cerebral spinal fluid (CSF) and the CNS. Additionally, in these animals, the half-life of SOD1 was longest in the CNS when compared with other tissues. Evaluation of this method in human subjects demonstrated successful incorporation of the isotope label in the CSF and confirmed that SOD1 is a long-lived protein in the CSF of healthy individuals. Together, the results of this study provide important insight into SOD1 kinetics and support application of this technique to the design and implementation of clinical trials that target long-lived CNS proteins. PMID:26075819

In vivo kinetic approach reveals slow SOD1 turnover in the CNS.

PubMed

Crisp, Matthew J; Mawuenyega, Kwasi G; Patterson, Bruce W; Reddy, Naveen C; Chott, Robert; Self, Wade K; Weihl, Conrad C; Jockel-Balsarotti, Jennifer; Varadhachary, Arun S; Bucelli, Robert C; Yarasheski, Kevin E; Bateman, Randall J; Miller, Timothy M

2015-07-01

Therapeutic strategies that target disease-associated transcripts are being developed for a variety of neurodegenerative syndromes. Protein levels change as a function of their half-life, a property that critically influences the timing and application of therapeutics. In addition, both protein kinetics and concentration may play important roles in neurodegeneration; therefore, it is essential to understand in vivo protein kinetics, including half-life. Here, we applied a stable isotope-labeling technique in combination with mass spectrometric detection and determined the in vivo kinetics of superoxide dismutase 1 (SOD1), mutation of which causes amyotrophic lateral sclerosis. Application of this method to human SOD1-expressing rats demonstrated that SOD1 is a long-lived protein, with a similar half-life in both the cerebral spinal fluid (CSF) and the CNS. Additionally, in these animals, the half-life of SOD1 was longest in the CNS when compared with other tissues. Evaluation of this method in human subjects demonstrated successful incorporation of the isotope label in the CSF and confirmed that SOD1 is a long-lived protein in the CSF of healthy individuals. Together, the results of this study provide important insight into SOD1 kinetics and support application of this technique to the design and implementation of clinical trials that target long-lived CNS proteins.

Stable isotope deltas: Tiny, yet robust signatures in nature

USGS Publications Warehouse

Brand, Willi A.; Coplen, Tyler B.

2012-01-01

Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg

Oxidation of tertiary amines by cytochrome p450-kinetic isotope effect as a spin-state reactivity probe.

PubMed

Li, Chunsen; Wu, Wei; Cho, Kyung-Bin; Shaik, Sason

2009-08-24

Two types of tertiary amine oxidation processes, namely, N-dealkylation and N-oxygenation, by compound I (Cpd I) of cytochrome P450 are studied theoretically using hybrid DFT calculations. All the calculations show that both N-dealkylation and N-oxygenation of trimethylamine (TMA) proceed preferentially from the low-spin (LS) state of Cpd I. Indeed, the computed kinetic isotope effects (KIEs) for the rate-controlling hydrogen abstraction step of dealkylation show that only the KIE(LS) fits the experimental datum, whereas the corresponding value for the high-spin (HS) process is much higher. These results second those published before for N,N-dimethylaniline (DMA), and as such, they further confirm the conclusion drawn then that KIEs can be a sensitive probe of spin state reactivity. The ferric-carbinolamine of TMA decomposes most likely in a non-enzymatic reaction since the Fe-O bond dissociation energy (BDE) is negative. The computational results reveal that in the reverse reaction of N-oxygenation, the N-oxide of aromatic amine can serve as a better oxygen donor than that of aliphatic amine to generate Cpd I. This capability of the N-oxo derivatives of aromatic amines to transfer oxygen to the heme, and thereby generate Cpd I, is in good accord with experimental data previously reported.

Geomagnetically trapped light isotopes observed with the detector NINA

NASA Astrophysics Data System (ADS)

Bakaldin, A.; Galper, A.; Koldashov, S.; Korotkov, M.; Leonov, A.; Mikhailov, V.; Murashov, A.; Voronov, S.; Bidoli, V.; Casolino, M.; De Pascale, M.; Furano, G.; Iannucci, A.; Morselli, A.; Picozza, P.; Sparvoli, R.; Boezio, M.; Bonvicini, V.; Cirami, R.; Vacchi, A.; Zampa, N.; Ambriola, M.; Bellotti, R.; Cafagna, F.; Ciacio, F.; Circella, M.; De Marzo, C.; Adriani, O.; Papini, P.; Spillantini, P.; Straulino, S.; Vannuccini, E.; Ricci, M.; Castellini, G.

2002-08-01

The detector New Instrument for Nuclear Analysis (NINA) aboard the satellite Resurs-01-N4 detected hydrogen and helium isotopes geomagnetically trapped, while crossing the South Atlantic Anomaly. Deuterium and tritium at L shell < 1.2 were unambiguously recognized. The 3He and 4He power law spectra, reconstructed at L shell = 1.2 and B < 0.22 G, have indices equal to 2.30 +/- 0.08 in the energy range 12-50 MeV nucleon-1 and 3.4 +/- 0.2 in 10-30 MeV nucleon-1, respectively. The measured 3He/4He ratio and the reconstructed deuterium profile as a function of L shell bring one to the conclusion that the main source of radiation belt light isotopes at Resurs altitudes (~800 km) and for energy greater than 10 MeV nucleon-1 is the interaction of trapped protons with residual atmospheric helium.

Activation Thermodynamics and H/D Kinetic Isotope Effect of the H ox to H red H + Transition in [FeFe] Hydrogenase

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

Ratzloff, Michael W.; Wilker, Molly B.; Mulder, David W.

Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here in this paper we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The H ox→H redH + reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol -1 and a ~2.5-foldmore » kinetic isotope effect. Overall these results support electron injection from CdSe into CaI involving F-clusters, and that the H ox→H redH + step of catalytic proton reduction in CaI proceeds by a proton-dependent process.« less

Activation Thermodynamics and H/D Kinetic Isotope Effect of the H ox to H red H + Transition in [FeFe] Hydrogenase

DOE PAGES

Ratzloff, Michael W.; Wilker, Molly B.; Mulder, David W.; ...

2017-08-29

Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here in this paper we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The H ox→H redH + reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol -1 and a ~2.5-foldmore » kinetic isotope effect. Overall these results support electron injection from CdSe into CaI involving F-clusters, and that the H ox→H redH + step of catalytic proton reduction in CaI proceeds by a proton-dependent process.« less

13C 18O clumping in speleothems: Observations from natural caves and precipitation experiments

NASA Astrophysics Data System (ADS)

Daëron, M.; Guo, W.; Eiler, J.; Genty, D.; Blamart, D.; Boch, R.; Drysdale, R.; Maire, R.; Wainer, K.; Zanchetta, G.

2011-06-01

The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ 18O. Interpreting speleothem δ 18O records in terms of absolute paleotemperatures and δ 18O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ47 (a geochemical variable reflecting the statistical overabundance of 13C 18O bonds in CO 2 evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ47 value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation. Here we report Δ47 values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ47 and heavier δ 18O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ47 disequilibrium and that of δ 18O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ 18O and Δ47 values, probably inherited from prior degassing within the cave system. In addition

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

PubMed

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

2016-03-01

Microbial degradation of phenol and cresols can occur under oxic and anoxic conditions by different degradation pathways. One recent technique to take insight into reaction mechanisms is compound-specific isotope analysis (CSIA). While enzymes and reaction mechanisms of several degradation pathways have been characterized in (bio)chemical studies, associated isotope fractionation patterns have been rarely reported, possibly due to constraints in current analytical methods. In this study, carbon enrichment factors and apparent kinetic isotope effects (AKIEc) of the initial steps of different aerobic and anaerobic phenol and cresols degradation pathways were analyzed by isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). Significant isotope fractionation was detected for aerobic ring hydroxylation, anoxic side chain hydroxylation, and anoxic fumarate addition, while anoxic carboxylation reactions produced small and inconsistent fractionation. The results suggest that several microbial degradation pathways of phenol and cresols are detectable in the environment by CSIA. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chromium isotope heterogeneity in the mantle

NASA Astrophysics Data System (ADS)

Xia, Jiuxing; Qin, Liping; Shen, Ji; Carlson, Richard W.; Ionov, Dmitri A.; Mock, Timothy D.

2017-04-01

To better constrain the Cr isotopic composition of the silicate Earth and to investigate potential Cr isotopic fractionation during high temperature geological processes, we analyzed the Cr isotopic composition of different types of mantle xenoliths from diverse geologic settings: fertile to refractory off-craton spinel and garnet peridotites, pyroxenite veins, metasomatised spinel lherzolites and associated basalts from central Mongolia, spinel lherzolites and harzburgites from North China, as well as cratonic spinel and garnet peridotites from Siberia and southern Africa. The δ53CrNIST 979 values of the peridotites range from - 0.51 ± 0.04 ‰ (2SD) to + 0.75 ± 0.05 ‰ (2SD). The results show a slight negative correlation between δ53Cr and Al2O3 and CaO contents for most mantle peridotites, which may imply Cr isotopic fractionation during partial melting of mantle peridotites. However, highly variable Cr isotopic compositions measured in Mongolian peridotites cannot be caused by partial melting alone. Instead, the wide range in Cr isotopic composition of these samples most likely reflects kinetic fractionation during melt percolation. Chemical diffusion during melt percolation resulted in light Cr isotopes preferably entering into the melt. Two spinel websterite veins from Mongolia have extremely light δ53Cr values of - 1.36 ± 0.04 ‰ and - 0.77 ± 0.06 ‰, respectively, which are the most negative Cr isotopic compositions yet reported for mantle-derived rocks. These two websterite veins may represent crystallization products from the isotopically light melt that may also metasomatize some peridotites in the area. The δ53Cr values of highly altered garnet peridotites from southern Africa vary from - 0.35 ± 0.04 ‰ (2SD) to + 0.12 ± 0.04 ‰ (2SD) and increase with increasing LOI (Loss on Ignition), reflecting a shift of δ53Cr to more positive values by secondary alteration. The Cr isotopic composition of the pristine, fertile upper mantle is

SAMPEX observations of energetic hydrogen isotopes in the inner zone

NASA Technical Reports Server (NTRS)

Looper, M. D.; Blake, J. B.; Cummings, J. R.; Mewaldt, R. A.

1996-01-01

We report observations of geomagnetically-trapped hydrogen isotopes at low altitudes, near the feet of field lines in the inner zone, made with the PET instrument aboard the SAMPEX satellite. We have mapped protons from 19 to 500 MeV, and have discovered a collocated belt of deuterons, which we have mapped from 18 to 58 MeV/nucleon. We found deuterium at about 1% of the level of the proton flux at the same energy per nucleon, and no tritium at energies of tens of MeV/nucleon with an upper limit of about 0.1% of the proton flux. Protons and deuterons showed similar time dependence, with fluxes approximately tripling from July 1992 to March 1996, and similar pitch-angle dependence. The high-L limits of the proton and deuteron belts as functions of energy were organized by rigidity, as was to be expected if these limits were set for both species by inability of particles to sustain adiabatic motion and stable trapping.

Compound- and position-specific carbon isotopic signatures of abiogenic hydrocarbons from on-land serpentinite-hosted Hakuba Happo hot spring in Japan

NASA Astrophysics Data System (ADS)

Suda, Konomi; Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro; Ueno, Yuichiro

2017-06-01

It has been proposed that serpentinite-hosted hydrothermal/hot spring systems played a significant role in the origin and early evolution of life on early Earth because abiogenic synthesis of organic compounds may accompany serpentinization. However, production mechanisms for apparently abiogenic hydrocarbons that have been observed in the ongoing serpentinizing systems are still poorly constrained. We report a new geochemical study of hydrocarbons in an on-land serpentinite-hosted hot spring in Hakuba Happo, Japan. We have conducted both compound-specific and position-specific carbon isotopic analyses of the observed C1 to C5 hydrocarbons. A positive linear relationship between the δ13C values and the inverse carbon number is found in C1 to C5 straight-chain alkanes in the Happo sample. This isotopic trend is consistent with a simple polymerization model developed in this study. Our model assumes that, for any particular alkane, all of the subsequently added carbons have the same isotopic composition, and those are depleted in 13C with respect to the first carbon in the growing carbon chain. The fit of this model suggests that Happo alkanes can be produced via polymerization from methane with a constant kinetic isotopic fractionation of -8.9 ± 1.0‰. A similar carbon isotopic relationship among alkanes has been observed in some serpentinite-hosted seafloor hydrothermal systems, indicating that the same process is responsible for the abiological hydrocarbon in general serpentinization fields, not only in the Hakuba Happo hot spring. Moreover, our model is also applicable to other potentially abiogenic natural gases and experimentally synthesized hydrocarbon products. For the first time, the intramolecular 13C composition of propane from a natural sample derived from a serpentinite-hosted system was determined. The intramolecular 13C distribution in propane shows the important potential to identify different polymerization mechanisms that cannot be discriminated

Wave-particle energy exchange directly observed in a kinetic Alfvén-branch wave

PubMed Central

Gershman, Daniel J.; F-Viñas, Adolfo; Dorelli, John C.; Boardsen, Scott A.; Avanov, Levon A.; Bellan, Paul M.; Schwartz, Steven J.; Lavraud, Benoit; Coffey, Victoria N.; Chandler, Michael O.; Saito, Yoshifumi; Paterson, William R.; Fuselier, Stephen A.; Ergun, Robert E.; Strangeway, Robert J.; Russell, Christopher T.; Giles, Barbara L.; Pollock, Craig J.; Torbert, Roy B.; Burch, James L.

2017-01-01

Alfvén waves are fundamental plasma wave modes that permeate the universe. At small kinetic scales, they provide a critical mechanism for the transfer of energy between electromagnetic fields and charged particles. These waves are important not only in planetary magnetospheres, heliospheres and astrophysical systems but also in laboratory plasma experiments and fusion reactors. Through measurement of charged particles and electromagnetic fields with NASA's Magnetospheric Multiscale (MMS) mission, we utilize Earth's magnetosphere as a plasma physics laboratory. Here we confirm the conservative energy exchange between the electromagnetic field fluctuations and the charged particles that comprise an undamped kinetic Alfvén wave. Electrons confined between adjacent wave peaks may have contributed to saturation of damping effects via nonlinear particle trapping. The investigation of these detailed wave dynamics has been unexplored territory in experimental plasma physics and is only recently enabled by high-resolution MMS observations. PMID:28361881

Wave-particle energy exchange directly observed in a kinetic Alfvén-branch wave.

