Stable isotope analysis of stream organisms - a useful tool for monitoring changes in catchment conditions and effects on stream ecosystems?

EPA Science Inventory

Stable isotope analyses of stream organisms usually are performed as discrete site experiments (e.g., to study the effect of a direct manipulation), synoptically (e.g. to illustrate effects of longitudinal variation of influencing factors), or, less frequently, over the course of...

Stable Isotope Analysis of stream organisms -- a potential tool for monitoring changes in catchment conditions and effects on stream ecosystems

EPA Science Inventory

Stable isotope analyses of stream organisms are performed usually as discrete site experiments (e.g., to study the effect of a direct manipulation), synoptically (e.g. to illustrate effects of longitudinal variation of influencing factors), or, less frequently, over the course of...

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.

A Computational Framework for High-Throughput Isotopic Natural Abundance Correction of Omics-Level Ultra-High Resolution FT-MS Datasets

PubMed Central

Carreer, William J.; Flight, Robert M.; Moseley, Hunter N. B.

2013-01-01

New metabolomics applications of ultra-high resolution and accuracy mass spectrometry can provide thousands of detectable isotopologues, with the number of potentially detectable isotopologues increasing exponentially with the number of stable isotopes used in newer isotope tracing methods like stable isotope-resolved metabolomics (SIRM) experiments. This huge increase in usable data requires software capable of correcting the large number of isotopologue peaks resulting from SIRM experiments in a timely manner. We describe the design of a new algorithm and software system capable of handling these high volumes of data, while including quality control methods for maintaining data quality. We validate this new algorithm against a previous single isotope correction algorithm in a two-step cross-validation. Next, we demonstrate the algorithm and correct for the effects of natural abundance for both 13C and 15N isotopes on a set of raw isotopologue intensities of UDP-N-acetyl-D-glucosamine derived from a 13C/15N-tracing experiment. Finally, we demonstrate the algorithm on a full omics-level dataset. PMID:24404440

Experimental determination of barium isotope fractionation during diffusion and adsorption processes at low temperatures

NASA Astrophysics Data System (ADS)

van Zuilen, Kirsten; Müller, Thomas; Nägler, Thomas F.; Dietzel, Martin; Küsters, Tim

2016-08-01

Variations in barium (Ba) stable isotope abundances measured in low and high temperature environments have recently received increasing attention. The actual processes controlling Ba isotope fractionation, however, remain mostly elusive. In this study, we present the first experimental approach to quantify the contribution of diffusion and adsorption on mass-dependent Ba isotope fractionation during transport of aqueous Ba2+ ions through a porous medium. Experiments have been carried out in which a BaCl2 solution of known isotopic composition diffused through u-shaped glass tubes filled with silica hydrogel at 10 °C and 25 °C for up to 201 days. The diffused Ba was highly fractionated by up to -2.15‰ in δ137/134Ba, despite the low relative difference in atomic mass. The time-dependent isotope fractionation can be successfully reproduced by a diffusive transport model accounting for mass-dependent differences in the effective diffusivities of the Ba isotope species (D137Ba /D134Ba =(m134 /m137) β). Values of β extracted from the transport model were in the range of 0.010-0.011. Independently conducted batch experiments revealed that adsorption of Ba onto the surface of silica hydrogel favoured the heavier Ba isotopes (α = 1.00015 ± 0.00008). The contribution of adsorption on the overall isotope fractionation in the diffusion experiments, however, was found to be small. Our results contribute to the understanding of Ba isotope fractionation processes, which is crucial for interpreting natural isotope variations and the assessment of Ba isotope ratios as geochemical proxies.

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 modern and ancient environments. PMID:26733949

Conformational effect of dicyclo-hexano-18-crown-6 on isotopic fractionation of zinc: DFT approach

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

Boda, A.; Singha Deb, A. K.; Ali, Sk. M.

2014-04-24

Generalized gradient approximated BP86 density functional employing triple zeta valence plus polarization (TZVP) basis set has been used to compute the reduced partition function ratio and isotopic separation factor for zinc isotopes. The isotopic separation factor was found to be in good agreement with the experimental results. The isotopic separation factor was found to depend on the conformation of the crown ether ligand. The trans-trans conformation shows the highest fractionation compared to cis-cis conformer. The present theoretical results can thus be used to plan the isotope separation experiments.

Surface area dependence of calcium isotopic reequilibration in carbonates: Implications for isotopic signatures in the weathering zone

NASA Astrophysics Data System (ADS)

Fernandez, N. M.; Druhan, J. L.; Potrel, A.; Jacobson, A. D.

2016-12-01

The concept of dynamic equilibrium carries the implicit assumption of continued isotopic exchange between a mineral and the surrounding fluid. While this effect has received much attention in the marine paleoproxy literature, it has been relatively overlooked in application to the terrestrial environment. In weathering systems, a potential consequence is that rapid reequilibration may alter or erase isotopic signatures generated during secondary mineral formation. The extent and timescale over which isotopic signatures are reset in these hydrologic systems is unknown. Using reactive transport modeling, we show isotopic reequilibration under conditions reflecting terrestrial hydrologic settings to be significant and dependent on the reactive surface area of the solid. In particular, we suggest that the non-traditional stable isotopes commonly used in application to carbonates (e.g., Ca, Mg, Sr) are sensitive to these effects due to their rapid reaction rates. We aim to characterize the dependence of Ca isotopic reequilibration on surface area during calcite precipitation via batch experiments conducted at ambient temperature over 48-hour time periods. Calcite precipitation was performed in a closed batch reactor utilizing a controlled free-drift method. The batch reactors contained mixed supersaturated solutions of CaCl2 and NaHCO3 at an initial pH of 8.54. Precipitation was initiated by seed inoculation of calcite crystals with two distinct, pre-constrained surface areas. All experiments achieved the same final state of chemical equilibrium, but as expected, the fastest approach to equilibrium occurred for experiments employing calcite seeds with the highest surface area. This implies that differences in equilibrated Ca isotope ratios (δ44/40Ca) should reflect differences in surface area. This prediction is upheld by models of the experiments, indicating a measureable difference in δ44Ca during calcite precipitation where the higher surface area corresponds to lower δ44Ca values and a faster approach to isotopic equilibrium. The dependence of δ44Ca resetting on calcite surface areas has broad ramifications for tracing carbonate weathering in the Critical Zone.

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, simple model studies suggest that the soil uptake of CH3Br and hence its isotopic effect is largely controlled by diffusion resulting in an even smaller apparent isotopic fractionation. As a consequence, the estimated source signature for the unknown source is discussed with respect to the assumptions made for the soil sink.

Effect of NO2(-) on stable isotope fractionation during bacterial sulfate reduction.

PubMed

Einsiedl, Florian

2009-01-01

The effects of low NO2(-) concentrations on stable isotope fractionation during dissimilatory sulfate reduction by strain Desulfovibrio desulfuricans were investigated. Nitrite, formed as an intermediate during nitrification and denitrification processes in marine and freshwater habitats, inhibits the reduction of the sulfuroxy intermediate SO3(2-) to H2S even at low concentrations. To gain an understanding of the inhibition effect of the reduction of the sulfuroxy intermediate on stable isotope fractionation in sulfur and oxygen during bacterial sulfate reduction, nitrite was added in the form of short pulses. In the batch experiments that contained 0.02, 0.05, and 0.1 mM nitrite, sulfur enrichment factors epsilon of -12 +/- 1.6, -15 +/- 1.1, and -26 +/- 1.3 per thousand, respectively were observed. In the control experiment (no addition of nitrite) a sulfur enrichment factor epsilon of around -11 per thousand was calculated. In the experiments that contained no 18O enriched water (delta18O: -10 per thousand) and nitrite concentrations of 0.02, 0.05, and 0.1 mM, delta18O values in the remaining sulfate were fairly constant during the experiments (delta18O sulfate: approximately equal to 10 per thousand) and were similar to those obtained from the control experiment (no nitrite and no enriched water). However, in the batch experiments that contained 18O enriched water (+700 per thousand) and nitrite concentrations of 0.05 and 0.1 mM increasing delta18O values in the remaining sulfate from around 15 per thousand to approximately 65 and 85 per thousand, respectively, were found. Our experiments that contained isotopic enriched water and nitrite show clear evidence that the ratio of forward and backward fluxes regulated by adenosine-5'-phosphosulfate reductase (APSR) controls the extent of sulfur isotope fractionation during bacterial sulfate reduction in strain Desulfovibrio desulfuricans. Since the metabolic sulfuroxy intermediate SO3(2-) exchanges with water, evidence of 18O enriched water in the remaining sulfate in the experiments that contained nitrite also demonstrates that SO3(2-) recycling to sulfate affects sulfur and oxygen isotope fractionation during bacterial sulfate reduction to some extent. Even though reduction of adenosine-5'-phosphosulfate (APS) to sulfite of -25 per thousand was not fully expressed, SO3(2-) was recycled to SO4(2-). On the basis of the results of this study a sulfur isotope fractionation for APSR of upto approximately -30 per thousand can be assumed. However, reported NO2(-) concentrations of up to 20 microM in freshwater and marine habitats may not significantly impact the ability to use stable isotope analysis in assessing bacterial sulfate reduction.

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.

Experimental Assessment of Carbon Isotopes of Light Hydrocarbons under Different Redox Conditions

NASA Astrophysics Data System (ADS)

Fu, Q.; Chen, X.

2017-12-01

Hydrocarbons can be derived from a variety of carbon sources, by different processes, and under a wide range of physicochemical conditions. Other than bacterial activities facilitating biogenic hydrocarbon formation at low temperatures, decomposition of complex organic matter in sedimentary rocks at elevated temperatures produce thermogenic hydrocarbons, whereas abiogenic hydrocarbons are mainly generated through Fischer-Tropsch type synthesis with mineral catalysts. The carbon isotope has been used extensively to distinguish hydrocarbons of different origins and their formation conditions. For each type of hydrocarbons, however, environmental conditions may change reaction pathways and corresponding isotope fractionations. To better understand the variation of carbon isotopes caused by environmental variables, mineral constraints in particular, a series of laboratory experiments are conducted. In experiments where thermogenic hydrocarbons are formed, oil shale is the source material with different gypsum contents (0, 0.3, 0.5, and 1 wt.%). The abundance of generated light straight chain hydrocarbons decreases with increasing gypsum content, but their carbon isotopes become heavier. For example, the δ13C value of methane increases from -55.1‰ to -41.4‰ with gypsum varying between 0 and 1 wt.%. In similar experiments with the presence of MnO2, carbon isotope values of light alkanes are also higher, but with limited magnitudes (e.g., 3 to 4‰ for methane). In another experiment with dissolved H2 gas of 100 mmol/kg, light alkanes become depleted in 13C than experiments without H2. For example, there is a depletion of 2.7‰ for methane. The variation of carbon isotope values of light alkanes suggests the redox condition, constrained by mineral assemblage, fluid composition, and physical environment, play an important role in isotope fractionation. The pathway of hydrocarbon generation may be different under oxidized or reducing conditions. A set of experiments, in which abiogenic hydrocarbons are formed, is currently in progress. Combined together, they would facilitate our understanding of carbon isotope fractionation under geological conditions, and effective use of carbon isotopes as a diagnostic tool for hydrocarbons that are poorly understood in terms of origin and evolution.

Future stable water isotope projection with an isotope-AGCM driven by CMIP5 SSTs

NASA Astrophysics Data System (ADS)

Yoshimura, K.

2016-12-01

Stable water isotope ratios (dD and d18O) are widely used as proxy of past climate changes, and it is extremely important to understand and predict the mechanism of current isotopic spatio-temporal behavior with regard to the on-going climate change. However, as compared many studies on reproduction of isotopes for the past, there are few studies on future projection of isotopes. Therefore, in this study, a set of experiments using an isotope-incorporate AGCM (IsoGSM) with SST and sea ice field simulated from multiple CMIP5 models, namely MIROC5, CCSM4, and MRI-CGCM3, were conducted for the end of 20th century (1980-1990) and the end of 21st century (2080-2090) under RCP2.6 and RCP8.5 scenarios. Thus the responses in stable water isotope ratio in precipitation and water vapor in accordance to the global warming were investigated. As results, the changes in global surface air temperature were about +1K and +3K with RCP2.6 and RCP8.5, respectively. Similarly, the global precipitation changes were about +0.07mm/day (about +2%) and +0.18mm/day (about +5%), and the global precipitable water changes were about +2mm (+7%) and +6mm (+24%), respectively. The moisture was increased in accordance to the Clausius-Clapayron theory (7%/K), but the increase in precipitation is not that large. This indicates that the global hydrological cycle was slowed down in the globally warmed experiments. On the other hand, for the isotopic signals, the changes in globally averaged d18O in precipitation were about 0.2‰ and 0.4‰, and those in precipitable water were 0.2‰ and 0.5‰, in RCP2.6 and RCP8.5, respectively. It is well-known that there are temperature effect (positive correlation in air temperature and precipitation isotopes) and amount effect (negative correlation in precipitation amount and isotopes), but in the globally warmed world, these effects were offset, and only weaker temperature effect was appeared in the global mean isotope signals. Regional details will be shown in the presentation.

Hydrogen and carbon isotope systematics in hydrogenotrophic methanogenesis under H2-limited and H2-enriched conditions: implications for the origin of methane and its isotopic diagnosis

NASA Astrophysics Data System (ADS)

Okumura, Tomoyo; Kawagucci, Shinsuke; Saito, Yayoi; Matsui, Yohei; Takai, Ken; Imachi, Hiroyuki

2016-12-01

Hydrogen and carbon isotope systematics of H2O-H2-CO2-CH4 in hydrogenotrophic methanogenesis and their relation to H2 availability were investigated. Two H2-syntrophic cocultures of fermentatively hydrogenogenic bacteria and hydrogenotrophic methanogens under conditions of <102 Pa-H2 and two pure cultures of hydrogenotrophic methanogens under conditions of 105 Pa-H2 were tested. Carbon isotope fractionation between CH4 and CO2 during hydrogenotrophic methanogenesis was correlated with pH2, as indicated in previous studies. The hydrogen isotope ratio of CH4 produced during rapid growth of the thermophilic methanogen Methanothermococcus okinawensis under high pH2 conditions ( 105 Pa) was affected by the isotopic composition of H2, as concluded in a previous study of Methanothermobacter thermautotrophicus. This " {δ D}_{{H}_2} effect" is a possible cause of the diversity of previously reported values for hydrogen isotope fractionation between CH4 and H2O examined in H2-enriched culture experiments. Hydrogen isotope fractionation between CH4 and H2O, defined by (1000 + {δ D}_{{CH}_4} )/(1000 + {δ D}_{{H}_2O} ), during hydrogenotrophic methanogenesis of the H2-syntrophic cocultures was in the range 0.67-0.69. The hydrogen isotope fractionation of our H2-syntrophic dataset overlaps with those obtained not only from low- pH2 experiments reported so far but also from natural samples of "young" methane reservoirs (0.66-0.74). Conversely, such hydrogen isotope fractionation is not consistent with that of "aged" methane in geological samples (≥0.79), which has been regarded as methane produced via hydrogenotrophic methanogenesis from the carbon isotope fractionation. As a possible process inducing the inconsistency in hydrogen isotope signatures between experiments and geological samples, we hypothesize that the hydrogen isotope signature of CH4 imprinted at the time of methanogenesis, as in the experiments and natural young methane, may be altered by diagenetic hydrogen isotope exchange between extracellular CH4 and H2O through reversible reactions of the microbial methanogenic pathway in methanogenic region and/or geological methane reservoirs.

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.

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.

Effects of Low-Molecular-Weight Organic Acids on the Dissolution of Hydroxyapatite Nanoparticles in Batch and Column Experiments: A Perspective from Phosphate Oxygen Isotope Fractionation

NASA Astrophysics Data System (ADS)

Wang, D.; Jaisi, D. P.; Jin, Y.

2015-12-01

Hydroxyapatite nanoparticles (HANPs) are increasingly being advocated as an efficient and environment-friendly "green" phosphorus nanofertilizer attributed to their nanoscale dimension, large reactive surface area, and low leaching potential. However, knowledge of how naturally occurring low-molecular-weight organic acids (LMWOAs) that are secreted by plant roots mediate the dissolution of HANPs (releasing PO43- ion for plant growth) is nonexistent. Here three most commonly encountered LMWOAs (acetic acid, oxalic acid, and citric acid) at environmentally relevant concentration (1 mM) were evaluated for their effects on HANPs' dissolution in static batch and dynamic column systems. Particularly, phosphate oxygen isotope fractionation of HANPs during dissolution was examined to disentangle mechanisms controlling the evolution of O-isotopic composition of dissolved PO43- ion. Our results reveal that in batch experiments the dissolution of HANPs was fast but the overall dissolution efficiency of HANPs was limited (≤30%). In contrast, ~100% HANPs were dissolved in columns where LMWOAs were continuously injected. The limited dissolution of HANPs in static batch systems was due primarily to pH buffer effect (pH increased sharply when LMWOA was added in HANPs suspension), whereas in dynamic column systems the HANPs were continuously dissolved by low pH LMWOAs and leached away. Regardless of LMWOA type and experimental system, the isotopically light phosphate (P16O4) was preferentially released during dissolution and the O-isotopic composition of dissolved PO43- ion increased gradually with increasing dissolution due to equilibrium isotope effect between dissolved PO43- ion and HANPs. However, the overall magnitude of O-isotopic fractionation of dissolved PO43- ion was less in batch than in column systems, due to less mass transfer between dissolved PO43- ions and HANPs in batch relative to column experiments. Our findings provide new insights into bioavailability, transformation, and evolution of O-isotopic signatures of phosphate-based nanoparticles in agricultural soils particularly in the rhizosphere where such LMWOAs are ubiquitous.

C Diffusion in Fe: Isotope Effects and Other Complexities

NASA Astrophysics Data System (ADS)

Watson, E. B.; Muller, T.; Trail, D.; Van Orman, J. A.; Papineau, D.

2011-12-01

Carbon is a minor but significant component of iron meteorites, and probably also of planetary cores, including that of Earth. Given the dynamical nature of core-forming processes, C diffusion in the metal phase may play a role in C equilibration between Fe-Ni metal and silicate, carbide or oxide at some stage. Despite its relevance to steel-making, C diffusion in Fe is not well characterized over the range of conditions of interest in planetary bodies, and the likelihood of an isotope mass effect on C diffusion has not been explored. The prospect of incomplete diffusive equilibration of carbon in Fe-Ni raises the possibility that carbon isotopes might be fractionated by diffusion during core formation and evolution-perhaps to an extent that could affect the C isotope ratio of the bulk silicate Earth. Here we report results of preliminary experiments addressing the isotopic mass effect on C diffusion in Fe. Initial low-pressure experiments were conducted by placing a layer of ^{13}C-enriched graphite ( 20% ^{13}C) at the end of a high-purity, polycrystalline Fe cylinder in a silica glass container. These diffusion couples were run in a piston-cylinder apparatus at 1.5 GPa and 1000-1100^{o}C for several hours, and the resulting C-uptake profiles in the Fe cylinders were measured by EPMA and SIMS. In traverses moving away from the original C-Fe interface, total carbon decreases monotonically and becomes significantly lighter, indicating that ^{12}C diffuses faster than ^{13}C. Preliminary estimates of β in the relative isotope diffusivity relation D_{1}/D_{2} = [M_{2}/M_{1}]^{β} (where D is diffusivity and M is mass of isotopes 1 and 2) suggest values as high as 0.5, corresponding to predictions for gaseous diffusion. Isotope mass effects approaching this magnitude have been observed previously for diffusion in metals, and are expected to be highest for interstitial diffusion. Such a high β value will lead to major C isotope fractionation in some partial equilibration scenarios in planets and meteorite parent bodies. Caution is warranted at this point, however, because D_{carbon} is sensitive to carbon concentration, complicating quantification of the isotope effect.

Review of computer simulations of isotope effects on biochemical reactions: From the Bigeleisen equation to Feynman's path integral.

PubMed

Wong, Kin-Yiu; Xu, Yuqing; Xu, Liang

2015-11-01

Enzymatic reactions are integral components in many biological functions and malfunctions. The iconic structure of each reaction path for elucidating the reaction mechanism in details is the molecular structure of the rate-limiting transition state (RLTS). But RLTS is very hard to get caught or to get visualized by experimentalists. In spite of the lack of explicit molecular structure of the RLTS in experiment, we still can trace out the RLTS unique "fingerprints" by measuring the isotope effects on the reaction rate. This set of "fingerprints" is considered as a most direct probe of RLTS. By contrast, for computer simulations, oftentimes molecular structures of a number of TS can be precisely visualized on computer screen, however, theoreticians are not sure which TS is the actual rate-limiting one. As a result, this is an excellent stage setting for a perfect "marriage" between experiment and theory for determining the structure of RLTS, along with the reaction mechanism, i.e., experimentalists are responsible for "fingerprinting", whereas theoreticians are responsible for providing candidates that match the "fingerprints". In this Review, the origin of isotope effects on a chemical reaction is discussed from the perspectives of classical and quantum worlds, respectively (e.g., the origins of the inverse kinetic isotope effects and all the equilibrium isotope effects are purely from quantum). The conventional Bigeleisen equation for isotope effect calculations, as well as its refined version in the framework of Feynman's path integral and Kleinert's variational perturbation (KP) theory for systematically incorporating anharmonicity and (non-parabolic) quantum tunneling, are also presented. In addition, the outstanding interplay between theory and experiment for successfully deducing the RLTS structures and the reaction mechanisms is demonstrated by applications on biochemical reactions, namely models of bacterial squalene-to-hopene polycyclization and RNA 2'-O-transphosphorylation. For all these applications, we used our recently-developed path-integral method based on the KP theory, called automated integration-free path-integral (AIF-PI) method, to perform ab initio path-integral calculations of isotope effects. As opposed to the conventional path-integral molecular dynamics (PIMD) and Monte Carlo (PIMC) simulations, values calculated from our AIF-PI path-integral method can be as precise as (not as accurate as) the numerical precision of the computing machine. Lastly, comments are made on the general challenges in theoretical modeling of candidates matching the experimental "fingerprints" of RLTS. This article is part of a Special Issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

Assessment of shock effects on amphibole water contents and hydrogen isotope compositions: 1. Amphibolite experiments

NASA Astrophysics Data System (ADS)

Minitti, Michelle E.; Rutherford, Malcolm J.; Taylor, Bruce E.; Dyar, M. Darby; Schultz, Peter H.

2008-02-01

Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10‰). Extrapolating the shock signature of the regrouped data to grains that experienced Martian meteorite-like shock pressures suggests that shock-induced water losses and hydrogen isotope enrichments could approach 1 wt.% H 2O and Δ D = + 100‰, respectively. If these values are valid, then impact shock effects could explain a substantial fraction of the low water contents and variable hydrogen isotope compositions of the Martian meteorite kaersutites.

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 produced in the microbial experiment, even larger than that seen in our Fe(II)-bearing abiologic experiments, suggests that δ30Si can be a potential tracer for magnetite of a microbial origin, or, vice versa, for microbial activities in magnetite. [1] Zheng et al., 2016, GCA 187, 102-122. [2] Reddy et al., 2016, GCA 190, 85-99.

Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

USGS Publications Warehouse

Balci, N.; Bullen, T.D.; Witte-Lien, K.; Shanks, Wayne C.; Motelica, M.; Mandernack, K.W.

2006-01-01

Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42- and Cl- salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor ??Fe(III)aq-Fe(II)aq???1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (???1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (???1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9??? (??Fe(III)aq-Fe(II)aq ???1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments revealed that 56Fe/54Fe ratios of Fe(III)aq were generally equal to or greater than those of Fe(III)ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record. ?? 2005 Elsevier Inc. All rights reserved.

Hydrogen isotope separation using molecular sieve of synthetic zeolite 3A

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

Kotoh, K.; Kimura, K.; Nakamura, Y.

2008-07-15

It is known that hydrogen isotope molecules can be adsorbed easily onto synthetic zeolite 4A, 5A, and 13X at the liquid-nitrogen temperature of 77.4 K. We show here that hydrogen and deuterium are not adsorptive onto zeolite 3A at the same temperature. This phenomenon is explained by assuming the molecular sieve function in zeolite-3A-crystalline lattice structure. From a series of pseudo-isobaric experiments, it is also shown that the sieving phenomenon appears in a range above 77.4 K. This behavior is interpreted as resulting on the dependence of sieve's mesh size on temperature, where the sieving effect is considered to appearmore » at a certain temperature. In this interpretation, an isotopic difference between hydrogen and deuterium is suggested to exist in the sieving effect appearance temperatures. This is endorsed in the result of pseudo-isobaric experiments. This temperature deference is very significant because that indicates the possibility of an effective method of hydrogen isotope separation. This possibility is verified through an experimental series of adsorption-desorption with a mixture of H{sub 2} and D{sub 2}, where the gas samples adsorbed through the sieve operated at intentionally selected temperatures are isolated and then analyzed. The result demonstrates remarkable values of isotope separation factor. (authors)« less

Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data.

PubMed

Estrada, Nubia Luz; Böhlke, J K; Sturchio, Neil C; Gu, Baohua; Harvey, Greg; Burkey, Kent O; Grantz, David A; McGrath, Margaret T; Anderson, Todd A; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B; Jackson, W Andrew

2017-10-01

Natural perchlorate (ClO 4 - ) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ 37 Cl, δ 18 O, and Δ 17 O), indicating that ClO 4 - may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO 4 - , but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO 4 - in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO 4 - was transported from solutions into plants similarly to NO 3 - but preferentially to Cl - (4-fold). The ClO 4 - isotopic compositions of initial ClO 4 - reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO 4 - uptake or accumulation. The ClO 4 - isotopic composition of field-grown snap beans was also consistent with that of ClO 4 - in varying proportions from irrigation water and precipitation. NO 3 - uptake had little or no effect on NO 3 - isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε ( 15 N/ 18 O) ratio of 1.05 was observed between NO 3 - in hydroponic solutions and leaf extracts, consistent with partial NO 3 - reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO 4 - in commercial produce, as illustrated by spinach, for which the ClO 4 - isotopic composition was similar to that of indigenous natural ClO 4 - . Our results indicate that some types of plants can accumulate and (presumably) release ClO 4 - to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO 4 - and NO 3 - in plants may be useful for determining sources of fertilizers and sources of ClO 4 - in their growth environments and consequently in food supplies. Copyright © 2017 Elsevier B.V. All rights reserved.

Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data

USGS Publications Warehouse

Estrada, Nubia Luz; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua; Harvey, Greg; Burkey, Kent O.; Grantz, David A.; McGrath, Margaret T.; Anderson, Todd A.; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B.; Jackson, W. Andrew

2017-01-01

Natural perchlorate (ClO4−) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ37Cl, δ18O, and Δ17O), indicating that ClO4− may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO4−, but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO4− in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO4− was transported from solutions into plants similarly to NO3− but preferentially to Cl− (4-fold). The ClO4− isotopic compositions of initial ClO4− reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO4− uptake or accumulation. The ClO4− isotopic composition of field-grown snap beans was also consistent with that of ClO4− in varying proportions from irrigation water and precipitation. NO3− uptake had little or no effect on NO3− isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε (15N/18O) ratio of 1.05 was observed between NO3− in hydroponic solutions and leaf extracts, consistent with partial NO3− reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO4− in commercial produce, as illustrated by spinach, for which the ClO4− isotopic composition was similar to that of indigenous natural ClO4−. Our results indicate that some types of plants can accumulate and (presumably) release ClO4− to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO4−and NO3− in plants may be useful for determining sources of fertilizers and sources of ClO4− in their growth environments and consequently in food supplies.

Data-driven Approaches to Teaching Stable Isotopes in Hydrology and Environmental Geochemistry

NASA Astrophysics Data System (ADS)

Jefferson, A.; Merchant, W. R.; Dees, D.; Griffith, E. M.; Ortiz, J. D.

2016-12-01

Stable isotopes have revolutionized our understanding of watershed hydrology and other earth science processes. However, students may struggle to correctly interpret isotope ratios and few students understand how isotope measurements are made. New laser-based technologies lower the barrier to entry for giving students hands on experience with isotope measurements and data analysis. We hypothesizedthat integrating such activities into the curriculum would increase student content knowledge, perceptions, and motivation to learn. This project assessed the impact that different pedagogical approaches have on student learning of stable isotope concepts in upper-division geoscience courses. An isotope hydrograph separation module was developed and taught for a Watershed Hydrology course, and a Rayleigh distillation activity was developed and deployed for Environmental Geochemistry and Sedimentology/Stratigraphy classes. Groups of students were exposed to this content via (1) a lecture-only format; (2) a paper-based data analysis activity; and (3) hands-on data collection, sometimes including spectrometer analysis. Pre- and post-tests measured gains in content knowledge while approaches to learning and motivational questionnaires instruments were used to identify the effects of the classroom environment on learning approaches and motivation. Focus group interviews were also conducted to verify the quantitative data. All instructional styles appear to be equally effective at increasing student content knowledge of stable isotopes in the geosciences, but future studies need to move beyond "exam question" style assessment of learning. Our results may reflect that hands-on experiences are not new to upper-level geosciences students, because this is the way that many classes are taught in the geosciences (labs, field trips). Thus, active learning approaches may not have had the impact they would with other groups. The "messiness" of hands-on activities and authentic research experiences may be perceived as negatives by students, particularly those who use surface learning techniques and extrinsic motivation.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

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…

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Rate dependent fractionation of sulfur isotopes in through-flowing systems

NASA Astrophysics Data System (ADS)

Giannetta, M.; Sanford, R. A.; Druhan, J. L.

2017-12-01

The fidelity of reactive transport models in quantifying microbial activity in the subsurface is often improved through the use stable isotopes. However, the accuracy of current predictions for microbially mediated isotope fractionations within open through-flowing systems typically depends on nutrient availability. This disparity arises from the common application of a single `effective' fractionation factor assigned to a given system, despite extensive evidence for variability in the fractionation factor between eutrophic environments and many naturally occurring, nutrient-limited environments. Here, we demonstrate a reactive transport model with the capacity to simulate a variable fractionation factor over a range of microbially mediated reduction rates and constrain the model with experimental data for nutrient limited conditions. Two coupled isotope-specific Monod rate laws for 32S and 34S, constructed to quantify microbial sulfate reduction and predict associated S isotope partitioning, were parameterized using a series of batch reactor experiments designed to minimize microbial growth. In the current study, we implement these parameterized isotope-specific rate laws within an open, through-flowing system to predict variable fractionation with distance as a function of sulfate reduction rate. These predictions are tested through a supporting laboratory experiment consisting of a flow-through column packed with homogenous porous media inoculated with the same species of sulfate reducing bacteria used in the previous batch reactors, Desulfovibrio vulgaris. The collective results of batch reactor and flow-through column experiments support a significant improvement for S isotope predictions in isotope-sensitive multi-component reactive transport models through treatment of rate-dependent fractionation. Such an update to the model will better equip reactive transport software for isotope informed characterization of microbial activity within energy and nutrient limited environments.

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 applicability of our new non-destructive approach to field conditions.

The isotope mass effect on chlorine diffusion in dacite melt, with implications for fractionation during bubble growth

NASA Astrophysics Data System (ADS)

Fortin, Marc-Antoine; Watson, E. Bruce; Stern, Richard

2017-12-01

Previous experimental studies have revealed that the difference in diffusivity of two isotopes can be significant in some media and can lead to an observable fractionation effect in silicate melts based on isotope mass. Here, we report the first characterization of the difference in diffusivities of stable isotopes of Cl (35Cl and 37Cl). Using a piston-cylinder apparatus, we generated quenched melts of dacitic composition enriched in Cl; from these we fabricated diffusion couples in which Cl atoms were induced to diffuse in a chemical gradient at 1200 to 1350 °C and 1 GPa. We analyzed the run products by secondary ion mass spectrometry (SIMS) for their isotopic compositions along the diffusion profiles, and we report a diffusivity ratio for 37Cl/35Cl of 0.995 ± 0.001 (β = 0.09 ± 0.02). No significant effect of temperature on the diffusivity ratio was discernable over the 150 °C range covered by our experiments. The observed 0.5% difference in diffusivity of the two isotopes could affect our interpretation of isotopic measurements of Cl isotopes in bubble-bearing or degassed magmas, because bubble growth is regulated in part by the diffusive supply of volatiles to the bubble from the surrounding melt. Through numerical simulations, we constrain the extent of Cl isotopic fractionation between bubble and host melt during this process. Bubble growth rates vary widely in nature-which implies a substantial range in the expected magnitude of isotopic fractionation-but plausible growth scenarios lead to Cl isotopic fractionations up to about 5‰ enrichment of 35Cl relative to 37Cl in the bubble. This effect should be considered when interpreting Cl isotopic measurements of systems that have experienced vapor exsolution.

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.

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

Substrate and Enzyme Specificity of the Kinetic Isotope Effects Associated with the Dioxygenation of Nitroaromatic Contaminants.

PubMed

Pati, Sarah G; Kohler, Hans-Peter E; Pabis, Anna; Paneth, Piotr; Parales, Rebecca E; Hofstetter, Thomas B

2016-07-05

Compound-specific isotope analysis (CSIA) is a promising approach for tracking biotransformation of organic pollutants, but isotope fractionation associated with aromatic oxygenations is only poorly understood. We investigated the dioxygenation of a series of nitroaromatic compounds to the corresponding catechols by two enzymes, namely, nitrobenzene and 2-nitrotoluene dioxygenase (NBDO and 2NTDO) to elucidate the enzyme- and substrate-specificity of C and H isotope fractionation. While the apparent (13)C- and (2)H-kinetic isotope effects of nitrobenzene, nitrotoluene isomers, 2,6-dinitrotoluene, and naphthalene dioxygenation by NBDO varied considerably, the correlation of C and H isotope fractionation revealed a common mechanism for nitrobenzene and nitrotoluenes. Similar observations were made for the dioxygenation of these substrates by 2NTDO. Evaluation of reaction kinetics, isotope effects, and commitment-to-catalysis based on experiment and theory showed that rates of dioxygenation are determined by the enzymatic O2 activation and aromatic C oxygenation. The contribution of enzymatic O2 activation to the reaction rate varies for different nitroaromatic substrates of NBDO and 2NTDO. Because aromatic dioxygenation by nonheme iron dioxygenases is frequently the initial step of biodegradation, O2 activation kinetics may also have been responsible for the minor isotope fractionation reported for the oxygenation of other aromatic contaminants.

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 occurring first at the level of secondary roots, and second at the level of leaves. (2) No Ca isotope difference was observed neither between old and young organs, (except for H6 leaves), nor between the two growth stages (except for H6 roots). This suggest that the mechanisms controlling isotopic fractionations of Ca within common beans do not vary during growth, and that the nutrients stored in the cotyledons have only a minor effect on the Ca isotope fractionations of plants harvested after 10 days. (3) Strongest Ca isotope fractionations were observed at the nutritive solution/root interface. This implies that the mechanisms of light isotope enrichments in the plant are mainly due to transport processes taking place at this interface. (4) The non infinite L6 nutritive solution became enriched in 44Ca during the experiment compared to the infinite L6 nutritive solution and all the other solutions (L4, H4, and H6). This enrichment can be explained by Rayleigh fractionation or isotopic equilibrium. (5) Bean organs, from L4 and non infinite L6 experiment conditions, were enriched in 44Ca compared to stems and roots cultivated under H4, H6 and infinite L6 conditions. This might be due to the limited Ca in the nutritive solutions that cause smallest Ca isotope fractionations in the bean organs. All these results show that there is no simple correlation between Ca isotopic variations, Ca content and pH of the nutrient solution, and that physiological effects have also to be involved. They confirm the potential of the Ca isotopic system for tracing biological fractionations in natural ecosystems.

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 inorganic precipitation experiments.

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

Comparison of the oxygen and hydrogen isotopes in the juices of fast-growing vegetables and slow-growing fruits.

PubMed

Bong, Yeon-Sik; Lee, Kwang-Sik; Shin, Woo-Jin; Ryu, Jong-Sik

2008-09-01

We have analyzed the oxygen and hydrogen isotopic composition of juices from fruits and vegetables collected from a small orchard in order to investigate the differences in isotopic enrichment and evaporation intensity between fast-growing vegetables and slow-growing fruits grown under the same climatic conditions. The oxygen and hydrogen isotope levels were much higher in the juices of the fruits and vegetables than in the source waters in which they grew because of evaporation effects. According to our data, fast-growing vegetables are subject to greater evaporation than slow-growing fruits. An evaporation experiment using the source water showed that the oxygen and hydrogen isotopic composition of the 60-80% residual fraction was similar to that of the isotopically enriched grape juice, whereas those of the plume and tomato juices were very close to that of the 80-90% residual fraction, thus proving the effect of evaporation. Copyright (c) 2008 John Wiley & Sons, Ltd.

Vibrational Spectroscopy of the CCl[subscript 4] v[subscript 1] Mode: Theoretical Prediction of Isotopic Effects

ERIC Educational Resources Information Center

Gaynor, James D.; Wetterer, Anna M.; Cochran, Rea M.; Valente, Edward J.; Mayer, Steven G.

2015-01-01

Raman spectroscopy is a powerful experimental technique, yet it is often missing from the undergraduate physical chemistry laboratory curriculum. Tetrachloromethane (CCl[subscript 4]) is the ideal molecule for an introductory vibrational spectroscopy experiment and the symmetric stretch vibration contains fine structure due to isotopic variations…

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

Laser ion source for isobaric heavy ion collider experiment.

PubMed

Kanesue, T; Kumaki, M; Ikeda, S; Okamura, M

2016-02-01

Heavy-ion collider experiment in isobaric system is under investigation at Relativistic Heavy Ion Collider. For this experiment, ion source is required to maximize the abundance of the intended isotope. The candidate of the experiment is (96)Ru + (96)Zr. Since the natural abundance of particular isotope is low and composition of isotope from ion source depends on the composites of the target, an isotope enriched material may be needed as a target. We studied the performance of the laser ion source required for the experiment for Zr ions.

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 data correction not be routinely applied for paleo-climate reconstruction, and that P/R ratios should only be obtained by direct measurement by respirometry.

Oxygen isotope fractionation effects in soil water via interaction with cations (Mg, Ca, K, Na) adsorbed to phyllosilicate clay minerals

NASA Astrophysics Data System (ADS)

Oerter, Erik; Finstad, Kari; Schaefer, Justin; Goldsmith, Gregory R.; Dawson, Todd; Amundson, Ronald

2014-07-01

In isotope-enabled hydrology, soil and vadose zone sediments have been generally considered to be isotopically inert with respect to the water they host. This is inconsistent with knowledge that clay particles possessing an electronegative surface charge and resulting cation exchange capacity (CEC) interact with a wide range of solutes which, in the absence of clays, have been shown to exhibit δ18O isotope effects that vary in relation to the ionic strength of the solutions. To investigate the isotope effects caused by high CEC clays in mineral-water systems, we created a series of monominerallic-water mixtures at gravimetric water contents ranging from 5% to 32%, consisting of pure deionized water of known isotopic composition with homoionic (Mg, Ca, Na, K) montmorillonite. Similar mixtures were also created with quartz to determine the isotope effect of non-, or very minimally-, charged mineral surfaces. The δ18O value of the water in these monominerallic soil analogs was then measured by isotope ratio mass spectrometry (IRMS) after direct headspace CO2 equilibration. Mg- and Ca-exchanged homoionic montmorillonite depleted measured δ18O values up to 1.55‰ relative to pure water at 5% water content, declining to 0.49‰ depletion at 30% water content. K-montmorillonite enriched measured δ18O values up to 0.86‰ at 5% water content, declining to 0.11‰ enrichment at 30% water. Na-montmorillonite produces no measureable isotope effect. The isotope effects observed in these experiments may be present in natural, high-clay soils and sediments. These findings have relevance to the interpretation of results of direct CO2-water equilibration approaches to the measurement of the δ18O value of soil water. The adsorbed cation isotope effect may bear consideration in studies of pedogenic carbonate, plant-soil water use and soil-atmosphere interaction. Finally, the observed isotope effects may prove useful as molecular scale probes of the nature of mineral-water interactions.

Position-specific 13C distributions within propane from experiments and natural gas samples

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael D.; Eiler, John M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, 'bulk' isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems.

Position-specific 13C distributions within propane from experiments and natural gas samples

USGS Publications Warehouse

Piasecki, Alison; Sessions, Alex L.; Lawson, Michael; Ferreira, A.A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael; Eilers, J.M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, ‘bulk’ isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems.

The activity-composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: III. Vapor-liquid water equilibration of NaCl solutions to 350°C

NASA Astrophysics Data System (ADS)

Horita, Juske; Cole, David R.; Wesolowski, David J.

1995-03-01

The effect of dissolved NaCl on equilibrium oxygen and hydrogen isotope fractionation factors between liquid water and water vapor was precisely determined in the temperature range from 130-350°C, using two different types of apparatus with static or dynamic sampling techniques of the vapor phase. The magnitude of the oxygen and hydrogen isotope effects of NaCl is proportional to the molality of liquid NaCl solutions at a given temperature. Dissolved NaCl lowers appreciably the hydrogen isotope fractionation factor between liquid water and water vapor over the entire temperature range. NaCl has little effect on the oxygen isotope fractionation factor at temperatures below about 200°C, with the magnitude of the salt effect gradually increasing from 200-350°C. Our results are at notable variance with those of Truesdell (1974) and Kazahaya (1986), who reported large oxygen and hydrogen isotope effects of NaCl with very complex dependencies on temperature and NaCl molality. Our high-temperature results have been regressed along with our previous results between 50 and 100°C (Horita et al., 1993a) and the low-temperature literature data to simple equations which are valid for NaCl solutions from 0 to at least 5 molal NaCl in the temperature range from 10-350°C. Our preliminary results of oxygen isotope fractionation in the system CaCO3-water ± NaCl at 300°C and 1 kbar are consistent with those obtained from the liquid-vapor equilibration experiments, suggesting that the isotope salt effects are common to systems involving brines and any other coexisting phases or species (gases, minerals, dissolved species, etc.). The observed NaCl isotope effects at elevated temperatures should be taken into account in the interpretation of isotopic data of brine-dominated natural systems.

Ti Isotopes: Echoes of Grain-Scale Heterogenaity in the Protoplanetary Disk

NASA Technical Reports Server (NTRS)

Jordan, M. K.; Kohl, I. E.; McCain, K. A.; Simon, J. I.; Young, E. D.

2017-01-01

Calcium-aluminum-rich inclusions (CAIs) are the oldest surviving solids to have formed in the Solar System. Their chemical and isotopic compositions provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of how solids formed in the solar nebula, an important step in the eventual process of planet building. The isotopic compositions of CAIs are primarily controlled by volatility. Evaporation/sublimation are well understood through both theory and experimental work to produce an enrichment in the heavy isotopes of an element, but less is understood about the effects of condensation. Mass-dependent fractionation can potentially provide a record of nebular condensation. Ti is not likely to experience evaporation due to its refractory nature, making it a useful tool for assessing the effects of condensation. We have undertaken a study of the stable isotope fractionation of Ti isotopes as a tracer of processes that predate the last evaporation events affecting CAIs. We compare the 49Ti/47Ti stable isotope ratio with excess 50Ti common in CAIs. We have collected Ti, Mg, Si, and Ca isotope data for a suite of CAIs in order to search for heterogeneity in each of these isotope systems, and for potential correlations among them. We compare our results to expectations for condensation.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

NASA Astrophysics Data System (ADS)

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-10-01

;Clumped-isotope; thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope ;clumps;). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3- and CO32-. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral-solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3-) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

A preliminary study on isotopic evolution of ice by a melting experiment

NASA Astrophysics Data System (ADS)

Ham, J. Y.; Lee, J.; Lee, W. S.; Han, Y.; Hur, S. D.

2016-12-01

Evidences of melted snow at surface were found on some ice cores. Melted layers may generate a significant error when paleo-temperature was retrieved from ice cores using stable water isotopes. To resolve this problem, it is necessary to understand the isotopic changes of ice and its meltwater that is made during the ice and snow melting. Isotopic fractionations between liquid water and snow have been discussed by Taylor et al. (2002) and Lee et al. (2009). The goal of this work is to understand isotopic evolution of ice and its meltwater. Melting experiments in a cold room were designed and conducted with heat source (infrared lamp) to mimic solar radiation. Melting rates were calculated in terms of specific discharge (g/min). To control melting rates, distances between ice surface and heat source were adjusted in various conditions (1 cm, 10 cm and 20 cm). The experiments were conducted by three different melting rates, 1.6 g/min, 3.5 g/min and 5.8 g/min. We used cubic ice that has 3 cm in width, length and height in dimension with 1.5 kg or 2 kg of ice used totally. The total time spent melting the whole ice was 592, 783, and 1180 minutes, respectively. Cold room temperature was range of -1 to 1°C, which removes an effect of air temperature. Meltwater samples were collected and isotopic compositions of oxygen and hydrogen were determined by a cavity ring down spectrometer (Picarro L-1120) installed at the Korea Polar Research Institute. We also analyzed bulk water and bulk ice to make the ice used in the experiments (-8.20 ‰ and -58.73 ‰ for oxygen and hydrogen isotopes, respectively). The isotopic compositions of meltwater increased linearly or to a second degree polynomial. The isotopic variations were larger in the lower melting rates, compared to the higher melting rates (0.65 of lower melting rates vs. 0.35 higher melting rates for oxygen isotope). The slope of linear regression between oxygen and hydrogen ranged 6.2, 7.3 and 6.2, which is less than that of the Global Meteoric Water Line (8) and the sublimation (7.7) suggested by Earman et al. (2006). We believe that isotopic exchange between liquid water and ice plays a crucial role in the variations of isotopes for the ice and its meltwater. We will modify a physically based 1-D model used in the previous studies to better understand the isotopic compositions of ice and its meltwater.

Isotope dependence of the Zeeman effect in lithium-like calcium

PubMed Central

Köhler, Florian; Blaum, Klaus; Block, Michael; Chenmarev, Stanislav; Eliseev, Sergey; Glazov, Dmitry A.; Goncharov, Mikhail; Hou, Jiamin; Kracke, Anke; Nesterenko, Dmitri A.; Novikov, Yuri N.; Quint, Wolfgang; Minaya Ramirez, Enrique; Shabaev, Vladimir M.; Sturm, Sven; Volotka, Andrey V.; Werth, Günter

2016-01-01

The magnetic moment μ of a bound electron, generally expressed by the g-factor μ=−g μB s ħ−1 with μB the Bohr magneton and s the electron's spin, can be calculated by bound-state quantum electrodynamics (BS-QED) to very high precision. The recent ultra-precise experiment on hydrogen-like silicon determined this value to eleven significant digits, and thus allowed to rigorously probe the validity of BS-QED. Yet, the investigation of one of the most interesting contribution to the g-factor, the relativistic interaction between electron and nucleus, is limited by our knowledge of BS-QED effects. By comparing the g-factors of two isotopes, it is possible to cancel most of these contributions and sensitively probe nuclear effects. Here, we present calculations and experiments on the isotope dependence of the Zeeman effect in lithium-like calcium ions. The good agreement between the theoretical predicted recoil contribution and the high-precision g-factor measurements paves the way for a new generation of BS-QED tests. PMID:26776466

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

EXAFS Reveals the Mechanism of U Isotope Fractionation During Adsorption to Mn Oxyhydroxide

NASA Astrophysics Data System (ADS)

Wasylenki, L. E.; Brennecka, G.; Bargar, J.; Weyer, S.; Anbar, A. D.

2010-12-01

Natural variations in the ratio of 238U/235U due to “stable” isotope fractionation have now been reported for a range of geological samples [1-3]. Among the observed variations are a small difference in 238U/235U between seawater and ferromanganese sediments (seawater slightly heavier) and a larger difference, with opposite sense, between seawater and black shales (seawater lighter). These variations suggest that long-term changes in the proportions of oxic and anoxic/sulfidic sinks for U in the ocean over Earth’s history may be recorded as shifts in the isotopic compositions of marine sediments. Thus U isotopes are a potential paleoredox proxy for the oceans, as suggested by [4]. In order to investigate the mechanism behind fractionation of U isotopes in oxidizing marine environments, we previously conducted simple adsorption experiments in which an isotopically known pool of dissolved U partly adsorbed onto synthetic birnessite, a common Mn oxyhydroxide in hydrogenetic ferromanganese crusts. Our experimental result agreed very well with that observed between seawater and natural ferromanganese sediments: δ238U/235U of adsorbed U was 0.2‰ lighter than δ238U/235U of dissolved U [5]. The magnitude of fractionation is constant as a function of experimental duration and fraction of U adsorbed, suggesting an equilibrium isotope effect. Many metal isotope effects are driven by changes in oxidation state for the metal of interest. Because both dissolved and adsorbed U are hexavalent in this system, a redox reaction cannot be causing isotope fractionation. We therefore hypothesized that a difference in uranium’s coordination environment between dissolved and adsorbed U is likely responsible for the isotope effect. We analyzed a sample from our experimental study with extended X-ray absorption fine structure (EXAFS) spectroscopy. Comparison of the EXAFS spectrum of U adsorbed on birnessite with the spectra of aqueous U species (UO22+ and UO2(CO3)34-) reveals subtle, but important differences in the U-O coordination shell between dissolved and adsorbed U. In particular, there is an increase in disorder in the bond distances to equatorial oxygens in the adsorbed complex. Our EXAFS data support our hypothesis that a difference in coordination chemistry drives the isotope effect observed in our experiments. The same mechanism may well explain the U isotope fractionation observed between seawater and hydrogenetic ferromanganese nodules, although a similar investigation of U isotope behavior during adsorption to Fe oxyhydroxides should be undertaken. [1] Weyer et al. (2008) GCA 72, 345. [2] Stirling et al. (2007) EPSL 264, 208. [3] Bopp et al. (2009) Geology, 37, 611. [4] Montoya-Pino et al. (2010) Geology 38, 315. [5] Brennecka et al. (2008) GCA 72(12) Suppl., A114.

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

PubMed

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

2014-01-01

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

Disequilibrium δ18O values in microbial carbonates as a tracer of metabolic production of dissolved inorganic carbon

NASA Astrophysics Data System (ADS)

Thaler, Caroline; Millo, Christian; Ader, Magali; Chaduteau, Carine; Guyot, François; Ménez, Bénédicte

2017-02-01

Carbon and oxygen stable isotope compositions of carbonates are widely used to retrieve paleoenvironmental information. However, bias may exist in such reconstructions as carbonate precipitation is often associated with biological activity. Several skeleton-forming eukaryotes have been shown to precipitate carbonates with significant offsets from isotopic equilibrium with water. Although poorly understood, the origin of these biologically-induced isotopic shifts in biogenic carbonates, commonly referred to as "vital effects", could be related to metabolic effects that may not be restricted to mineralizing eukaryotes. The aim of our study was to determine whether microbially-mediated carbonate precipitation can also produce offsets from equilibrium for oxygen isotopes. We present here δ18O values of calcium carbonates formed by the activity of Sporosarcina pasteurii, a carbonatogenic bacterium whose ureolytic activity produces ammonia (thus increasing pH) and dissolved inorganic carbon (DIC) that precipitates as solid carbonates in the presence of Ca2+. We show that the 1000 lnαCaCO3-H2O values for these bacterially-precipitated carbonates are up to 24.7‰ smaller than those expected for precipitation at isotopic equilibrium. A similar experiment run in the presence of carbonic anhydrase (an enzyme able to accelerate oxygen isotope equilibration between DIC and water) resulted in δ18O values of microbial carbonates in line with values expected at isotopic equilibrium with water. These results demonstrate for the first time that bacteria can induce calcium carbonate precipitation in strong oxygen isotope disequilibrium with water, similarly to what is observed for eukaryotes. This disequilibrium effect can be unambiguously ascribed to oxygen isotope disequilibrium between DIC and water inherited from the oxygen isotope composition of the ureolytically produced CO2, probably combined with a kinetic isotope effect during CO2 hydration/hydroxylation. The fact that both disequilibrium effects are triggered by the metabolic production of CO2, which is common in many microbially-mediated carbonation processes, leads us to propose that metabolically-induced offsets from isotopic equilibrium in microbial carbonates may be more common than previously considered. Therefore, precaution should be taken when using the oxygen isotope signature of microbial carbonates for diagenetic and paleoenvironmental reconstructions.

Mass-independent isotope fractionation of Mo, Ru, Cd, and Te

NASA Astrophysics Data System (ADS)

Fujii, T.; Moynier, F.; Albarède, F.

2006-12-01

The variation of the mean charge distribution in the nucleus with the neutron number of different isotopes induces a tenuous shift of the nuclear field. The mass fractionation induced during phase changes is irregular, notably with 'staggering' between odd and even masses, and becomes increasingly non-linear for neutron-rich isotopes. A strong correlation is observed between the deviation of the isotopic effects from the linear dependence with mass and the corresponding nuclear charge radii. We first demonstrated on a number of elements the existence of such mass-independent isotope fractionation in laboratory experiments of solvent extraction with a macrocyclic compound. The isotope ratios were analyzed by multiple-collector inductively coupled plasma mass spectrometry with a typical precision of <100 ppm. The isotopes of odd and even atomic masses are enriched in the solvent to an extent that closely follows the variation of their nuclear charge radii. The present results fit Bigeleisen's (1996) model, which is the standard mass-dependent theory modified to include a correction term named the nuclear field shift effect. For heavy elements like uranium, the mass-independent effect is important enough to dominate the mass-dependent effect. We subsequently set out to compare the predictions of Bigeleisen's theory with the isotopic anomalies found in meteorites. Some of these anomalies are clearly inconsistent with nucleosynthetic effects (either s- or r-processes). Isotopic variations of Mo and Ru in meteorites, especially in Allende (CV3), show a clear indication of nucleosynthetic components. However, the mass-independent anomaly of Ru observed in Murchison (CM2) is a remarkable exception which cannot be explained by the nucleosynthetic model, but fits the nuclear field shift theory extremely well. The abundances of the even atomic mass Te isotopes in the leachates of carbonaceous chondrites, Allende, Murchison, and Orgueil, fit a mass-dependent law well, but the odd atomic mass isotope ^{125}Te clearly deviates from this correlation. The nuclear field shift theory shows that there is no effect on ^{130}Te but that the ^{125}Te anomaly is real. Carbonaceous chondrites do not reveal significant isotope fractionation of Cd isotopes, but a nuclear field shift effect is clearly present in type-3 (unequilibrated) ordinary chondrites. The nuclear field shift effect is temperature dependent and is probably more frequent in nature than commonly thought. It remains, together with nucleosynthetric anomalies, perfectly visible through the normalization of isotopic ratios to a reference value. In meteorites, this effect may originate both during condensation/evaporation processes in the nebular gas and during the metamorphism of the meteorite parent bodies.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

USGS Publications Warehouse

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-01-01

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium.Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral–solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3−) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Irrigation and fertilization effects on foliar and soil carbon and nitrogen isotope ratios in a loblolly pine stand

Treesearch

Woo-Jung Choi; Scott X. Chang; H. Lee Allen; Daniel L. Kelting; Hee-Myong Ro

2005-01-01

We examined 813C and 815N in needle (current and 1-year-old) and soil samples collected on two occasions (July and September 1999) from a 15-year-old loblolly pine (Pinus taeda L.) stand in an irrigation and fertilization experiment to investigate whether these treatments leave specific isotope signals in...

Delayed signatures of underground nuclear explosions

PubMed Central

Carrigan, Charles R.; Sun, Yunwei; Hunter, Steven L.; Ruddle, David G.; Wagoner, Jeffrey L.; Myers, Katherine B. L.; Emer, Dudley F.; Drellack, Sigmund L.; Chipman, Veraun D.

2016-01-01

Radionuclide signals from underground nuclear explosions (UNEs) are strongly influenced by the surrounding hydrogeologic regime. One effect of containment is delay of detonation-produced radioxenon reaching the surface as well as lengthening of its period of detectability compared to uncontained explosions. Using a field-scale tracer experiment, we evaluate important transport properties of a former UNE site. We observe the character of signals at the surface due to the migration of gases from the post-detonation chimney under realistic transport conditions. Background radon signals are found to be highly responsive to cavity pressurization suggesting that large local radon anomalies may be an indicator of a clandestine UNE. Computer simulations, using transport properties obtained from the experiment, track radioxenon isotopes in the chimney and their migration to the surface. They show that the chimney surrounded by a fractured containment regime behaves as a leaky chemical reactor regarding its effect on isotopic evolution introducing a dependence on nuclear yield not previously considered. This evolutionary model for radioxenon isotopes is validated by atmospheric observations of radioxenon from a 2013 UNE in the Democratic People’s Republic of Korea (DPRK). Our model produces results similar to isotopic observations with nuclear yields being comparable to seismic estimates. PMID:26979288

Delayed signatures of underground nuclear explosions

NASA Astrophysics Data System (ADS)

Carrigan, Charles R.; Sun, Yunwei; Hunter, Steven L.; Ruddle, David G.; Wagoner, Jeffrey L.; Myers, Katherine B. L.; Emer, Dudley F.; Drellack, Sigmund L.; Chipman, Veraun D.

2016-03-01

Radionuclide signals from underground nuclear explosions (UNEs) are strongly influenced by the surrounding hydrogeologic regime. One effect of containment is delay of detonation-produced radioxenon reaching the surface as well as lengthening of its period of detectability compared to uncontained explosions. Using a field-scale tracer experiment, we evaluate important transport properties of a former UNE site. We observe the character of signals at the surface due to the migration of gases from the post-detonation chimney under realistic transport conditions. Background radon signals are found to be highly responsive to cavity pressurization suggesting that large local radon anomalies may be an indicator of a clandestine UNE. Computer simulations, using transport properties obtained from the experiment, track radioxenon isotopes in the chimney and their migration to the surface. They show that the chimney surrounded by a fractured containment regime behaves as a leaky chemical reactor regarding its effect on isotopic evolution introducing a dependence on nuclear yield not previously considered. This evolutionary model for radioxenon isotopes is validated by atmospheric observations of radioxenon from a 2013 UNE in the Democratic People’s Republic of Korea (DPRK). Our model produces results similar to isotopic observations with nuclear yields being comparable to seismic estimates.

Delayed signatures of underground nuclear explosions.

PubMed

Carrigan, Charles R; Sun, Yunwei; Hunter, Steven L; Ruddle, David G; Wagoner, Jeffrey L; Myers, Katherine B L; Emer, Dudley F; Drellack, Sigmund L; Chipman, Veraun D

2016-03-16

Radionuclide signals from underground nuclear explosions (UNEs) are strongly influenced by the surrounding hydrogeologic regime. One effect of containment is delay of detonation-produced radioxenon reaching the surface as well as lengthening of its period of detectability compared to uncontained explosions. Using a field-scale tracer experiment, we evaluate important transport properties of a former UNE site. We observe the character of signals at the surface due to the migration of gases from the post-detonation chimney under realistic transport conditions. Background radon signals are found to be highly responsive to cavity pressurization suggesting that large local radon anomalies may be an indicator of a clandestine UNE. Computer simulations, using transport properties obtained from the experiment, track radioxenon isotopes in the chimney and their migration to the surface. They show that the chimney surrounded by a fractured containment regime behaves as a leaky chemical reactor regarding its effect on isotopic evolution introducing a dependence on nuclear yield not previously considered. This evolutionary model for radioxenon isotopes is validated by atmospheric observations of radioxenon from a 2013 UNE in the Democratic People's Republic of Korea (DPRK). Our model produces results similar to isotopic observations with nuclear yields being comparable to seismic estimates.

Isotope and mixture effects on neoclassical transport in the pedestal

NASA Astrophysics Data System (ADS)

Pusztai, Istvan; Buller, Stefan; Omotani, John T.; Newton, Sarah L.

2017-10-01

The isotope mass scaling of the energy confinement time in tokamak plasmas differs from gyro-Bohm estimates, with implications for the extrapolation from current experiments to D-T reactors. Differences in mass scaling in L-mode and various H-mode regimes suggest that the isotope effect may originate from the pedestal. In the pedestal, sharp gradients render local diffusive estimates invalid, and global effects due to orbit-width scale profile variations have to be taken into account. We calculate neoclassical cross-field fluxes from a radially global drift-kinetic equation using the PERFECT code, to study isotope composition effects in density pedestals. The relative reduction to the peak heat flux due to global effects as a function of the density scale length is found to saturate at an isotope-dependent value that is larger for heavier ions. We also consider D-T and H-D mixtures with a focus on isotope separation. The ability to reproduce the mixture results via single-species simulations with artificial ``DT'' and ``HD'' species has been considered. These computationally convenient single ion simulations give a good estimate of the total ion heat flux in corresponding mixtures. Funding received from the International Career Grant of Vetenskapsradet (VR) (330-2014-6313) with Marie Sklodowska Curie Actions, Cofund, Project INCA 600398, and Framework Grant for Strategic Energy Research of VR (2014-5392).

Effects of climatic seasonality on the isotopic composition of evaporating soil waters

NASA Astrophysics Data System (ADS)

Benettin, Paolo; Volkmann, Till H. M.; von Freyberg, Jana; Frentress, Jay; Penna, Daniele; Dawson, Todd E.; Kirchner, James W.

2018-05-01

Stable water isotopes are widely used in ecohydrology to trace the transport, storage, and mixing of water on its journey through landscapes and ecosystems. Evaporation leaves a characteristic signature on the isotopic composition of the water that is left behind, such that in dual-isotope space, evaporated waters plot below the local meteoric water line (LMWL) that characterizes precipitation. Soil and xylem water samples can often plot below the LMWL as well, suggesting that they have also been influenced by evaporation. These soil and xylem water samples frequently plot along linear trends in dual-isotope space. These trend lines are often termed "evaporation lines" and their intersection with the LMWL is often interpreted as the isotopic composition of the precipitation source water. Here we use numerical experiments based on established isotope fractionation theory to show that these trend lines are often by-products of the seasonality in evaporative fractionation and in the isotopic composition of precipitation. Thus, they are often not true evaporation lines, and, if interpreted as such, can yield highly biased estimates of the isotopic composition of the source water.