PubMed

Gershman, Daniel J; F-Viñas, Adolfo; Dorelli, John C; Boardsen, Scott A; Avanov, Levon A; Bellan, Paul M; Schwartz, Steven J; Lavraud, Benoit; Coffey, Victoria N; Chandler, Michael O; Saito, Yoshifumi; Paterson, William R; Fuselier, Stephen A; Ergun, Robert E; Strangeway, Robert J; Russell, Christopher T; Giles, Barbara L; Pollock, Craig J; Torbert, Roy B; Burch, James L

2017-03-31

Alfvén waves are fundamental plasma wave modes that permeate the universe. At small kinetic scales, they provide a critical mechanism for the transfer of energy between electromagnetic fields and charged particles. These waves are important not only in planetary magnetospheres, heliospheres and astrophysical systems but also in laboratory plasma experiments and fusion reactors. Through measurement of charged particles and electromagnetic fields with NASA's Magnetospheric Multiscale (MMS) mission, we utilize Earth's magnetosphere as a plasma physics laboratory. Here we confirm the conservative energy exchange between the electromagnetic field fluctuations and the charged particles that comprise an undamped kinetic Alfvén wave. Electrons confined between adjacent wave peaks may have contributed to saturation of damping effects via nonlinear particle trapping. The investigation of these detailed wave dynamics has been unexplored territory in experimental plasma physics and is only recently enabled by high-resolution MMS observations.

Isotopic modeling of the sub-cloud evaporation effect in precipitation.

PubMed

Salamalikis, V; Argiriou, A A; Dotsika, E

2016-02-15

In dry and warm environments sub-cloud evaporation influences the falling raindrops modifying their final stable isotopic content. During their descent from the cloud base towards the ground surface, through the unsaturated atmosphere, hydrometeors are subjected to evaporation whereas the kinetic fractionation results to less depleted or enriched isotopic signatures compared to the initial isotopic composition of the raindrops at cloud base. Nowadays the development of Generalized Climate Models (GCMs) that include isotopic content calculation modules are of great interest for the isotopic tracing of the global hydrological cycle. Therefore the accurate description of the underlying processes affecting stable isotopic content can improve the performance of iso-GCMs. The aim of this study is to model the sub-cloud evaporation effect using a) mixing and b) numerical isotope evaporation models. The isotope-mixing evaporation model simulates the isotopic enrichment (difference between the ground and the cloud base isotopic composition of raindrops) in terms of raindrop size, ambient temperature and relative humidity (RH) at ground level. The isotopic enrichment (Δδ) varies linearly with the evaporated raindrops mass fraction of the raindrop resulting to higher values at drier atmospheres and for smaller raindrops. The relationship between Δδ and RH is described by a 'heat capacity' model providing high correlation coefficients for both isotopes (R(2)>80%) indicating that RH is an ideal indicator of the sub-cloud evaporation effect. Vertical distribution of stable isotopes in falling raindrops is also investigated using a numerical isotope-evaporation model. Temperature and humidity dependence of the vertical isotopic variation is clearly described by the numerical isotopic model showing an increase in the isotopic values with increasing temperature and decreasing RH. At an almost saturated atmosphere (RH=95%) sub-cloud evaporation is negligible and the isotopic

Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

NASA Astrophysics Data System (ADS)

Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

2018-02-01

The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at

Role of deuterium desorption kinetics on the thermionic emission properties of polycrystalline diamond films with respect to kinetic isotope effects

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

Paxton, W. F., E-mail: william.f.paxton@vanderbilt.edu; Howell, M.; Kang, W. P.

2014-06-21

The desorption kinetics of deuterium from polycrystalline chemical vapor deposited diamond films were characterized by monitoring the isothermal thermionic emission current behavior. The reaction was observed to follow a first-order trend as evidenced by the decay rate of the thermionic emission current over time which is in agreement with previously reported studies. However, an Arrhenius plot of the reaction rates at each tested temperature did not exhibit the typical linear behavior which appears to contradict past observations of the hydrogen (or deuterium) desorption reaction from diamond. This observed deviation from linearity, specifically at lower temperatures, has been attributed to non-classicalmore » processes. Though no known previous studies reported similar deviations, a reanalysis of the data obtained in the present study was performed to account for tunneling which appeared to add merit to this hypothesis. Additional investigations were performed by reevaluating previously reported data involving the desorption of hydrogen (as opposed to deuterium) from diamond which further indicated this reaction to be dominated by tunneling at the temperatures tested in this study (<775 °C). An activation energy of 3.19 eV and a pre-exponential constant of 2.3 × 10{sup 12} s{sup −1} were determined for the desorption reaction of deuterium from diamond which is in agreement with previously reported studies.« less

Constraining the role of iron in environmental nitrogen transformations. Dual stable isotope systematics of abiotic NO 2- reduction by Fe(II) and its production of N 2O

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

Johnston, David; Wankel, Scott David; Buchwald, Carolyn

Redox reactions involving nitrogen and iron have been shown to have important implications for mobilization of priority contaminants. Thus, an understanding of the linkages between their biogeochemical cycling is critical for predicting subsurface mobilization of radionuclides such as uranium. Despite mounting evidence for biogeochemical interactions between iron and nitrogen, our understanding of their environmental importance remains limited. Here we present an investigation of abiotic nitrite (NO 2 -) reduction by Fe(II) or ‘chemodenitrification,’ and its relevance to the production of nitrous oxide (N 2O), specifically focusing on dual (N and O) isotope systematics under a variety of environmentally relevant conditions.more » We observe a range of kinetic isotope effects that are regulated by reaction rates, with faster rates at higher pH (~8), higher concentrations of Fe(II) and in the presence of mineral surfaces. A clear non-linear relationship between rate constant and kinetic isotope effects of NO 2 - reduction was evident (with larger isotope effects at slower rates) and is interpreted as reflecting the dynamics of Fe(II)-N reaction intermediates. N and O isotopic composition of product N 2O also suggests a complex network of parallel and/or competing pathways. Our findings suggest that NO 2 - reduction by Fe(II) may represent an important abiotic source of environmental N 2O, especially in iron-rich environments experiencing dynamic redox variations. This study provides a multi-compound, multi-isotope framework for evaluating the environmental occurrence of abiotic NO 2 - reduction and N 2O formation, helping future studies constrain the relative roles of abiotic and biological N 2O production pathways.« less

Carbon kinetic isotope effect in the oxidation of methane by the hydroxyl radical

NASA Technical Reports Server (NTRS)

Cantrell, Christopher A.; Shetter, Richard E.; Mcdaniel, Anthony H.; Calvert, Jack G.; Davidson, James A.

1990-01-01

The reaction of the hydroxyl radical (HO) with the stable carbon isotopes of methane has been studied as a function of temperature from 273 to 353 K. The measued ratio of the rate coefficients for reaction with (C-12)H4 relative to (C-13)H4 (k12/k13) was 1.0054 (+ or - 0.0009 at the 95 percent confidence interval), independent of temperature within the precision of the measurement, over the range studied. The precision of the present value is much improved over that of previous studies, and this result provides important constraints on the current understanding of the cycling of methane through the atmosphere through the use of carbon isotope measurements.

Mechanistic Insights into RNA Transphosphorylation from Kinetic Isotope Effects and Linear Free Energy Relationships of Model Reactions

PubMed Central

Chen, Haoyuan; Giese, Timothy J.; Huang, Ming; Wong, Kin-Yiu; Harris, Michael E.; York, Darrin M.

2015-01-01

Phosphoryl transfer reactions are ubiquitous in biology, and the understanding of the mechanisms whereby these reactions are catalyzed by protein and RNA enzymes is central to reveal design principles for new therapeutics. Two of the most powerful experimental probes of chemical mechanism involve the analysis of linear free energy relations (LFERs) and the measurement of kinetic isotope effects (KIEs). These experimental data report directly on differences in bonding between the ground state and the rate-controlling transition state, which is the most critical point along the reaction free energy pathway. However, interpretation of LFER and KIE data in terms of transition state structure and bonding optimally requires the use of theoretical models. In this work, we apply density-functional calculations to determine KIEs for a series of phosphoryl transfer reactions of direct relevance to the 2’-O-transphosphorylation that leads to cleavage of the phosphodiester backbone of RNA. We first examine a well-studied series of phosphate and phosphorothioate mono-, di- and triesters that are useful as mechanistic probes and for which KIEs have been measured. Close agreement is demonstrated between the calculated and measured KIEs, establishing the reliability of our quantum model calculations. Next, we examine a series of RNA transesterification model reactions with a wide range of leaving groups in order to provide a direct connection between observed Brønsted coefficients and KIEs with the structure and bonding in the transition state. These relations can be used for prediction or to aid in the interpretation of experimental data for similar non-enzymatic and enzymatic reactions. Finally, we apply these relations to RNA phosphoryl transfer catalyzed by ribonuclease A, and demonstrate the reaction coordinate-KIE correlation is reasonably preserved. A prediction of the secondary deuterium KIE in this reaction is also provided. These results demonstrate the utility of

Mechanistic insights into RNA transphosphorylation from kinetic isotope effects and linear free energy relationships of model reactions.

PubMed

Chen, Haoyuan; Giese, Timothy J; Huang, Ming; Wong, Kin-Yiu; Harris, Michael E; York, Darrin M

2014-10-27

Phosphoryl transfer reactions are ubiquitous in biology and the understanding of the mechanisms whereby these reactions are catalyzed by protein and RNA enzymes is central to reveal design principles for new therapeutics. Two of the most powerful experimental probes of chemical mechanism involve the analysis of linear free energy relations (LFERs) and the measurement of kinetic isotope effects (KIEs). These experimental data report directly on differences in bonding between the ground state and the rate-controlling transition state, which is the most critical point along the reaction free energy pathway. However, interpretation of LFER and KIE data in terms of transition-state structure and bonding optimally requires the use of theoretical models. In this work, we apply density-functional calculations to determine KIEs for a series of phosphoryl transfer reactions of direct relevance to the 2'-O-transphosphorylation that leads to cleavage of the phosphodiester backbone of RNA. We first examine a well-studied series of phosphate and phosphorothioate mono-, di- and triesters that are useful as mechanistic probes and for which KIEs have been measured. Close agreement is demonstrated between the calculated and measured KIEs, establishing the reliability of our quantum model calculations. Next, we examine a series of RNA transesterification model reactions with a wide range of leaving groups in order to provide a direct connection between observed Brønsted coefficients and KIEs with the structure and bonding in the transition state. These relations can be used for prediction or to aid in the interpretation of experimental data for similar non-enzymatic and enzymatic reactions. Finally, we apply these relations to RNA phosphoryl transfer catalyzed by ribonuclease A, and demonstrate the reaction coordinate-KIE correlation is reasonably preserved. A prediction of the secondary deuterium KIE in this reaction is also provided. These results demonstrate the utility of

Insights into dechlorination of PCE and TCE from carbon isotope fractionation by vitamin B12

NASA Astrophysics Data System (ADS)

Slater, G.; Sherwood Lollar, B.; Lesage, S.; Brown, S.

2003-04-01

Reductive dechlorination of perchloroethylene (PCE) and trichloroethylene (TCE) by vitamin B12 is both a potential remediation technique and an analogue of the microbial reductive dechlorination reaction. Stable carbon isotopic analysis, an effective and powerful tool for the investigation and monitoring of contaminant remediation, was used to characterize the isotopic effects of reductive dechlorination of PCE and TCE by vitamin B12 in laboratory microcosms. 10 mg/L vitamin B12 degraded greater than 90% of an initial concentration of PCE of 20 mg/L. TCE, the primary product of PCE degradation, accounted for between 64 - 72% of the PCE degraded. In experiments with TCE, 147 mg/L vitamin B12 degraded greater than 90% of an initial concentration of TCE of 20 mg/L. Cis-dichloroethene (cDCE), the primary product of TCE degradation, accounted for between 30 - 35% of the TCE degraded. Degradation of both PCE and TCE exhibited first order kinetics. Strong isotopic fractionation of the reactant PCE and of the reactant TCE was observed over the course of degradation. This fractionation could be described by a Rayleigh model with enrichment factors between -16.5 ppm and -15.8 ppm for PCE, and -17.2 ppm and -16.6 ppm for TCE. Fractionation was similar in all four experiments, with a mean enrichment factor of -16.5 +/- 0.6 ppm. These large enrichment factors indicate that isotopic analysis can be used to assess the occurrence of dechlorination of PCE and TCE by vitamin B12 in remediation situations. Significantly, the Rayleigh model could be used to predict the isotopic compositions of the major products of the reaction as well as the reactant, notwithstanding the lack of complete mass balance observed between product and reactant. This evidence suggests that isotopic fractionation is taking place during complexation of the chlorinated ethenes to vitamin B12, as has been suggested for reductive dechlorination by zero valent iron. The differences between e for this reaction and

Nitrification in the euphotic zone as evidenced by nitrate dual isotopic composition: Observations from Monterey Bay, California

USGS Publications Warehouse

Wankel, Scott D.; Kendall, C.; Pennington, J.T.; Chavez, F.P.; Paytan, A.

2007-01-01

Coupled measurements of nitrate (NO3-), nitrogen (N), and oxygen (O) isotopic composition (??15NNO3 and ??18ONO3) were made in surface waters of Monterey Bay to investigate multiple N cycling processes occurring within surface waters. Profiles collected throughout the year at three sites exhibit a wide range of values, suggesting simultaneous and variable influence of both phytoplankton NO3- assimilation and nitrification within the euphotic zone. Specifically, increases ??18ONO3 were consistently greater than those in ??15NN03. A coupled isotope steady state box model was used to estimate the amount of NO3- supplied by nitrification in surface waters relative to that supplied from deeper water. The model highlights the importance of the branching reaction during ammonium (NH4+) consumption, in which NH4+ either serves as a substrate for regenerated production or for nitrification. Our observations indicate that a previously unrecognized proportion of nitrate-based productivity, on average 15 to 27%, is supported by nitrification in surface waters and should not be considered new production. This work also highlights the need for a better understanding of isotope effects of NH4+ oxidation, NH4+ assimilation, and NO4+ assimilation in marine environments.

Inverse kinetic solvent isotope effect in TiO2 photocatalytic dehalogenation of non-adsorbable aromatic halides: a proton-induced pathway.