U-Pb isotopic systematics of shock-loaded and annealed baddeleyite: Implications for crystallization ages of Martian meteorite shergottites

NASA Astrophysics Data System (ADS)

Niihara, Takafumi; Kaiden, Hiroshi; Misawa, Keiji; Sekine, Toshimori; Mikouchi, Takashi

2012-08-01

Shock-recovery and annealing experiments on basalt-baddeleyite mixtures were undertaken to evaluate shock effects on U-Pb isotopic systematics of baddeleyite. Shock pressures up to 57 GPa caused fracturing of constituent phases, mosaicism of olivine, maskelynitization of plagioclase, and melting, but the phase transition from monoclinic baddeleyite structure to high-pressure/temperature polymorphs of ZrO2 was not confirmed. The U-Pb isotopic systems of the shock-loaded baddeleyite did not show a large-scale isotopic disturbance. The samples shock-recovered from 47 GPa were then employed for annealing experiments at 1000 or 1300 °C, indicating that the basalt-baddeleyite mixture was almost totally melted except olivine and baddeleyite. Fine-grained euhedral zircon crystallized from the melt was observed around the relict baddeleyite in the sample annealed at 1300 °C for 1 h. The U-Pb isotopic systems of baddeleyite showed isotopic disturbances: many data points for the samples annealed at 1000 °C plotted above the concordia. Both radiogenic lead loss/uranium gain and radiogenic lead gain/uranium loss were observed in the baddeleyite annealed at 1300 °C. Complete radiogenic lead loss due to shock metamorphism and subsequent annealing was not observed in the shock-loaded/annealed baddeleyites studied here. These results confirm that the U-Pb isotopic systematics of baddeleyite are durable for shock metamorphism. Since shergottites still preserve Fe-Mg and/or Ca zonings in major constituent phases (i.e. pyroxene and olivine), the shock effects observed in Martian baddeleyites seem to be less intense compared to that under the present experimental conditions. An implication is that the U-Pb systems of baddeleyite in shergottites will provide crystallization ages of Martian magmatic rocks.

Hydrogen isotope fractionation during lipid biosynthesis by Haloarcula marismortui

NASA Astrophysics Data System (ADS)

Dirghangi, Sitindra S.; Pagani, Mark

2013-10-01

We studied the controls on the fractionation of hydrogen isotopes during lipid biosynthesis by Haloarcula marismortui, a halophilic archaea, in pure culture experiments by varying organic substrate, the hydrogen isotope composition (D/H) of water, temperature, and salinity. Cultures were grown on three substrates: succinate, pyruvate and glycerol with known hydrogen isotope compositions, and in water with different hydrogen isotopic compositions. All culture series grown on a particular substrate show strong correlations between δDarchaeol and δDwater. However, correlations are distinctly different for cultures grown on different substrates. Our results indicate that the metabolic pathway of substrate exerts a fundamental influence on the δD value of lipids, likely by influencing the D/H composition of NADPH (nicotinamide adenine dinucleotide phosphate), the reducing agent that contributes hydrogen to carbon atoms during lipid biosynthesis. Temperature and salinity have smaller, but similar effects on δDlipid, primarily due to the way temperature and salinity influence growth rate, as well as temperature effects on the activity of enzymes.

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.

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. Comparing carbon isotope fractionation between CO2 and CH4 with clumped isotope data suggests the temporal variability may result from changes in methane oxidation.

Self diffusion of alkaline-Earth in Ca-Mg-aluminosilicate melts: Experimental improvements on the determination of the self-diffusion coefficients

NASA Technical Reports Server (NTRS)

Paillat, O.; Wasserburg, G. J.

1993-01-01

Experimental studies of self-diffusion isotopes in silicate melts often have quite large uncertainties when comparing one study to another. We designed an experiment in order to improve the precision of the results by simultaneously studying several elements (Mg, Ca, Sr, Ba) during the same experiment thereby greatly reducing the relative experimental uncertainties. Results show that the uncertainties on the diffusion coefficients can be reduced to 10 percent, allowing a more reliable comparison of differences of self-diffusion coefficients of the elements. This type of experiment permits us to study precisely and simultaneously several elements with no restriction on any element. We also designed an experiment to investigate the possible effects of multicomponent diffusion during Mg self-diffusion experiments by comparing cases where the concentrations of the elements and the isotopic compositions are different. The results suggest that there are differences between the effective means of transport. This approach should allow us to investigate the importance of multicomponent diffusion in silicate melts.

Isotopic composition of water vapor near the air-water interface

NASA Astrophysics Data System (ADS)

Zannoni, Daniele; Bergamasco, Andrea; Peschiutta, Mirco; Rampazzo, Giancarlo; Stenni, Barbara

2017-04-01

Evaporation is a key process in water cycle that links liquid water to the atmosphere. In the last fifty years stable isotopes of hydrogen and oxygen have been intensively used to describe climate processes related to evaporation and precipitation, ranging in different spatial and temporal scales. Evaporation introduces large isotopic effects in the phases involved. The well known Craig-Gordon model (Craig & Gordon, 1965) describes those isotopic effects involving several steps and different processes, moving from the air-water interface to the free atmosphere. However, very few works in literature have tested the vertical behavior of the Craig-Gordon model in natural conditions on both fresh and marine waters. In this work we present the results from four field experiments aimed to describe the vertical variability of δ18O and δD in the first few meters over a large water body (the coastal lagoon of Venice, northern Italy) and to test the Craig-Gordon model in such conditions. Each experiment involved cryotrapping of water vapor at different height over the water surface (0.1m, 2m and 4m) and the sampling of the liquid water at two depth (surface and 0.5m). During the experiments, water vapor was also sampled in the nearest mainland (˜2.5 km from gradient measurements) to determine the isotopic composition of background water vapor. Liquid samples were then analyzed with a Picarro L1102-i and Thermo-Fisher Delta Plus Advantage for water vapor and lagoon water, respectively. The last two experiments have also involved simultaneous measurements of relative humidity using commercially-available humidity probes at each height. This approach was used to determine a reference scale in order to compare observations to modeled estimates. Despite the coarse time resolution due to cryotrapping method (measurements are averaged over 1.5 hours), preliminary results show measurable differences in the isotopic composition of water vapor along the vertical gradient and good agreement between observations and predicted values from the model. Even if this work is an exploratory phase it shows an interesting potential to grow our understanding of the processes involved as well as a useful implementation for future studies focused on fractionation of water isotopes due to evaporation in natural conditions. References Craig, H., & Gordon, L. I. (1965). Deuterium and oxygen 18 variations in the ocean and the marine atmosphere.

Parallel labeling experiments and metabolic flux analysis: Past, present and future methodologies.

PubMed

Crown, Scott B; Antoniewicz, Maciek R

2013-03-01

Radioactive and stable isotopes have been applied for decades to elucidate metabolic pathways and quantify carbon flow in cellular systems using mass and isotope balancing approaches. Isotope-labeling experiments can be conducted as a single tracer experiment, or as parallel labeling experiments. In the latter case, several experiments are performed under identical conditions except for the choice of substrate labeling. In this review, we highlight robust approaches for probing metabolism and addressing metabolically related questions though parallel labeling experiments. In the first part, we provide a brief historical perspective on parallel labeling experiments, from the early metabolic studies when radioisotopes were predominant to present-day applications based on stable-isotopes. We also elaborate on important technical and theoretical advances that have facilitated the transition from radioisotopes to stable-isotopes. In the second part of the review, we focus on parallel labeling experiments for (13)C-metabolic flux analysis ((13)C-MFA). Parallel experiments offer several advantages that include: tailoring experiments to resolve specific fluxes with high precision; reducing the length of labeling experiments by introducing multiple entry-points of isotopes; validating biochemical network models; and improving the performance of (13)C-MFA in systems where the number of measurements is limited. We conclude by discussing some challenges facing the use of parallel labeling experiments for (13)C-MFA and highlight the need to address issues related to biological variability, data integration, and rational tracer selection. Copyright © 2012 Elsevier Inc. All rights reserved.

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.

13C metabolic flux analysis: optimal design of isotopic labeling experiments.

PubMed

Antoniewicz, Maciek R

2013-12-01

Measuring fluxes by 13C metabolic flux analysis (13C-MFA) has become a key activity in chemical and pharmaceutical biotechnology. Optimal design of isotopic labeling experiments is of central importance to 13C-MFA as it determines the precision with which fluxes can be estimated. Traditional methods for selecting isotopic tracers and labeling measurements did not fully utilize the power of 13C-MFA. Recently, new approaches were developed for optimal design of isotopic labeling experiments based on parallel labeling experiments and algorithms for rational selection of tracers. In addition, advanced isotopic labeling measurements were developed based on tandem mass spectrometry. Combined, these approaches can dramatically improve the quality of 13C-MFA results with important applications in metabolic engineering and biotechnology. Copyright © 2013 Elsevier Ltd. All rights reserved.

Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

USGS Publications Warehouse

Green, Christopher T.; Böhlke, John Karl; Bekins, Barbara A.; Phillips, Steven P.

2010-01-01

Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field‐scale (apparent) estimated reaction rates and isotopic fractionations and local‐scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample‐based estimates of “apparent” parameters with “true“ (intrinsic) values. For this aquifer, non‐Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport.

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 experiments were performed with bacterial nitric oxide reductase from Paracoccus denitrificans (cNOR). In this case both Nα and Nβ exhibited inverse isotope effects, while O had a normal isotope effect. Together, these data highlight the utility in using stable isotopes as both tracers and mechanistic probes when studying metabolic processes.

Isotopic Expression of Soil Denitrification across Gradients in Nitrogen and Carbon Availability

NASA Astrophysics Data System (ADS)

Walker, R.; Houlton, B. Z.; Perakis, S. S.

2016-12-01

Denitrification removes biologically available nitrogen (N) from ecosystems, making it an important control over the biosphere's N balance, with implications for air quality, human health and climate change. Despite its importance, estimates of the global soil denitrification flux remain highly uncertain. Major challenges lie in directly measuring the gaseous by-products of denitrification and scaling this complex microbial processes in both space and time. Process-based models constrained by empirical isotopic evidence have emerged as a method to help overcome these challenges. These models use the terrestrial 15N budget, along with soil moisture and N input data, to quantify denitrification fluxes and its gaseous forms, including NO, N2O and N2. However, the robustness of this method is limited by incomplete understanding of isotopic expression of denitrification and how it varies across known controls, such as carbon (C) and nitrate (NO3) availability. Here, we present a quantitative assessment of the isotope effect expression of in situ soil denitrification across gradients in N and C concentrations. This experiment tests the hypothesis that isotopic expression of soil denitrification (a kinetic process) increases with NO3 availability (reaction substrate) and decreases with increasing availability of organic C (electron donor). To test the impact of NO3 availability on the isotope effect of denitrification, field incubations experiments were conducted across a natural soil N gradient, ranging from 0.11 to 0.69% N. Similarly, the impact of electron donor availability was tested by conducting field incubations across a natural soil C gradient ranging from 1.94 to 11.60%. Data show that in lower N sites, the percent of NO3 consumed during the incubation was higher, while C availability neither affected the fraction of NO3 consumed nor the rate of consumption. These findings suggest that greater NO3 concentrations allow for greater isotope expression of denitrification in soil, supporting the working hypothesis. These results will be complemented by laboratory experiments in which NO3 concentration, C availability, and temperature are systematically varied. Future goals include the incorporation of these data into existing models to improve estimates of global N fluxes.

Investigation of the quasi-simultaneous arrival (QSA) effect on a CAMECA IMS 7f-GEO.

PubMed

Jones, Clive; Fike, David A; Peres, Paula

2017-04-15

IMS 7f-GEO isotope ratio applications increasingly involve analyses (e.g., S - or O - isotopes, coupled with primary ion currents <30 pA) for which quasi-simultaneous arrival (QSA) could compromise precision and accuracy of data. QSA and associated correction have been widely investigated for the CAMECA NanoSIMS instruments, but not for the IMS series. Sulfur and oxygen isotopic ratio experiments were performed using an electron multiplier (EM) detector, employing Cs + primary ion currents of 1, 2, 5 and 11.5 pA (nominal) and a variety of secondary ion transmissions to vary QSA probability. An experiment to distinguish between QSA undercounting and purported aperture-related mass fractionation was performed using an EM for 16 O - and 18 O - plus an additional 16 O - measurement using a Faraday cup (FC) detector. An experiment to investigate the accuracy of the QSA correction was performed by comparing S isotopic ratios obtained using an EM with those obtained on the same sample using dual FCs. The QSA effect was observed on the IMS-7f-GEO, and QSA coefficients (β) of ~0.66 were determined, in agreement with reported NanoSIMS measurements, but different from the value (0.5) predicted using Poisson statistics. Aperture-related fractionation was not sufficient to explain the difference but uncertainties in primary ion flux measurement could play a role. When QSA corrected, the isotope ratio data obtained using the EM agreed with the dual FC data, within statistical error. QSA undercounting could compromise isotope ratio analyses requiring ~1 × 10 5 counts per second for the major isotope and primary currents <20 pA. The error could be >8‰ for a 1 pA primary current. However, correction can be accurately applied. For instrumental mass fractionation (IMF)-corrected data, the magnitude of the error resulting from not correcting for QSA is dependent on the difference in secondary ion count rate between the unknown and standard analyses. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Study of the cosmogenic activation in NaI(Tl) crystals within the ANAIS experiment

NASA Astrophysics Data System (ADS)

Villar, P.; Amaré, J.; Cebrián, S.; Coarasa, I.; García, E.; Martínez, M.; Oliván, M. A.; Ortigoza, Y.; Ortiz de Solórzano, A.; Puimedón, J.; Sarsa, M. L.; Villar, J. A.

2018-03-01

The direct detection of galactic dark matter particles requires ultra-low background conditions. NaI(Tl) crystals are applied in the search for these dark matter particles through their interactions in the detector by measuring the scintillation signal produced. The production of long-lived isotopes in materials due to the exposure to cosmic rays on Earth’s surface can be an hazard for these ultra-low background demanding experiments, typically performed underground. Therefore, production rates of cosmogenic isotopes in all the materials present in the experimental set-up, as well as the corresponding cosmic rays exposure history, must be both well-known in order to assess the relevance of this effect in the achievable sensitivity of a given experiment. Here, analysis of the cosmogenic studies developed from the ANAIS experiment NaI(Tl) detectors are presented. Installed inside a convenient shielding at the Canfranc Underground Laboratory just after finishing surface exposure to cosmic rays and thanks to the prompt data taking developed, identification and quantification of isotopes with half-lives of the order of tens of days were allowed, and thanks to the long-term operation of the detectors long-lived isotopes have been also identified and quantified. Main results for the activation yields of iodine and tellurium isotopes, 22Na, 113Sn, 109Cd, and tritium are presented in this work, together with the estimate of the production rates for their activation by cosmic nucleons while on Earth’s surface based on a selection of excitation functions over the entire energy range of cosmic nucleons.

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

USGS Publications Warehouse

Balci, N.; Shanks, Wayne C.; Mayer, B.; Mandernack, K.W.

2007-01-01

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on ??18O and ??34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)aq as an oxidant with varying ??18OH2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ???2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ???2.7. The ??34SSO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (???-0.7???) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (??18 OSO4 s(-) H2 O) of ???3.5??? was determined for the anaerobic (biological and abiotic) experiments. This measured ??18 OSO42 - s(-) H2 O value was then used to estimate the oxygen isotope fractionation effects (??18 OSO42 - s(-) O2) between sulfate and dissolved oxygen in the aerobic experiments which were -10.0???, -10.8???, and -9.8??? for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between ??18OSO4 values in the biological and abiotic experiments, it is suggested that ??18OSO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions. ?? 2007 Elsevier Ltd. All rights reserved.

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 precursor phase in diamond-growth experiments in carbonatite systems and natural diamonds. [1] Chacko et al. (2001) Rev Min Geochem; Deines & Eggler (2009) GCA; [3] Scheele & Hoefs (1992) CMP; [4] Chacko et al. (1991) GCA

Temporal and spatial distribution of isotopes in river water in Central Europe: 50 years experience with the Austrian network of isotopes in rivers.

PubMed

Rank, Dieter; Wyhlidal, Stefan; Schott, Katharina; Weigand, Silvia; Oblin, Armin

2018-05-01

The Austrian network of isotopes in rivers comprises about 15 sampling locations and has been operated since 1976. The Danube isotope time series goes back to 1963. The isotopic composition of river water in Central Europe is mainly governed by the isotopic composition of precipitation in the catchment area; evaporation effects play only a minor role. Short-term and long-term isotope signals in precipitation are thus transmitted through the whole catchment. The influence of climatic changes has become observable in the long-term stable isotope time series of precipitation and surface waters. Environmental 3 H values were around 8 TU in 2015, short-term 3 H pulses up to about 80 TU in the rivers Danube and March were a consequence of releases from nuclear power plants. The complete isotope data series of this network will be included in the Global Network of Isotopes in Rivers database of the International Atomic Energy Agency (IAEA) in 2017. This article comprises a review of 50 years isotope monitoring on rivers and is also intended to provide base information on the (isotope-)hydrological conditions in Central Europe specifically for the end-users of these data, e.g. for modelling hydrological processes. Furthermore, this paper includes the 2006-2015 supplement adding to the Danube isotope set published earlier.

Magnesium isotope fractionation between brucite [Mg(OH)2] and Mg aqueous species: Implications for silicate weathering and biogeochemical processes

NASA Astrophysics Data System (ADS)

Li, Weiqiang; Beard, Brian L.; Li, Chengxiang; Johnson, Clark M.

2014-05-01

Brucite, with its octahedral structure, has a lattice configuration that is similar to the Mg-bearing octahedral layers in phyllosilicates. Understanding stable Mg isotope fractionation between brucite and aqueous solution therefore bears on interpretation of Mg isotope data in natural weathering systems. In this study, we experimentally determined Mg isotope fractionation between brucite and two Mg aqueous species, the free Mg aquo ion ([Mg(OH2)6]2+) and EDTA-bonded Mg (Mg-EDTA2-). Results from recrystallization and brucite synthesis experiments suggest mild preferential partitioning of light Mg isotopes into brucite compared to Mg aquo ions at low temperatures, where measured ΔMgbrucite-Mg26 fractionation increased from ca. -0.3‰ at 7 °C, to ca. -0.2‰ at 22 °C, to ca. 0‰ at 40 °C. MgO hydrolysis experiments in EDTA-bearing solutions suggest that the ΔMgbrucite-Mg-EDTA26 fractionation is ⩾+2.0‰ at 22 °C, indicating that light Mg isotopes strongly partition into Mg-EDTA complex relative to brucite, as well as relative to Mg aquo ions. Magnesium atoms in brucite, Mg aquo ions, and Mg-EDTA complexes are all octahedrally coordinated, and the measured Mg isotope fractionations correlate with average bond lengths for Mg. Aqueous Mg ions have the shortest bond length among the three phases, and enrich heavy Mg isotopes relative to brucite and Mg-EDTA. In contrast, Mg-EDTA has the longest average bond length for Mg, and enriches light Mg isotopes relative to Mg aquo ions and brucite; the relatively long Mg-EDTA bond suggests that organically bound Mg may commonly have low 26Mg/24Mg ratios, which may explain proposed "vital" effects for stable Mg isotopes. Such relations between bond length and Mg isotope fractionation could be extended to other phyllosilicates such as serpentine- and clay-group minerals where Mg is also octahedrally coordinated.

Delayed signatures of underground nuclear explosions

DOE PAGES

Carrigan, Charles R.; Sun, Yunwei; Hunter, Steven L.; ...

2016-03-16

Radionuclide signals from underground nuclear explosions (UNEs) are strongly influenced by the surrounding hydrogeologic regime. One effect of containment is delay of detonation-produced radioxenon reaching the surface as well as lengthening of its period of detectability compared to uncontained explosions. Using a field-scale tracer experiment, we evaluate important transport properties of a former UNE site. Here, we observe the character of signals at the surface due to the migration of gases from the post-detonation chimney under realistic transport conditions. Background radon signals are found to be highly responsive to cavity pressurization suggesting that large local radon anomalies may be anmore » indicator of a clandestine UNE. Computer simulations, using transport properties obtained from the experiment, track radioxenon isotopes in the chimney and their migration to the surface. They show that the chimney surrounded by a fractured containment regime behaves as a leaky chemical reactor regarding its effect on isotopic evolution introducing a dependence on nuclear yield not previously considered. This evolutionary model for radioxenon isotopes is validated by atmospheric observations of radioxenon from a 2013 UNE in the Democratic People’s Republic of Korea (DPRK). In conclusion, our model produces results similar to isotopic observations with nuclear yields being comparable to seismic estimates.« less

Accurate experimental determination of the isotope effects on the triple point temperature of water. I. Dependence on the 2H abundance

NASA Astrophysics Data System (ADS)

Faghihi, V.; Peruzzi, A.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; van Geel, J.; Meijer, H. A. J.

2015-12-01

Variation in the isotopic composition of water is one of the major contributors to uncertainty in the realization of the triple point of water (TPW). Although the dependence of the TPW on the isotopic composition of the water has been known for years, there is still a lack of a detailed and accurate experimental determination of the values for the correction constants. This paper is the first of two articles (Part I and Part II) that address quantification of isotope abundance effects on the triple point temperature of water. In this paper, we describe our experimental assessment of the 2H isotope effect. We manufactured five triple point cells with prepared water mixtures with a range of 2H isotopic abundances encompassing widely the natural abundance range, while the 18O and 17O isotopic abundance were kept approximately constant and the 18O  -  17O ratio was close to the Meijer-Li relationship for natural waters. The selected range of 2H isotopic abundances led to cells that realised TPW temperatures between approximately  -140 μK to  +2500 μK with respect to the TPW temperature as realized by VSMOW (Vienna Standard Mean Ocean Water). Our experiment led to determination of the value for the δ2H correction parameter of A2H  =  673 μK / (‰ deviation of δ2H from VSMOW) with a combined uncertainty of 4 μK (k  =  1, or 1σ).

Experimental investigation of sulphur isotope partitioning during outgassing of hydrogen sulphide from diluted aqueous solutions and seawater.

PubMed

Baune, Claudia; Bottcher, Michael E

2010-12-01

The diffusion of hydrogen sulphide across the sediment-water interface and subsequent liberation to the atmosphere may occur in iron-deficient coastal marine environments with enhanced microbial activity in surface sediments and corresponding accumulation of dissolved H2S in near-surface pore waters. The involvement of analogue processes in periods of global mass extinctions during Earth's history (e.g. at the Permian-Triassic boundary) is currently in discussion [L.R. Kump, A. Pavlov, and M. Arthur,Massive Release of Hydrogen Sulfide to the Surface Ocean and Atmosphere During Intervals of Oceanic Anoxia, Geology 33, 397 (2005)]. The outgassing of H₂S is associated with a fractionation of the stable sulphur isotopes, which has so far only been investigated experimentally at selected acidic and neutral pH values, and no experiments with seawater had been carried out. In this communication, we report on sulphur isotope fractionation that takes place during the experimental degassing of H₂S from aqueous solution by an inert gas (N₂) at 21 °C. Experiments were conducted in the pH range between 2.6 and 10.8, corresponding to the dominance fields of dissolved hydrogen sulphide (H₂S(aq)), bisulphide (HS-(aq)), and mixtures of both sulphide species. Overall isotope enrichment factors between -1.6 and +3.0‰ were observed, with the residual dissolved sulphide being enriched or depleted in ³⁴S compared to the liberated H₂S at low and high pH values, respectively. The difference in the low and high pH isotope fractionation effects can be explained by isotope exchange between H₂S(aq) and HS-(aq) [B. Fry, H. Gest, and J.M. Hayes, Sulfur Isotope Effects Associated with Protonation of HS- and Volatilization of H₂S, Chem. Geol. (Isot. Geosci. Sec.) 58, 253 (1986); R. Geßler and K. von Gehlen, Investigation of Sulfur Isotope Fractionation Between H2S Gas and Aqueous Solutions, Fresenius J. Anal. Chem. 324, 130 (1986)] followed by the subsequent transfer of H₂S(aq) to the gaseous phase. The assumption of pure physical outgassing of H₂S(aq) at low pH values leads to an isotope enrichment factor of -0.9 ± 0.4‰ (n = 14) which is caused by the combined differences in dehydration and diffusion coefficients of H₂³²S(aq) and H₂³⁴S(aq). In the pH range of natural surface and shallow pore waters, ³⁴S will be equal to or enriched in the gaseous phase compared to the aqueous solution, therefore creating no or a slight enrichment of ³²S in the aqueous solution. Experiments in seawater solution showed no significant influence of increased ionic strength and changed corresponding aqueous speciation on sulphur isotope effects.

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.

Uranium isotope fractionation in biogenic carbonates: biological effects

NASA Astrophysics Data System (ADS)

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

2017-12-01

Recent laboratory experiments have demonstrated small but potentially significant isotope fractionation ( 0.10 ‰ for 238U/235U) during uranium (U) incorporation into abiotic calcite and aragonite, with heavier U isotopes preferentially enriched in the precipitates [1]. In contrast, measurements of natural biogenic carbonates to date have not been able to resolve significant U isotopic fractionation from seawater although this might be expected given a typical measurement precision of ± 0.10 ‰. Determining whether or not biogenic carbonates display U isotope fractionation similar to abiotic carbonates could have important implications for understanding the mechanisms of U incorporation into various biogenic carbonates. Furthermore, because most marine carbonates are biogenic, the extent of isotopic fractionation, if any, could have important implications for the interpretation of sedimentary carbonates record similar to effects observed for Cr and B isotopes [2, 3]. To resolve this discrepancy, we utilized a higher precision 238U/235U method which uses larger sample sizes to improve measurement precision of natural samples to ± 0.02 ‰ (2 se, N = 6) [4]. Using this method, we have surveyed 238U/235U in primary biogenic skeletal carbonates including scleractinian corals, green and red algae, and mollusks, as well as non-skeletal carbonates such as stromatolites, ooids, and carbonate sands from the Bahamas, Gulf of California, and French Polynesia. New high-precision U isotopes measurements reveal that biogenic skeletal carbonates are typically 0.02 - 0.08 ‰ heavier than modern seawater. Scleractinian corals display values closest to seawater (- 0.37 ‰), while green algae, red algae, mollusks, and echinoderms display variable but larger extents of fractionation up to 0.08 ‰. The direction and magnitude of U isotope fractionation in these biogenic precipitates are generally consistent with results from abiotic coprecipitation experiments, but may be subject to variations in U speciation and carbonate chemistry at calcification sites. [1] Chen et a., (2016), GCA, 188, 189-207. [2] Wang et a., (2016), Geobiology, 5, 51-64. [3] Pagani et al., (2005) GCA, 69, 953-961. [4] Andersen et al., (2016) CG, 420, 11-22.

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-reduction pathway and suppressed the photo-oxidation reaction. Photochemical oxidation experiments of Hg(0) were performed in quartz reaction chambers using natural sunlight. Solutions of aqueous Hg(0) were prepared by continuously bubbling vapor Hg(0) generated by a gas-liquid separator into the quartz reaction chamber filled with water. Experiments were conducted in the presence of Cl- and other potential oxidants such as semiquinone, hydroxyl radicals and H2O2 to assess if the presence of these different oxidants showed significant differences in the expression of Hg isotopic fractionation during the photo-oxidation process. For experiments run in the presence of Cl- only, ~2% of Hg was oxidized at the end of 7 hours whereas in the presence of both semiquinone radical and Cl- , approximately 20% of Hg was oxidized at the end of 6 hours. In the experiment with hydroxyl radicals present, ~ 7% of Hg was oxidized at the end of 6.5 hours. Another set of experiments were conducted where the net photo-reduction was mimicked, which allowed both photo-oxidation and photo-reduction to occur. Isotopic results and their implications on the redox cycle of mercury obtained from these experiments will be discussed in detail.

ICT: isotope correction toolbox.

PubMed

Jungreuthmayer, Christian; Neubauer, Stefan; Mairinger, Teresa; Zanghellini, Jürgen; Hann, Stephan

2016-01-01

Isotope tracer experiments are an invaluable technique to analyze and study the metabolism of biological systems. However, isotope labeling experiments are often affected by naturally abundant isotopes especially in cases where mass spectrometric methods make use of derivatization. The correction of these additive interferences--in particular for complex isotopic systems--is numerically challenging and still an emerging field of research. When positional information is generated via collision-induced dissociation, even more complex calculations for isotopic interference correction are necessary. So far, no freely available tools can handle tandem mass spectrometry data. We present isotope correction toolbox, a program that corrects tandem mass isotopomer data from tandem mass spectrometry experiments. Isotope correction toolbox is written in the multi-platform programming language Perl and, therefore, can be used on all commonly available computer platforms. Source code and documentation can be freely obtained under the Artistic License or the GNU General Public License from: https://github.com/jungreuc/isotope_correction_toolbox/ {christian.jungreuthmayer@boku.ac.at,juergen.zanghellini@boku.ac.at} Supplementary data are available at Bioinformatics online. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

The effects of nitrogen pollutants on the isotopic signal (δ15N) of Ulva lactuca: Microcosm experiments.

PubMed

Orlandi, Lucia; Calizza, Edoardo; Careddu, Giulio; Carlino, Pasquale; Costantini, Maria Letizia; Rossi, Loreto

2017-02-15

Effects of two chemical forms of Nitrogen (NH 4 + and NO 3 - ) on δ 15 N in Ulva lactuca were analysed separately and in mixture at two concentrations. We assessed whether the δ 15 N values of U. lactuca discriminate between Nitrogen from synthetic fertilisers (inorganic) and from fresh cow manure (organic), and the isotopic ability of the macroalga to reflect Nitrogen concentrations. Isotopic signature and N content of the macroalga reflected different nitrogenous sources and their concentrations after 48h. The inorganic Nitrogen source (NH 4 NO 3 ) altered the isotopic values of the macroalgae more than Nitrogen from fresh cow manure (NO 3 - ). δ 15 N values observed in the mixed solution did not differ from those displayed in NH 4 NO 3 treatment alone. We conclude that stable isotope analysis of U. lactuca collected in an unpolluted site and experimentally submerged in sites suspected of being affected by disturbance is a useful tool for rapid monitoring of anthropogenic discharges of Nitrogen pollutants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of 10B isotope and vacancy defects on the phonon modes of two-dimensional hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Sherajul Islam, Md.; Anindya, Khalid N.; Bhuiyan, Ashraful G.; Tanaka, Satoru; Makino, Takayuki; Hashimoto, Akihiro

2018-02-01

We report the details of the effects of the 10B isotope and those of B and N vacancies combined with the isotope on the phonon modes of two-dimensional hexagonal boron nitride (h-BN). The phonon density of states and localization problems are solved using the forced vibrational method, which is suitable for an intricate and disordered system. We observe an upward shift of Raman-active E2g-mode optical phonons (32 cm-1) for a 100% 10B isotope, which matches well with the experiment and simple harmonic oscillator model. However, a downward shift of E2g-mode phonons is observed for B or N vacancies and the combination of the isotope and vacancy-type disordered BN. Strong localized eigenmodes are found for all types of defects, and a typical localization length is on the order of ˜7 nm for naturally occurring BN samples. These results are very important for understanding the heat dissipation and electron transport properties of BN-based nanoelectronics.

Evaluation of the plasma hydrogen isotope content by residual gas analysis at JET and AUG

NASA Astrophysics Data System (ADS)

Drenik, A.; Alegre, D.; Brezinsek, S.; De Castro, A.; Kruezi, U.; Oberkofler, M.; Panjan, M.; Primc, G.; Reichbauer, T.; Resnik, M.; Rohde, V.; Seibt, M.; Schneider, P. A.; Wauters, T.; Zaplotnik, R.; ASDEX-Upgrade, the; EUROfusion MST1 Teams; contributors, JET

2017-12-01

The isotope content of the plasma reflects on the dynamics of isotope changeover experiments, efficiency of wall conditioning and the performance of a fusion device in the active phase of operation. The assessment of the isotope ratio of hydrogen and methane molecules is used as a novel method of assessing the plasma isotope ratios at JET and ASDEX-Upgrade (AUG). The isotope ratios of both molecules in general shows similar trends as the isotope ratio detected by other diagnostics. At JET, the absolute values of RGA signals are in relatively good agreement with each other and with spectroscopy data, while at AUG the deviation from neutral particle analyser data are larger, and the results show a consistent spatial distribution of the isotope ratio. It is further shown that the isotope ratio of the hydrogen molecule can be used to study the degree of dissociation of the injected gas during changeover experiments.