PubMed

Chang, Wei; Sun, Chunyan; Pang, Xibin; Sheng, Hua; Li, Yue; Ji, Hongwei; Song, Wenjing; Chen, Chuncheng; Ma, Wanhong; Zhao, Jincai

2015-02-09

An efficient redox reaction between organic substrates in solution and photoinduced h(+) vb /e(-) cb on the surface of photocatalysts requires the substrates or solvent to be adsorbed onto the surface, and is consequentially marked by a normal kinetic solvent isotope effect (KSIE ≥ 1). Reported herein is a universal inverse KSIE (0.6-0.8 at 298 K) for the reductive dehalogenation of aromatic halides which cannot adsorb onto TiO2 in a [D0 ]methanol/[D4 ]methanol solution. Combined with in situ ATR-FTIR spectroscopy investigations, a previously unknown pathway for the transformation of these aromatic halides in TiO2 photocatalysis was identified: a proton adduct intermediate, induced by released H(+) /D(+) from solvent oxidation, accompanies a change in hybridization from sp(2) to sp(3) at a carbon atom of the aromatic halides. The protonation event leads these aromatic halides to adsorb onto the TiO2 surface and an ET reaction to form dehalogenated products follows. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Origin of uranium isotope variations in early solar nebula condensates.

PubMed

Tissot, François L H; Dauphas, Nicolas; Grossman, Lawrence

2016-03-01

High-temperature condensates found in meteorites display uranium isotopic variations ((235)U/(238)U), which complicate dating the solar system's formation and whose origin remains mysterious. It is possible that these variations are due to the decay of the short-lived radionuclide (247)Cm (t 1/2 = 15.6 My) into (235)U, but they could also be due to uranium kinetic isotopic fractionation during condensation. We report uranium isotope measurements of meteoritic refractory inclusions that reveal excesses of (235)U reaching ~+6% relative to average solar system composition, which can only be due to the decay of (247)Cm. This allows us to constrain the (247)Cm/(235)U ratio at solar system formation to (1.1 ± 0.3) × 10(-4). This value provides new clues on the universality of the nucleosynthetic r-process of rapid neutron capture.

Investigation of isotope effects of ozone as a function of temperature

NASA Astrophysics Data System (ADS)

McMahon, Daniel J.

Ozone is an important oxidizer in the atmosphere and plays a crucial role as a cleanser, removing various compounds such NOx and SOx. It also is intriguing to those that study stable isotopes as it has a unique signature found in no other oxygen containing molecule. Ozone is observed to fractionate mass independently, which means it does not follow the typical delta 17O /delta18O = 0.52 ratio expected for molecules enriched with 17O and 18O. The magnitude of ozone's mass independent enrichment has been studied in laboratory experiments and atmospheric observations but its explanation is still incomplete. Symmetry of the isotopically substituted ozone is postulated to be the source of mass independent enrichment and this thesis will build on that explanation to examine the magnitude of isotopic enrichment as a function of temperature. Understanding of the kinetics of ozone formation has come a long way from early predictions of enrichments >200‰ However, while our ability to accurately model ozone's bulk isotopic enrichment has improved to include separate rates for the formation of asymmetric and symmetric ozone, rate experiments are sparse for 17O and of low precision. To improve our understanding of ozone's enrichment, this study presents a temperature dependent enrichment experiment and series of models to predict asymmetric mass independent fractionation. This also served to examine ozone's enrichment in the troposphere by using an open flow experimental setup which is in contrast to previous works examining ozone enrichment in a closed system. Our experimental observations show that under tropospheric conditions, ozone should have delta17O ≈ 75‰, delta18O ≈ 80‰, and delta 17O ≈ 33‰. The models were able to match experimental values, often within 1‰, and with minimal assumptions, predict asymmetric ozone to have delta17O=47.5‰. This value is important as ozone transfers its terminal atom to species it oxidizes and will be the starting point to

Increase in soil stable carbon isotope ratio relates to loss of organic carbon: results from five long-term bare fallow experiments.

PubMed

Menichetti, Lorenzo; Houot, Sabine; van Oort, Folkert; Kätterer, Thomas; Christensen, Bent T; Chenu, Claire; Barré, Pierre; Vasilyeva, Nadezda A; Ekblad, Alf

2015-03-01

Changes in the (12)C/(13)C ratio (expressed as δ(13)C) of soil organic C (SOC) has been observed over long time scales and with depth in soil profiles. The changes are ascribed to the different reaction kinetics of (12)C and (13)C isotopes and the different isotopic composition of various SOC pool components. However, experimental verification of the subtle isotopic shifts associated with SOC turnover under field conditions is scarce. We determined δ(13)C and SOC in soil sampled during 1929-2009 in the Ap-horizon of five European long-term bare fallow experiments kept without C inputs for 27-80 years and covering a latitudinal range of 11°. The bare fallow soils lost 33-65% of their initial SOC content and showed a mean annual δ(13)C increase of 0.008-0.024‰. The (13)C enrichment could be related empirically to SOC losses by a Rayleigh distillation equation. A more complex mechanistic relationship was also examined. The overall estimate of the fractionation coefficient (ε) was -1.2 ± 0.3‰. This coefficient represents an important input to studies of long-term SOC dynamics in agricultural soils that are based on variations in (13)C natural abundance. The variance of ε may be ascribed to site characteristics not disclosed in our study, but the very similar kinetics measured across our five experimental sites suggest that overall site-specific factors (including climate) had a marginal influence and that it may be possible to isolate a general mechanism causing the enrichment, although pre-fallow land use may have some impact on isotope abundance and fractionation.

Wave-particle energy exchange directly observed in a kinetic Alfvén-branch wave

DOE PAGES

Gershman, Daniel J.; F-Viñas, Adolfo; Dorelli, John C.; ...

2017-03-31

Alfvén waves are fundamental plasma wave modes that permeate the universe. At small kinetic scales, they provide a critical mechanism for the transfer of energy between electromagnetic fields and charged particles. These waves are important not only in planetary magnetospheres, heliospheres and astrophysical systems but also in laboratory plasma experiments and fusion reactors. Through measurement of charged particles and electromagnetic fields with NASA’s Magnetospheric Multiscale (MMS) mission, we utilize Earth’s magnetosphere as a plasma physics laboratory. Here we confirm the conservative energy exchange between the electromagnetic field fluctuations and the charged particles that comprise an undamped kinetic Alfvén wave. Electronsmore » confined between adjacent wave peaks may have contributed to saturation of damping effects via nonlinear particle trapping. As a result, the investigation of these detailed wave dynamics has been unexplored territory in experimental plasma physics and is only recently enabled by high-resolution MMS observations.« less

Wave-particle energy exchange directly observed in a kinetic Alfvén-branch wave

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

Gershman, Daniel J.; F-Viñas, Adolfo; Dorelli, John C.

Alfvén waves are fundamental plasma wave modes that permeate the universe. At small kinetic scales, they provide a critical mechanism for the transfer of energy between electromagnetic fields and charged particles. These waves are important not only in planetary magnetospheres, heliospheres and astrophysical systems but also in laboratory plasma experiments and fusion reactors. Through measurement of charged particles and electromagnetic fields with NASA’s Magnetospheric Multiscale (MMS) mission, we utilize Earth’s magnetosphere as a plasma physics laboratory. Here we confirm the conservative energy exchange between the electromagnetic field fluctuations and the charged particles that comprise an undamped kinetic Alfvén wave. Electronsmore » confined between adjacent wave peaks may have contributed to saturation of damping effects via nonlinear particle trapping. As a result, the investigation of these detailed wave dynamics has been unexplored territory in experimental plasma physics and is only recently enabled by high-resolution MMS observations.« less

An efficient climate model with water isotope physics: NEEMY

NASA Astrophysics Data System (ADS)

Hu, J.; Emile-Geay, J.

2015-12-01

This work describes the development of an isotope-enabled atmosphere-ocean global climate model, NEEMY. This is a model of intermediate complexity, which can run 100 model years in 30 hours using 33 CPUs. The atmospheric component is the SPEEDY-IER (Molteni et al. 2003; Dee et al. 2015a), which is a water isotope-enabled (with equilibrium and kinetic fractionation schemes in precipitation, evaporation and soil moisture) simplified atmospheric general circulation model, with T30 horizontal resolution and 8 vertical layers. The oceanic component is NEMO 3.4 (Madec 2008), a state-of-the-art oceanic model (~2° horizontal resolution and 31 vertical layers) with an oceanic isotope module (a passive tracer scheme). A 1000-year control run shows that NEEMY is stable and its energy is conserved. The mean state is comparable to that of CMIP3-era CGCMs, though much cheaper to run. Atmospheric teleconnections such as the NAO and PNA are simulated very well. NEEMY also simulates the oceanic meridional overturning circulation well. The tropical climate variability is weaker than observations, and the climatology exhibits a double ITCZ problem despite bias corrections. The standard deviation of the monthly mean Nino3.4 index is 0.61K, compared to 0.91K in observations (Reynolds et al. 2002). We document similarities and differences with a close cousin, SPEEDY-NEMO (Kucharski et al. 2015). With its fast speed and relatively complete physical processes, NEEMY is suitable for paleoclimate studies ; we will present some forced simulations of the past millennium and their use in forward-modeling climate proxies, via proxy system models (PSMs, Dee et al 2015b). References Dee, S., D. Noone, N. Buenning, J. Emile-Geay, and Y. Zhou, 2015a: SPEEDY-IER: A fast atmospheric GCM with water isotope physics. J. Geophys. Res. Atmos., 120: 73-91. doi:10.1002/2014JD022194. Dee, S. G., J. Emile-Geay, M. N. Evans, Allam, A., D. M. Thompson, and E. J. Steig, 2015b: PRYSM: an open-source framework

Kinetic Deuterium Isotope Effects in the Combustion of Nitramine Propellants

DTIC Science & Technology

1988-07-01

Transition state 33 7. Possible Isotope Effects in HMX -d., and RDX -d. 38 8. HMX synthesis 48 9. a- HMX 52 10. V- HMX 53 11. RDX Synthesis 55 12 Pellet...configuration of the transition state in HMX decomposition could be rade. KDIE in RDX Decomposition The KDIE values obtained for RDX decomposition -ire...0.13 HMX -d 8 60.3 35.7 8.6 0.10 RDX 61.2 36.7 11.8 0.10 RDX -de 53.7 22.8 8.3 0.11 DSC EXPERIMENTS The 13 -+ 8 phase

Technical note: An inverse method to relate organic carbon reactivity to isotope composition from serial oxidation

NASA Astrophysics Data System (ADS)

Hemingway, Jordon D.; Rothman, Daniel H.; Rosengard, Sarah Z.; Galy, Valier V.

2017-11-01

Serial oxidation coupled with stable carbon and radiocarbon analysis of sequentially evolved CO2 is a promising method to characterize the relationship between organic carbon (OC) chemical composition, source, and residence time in the environment. However, observed decay profiles depend on experimental conditions and oxidation pathway. It is therefore necessary to properly assess serial oxidation kinetics before utilizing decay profiles as a measure of OC reactivity. We present a regularized inverse method to estimate the distribution of OC activation energy (E), a proxy for bond strength, using serial oxidation. Here, we apply this method to ramped temperature pyrolysis or oxidation (RPO) analysis but note that this approach is broadly applicable to any serial oxidation technique. RPO analysis directly compares thermal reactivity to isotope composition by determining the E range for OC decaying within each temperature interval over which CO2 is collected. By analyzing a decarbonated test sample at multiple masses and oven ramp rates, we show that OC decay during RPO analysis follows a superposition of parallel first-order kinetics and that resulting E distributions are independent of experimental conditions. We therefore propose the E distribution as a novel proxy to describe OC thermal reactivity and suggest that E vs. isotope relationships can provide new insight into the compositional controls on OC source and residence time.

Laboratory determination of the carbon kinetic isotope effects (KIEs) for reactions of methyl halides with various nucleophiles in solution

USGS Publications Warehouse

Baesman, S.M.; Miller, L.G.

2005-01-01

Large carbon kinetic isotope effects (KIEs) were measured for reactions of methyl bromide (MeBr), methyl chloride (MeCl), and methyl iodide (MeI) with various nucleophiles at 287 and 306 K in aqueous solutions. Rates of reaction of MeBr and MeI with H2O (neutral hydrolysis) or Cl- (halide substitution) were consistent with previous measurements. Hydrolysis rates increased with increasing temperature or pH (base hydrolysis). KIEs for hydrolysis were 51 ?? 6??? for MeBr and 38 ?? 8??? for MeI. Rates of halide substitution increased with increasing temperature and greater reactivity of the attacking nucleophile, with the fastest reaction being that of MeI with Br-. KIEs for halide substitution were independent of temperature but varied with the reactant methyl halide and the attacking nucleophile. KIEs were similar for MeBr substitution with Cl- and MeCl substitution with Br- (57 ?? 5 and 60 ?? 9??? respectively). The KIE for halide exchange of MeI was lower overall (33 ?? 8??? and was greater for substitution with Br- (46 ?? 6???) than with Cl- (29 ?? 6???). ?? Springer Science + Business Media, Inc. 2005.

A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

NASA Astrophysics Data System (ADS)

Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

2014-12-01

Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar

Isotope fractionation by multicomponent diffusion (Invited)

NASA Astrophysics Data System (ADS)

Watkins, J. M.; Liang, Y.; Richter, F. M.; Ryerson, F. J.; DePaolo, D. J.

2013-12-01

the rate of CaO diffusion; in A-B, the total variation is 2.5‰ whereas in D-E it is only 1.3‰. The diffusion of isotopes in a multicomponent system is modeled using a new expression for the isotope-specific diffusive flux that includes self diffusion terms in addition to the multicomponent chemical diffusion matrix. Kinetic theory predicts a mass dependence on isotopic mobility, i.e., self diffusivity, but it is unknown whether or how the mass dependence on self diffusivity translates into a mass dependence on chemical diffusion coefficients. The new experimental results allow us to assess several empirical expressions relating the self diffusivity and its mass dependence to the elements of the diffusion matrix and their mass dependence. Several plausible theoretical treatments can fit the data equally well. We are currently at the stage where experiments are guiding the theoretical treatment of the isotope fractionation by diffusion problem, underscoring the importance of experiments for aiding interpretations of isotopic variations in nature.

A novel methodology to investigate isotopic biosignatures

NASA Astrophysics Data System (ADS)

Horner, T. J.; Lee, R. B. Y.; Henderson, G. M.; Rickaby, R. E. M.

2012-04-01

An enduring goal of trace metal isotopic studies of Earth History is to find isotopic 'fingerprints' of life or of life's individual physiochemical processes. Generally, such signatures are sought by relating an isotopic effect observed in controlled laboratory conditions or a well-characterized environment to a more complex system or the geological record. However, such an approach is ultimately limited because life exerts numerous isotopic fractionations on any one element so it is hard to dissect the resultant net fractionation into its individual components. Further, different organisms, often with the same apparent cellular function, can express different isotopic fractionation factors. We have used a novel method to investigate the isotopic fractionation associated with a single physiological process-enzyme specific isotopic fractionation. We selected Cd isotopes since only one biological use of Cd is known, CdCA (a Cd/Zn carbonic anhydrase from the coastal diatom T. Weissflogii). Thus, our investigation can also inform the long standing mystery as to why this generally toxic element appears to have a nutrient-like dissolved isotopic and concentration profile in the oceans. We used the pET-15b plasmid to insert the CdCA gene into the E. coli genome. There is no known biochemical function for Cd in E. coli, making it an ideal vector for studying distinct physiological processes within a single organism. The uptake of Cd and associated isotopic fractionation was determined for both normal cells and those expressing CdCA. It was found that whole cells always exhibited a preference for the light isotopes of Cd, regardless of the expression of CdCA; adsorption of Cd to cell surfaces was not seen to cause isotopic fractionation. However, the cleaning procedure employed exerted a strong control on the observed isotopic composition of cells. Using existing protein purification techniques, we measured the Cd isotopic composition of different subcellular fractions of E

Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary

NASA Astrophysics Data System (ADS)

Chen, Mengli; Boyle, Edward A.; Lee, Jong-Mi; Nurhati, Intan; Zurbrick, Cheryl; Switzer, Adam D.; Carrasco, Gonzalo

2016-11-01

Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary

PubMed Central

Chen, Mengli; Lee, Jong-Mi; Nurhati, Intan; Zurbrick, Cheryl; Switzer, Adam D.; Carrasco, Gonzalo

2016-01-01

Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element

Experimental identification of mechanisms controlling calcium isotopic fractionations by the vegetation.

NASA Astrophysics Data System (ADS)

Cobert, Florian; Schimtt, Anne-Désirée.; Bourgeade, Pascale; Stille, Peter; Chabaux, François; Badot, Pierre-Marie; Jaegler, Thomas

2010-05-01

This study aims to better understand the role of vegetation on the Ca cycle at the level of the critical zone of the Earth, in order to specify the mechanisms controlling the Ca absorption by plants at the rock/plant interface. To do this, we performed experiments using hydroponic plant cultures in a way that we could control the co-occuring geochemical and physiological process and determine the impact of the nutritive solution on the Ca cycle within plants. A dicotyledon and calcicole plant with rapid growth, the French bean (Phaseolus vulgaris L.), has been chosen to have access to one complete growth cycle. Several experiments have been conducted with two Ca concentrations, 6 (L) and 60 (H) ppm and two pH values (4 and 6) in the nutritive solution, for which the Ca concentration was maintained constant, so its Ca content is considered as infinite. A second experiment (non infinite L6) allowed Ca depletion in the solution through time; therefore, response effects on the Ca isotopic signatures in the plant organs and in the nutritive solution were observed. We determined Ca concentrations and isotopic ratios in the nutritive solution and in different organs (main roots, secondary roots, old and young stems, old and young leaves and fruits) at two different growth stages (10 days and 6 weeks). Preliminary results show that: (1) the roots (main and secondary) were enriched in the light isotope (40Ca) compared to the nutritive solution, and leaves were enriched in the heavy isotope (44Ca) compared to stems. These results are in accord with previously published field studies (Wigand et al., 2005; Page et al., 2008; Cenki-Tok et al., 2009; Holmden and Bélanger, 2010). Leaves and secondary roots were however enriched in the heavy isotope (44Ca) compared to bean pods, stems and main roots. These results could be related to kinetic fractionation processes occurring either during the Ca root uptake, or during the Ca transport within the plant, or physiological mechanisms

Molybdenum isotope systematics in subduction zones

NASA Astrophysics Data System (ADS)

König, Stephan; Wille, Martin; Voegelin, Andrea; Schoenberg, Ronny

2016-08-01

This study presents Mo isotope data for arc lavas from different subduction zones that range between δ 98 / 95 Mo = - 0.72 and + 0.07 ‰. Heaviest isotope values are observed for the most slab fluid dominated samples. Isotopically lighter signatures are related to increasing relevance of terrigenous sediment subduction and sediment melt components. Our observation complements previous conclusions that an isotopically heavy Mo fluid flux likely mirrors selective incorporation of isotopically light Mo in secondary minerals within the subducting slab. Analogue to this interpretation, low δ 98 / 95 Mo flux that coincides with terrigenous sediment subduction and sediment melting cannot be simply related to a recycled input signature. Instead, breakdown of the controlling secondary minerals during sediment melting may release the light component and lead to decreasing δ 98 / 95 Mo influx into subarc mantle sources. The natural range between slab dehydration and hydrous sediment melting may thus cause a large spread of δ 98 / 95 Mo in global subduction zone magmas.

Partitioning and kinetics of methylmercury among organs in captive mink (Neovison vison): A stable isotope tracer study.

PubMed

Evans, R Douglas; Hickie, Brendan; Rouvinen-Watt, Kirsti; Wang, Wei

2016-03-01

Despite the importance of methylmercury (MeHg) as a neurotoxin, we have relatively few good data on partitioning and kinetics of MeHg among organs, particularly across the blood-brain barrier, for mammals that consume large quantities of fish. The objective of this study was to determine the partition coefficients between blood and brain, liver and kidney and fur for MeHg under steady-state conditions and to measure the half-lives for MeHg in these organs. Captive mink (Neovison vison) were fed a diet enriched with two stable isotopes of Hg, Me(199)Hg and Me(201)Hg for a period of 60 days. After a period of 10 days the diet was changed to contain only Me(201)Hg so that, between days 10 and 60, we were able to measure both uptake and elimination rates from blood, brain, liver kidney and fur. Liver and kidney response was very rapid, closely following changes in blood concentrations but there was a small lag time between peak blood concentrations and peak brain concentrations. Half-lives for MeHg were 15.4, 10.2 and 13.4 days for brain, liver and kidney, respectively. There was no measurable conversion of the MeHg to inorganic Hg (IHg) in the brain over the 60 day period, unlike in liver and kidney. Copyright © 2016 Elsevier B.V. All rights reserved.

Thermal equilibration of iron meteorite and pallasite parent bodies recorded at the mineral scale by Fe and Ni isotope systematics

NASA Astrophysics Data System (ADS)

Chernonozhkin, Stepan M.; Weyrauch, Mona; Goderis, Steven; Oeser, Martin; McKibbin, Seann J.; Horn, Ingo; Hecht, Lutz; Weyer, Stefan; Claeys, Philippe; Vanhaecke, Frank

2017-11-01

In this work, a femtosecond laser ablation (LA) system coupled to a multi-collector inductively coupled plasma-mass spectrometer (fs-LA-MC-ICP-MS) was used to obtain laterally resolved (30-80 μm), high-precision combined Ni and Fe stable isotope ratio data for a variety of mineral phases (olivine, kamacite, taenite, schreibersite and troilite) composing main group pallasites (PMG) and iron meteorites. The stable isotopic signatures of Fe and Ni at the mineral scale, in combination with the factors governing the kinetic or equilibrium isotope fractionation processes, are used to interpret the thermal histories of small differentiated asteroidal bodies. As Fe isotopic zoning is only barely resolvable within the internal precision level of the isotope ratio measurements within a single olivine in Esquel PMG, the isotopically lighter olivine core relative to the rim (Δ56/54Ferim-core = 0.059‰) suggests that the olivines were largely thermally equilibrated. The observed hint of an isotopic and concentration gradient for Fe of crudely similar width is interpreted here to reflect Fe loss from olivine in the process of partial reduction of the olivine rim. The ranges of the determined Fe and Ni isotopic signatures of troilite (δ56/54Fe of -0.66 to -0.09‰) and schreibersite (δ56/54Fe of -0.48 to -0.09‰, and δ62/60Ni of -0.64 to +0.29‰) may result from thermal equilibration. Schreibersite and troilite likely remained in equilibrium with their enclosing metal to temperatures significantly below their point of crystallization. The Ni isotopic signatures of bulk metal and schreibersite correlate negatively, with isotopically lighter Ni in the metal of PMGs and isotopically heavier Ni in the metal of the iron meteorites analyzed. As such, the light Ni isotopic signatures previously observed in PMG metal relative to chondrites may not result from heterogeneity in the Solar Nebula, but rather reflect fractionation in the metal-schreibersite system. Comparison between

Entrainment and cloud evaporation deduced from the stable isotope chemistry of clouds during ORACLES

NASA Astrophysics Data System (ADS)

Noone, D.; Henze, D.; Rainwater, B.; Toohey, D. W.

2017-12-01

The magnitude of the influence of biomass burning aerosols on cloud and rain processes is controlled by a series of processes which are difficult to measure directly. A consequence of this limitation is the emergence of significant uncertainty in the representation of cloud-aerosol interactions in models and the resulting cloud radiative forcing. Interaction between cloud and the regional atmosphere causes evaporation, and the rate of evaporation at cloud top is controlled in part by entrainment of air from above which exposes saturated cloud air to drier conditions. Similarly, the size of cloud droplets also controls evaporation rates, which in turn is linked to the abundance of condensation nuclei. To quantify the dependence of cloud properties on biomass burning aerosols the dynamic relationship between evaporation, drop size and entrainment on aerosol state, is evaluated for stratiform clouds in the southeast Atlantic Ocean. These clouds are seasonally exposed to biomass burning plumes from agricultural fires in southern Africa. Measurements of the stable isotope ratios of cloud water and total water are used to deduce the disequilibrium responsible for evaporation within clouds. Disequilibrium is identified by the relationship between hydrogen and oxygen isotope ratios of water vapor and cloud water in and near clouds. To obtain the needed information, a custom-built, dual inlet system was deployed alongside isotopic gas analyzers on the NASA Orion aircraft as part of the Observations of Aerosols above Clouds and their Interactions (ORACLES) campaign. The sampling system obtains both total water and cloud liquid content for the population of droplets above 7 micrometer diameter. The thermodynamic modeling required to convert the observed equilibrium and kinetic isotopic is linked to evaporation and entrainment is described, and the performance of the measurement system is discussed.

Tracking the weathering of basalts on Mars using lithium isotope fractionation models

PubMed Central

Losa‐Adams, Elisabeth; Gil‐Lozano, Carolina; Gago‐Duport, Luis; Uceda, Esther R.; Squyres, Steven W.; Rodríguez, J. Alexis P.; Davila, Alfonso F.; McKay, Christopher P.

2015-01-01

Abstract Lithium (Li), the lightest of the alkali elements, has geochemical properties that include high aqueous solubility (Li is the most fluid mobile element) and high relative abundance in basalt‐forming minerals (values ranking between 0.2 and 12 ppm). Li isotopes are particularly subject to fractionation because the two stable isotopes of lithium—7Li and 6Li—have a large relative mass difference (∼15%) that results in significant fractionation between water and solid phases. The extent of Li isotope fractionation during aqueous alteration of basalt depends on the dissolution rate of primary minerals—the source of Li—and on the precipitation kinetics, leading to formation of secondary phases. Consequently, a detailed analysis of Li isotopic ratios in both solution and secondary mineral lattices could provide clues about past Martian weathering conditions, including weathering extent, temperature, pH, supersaturation, and evaporation rate of the initial solutions in contact with basalt rocks. In this paper, we discuss ways in which Martian aqueous processes could have lead to Li isotope fractionation. We show that Li isotopic data obtained by future exploration of Mars could be relevant to highlighting different processes of Li isotopic fractionation in the past, and therefore to understanding basalt weathering and environmental conditions early in the planet's history. PMID:27642264

Stable Isotope Systematics of Martian Perchlorate

NASA Astrophysics Data System (ADS)

Martin, P.; Farley, K. A.; Archer, D., Jr.; Atreya, S. K.; Conrad, P. G.; Eigenbrode, J. L.; Fairen, A.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Malespin, C.; Ming, D. W.; Navarro-Gonzalez, R.; Sutter, B.

2015-12-01

Chlorine isotopic compositions in HCl released during evolved gas analysis (EGA) runs have been detected by the Sample Analysis at Mars (SAM) instrument on the Curiosity rover ranging from approximately -9‰ to -50‰ δ37Cl, with two spatially and isotopically separated groups of samples averaging -15‰ and -45‰. These extremely low values are the first such detection of any known natural material; common terrestrial values very rarely exceed ±5‰, and the most extreme isotopic signature yet detected elsewhere in the solar system are values of around +24‰ on the Moon. The only other known location in the solar system with large negative chlorine isotopes is the Atacama Desert, where perchlorate with -14‰ δ37Cl has been detected. The Atacama perchlorate has unusual Δ17O signatures associated with it, indicating a formation mechanism involving O3, which suggests an atmospheric origin of the perchlorate and associated large isotopic anomalies. Identification of non-zero positive Δ17O signatures in the O2 released during EGA runs would allow definitive evidence for a similar process having occurred on Mars. Perchlorate is thought to be the most likely source of HCl in EGA runs due to the simultaneous onset of O2 release. If perchlorate is indeed the HCl source, atmospheric chemistry could be responsible for the observed isotopic anomalies, with variable extents of perchlorate production producing the isotopic variability. However, chloride salts have also been observed to release HCl upon heating; if the timing of O2 release is merely coincidental, observed HCl could be coming from chlorides. At thermodynamic equilibrium, the fractionation factor of perchlorate reduction is 0.93, meaning that differing amounts of post-deposition reduction of isotopically normal perchlorate to chloride could account for the highly variable Cl isotopes. Additionally, post-deposition reduction could account for the difference between the two Cl isotopic groups if perchlorate

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

NASA Technical Reports Server (NTRS)

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

1988-01-01

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

Importance of depth and intensity of convection on the isotopic composition of water vapor as seen from IASI and TES δD observations

NASA Astrophysics Data System (ADS)

Lacour, Jean-Lionel; Risi, Camille; Worden, John; Clerbaux, Cathy; Coheur, Pierre-François

2018-01-01

We use tropical observations of the water vapor isotopic composition, derived from IASI and TES spaceborne measurements, to show that the isotopic composition of water vapor in the free troposphere is sensitive to both the depth and the intensity of convection. We find that for any given precipitation intensity, vapor associated with deep convection is isotopically depleted relative to vapor associated with shallow convection. The intensity of precipitation also plays a role as for any given depth of convection, the relative enrichment of water vapor decreases as the intensity of precipitation increases. Shallow convection, via the uplifting of enriched boundary layer air into the free troposphere and the convective detrainment, enriches the free troposphere. In contrast, deep convection is associated with processes that deplete the water vapor in the free troposphere, such as rain re-evaporation. The results of this study allow for a better identification of the parameters controlling the isotopic composition of the free troposphere and indicate that the isotopic composition of water vapor can be used to evaluate the relative contributions of shallow and deep convection in global models.