Fractionation of Nitrogen and Oxygen Isotopes and Roles of Bacteria during Denitrification

NASA Astrophysics Data System (ADS)

Kang, J.; Buyanjargal, A.; Jeen, S. W.

2017-12-01

Nitrate in groundwater can cause health and environmental problems when not properly treated. The purpose of this study was to develop a treatment method for nitrate in groundwater using organic carbon-based reactive mixtures (i.e., wood chips and gravel) through column experiments and to evaluate reaction mechanisms responsible for the treatment. The column experiments were operated for a total of 19 months. The results from the geochemical analyses for the experiments suggest that cultures of denitrifying bacteria used organic carbon while utilizing nitrate as their electron acceptor via denitrification process. Proteobacteria was the most abundant phylum in all samples, accounting for 45.7% of the bacterial reads, followed by Firmicutes (22.6%) and Chlorobi (10.6%). Bacilli, Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, and Actinobacteria_c consisted of 32, 30, 23, 11, and 2% of denitrifying bacteria class. The denitrification process caused fractionation of nitrogen and oxygen isotopes of nitrate while nitrate concentration decreased. When fitted to the Rayleigh's fractionation model, enrichment factors (ɛ) were 11.5‰ and 5.6‰ for 15N and 18O isotopes, respectively. Previous studies suggested that nitrogen isotope enrichment factors of denitrification are within the range of 4.7 to 40‰ and oxygen isotopic enrichment factors are between 8 and 18.3‰. This study shows that nitrate in groundwater can be effectively treated using passive treatment systems, such as permeable reactive barriers (PRBs), and denitrificaton is the dominant process reponsible for the removal of nitrate.

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

Non-chondritic iron isotope ratios in planetary mantles as a result of core formation

NASA Astrophysics Data System (ADS)

Elardo, Stephen M.; Shahar, Anat

2017-02-01

Information about the materials and conditions involved in planetary formation and differentiation in the early Solar System is recorded in iron isotope ratios. Samples from Earth, the Moon, Mars and the asteroid Vesta reveal significant variations in iron isotope ratios, but the sources of these variations remain uncertain. Here we present experiments that demonstrate that under the conditions of planetary core formation expected for the Moon, Mars and Vesta, iron isotopes fractionate between metal and silicate due to the presence of nickel, and enrich the bodies' mantles in isotopically light iron. However, the effect of nickel diminishes at higher temperatures: under conditions expected for Earth's core formation, we infer little fractionation of iron isotopes. From our experimental results and existing conceptual models of magma ocean crystallization and mantle partial melting, we find that nickel-induced fractionation can explain iron isotope variability found in planetary samples without invoking nebular or accretionary processes. We suggest that near-chondritic iron isotope ratios of basalts from Mars and Vesta, as well as the most primitive lunar basalts, were achieved by melting of isotopically light mantles, whereas the heavy iron isotope ratios of terrestrial ocean floor basalts are the result of melting of near-chondritic Earth mantle.

Stable carbon isotope fractionation of trans-1,2-dichloroethylene during co-metabolic degradation by methanotrophic bacteria

USGS Publications Warehouse

Brungard, Karen L.; Munakata-Marr, Junko; Johnson, Craig A.; Mandernack, Kevin W.

2003-01-01

Changes in the carbon isotope ratio (δ13C) of trans-1,2-dichloroethylene (t-DCE) were measured during its co-metabolic degradation by Methylomonas methanica, a type I methanotroph, and Methylosinus trichosporium OB3b, a type II methanotroph. In closed-vessel incubation experiments with each bacterium, the residual t-DCE became progressively enriched in 13C, indicating isotopic fractionation. From these experiments, the biological fractionation during t-DCE co-metabolism, expressed as ε, was measured to be -3.50/00 for the type I culture and -6.70/00 for the type II culture. This fractionation effect and subsequent enrichment in the δ13C of the residual t-DCE can thus be applied to determine the extent of biodegradation of DCE by these organisms. Based on these results, isotopic fractionation clearly warrants further study, as measured changes in the δ13C values of chlorinated solvents could ultimately be used to monitor the extent of biodegradation in laboratory or field settings where co-metabolism by methanotrophs occurs.

Effects of preservation methods of muscle tissue from upper-trophic level reef fishes on stable isotope values (δ (13)C and δ (15)N).

PubMed

Stallings, Christopher D; Nelson, James A; Rozar, Katherine L; Adams, Charles S; Wall, Kara R; Switzer, Theodore S; Winner, Brent L; Hollander, David J

2015-01-01

Research that uses stable isotope analysis often involves a delay between sample collection in the field and laboratory processing, therefore requiring preservation to prevent or reduce tissue degradation and associated isotopic compositions. Although there is a growing literature describing the effects of various preservation techniques, the results are often contextual, unpredictable and vary among taxa, suggesting the need to treat each species individually. We conducted a controlled experiment to test the effects of four preservation methods of muscle tissue from four species of upper trophic-level reef fish collected from the eastern Gulf of Mexico (Red Grouper Epinephelus morio, Gag Mycteroperca microlepis, Scamp Mycteroperca phenax, and Red Snapper Lutjanus campechanus). We used a paired design to measure the effects on isotopic values for carbon and nitrogen after storage using ice, 95% ethanol, and sodium chloride (table salt), against that in a liquid nitrogen control. Mean offsets for both δ (13)C and δ (15)N values from controls were lowest for samples preserved on ice, intermediate for those preserved with salt, and highest with ethanol. Within species, both salt and ethanol significantly enriched the δ (15)N values in nearly all comparisons. Ethanol also had strong effects on the δ (13)C values in all three groupers. Conversely, for samples preserved on ice, we did not detect a significant offset in either isotopic ratio for any of the focal species. Previous studies have addressed preservation-induced offsets in isotope values using a mass balance correction that accounts for changes in the isotope value to that in the C/N ratio. We tested the application of standard mass balance corrections for isotope values that were significantly affected by the preservation methods and found generally poor agreement between corrected and control values. The poor performance by the correction may have been due to preferential loss of lighter isotopes and corresponding low levels of mass loss with a substantial change in the isotope value of the sample. Regardless of mechanism, it was evident that accounting for offsets caused by different preservation methods was not possible using the standard correction. Caution is warranted when interpreting the results from specimens stored in either ethanol or salt, especially when using those from multiple preservation techniques. We suggest the use of ice as the preferred preservation technique for muscle tissue when conducting stable isotope analysis as it is widely available, inexpensive, easy to transport and did not impart a significant offset in measured isotopic values. Our results provide additional evidence that preservation effects on stable isotope analysis can be highly contextual, thus requiring their effects to be measured and understood for each species and isotopic ratio of interest before addressing research questions.

Fractionation of stable isotopes in perchlorate and nitrate during in situ biodegradation in a sandy aquifer

USGS Publications Warehouse

Hatzinger, P.B.; Böhlke, J.K.; Sturchio, N.C.; Gu, B.; Heraty, L.J.; Borden, R.C.

2009-01-01

Environmental context. Perchlorate (ClO4-) and nitrate (NO3-) are common co-contaminants in groundwater, with both natural and anthropogenic sources. Each of these compounds is biodegradable, so in situ enhanced bioremediation is one alternative for treating them in groundwater. Because bacteria typically fractionate isotopes during biodegradation, stable isotope analysis is increasingly used to distinguish this process from transport or mixing-related decreases in contaminant concentrations. However, for this technique to be useful in the field to monitor bioremediation progress, isotope fractionation must be quantified under relevant environmental conditions. In the present study, we quantify the apparent in situ fractionation effects for stable isotopes in ClO4- (Cl and O) and NO3- (N and O) resulting from biodegradation in an aquifer. Abstract. An in situ experiment was performed in a shallow alluvial aquifer in Maryland to quantify the fractionation of stable isotopes in perchlorate (Cl and O) and nitrate (N and O) during biodegradation. An emulsified soybean oil substrate that was previously injected into this aquifer provided the electron donor necessary for biological perchlorate reduction and denitrification. During the field experiment, groundwater extracted from an upgradient well was pumped into an injection well located within the in situ oil barrier, and then groundwater samples were withdrawn for the next 30 h. After correction for dilution (using Br- as a conservative tracer of the injectate), perchlorate concentrations decreased by 78% and nitrate concentrations decreased by 82% during the initial 8.6 h after the injection. The observed ratio of fractionation effects of O and Cl isotopes in perchlorate (18O/37Cl) was 2.6, which is similar to that observed in the laboratory using pure cultures (2.5). Denitrification by indigenous bacteria fractionated O and N isotopes in nitrate at a ratio of ???0.8 (18O/15N), which is within the range of values reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (18O/37Cl, 18O/15N) derived from homogeneous laboratory systems (e.g. pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion. ?? CSIRO 2009.

A preliminary assessment on the use of biochar as a soil additive for reducing soil-to-plant uptake of cesium isotopes in radioactively contaminated environments

DOE PAGES

Hamilton, Terry F.; Martinelli, Roger E.; Kehl, Steven R.; ...

2015-10-19

A series of K d tracer batch experiments were conducted in this paper to assess the absorptive-desorption properties of Biochar as a potential agent to selectively sequester labile soil Cs or otherwise help reduce the uptake of Cs isotopes into plants. A parallel experiment was conducted for strontium. Fine-grained fractionated Woodlands tree Biochar was found to have a relatively high affinity for Cs ions (K d > 100) relative to coral soil (K d < 10) collected from the Marshall Islands. The Biochar material also contains an abundance of K (and Mg). Finally, these findings support a hypothesis that themore » addition of Biochar as a soil amendment may provide a simple yet effective method for reducing soil-to-plant transfer of Cs isotopes in contaminated environments.« less

Oxygen and nitrogen isotope effects duing nitrification and denitrification occuring in Midwesern soils

NASA Astrophysics Data System (ADS)

Michalski, G. M.; Wilkens, B.; Sanchez, A. V.; Yount, J.

2017-12-01

The processes of nitrification and denitrification are key steps in the biogeochemical cycling of N and are a main control on ecosystem productivity. These processes are ephemeral and often difficult to assess across wide spatial and temporal scales. Natural abundance stable isotopes are a way of potentially assessing these two processes across multiple scales. We have conducted incubation experiments to assess the N and O isotope effects occurring during denitrification in soils typical of the Midwestern United States. Nitrification was examined by incubating soils amended with ammonium (with a known δ15N) mixed with H2O and O2 that had different δ18O values and then measured the δ15N and δ18O of the product nitrate. The fraction of nitrate oxygen arising from H2O and O2 was determined along with the N and O kinetic isotope effect (KIE). For denitrification, nitrate with a known δ15N, δ17O, and δ18O, was incubated in anaerobic soils from 12-48 hours. The residual nitrate was analyzed for isotope change and the KIE for O and N as well as exchange with H2O was determined. These data can be useful for interpreting nitrate isotopes in agricultural fields as a way off assessing nitrification and denitrification is agricultural ecosystems such as the IML-CZO.

Intramolecular stable isotope distributions detect plant metabolic responses on century time scales

NASA Astrophysics Data System (ADS)

Schleucher, Jürgen; Ehlers, Ina; Augusti, Angela; Betson, Tatiana

2014-05-01

Plants respond to environmental changes on a vast range of time scales, and plant gas exchanges constitute important feedback mechanisms in the global C cycle. Responses on time scales of decades to centuries are most important for climate models, for prediction of crop productivity, and for adaptation to climate change. Unfortunately, responses on these timescale are least understood. We argue that the knowledge gap on intermediate time scales is due to a lack of adequate methods that can bridge between short-term manipulative experiments (e.g. FACE) and paleo research. Manipulative experiments in plant ecophysiology give information on metabolism on time scales up to years. However, this information cannot be linked to results from retrospective studies in paleo research, because little metabolic information can be derived from paleo archives. Stable isotopes are prominent tools in plant ecophysiology, biogeochemistry and in paleo research, but in all applications to date, isotope ratios of whole molecules are measured. However, it is well established that stable isotope abundance varies among intramolecular groups of biochemical metabolites, that is each so-called "isotopomer" has a distinct abundance. This intramolecular variation carries information on metabolic regulation, which can even be traced to individual enzymes (Schleucher et al., Plant, Cell Environ 1999). Here, we apply intramolecular isotope distributions to study the metabolic response of plants to increasing atmospheric [CO2] during the past century. Greenhouse experiments show that the deuterium abundance among the two positions in the C6H2 group of photosynthetic glucose depends on [CO2] during growth. This is observed for all plants using C3 photosynthesis, and reflects the metabolic flux ratio between photorespiration and photosynthesis. Photorespiration is a major C flux that limits assimilation in C3 plants, which encompass the overwhelming fraction of terrestrial photosynthesis and the vast majority of crop species. To access century time scales, we traced this metabolic signal in historic material of two crop species during the past 100 years and find the same response as predicted from the greenhouse experiments. This allows estimating how much photorespiration has been reduced due to the anthropogenic CO2 emission during the 20th century, and shows that plants have not acclimated to increasing [CO2] during more than 100 generations. In summary, we demonstrate that metabolic responses of plants to environmental changes create intramolecular isotope signals. These signals can be identified in manipulation experiments and can be retrieved from plant archives. The isotope abundance of each intramolecular position is set by specific isotope fractionations, such as enzyme isotope effects or hydrogen exchange with xylem water (Augusti et al., Chem. Geol. 2008). Therefore it may be possible to simultaneously reconstruct several physiologic or climate signals from an archive of a single molecule. The principles governing intramolecular isotope distributions are general for all metabolites and isotopes (D, 13C), therefore intramolecular isotope distributions can multiply the information content of paleo archives. In particular, they allow extraction of metabolic information on long time scales, thereby connecting plant physiology with paleo research.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

NASA Astrophysics Data System (ADS)

Socki, R. A.; Fu, Q.; Niles, P. B.; Gibson, E. K.

2012-03-01

We report results of experiments to measure the H-isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high-temperature extraction furnace to make quantitative H-isotope measurements.

Overview and Brief History of the Boron Isotope Proxy for Past Seawater pH

NASA Astrophysics Data System (ADS)

Hoenisch, B.; Hemming, G.

2007-05-01

In 1992 Hemming and Hanson (GCA, vol. 56, p. 537-543) showed that a variety of modern marine carbonates revealed a boron isotopic composition close to the isotopic composition of dissolved borate at modern seawater pH, suggesting this was the boron species preferentially adsorbed and incorporated into marine carbonates. With a constant offset between the trigonal and tetrahedrally coordinated boron species and a pH-dependent variation in their fractions, it appeared that this system would be sensitive to pH changes in the natural range of seawater. Accordingly, it was suggested that the boron isotope composition of marine carbonates is a proxy for past seawater pH. Subsequent culture studies with living planktic foraminifers and corals, as well as synthetic precipitation experiments confirmed that the boron isotopic composition follows the isotopic composition of borate across a wide range of seawater pH. In order to use the proxy with confidence, however, all other controls apart from pH need to be thoroughly understood. Recent laboratory and sediment experiments have demonstrated that vital effects and partial shell dissolution have the potential to modify the primary seawater pH signal recorded in the boron isotopic composition of planktic foraminifers. However it has also been shown that careful sample selection allows for avoiding these potential complications. A record of reconstructed surface seawater pH and estimated aqueous PCO2 shows a remarkable match between boron isotope based atmospheric pCO2 estimates and the Vostok ice core CO2 record. This convincingly demonstrates that boron isotopes in planktic foraminifers allow quantitative estimates of atmospheric pCO2 in the past, and confirms that glacial surface ocean pH was ~0.2 units higher compared to interglacial periods. We are going to review and discuss the achievements generated in Gil Hanson's lab over the past 15 years in the light of recent empirical measurements of the boron isotope fractionation between boric acid and borate in seawater.

Biodegradation of Chlorofluorocarbons in a Groundwater Plume using Compound Specific Carbon Isotope Analysis

NASA Astrophysics Data System (ADS)

Phillips, E.; Manna, J.; Horst, A.; Gilevska, T.; Sherwood Lollar, B.; Mack, E. E.; Seger, E.; Lutz, E. J.; Norcoss, S.; Morgan, S. E.; West, K. A.; Dworatzek, S.; Webb, J.

2017-12-01

Compound specific isotope analysis (CSIA) measures isotope ratios of organic hydrocarbons to monitor intrinsic bioremediation processes that can transform contaminants in field settings. The fraction of original contaminant remaining can be determined using the measured isotope ratio of the contaminant by an experimentally determined fractionation factor. In this study, two separate biotransformation experiments were performed in the Stable Isotope Laboratory at the University of Toronto using CSIA. In these two experiments, a mixed culture derived from a contaminated site was amended with trichlorotrifluoroethane (CFC-113), or trichlorofluoromethane (CFC-11), respectively. The concentrations and carbon isotope ratios of CFC-113, or CFC-11 were analyzed to calculate the fractionation factor for the transformation of each compound. Subsequently, groundwater samples from 9 wells at a historically contaminated site were collected and analyzed. The experimentally determined fractionation factors were then used to evaluate the extent of transformation that had occurred at the field site. In the laboratory studies, significant carbon isotope fractionation was observed for both CFC-113 and CFC-11 as biotransformation proceeded. This significant fractionation is beneficial when evaluating biotransformation at field sites as it can be clearly differentiated from the effects of other physical processes such as transport, or volatilization. Although there was significant variation in the carbon isotope values of CFC-113 between different well locations at the field site, these variations may be due to differences in source carbon isotope signatures. For CFC-11, much more significant isotopic variation was observed within the same well and between wells, showing trends consistent with in situ biotransformation. Results from this study demonstrate that CSIA can be successfully applied to evaluate the extent of transformation of chlorofluorocarbons (CFCs) at contaminated field sites, which has not been shown previously. This study also demonstrates that biotransformation may play a more significant role in the natural attenuation of CFCs than has previously been recognized.

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

USGS Publications Warehouse

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

1987-01-01

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

Quantification of isotopic turnover in agricultural systems

NASA Astrophysics Data System (ADS)

Braun, A.; Auerswald, K.; Schnyder, H.

2012-04-01

The isotopic turnover, which is a proxy for the metabolic rate, is gaining scientific importance. It is quantified for an increasing range of organisms, from microorganisms over plants to animals including agricultural livestock. Additionally, the isotopic turnover is analyzed on different scales, from organs to organisms to ecosystems and even to the biosphere. In particular, the quantification of the isotopic turnover of specific tissues within the same organism, e.g. organs like liver and muscle and products like milk and faeces, has brought new insights to improve understanding of nutrient cycles and fluxes, respectively. Thus, the knowledge of isotopic turnover is important in many areas, including physiology, e.g. milk synthesis, ecology, e.g. soil retention time of water, and medical science, e.g. cancer diagnosis. So far, the isotopic turnover is quantified by applying time, cost and expertise intensive tracer experiments. Usually, this comprises two isotopic equilibration periods. A first equilibration period with a constant isotopic input signal is followed by a second equilibration period with a distinct constant isotopic input signal. This yields a smooth signal change from the first to the second signal in the object under consideration. This approach reveals at least three major problems. (i) The input signals must be controlled isotopically, which is almost impossible in many realistic cases like free ranging animals. (ii) Both equilibration periods may be very long, especially when the turnover rate of the object under consideration is very slow, which aggravates the first problem. (iii) The detection of small or slow pools is improved by large isotopic signal changes, but large isotopic changes also involve a considerable change in the input material; e.g. animal studies are usually carried out as diet-switch experiments, where the diet is switched between C3 and C4 plants, since C3 and C4 plants differ strongly in their isotopic signal. The additional change in nutrition induces changes in physiology that are likely to bias the estimation of the isotopic turnover. We designed an experiment with lactating cows which were successively exposed to the diet's natural isotopic variation and a diet-switch. We examined whether the same turnover information can be obtained from the natural (uncontrolled, short-term) isotopic variation as from the diet-switch experiment. Statistical methods to retrieve the turnover characteristics comprised multi-pool compartmental modeling for the diet-switch experiment as well as correlation analysis to perform wiggle-matching and quantification of autocorrelation (geostatistics) for the analysis of the natural variation. All three methods yielded similar results but differed in their strengths and weaknesses that will be highlighted. Combining the strengths of the new methods can make this tool even more advantageous than diet-switch experiments in many cases. In particular, the new approach empowers studying isotope turnover under a wider range of keepings, wildlife conditions and species, yielding turnover estimates that are not biased by changes in nutrition.

Comparisons of multiple isotope systems in the aragonitic shells of cultured Arctica islandica clams

NASA Astrophysics Data System (ADS)

Liu, Y. W.; Aciego, S.; Wanamaker, A. D.

2014-12-01

Previous work using oxygen and stable carbon isotopes from Arctica islandica shells has shown that this archive can provide information on past seawater temperatures, carbon cycling and ocean circulation. However, relatively less attention has been devoted to other "non-traditional" isotope systems within this proxy archive. In this study, we report the boron (δ11B) and strontium isotopic values (87Sr/86Sr and δ88/86Sr) from A. islandicashells collected and cultured from the Gulf of Maine. The long-lived ocean quahog, A. islandica was collected and cultured in the Gulf of Maine for 8 months. Our high-resolution δ11B records from the experiment show 5-7‰ of increase through the culture, with low values from January to May and higher values after May. The 87Sr/86Sr ratios from both tank water and shell samples suggest that the shell material reflects ambient ocean chemistry without interferences from terrestrial sources. Although It has been suggested that stable Sr isotopic ratios (δ88/86Sr) in biogenic carbonates are influenced by the temperature of the precipitating fluid, our nearly identical δ88/86Sr data do not support this hypothesis despite a 15 °C temperature change during the experiment. Based on the in-situ measurements of culture seawater temperature, salinity and pH, and two commonly used fractionation factors (α3-4) for corals and forams, we predicted the range in shell δ11B values for the experiment. Our boron results are at the extreme ends of the two prediction lines suggesting the potential usage of the bivalve shells as seawater pH indicator. However, the wider range in δ11B in this experiment than the predictions based on other carbonate organisms (only 2 to 3‰) suggests that a species-specific fractionation factor may be required. Recent work from an additional constant temperature experiment (10 and 15 °C) in the Gulf of Maine will allow us to further evaluate temperature influences and potential vital effects on the shell boron isotope values.

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.

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

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

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

2010-02-01

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

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

NASA Astrophysics Data System (ADS)

Shuai, Yanhua; Douglas, Peter M. J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael D.; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-02-01

Multiply isotopically substituted molecules ('clumped' isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature-time conditions corresponding to 'low,' 'mature,' and 'over-mature' stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions ('high' to 'over-mature' stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where 'secondary' cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

Calcium isotope systematics at hydrothermal conditions: Mid-ocean ridge vent fluids and experiments in the CaSO4-NaCl-H2O system

NASA Astrophysics Data System (ADS)

Scheuermann, Peter P.; Syverson, Drew D.; Higgins, John A.; Pester, Nicholas J.; Seyfried, William E.

2018-04-01

Two sets of hydrothermal experiments were performed to explore Ca isotope fractionation and exchange rates at hydrothermal conditions (410-450 °C, 31.0-50.0 MPa). The first set of experiments determined the magnitude of vapor-liquid Ca isotope fractionation and anhydrite solubility in the CaSO4-NaCl-H2O system. The data indicate no statistical difference between the Ca isotopic composition of coexisting vapor and liquid. The second set of experiments utilized an anomalous 43Ca spike to determine the rate of Ca exchange between fluid and anhydrite as a function of total dissolved Ca concentration. Results show that the rate of exchange increases with dissolved Ca concentrations (12-23 mM/kg), but no change in exchange rate is observed when the Ca concentration increases from 23 to 44 mM/kg Ca. 74-142 days are required to achieve 90% anhydrite-fluid Ca isotope exchange at the conditions investigated, while only several hours are necessary for vapor-liquid isotopic equilibrium. The lack of vapor-liquid Ca isotope fractionation in our experiments is consistent with δ44Ca of mid-ocean ridge hydrothermal vent fluids that remain constant, regardless of chlorinity. Moreover, the narrow range of end member fluid δ44Ca, -0.98 to -1.13‰ (SW), is largely indistinguishable from MORB δ44Ca, suggesting that neither phase separation nor fluid-rock interactions at depth significantly fractionate Ca isotopes in modern high-temperature mid-ocean ridge hydrothermal systems.

Carbon Isotopes of Alkanes in Hydrothermal Abiotic Organic Synthesis Processes at High Temperatures and Pressures: An Experimental Study

NASA Technical Reports Server (NTRS)

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

2010-01-01

Observation of methane in the Martian atmosphere has been reported by different detection techniques [1-4]. With more evidence showing extensive water-rock interaction in Martian history [5-7], abiotic formation by Fischer-Tropsch Type (FTT) synthesis during serpentization reactions may be one possible process responsible for methane generation on Mars [8, 9]. While the experimental studies performed to date leave little doubt that chemical reactions exist for the abiotic synthesis of organic compounds by mineral surface-catalyzed reactions [10-12], little is known about the reaction pathways by which CO2 and/or CO are reduced under hydrothermal conditions. Carbon and hydrogen isotope measurements of alkanes have been used as an effective tool to constrain the origin and reaction pathways of hydrocarbon formation. Alkanes generated by thermal breakdown of high molecular weight organic compounds have carbon and hydrogen isotopic signatures completely distinct from those formed abiotically [13-15]. Recent experimental studies, however, showed that different abiogenic hydrocarbon formation processes (e.g., polymerization vs. depolymerization) may have different carbon and hydrogen isotopic patterns [16]. Results from previous experiments studying decomposition of higher molecular weight organic compounds (lignite) also suggested that pressure could be a crucial factor affecting fractionation of carbon isotopes [17]. Under high pressure conditions, no experimental data are available describing fractionation of carbon isotope during mineral catalyzed FTT synthesis. Thus, hydrothermal experiments present an excellent opportunity to provide the requisite carbon isotope data. Such data can also be used to identify reaction pathways of abiotic organic synthesis under experimental conditions.

IsoCor: correcting MS data in isotope labeling experiments.

PubMed

Millard, Pierre; Letisse, Fabien; Sokol, Serguei; Portais, Jean-Charles

2012-05-01

Mass spectrometry (MS) is widely used for isotopic labeling studies of metabolism and other biological processes. Quantitative applications-e.g. metabolic flux analysis-require tools to correct the raw MS data for the contribution of all naturally abundant isotopes. IsoCor is a software that allows such correction to be applied to any chemical species. Hence it can be used to exploit any isotopic tracer, from well-known ((13)C, (15)N, (18)O, etc) to unusual ((57)Fe, (77)Se, etc) isotopes. It also provides new features-e.g. correction for the isotopic purity of the tracer-to improve the accuracy of quantitative isotopic studies, and implements an efficient algorithm to process large datasets. Its user-friendly interface makes isotope labeling experiments more accessible to a wider biological community. IsoCor is distributed under OpenSource license at http://metasys.insa-toulouse.fr/software/isocor/

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 dissolution of two Cr(III)-Cl solids (dried NIST SRM979 standard and commercial CrCl3·6H2O salt) in 0.01 M HCl (pH ≈ 2). The ε53/52Cr(CrCl2+/CrCl2+) for the CrCl2+ to CrCl2+ reaction is -0.19‰ (SRM979) and -0.38‰ (salt) and the ε53/52Cr(Cr3+/CrCl2+) for the CrCl2+ to Cr3+ reaction is consistent for both experiments at -0.49‰ (SRM979) and -0.51‰ (salt). Experiments where SRM979 is dissolved in 0.1 and 1 M HCl for a longer aging period provide preliminary evidence that the Cr3+/CrCl2+ Cr(III) isotopic fractionation scales with HCl concentration (transformation rate). Chromium(III) dissolved in 6 M HCl and aged 5 months still yields an inter-species Cr isotope distribution that is apparently inherited from kinetic effects (light Cr isotopes in Cr3+), attesting to the slow development of inter-species isotopic equilibrium, which instead predicts progressively heavier Cr isotopes from CrCl2+ to CrCl2+ to Cr3+. The kinetic Cr(III) isotopic fractionation documented herein is proposed to be relevant to understanding systems where aqueous Cr(III)-Cl species may be temporarily stable (e.g., metamorphic and hydrothermal systems or lateritic weathering). Further, the complexation of Cr(III) with other ligands (e.g., CO32-, organics), combined with additional kinetic effects of Cr(III) potentially occurring in soils or sediment, must be explored prior to establishing the significance of empirical stable Cr isotope signatures in marine and continental environments. Further understanding of non-redox effects may lead to stable Cr isotopes developing as a proxy for system pH or ligand chemistry.

Experimental investigation on the carbon isotope fractionation of methane during gas migration by diffusion through sedimentary rocks at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Zhang, Tongwei; Krooss, Bernhard M.

2001-08-01

Molecular transport (diffusion) of methane in water-saturated sedimentary rocks results in carbon isotope fractionation. In order to quantify the diffusive isotope fractionation effect and its dependence on total organic carbon (TOC) content, experimental measurements have been performed on three natural shale samples with TOC values ranging from 0.3 to 5.74%. The experiments were conducted at 90°C and fluid pressures of 9 MPa (90 bar). Based on the instantaneous and cumulative composition of the diffused methane, effective diffusion coefficients of the 12CH4 and 13CH4 species, respectively, have been calculated. Compared with the carbon isotopic composition of the source methane (δ13C1 = -39.1‰), a significant depletion of the heavier carbon isotope (13C) in the diffused methane was observed for all three shales. The degree of depletion is highest during the initial non-steady state of the diffusion process. It then gradually decreases and reaches a constant difference (Δ δ = δ13Cdiff -δ13Csource) when approaching the steady-state. The degree of the isotopic fractionation of methane due to molecular diffusion increases with the TOC content of the shales. The carbon isotope fractionation of methane during molecular migration results practically exclusively from differences in molecular mobility (effective diffusion coefficients) of the 12CH4 and 13CH4 entities. No measurable solubility fractionation was observed. The experimental isotope-specific diffusion data were used in two hypothetical scenarios to illustrate the extent of isotopic fractionation to be expected as a result of molecular transport in geological systems with shales of different TOC contents. The first scenario considers the progression of a diffusion front from a constant source (gas reservoir) into a homogeneous ;semi-infinite; shale caprock over a period of 10 Ma. In the second example, gas diffusion across a 100 m caprock sequence is analyzed in terms of absolute quantities and isotope fractionation effects. The examples demonstrate that methane losses by molecular diffusion are small in comparison with the contents of commercial size gas accumulations. The degree of isotopic fractionation is related inversely to the quantity of diffused gas so that strong fractionation effects are only observed for relatively small portions of gas. The experimental data can be readily used in numerical basin analysis to examine the effects of diffusion-related isotopic fractionation on the composition of natural gas reservoirs.

Effect of Silicon on the Activity Coefficient of Rhenium in Fe-Si Liquids: Implications for HSE and Os Isotopes in Planetary Mantles

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K.; Yang, S.; Humayun, M.