Effect of Zn2+ binding and enzyme active site on the transition state for RNA 2′-O-transphosphorylation interpreted through kinetic isotope effects

PubMed Central

Chen, Haoyuan; Piccirilli, Joseph A.; Harris, Michael E.; York, Darrin M.

2016-01-01

Divalent metal ions, due to their ability to stabilize high concentrations of negative charge, are important for RNA folding and catalysis. Detailed models derived from the structures and kinetics of enzymes and from computational simulations have been developed. However, in most cases the specific catalytic modes involving metal ions and their mechanistic roles and effects on transition state structures remains controversial. Valuable information about the nature of the transition state is provided by measurement of kinetic isotope effects (KIEs). However, KIEs reflect changes in all bond vibrational modes that differ between the ground state and transition state. QM calculations are therefore essential for developing structural models of the transition state and evaluating mechanistic alternatives. Herein, we present computational models for Zn2+ binding to RNA 2′O-transphosphorylation reaction models that aid in the interpretation of KIE experiments. Different Zn2+ binding modes produce distinct KIE signatures, and one binding mode involving two zinc ions is in close agreement with KIEs measured for non-enzymatic catalysis by Zn2+ aquo ions alone. Interestingly, the KIE signatures in this specific model are also very close to those in RNase A catalysis. These results allow a quantitative connection to be made between experimental KIE measurements and transition state structure and bonding, and provide insight into RNA 2′O-transphosphorylation reactions catalyzed by metal ions and enzymes. PMID:25812974

Kinetic-freezing and unfreezing of local-region fluctuations in a glass structure observed by heat capacity hysteresis.

PubMed

Aji, D P B; Johari, G P

2015-06-07

Fluctuations confined to local regions in the structure of a glass are observed as the Johari-Goldstein (JG) relaxation. Properties of these regions and their atomic configuration are currently studied by relaxation techniques, by electron microscopy, and by high-energy X-ray scattering and extended x-ray absorption fine structure methods. One expects that these fluctuations (i) would kinetically freeze on cooling a glass, and the temperature coefficient of its enthalpy, dH/dT, would consequently show a gradual decrease with decrease in T, (ii) would kinetically unfreeze on heating the glass toward the glass-liquid transition temperature, Tg, and dH/dT would gradually increase, and (iii) there would be a thermal hysteresis indicating the time and temperature dependence of the enthalpy. Since no such features have been found, thermodynamic consequences of these fluctuations are debated. After searching for these features in glasses of different types, we found it in one of the most stable metal alloy glasses of composition Pd40Ni10Cu30P20. On cooling from its Tg, dH/dT decreased along a broad sigmoid-shape path as local-region fluctuations kinetically froze. On heating thereafter, dH/dT increased along a similar path as these fluctuations unfroze, and there is hysteresis in the cooling and heating paths, similar to that observed in the Tg-endotherm range. After eliminating other interpretations, we conclude that local-region fluctuations seen as the JG relaxation in the non-equilibrium state of a glass contribute to its entropy, and we suggest conditions under which such fluctuations may be observed.

Carbon isotopes in biological carbonates: Respiration and photosynthesis

USGS Publications Warehouse

McConnaughey, T.A.; Burdett, J.; Whelan, J.F.; Paull, C.K.

1997-01-01

Respired carbon dioxide is an important constituent in the carbonates of most air breathing animals but is much less important in the carbonates of most aquatic animals. This difference is illustrated using carbon isotope data from freshwater and terrestrial snails, ahermatypic corals, and chemoautotrophic and methanotrophic pelecypods. Literature data from fish otoliths and bird and mammal shell and bone carbonates are also considered. Environmental CO2/O2 ratios appear to be the major controlling variable. Atmospheric CO2/O2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO2 in the course of obtaining O2. Tissue CO2 therefore, does not isotopically equilibrate with environmental CO2 as thoroughly in air breathers as in aquatic animals, and this is reflected in skeletal carbonates. Animals having efficient oxygen transport systems, such as vertebrates, also accumulate more respired CO2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO2 uptake is several times faster than respiratory CO2 release. Photosynthesis, therefore, affects skeletal ??13C more strongly than does respiration. Corals also illustrate how "metabolic" effects on skeletal isotopic composition can be estimated, despite the presence of much larger "kinetic" isotope effects. Copyright ?? 1997 Elsevier Science Ltd.

Carbon isotopes in biological carbonates: Respiration and photosynthesis

NASA Astrophysics Data System (ADS)

McConnaughey, Ted A.; Burdett, Jim; Whelan, Joseph F.; Paull, Charles K.

1997-02-01

Respired carbon dioxide is an important constituent in the carbonates of most air breathing animals but is much less important in the carbonates of most aquatic animals. This difference is illustrated using carbon isotope data from freshwater and terrestrial snails, ahermatypic corals, and chemoautotrophic and methanotrophic pelecypods. Literature data from fish otoliths and bird and mammal shell and bone carbonates are also considered. Environmental CO 2/O 2 ratios appear to be the major controlling variable. Atmospheric CO 2/O 2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO 2 in the course of obtaining 0 2. Tissue CO 2 therefore, does not isotopically equilibrate with environmental CO 2 as thoroughly in air breathers as in aquatic animals, and this is reflected in skeletal carbonates. Animals having efficient oxygen transport systems, such as vertebrates, also accumulate more respired CO 2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO 2 uptake is several times faster than respiratory CO 2 release. Photosynthesis, therefore, affects skeletal δ13C more strongly than does respiration. Corals also illustrate how "metabolic" effects on skeletal isotopic composition can be estimated, despite the presence of much larger "kinetic" isotope effects.

Oxygen isotope exchange kinetics of mineral pairs in closed and open systems: Applications to problems of hydrothermal alteration of igneous rocks and Precambrian iron formations

USGS Publications Warehouse

Gregory, R.T.; Criss, R.E.; Taylor, H.P.

1989-01-01

heat-balance constraints, we can utilize the 18O 16O data on natural mineral assemblages to calculate the kinetic rate constants (k's) and the effective diffusion constants (D's) for mineral-H2O exchange: these calculated values (kqtz ??? 10-14, kfeld ??? 10-13-10-12) agree with experimental determinations of such constants. In nature, once the driving force or energy source for the external infiltrating fluid phase is removed, the disequilibrium mineral-pair arrays will either: (1) remain "frozen" in their existing state, if the temperatures are low enough, or (2) re-equilibrate along specific closed-system exchange vectors determined solely by the temperature path and the mineral modal proportions. Thus, modal mineralogical information is a particularly important parameter in both the open- and closed-system scenarios, and should in general always be reported in stable-isotopic studies of mineral assemblages. These concepts are applied to an analysis of 18O 16O systematics of gabbros (Plagioclase-clinopyroxene and plagioclase-amphibole pairs), granitic plutons (quartz-feldspar pairs), and Precambrian siliceous iron formations (quartz-magnetite pairs). In all these examples, striking regularities are observed on ??-?? and ??-?? plots, but we point out that ??-?? plots have many advantages over their equivalent ??-?? diagrams, as the latter are more susceptible to misinterpretation. Using the equations developed in this study, these regularities can be interpreted to give semiquantitative information on the exchange histories of these rocks subsequent to their formation. In particular, we present a new interpretation indicating that Precambrian cherty iron formations have in general undergone a complex fluid exchange history in which the iron oxide (magnetite precursor?) has exchanged much faster with low-temperature (< 400??C) fluids than has the relatively inert quartz. ?? 1989.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Mass Independent Fractionation of Cadmium Isotopes During Thermal Ionization

NASA Astrophysics Data System (ADS)

Abouchami, W.; Galer, S. J.; Feldmann, H.; Schmitt, A. D.

2008-12-01

explained by appealing to the nuclear spin (and magnetic moment) of odd nuclei alone. The "magnetic isotope effect" is a consequence of hyperfine coupling, in which an electron interacts with a nucleus of non-zero magnetic moment - i.e. one that has an odd number of nucleons (Turro, 1983; Buchachenko, 1995, 2001). This is purely a kinetic phenomenon in which the life-time, and thus the outcome, of reaction transition states is altered by the hyperfine splitting present in atoms with odd nuclei. The mechanism by which silica gel activator enhances the thermal ionization of elements such as Cd, Pb and Zn has been outlined by Kessinger and Delmore (2002). The first step involves the in-situ reduction of Cd2+ ions to Cd metal in the molten silica gel-phosphoric acid glass. It is most likely in this step - whereby two electrons are added - that a suitably long-lived transition state exists, during which the magnetic isotope effect enhances (or inhibits) reduction of masses 111 and 113 to metal species compared to those of even isotopes of Cd. The resulting "odd" and "even" populations of Cd-metal in the molten silica gel then cannot be related simply in terms of MDF. Overall, the magnetic isotope effect provides the best explanation of the MIF effects observed for Pb, Cd and Zn during thermal ionization with silica gel activator, and, probably, why the measured fractionation is always biased towards light isotopes.

An observational constraint on stomatal function in forests: evaluating coupled carbon and water vapor exchange with carbon isotopes in the Community Land Model (CLM4.5)

NASA Astrophysics Data System (ADS)

Raczka, Brett; Duarte, Henrique F.; Koven, Charles D.; Ricciuto, Daniel; Thornton, Peter E.; Lin, John C.; Bowling, David R.

2016-09-01

Land surface models are useful tools to quantify contemporary and future climate impact on terrestrial carbon cycle processes, provided they can be appropriately constrained and tested with observations. Stable carbon isotopes of CO2 offer the potential to improve model representation of the coupled carbon and water cycles because they are strongly influenced by stomatal function. Recently, a representation of stable carbon isotope discrimination was incorporated into the Community Land Model component of the Community Earth System Model. Here, we tested the model's capability to simulate whole-forest isotope discrimination in a subalpine conifer forest at Niwot Ridge, Colorado, USA. We distinguished between isotopic behavior in response to a decrease of δ13C within atmospheric CO2 (Suess effect) vs. photosynthetic discrimination (Δcanopy), by creating a site-customized atmospheric CO2 and δ13C of CO2 time series. We implemented a seasonally varying Vcmax model calibration that best matched site observations of net CO2 carbon exchange, latent heat exchange, and biomass. The model accurately simulated observed δ13C of needle and stem tissue, but underestimated the δ13C of bulk soil carbon by 1-2 ‰. The model overestimated the multiyear (2006-2012) average Δcanopy relative to prior data-based estimates by 2-4 ‰. The amplitude of the average seasonal cycle of Δcanopy (i.e., higher in spring/fall as compared to summer) was correctly modeled but only when using a revised, fully coupled An - gs (net assimilation rate, stomatal conductance) version of the model in contrast to the partially coupled An - gs version used in the default model. The model attributed most of the seasonal variation in discrimination to An, whereas interannual variation in simulated Δcanopy during the summer months was driven by stomatal response to vapor pressure deficit (VPD). The model simulated a 10 % increase in both photosynthetic discrimination and water-use efficiency (WUE

An observational constraint on stomatal function in forests: evaluating coupled carbon and water vapor exchange with carbon isotopes in the Community Land Model (CLM4.5)

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

Raczka, Brett; Duarte, Henrique F.; Koven, Charles D.

Land surface models are useful tools to quantify contemporary and future climate impact on terrestrial carbon cycle processes, provided they can be appropriately constrained and tested with observations. Stable carbon isotopes of CO 2 offer the potential to improve model representation of the coupled carbon and water cycles because they are strongly influenced by stomatal function. Recently, a representation of stable carbon isotope discrimination was incorporated into the Community Land Model component of the Community Earth System Model. Here, we tested the model's capability to simulate whole-forest isotope discrimination in a subalpine conifer forest at Niwot Ridge, Colorado, USA. Wemore » distinguished between isotopic behavior in response to a decrease of δ 13C within atmospheric CO 2 (Suess effect) vs. photosynthetic discrimination (Δ canopy), by creating a site-customized atmospheric CO 2 and δ 13C of CO 2 time series. We implemented a seasonally varying V cmax model calibration that best matched site observations of net CO 2 carbon exchange, latent heat exchange, and biomass. The model accurately simulated observed δ 13C of needle and stem tissue, but underestimated the δ 13C of bulk soil carbon by 1–2 ‰. The model overestimated the multiyear (2006–2012) average Δ canopy relative to prior data-based estimates by 2–4 ‰. The amplitude of the average seasonal cycle of Δ canopy (i.e., higher in spring/fall as compared to summer) was correctly modeled but only when using a revised, fully coupled A n- g s (net assimilation rate, stomatal conductance) version of the model in contrast to the partially coupled A n- g s version used in the default model. The model attributed most of the seasonal variation in discrimination to A n, whereas interannual variation in simulated Δ canopy during the summer months was driven by stomatal response to vapor pressure deficit (VPD). The model simulated a 10 % increase in both photosynthetic discrimination and

An observational constraint on stomatal function in forests: evaluating coupled carbon and water vapor exchange with carbon isotopes in the Community Land Model (CLM4.5)

DOE PAGES

Raczka, Brett; Duarte, Henrique F.; Koven, Charles D.; ...

2016-09-19

Land surface models are useful tools to quantify contemporary and future climate impact on terrestrial carbon cycle processes, provided they can be appropriately constrained and tested with observations. Stable carbon isotopes of CO 2 offer the potential to improve model representation of the coupled carbon and water cycles because they are strongly influenced by stomatal function. Recently, a representation of stable carbon isotope discrimination was incorporated into the Community Land Model component of the Community Earth System Model. Here, we tested the model's capability to simulate whole-forest isotope discrimination in a subalpine conifer forest at Niwot Ridge, Colorado, USA. Wemore » distinguished between isotopic behavior in response to a decrease of δ 13C within atmospheric CO 2 (Suess effect) vs. photosynthetic discrimination (Δ canopy), by creating a site-customized atmospheric CO 2 and δ 13C of CO 2 time series. We implemented a seasonally varying V cmax model calibration that best matched site observations of net CO 2 carbon exchange, latent heat exchange, and biomass. The model accurately simulated observed δ 13C of needle and stem tissue, but underestimated the δ 13C of bulk soil carbon by 1–2 ‰. The model overestimated the multiyear (2006–2012) average Δ canopy relative to prior data-based estimates by 2–4 ‰. The amplitude of the average seasonal cycle of Δ canopy (i.e., higher in spring/fall as compared to summer) was correctly modeled but only when using a revised, fully coupled A n- g s (net assimilation rate, stomatal conductance) version of the model in contrast to the partially coupled A n- g s version used in the default model. The model attributed most of the seasonal variation in discrimination to A n, whereas interannual variation in simulated Δ canopy during the summer months was driven by stomatal response to vapor pressure deficit (VPD). The model simulated a 10 % increase in both photosynthetic discrimination and

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

USGS Publications Warehouse

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

2015-01-01

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

Bacterial versus human thymidylate synthase: Kinetics and functionality

PubMed Central

Strutzenberg, Timothy S.; Ghosh, Ananda K.; Iqbal, Tasnia; Kohen, Amnon

2018-01-01

Thymidylate Synthase (TSase) is a highly conserved enzyme that catalyzes the production of the DNA building block thymidylate. Structurally, functionally and mechanistically, bacterial and mammalian TSases share remarkable similarities. Because of this closeness, bacterial enzymes have long been used as model systems for human TSase. Furthermore, while TSase inhibitors have long served as chemotherapeutic drugs, no TSase inhibitor serves as an antibiotic. Despite their high resemblance, the mammalian TSases are distinct in a few known aspects, such as having a N-terminal tail and two insertions in the primary sequence and active/inactive conformations. Here, we aim to comprehensively characterize human (hs) TSase and delineate its contrasts and the similarities to the well-studied Escherichia coli (ec) TSase. We found that, in contrast to ecTSase, Mg2+ does not enhance reaction rates for hsTSase. The temperature dependence of intrinsic kinetic isotope effects (KIEs), on the other hand, suggests that Mg2+ has little or no impact on the transition state of hydride transfer in either enzyme, and that the transition state for the hydride transfer in hsTSase is looser than in ecTSase. Additionally, the substrates’ binding order is strictly ordered for ecTSase but slightly less ordered for hsTSase. The observed kinetic and functional differences between bacterial and human enzymes may aid in the development of antibiotic drugs with reduced toxicity. PMID:29715278

Modelling and intepreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2012-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, droplet size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

Modelling and interpreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2013-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed-phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters, including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, particle size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

The protonation state around TyrD/TyrD• in photosystem II is reflected in its biphasic oxidation kinetics.

PubMed

Sjöholm, Johannes; Ho, Felix; Ahmadova, Nigar; Brinkert, Katharina; Hammarström, Leif; Mamedov, Fikret; Styring, Stenbjörn

2017-02-01

The tyrosine residue D2-Tyr160 (Tyr D ) in photosystem II (PSII) can be oxidized through charge equilibrium with the oxygen evolving complex in PSII. The kinetics of the electron transfer from Tyr D has been followed using time-resolved EPR spectroscopy after triggering the oxidation of pre-reduced Tyr D by a short laser flash. After its oxidation Tyr D is observed as a neutral radical (Tyr D • ) indicating that the oxidation is coupled to a deprotonation event. The redox state of Tyr D was reported to be determined by the two water positions identified in the crystal structure of PSII [Saito et al. (2013) Proc. Natl. Acad. Sci. USA 110, 7690]. To assess the mechanism of the proton coupled electron transfer of Tyr D the oxidation kinetics has been followed in the presence of deuterated buffers, thereby resolving the kinetic isotope effect (KIE) of Tyr D oxidation at different H/D concentrations. Two kinetic phases of Tyr D oxidation - the fast phase (msec-sec time range) and the slow phase (tens of seconds time range) were resolved as was previously reported [Vass and Styring (1991) Biochemistry 30, 830]. In the presence of deuterated buffers the kinetics was significantly slower compared to normal buffers. Furthermore, although the kinetics were faster at both high pH and pD values the observed KIE was found to be similar (~2.4) over the whole pL range investigated. We assign the fast and slow oxidation phases to two populations of PSII centers with different water positions, proximal and distal respectively, and discuss possible deprotonation events in the vicinity of Tyr D . Copyright © 2016 Elsevier B.V. All rights reserved.

Oxygen and chlorine isotopic fractionation during perchlorate biodegradation: Laboratory results and implications for forensics and natural attenuation studies

USGS Publications Warehouse

Sturchio, N.C.; Böhlke, J.K.; Beloso, Abelardo D.; Streger, S.H.; Heraty, L.J.; Hatzinger, P.B.

2007-01-01

Perchlorate is a widespread environmental contaminant having both anthropogenic and natural sources. Stable isotope ratios of O and Cl in a given sample of perchlorate may be used to distinguish its source(s). Isotopic ratios may also be useful for identifying the extent of biodegradation of perchlorate, which is critical for assessing natural attenuation of this contaminant in groundwater. For this approach to be useful, however, the kinetic isotopic fractionations of O and Cl during perchlorate biodegradation must first be determined as a function of environmental variables such as temperature and bacterial species. A laboratory study was performed in which the O and Cl isotope ratios of perchlorate were monitored as a function of degradation by two separate bacterial strains (Azospira suillum JPLRND and Dechlorospirillum sp. FBR2) at both 10??C and 22??C with acetate as the electron donor. Perchlorate was completely reduced by both strains within 280 h at 22??C and 615 h at 10??C. Measured values of isotopic fractionation factors were ??18O = -36.6 to -29.0??? and ??37Cl = -14.5 to -11.5???, and these showed no apparent systematic variation with either temperature or bacterial strain. An experiment using 18O-enriched water (??18O = +198???) gave results indistinguishable from those observed in the isotopically normal water (??18O = -8.1???) used in the other experiments, indicating negligible isotope exchange between perchlorate and water during biodegradation. The fractionation factor ratio ??18O/??37Cl was nearly invariant in all experiments at 2.50 ?? 0.04. These data indicate that isotope ratio analysis will be useful for documenting perchlorate biodegradation in soils and groundwater. The establishment of a microbial fractionation factor ratio (??18O/??37Cl) also has significant implications for forensic studies. ?? 2007 American Chemical Society.

Stable Carbon Isotope Fractionation during Bacterial Acetylene Fermentation: Potential for Life Detection in Hydrocarbon-Rich Volatiles of Icy Planet(oid)s.

PubMed

Miller, Laurence G; Baesman, Shaun M; Oremland, Ronald S

2015-11-01

We report the first study of stable carbon isotope fractionation during microbial fermentation of acetylene (C2H2) in sediments, sediment enrichments, and bacterial cultures. Kinetic isotope effects (KIEs) averaged 3.7 ± 0.5‰ for slurries prepared with sediment collected at an intertidal mudflat in San Francisco Bay and 2.7 ± 0.2‰ for a pure culture of Pelobacter sp. isolated from these sediments. A similar KIE of 1.8 ± 0.7‰ was obtained for methanogenic enrichments derived from sediment collected at freshwater Searsville Lake, California. However, C2H2 uptake by a highly enriched mixed culture (strain SV7) obtained from Searsville Lake sediments resulted in a larger KIE of 9.0 ± 0.7‰. These are modest KIEs when compared with fractionation observed during oxidation of C1 compounds such as methane and methyl halides but are comparable to results obtained with other C2 compounds. These observations may be useful in distinguishing biologically active processes operating at distant locales in the Solar System where C2H2 is present. These locales include the surface of Saturn's largest moon Titan and the vaporous water- and hydrocarbon-rich jets emanating from Enceladus. Acetylene-Fermentation-Isotope fractionation-Enceladus-Life detection.

Properties of the surface snow in Princess Elizabeth Land, East Antarctica - climate and non-climate dependent variability of the surface mass balance and stable water isotopic composition

NASA Astrophysics Data System (ADS)

Vladimirova, D.; Ekaykin, A.; Lipenkov, V.; Popov, S. V.; Petit, J. R.; Masson-Delmotte, V.

2017-12-01

Glaciological and meteorological observations conducted during the past four decades in Princess Elizabeth Land, East Antarctica, are compiled. The database is used to investigate spatial patterns of surface snow isotopic composition and surface mass balance, including detailed information near subglacial lake Vostok. We show diverse relationships between snow isotopic composition and surface temperature. In the most inland part (elevation 3200-3400 m a.s.l.), surface snow isotopic composition varies independently from surface temperature, and is closely related to the distance to the open water source (with a slope of 0.98±0.17 ‰ per 100 km). Surface mass balance values are higher along the ice sheet slope, and relatively evenly distributed inland. The minimum values of snow isotopic composition and surface mass balance are identified in an area XX km southwestward from Vostok station. The spatial distribution of deuterium excess delineates regions influenced by the Indian Ocean and Pacific Ocean air masses, with Vostok area being situated close to their boundary. Anomalously high deuterium excess values are observed near Dome A, suggesting high kinetic fractionation for its moisture source, or specifically high post-deposition artifacts. The dataset is available for further studies such as the assessment of skills of general circulation or regional atmospheric models, and the search for the oldest ice.

Sulfur isotopic and proteomic profiles of sulfate reducers grown under differential steady-states

NASA Astrophysics Data System (ADS)

Leavitt, W.; Venceslau, S.; Waldbauer, J.; Smith, D. A.; Boidi, F. J.; Bradley, A. S.

2016-12-01

Microbial sulfate reducers (MSR) drive the Earth's biogeochemical sulfur cycle. At the heart of this energy metabolism is a cascade of redox transformations coupling organic carbon and/or hydrogen oxidation to the dissimilatory reduction of sulfate to sulfide. The product sulfide is depleted in the heavier isotopes of sulfur, relative to the reactant sulfate, consistent with a normal kinetic isotope effect. However, the magnitude of the net fractionation during MSR can range over a range of 70 permil, consistent with a multi-step set of reactions. This range in MSR fractionation has been shown to mainly depend on: i) the cell-specific sulfate reduction rate (csSRR), and ii) the ambient sulfate concentration. However, the fractionation under identical conditions differs among strains (Bradley et al. 2016. Geobio), and so must also be mediated by strain-specific processes, such as the nature and quantity of individual proteins involved in sulfate reduction, electron transport, and growth. In recent work we have examined the influence of electron donor, electron acceptor, and co-limitation under controlled steady-state culture conditions in order better inform models of MSR isotope fractionation, and the physiological and isotopic response to differential environmental forcings (e.g. Leavitt et al. (2013) PNAS). Recent models of the fractionation response to MSR rate (c.f. Bradley 2016; Wing & Halevy, 2016) make specific predictions for the responses of the cellular metabolome and proteome. Here we compare the steady-state S-isotopic fractionation and proteome of `fast' versus `slow' grown D. vulgaris, using replicate chemostats under electron donor limitation. We observe clear and statistically robust changes in some key central MSR and C-metabolism enzymes, though a host of the critical energy-transfer enzymes show no statistically discernable change. We discuss these results in light of recent theoretical advances and their relevance to modern and ancient

Microbes: Agents of Isotopic Change

NASA Astrophysics Data System (ADS)

Fogel, M. L.

2012-12-01

Microbes drive many of the important oxidation and reduction reactions on Earth; digest almost all forms of organic matter; and can serve as both primary and secondary producers. Because of their versatile biochemistry and physiology, they impart unique isotopic signatures to organic and inorganic materials, which have proven to be key measurements for understanding elemental cycling now and throughout Earth's history. Understanding microbial isotope fractionations in laboratory experiments has been important for interpreting isotopic patterns measured in natural settings. In fact, the pairing of simple experiment with natural observation has been the pathway for interpreting the fingerprint of microbial processes in ancient sediments and rocks. Examples of how key experiments have explained stable isotope fractionations by microbes and advanced the field of microbial ecology will be presented. Learning the isotopic signatures of Earth's microbes is a valuable exercise for predicting what isotopic signatures could be displayed by possible extant or extinct extraterrestrial life. Given the potential for discovery on Mars, Enceladus, and other solar system bodies, new methods and techniques for pinpointing what is unique about microbial isotope signatures is particularly relevant.

The carbon isotope biogeochemistry of methane production in anoxic sediments. 1: Field observations

NASA Technical Reports Server (NTRS)

Blair, Neal E.; Boehme, Susan E.; Carter, W. Dale, Jr.

1993-01-01

The natural abundance C-13/C-12 ratio of methane from anoxic marine and freshwater sediments in temperate climates varies seasonally. Carbon isotopic measurements of the methanogenic precursors, acetate and dissolved inorganic carbon, from the marine sediments of Cape Lookout Bight, North Carolina were used to determine the sources of the seasonal variations at that site. Movement of the methanogenic zone over an isotopic gradient within the dissolved CO2 pool appears to be the dominant control of the methane C-13/C-12 ratio from February to June. The onset of acetoclastic methane-production is a second important controlling process during mid-summer. An apparent temperature dependence on the fractionation factor for CO2-reduction may have a significant influence on the isotopic composition of methane throughout the year.

Stable carbon isotope ratios in atmospheric methane and some of its sources

NASA Technical Reports Server (NTRS)

Tyler, Stanley C.

1986-01-01

Ratios of C-13/C-12 have been measured in atmospheric methane and in methane collected from sites and biota that represent potentially large sources of atmospheric methane. These include temperate marshes (about -48 percent to about -54 percent), landfills (about -51 percent to about -55 percent), and the first reported values for any species of termite (-72.8 + or - 3.1 percent for Reticulitermes tibialis and -57.3 + or - 1.6 percent for Zootermopsis angusticollis). Numbers in parentheses are delta C-13 values with respect to PDB (Peedee belemnite) carbonate. Most methane sources reported thus far are depleted in C-13 with respect to atmospheric methane (-47.0 + or - 0.3 percent). Individual sources of methane should have C-13/C-12 ratios characteristic of mechanisms of CH4 formation and consumption prior to release to the atmosphere. The mass-weighted average isotopic composition of all sources should equal the mean C-13 of atmospheric methane, corrected for a kinetic isotope effect in the OH attack of CH4. Assuming the kinetic isotope effect to be small (about -3.0 percent correction to -47.0), as in the literature, the new values given here for termite methane do not help to explain the apparent discrepancy between C-13/C-12 ratios of the known CH4 sources and that of atmospheric CH4.

Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3 (-) and SO3 (2-) in Aqueous Solution.