2018-01-01

Metallic cores contain light alloying elements that can be a combination of S, C, Si, and O, all of which have important chemical and physical influences. For Earth, Si may be the most abundant light element in the core. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE), and thus the partitioning behavior of those elements between core and mantle. The effect of Si on the highly siderophile elements is only beginning to be studied and the effects on Au, Pd and Pt are significant. Here we report new experiments designed to quantify the effect of Si on the partitioning of Re between metal and silicate melt. A solid understanding of Re partitioning is required for a complete understanding of the Re-Os isotopic systems. The results will be applied to understanding the HSEs and Os isotopic data for planetary mantles, and especially Earth.

Further analysis of the IRIS iron isotope experiment

NASA Technical Reports Server (NTRS)

Tarle, G.; Ahlen, S. P.; Cartwright, B. G.; Solarz, M.

1980-01-01

The IRIS Fe isotope experiment was extended to atomic charges of Z = 19, with isotopic distributions for 500 events ranging from 18 to 28. Normalization of the detector response functions at Fe-56 produced a single well resolved peak at Sc-45, establishing the resolution and mass scale of the device over the entire charge region. The abundance distributions for the predominantly primary isotopes Ca-40, Fe-54, Fe-56, Ni-58, and Ni-60 do not indicate a large admixture of material with distinctly nonsolar abundances.

The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

NASA Astrophysics Data System (ADS)

von Sperber, C.; Tamburini, F.; Bernasconi, S. M.; Frossard, E.

2013-12-01

Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi) (1-2). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. The enzymatic hydrolysis leads, via a nucleophilic attack, to the incorporation of one oxygen atom from the water into the newly formed Pi molecule. During the incorporation, an isotopic fractionation occurs, which might be used to identify the origin of Pi in the environment (3-6). While the effect of phosphomonoesterases and phosphodiesterases on the oxygen isotope composition of phosphate has been examined, there are, so far, no studies dealing with the effect of phytases (4-6). Phytases catalyze the hydrolysis of myo-inositol-hexakis-phosphate (IP6), which is an important component of organic P in many ecosystems (7). Enzymatic assays with phytase from wheat germ and Aspergillus niger were prepared under sterile and temperature controlled conditions in order to determine the effect of phytases on the oxygen isotope composition of phosphate, which has been liberated from IP6 via enzymatic hydrolysis. Assays with phytase from wheat germ lead to a turnover of the substrate close to 100%, while assays with phytase from Aspergillus niger lead to a turnover of the substrate close to 80%. In the case of the assays with phytase from wheat germ, our results indicate that one sixth of the total 24 oxygen which are associated to the phosphates in IP6 are exchanged with oxygen from water. From this we conclude that the incorporation of one oxygen atom from water occurs only at four phosphate molecules of IP6, while two phosphate molecules do not experience an incorporation of oxygen. This suggests that during the enzymatic hydrolysis, four P-O bonds and two C-O bonds are broken. Provided that, the isotopic fractionation can be calculated with an isotopic mass balance resulting in -8.4‰ (×3.6 SD). This is a value very similar to those reported for acid phosphatases (6). In contrast, the results from assays with phytase from Aspergillus niger indicate that the exchange of oxygen occurs at more than one third of the total 24 oxygen which are associated to the phosphates in IP6. In addition, we observe a change in the oxygen isotope composition of Pi when using myo-inositol and potassium-dihydrogen-phosphate as sole substrates in the enzymatic assays with phytase from Aspergillus niger. These observations suggest that the reformation of IP6 from the two products of the reaction (myo-inositol and Pi) is taking place at a rate, which is within the time scale of the experiment. In this case, the isotopic fractionation caused by phytase from Aspergillus niger will be determined by the equilibrium of the reaction. Further experiments are in process to verify these findings.

Sauna, sweat and science - quantifying the proportion of condensation water versus sweat using a stable water isotope ((2)H/(1)H and (18)O/(16)O) tracer experiment.

PubMed

Zech, Michael; Bösel, Stefanie; Tuthorn, Mario; Benesch, Marianne; Dubbert, Maren; Cuntz, Matthias; Glaser, Bruno

2015-01-01

Most visitors of a sauna appreciate the heat pulse that is perceived when water is poured on the stones of a sauna stove. However, probably only few bathers are aware that this pleasant heat pulse is caused by latent heat being released onto our skin due to condensation of water vapour. In order to quantify the proportion of condensation water versus sweat to dripping water of test persons we conducted sauna experiments using isotopically labelled (δ(18)O and δ(2)H) thrown water as tracer. This allows differentiating between 'pure sweat' and 'condensation water'. Two ways of isotope mass balance calculations were applied and yielded similar results for both water isotopes. Accordingly, condensation contributed considerably to dripping water with mean proportions of 52 ± 12 and 54 ± 7% in a sauna experiment in winter semester 2011/12 and 30 ± 13 and 33 ± 6% in a sauna experiment in winter semester 2012/13, respectively, depending on the way of calculating the isotope mass balance. It can be concluded from the results of our dual isotope labelling sauna experiment that it is not all about sweat in the sauna.

Calcium isotope analysis by mass spectrometry.

PubMed

Boulyga, Sergei F

2010-01-01

The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use of biological isotope fractionation in medical studies, paleoclimatic and paleoceanographic, and other terrestrial as well as extraterrestrial investigations. 2009 Wiley Periodicals, Inc.

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 provide important mechanistic details about the overall TSR process.

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 with the HCN-hydrogen systematically enriched in 2H by more than 50 ‰. In the reaction of HCN with chromium, H2 and chromium-containing solid residues are formed quantitatively.

Combined 34S, 33S and 18O isotope fractionations record different intracellular steps of microbial sulfate reduction

NASA Astrophysics Data System (ADS)

Antler, Gilad; Turchyn, Alexandra V.; Ono, Shuhei; Sivan, Orit; Bosak, Tanja

2017-04-01

Several enzymatic steps in microbial sulfate reduction (MSR) fractionate the isotope ratios of 33S/32S, 34S/32S and 18O/16O in extracellular sulfate, but the effects of different intracellular processes on the isotopic composition of residual sulfate are still not well quantified. We measured combined multiple sulfur (33S/32S, 34S/32S) and oxygen (18O/16O) isotope ratios of sulfate in pure cultures of a marine sulfate reducing bacterium Desulfovibrio sp. DMSS-1 grown on different organic substrates. These measurements are consistent with the previously reported correlations of oxygen and sulfur isotope fractionations with the cell-specific rate of MSR: faster reduction rates produced smaller isotopic fractionations for all isotopes. Combined isotope fractionation of oxygen and multiple sulfur isotopes are also consistent with the relationship between the rate limiting step during microbial sulfate reduction and the availability of the DsrC subunit. These experiments help reconstruct and interpret processes that operate in natural pore waters characterized by high 18O/16O and moderate 34S/32S ratios and suggest that some multiple isotope signals in the environment cannot be explained by microbial sulfate reduction alone. Instead, these signals support the presence of active, but slow sulfate reduction as well as the reoxidation of sulfide.

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.

A Progress Report to the EARTHTIME Argon Inter-Calibration Pipette System (APSI): Still Smoking from the Same Pipe

NASA Astrophysics Data System (ADS)

Turrin, B. D.; Swisher, C. C., III; Hemming, S. R.; Renne, P. R.; Hodges, K. V.; Van Soest, M. C.; Heizler, M. T.; Deino, A. L.

2016-12-01

Five of the seven 40Ar/39Ar dating labs have completed measurements of the APIS calibration gases. The APIS experiment, while being frustratingly slow, has allowed us to make major progress towards identifying the sources of the dispersion in the original EARTHTIME experiment. In addition to the traveling APIS, many labs have been testing best procedures and making improvements. As a result of the initial experiment, we have reduce the 2% dispersion in the original experiment to 3‰. The community continues to work toward the common goal of 0.1% comparability. As you may imagine we are not all of one mind, and there is still more to be done. However, we argue that at this point we have isolated three potential causes of the observed dispersion: 1) Isotopic fractionation of the Ar reference gas. This was found to occur during a loading of the pipette reservoir, highlighting the possibility that it could also happen with other reservoir or pipette loadings in other labs. Any "splitting" of the sample to reduce overall volume could also result in "procedural" isotopic fraction; 2) Pressure dependent instrumental mass fraction, which is known to occur within the ion-source. Isotopic fraction can also occur with a secondary electron multiplier detector; 3) "Time Zero" selection bias. This bias may have the largest effect on the original experiment. Because of the great differences in age of the standards, the abundances of the measures isotopes also vary, often resulting in variable gas evolution trends during mass spectrometer measurement. As a community, we continue to compare results between laboratories chronometers (i.e. U-Pb and 40Ar/39Ar). Toward this goal the Ar community would be best be served by taking similar steps as the U-Pb community, such as the development and application of a community tracer solution and the distribution of synthetic zircon. For the Ar EARTHIME community the equivalent of this would be the development of synthetic gas standards with multiple pipettes for participating labs. The EARTHIME gas standards would deliver various controlled volumes and isotopic compositions of Ar to the mass spectrometer. This would be useful for evaluating "procedural" isotopic fractionation and ion detector linearity. The APIS experiment has served as a "proof-of concept" for this.

Evaporation induced 18O and 13C enrichment in lake systems: A global perspective on hydrologic balance effects

NASA Astrophysics Data System (ADS)

Horton, Travis W.; Defliese, William F.; Tripati, Aradhna K.; Oze, Christopher

2016-01-01

Growing pressure on sustainable water resource allocation in the context of global development and rapid environmental change demands rigorous knowledge of how regional water cycles change through time. One of the most attractive and widely utilized approaches for gaining this knowledge is the analysis of lake carbonate stable isotopic compositions. However, endogenic carbonate archives are sensitive to a variety of natural processes and conditions leaving isotopic datasets largely underdetermined. As a consequence, isotopic researchers are often required to assume values for multiple parameters, including temperature of carbonate formation or lake water δ18O, in order to interpret changes in hydrologic conditions. Here, we review and analyze a global compilation of 57 lacustrine dual carbon and oxygen stable isotope records with a topical focus on the effects of shifting hydrologic balance on endogenic carbonate isotopic compositions. Through integration of multiple large datasets we show that lake carbonate δ18O values and the lake waters from which they are derived are often shifted by >+10‰ relative to source waters discharging into the lake. The global pattern of δ18O and δ13C covariation observed in >70% of the records studied and in several evaporation experiments demonstrates that isotopic fractionations associated with lake water evaporation cause the heavy carbon and oxygen isotope enrichments observed in most lakes and lake carbonate records. Modeled endogenic calcite compositions in isotopic equilibrium with lake source waters further demonstrate that evaporation effects can be extreme even in lake records where δ18O and δ13C covariation is absent. Aridisol pedogenic carbonates show similar isotopic responses to evaporation, and the relevance of evaporative modification to paleoclimatic and paleotopographic research using endogenic carbonate proxies are discussed. Recent advances in stable isotope research techniques present unprecedented opportunities to overcome the underdetermined nature of stable isotopic data through integration of multiple isotopic proxies, including dual element 13C-excess values and clumped isotope temperature estimates. We demonstrate the utility of applying these multi-proxy approaches to the interpretation of paleohydroclimatic conditions in ancient lake systems. Understanding past, present, and future hydroclimatic systems is a global imperative. Significant progress should be expected as these modern research techniques become more widely applied and integrated with traditional stable isotopic proxies.

Nitrogen Isotope Evidence for a Shift in Eastern Beringian Nitrogen Cycle after the Terminal Pleistocene

NASA Astrophysics Data System (ADS)

Tahmasebi, F.; Longstaffe, F. J.; Zazula, G.

2016-12-01

The loess deposits of eastern Beringia, a region in North America between 60° and 70°N latitude and bounded by Chukchi Sea to the west and the Mackenzie River to the east, are a magnificent repository of Late Pleistocene megafauna fossils. The stable carbon and nitrogen isotope compositions of these fossils are measured to determine the paleodiet of these animals, and hence the paleoenvironment of this ecosystem during the Quaternary. For this approach to be most successful, however, requires consideration of possible changes in nutrient cycling and hence the carbon and nitrogen isotopic compositions of vegetation in this ecosystem. To test for such a shift following the terminal Pleistocene, we analyzed the stable carbon and nitrogen isotope compositions of modern plants and bone collagen of Arctic ground squirrels from Yukon Territory, and fossil plants and bones recovered from Late Pleistocene fossil Arctic ground squirrel nests. The data for modern samples provided a measure of the isotopic fractionation between ground squirrel bone collagen and their diet. The over-wintering isotopic effect of decay on typical forage grasses was also measured to evaluate its role in determining fossil plant isotopic compositions. The grasses showed only a minor change ( 0-1 ‰) in carbon isotope composition, but a major change ( 2-10 ‰) in nitrogen isotope composition over the 317-day experiment. Based on the modern carbon isotope fractionation between ground squirrel bone collagen and their diet, the modern vegetation carbon isotopic baseline provides a suitable proxy for the Late Pleistocene of eastern Beringia, after accounting for the Suess effect. However, the predicted nitrogen isotope composition of vegetation comprising the diet of fossil ground squirrels remains 2.5 ‰ higher than modern grasslands in this area, even after accounting for possible N-15 enrichment during decay. This result suggests a change in N cycling in this region since the Late Pleistocene.

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.

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 compounds is critical for understanding deep subsurface ecosystems and the origin of organic compounds on Mars and other planets.

Accurate experimental determination of the isotope effects on the triple point temperature of water. II. Combined dependence on the 18O and 17O abundances

NASA Astrophysics Data System (ADS)

Faghihi, V.; Kozicki, M.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; Peruzzi, A.; Meijer, H. A. J.

2015-12-01

This paper is the second of two articles on the quantification of isotope effects on the triple point temperature of water. In this second article, we address the combined effects of 18O and 17O isotopes. We manufactured five triple point cells with waters with 18O and 17O abundances exceeding widely the natural abundance range while maintaining their natural 18O/17O relationship. The 2H isotopic abundance was kept close to that of VSMOW (Vienna Standard Mean Ocean Water). These cells realized triple point temperatures ranging between  -220 μK to 1420 μK with respect to the temperature realized by a triple point cell filled with VSMOW. Our experiment allowed us to determine an accurate and reliable value for the newly defined combined 18, 17O correction parameter of AO  =  630 μK with a combined uncertainty of 10 μK. To apply this correction, only the 18O abundance of the TPW needs to be known (and the water needs to be of natural origin). Using the results of our two articles, we recommend a correction equation along with the coefficient values for isotopic compositions differing from that of VSMOW and compare the effect of this new equation on a number of triple point cells from the literature and from our own institute. Using our correction equation, the uncertainty in the isotope correction for triple point cell waters used around the world will be  <1 μK.

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

USGS Publications Warehouse

Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C.

2010-01-01

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

Experimental protocols for and studies of the effects of surface passivation and water isotopes on the gliding speed of microtubules propelled by kinesin-1

NASA Astrophysics Data System (ADS)

Maloney, Roger Andrew

This dissertation explores how the kinesin-1 and microtubule system is affected by surface passivation and water isotopes. Surface passivation was found to affect the gliding speed that microtubules exhibit in the gliding motility assay and the lengths of microtubules supported by the passivation. It was also found that gliding speeds of microtubules are very sensitive to temperature changes. Studies changing the water isotope were a first attempt to investigate if changing the solvent changed the osmotic pressure of the solution kinesin and microtubules were in. No osmotic pressure changes were observed, however, the experiments using different isotopes of water did illuminate the possibility that kinesin may be sensitive to viscosity changes in the solvent. This experiment also suggests further experiments that can be specifically designed to probe osmotic pressure changes. This thesis was also the first thesis ever, to the best of the author's knowledge, to be done in a completely open format. All information and notebook entries that are related to it, as well as the thesis itself, can be found on the website OpenWetWare. The thesis can also be found there including all the different versions that went into its editing. The philosophy and process of making data open and accessible to every one is also discussed.

Oxygen isotope fractionation in divalent metal carbonates

USGS Publications Warehouse

O'Neil, J.R.; Clayton, R.N.; Mayeda, T.K.

1969-01-01

Equilibrium fractionation factors for the distribution of 18O between alkaline-earth carbonates and water have been measured over the temperature range 0-500??C. The fractionation factors ?? can be represented by the equations CaCO3-H2O, 1000 ln??=2.78(106 T-2)-3.39, SrCO3-H 2O, 1000 ln??=2.69(106 T-2)-3.74, BaCO3-H2O, 1000 ln??=2.57(106 T -2)-4.73. Measurements on MnCO3, CdCO3, and PbCO3 were made at isolated temperatures. A statistical-mechanical calculation of the isotopic partition function ratios gives reasonably good agreement with experiment. Both cationic size and mass are important in isotopic fractionation, the former predominantly in its effect on the internal vibrations of the anion, the latter in its effect on the lattice vibrations.

Freezing and fractionation: effects of preservation on carbon and nitrogen stable isotope ratios of some limnetic organisms.

PubMed

Wolf, J Marshall; Johnson, Brett; Silver, Douglas; Pate, William; Christianson, Kyle

2016-03-15

Stable isotopes of carbon and nitrogen have become important natural tracers for studying food-web structure and function. Considerable research has demonstrated that chemical preservatives and fixatives shift the isotopic ratios of aquatic organisms. Much less is known about the effects of freezing as a preservation method although this technique is commonly used. We conducted a controlled experiment to test the effects of freezing (-10 °C) and flash freezing (–79 °C) on the carbon and nitrogen isotope ratios of zooplankton (Cladocera), Mysis diluviana and Rainbow Trout (Oncorhynchus mykiss). Subsamples (~0.5 mg) of dried material were analyzed for percentage carbon, percentage nitrogen, and the relative abundance of stable carbon and nitrogen isotopes (δ13C and δ15N values) using a Carlo Erba NC2500 elemental analyzer interfaced to a ThermoFinnigan MAT Delta Plus isotope ratio mass spectrometer. The effects of freezing were taxon-dependent. Freezing had no effect on the isotopic or elemental values of Rainbow Trout muscle. Effects on the δ13C and δ15N values of zooplankton and Mysis were statistically significant but small relative to typical values of trophic fractionation. The treatment-control offsets had larger absolute values for Mysis (δ13C: ≤0.76 ± 0.41‰, δ15N: ≤0.37 ± 0.16‰) than for zooplankton (δ13C: ≤0.12 ± 0.06‰, δ15N: ≤0.30 ± 0.27‰). The effects of freezing were more variable for the δ13C values of Mysis, and more variable for the δ15N values of zooplankton. Generally, both freezing methods reduced the carbon content of zooplankton and Mysis, but freezing had a negative effect on the %N of zooplankton and a positive effect on the %N of Mysis. The species-dependencies and variability of freezing effects on aquatic organisms suggest that more research is needed to understand the mechanisms responsible for freezing-related fractionation before standardized protocols for freezing as a preservation method can be adopted.

Relating carbon and nitrogen isotope effects to reaction mechanisms during aerobic or anaerobic degradation of RDX (Hexahydro-1,3,5-Trinitro-1,3,5-Triazine) by pure bacterial cultures

USGS Publications Warehouse

Fuller, Mark E.; Heraty, Linnea J.; Condee, Charles W.; Vainberg, Simon; Sturchio, Neil C.; Böhlke, John Karl; Hatzinger, Paul B.

2016-01-01

Kinetic isotopic fractionation of carbon and nitrogen during RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) biodegradation was investigated with pure bacterial cultures under aerobic and anaerobic conditions. Relatively large bulk enrichments in 15N were observed during biodegradation of RDX via anaerobic ring cleavage (ε15N = −12.7‰ ± 0.8‰) and anaerobic nitro reduction (ε15N = −9.9‰ ± 0.7‰), in comparison to smaller effects during biodegradation via aerobic denitration (ε15N = −2.4‰ ± 0.2‰). 13C enrichment was negligible during aerobic RDX biodegradation (ε13C = −0.8‰ ± 0.5‰) but larger during anaerobic degradation (ε13C = −4.0‰ ± 0.8‰), with modest variability among genera. Dual-isotope ε13C/ε15N analyses indicated that the three biodegradation pathways could be distinguished isotopically from each other and from abiotic degradation mechanisms. Compared to the initial RDX bulk δ15N value of +9‰, δ15N values of the NO2− released from RDX ranged from −7‰ to +2‰ during aerobic biodegradation and from −42‰ to −24‰ during anaerobic biodegradation. Numerical reaction models indicated that N isotope effects of NO2− production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε15N-NO2− values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO2− formation associated with anaerobic ring cleavage. These results indicate the potential for isotopic analysis of residual RDX for the differentiation of degradation pathways and indicate that further efforts to examine the isotopic composition of potential RDX degradation products (e.g., NOx) in the environment are warranted.

Deuterium Isotope Effects During HMX Combustion: Chemical Kinetic Burn Rate Control Mechanism Verified

DTIC Science & Technology

1989-01-01

experience de gen dieses Experiments. Der 10 KDIE-Wert legt nahe. dab die combustion statique. La valeur de l’effet isotopique primaire laisse...anomaler combustion globale. Des 6tudes publifes par ailleurs confirment cette KDIE-Wert bei 10,4 MPa wirL angegeben. Diese KDIE-Experimente hypoth~se

Review of Nuclear Physics Experiments for Space Radiation

NASA Technical Reports Server (NTRS)

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

2011-01-01

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

Do Hf isotopes in magmatic zircons represent those of their host rocks?

NASA Astrophysics Data System (ADS)

Wang, Di; Wang, Xiao-Lei; Cai, Yue; Goldstein, Steven L.; Yang, Tao

2018-04-01

Lu-Hf isotopic system in zircon is a powerful and widely used geochemical tracer in studying petrogenesis of magmatic rocks and crustal evolution, assuming that zircon Hf isotopes can represent initial Hf isotopes of their parental whole rock. However, this assumption may not always be valid. Disequilibrium partial melting of continental crust would preferentially melt out non-zircon minerals with high time-integrated Lu/Hf ratios and generate partial melts with Hf isotope compositions that are more radiogenic than those of its magma source. Dissolution experiments (with hotplate, bomb and sintering procedures) of zircon-bearing samples demonstrate this disequilibrium effect where partial dissolution yielded variable and more radiogenic Hf isotope compositions than fully dissolved samples. A case study from the Neoproterozoic Jiuling batholith in southern China shows that about half of the investigated samples show decoupled Hf isotopes between zircons and the bulk rocks. This decoupling could reflect complex and prolonged magmatic processes, such as crustal assimilation, magma mixing, and disequilibrium melting, which are consistent with the wide temperature spectrum from ∼630 °C to ∼900 °C by Ti-in-zircon thermometer. We suggest that magmatic zircons may only record the Hf isotopic composition of their surrounding melt during crystallization and it is uncertain whether their Hf isotopic compositions can represent the primary Hf isotopic compositions of the bulk magmas. In this regard, using zircon Hf isotopic compositions to trace crustal evolution may be biased since most of these could be originally from disequilibrium partial melts.

Isotope engineering of van der Waals interactions in hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Vuong, T. Q. P.; Liu, S.; van der Lee, A.; Cuscó, R.; Artús, L.; Michel, T.; Valvin, P.; Edgar, J. H.; Cassabois, G.; Gil, B.

2018-02-01

Hexagonal boron nitride is a model lamellar compound where weak, non-local van der Waals interactions ensure the vertical stacking of two-dimensional honeycomb lattices made of strongly bound boron and nitrogen atoms. We study the isotope engineering of lamellar compounds by synthesizing hexagonal boron nitride crystals with nearly pure boron isotopes (10B and 11B) compared to those with the natural distribution of boron (20 at% 10B and 80 at% 11B). On the one hand, as with standard semiconductors, both the phonon energy and electronic bandgap varied with the boron isotope mass, the latter due to the quantum effect of zero-point renormalization. On the other hand, temperature-dependent experiments focusing on the shear and breathing motions of adjacent layers revealed the specificity of isotope engineering in a layered material, with a modification of the van der Waals interactions upon isotope purification. The electron density distribution is more diffuse between adjacent layers in 10BN than in 11BN crystals. Our results open perspectives in understanding and controlling van der Waals bonding in layered materials.

Isotope engineering of van der Waals interactions in hexagonal boron nitride.

PubMed

Vuong, T Q P; Liu, S; Van der Lee, A; Cuscó, R; Artús, L; Michel, T; Valvin, P; Edgar, J H; Cassabois, G; Gil, B

2018-02-01

Hexagonal boron nitride is a model lamellar compound where weak, non-local van der Waals interactions ensure the vertical stacking of two-dimensional honeycomb lattices made of strongly bound boron and nitrogen atoms. We study the isotope engineering of lamellar compounds by synthesizing hexagonal boron nitride crystals with nearly pure boron isotopes ( 10 B and 11 B) compared to those with the natural distribution of boron (20 at% 10 B and 80 at% 11 B). On the one hand, as with standard semiconductors, both the phonon energy and electronic bandgap varied with the boron isotope mass, the latter due to the quantum effect of zero-point renormalization. On the other hand, temperature-dependent experiments focusing on the shear and breathing motions of adjacent layers revealed the specificity of isotope engineering in a layered material, with a modification of the van der Waals interactions upon isotope purification. The electron density distribution is more diffuse between adjacent layers in 10 BN than in 11 BN crystals. Our results open perspectives in understanding and controlling van der Waals bonding in layered materials.

Fe Isotope Fractionation During Fe(III) Reduction to Fe(II)

NASA Astrophysics Data System (ADS)

Baker, E. A.; Greene, S.; Hardin, E. E.; Hodierne, C. E.; Rosenberg, A.; John, S.

2014-12-01

The redox chemistry of Fe(III) and Fe(II) is tied to a variety of earth processes, including biological, chemical, or photochemical reduction of Fe(III) to Fe(II). Each process may fractionate Fe isotopes, but the magnitudes of the kinetic isotope effects have not been greatly explored in laboratory conditions. Here, we present the isotopic fractionation of Fe during reduction experiments under a variety of experimental conditions including photochemical reduction of Fe(III) bound to EDTA or glucaric acid, and chemical reduction of Fe-EDTA by sodium dithionite, hydroxylamine hydrochloride, Mn(II), and ascorbic acid. A variety of temperatures and pHs were tested. In all experiments, Fe(III) bound to an organic ligand was reduced in the presence of ferrozine. Ferrozine binds with Fe(II), forming a purple complex which allows us to measure the extent of reaction. The absorbance of the experimental solutions was measured over time to determine the Fe(II)-ferrozine concentration and thus the reduction rate. After about 5% of the Fe(III) was reduced, Fe(III)-EDTA and Fe(II)-ferrozine were separated using a C-18 column to which Fe(II)-ferrozine binds. The Fe(II) was eluted and purified through anion exchange chromatography for analysis of δ56Fe by MC-ICPMS. Preliminary results show that temperature and pH both affect reduction rate. All chemical reductants tested reduce Fe(III) at a greater rate as temperature increases. The photochemical reductant EDTA reduces Fe(III) at a greater rate under more acidic conditions. Comparison of the two photochemical reductants shows that glucaric acid reduces Fe(III) significantly faster than EDTA. For chemical reduction, the magnitude of isotopic fractionation depends on the reductant used. Temperature and pH also affect the isotopic fractionation of Fe. Experiments using chemical reductants show that an increase in temperature at low temperatures produces lighter 56Fe ratios, while at high temperatures some reductants produce heavier 56Fe ratios. The magnitude of isotope fractionation is not related to the reduction rate generalized over all reductants. The measured isotopic fractionations produce δ56Fe from -3.82 to +3.05 across all of the reductants tested, highlighting the large impact that redox chemistry may have on fractionating Fe isotopes in the environment.

Inadequacy, Impurity and Infidelity; Modifying the Modified Brendel Alpha-Cellulose Extraction Method for Resinous Woods in Stable Isotope Dendroclimatology

NASA Astrophysics Data System (ADS)

Brookman, T. H.; Whittaker, T. E.; King, P. L.; Horton, T. W.

2011-12-01

Stable isotope dendroclimatology is a burgeoning field in palaeoclimate science due to its unique potential to contribute (sub)annually resolved climate records, over millennial timescales, to the terrestrial palaeoclimate record. Until recently the time intensive methods precluded long-term climate reconstructions. Advances in continuous-flow mass spectrometry and isolation methods for α-cellulose (ideal for palaeoclimate studies as, unlike other wood components, it retains its initial isotopic composition) have made long-term, calendar dated palaeoclimate reconstructions a viable proposition. The Modified Brendel (mBrendel) α-cellulose extraction method is a fast, cost-effective way of preparing whole-wood samples for stable oxygen and carbon isotope analysis. However, resinous woods often yield incompletely processed α-cellulose using the standard mBrendel approach. As climate signals may be recorded by small (<1%) isotopic shifts it is important to investigate if incomplete processing affects the accuracy and precision of tree-ring isotopic records. In an effort to address this methodological issue, we investigated three highly resinous woods: kauri (Agathis australis), ponderosa pine (Pinus ponderosa) and huon pine (Lagarastrobus franklinii). Samples of each species were treated with 16 iterations of the mBrendel, varying reaction temperature, time and reagent volumes. Products were investigated using microscopic and bulk transmission Fourier Transform infrared spectroscopy (FITR) to reveal variations in the level of processing; poorly-digested fibres display a peak at 1520cm-1 suggesting residual lignin and a peak at ~1600cm-1 in some samples suggests retained resin. Despite the different levels of purity, replicate analyses of samples processed by high temperature digestion yielded consistent δ18O within and between experiments. All α-cellulose samples were 5-7% enriched compared to the whole-wood, suggesting that even incomplete processing at high temperature can provide acceptable δ18O analytical external precision. For kauri, short, lower temperature extractions produced α-cellulose with δ18O consistently ~1% lower than longer, higher temperature kauri experiments. These findings suggest that temperature and time are significant variables that influence the analytical precision of α-cellulose stable isotope analysis and that resinous hardwoods (e.g. kauri) may require longer and/or hotter digestions than softwoods. The effects of mBrendel variants on the carbon isotope ratio precision of α-cellulose extracts will also be presented. Our findings indicate that the standard mBrendel α-cellulose extraction method may not fully remove lignins and resins depending on the type of wood being analysed. Residual impurities can decrease analytical precision and accuracy. Fortunately, FTIR analysis prior to isotopic analysis is a relatively fast and cost effective way to determine α-cellulose extract purity, ultimately improving the data quality, accuracy and utility of tree-ring based stable isotopic climate records.

Isotopic composition of atmospheric moisture from pan water evaporation measurements.

PubMed

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2006-12-01

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

Diffusion-controlled magnesium isotopic fractionation of a single crystal forsterite evaporated from the solid state

NASA Technical Reports Server (NTRS)

Wang, Jianhua; Davis, Andrew M.; Hashimoto, Akihiko; Clayton, Robert N.

1993-01-01

Though the origin of calcium- and aluminum-rich inclusions (CAI's) in carbonaceous chondrites is till a disputed issue, evaporation is no doubt one of the most important processes for the formation of CAI's in the early solar nebula. The mechanism for production of large isotopic mass fractionation effects in magnesium, silicon, oxygen, and chromium in CAI's can be better understood by examining isotopic fractionation during the evaporation of minerals. New evaporation experiments were performed on single-crystal forsterite. The magnesium isotopic distribution near the evaporating surfaces of the residues using a modified AEI IM-20 ion microprobe to obtain rastered beam depth profiles was measured. A theoretical model was used to explain the profiles and allowed determination of the diffusion coefficient of Mg(++) in forsterite at higher temperatures than previous measurements. The gas/solid isotopic fractionation factor for magnesium for evaporation from solid forsterite was also determined and found to be nearly the same as that for evaporation of liquid Mg2SiO4.

A new sniffer probe for the determination of hydrogen isotope ratios in the W7-AS stellarator

NASA Astrophysics Data System (ADS)

Zebisch, P.; Taglauer, E.

1999-07-01

An improved sniffer probe was constructed for measurements of the hydrogen isotope ratio and impurities in the plasma edge of the W7-AS stellarator. Details of the new design and the probe performance are presented. The new design allows changing the head without breaking the vacuum in the torus. It has a high mechanical stability, effective screening of the magnetic field and high sensitivity. The gas dynamic properties of the probe are analyzed using transmission line calculus, resulting in a rise time of 114 ms for hydrogen. During the 1997 spring measurement campaign, H/D isotope ratio measurements were carried through showing considerable outgassing of the walls during and after the discharge. He glow discharges reduce the isotope ratio drastically. Results from a typical experiment day are presented together with the analytic procedure for determining the isotope ratio in both the plasma edge and in the neutral gas region between the plasma and the vessel walls.

Measurement of Proton-induced Radiation in Animal Tissue

NASA Astrophysics Data System (ADS)

Sękowski, P.; Skwira-Chalot, I.; Matulewicz, T.

Hadron therapy, because of the dosimetric and radiobiological advantages, is more and more often used in tumour treatment. This treatment method leads also to the radioactive effects induced by energetic protons on nuclei. Nuclear reactions may lead to the production of radioactive isotopes. In the present experiment, two animal (human-like) tissue samples were irradiated with 60 MeV protons. Gamma-ray spectroscopy and lifetime measurements allowed identifying isotopes produced during the irradiation, e.g. $^{18}$F and $^{34m}$Cl.

Oxygen isotope effects of enzyme-catalyzed organophosphorus hydrolysis reactions: implications for interpretation of dissolved PO4 δ18O values in natural waters

NASA Astrophysics Data System (ADS)

Liang, Y.; Blake, R. E.

2002-12-01

The geochemical cycling of P in Earth surface environments is controlled largely by biota. It has been recently demonstrated that intracellular cycling of P in microbial cultures and biological turnover of P in natural waters leads to temperature-dependent O isotope equilibrium between dissolved inorganic PO4 (Pi) and ambient water, and that the δ18O of Pi can be a useful tracer of biological reactions and P cycling in aquatic systems/sediments. Oxygen isotope exchange between Pi and water during biological turnover of P is catalyzed by enzymes at low-temperature. Phosphoenzymes play a crucial role in the intracellular functions of all living organisms and also have important extracellular functions in aquatic ecosystems such as regeneration of Pi from organophosphorus compounds (e.g., phosphoesters). Laboratory experiments indicate that extracellular enzyme reactions may result in incomplete Pi turnover and non-equilibrium Pi-water O isotope exchange. Determination of the O isotope effects of phosphoenzyme-catalyzed reactions is fundamental to the understanding of mechanisms of PO4-water O isotope exchange, pathways of biogeochemical P cycling, and interpretation of PO4 δ18O values from natural systems. Here we report on the O isotope fractionation between enzymatically-released Pi and water, in cell-free abiotic systems. Alkaline phosphatase (Apase) is a non-specific phosphohydrolase commonly found in fresh and marine coastal waters that catalyzes the hydrolysis of Pi from phosphomonoesters. We examined the O isotope effects of Apase derived from both microbial and eukaryotic sources and acting on different phosphomonoester substrates (e.g., α-D-Glucose 1-Phosphate, β-Glycerophosphate, AMP) in 18O-labeled waters. Oxygen isotope ratios of Pi released by Apase indicate that only 1 of the 4 O atoms in PO4 is incorporated from water with little or no apparent O isotopic fractionation at the site of incorporation. This observation is consistent with phosphomonoester structure and the Apase active site configuration and reaction mechanism. 5'-nucleotidase is another important phosphoenzyme identified in marine ecosystems. The O isotope effects of 5'-nucleotidase- catalyzed reactions will also be presented and implications of these results for interpretation of PO4 δ18O values in natural systems will be discussed.

Uranium isotope fractionation induced by aqueous speciation: Implications for U isotopes in marine CaCO3 as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Chen, Xinming; Romaniello, Stephen J.; Anbar, Ariel D.

2017-10-01

Natural variations of 238U/235U in marine CaCO3 rocks are being explored as a novel paleoredox proxy to investigate oceanic anoxia events. Although it is generally assumed that U isotopes in CaCO3 directly record 238U/235U of seawater, recently published laboratory experiments demonstrate slight U isotope fractionation during U(VI) incorporation into abiotic calcium carbonates. This fractionation is hypothesized to depend on aqueous U(VI) speciation, which is controlled by pH, ionic strength, pCO2 and Mg2+ and Ca2+ concentrations. Secular variation in seawater chemistry could lead to changes in aqueous U(VI) speciation, and thus, may affect the extent of U isotope fractionation during U(VI) incorporation into CaCO3. In this study, we combine estimates of seawater composition over the Phanerozoic with a model of aqueous U speciation and isotope fractionation to explore variations in the expected offset between the U isotope composition of seawater and primary marine CaCO3 through time. We find that U isotope fractionation between U in primary marine CaCO3 and seawater could have varied between 0.11 and 0.23‰ over the Phanerozoic due to secular variations in seawater chemistry. Such variations would significantly impact estimates of the extent of marine anoxia derived from the U isotope record. For example, at the Permo-Triassic boundary, this effect might imply that the estimated extent of anoxia is ∼32% more extreme than previously inferred. One significant limitation of our model is that the existing experimental database covers only abiotic carbonate precipitation, and does not include a possible range of biological effects which might enhance or suppress the range of isotopic fractionation calculated here. As biotic carbonates dominate the marine carbonate record, more work is need to assess controls on U isotopic fractionation into biotic marine carbonates.

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 whose chemical compositions and magnesium and silicon isotopic compositions have been previously measured.« less

Determining Carbon and Oxygen Stable Isotope Systematics in Brines at Elevated p/T Conditions to Enhance Monitoring of CO2 Induced Processes in Carbon Storage Reservoirs

NASA Astrophysics Data System (ADS)

Becker, V.; Myrttinen, A.; Mayer, B.; Barth, J. A.

2012-12-01

Stable carbon isotope ratios (δ13C) are a powerful tool for inferring carbon sources and mixing ratios of injected and baseline CO2 in storage reservoirs. Furthermore, CO2 releasing and consuming processes can be deduced if the isotopic compositions of end-members are known. At low CO2 pressures (pCO2), oxygen isotope ratios (δ18O) of CO2 usually assume the δ18O of the water plus a temperature-dependent isotope fractionation factor. However, at very high CO2 pressures as they occur in CO2 storage reservoirs, the δ18O of the injected CO2 may in fact change the δ18O of the reservoir brine. Hence, changing δ18O of brine constitutes an additional tracer for reservoir-internal carbon dynamics and allows the determination of the amount of free phase CO2 present in the reservoir (Johnson et al. 2011). Further systematic research to quantify carbon and oxygen isotope fractionation between the involved inorganic carbon species (CO2, H2CO3, HCO3-, CO32-, carbonate minerals) and kinetic and equilibrium isotope effects during gas-water-rock interactions is necessary because p/T conditions and salinities in CO2 storage reservoirs may exceed the boundary conditions of typical environmental isotope applications, thereby limiting the accuracy of stable isotope monitoring approaches in deep saline formations (Becker et al. 2011). In doing so, it is crucial to compare isotopic patterns observed in laboratory experiments with artificial brines to similar experiments with original fluids from representative field sites to account for reactions of dissolved inorganic carbon (DIC) with minor brine components. In the CO2ISO-LABEL project, funded by the German Ministry for Education and Research, multiple series of laboratory experiments are conducted to determine the influence of pressure, temperature and brine composition on the δ13C of DIC and the δ18O of brines in water-CO2-rock reactions with special focus placed on kinetics and stable oxygen and carbon isotope fractionation factors. Laboratory experiments with original reservoir fluids from CO2 storage reservoirs in Canada using supercritical fluid extraction reactors are being conducted at temperatures of up to 200 °C and CO2 pressures of up to 20 MPa. Preliminary results show that equilibration times for δ18O in high saline waters increase by an order of magnitude compared to fresh water, with exact times depending on CO2 partial pressure, stirring and the contact area between the phases. References Becker, V. et al., 2011. Predicting δ13CDIC dynamics in CCS: A scheme based on a review of inorganic carbon chemistry under elevated pressures and temperatures. International Journal of Greenhouse Gas Control, 5, pp.1250-1258. Johnson, G. et al., 2011. Using oxygen isotope ratios to quantitatively assess trapping mechanisms during CO2 injection into geological reservoirs: The Pembina case study. Chemical Geology, 283(3-4), pp.185-193.

A new investigation on the water isotopes in the Badain Jaran Desert, China, for inferring water origination

NASA Astrophysics Data System (ADS)

Wu, X.; Wang, Y.; Wang, X. S.; Hu, B.

2017-12-01

Stable isotope δ2H, δ18O and d-excess values of water have previously been used to study the hydraulic connection of groundwater between the surrounding areas such as Heihe River Basin, Qilian Mountain and the Badain Jaran desert (BJD), China. We choose to focus on the effects of strong evaporation on the isotopic characteristics of water in the desert to better understand the origin of water in the BJD. A series of evaporation experiments were conducted in the desert to examine how it may change during evaporation and infiltration under local environmental conditions. Evaporation from open water was monitored in two experiments using local groundwater and lake water, respectively. And evaporation of soil water was observed in three pits which were excavated to different depths below a flat ground surface to install the evaporation-infiltration systems. Water samples were also collected from lakes, a spring and local unconfined aquifer for analyses of stable hydrogen and oxygen isotope ratios, and d-excess values in the BJD. The results show that water isotope contents became progressively enriched along an evaporation line, and the d-excess values decreased with the evaporation. The strong relationship of d-excess and δ18O values was observed from both the experiments and the water samples of groundwater and lakes, which is considered to be a signature of strong evaporation. Also, all the values of groundwater and lake water samples fall along with the evaporation line established through the evaporation experiments, indicating that lakes and groundwater in the study area have evolved from meteoric precipitation under modern or similar to modern climatic conditions. Analysis of a few previously published d-excess and δ18O values of groundwater from the BJD, Lake Eyre Basin, Australia, and Jabal Hafit mountain, United Arab Emirates reveals strong relationships between the two, suggesting similar recharge processes as observed in the BJD. This study demonstrated that the characteristic water isotopic patterns resulting from evaporation could be utilized to help resolve ambiguities in the interpretation of water isotope data in terms of recharge sources, especially, in the arid regions, such as the central Australia and the deserts of United Arab Emirates.

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

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

PubMed

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

2013-08-01

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

Vapour-Phase Processes Control Liquid-Phase Isotope Profiles in Unsaturated Sphagnum Moss

NASA Astrophysics Data System (ADS)

Edwards, T. W.; Yi, Y.; Price, J. S.; Whittington, P. N.

2009-05-01

Seminal work in the early 1980s clearly established the basis for predicting patterns of heavy-isotope enrichment of pore waters in soils undergoing evaporation. A key feature of the process under steady-state conditions is the development of stable, convex-upward profiles whose shape is controlled by the balance between downward-diffusing heavy isotopologues concentrated by evaporative enrichment at the surface and the upward capillary flow of bulk water that maintains the evaporative flux. We conducted an analogous experiment to probe evaporation processes within 20-cm columns of unsaturated, living and dead (but undecomposed) Sphagnum moss evaporating under controlled conditions, while maintaining a constant water table. The experiment provided striking evidence of the importance of vapour-liquid mass and isotope exchange in the air-filled pores of the Sphagnum columns, as evidenced by the rapid development of hydrologic and isotopic steady-state within hours, rather than days, i.e., an order of magnitude faster than possible by liquid-phase processes alone. This is consistent with the notion that vapour-phase processes effectively "short-circuit" mass and isotope fluxes within the Sphagnum columns, as proposed also in recent characterizations of water dynamics in transpiring leaves. Additionally, advection-diffusion modelling of our results supports independent estimates of the effective liquid-phase diffusivities of the respective heavy water isotopologues, 2.380 x 10-5 cm2 s-1 for 1H1H18O and 2.415 x 10-5 cm2 s-1 for 1H2H16O, which are in notably good agreement with the "default" values that are typically assumed in soil and plant water studies.

Fractionation of stable isotopes in perchlorate and nitrate during in situ biodegradation in a sandy aquifer

USGS Publications Warehouse

Hatzinger, P.B.; Bohlke, John Karl; Sturchio, N.C.; Gu, B.; Heraty, L.J.; Borden, R.C.

2009-01-01

An in situ experiment was performed in a shallow alluvial aquifer in Maryland to quantify the fractionation of stable isotopes in perchlorate (Cl and O) and nitrate (N and O) during biodegradation. An emulsified soybean oil substrate that was previously injected into this aquifer provided the electron donor necessary for biological perchlorate reduction and denitrification. During the field experiment, groundwater extracted from an upgradient well was pumped into an injection well located within the in situ oil barrier, and then groundwater samples were withdrawn for the next 30 h. After correction for dilution (using Br– as a conservative tracer of the injectate), perchlorate concentrations decreased by 78% and nitrate concentrations decreased by 82% during the initial 8.6 h after the injection. The observed ratio of fractionation effects of O and Cl isotopes in perchlorate (e18O/e37Cl) was 2.6, which is similar to that observed in the laboratory using pure cultures (2.5). Denitrification by indigenous bacteria fractionated O and N isotopes in nitrate at a ratio of ~0.8 (e18O/e15N), which is within the range of values reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (e18O/e37Cl, e18O/e15N) derived from homogeneous laboratory systems (e.g. pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent e values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion.

Fractionation of stable isotopes in perchlorate and nitrate during in situ biodegradation in a sandy aquifer

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

Hatzinger, Paul B.; Bohlke, J. K.; Sturchio, N. C.

An in situ experiment was performed in a shallow alluvial aquifer in Maryland to quantify the fractionation of stable isotopes in perchlorate (Cl and O) and nitrate (N and O) during biodegradation. An emulsified soybean oil substrate that was previously injected into this aquifer provided the electron donor necessary for biological perchlorate reduction and denitrification. During the field experiment, groundwater extracted from an upgradient well was pumped into an injection well located within the in situ oil barrier, and then groundwater samples were withdrawn for the next 30 h. After correction for dilution (using Br-as a conservative tracer of themore » injectate), perchlorate concentrations decreased by 78 % and nitrate concentrations decreased by 87 %, during the initial 8.6 h after the injection. The observed ratio of fractionation effects of O and Cl isotopes in perchlorate (ε18O/ε37Cl) was 2.6, which is similar to that observed in the laboratory using pure cultures (2.5). Denitrification by indigenous bacteria fractionated O and N isotopes in nitrate at a ratio of approximately 0.8 (ε18O/ε15N), which is within the range of values reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (ε18O/ε37Cl, ε18O/ε15N) derived from homogeneous laboratory systems (e.g., pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent  values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion.« less

Isotopic tracing of perchlorate in the environment

USGS Publications Warehouse

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

2012-01-01

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

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

USGS Publications Warehouse

Shuai, Yanhua; Douglas, Peter M.J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-01-01

Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

Thermal Diffusion Fractionation of Cr and V Isotope in Silicate Melt

NASA Astrophysics Data System (ADS)

Lin, X.; Lundstrom, C.

2017-12-01

Earth's mantle is isotopically heavy relative to chondrites for V, Cr and some other siderophile elements. A possible solution is that isotopic fractionation by thermal diffusion occurs in a thermal boundary layer between solid mantle and an underlying basal magma ocean (BMO:Labrosse et al.,2007). If so, isotopically light composition might partition into the core, resulting in a complimentary isotopically heavy solid mantle. To verify how much fractionation could happen in this process, piston cylinder experiment were conducted to investigate the fractionation of Cr and V isotope ratios in partially molten silicate under an imposed temperature gradient from 1650 °C to 1350 °C at 1 GPa for 10 to 50 hours to reach a steady state isotopic profile. The temperature profile for experiments was determined by the spinel-growth method at the same pressure and temperature. Experimental runs result in 100% glass at the hot end progressing to nearly 100 % olivine at the cold end. Major and minor element concentrations of run products show systematic changes with temperature. Glass MgO contents increase and Al2O3 and CaO contents decrease by several weight percent as temperature increases across the charge. These are well modeled using IRIDIUM (Boudreau 2003) to simulate the experiments. Isotopic composition measurements of Cr and V at different temperatures are in progress, providing the first determinations of thermal diffusion isotopic sensitivity, Ω (permil isotopic fractionation per temperature offset per mass unit) for these elements. These results will be compared with previously determined Ω for network formers and modifiers and used in a BMO-based thermal diffusion model for formation of Earth's isotopically heavy mantle.

Experimental evidence for Mo isotope fractionation between metal and silicate liquids

NASA Astrophysics Data System (ADS)

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

2013-10-01

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

Lithium isotope fractionation by diffusion in minerals Part 2: Olivine

NASA Astrophysics Data System (ADS)

Richter, Frank; Chaussidon, Marc; Bruce Watson, E.; Mendybaev, Ruslan; Homolova, Veronika

2017-12-01

Recent experiments have shown that lithium isotopes can be significantly fractionated by diffusion in silicate liquids and in augite. Here we report new laboratory experiments that document similarly large lithium isotopic fractionation by diffusion in olivine. Two types of experiments were used. A powder-source method where lithium from finely ground spodumene (LiAlSi2O6) diffused into oriented San Carlos olivine, and piston cylinder annealing experiments where Kunlun clinopyroxene (∼30 ppm lithium) and oriented San Carlos olivine (∼2 ppm lithium) were juxtaposed. The lithium concentration along traverses across the run products was measured using both laser ablation as a source for a Varian 820-MS quadrupole mass spectrometer and a CAMECA 1270 secondary ion mass spectrometer. The CAMECA 1270 was also used to measure the lithium isotopic fractionation across olivine grains recovered from the experiments. The lithium isotopes were found to be fractionationed by many tens of permil in the diffusion boundary layer at the grain edges as a result of 6Li diffusing significantly faster than 7Li. The lithium concentration and isotopic fractionation data across the olivine recovered from the different experiments were modeled using calculations in which lithium was assumed to be of two distinct types - one being fast diffusing interstitial lithium, the other much less mobile lithium on a metal site. The two-site diffusion model involves a large number of independent parameters and we found that different choices of the parameters can produce very comparable fits to the lithium concentration profiles and associated isotopic fractionation. Because of this nonuniqueness we are able to determine only a range for the relative diffusivity of 6Li compared to 7Li. When the mass dependence of lithium diffusion is parameterized as D6Li /D7Li =(7 / 6) β , the isotope fractionation for diffusion along the a and c crystallographic direction of olivine can be fit by β = 0.4 ± 0.1 while the fractionation in the b direction appears to be somewhat lower. Model calculations were also used to fit the lithium concentration and isotopic fractionation across a natural olivine grain from a peridotite xenolith from the Eastern North China Craton. The isotopic data were fit using β values (0.3-0.36) similar to that of the laboratory experiments. This, along with the fact that the isotopic fractionation is restricted to that part of the mineral with a gradient in lithium concentration, is strong evidence that the lithium zoning of this mineral grain is the result of lithium loss by diffusion and thus that it can be used, as illustrated, to constrain the cooling history.

The Application of Methane Clumped Isotope Measurements to Determine the Source of Large Methane Seeps in Alaskan Lakes

NASA Astrophysics Data System (ADS)

Douglas, P. M.; Stolper, D. A.; Eiler, J. M.; Sessions, A. L.; Walter Anthony, K. M.

2014-12-01

Natural methane emissions from the Arctic present an important potential feedback to global warming. Arctic methane emissions may come from either active microbial sources or from deep fossil reservoirs released by the thawing of permafrost and melting of glaciers. It is often difficult to distinguish between and quantify contributions from these methane sources based on stable isotope data. Analyses of methane clumped isotopes (isotopologues with two or more rare isotopes such as 13CH3D) can complement traditional stable isotope-based classifications of methane sources. This is because clumped isotope abundances (for isotopically equilibrated systems) are a function of temperature and can be used to identify pathways of methane generation. Additionally, distinctive effects of mixing on clumped isotope abundances make this analysis valuable for determining the origins of mixed gasses. We find large variability in clumped isotope compositions of methane from seeps in several lakes, including thermokarst lakes, across Alaska. At Lake Sukok in northern Alaska we observe the emission of dominantly thermogenic methane, with a formation temperature of at least 100° C. At several other lakes we find evidence for mixing between thermogenic methane and biogenic methane that forms in low-temperature isotopic equilibrium. For example, at Eyak Lake in southeastern Alaska, analysis of three methane samples results in a distinctive isotopic mixing line between a high-temperature end-member that formed between 100-170° C, and a biogenic end-member that formed in isotopic equilibrium between 0-20° C. In this respect, biogenic methane in these lakes resembles observations from marine gas seeps, oil degradation, and sub-surface aquifers. Interestingly, at Goldstream Lake in interior Alaska, methane with strongly depleted clumped-isotope abundances, indicative of disequilibrium gas formation, is found, similar to observations from methanogen culture experiments.

Inside HOLMES experiment: 163Ho metallic target production for the micro-calorimeter absorber

NASA Astrophysics Data System (ADS)

Pizzigoni, G.; Alpert, B.; Balata, M.; Bennett, D.; Biasotti, M.; Boragno, C.; Brofferio, C.; De Gerone, M.; Dressler, R.; Faverazani, M.; Ferri, E.; Folwer, J.; Gatti, F.; Giachero, A.; Heinitz, S.; Hilton, G.; Köster, U.; Lusignoli, M.; Maino, M.; Mates, J.; Nisi, S.; Nizzolo, R.; Nucciotti, A.; Pessina, G.; Puiu, A.; Ragazzi, S.; Reintsema, C.; Ribeiro Gomes, M.; Shmidt, D.; Schumann, D.; Sisti, M.; Swetz, D.; Terranova, F.; Ullom, J.; Day, P. K.

2016-07-01

The main goal in the HOLMES experiment is the neutrino mass measurement using an array of 1000 micro-calorimeters with standard metallic absorber. A good isotope for such measurement is the 163Ho, those isotopes embedded in the metallic absorber will be 1011-1013. Since 163Ho is not available in nature, a dedicated process must be set up to produce the amount needed for this neutrino mass experiment. The process with the highest born-up cross-section is the neutron irradiation of Er2O3 enriched in 162Er: 162Er(n,γ)163Er →163Ho+νe, where the decay is an EC with half-life of about 75 min and the (n,γ) is about 20 barns for thermal neutron. After the neutron irradiation in the oxide powder there are several radioactive isotopes which are potentially disturbing because of the background that they cause below 5 keV. The chemical separation of holmium from the irradiation enriched Er2O3 powder is therefore mandatory and will be performed by means of ion exchange chromatography. On the end of those processes the oxide powder enriched in 162Er will have the 163Ho isotope number required. The holmium chemical state influences the end point of the EC spectrum, in order to avoid such effect it is necessary to embed in the absorber only the metallic isotope. Reduction and distillation technique allowed us to obtain a pure metallic holmium, starting from natural oxide holmium. This technique will be applied on the irradiated oxide powder to obtain the metallic 163Ho, ready to be embedded in the micro-calorimeter absorber.

Projectile fragmentation of 40,48Ca and isotopic scaling in a transport approach

NASA Astrophysics Data System (ADS)

Mikhailova, T. I.; Erdemchimeg, B.; Artukh, A. G.; Di Toro, M.; Wolter, H. H.

2016-07-01

We investigate theoretically projectile fragmentation in reactions of 40,48Ca on 9Be and 181Ta targets using a Boltzmann-type transport approach, which is supplemented by a statistical decay code to describe the de-excitation of the hot primary fragments. We determine the thermodynamical properties of the primary fragments and calculate the isotope distributions of the cold final fragments. These describe the data reasonably well. For the pairs of projectiles with different isotopic content we analyze the isotopic scaling (or isoscaling) of the final fragment distributions, which has been used to extract the symmetry energy of the primary source. The calculation exhibits isoscaling behavior for the total yields as do the experiments. We also perform an impact-parameter-dependent isoscaling analysis in view of the fact that the primary systems at different impact parameters have very different properties. Then the isoscaling behavior is less stringent, which we can attribute to specific structure effects of the 40,48Ca pair. The symmetry energy determined in this way depends on these structure effects.

Projectile fragmentation of {sup 40,48}Ca and isotopic scaling in a transport approach

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

Mikhailova, T. I., E-mail: tmikh@jinr.ru; Erdemchimeg, B.; Artukh, A. G.

2016-07-15

We investigate theoretically projectile fragmentation in reactions of {sup 40,48}Ca on {sup 9}Be and {sup 181}Ta targets using a Boltzmann-type transport approach, which is supplemented by a statistical decay code to describe the de-excitation of the hot primary fragments. We determine the thermodynamical properties of the primary fragments and calculate the isotope distributions of the cold final fragments. These describe the data reasonably well. For the pairs of projectiles with different isotopic content we analyze the isotopic scaling (or isoscaling) of the final fragment distributions, which has been used to extract the symmetry energy of the primary source. The calculationmore » exhibits isoscaling behavior for the total yields as do the experiments. We also perform an impact-parameter-dependent isoscaling analysis in view of the fact that the primary systems at different impact parameters have very different properties. Then the isoscaling behavior is less stringent, which we can attribute to specific structure effects of the {sup 40,48}Ca pair. The symmetry energy determined in this way depends on these structure effects.« less

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.

The Determination of the Natural Abundance of the Isotopes of Chlorine: An Introductory Experiment in Mass Spectrometry.

ERIC Educational Resources Information Center

O'Malley, Rebecca M.

1982-01-01

Describes a laboratory experiment which introduces basic principles and experimental techniques of mass spectrometry for fourth year undergraduate (B.Sc.) students. Laboratory procedures, background information, and discussion of results are provided for the experiment in which the natural isotopic abundance of chlorine is determined. (Author/JN)

Main features of detectors and isotopes to investigate double beta decay with increased sensitivity

NASA Astrophysics Data System (ADS)

Barabash, A. S.

2018-03-01

The current situation in double beta decay experiments, the characteristics of modern detectors and the possibility of increasing the sensitivity to neutrino mass in future experiments are discussed. The issue of the production and use of enriched isotopes in double beta decay experiments is discussed in addition.

Rapid two-dimensional ALSOFAST-HSQC experiment for metabolomics and fluxomics studies: application to a 13C-enriched cancer cell model treated with gold nanoparticles.

PubMed

Schätzlein, Martina Palomino; Becker, Johanna; Schulze-Sünninghausen, David; Pineda-Lucena, Antonio; Herance, José Raul; Luy, Burkhard

2018-04-01

Isotope labeling enables the use of 13 C-based metabolomics techniques with strongly improved resolution for a better identification of relevant metabolites and tracing of metabolic fluxes in cell and animal models, as required in fluxomics studies. However, even at high NMR-active isotope abundance, the acquisition of one-dimensional 13 C and classical two-dimensional 1 H, 13 C-HSQC experiments remains time consuming. With the aim to provide a shorter, more efficient alternative, herein we explored the ALSOFAST-HSQC experiment with its rapid acquisition scheme for the analysis of 13 C-labeled metabolites in complex biological mixtures. As an initial step, the parameters of the pulse sequence were optimized to take into account the specific characteristics of the complex samples. We then applied the fast two-dimensional experiment to study the effect of different kinds of antioxidant gold nanoparticles on a HeLa cancer cell model grown on 13 C glucose-enriched medium. As a result, 1 H, 13 C-2D correlations could be obtained in a couple of seconds to few minutes, allowing a simple and reliable identification of various 13 C-enriched metabolites and the determination of specific variations between the different sample groups. Thus, it was possible to monitor glucose metabolism in the cell model and study the antioxidant effect of the coated gold nanoparticles in detail. Finally, with an experiment time of only half an hour, highly resolved 1 H, 13 C-HSQC spectra using the ALSOFAST-HSQC pulse sequence were acquired, revealing the isotope-position-patterns of the corresponding 13 C-nuclei from carbon multiplets. Graphical abstract Fast NMR applied to metabolomics and fluxomics studies with gold nanoparticles.

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

NASA Technical Reports Server (NTRS)

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

2011-01-01

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

A Hydrogen Exchange Method Using Tritium and Sephadex: Its Application to Ribonuclease*

PubMed Central

Englander, S. Walter

2012-01-01

A new method for measuring the hydrogen exchange of macromolecules in solution is described. The method uses tritium to trace the movement of hydrogen, and utilizes Sephadex columns to effect, in about 2 minutes, a separation between tritiated macromolecule and tritiated solvent great enough to allow the measurement of bound tritium. High sensitivity and freedom from artifact is demonstrated and the possible value of the technique for investigation of other kinds of colloid-small molecule interaction is indicated. Competition experiments involving tritium, hydrogen, and deuterium indicate the absence of any equilibrium isotope effect in the ribonuclease-hydrogen isotope system, though a secondary kinetic isotope effect is apparent when ribonuclease is largely deuterated. Ribonuclease shows four clearly distinguishable kinetic classes of exchangeable hydrogens. Evidence is marshaled to suggest the independently measurable classes II, III, and IV (in order of decreasing rate of exchange) to represent “random-chain” peptides, peptides involved in α-helix, and otherwise shielded side-chain and peptide hydrogens, respectively. PMID:14075117

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

Hamilton, Terry F.; Martinelli, Roger E.; Kehl, Steven R.

A series of K d tracer batch experiments were conducted in this paper to assess the absorptive-desorption properties of Biochar as a potential agent to selectively sequester labile soil Cs or otherwise help reduce the uptake of Cs isotopes into plants. A parallel experiment was conducted for strontium. Fine-grained fractionated Woodlands tree Biochar was found to have a relatively high affinity for Cs ions (K d > 100) relative to coral soil (K d < 10) collected from the Marshall Islands. The Biochar material also contains an abundance of K (and Mg). Finally, these findings support a hypothesis that themore » addition of Biochar as a soil amendment may provide a simple yet effective method for reducing soil-to-plant transfer of Cs isotopes in contaminated environments.« less

Experimental controls on D/H and 13C/12C ratios of kerogen, bitumen and oil during hydrous pyrolysis

USGS Publications Warehouse

Schimmelmann, A.; Boudou, J.-P.; Lewan, M.D.; Wintsch, R.P.

2001-01-01

Large isotopic transfers between water-derived hydrogen and organic hydrogen occurred during hydrous pyrolysis experiments of immature source rocks, in spite of only small changes in organic 13C/12C. Experiments at 330 ??C over 72 h using chips or powder containing kerogen types I and III identify the rock/water ratio as a main factor affecting ????D for water and organic hydrogen. Our data suggest that larger rock permeability and smaller rock grain size increase the H-isotopic transfer between water-derived hydrogen and thermally maturing organic matter. Increasing hydrostatic pressure may have a similar effect, but the evidence remains inconclusive. ?? 2001 Elsevier Science Ltd. All rights reserved.

Isotope shift, nonlinearity of King plots, and the search for new particles

NASA Astrophysics Data System (ADS)

Flambaum, V. V.; Geddes, A. J.; Viatkina, A. V.