PubMed

Wang, Qian; Zhao, Hong Yan; Man, Wai-Lun; Lam, William W Y; Lau, Kai-Chung; Lau, Tai-Chu

2016-07-25

The kinetics and mechanism of the reaction of S(IV) (SO3 (2-) +HSO3 (-) ) with a ruthenium(VI) nitrido complex, [(L)Ru(VI) (N)(OH2 )](+) (Ru(VI) N, L=N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion), in aqueous acidic solutions are reported. The kinetic results are consistent with parallel pathways involving oxidation of HSO3 (-) and SO3 (2-) by Ru(VI) N. A deuterium isotope effect of 4.7 is observed in the HSO3 (-) pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N-S bond formation (partial N-atom transfer) between Ru(VI) N and HSO3 (-) and H(+) transfer from HSO3 (-) to a H2 O molecule. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparing potential-driven DBI-inspired non-minimal kinetic coupling (Dinkic) inflation with observational data

NASA Astrophysics Data System (ADS)

Chen, Jun; Hou, Wenjie; Qiu, Taotao; Hou, Defu

2018-04-01

In our previous work [1], a new kind of inflation model was proposed, which has the interesting property that its perturbation equation of motion gets a correction of k 4, due to the non-linearity of the kinetic term. Nonetheless, the scale-invariance of the power spectrum remains valid, both in large-k and small-k limits. In this paper, we investigate in detail the spectral index, the index running and the tensor/scalar ratio in this model, especially in the potential-driven case, and compare the results with the current PLANCK/BICEP observational data. We also discuss the tensor spectrum in this case, which is expected to be tested by future observations of primordial gravitational waves. Supported by NSFC (11405069, 11653002, 11735007, 111375070)

Laser Spectroscopic Study on Oxygen Isotope Effects in Ozone Surface Decomposition

NASA Astrophysics Data System (ADS)

Minissale, Marco; Boursier, Corinne; Elandaloussi, Hadj; Te, Yao; Jeseck, Pascal; Rouille, Christian; Zanon-Willette, Thomas; Janssen, Christof

2016-04-01

The isotope kinetics of ozone formation in the Chapman reaction [1] O + O2 + M → O3 + M (1) provides the primary example for a chemically induced oxygen isotope anomaly and is associated with large [2] and mass independent [3] oxygen isotope enrichments in the product molecule, linked to a symmetry selection in the ozone formation kinetics [4-5]. The isotopic composition of ozone and its transfer to other molecules is a powerful tracer in the atmospheric and biogeochemical sciences [6] and serves as a primary model for a possible explanation of the oxygen isotopic heterogeneity in the Solar system [7-8]. Recently, the isotope fractionation in the photolytic decomposition process O3 + hν → O2 + O (2) using visible light has been studied in detail [9-10]. Much less is currently known about the isotope fractionation in the dry deposition or in the gas phase thermal decomposition of ozone O3 + M → O2 + O +M. (3) Here we report on first spectroscopic studies of non-photolytic ozone decomposition using a cw-quantum cascade laser at 9.5 μm. The concentration of individual ozone isotopomers (16O3,16O16O17O, and 16O17O16O) in a teflon coated reaction cell is followed in real time at temperatures between 25 and 150 °C. Observed ozone decay rates depend on homogeneous (reaction (3)) processes in the gas phase and on heterogeneous reactions on the wall. A preliminary analysis reveals agreement with currently recommended ozone decay rates in the gas phase and the absence of a large symmetry selection in the surface decomposition process, indicating the absence of a mass independent fractionation effect. This result is in agreement with previous mass spectrometer (MS) studies on heterogeneous ozone formation on pyrex [11], but contradicts an earlier MS study [12] on ozone surface decomposition on pyrex and quartz. Implications for atmospheric chemistry will be discussed. [1] Morton, J., Barnes, J., Schueler, B. and Mauersberger, K. J. Geophys. Res. 95, 901 - 907 (1990

Kinetic-freezing and unfreezing of local-region fluctuations in a glass structure observed by heat capacity hysteresis

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

Aji, D. P. B.; Johari, G. P., E-mail: joharig@mcmaster.ca

Fluctuations confined to local regions in the structure of a glass are observed as the Johari-Goldstein (JG) relaxation. Properties of these regions and their atomic configuration are currently studied by relaxation techniques, by electron microscopy, and by high-energy X-ray scattering and extended x-ray absorption fine structure methods. One expects that these fluctuations (i) would kinetically freeze on cooling a glass, and the temperature coefficient of its enthalpy, dH/dT, would consequently show a gradual decrease with decrease in T, (ii) would kinetically unfreeze on heating the glass toward the glass-liquid transition temperature, T{sub g}, and dH/dT would gradually increase, and (iii)more » there would be a thermal hysteresis indicating the time and temperature dependence of the enthalpy. Since no such features have been found, thermodynamic consequences of these fluctuations are debated. After searching for these features in glasses of different types, we found it in one of the most stable metal alloy glasses of composition Pd{sub 40}Ni{sub 10}Cu{sub 30}P{sub 20}. On cooling from its T{sub g}, dH/dT decreased along a broad sigmoid-shape path as local-region fluctuations kinetically froze. On heating thereafter, dH/dT increased along a similar path as these fluctuations unfroze, and there is hysteresis in the cooling and heating paths, similar to that observed in the T{sub g}-endotherm range. After eliminating other interpretations, we conclude that local-region fluctuations seen as the JG relaxation in the non-equilibrium state of a glass contribute to its entropy, and we suggest conditions under which such fluctuations may be observed.« less

Characterization of calcium isotopes in natural and synthetic barite

USGS Publications Warehouse

Griffith, E.M.; Schauble, E.A.; Bullen, T.D.; Paytan, A.

2008-01-01

The mineral barite (BaSO4) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (??44/40Ca = -2.01 ?? 0.15???) but are different from hydrothermal and cold seep barite samples (??44/40Ca = -4.13 to -2.72???). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, ??44/40Ca = -3.42 to -2.40???. Temperature, saturation state, a Ba2 + / a SO42 -, and aCa2+/aBa2+ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower 44Ca/40Ca than calcite, by -9??? at 0 ??C and -8??? at 25 ??C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower ??44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca2+ substitution for Ba2+ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca2+ and other elements in inorganic and biogenic minerals. ?? 2008 Elsevier Ltd.

Environmental isotope investigation for the identification of source of springs observed in the hillock on the left flank of Gollaleru Earthen Dam, Andhra Pradesh, India

NASA Astrophysics Data System (ADS)

Noble, J.; Arzoo Ansari, MD

2017-07-01

A hydrometric, hydrochemical and environmental isotopic study was conducted to identify the source and origin of observed springs on the foot of the hillock abutting the left flank of the Gollaleru earthen dam, Nandyal, Andhra Pradesh, India. Water samples (springs, reservoir water and groundwater) in and around the dam area were collected and analyzed for environmental isotopes (δ^{18}!O, δ2H and 3H) and hydrochemistry. Reservoir level, spring discharges and physico-chemical parameters (temperature, electrical conductivity, pH, etc.) were monitored in-situ. Isotopic results indicated that the source of springs is from the Owk reservoir and groundwater contribution to the springs is insignificant. Based on hydrometric observations, it is inferred that the springs might be originated from the reservoir level of 209 m amsl. It is found that the lower spring discharges were derived from diffuse sources (seepage) which could be a mixture of reservoir water and the groundwater, while the relatively higher spring discharges were resulted from concentrated sources (leakage) from the reservoir. Thus, the study portraits the usefulness of isotope techniques in understanding the dam seepage/leakage related problems.

Study on strontium isotope abundance-ratio measurements by using a 13-MeV proton beam

NASA Astrophysics Data System (ADS)

Jeong, Cheol-Ki; Jang, Han; Lee, Goung-Jin

2016-09-01

The Rb-Sr dating method is used in dating Paleozoic and Precambrian rocks. This method measures the 87Rb and the 87Sr concentrations by using thermal ionization mass spectrometry (TIMS) [J. Hefne et al., Inter. J. Phys. Sci. 3(1), 28 (2008)]. In addition, it calculates the initial 87Sr/86Sr ratio to increase the reliability of Rb-Sr dating. In this study, the 87Sr/86Sr ratio was measured by using a 13-MeV proton accelerator. Proton kinetic energies are in the range of tens of megaelectronvolts, and protons have large absorption cross-sections for ( p, n) reactions with most substances. After absorbing a proton with such a high kinetic energy, an element is converted into a nuclide with its atomic number increased by one via nuclear transmutation. These nuclides usually have short half-lives and return to the original state through radioactive decay. When a strontium sample is irradiated with protons, nuclear transmutation occurs; thus, the strontium isotope present in the sample changes to a yttrium isotope, which is an activated radioisotope. Based on this, the 87Sr/86Sr ratio was calculated by analyzing the gamma-rays emitted by each yttrium isotope. The KIRAMS-13 cyclotron at the Cyclotron Center of Chosun University, where 13-MeV protons can be extracted, was utilized in our experiment. The 87Sr/86Sr isotope ratio was computed for samples irradiated with these protons, and the result was similar to the isotope ratio for the Standard Reference Material, i.e., 98.2 ± 3.4%. As part of the analysis, proton activation analyses were performed using 13-MeV protons, and the experimental results of this research suggest a possible approach for measuring the strontium-isotope abundance ratio of samples.

Isotopic incorporation rates for shark tissues from a long-term captive feeding study.

PubMed

Kim, Sora Lee; del Rio, Carlos Martínez; Casper, Dave; Koch, Paul L

2012-07-15

Stable isotope analysis has provided insight into the dietary and habitat patterns of many birds, mammals and teleost fish. A crucial biological parameter to interpret field stable isotope data is tissue incorporation rate, which has not been well studied in large ectotherms. We report the incorporation of carbon and nitrogen into the tissues of leopard sharks (Triakis semifasciata). Because sharks have relatively slow metabolic rates and are difficult to maintain in captivity, no long-term feeding study has been conducted until the point of isotopic steady state with a diet. We kept six leopard sharks in captivity for 1250 days, measured their growth, and serially sampled plasma, red blood cells and muscle for stable carbon and nitrogen isotope analysis. A single-compartment model with first-order kinetics adequately described the incorporation patterns of carbon and nitrogen isotopes for these three tissues. Both carbon and nitrogen were incorporated faster in plasma than in muscle and red blood cells. The rate of incorporation of carbon into muscle was similar to that predicted by an allometric equation relating isotopic incorporation rate to body mass that was developed previously for teleosts. In spite of their large size and unusual physiology, the rates of isotopic incorporation in sharks seem to follow the same patterns found in other aquatic ectotherms.

Intracellular Cadmium Isotope Fractionation

NASA Astrophysics Data System (ADS)

Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

2011-12-01

Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

Verification of the isotopic composition of precipitation simulated by a regional isotope circulation model over Japan.

PubMed

Tanoue, Masahiro; Ichiyanagi, Kimpei; Yoshimura, Kei

2016-01-01

The isotopic composition (δ(18)O and δ(2)H) of precipitation simulated by a regional isotope circulation model with a horizontal resolution of 10, 30 and 50 km was compared with observations at 56 sites over Japan in 2013. All simulations produced reasonable spatio-temporal variations in δ(18)O in precipitation over Japan, except in January. In January, simulated δ(18)O values in precipitation were higher than observed values on the Pacific side of Japan, especially during an explosively developing extratropical cyclone event. This caused a parameterisation of precipitation formulation about the large fraction of precipitated water to liquid detrained water in the lower troposphere. As a result, most water vapour that transported from the Sea of Japan precipitated on the Sea of Japan side. The isotopic composition of precipitation was a useful verification tool for the parameterisation of precipitation formulation as well as large-scale moisture transport processes in the regional isotope circulation model.

Diffusion coefficients of Mg isotopes in enstatite and forsterite melts calculated by first-principles molecular dynamic simulations

NASA Astrophysics Data System (ADS)

Huang, F.; Qi, Y.; Liu, X.; He, L.

2016-12-01

Stable isotopes can be fractionated by kinetic chemical diffusion because diffusion coefficients (D) of isotopes are mass-dependent. Diffusive isotopic fractionation recorded in rocks and minerals provide unique temporal constrains on geological processes. The mass dependence of D can be described in the form of Di/Dj= (mj/mi)β, where m denotes masses of isotope i and j, and β is an emperical parameter used to quantify the diffusive transport of isotopes [1]. β values can be estimated by experimental calibration and observation of natural samples, which are still rarely reported because it is challenging to precisely quantify the boundary conditions of diffusion processes [2,3,4]. Recent advances in computation technique provide a new way to theoretically calculate β values. For instance, classical molecular dynamics with empirical potential have been used to simulate interactions between atoms and estimate β of Mg isotopes in MgSiO3 melt [3]. Here, to further consider the effect of bonding and electron properties on β values, we apply first-principles Born-Oppenheimer Molecular Dynamics and pseudo-isotope methods (assuming mj/mi = 1/24, 1/4, 2, and 5) to estimate β for MgSiO3 and Mg2SiO4 melts. Our calculation shows that β of Mg isotopes with pseudo-mass ratios are consistent, indicating the reliability of the pseudo-isotope method. For MgSiO3 melt, β is 0.18 at 4000K and 0 GPa, higher than the value calculatedusing molecular dynamics simulations (0.135) [3]. For Mg2SiO4 melt at 0 GPa, β values are: 0.23 ± 0.04 at 2300K, 0.24 ± 0.07 at 3000K, and 0.24 ± 0.01 at 4000K. Notably, β of MgSiO3 and Mg2SiO4 melts are significantly higher than the value determined by diffusion experiments (0.05) [2]. These results indicate that β values are not sensitive to temperature, but dependent on melt composition.

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

NASA Astrophysics Data System (ADS)

Immenhauser, A.; Buhl, D.; Richter, D.; Niedermayr, A.; Riechelmann, D.; Dietzel, M.; Schulte, U.

2010-08-01

The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ 26Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ 26Mg values of loess-derived soil above the cave (-1.0 ± 0.5‰), soil water (-1.2 ± 0.5‰), the carbonate hostrock (-3.8 ± 0.5‰), dripwater in the cave (-1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; -4.3 ± 0.6‰), cave loam (-0.6 ± 0.1‰) and runoff water (-1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000ln αMg-cc-Mg(aq) = -2.4‰. A similar Mg-isotope fractionation (1000ln αMg-cc-Mg(aq) ≈ -2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, 26Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg 2+ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for

Fractionation of mercury isotopes by photo-oxidation in aquatic systems

NASA Astrophysics Data System (ADS)

Ghosh, S.; Bergquist, B. A.; Blum, J. D.