2018-03-01

We derive a mean-field relativistic formula for the isotope shift of an electronic energy level for arbitrary angular momentum; we then use it to predict the spectra of superheavy metastable neutron-rich isotopes belonging to the hypothetical island of stability. Our results may be applied to the search for superheavy atoms in astrophysical spectra using the known values of the transition frequencies for the neutron-deficient isotopes produced in the laboratory. An example of a relevant astrophysical system may be the spectra of the Przybylski's star where superheavy elements up to Z =99 have been possibly identified. In addition, it has been recently suggested to use the measurements of King plot nonlinearity in a search for hypothetical new light bosons. On the other hand, one can find the nonlinear corrections to the King plot arising already in the standard model framework. We investigate contributions to the nonlinearity arising from relativistic effects in the isotope field shift, the nuclear polarizability, and many-body effects. It is found that the nuclear polarizability contribution can lead to the significant deviation of the King plot from linearity. Therefore, the measurements of the nonlinearity of King plots may be applied to obtain the nuclear polarizability change between individual isotopes. We then proceed with providing a rough analytical estimate of the nonlinearity arising solely from the effect of a hypothetical scalar boson. Our predictions give theoretical limitations on the sensitivity of the search for new interactions and should help to identify the most suitable atoms for corresponding experiments.

NASA Glenn Research Center Experience with LENR Phenomenon

NASA Technical Reports Server (NTRS)

Wrbanek, Susan Y.; Fralick, Gustave C.; Wrbanek, John D.; Niedra, Janis M.

2012-01-01

Since 1989 NASA Glenn Research Center (GRC) has performed some small-scale limited experiments that show evidence of effects claimed by some to be evidence of Low Energy Nuclear Reactions (LENR). The research at GRC has involved observations and work on measurement techniques for observing the temperature effects in reactions of isotopes of hydrogen with palladium hydrides. The various experiments performed involved loading Pd with gaseous H2 and D2, and exposing Pd thin films to multi-bubble sonoluminescence in regular and deuterated water. An overview of these experiments and their results will be presented.

NASA Glenn Research Center Experience with "LENR Phenomenon"

NASA Technical Reports Server (NTRS)

Wrbanek, Susan Y.; Fralick, Gustave C.; Wrbanek, John D.; Niedra, Janis M.

2012-01-01

Since 1989 NASA Glenn Research Center (GRC) has performed some small-scale limited experiments that show evidence of effects claimed by some to be evidence of Low Energy Nuclear Reactions (LENR). The research at GRC has involved observations and work on measurement techniques for observing the temperature effects in reactions of isotopes of hydrogen with palladium hydrides. The various experiments performed involved loading Pd with gaseous H2 and D2, and exposing Pd thin films to multi-bubble sonoluminescence in regular and deuterated water. An overview of these experiments and their results will be presented.

Catalytic recombination of dissociation products with Pt/SnO2 for rare and common isotope long-life, closed-cycle CO2 lasers

NASA Technical Reports Server (NTRS)

Brown, Kenneth G.; Sidney, B. D.; Schryer, D. R.; Upchurch, B. T.; Miller, I. M.

1986-01-01

This paper reports results on recombination of pulsed CO2 laser dissociation products with Pt/SnO2 catalysts, and supporting studies in a surrogate laboratory catalyst reactor. The closed-cycle, pulsed CO2 laser has been continuously operated for one million pulses with an overall power degradation of less than 5 percent by flowing the laser gas mixture through a 2-percent Pt/SnO2 catalyst bed. In the surrogate laboratory reactor, experiments have been conducted to determine isotopic exchange with the catalyst when using rare-isotope gases. The effects of catalyst pretreatment, sample weight, composition, and temperature on catalyst efficiency have also been determined.

Isotopically pure magnesium isotope-24 is prepared from magnesium-24 oxide

NASA Technical Reports Server (NTRS)

Chellew, N. R.; Schilb, J. D.; Steunenberg, R. K.

1968-01-01

Apparatus is used to prepare isotopically pure magnesium isotope-24, suitable for use in neutron scattering and polarization experiments. The apparatus permits thermal reduction of magnesium-24 oxide with aluminum and calcium oxide, and subsequent vaporization of the product metal in vacuum. It uses a resistance-heated furnace tube and cap assembly.

Constraining Thermal Histories by Monte Carlo Simulation of Mg-Fe Isotopic Profiles in Olivine

NASA Astrophysics Data System (ADS)

Sio, C. K. I.; Dauphas, N.

2016-12-01

In thermochronology, random time-temperature (t-T) paths are generated and used as inputs to model fission track data. This random search method is used to identify a range of acceptable thermal histories that can describe the data. We have extended this modeling approach to magmatic systems. This approach utilizes both the chemical and stable isotope profiles measured in crystals as model constraints. Specifically, the isotopic profiles are used to determine the relative contribution of crystal growth vs. diffusion in generating chemical profiles, and to detect changes in melt composition. With this information, tighter constraints can be placed on the thermal evolution of magmatic bodies. We use an olivine phenocryst from the Kilauea Iki lava lake, HI, to demonstrate proof of concept. We treat this sample as one with little geologic context, then compare our modeling results to the known thermal history experienced by that sample. To complete forward modeling, we use MELTS to estimate the boundary condition, initial and quench temperatures. We also assume a simple relationship between crystal growth and cooling rate. Another important parameter is the isotopic effect for diffusion (i.e., the relative diffusivity of the light vs. heavy isotope of an element). The isotopic effects for Mg and Fe diffusion in olivine have been estimated based on natural samples; experiments to better constrain these parameters are underway. We find that 40% of the random t-T paths can be used to fit the Mg-Fe chemical profiles. However, only a few can be used to simultaneously fit the Mg-Fe isotopic profiles. These few t-T paths are close to the independently determined t-T history of the sample. This modeling approach can be further extended other igneous and metamorphic systems where data exist for diffusion rates, crystal growth rates, and isotopic effects for diffusion.

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.

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 to these modern observations, clumped-isotope analyses of a flowstone from Villars cave (France) offer evidence that the amount of disequilibrium affecting Δ47 in a single speleothem can experience large variations at time scales of 10 kyr. Application of clumped-isotope thermometry to speleothem records calls for an improved physical understanding of DIC fractionation processes in karst waters, and for the resolution of important issues regarding equilibrium calibration of Δ47 in inorganic carbonates.

Isotopologue Distributions of Peptide Product Ions by Tandem Mass Spectrometry: Quantitation of Low Levels of Deuterium Incorporation1

PubMed Central

Wang, Benlian; Sun, Gang; Anderson, David R.; Jia, Minghong; Previs, Stephen; Anderson, Vernon E.

2007-01-01

Protonated molecular peptide ions and their product ions generated by tandem mass spectrometry appear as isotopologue clusters due to the natural isotopic variations of carbon, hydrogen, nitrogen, oxygen and sulfur. Quantitation of the isotopic composition of peptides can be employed in experiments involving isotope effects, isotope exchange, isotopic labeling by chemical reactions, and studies of metabolism by stable isotope incorporation. Both ion trap and quadrupole-time of flight mass spectrometry are shown to be capable of determining the isotopic composition of peptide product ions obtained by tandem mass spectrometry with both precision and accuracy. Tandem mass spectra obtained in profile-mode of clusters of isotopologue ions are fit by non-linear least squares to a series of Gaussian peaks (described in the accompanying manuscript) which quantify the Mn/M0 values which define the isotopologue distribution (ID). To determine the isotopic composition of product ions from their ID, a new algorithm that predicts the Mn/M0 ratios is developed which obviates the need to determine the intensity of all of the ions of an ID. Consequently a precise and accurate determination of the isotopic composition a product ion may be obtained from only the initial values of the ID, however the entire isotopologue cluster must be isolated prior to fragmentation. Following optimization of the molecular ion isolation width, fragmentation energy and detector sensitivity, the presence of isotopic excess (2H, 13C, 15N, 18O) is readily determined within 1%. The ability to determine the isotopic composition of sequential product ions permits the isotopic composition of individual amino acid residues in the precursor ion to be determined. PMID:17559791

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

PubMed

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

2006-01-01

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

Sulfur isotope fractionation between fluid and andesitic melt: An experimental study

USGS Publications Warehouse

Fiege, Adrian; Holtz, François; Shimizu, Nobumichi; Mandeville, Charles W.; Behrens, Harald; Knipping, Jaayke L.

2014-01-01

Glasses produced from decompression experiments conducted by Fiege et al. (2014a) were used to investigate the fractionation of sulfur isotopes between fluid and andesitic melt upon magma degassing. Starting materials were synthetic glasses with a composition close to a Krakatau dacitic andesite. The glasses contained 4.55–7.95 wt% H2O, ∼140 to 2700 ppm sulfur (S), and 0–1000 ppm chlorine (Cl). The experiments were carried out in internally heated pressure vessels (IHPV) at 1030 °C and oxygen fugacities (fO2) ranging from QFM+0.8 log units up to QFM+4.2 log units (QFM: quartz–fayalite–magnetite buffer). The decompression experiments were conducted by releasing pressure (P) continuously from ∼400 MPa to final P of 150, 100, 70 and 30 MPa. The decompression rate (r) ranged from 0.01 to 0.17 MPa/s. The samples were annealed for 0–72 h (annealing time, tA) at the final P and quenched rapidly from 1030 °C to room temperature (T).The decompression led to the formation of a S-bearing aqueous fluid phase due to the relatively large fluid–melt partitioning coefficients of S. Secondary ion mass spectrometry (SIMS) was used to determine the isotopic composition of the glasses before and after decompression. Mass balance calculations were applied to estimate the gas–melt S isotope fractionation factor αg-m.No detectable effect of r and tA on αg-m was observed. However, SIMS data revealed a remarkable increase of αg-m from ∼0.9985 ± 0.0007 at >QFM+3 to ∼1.0042 ± 0.0042 at ∼QFM+1. Noteworthy, the isotopic fractionation at reducing conditions was about an order of magnitude larger than predicted by previous works. Based on our experimental results and on previous findings for S speciation in fluid and silicate melt a new model predicting the effect of fO2 on αg-m (or Δ34Sg–m) in andesitic systems at 1030 °C is proposed. Our experimental results as well as our modeling are of high importance for the interpretation of S isotope signatures in natural samples (e.g., melt inclusions or volcanic gases).

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'.

Mercury isotope fractionation during ore retorting in the Almadén mining district, Spain

USGS Publications Warehouse

Gray, John E.; Pribil, Michael J.; Higueras, Pablo L.

2013-01-01

Almadén, Spain, is the world's largest mercury (Hg) mining district, which has produced over 250,000 metric tons of Hg representing about 30% of the historical Hg produced worldwide. The objective of this study was to measure Hg isotopic compositions of cinnabar ore, mine waste calcine (retorted ore), elemental Hg (Hg0(L)), and elemental Hg gas (Hg0(g)), to evaluate potential Hg isotopic fractionation. Almadén cinnabar ore δ202Hg varied from − 0.92 to 0.15‰ (mean of − 0.56‰, σ = 0.35‰, n = 7), whereas calcine was isotopically heavier and δ202Hg ranged from − 0.03‰ to 1.01‰ (mean of 0.43‰, σ = 0.44‰, n = 8). The average δ202Hg enrichment of 0.99‰ between cinnabar ore and calcines generated during ore retorting indicated Hg isotopic mass dependent fractionation (MDF). Mass independent fractionation (MIF) was not observed in any of the samples in this study. Laboratory retorting experiments of cinnabar also were carried out to evaluate Hg isotopic fractionation of products generated during retorting such as calcine, Hg0(L), and Hg0(g). Calcine and Hg0(L) generated during these retorting experiments showed an enrichment in δ202Hg of as much as 1.90‰ and 0.67‰, respectively, compared to the original cinnabar ore. The δ202Hg for Hg0(g) generated during the retorting experiments was as much as 1.16‰ isotopically lighter compared to cinnabar, thus, when cinnabar ore was roasted, the resultant calcines formed were isotopically heavier, whereas the Hg0(g) generated was isotopically lighter in Hg isotopes.

Fractionation of silver isotopes in native silver explained by redox reactions

NASA Astrophysics Data System (ADS)

Mathur, Ryan; Arribas, Antonio; Megaw, Peter; Wilson, Marc; Stroup, Steven; Meyer-Arrivillaga, Danilo; Arribas, Isabel

2018-03-01

Scant data exist on the silver isotope composition of native silver specimens because of the relative newness of the technique. This study increases the published dataset by an order of magnitude and presents 80 silver new isotope analyses from native silver originating from a diverse set of worldwide deposits (8 deposit types, 33 mining districts in five continents). The measured isotopic range (defined as δ109Ag/107Ag in per mil units compared to NIST 978 Ag isotope standard) is +2.1 to -0.86‰ (2σ errors less than 0.015); with no apparent systematic correlations to date with deposit type or even within districts. Importantly, the data centering on 0‰ all come from high temperature hypogene/primary deposits whereas flanking and overlapping data represent secondary supergene deposits. To investigate the causes for the more fractionated values, several laboratory experiments involving oxidation of silver from natural specimens of Ag-rich sulfides and precipitation and adsorption of silver onto reagent grade MnO2 and FeOOH were conducted. Simple leach experiments demonstrate little Ag isotope fractionation occurred through oxidation of Ag from native Ag (Δsolution-native109Ag = 0.12‰). In contrast, significant fractionation occurred through precipitation of native Ag onto MnO2 (up to Δsolution-MnO2109Ag = 0.68‰, or 0.3amu). Adsorption of silver onto the MnO2 and FeOOH did not produce as large fractionation as precipitation (mean value of Δsolution-MnO2109Ag = 0.10‰). The most likely cause for the isotopic variations seen relates to redox effects such as the reduction of silver from Ag (I) to Ag° that occurs during precipitation onto the mineral surface. Since many Ag deposits have halos dominated by MnO2 and FeOOH phases, potential may exist for the silver isotope composition of ores and surrounding geochemical haloes to be used to better understand ore genesis and potential exploration applications. Aside from the Mn oxides, surface fluid silver isotope compositions might provide information about geochemical reactions relevant to both environmental and hydrometallurgical applications.

On structural identifiability analysis of the cascaded linear dynamic systems in isotopically non-stationary 13C labelling experiments.

PubMed

Lin, Weilu; Wang, Zejian; Huang, Mingzhi; Zhuang, Yingping; Zhang, Siliang

2018-06-01

The isotopically non-stationary 13C labelling experiments, as an emerging experimental technique, can estimate the intracellular fluxes of the cell culture under an isotopic transient period. However, to the best of our knowledge, the issue of the structural identifiability analysis of non-stationary isotope experiments is not well addressed in the literature. In this work, the local structural identifiability analysis for non-stationary cumomer balance equations is conducted based on the Taylor series approach. The numerical rank of the Jacobian matrices of the finite extended time derivatives of the measured fractions with respect to the free parameters is taken as the criterion. It turns out that only one single time point is necessary to achieve the structural identifiability analysis of the cascaded linear dynamic system of non-stationary isotope experiments. The equivalence between the local structural identifiability of the cascaded linear dynamic systems and the local optimum condition of the nonlinear least squares problem is elucidated in the work. Optimal measurements sets can then be determined for the metabolic network. Two simulated metabolic networks are adopted to demonstrate the utility of the proposed method. Copyright © 2018 Elsevier Inc. All rights reserved.

Open sd-shell nuclei from first principles

DOE PAGES

Jansen, Gustav R.; Signoracci, Angelo J.; Hagen, Gaute; ...

2016-07-05

We extend the ab initio coupled-cluster effective interaction (CCEI) method to open-shell nuclei with protons and neutrons in the valence space, and compute binding energies and excited states of isotopes of neon and magnesium. We employ a nucleon-nucleon and three-nucleon interaction from chiral effective field theory evolved to a lower cutoff via a similarity renormalization group transformation. We find good agreement with experiment for binding energies and spectra, while charge radii of neon isotopes are underestimated. For the deformed nuclei 20Ne and 24Mg we reproduce rotational bands and electric quadrupole transitions within uncertainties estimated from an effective field theory formore » deformed nuclei, thereby demonstrating that collective phenomena in sd-shell nuclei emerge from complex ab initio calculations.« less

Open sd-shell nuclei from first principles

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

Jansen, Gustav R.; Signoracci, Angelo J.; Hagen, Gaute

We extend the ab initio coupled-cluster effective interaction (CCEI) method to open-shell nuclei with protons and neutrons in the valence space, and compute binding energies and excited states of isotopes of neon and magnesium. We employ a nucleon-nucleon and three-nucleon interaction from chiral effective field theory evolved to a lower cutoff via a similarity renormalization group transformation. We find good agreement with experiment for binding energies and spectra, while charge radii of neon isotopes are underestimated. For the deformed nuclei 20Ne and 24Mg we reproduce rotational bands and electric quadrupole transitions within uncertainties estimated from an effective field theory formore » deformed nuclei, thereby demonstrating that collective phenomena in sd-shell nuclei emerge from complex ab initio calculations.« less

Relating Carbon and Nitrogen Isotope Effects to Reaction Mechanisms during Aerobic or Anaerobic Degradation of RDX (Hexahydro-1,3,5-Trinitro-1,3,5-Triazine) by Pure Bacterial Cultures

PubMed Central

Heraty, Linnea; Condee, Charles W.; Vainberg, Simon; Sturchio, Neil C.; Böhlke, J. K.; Hatzinger, Paul B.

2016-01-01

ABSTRACT Kinetic isotopic fractionation of carbon and nitrogen during RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) biodegradation was investigated with pure bacterial cultures under aerobic and anaerobic conditions. Relatively large bulk enrichments in 15N were observed during biodegradation of RDX via anaerobic ring cleavage (ε15N = −12.7‰ ± 0.8‰) and anaerobic nitro reduction (ε15N = −9.9‰ ± 0.7‰), in comparison to smaller effects during biodegradation via aerobic denitration (ε15N = −2.4‰ ± 0.2‰). 13C enrichment was negligible during aerobic RDX biodegradation (ε13C = −0.8‰ ± 0.5‰) but larger during anaerobic degradation (ε13C = −4.0‰ ± 0.8‰), with modest variability among genera. Dual-isotope ε13C/ε15N analyses indicated that the three biodegradation pathways could be distinguished isotopically from each other and from abiotic degradation mechanisms. Compared to the initial RDX bulk δ15N value of +9‰, δ15N values of the NO2− released from RDX ranged from −7‰ to +2‰ during aerobic biodegradation and from −42‰ to −24‰ during anaerobic biodegradation. Numerical reaction models indicated that N isotope effects of NO2− production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε15N-NO2− values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO2− formation associated with anaerobic ring cleavage. These results indicate the potential for isotopic analysis of residual RDX for the differentiation of degradation pathways and indicate that further efforts to examine the isotopic composition of potential RDX degradation products (e.g., NOx) in the environment are warranted. IMPORTANCE This work provides the first systematic evaluation of the isotopic fractionation of carbon and nitrogen in the organic explosive RDX during degradation by different pathways. It also provides data on the isotopic effects observed in the nitrite produced during RDX biodegradation. Both of these results could lead to better understanding of the fate of RDX in the environment and help improve monitoring and remediation technologies. PMID:27016566

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

DOEpatents

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

2014-12-09

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

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 proposed end member value of 37‰ can be expected during fungal denitrification. The observation in pure microbial culture of constant SP can only be reconciled if the rate of nitrite and NO reduction are the same (thereby maintaining a steady NO concentration in the cell), and, further, that the magnitude of the P450nor NO binding constant (Kd) maintains the extent of the reaction (1-f) at 65%.

Fractionated Mercury Isotopes in Fish: The Effects of Nuclear Mass, Spin, and Volume

NASA Astrophysics Data System (ADS)

Das, R.; Odom, A. L.

2007-12-01

Mercury is long known as a common environmental contaminant. In methylated form it is even more toxic and the methylation process is facilitated by microbial activities. Methyl mercury easily crosses cell membrane and accumulates in soft tissues of fishes and finally biomagnifies with increasing trophic levels. Natural variations in the isotopic composition of mercury have been reported and such variations have emphasized mass dependent fractionations, while theory and laboratory experiments indicate that mass-independent isotopic fractionation (MIF) effects are likely to be found as well. This study focuses on the MIF of mercury isotopes in the soft tissues of fishes. Samples include both fresh water and marine fish, from different continents and oceans. Approximately 1 gm of fish soft tissue was dissolved in 5 ml of conc. aqua regia for 24 hrs and filtered through a ¬¬¬100 μm filter paper and diluted with DI water. Hg is measured as a gaseous phase generated by reduction of the sample with SnCl2 in a continuous- flow cold-vapor generator connected to a Thermo-Finnigan Neptune MC-ICPMS. To minimize instrumental fractionation isotope ratios were measured by sample standard bracketing and reported as δ‰ relative to NIST SRM 3133 Hg standard where δAHg = [(A Hg/202Hg)sample/(A Hg/202Hg)NIST313] -1 ×1000‰. In this study we have measured the isotope ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg and 204Hg/202Hg. In all the fish samples δ198Hg, δ200Hg, δ202Hg, δ204Hg define a mass- dependent fractionation sequence, where as the δ199Hg and δ201Hg depart from the mass- dependent fractionation line and indicate an excess of the odd-N isotopes. The magnitude of the deviation (ΔAHg where A=199 or 201) as obtained by difference between the measured δ199Hg and δ201Hg of the samples and the value obtained by linear scaling defined by the even-N isotopes ranges from approximately 0.2 ‰ to 3‰. The ratios of Δ199Hg /Δ201Hg range from 0.8 to 1.3, and thus more than one mass-independent isotope effect is inferred. MIF of mercury can be caused by the nuclear volume effect. Schauble, 2007 has calculated nuclear volume fractionation scaling factors for a number of common mercury chemical species in equilibrium with Hg° vapor. From his calculations the nuclear field shift effect is larger in Δ199Hg than in Δ201Hg by approximately a factor of two. The predominant mercury chemical species in fish is methylmercury cysteine. From the experimental studies of Buchachenko and others (2004) on the reaction of methylmercury chloride with creatine kinase it seems reasonable to predicted that the thiol functional groups of cysteine gets enriched in 199Hg and 201Hg. Here the magnetic isotope effect (MIE) produces a kinetic partial separation of isotopes with non-zero nuclear spin quantum numbers from the even-N isotopes. The ratio of enrichment of Δ201Hg /Δ199Hg is predicted from theory to be 1.11, which is the ratio of the magnetic moments of 199Hg and 201Hg. Because mercury possesses two odd-N isotopes, it is possible to detect and evaluate the effects of two distinct, mass-independent isotope fractionating processes. From the data obtained on fish samples, we can deconvolute the contributions of the isotope effects of nuclear mass, spin and volume. For these samples the role of spin or the magnetic isotope effect is the most dominant.

Impact of isotopic disorders on thermal transport properties of nanotubes and nanowires

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

Sun, Tao; Kang, Wei; Wang, Jianxiang, E-mail: jxwang@pku.edu.cn

2015-01-21

We present a one-dimensional lattice model to describe thermal transport in isotopically doped nanotubes and nanowires. The thermal conductivities thus predicted, as a function of isotopic concentration, agree well with recent experiments and other simulations. Our results display that for any given concentration of isotopic atoms in a lattice without sharp atomic interfaces, the maximum thermal conductivity is attained when isotopic atoms are placed regularly with an equal space, whereas the minimum is achieved when they are randomly inserted with a uniform distribution. Non-uniformity of disorder can further tune the thermal conductivity between the two values. Moreover, the dependence ofmore » the thermal conductivity on the nanoscale feature size becomes weak at low temperature when disorder exists. In addition, when self-consistent thermal reservoirs are included to describe diffusive nanomaterials, the thermal conductivities predicted by our model are in line with the results of macroscopic theories with an interfacial effect. Our results suggest that the disorder provides an additional freedom to tune the thermal properties of nanomaterials in many technological applications including nanoelectronics, solid-state lighting, energy conservation, and conversion.« less

Mass dependence of spectral and angular distributions of Cherenkov radiation from relativistic isotopes in solid radiators and its possible application as mass selector

NASA Astrophysics Data System (ADS)

Bogdanov, O. V.; Rozhkova, E. I.; Pivovarov, Yu. L.; Kuzminchuk-Feuerstein, N.

2018-02-01

The first proof of principle experiment with a prototype of a Time-of-Flight (TOF) - Cherenkov detector of relativistic heavy ions (RHI) exploiting a liquid Iodine Naphthalene radiator has been performed at Cave C at GSI (Darmstadt, Germany). A conceptual design for a liquid Cherenkov detector was proposed as a prototype for the future TOF measurements at the Super-FRS by detection of total number of Cherenkov photons. The ionization energy loss of RHI in a liquid radiator decreases only slightly this number, while in a solid radiator changes sufficiently not the total number of ChR photons, but ChR angular and spectral distributions. By means of computer simulations, we showed that these distributions are very sensitive to the isotope mass, due to different stopping powers of isotopes with initial equal relativistic factors. The results of simulations for light (Li, Be) and heavy (Xe) isotopes at 500-1000 MeV/u are presented indicating the possibility to use the isotopic effect in ChR of RHI as the mass selector.

The RaDIATE High-Energy Proton Materials Irradiation Experiment at the Brookhaven Linac Isotope Producer Facility

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

Ammigan, Kavin; et al.

The RaDIATE collaboration (Radiation Damage In Accelerator Target Environments) was founded in 2012 to bring together the high-energy accelerator target and nuclear materials communities to address the challenging issue of radiation damage effects in beam-intercepting materials. Success of current and future high intensity accelerator target facilities requires a fundamental understanding of these effects including measurement of materials property data. Toward this goal, the RaDIATE collaboration organized and carried out a materials irradiation run at the Brookhaven Linac Isotope Producer facility (BLIP). The experiment utilized a 181 MeV proton beam to irradiate several capsules, each containing many candidate material samples formore » various accelerator components. Materials included various grades/alloys of beryllium, graphite, silicon, iridium, titanium, TZM, CuCrZr, and aluminum. Attainable peak damage from an 8-week irradiation run ranges from 0.03 DPA (Be) to 7 DPA (Ir). Helium production is expected to range from 5 appm/DPA (Ir) to 3,000 appm/DPA (Be). The motivation, experimental parameters, as well as the post-irradiation examination plans of this experiment are described.« less

Comment on “Isotopic fractionation between Fe(III) and Fe(II) in aqueous solutions” by Clark Johnson et al., [Earth Planet. Sci. Lett. 195 (2002) 141–153

USGS Publications Warehouse

Bullen, Thomas D.; White, Arthur F.; Childs, Cyril W.

2003-01-01

In a recent contribution [1], Johnson et al. reported the equilibrium isotope fractionation factor between dissolved Fe(II) and Fe(III) in aqueous solutions at pH=2.5 and 5.5. They suggest that because the iron isotope fractionation observed in their experiments spans virtually the entire range observed in sedimentary rocks, Fe(II)–Fe(III) aqueous speciation may play a major role in determining iron isotope variations in nature where Fe(II) and Fe(III) can become physically separated. They discounted earlier conclusions by us and others [2] ;  [3] that significant equilibrium fractionation between specific coexisting Fe(II)- or Fe(III)-aqueous complexes (e.g., between aqueous Fe(II)(OH)x(aq)and Fe(II)(aq) ion) is capable of producing iron isotope contrasts that can be preserved in nature. This is an important contribution not only because the authors recognize the importance of abiotic equilibrium iron isotope fractionation in nature in contrast to previous assertions [4], but also because it will help to focus discussion on the development and evaluation of experimental approaches that can reveal abiotic fractionation mechanisms. However, in this Comment we propose that the experiments presented in this paper cannot be interpreted as straightforwardly as Johnson et al. contend. In particular, we show that in one of their critical experiments attainment of either isotope mass balance or equilibrium was not demonstrated, and thus the results of that experiment cannot be used to calculate an Fe(II)–Fe(III) equilibrium fractionation factor.

Variation of brine compositions resulting from flow from matrix or fracture permeability, investigated by high pressure laboratory experiments

NASA Astrophysics Data System (ADS)

Poszwa, A. C.; Coleman, M. L.; Pouya, A.; Ader, M.; Bounenni, A.

2003-04-01

Planning oil production from a chalk reservoir oilfield is difficult because the matrix usually has low permeability despite its high porosity. Most oil is thought to come from fracture porosity but the matrix contribution should increase as compaction occurs during production. To better understand the respective contributions from matrix and fracture, we studied the geochemical characteristics of fluids using high-pressure brine flow experiments on chalk cores. During the experiment axial load was changed relative to confining pressure to induce fractures and to close them again. We used chlorine stable isotope variations to study fluid pathway, because chlorine is a chemically conservative element in sedimentary systems and its isotopes fractionate only with physical processes like diffusion or adsorption that could occur mainly in the chalk matrix. A first experiment was performed on a very porous chalk from Henley (on-shore UK) and using a low-salinity brine. Large variations of brine Cl isotope composition were observed (from -0.56 to +0.08 per mil). The variations were correlated positively with the brine flux through the chalk and the permeability of the rock, both parameters controlled by the rock fracturing. A second experiment used brine with salinity similar to that of seawater. In this case, chemical and isotopic variations were not significant. From the beginning, the chalk structure seems to have been destroyed very quickly (induced fracture porosity collapsed) possibly because of the fluid nature, so that whatever pressure was applied, the permeability did not change significantly. Using Valhall reservoir chalk (offshore Norwegian North Sea) and fluid half the salinity of seawater in a third experiment, we obtained a large range of permeabilities. Brine isotopic trends were very similar on average to those of the first experiment even though variations were smaller (Cl isotopes from -0.09 to +0.29 per mil) and not significantly correlated simply to permeability values. The highest isotopic values were in brine flowed through chalk when the permeability was high and fractures opened; the lowest values were in brine flowed through the chalk when its permeability was reduced by closing fractures and increasing the relative contribution from matrix flow where diffusion processes fractionated chlorine isotopes. From this work it seems that the relative contributions from fracture and matrix permeability in reservoirs can be estimated from the geochemical compositions of brines that flowed from them.

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 organics that occurred at that time, and that the subsequent development of the biosphere resulted in shifts of δ15N towards higher values.

Ca isotope fractionation and Sr/Ca partitioning associated with anhydrite formation at mid-ocean ridge hydrothermal systems: An experimental approach

NASA Astrophysics Data System (ADS)

Syverson, D. D.; Scheuermann, P.; Pester, N. J.; Higgins, J. A.; Seyfried, W. E., Jr.

2016-12-01

The elemental and isotopic mass balance of Ca and Sr between seawater and basalt at mid-ocean ridge (MOR) hydrothermal systems is an integrated reflection of the various physiochemical processes, which induce chemical exchange, in the subseafloor. Specifically, the processes of anhydrite precipitation and recrystallization are recognized to be important controls on governing the Ca and Sr elemental and isotope compositions of high temperature vent fluids, however, few experimental data exist to constrain these geochemical effects. Thus, to better understand the associated Sr/Ca partitioning and Ca isotope fractionation and rate of exchange between anhydrite and dissolved constituents, anhydrite precipitation and recrystallization experiments were performed at 175, 250, and 350°C and 500 bar at chemical conditions indicative of active MOR hydrothermal systems. The experimental data suggest that upon entrainment of seawater into MOR hydrothermal systems, anhydrite will precipitate rapidly and discriminate against the heavy isotopes of Ca (Δ44/40Ca(Anh-Fluid) = -0.68 - -0.25 ‰), whereas Sr/Ca partitioning depends on the saturation state of the evolving hydrothermal fluid with respect to anhydrite at each PTX (KD(Anh-Fluid) = 1.24 - 0.55). Coupling experimental constraints with the temperature gradient inferred for high temperature MOR hydrothermal systems in the oceanic crust, data suggest that the Ca isotope and Sr elemental composition of anhydrite formed near the seafloor will be influenced by disequilibrium effects, while, at higher temperatures further into the oceanic crust, anhydrite will be representative of equilibrium Sr/Ca partitioning and Ca isotope fractionation conditions. These experimental observations are consistent with analyzed Sr/Ca and Ca isotope compositions of anhydrites and vent fluids sampled from modern MOR hydrothermal systems1,2 and can be used to further constrain the geochemical effects of hydrothermal circulation in the oceanic crust throughout Earth's history. 1 Tivey, M. K. Generation of Seafloor Hydrothermal Deposits. Oceanography 20, 50-66 (2007).2 Amini, M. et al. Calcium isotope (δ44/40Ca) fractionation along hydrothermal pathways, Logatchev field (Mid-Atlantic Ridge, 14°45'N). Geochimica et Cosmochimica Acta 72, 4107-4122 (2008).