2009-12-01

Mercury is a globally distributed pollutant that bioaccumulates in aquatic food webs, even in remote locations. The recent discovery of both large mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) has made the promise of tracing this neurotoxin through the environment by using its isotopes very exciting. So far, the only process demonstrated experimentally to produce large MIF for Hg (similar in magnitude to the MIF observed in natural samples such as fish) is photochemical reduction (Bergquist and Blum, 2007). During photo-reduction, MIF of the odd isotopes was observed with the odd isotopes (199Hg, 201Hg) being preferentially enriched in the aqueous phase. Bergquist and Blum, 2007, suggested that the cause of MIF was the magnetic isotope effect (MIE), which is purely a kinetic phenomenon involving radical pair intermediates. Radical pairs with odd isotopes, which have non-zero nuclear spin and magnetic moments, can undergo spin conversion faster than radical pairs with non-magnetic even isotopes. This allows the odd and even isotopes to be preferentially enriched in different reaction products. MIE is a complex phenomenon that is dependent on several factors including hyperfine coupling, life-time of the radical pair, coupling strength of the radical pair, spin-orbital coupling, diffusion factors, and the solvent cage (space) in which the reaction occurs. Only under rare circumstances will all the factors be suitable for the expression of MIE in natural reactions. The goal of this study was to conduct aqueous photo-oxidation reactions to investigate whether this redox pathway expresses MIF (in the form of MIE) similar to the photo-reduction pathway. In natural systems, net photo-reduction of Hg (II) species results in the release of Hg(0) vapor to the atmosphere. However this net photo-reduction is a combination of both photo-reduction and photo-oxidation. In their experiments, Bergquist and Blum 2007, only investigated the aqueous photo

Pyroxene Homogenization and the Isotopic Systematics of Eucrites

NASA Technical Reports Server (NTRS)

Nyquist, L. E.; Bogard, D. D.

1996-01-01

The original Mg-Fe zoning of eucritic pyroxenes has in nearly all cases been partly homogenized, an observation that has been combined with other petrographic and compositional criteria to establish a scale of thermal "metamorphism" for eucrites. To evaluate hypotheses explaining development of conditions on the HED parent body (Vesta?) leading to pyroxene homogenization against their chronological implications, it is necessary to know whether pyroxene metamorphism was recorded in the isotopic systems. However, identifying the effects of the thermal metamorphism with specific effects in the isotopic systems has been difficult, due in part to a lack of correlated isotopic and mineralogical studies of the same eucrites. Furthermore, isotopic studies often place high demands on analytical capabilities, resulting in slow growth of the isotopic database. Additionally, some isotopic systems would not respond in a direct and sensitive way to pyroxene homogenization. Nevertheless, sufficient data exist to generalize some observations, and to identify directions of potentially fruitful investigations.

Rare Isotopes Physics in the Multimessenger Era

NASA Astrophysics Data System (ADS)

Schatz, Hendrik

2018-06-01

While these isotopes only exist for fractions of seconds, their properties shape the resulting cosmic distribution of elements and the astronomical observables including spectra, neutrinos, and gravitational waves. The long standing challenge in nuclear astrophysics of the production of the relevant isotopes in the laboratory is now overcome with a new generation of rare isotope accelerator facilities now coming online. One example is the FRIB facility under construction at Michigan State University for the US Department of Energy, Office of Science, Office of Nuclear Physics. These new capabilities in nuclear physics coincide with advances in astronomy directly related to the cosmic sites where these isotopes are created, in particular in time domain and gravitational wave astronomy. I will discuss the importance of rare isotope physics in interpreting multi-messenger observations and how advances in nuclear physics and astronomy when combined promise to lead us towards a comprehensive theory of the origin of the elements.

Silicon isotopes fractionation in meteoric chemical weathering and hydrothermal alteration systems of volcanic rocks (Mayotte)

NASA Astrophysics Data System (ADS)

Basile-Doelsch, Isabelle; Puyraveau, Romain-Arnaud; Guihou, Abel; Haurine, Frederic; Deschamps, Pierre; rad, Setareh; Nehlig, Pierre

2017-04-01

Low temperature chemical weathering fractionates silicon (Si) isotopes while forming secondary silicates. The Si fractionation ranges of high temperature secondary phyllosilicates formed in hydrothermal alteration environments have not been investigated to date. Several parameters, including temperature, reaction rates, pH, ionic concentrations in solution, precipitation/dissolution series or kinetic versus equilibrium regime are not the same in hydrothermal alteration and surface weathering systems and may lead to different fractionation factors. In this work, we analyzed Si isotopes in these two types of alteration conditions in two profiles sampled on the volcanic island of Mayotte. In both profiles, Si-bearing secondary mineral was kaolinite. Both profiles showed 30Si depletion as a function of the degree of alteration but each with a distinct pattern. In the meteoric weathering profile, from the bottom to the top, a gradual decrease of the δ30Si from parent rock (-0.29 ± 0.13 ‰) towards the most weathered product (-2.05 ± 0.13 ‰) was observed. In the hydrothermal alteration profile, in which meteoric weathering was also superimposed at the top of the profile, an abrupt transition of the δ30Si was measured at the interface between parent-rock (-0.21 ± 0.11 ‰) and the altered products, with a minimum value of -3.06 ± 0.16 ‰˙ At the scale of Si-bearing secondary minerals, in the chemical weathering system, a Δ30Sikaol-parentrock of -1.9 ‰ was observed, in agreement with results in the literature. A low temperature kinetic fractionation 30ɛ of -2.29 ‰ was calculated using a simple steady state model. However, an unexpected Δ30Sikaol-parentrock of -2.85 ‰ was measured in the hydrothermal alteration site, pointing to possible mechanisms linked to dissolution/precipitation series and/or to ionic composition of the solution as the main controlling factors of fractionation in hydrothermal conditions. At the scale of the profiles, both δ30Si

Real-time observation of the isothermal crystallization kinetics in a deeply supercooled liquid

NASA Astrophysics Data System (ADS)

Zanatta, M.; Cormier, L.; Hennet, L.; Petrillo, C.; Sacchetti, F.

2017-03-01

Below the melting temperature Tm, crystals are the stable phase of typical elemental or molecular systems. However, cooling down a liquid below Tm, crystallization is anything but inevitable. The liquid can be supercooled, eventually forming a glass below the glass transition temperature Tg. Despite their long lifetimes and the presence of strong barriers that produces an apparent stability, supercooled liquids and glasses remain intrinsically a metastable state and thermodynamically unstable towards the crystal. Here we investigated the isothermal crystallization kinetics of the prototypical strong glassformer GeO2 in the deep supercooled liquid at 1100 K, about half-way between Tm and Tg. The crystallization process has been observed through time-resolved neutron diffraction for about three days. Data show a continuous reorganization of the amorphous structure towards the alpha-quartz phase with the final material composed by crystalline domains plunged into a low-density, residual amorphous matrix. A quantitative analysis of the diffraction patterns allows determining the time evolution of the relative fractions of crystal and amorphous, that was interpreted through an empirical model for the crystallization kinetics. This approach provides a very good description of the experimental data and identifies a predator-prey-like mechanism between crystal and amorphous, where the density variation acts as a blocking barrier.

Methyl-coenzyme M reductase from methanogenic archaea: isotope effects on label exchange and ethane formation with the homologous substrate ethyl-coenzyme M.

PubMed

Scheller, Silvan; Goenrich, Meike; Thauer, Rudolf K; Jaun, Bernhard

2013-10-09

Ethyl-coenzyme M (CH3CH2-S-CH2CH2-SO3(-), Et-S-CoM) serves as a homologous substrate for the enzyme methyl-coenzyme M reductase (MCR) resulting in the product ethane instead of methane. The catalytic reaction proceeds via an intermediate that already contains all six C-H bonds of the product. Because product release occurs after a second, rate-limiting step, many cycles of intermediate formation and reconversion to substrate occur before a substantial amount of ethane is released. In deuterated buffer, the intermediate becomes labeled, and C-H activation in the back reaction rapidly leads to labeled Et-S-CoM, which enables intermediate formation to be detected. Here, we present a comprehensive analysis of this pre-equilibrium. (2)H- and (13)C-labeled isotopologues of Et-S-CoM were used as the substrates, and the time course of each isotopologue was followed by NMR spectroscopy. A kinetic simulation including kinetic isotope effects allowed determination of the primary and α- and β-secondary isotope effects for intermediate formation and for the C-H/C-D bond activation in the ethane-containing intermediate. The values obtained are in accordance with those found for the native substrate Me-S-CoM (see preceding publication, Scheller, S.; Goenrich, M.; Thauer, R. K.; Jaun, B. J. Am. Chem. Soc. 2013, 135, DOI: 10.1021/ja406485z) and thus imply the same catalytic mechanism for both substrates. The experiment by Floss and co-workers, demonstrating a net inversion of configuration to chiral ethane with CH3CDT-S-CoM as the substrate, is compatible with the observed rapid isotope exchange if the isotope effects measured here are taken into account.

Iron and nickel isotope fractionation by diffusion, with applications to iron meteorites

NASA Astrophysics Data System (ADS)

Watson, Heather C.; Richter, Frank; Liu, Ankun; Huss, Gary R.

2016-10-01

Mass-dependent, kinetic fractionation of isotopes through processes such as diffusion can result in measurable isotopic signatures. When these signatures are retained in geologic materials, they can be used to help interpret their thermal histories. The mass dependence of the diffusion coefficient of isotopes 1 and 2 can be written as (D1 /D2) =(m2 /m1) β, where D1 and D2 are the diffusion coefficients of m1 and m2 respectively, and β is an empirical coefficient that relates the two ratios. Experiments have been performed to measure β in the Fe-Ni alloy system. Diffusion couple experiments between pure Fe and Ni metals were run in a piston cylinder at 1300-1400 °C and 1 GPa. Concentration and isotopic profiles were measured by electron microprobe and ion microprobe respectively. We find that a single β coefficient of β = 0.32 ± 0.04 can describe the isotopic effect in all experiments. This result is comparable to the isotope effect determined in many other similar alloy systems. The new β coefficient is used in a model of the isotopic profiles to be expected during the Widmanstätten pattern formation in iron meteorites. The results are consistent with previous estimates of the cooling rate of the iron meteorite Toluca. The application of isotopic constraints based on these results in addition to conventional cooling rate models could provide a more robust picture of the thermal history of these early planetary bodies.

Stable carbon and sulfur isotopes as records of the early biosphere

NASA Technical Reports Server (NTRS)

Desmarais, David J.

1989-01-01

The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

Kinetic study on the H + SiH4 abstraction reaction using an ab initio potential energy surface.

PubMed

Cao, Jianwei; Zhang, Zhijun; Zhang, Chunfang; Bian, Wensheng; Guo, Yin

2011-01-14

Variational transition state theory calculations with the correction of multidimensional tunneling are performed on a 12-dimensional ab initio potential energy surface for the H + SiH(4) abstraction reaction. The surface is constructed using a dual-level strategy. For the temperature range 200-1600 K, thermal rate constants are calculated and kinetic isotope effects for various isotopic species of the title reaction are investigated. The results are in very good agreement with available experimental data.

Stable Isotope (delta OXYGEN-18, Delta Deuterium, Delta CARBON-13) Dendroclimatological Studies in the Waterloo Region of Southern Ontario, Canada, Between AD 1610 and 1990.

NASA Astrophysics Data System (ADS)

Buhay, William Mark

Oxygen (delta^{18} O), hydrogen (delta^2H) and carbon (delta^{13}C) isotopes were measured in wood cellulose from elm, white pine and maple trees that grew in southwestern Ontario, Canada. The measured oxygen and hydrogen isotopic data were used for model-based reconstructions of delta^{18}{O}_{meteoric water}, mean annual temperature (MAT) and relative humidity for a period, AD 1610 to 1880, that precedes instrumental records of climate. The carbon isotope measurements were compared with the Cellulose Model inferred climate data to reveal additional environmental information. Modifications made to the Cellulose Model focused on the dynamics of oxygen and hydrogen isotopic fractionation in plants during evapotranspiration and photosynthetic assimilation. For instance, kinetic fractionation of ^{18}O was found to be predictable from theoretical considerations of leaf energy balance and boundary layer dynamics. Kinetic fractionation during evapotranspiration is sensitive to the nature of the boundary layer, which is controlled by leaf size and morphology. Generally, plants with small segmented leaves have a lower component of turbidity in the leaf boundary layer, which results in higher kinetic fractionation values, than do plants having large simple leaves and more turbulent boundary layers. Kinetic ^2H enrichment in plant leaf water can also be rationalized in terms of leaf size and morphology when an apparent temperature-dependent isotope effect, acting in opposition to evaporative enrichment, is taken into account. Accounting for this temperature -dependent isotope effect helps to: (1) reconcile hydrogen kinetic fractionation inconsistencies for different leaves; (2) explain a temperature effect previously attributed to variable biochemical fractionation during cellulose synthesis, and; (3) verify hydrogen biochemical effects in plants. This improved characterization of the oxygen and hydrogen isotopic effects in plants, using the modified Cellulose Model, helped

Isotope Effects Associated with N2O Production By Fungal and Bacterial Nitric Oxide Reductases: Implications for Tracing Microbial Production Pathways

NASA Astrophysics Data System (ADS)

Ostrom, N. E.; Yang, H.; Gandhi, H.; Hegg, E. L.

2014-12-01

Site preference (SP), the difference in δ15N between the central (α) and outer (β) N atoms in N2O, has emerged as a conservative tracer of microbial N2O production. The key advantages of SP relative to bulk isotopes are (1) that it is independent of the isotope composition of the substrates of nitrification and denitrification and (2) has not been shown to exhibit fractionation during production. In pure microbial culture distinct SP values for N2O production from bacterial denitrification, including nitrifier-denitrification (-10 to 0 ‰), relative to hydroxylamine oxidation and fungal denitrification (33-37 ‰) provide a promising basis to resolve production pathways. In this study, we determined the δ15N, δ18O, δ15Nα, and δ15Nβ of N2O generated by purified fungal (P450nor) and bacterial nitric oxide reductases. The isotope values were used to calculate SP values, enrichment factors (e), and kinetic isotope effects (KIEs). Both O and Nα displayed normal isotope effects during enzymatic NO reduction by the P450nor with e values of -25.7‰ (KIE = 1.0264) and -12.6‰ (KIE = 1.0127), respectively. However, bulk nitrogen (average δ15N of Nα and Nβ) and Nβ exhibited inverse isotope effects with e values of 14.0‰ (KIE = 0.9862) and 36.1‰ (KIE = 0.9651), respectively. The observed inverse isotope effect in δ15Nβ is consistent with reversible binding of the first NO in the P450nor reaction mechanism. Experiments with bacterial nitric oxide reductase are ongoing, however, preliminary data indicates a inverse isotope effect in the α and β positions and a normal isotope effect in δ18O. In contrast to the constant SP observed during N2O production observed in microbial cultures, the SP measured for purified P450nor was not constant, increasing from ~15‰ to ~29‰ during the course of the reaction. Our results clearly indicate that fractionation of SP during N2O production by P450nor is not zero, and that SP values higher and lower than the