Copper isotope fractionation between aqueous compounds relevant to low temperature geochemistry and biology

NASA Astrophysics Data System (ADS)

Fujii, Toshiyuki; Moynier, Frédéric; Abe, Minori; Nemoto, Keisuke; Albarède, Francis

2013-06-01

Isotope fractionation between the common Cu species present in solution (Cu+, Cu2+, hydroxide, chloride, sulfide, carbonate, oxalate, and ascorbate) has been investigated using both ab initio methods and experimental solvent extraction techniques. In order to establish unambiguously the existence of equilibrium isotope fractionation (as opposed to kinetic isotope fractionation), we first performed laboratory-scale liquid-liquid distribution experiments. Upon exchange between HCl medium and a macrocyclic complex, the 65Cu/63Cu ratio fractionated by -1.06‰ to -0.39‰. The acidity dependence of the fractionation was appropriately explained by ligand exchange reactions between hydrated H2O and Cl- via intramolecular vibrations. The magnitude of the Cu isotope fractionation among important Cu ligands was also estimated by ab initio methods. The magnitude of the nuclear field shift effect to the Cu isotope fractionation represents only ˜3% of the mass-dependent fractionation. The theoretical estimation was expanded to chlorides, hydroxides, sulfides, sulfates, and carbonates under different conditions of pH. Copper isotope fractionation of up to 2‰ is expected for different forms of Cu present in seawater and for different sediments (carbonates, hydroxides, and sulfides). We found that Cu in dissolved carbonates and sulfates is isotopically much heavier (+0.6‰) than free Cu. Isotope fractionation of Cu in hydroxide is minimal. The relevance of these new results to the understanding of metabolic processes was also discussed. Copper is an essential element used by a large number of proteins for electron transfer. Further theoretical estimates of δ65Cu in hydrated Cu(I) and Cu(II) ions, Cu(II) ascorbates, and Cu(II) oxalate predict Cu isotope fractionation during the breakdown of ascorbate into oxalate and account for the isotopically heavy Cu found in animal kidneys.

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

NASA Astrophysics Data System (ADS)

Perşoiu, A.; Bojar, A.-V.

2012-04-01

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

Reductive Outer-Sphere Single Electron Transfer Is an Exception Rather than the Rule in Natural and Engineered Chlorinated Ethene Dehalogenation.

PubMed

Heckel, Benjamin; Cretnik, Stefan; Kliegman, Sarah; Shouakar-Stash, Orfan; McNeill, Kristopher; Elsner, Martin

2017-09-05

Chlorinated ethenes (CEs) such as perchloroethylene, trichloroethylene and dichloroethylene are notorious groundwater contaminants. Although reductive dehalogenation is key to their environmental and engineered degradation, underlying reaction mechanisms remain elusive. Outer-sphere reductive single electron transfer (OS-SET) has been proposed for such different processes as Vitamin B 12 -dependent biodegradation and zerovalent metal-mediated dehalogenation. Compound-specific isotope effect ( 13 C/ 12 C, 37 Cl/ 35 Cl) analysis offers a new opportunity to test these hypotheses. Defined OS-SET model reactants (CO 2 radical anions, S 2- -doped graphene oxide in water) caused strong carbon (ε C = -7.9‰ to -11.9‰), but negligible chlorine isotope effects (ε Cl = -0.12‰ to 0.04‰) in CEs. Greater chlorine isotope effects were observed in CHCl 3 (ε C = -7.7‰, ε Cl = -2.6‰), and in CEs when the exergonicity of C-Cl bond cleavage was reduced in an organic solvent (reaction with arene radical anions in glyme). Together, this points to dissociative OS-SET (SET to a σ* orbital concerted with C-Cl breakage) in alkanes compared to stepwise OS-SET (SET to a π* orbital followed by C-Cl cleavage) in ethenes. The nonexistent chlorine isotope effects of chlorinated ethenes in all aqueous OS-SET experiments contrast strongly with pronounced Cl isotope fractionation in all natural and engineered reductive dehalogenations reported to date suggesting that OS-SET is an exception rather than the rule in environmental transformations of chlorinated ethenes.

Hadean Oceanography: Experimental Constraints on the Development of the Terrestrial Hydrosphere and the Origin of Life on Earth

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

Ryerson, F J

The oxygen isotopic compositions of the world's oldest mineral grains, zircon, have recently been used to infer the compositions of the rocks from which they crystallized. The results appear to require a source that had once experienced isotopic fractionation between clay minerals and liquid water, thereby implying the presence of liquid water at the Earth's surface prior to 4.4 billion years ago, less than 2 million years after accretion. This observation has important implications for the development of the Earth's continental crust. The inferred composition of the zircon source rock is directly dependent upon the oxygen isotopic fractionation between zirconmore » and melt, and zircon and water. These fractionation factors have not been determined experimentally, however, constituting the weak link in this argument. A series of experiments to measure these fractionation factors has been conducted. The experiments consist of finely powdered quartz, a polished single crystal of zircon and isotopically-enriched or isotopically normal water to provide a range of isotopic compositions. The experiments will be run until quartz is in isotopic equilibrium with water. Zircon was expected to partially equilibrate producing an oxygen isotopic diffusion profile perpendicular to the surface. Ion probe spot analysis of quartz and depth profiling of zircon will determine the bulk and surface isotopic compositions of the phases, respectively. The well-known quartz-water isotopic fractionation factors can be used to calculate the oxygen isotopic composition of the fluid, and with the zircon surface composition, the zircon-water fractionation factor. Run at temperatures up to 1000 C for as long as 500 hours have not produced diffusion profiles longer than 50 nm. The steep isotopic gradient at the samples surface precludes use of the diffusion profile for estimation on the surface isotopic composition. The short profiles may be the result of surface dissolution, although such dissolution cannot be resolved in SEM images. The sluggish nature of diffusion in zircon may require that fractionation factors be determined by direct hydrothermal synthesis of zircon rather than by mineral-fluid exchange.« less

Protein retention assessment of four levels of poultry by-product substitution of fishmeal in rainbow trout (Oncorhynchus mykiss) diets using stable isotopes of nitrogen (δ15N) as natural tracers.

PubMed

Badillo, Daniel; Herzka, Sharon Z; Viana, Maria Teresa

2014-01-01

This is second part from an experiment where the nitrogen retention of poultry by-product meal (PBM) compared to fishmeal (FM) was evaluated using traditional indices. Here a quantitative method using stable isotope ratios of nitrogen (δ(15)N values) as natural tracers of nitrogen incorporation into fish biomass is assessed. Juvenile rainbow trout (Oncorhynchus mykiss) were fed for 80 days on isotopically distinct diets in which 0, 33, 66 and 100% of FM as main protein source was replaced by PBM. The diets were isonitrogenous, isolipidic and similar in gross energy content. Fish in all treatments reached isotopic equilibrium by the end of the experiment. Two-source isotope mixing models that incorporated the isotopic composition of FM and PBM as well as that of formulated feeds, empirically derived trophic discrimination factors and the isotopic composition of fish that had reached isotopic equilibrium to the diets were used to obtain a quantitative estimate of the retention of each source of nitrogen. Fish fed the diets with 33 and 66% replacement of FM by PBM retained poultry by-product meal roughly in proportion to its level of inclusion in the diets, whereas no differences were detected in the protein efficiency ratio. Coupled with the similar biomass gain of fishes fed the different diets, our results support the inclusion of PBM as replacement for fishmeal in aquaculture feeds. A re-feeding experiment in which all fish were fed a diet of 100% FM for 28 days indicated isotopic turnover occurred very fast, providing further support for the potential of isotopic ratios as tracers of the retention of specific protein sources into fish tissues. Stable isotope analysis is a useful tool for studies that seek to obtain quantitative estimates of the retention of different protein sources.

Protein Retention Assessment of Four Levels of Poultry By-Product Substitution of Fishmeal in Rainbow Trout (Oncorhynchus mykiss) Diets Using Stable Isotopes of Nitrogen (δ15N) as Natural Tracers

PubMed Central

Badillo, Daniel; Herzka, Sharon Z.; Viana, Maria Teresa

2014-01-01

This is second part from an experiment where the nitrogen retention of poultry by-product meal (PBM) compared to fishmeal (FM) was evaluated using traditional indices. Here a quantitative method using stable isotope ratios of nitrogen (δ15N values) as natural tracers of nitrogen incorporation into fish biomass is assessed. Juvenile rainbow trout (Oncorhynchus mykiss) were fed for 80 days on isotopically distinct diets in which 0, 33, 66 and 100% of FM as main protein source was replaced by PBM. The diets were isonitrogenous, isolipidic and similar in gross energy content. Fish in all treatments reached isotopic equilibrium by the end of the experiment. Two-source isotope mixing models that incorporated the isotopic composition of FM and PBM as well as that of formulated feeds, empirically derived trophic discrimination factors and the isotopic composition of fish that had reached isotopic equilibrium to the diets were used to obtain a quantitative estimate of the retention of each source of nitrogen. Fish fed the diets with 33 and 66% replacement of FM by PBM retained poultry by-product meal roughly in proportion to its level of inclusion in the diets, whereas no differences were detected in the protein efficiency ratio. Coupled with the similar biomass gain of fishes fed the different diets, our results support the inclusion of PBM as replacement for fishmeal in aquaculture feeds. A re-feeding experiment in which all fish were fed a diet of 100% FM for 28 days indicated isotopic turnover occurred very fast, providing further support for the potential of isotopic ratios as tracers of the retention of specific protein sources into fish tissues. Stable isotope analysis is a useful tool for studies that seek to obtain quantitative estimates of the retention of different protein sources. PMID:25226392

Tracking Cats: Problems with Placing Feline Carnivores on δ18O, δD Isoscapes

PubMed Central

Pietsch, Stephanie J.; Hobson, Keith A.; Wassenaar, Leonard I.; Tütken, Thomas

2011-01-01

Background Several felids are endangered and threatened by the illegal wildlife trade. Establishing geographic origin of tissues of endangered species is thus crucial for wildlife crime investigations and effective conservation strategies. As shown in other species, stable isotope analysis of hydrogen and oxygen in hair (δDh, δ18Oh) can be used as a tool for provenance determination. However, reliably predicting the spatial distribution of δDh and δ18Oh requires confirmation from animal tissues of known origin and a detailed understanding of the isotopic routing of dietary nutrients into felid hair. Methodology/Findings We used coupled δDh and δ18Oh measurements from the North American bobcat (Lynx rufus) and puma (Puma concolor) with precipitation-based assignment isoscapes to test the feasibility of isotopic geo-location of felidae. Hairs of felid and rabbit museum specimens from 75 sites across the United States and Canada were analyzed. Bobcat and puma lacked a significant correlation between H/O isotopes in hair and local waters, and also exhibited an isotopic decoupling of δ18Oh and δDh. Conversely, strong δD and δ18O coupling was found for key prey, eastern cottontail rabbit (Sylvilagus floridanus; hair) and white-tailed deer (Odocoileus virginianus; collagen, bone phosphate). Conclusions/Significance Puma and bobcat hairs do not adhere to expected pattern of H and O isotopic variation predicted by precipitation isoscapes for North America. Thus, using bulk hair, felids cannot be placed on δ18O and δD isoscapes for use in forensic investigations. The effective application of isotopes to trace the provenance of feline carnivores is likely compromised by major controls of their diet, physiology and metabolism on hair δ18O and δD related to body water budgets. Controlled feeding experiments, combined with single amino acid isotope analysis of diets and hair, are needed to reveal mechanisms and physiological traits explaining why felid hair does not follow isotopic patterns demonstrated in many other taxa. PMID:21931770

Isotopic effect in experiments on lower hybrid current drive in the FT-2 tokamak

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

Lashkul, S. I., E-mail: Serguey.lashkul@mail.ioffe.ru; Altukhov, A. B.; Gurchenko, A. D., E-mail: aleksey.gurchenko@mail.ioffe.ru

To analyze factors influencing the limiting value of the plasma density at which lower hybrid (LH) current drive terminates, the isotopic factor (the difference in the LH resonance densities in hydrogen and deuterium plasmas) was used for the first time in experiments carried out at the FT-2 tokamak. It is experimentally found that the efficiency of LH current drive in deuterium plasma is appreciably higher than that in hydrogen plasma. The significant role of the parametric decay of the LH pumping wave, which hampers the use of the LH range of RF waves for current drive at high plasma densities,more » is confirmed. It is demonstrated that the parameters characterizing LH current drive agree well with the earlier results obtained at large tokamaks.« less

A Summary of Actinide Enrichment Technologies and Capability Gaps

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

Patton, Bradley D.; Robinson, Sharon M.

2017-01-01

The evaluation performed in this study indicates that a new program is needed to efficiently provide a national actinide radioisotope enrichment capability to produce milligram-to-gram quantities of unique materials for user communities. This program should leverage past actinide enrichment, the recent advances in stable isotope enrichment, and assessments of the future requirements to cost effectively develop this capability while establishing an experience base for a new generation of researchers in this vital area. Preliminary evaluations indicate that an electromagnetic isotope separation (EMIS) device would have the capability to meet the future needs of the user community for enriched actinides. Themore » EMIS technology could be potentially coupled with other enrichment technologies, such as irradiation, as pre-enrichment and/or post-enrichment systems to increase the throughput, reduce losses of material, and/or reduce operational costs of the base EMIS system. Past actinide enrichment experience and advances in the EMIS technology applied in stable isotope separations should be leveraged with this new evaluation information to assist in the establishment of a domestic actinide radioisotope enrichment capability.« less

Stable isotope probing to study functional components of complex microbial ecosystems.

PubMed

Mazard, Sophie; Schäfer, Hendrik

2014-01-01

This protocol presents a method of dissecting the DNA or RNA of key organisms involved in a specific biochemical process within a complex ecosystem. Stable isotope probing (SIP) allows the labelling and separation of nucleic acids from community members that are involved in important biochemical transformations, yet are often not the most numerically abundant members of a community. This pure culture-independent technique circumvents limitations of traditional microbial isolation techniques or data mining from large-scale whole-community metagenomic studies to tease out the identities and genomic repertoires of microorganisms participating in biological nutrient cycles. SIP experiments can be applied to virtually any ecosystem and biochemical pathway under investigation provided a suitable stable isotope substrate is available. This versatile methodology allows a wide range of analyses to be performed, from fatty-acid analyses, community structure and ecology studies, and targeted metagenomics involving nucleic acid sequencing. SIP experiments provide an effective alternative to large-scale whole-community metagenomic studies by specifically targeting the organisms or biochemical transformations of interest, thereby reducing the sequencing effort and time-consuming bioinformatics analyses of large datasets.

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.

Modeling and experiments on tritium permeation in fusion reactor blankets

NASA Astrophysics Data System (ADS)

Holland, D. F.; Longhurst, G. R.

The determination of tritium loss from helium-cooled fusion breeding blankets are discussed. The issues are: (1) applicability of present models to permeation at low tritium pressures; (2) effectiveness of oxide layers in reducing permeation; (3) effectiveness of hydrogen addition as a means to lower tritium permeation; and (4) effectiveness of conversion to tritiated water and subsequent trapping to reduce permeation. Theoretical models applicable to these issues are discussed, and results of experiments in two areas are presented; permeation of mixtures of hydrogen isotopes and conversion to tritiated water.

Modeling and Depletion Simulations for a High Flux Isotope Reactor Cycle with a Representative Experiment Loading

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

Chandler, David; Betzler, Ben; Hirtz, Gregory John

2016-09-01

The purpose of this report is to document a high-fidelity VESTA/MCNP High Flux Isotope Reactor (HFIR) core model that features a new, representative experiment loading. This model, which represents the current, high-enriched uranium fuel core, will serve as a reference for low-enriched uranium conversion studies, safety-basis calculations, and other research activities. A new experiment loading model was developed to better represent current, typical experiment loadings, in comparison to the experiment loading included in the model for Cycle 400 (operated in 2004). The new experiment loading model for the flux trap target region includes full length 252Cf production targets, 75Se productionmore » capsules, 63Ni production capsules, a 188W production capsule, and various materials irradiation targets. Fully loaded 238Pu production targets are modeled in eleven vertical experiment facilities located in the beryllium reflector. Other changes compared to the Cycle 400 model are the high-fidelity modeling of the fuel element side plates and the material composition of the control elements. Results obtained from the depletion simulations with the new model are presented, with a focus on time-dependent isotopic composition of irradiated fuel and single cycle isotope production metrics.« less

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.

2012-01-01

We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Cadmium isotope fractionation during adsorption to Mn-oxyhydroxide

NASA Astrophysics Data System (ADS)

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

2013-12-01

The heavy metal cadmium is of interest both as a toxic contaminant in groundwater and as a critical nutrient for some marine diatoms [1], yet little is known about the biogeochemistry of this element. Horner et al. [2] suggested that Cd stable isotopes could potentially enable reconstruction of biological use of Cd in the marine realm: since cultured diatoms fractionate Cd isotopes [3], and ferromanganese crusts appear to incorporate a faithful record of deepwater Cd isotopes [2], depth profiles in such crusts may yield information about the extent of Cd assimilation of isotopically light Cd by diatoms over time. Although no work has yet been published regarding the use of stable isotopes to track reactive transport of Cd in contaminated aquifers, others have recently demonstrated the potential of isotopes to track reactions affecting the mobility of other toxic metals (e.g., [4]). With both of these potential applications in mind, we conducted two sets of experiments, at low and high ionic strength, in which Cd partially adsorbed to potassium birnessite. Our goals are to quantify the fractionations and to constrain the mechanisms governing Cd isotope behavior during adsorption to an environmentally abundant scavenger of Cd. Suspensions of synthetic birnessite were doped with various amounts of dissolved Cd2+ at pH ~8.3. Following reaction, the dissolved and adsorbed pools of Cd were separated by filtration, purified by anion exchange chromatography, and analyzed by multicollector ICP-MS using a double-spike routine. In all cases, lighter isotopes preferentially adsorbed to the birnessite particles. At low ionic strength (I<0.01m), we observed a small fractionation of 0.15‰×0.05 (Δ114/112) that was constant as a function of the fraction of Cd adsorbed. This indicates a small equilibrium isotope effect, likely driven by a subtle shift in coordination geometry for Cd during adsorption. In a groundwater system with continuous flow of dissolved Cd, this 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.

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. To our knowledge, this is the first rigorous treatment of sulfur isotope fractionation subject to Monod kinetics in a mechanistic reactive transport model that considers the isotopic spatial distribution of both dissolved and solid phase sulfur species during microbially-mediated sulfate reduction. describe the design and results of the large-scale column experiment; demonstrate incorporation of the stable isotopes of sulfur in a dual-Monod kinetic expression such that fractionation is accurately modeled at both high and low substrate availability; verify accurate simulation of the chemical and isotopic gradients in reactant and product sulfur species using a kinetic fractionation factor obtained from field-scale analysis (Druhan et al., 2012); utilize the model to predict the final δ34S values of secondary sulfur minerals accumulated in the sediment over the course of the experiment. The development of rigorous isotope-specific Monod-type rate expressions are presented here in application to sulfur cycling during amended biostimulation, but are readily applicable to a variety of stable isotope systems associated with both steady state and transient biogenic redox environments. In other words, the association of this model with a uranium remediation experiment does not limit its applicability to more general redox systems. Furthermore, the ability of this model treatment to predict the isotopic composition of secondary minerals accumulated as a result of fractionating processes (item 4) offers an important means of interpreting solid phase isotopic compositions and tracking long-term stability of precipitates.

Reaction paths and host phases of uranium isotopes (235U; 238U), Saanich Inlet

NASA Astrophysics Data System (ADS)

Amini, M.; Holmden, C. E.; Francois, R. H.

2009-12-01

In recent times, Uranium has become increasingly the focus of stable isotope fractionation studies. Variations in 238U/235U have been reported as a result of redox reactions [1,2] from the nuclear field shift effect [3], and a mass-dependent, microbially-mediated, kinetic isotope effect [4]. The 238U/235U variability caused by changes in environmental redox conditions leads to an increase in the 238U/235U ratios of the reduced U species sequestered into marine sediments. This points to U isotope variability as a new tool to study ancient ocean redox changes. However, the process by which reduced sediments become enriched in the heavy isotopes of U is not yet known, and hence the utility of 238U/235U as a redox tracer remains to be demonstrated. In order to further constrain sedimentary U enrichment and related isotope effect, we are investigating U isotopic compositions of water samples and fresh surface sediment grab samples over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. U was sequentially extracted from sediments in order to characterize specific fractions for their isotopic composition. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10‰ (2sd). Fifteeen analyses of seawater yielded δ238U of -0.42±0.08‰ (2sd). The results for the water samples indicate a homogenous δ238U value throughout the Saanich Inlet water column that matches the global seawater signature. All of the water samples from above and below average -0.42±0.05‰ (2sd). In contrast, a plankton net sample yielded a distinctly different, (about 0.5‰ lighter) isotope value. Bacterial reduction experiments [4] have also shown isotope enrichment factors of about -0.3‰. In addition, metal isotope fractionation occurs during adsorption with the light isotope being preferentially adsorbed [5]. Whether plankton mediated chemical reduction or scavenging causes this fractionation will be further investigated by leaching experiments on sediment trap samples. By contrast, weak acidic leachates (at pH 6) of suboxic bottom sediments, tend towards higher δ238U values. For oxic sediments, U contents of this fraction were below detection limit. Stronger leaching at pH 3 removed most of the uranium from suboxic and oxic sediments. For oxic sediments, this fraction yields the seawater δ238U signature, while the U released from the suboxic sample is about 0.2‰ heavier. This matches the value for previously reported bulk analyses of suboxic sediments [1] implying that the reduced sedimentary U is released by this treatment,. Major and trace element analyses and XRD patterns will help relating this fraction to a specific mineral or reactive phase. [1] Weyer et al. (2007) GCA 72, 345-399. [2] Stirling et al. (2007) EPSL 264, 208-225. [3] Schauble (2007) GCA 71, 2170-2189. [4] Rademacher et al. (2006) Environ. Sci. Technol. 40,6943-6948. [5] Wasylenki (2009) GCA A1419.

Boundary conditions for the Swain-Schaad relationship as a criterion for hydrogen tunneling.

PubMed

Kohen, Amnon; Jensen, Jan H

2002-04-17

Hydrogen quantum mechanical tunneling has been suggested to play a role in a wide variety of hydrogen-transfer reactions in chemistry and enzymology. An important experimental criterion for tunneling is based on the breakdown of the semiclassical prediction for the relationship among the rates of the three isotopes of hydrogen (hydrogen -H, deuterium -D, and tritium -T). This is denoted the Swain-Schaad relationship. This study examines the breakdown of the Swain-Schaad relationship as criterion for tunneling. The semiclassical (no tunneling) limit used hereto (e.g., 3.34, for H/T to D/T kinetic isotope effects), was based on simple theoretical considerations of a diatomic cleavage of a stable covalent bond, for example, a C-H bond. Yet, most experimental evidence for a tunneling contribution has come from breakdown of those relationship for a secondary hydrogen, that is, not the hydrogen whose bond is being cleaved but its geminal neighbor. Furthermore, many of the reported experiments have been mixed-labeling experiments, in which a secondary H/T kinetic isotope effect was measured for C-H cleavage, while the D/T secondary effect accompanied C-D cleavage. In experiments of this type, the breakdown of the Swain-Schaad relationship indicates both tunneling and the degree of coupled motion between the primary and secondary hydrogens. We found a new semiclassical limit (e.g., 4.8 for H/T to D/T kinetic isotope effects), whose breakdown can serve as a more reliable experimental evidence for tunneling in this common mixed-labeling experiment. We study the tunneling contribution to C-H bond activation, for which many relevant experimental and theoretical data are available. However, these studies can be applied to any hydrogen-transfer reaction. First, an extension of the original approach was applied, and then vibrational analysis studies were carried out for a model system (the enzyme alcohol dehydrogenase). Finally, the effect of complex kinetics on the observed Swain-Schaad relationship was examined. All three methods yield a new semiclassical limit (4.8), above which tunneling must be considered. Yet, it was found that for many cases the original, localized limit (3.34), holds fairly well. For experimental results that are between the original and new limits (within statistical errors), several methods are suggested that can support or exclude tunneling. These new and clearer criteria provide a basis for future applications of the Swain-Schaad relationship to demonstrate tunneling in complex systems.

An Update on the Non-Mass-Dependent Isotope Fractionation under Thermal Gradient

NASA Technical Reports Server (NTRS)

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

2013-01-01

Mass flow and compositional gradient (elemental and isotope separation) occurs when flu-id(s) or gas(es) in an enclosure is subjected to a thermal gradient, and the phenomenon is named thermal diffusion. Gas phase thermal diffusion has been theoretically and experimentally studied for more than a century, although there has not been a satisfactory theory to date. Nevertheless, for isotopic system, the Chapman-Enskog theory predicts that the mass difference is the only term in the thermal diffusion separation factors that differs one isotope pair to another,with the assumptions that the molecules are spherical and systematic (monoatomic-like structure) and the particle collision is elastic. Our previous report indicates factors may be playing a role because the Non-Mass Dependent (NMD) effect is found for both symmetric and asymmetric, linear and spherical polyatomic molecules over a wide range of temperature (-196C to +237C). The observed NMD phenomenon in the simple thermal-diffusion experiments demands quantitative validation and theoretical explanation. Besides the pressure and temperature dependency illustrated in our previous reports, efforts are made in this study to address issues such as the role of convection or molecular structure and whether it is a transient, non-equilibrium effect only.

Status of the TRIGA-LASER experiment

NASA Astrophysics Data System (ADS)

Gorges, C.; Kaufmann, S.; Geppert, Ch.; Krämer, J.; Sánchez, R.; Nörtershäuser, W.

2017-11-01

We report on the newly developed control system called TRITON and the new data acquisition called TILDA as well as on improved isotope shift measurements of the isotopes 40,42,44,48Ca in the 4 s 2S1/2 → 4 p 2P3/2 (D2) transition at the TRIGA-LASER experiment in Mainz using collinear laser spectroscopy. Well known isotope shift measurements in the 4 s 2S1/2 → 4 p 2P1/2 (D1) transition act as calibration points to reduce the uncertainties in the D2-line to provide reference values for the determination of nuclear charge radii and quadrupole moments of neutron rich calcium isotopes at COLLAPS.

Uptake of alkaline earth metals in Alcyonarian spicules (Octocorallia)

NASA Astrophysics Data System (ADS)

Taubner, I.; Böhm, F.; Eisenhauer, A.; Garbe-Schönberg, D.; Erez, J.

2012-05-01

Alcyonarian corals (Octocorallia) living in shallow tropical seas produce spicules of high-Mg calcite with ˜13 mol% MgCO3. We cultured the tropical alcyonarian coral Rhythisma fulvum in experiments varying temperature (19-32 °C) and pH (8.15-8.44). Alkalinity depletion caused by spicule formation systematically varied in the temperature experiments increasing from 19 to 29 °C. Spicules were investigated for their elemental ratios (Mg/Ca, Sr/Ca) using ICP-OES, δ44/40Ca using TIMS, as well as δ18O and δ13C by IRMS. Mg/Ca increased with temperature from 146 to 164 mmol/mol, in good agreement with the range observed for marine inorganic calcite. Mg/Ca increased by 1.0 ± 0.4 mmol/mol/°C, similar to the sensitivity of Miliolid foraminifera. The pH experiments revealed a linear relationship between Mg/Ca and carbonate ion concentration of +0.03 ± 0.02 mmol/mol/μMol. Sr/Ca ranges from 2.5 to 2.9 mmol/mol being in good agreement with other high-Mg calcites. Temperature and pH experiments showed linear dependencies of Sr/Ca matching inorganic calcite trends and pointing to a decoupling of crystal precipitation rate and calcification rate. Ca isotopes range between 0.7‰ and 0.9‰ in good agreement with aragonitic scleractinian corals and calcitic coccoliths. Presumably Ca isotopes are fractionated by a biological mechanism that may be independent of the skeletal mineralogy. We observe no temperature trend, but a significant decrease of δ44/40Ca with increasing pH. This inverse correlation may characterise biologically controlled intracellular calcification. Oxygen isotope ratios are higher than expected for isotopic equilibrium with a temperature sensitivity of -0.15 ± 0.03‰/°C. Carbon isotope ratios are significantly lower than expected for equilibrium and positively correlated with temperature with a slope of 0.20 ± 0.04‰/°C. Many of our observations on trace element incorporation in R. fulvum may be explained by inorganic processes during crystal formation, which do not comply with the intracellular mode of calcification in Alcyonarian corals. The observed elemental and isotopic compositions, however, could be explained if the partitioning caused by biological mechanisms mimics the effects of inorganic processes.

Ultrafiltration by a compacted clay membrane-I. Oxygen and hydrogen isotopic fractionation

USGS Publications Warehouse

Coplen, T.B.; Hanshaw, B.B.

1973-01-01

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01 N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disc compacted to a porosity of 35 per cent by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5%. and in O18 by 0.8%. relative to the residual solution. No additional isotopic fractionation due to a salt filtering mechanism was observed at NaCl concentrations up to 0.01 N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. ?? 1973.

The molecular physics of photolytic fractionation of sulfur and oxygen isotopes in planetary atmospheres (Invited)

NASA Astrophysics Data System (ADS)

Johnson, M. S.; Schmidt, J. A.; Hattori, S.; Danielache, S.; Meusinger, C.; Schinke, R.; Ueno, Y.; Nanbu, S.; Kjaergaard, H. G.; Yoshida, N.

2013-12-01

Atmospheric photochemistry is able to produce large mass independent anomalies in atmospheric trace gases that can be found in geological and cryospheric records. This talk will present theoretical and experimental investigations of the molecular mechanisms producing photolytic fractionation of isotopes with special attention to sulfur and oxygen. The zero point vibrational energy (ZPE) shift and reflection principle theories are starting points for estimating isotopic fractionation, but these models ignore effects arising from isotope-dependent changes in couplings between surfaces, excited state dynamics, line densities and hot band populations. The isotope-dependent absorption spectra of the isotopologues of HCl, N2O, OCS, CO2 and SO2 have been examined in a series of papers and these results are compared with experiment and ZPE/reflection principle models. Isotopic fractionation in planetary atmospheres has many interesting applications. The UV absorption of CO2 is the basis of photochemistry in the CO2-rich atmospheres of the ancient Earth, and of Mars and Venus. For the first time we present accurate temperature and isotope dependent CO2 absorption cross sections with important implications for photolysis rates of SO2 and H2O, and the production of a mass independent anomaly in the Ox reservoir. Experimental and theoretical results for OCS have implications for the modern stratospheric sulfur budget. The absorption bands of SO2 are complex with rich structure producing isotopic fractionation in photolysis and photoexcitation.

Rapidly assessing changes in bone mineral balance using natural stable calcium isotopes

PubMed Central

Morgan, Jennifer L. L.; Skulan, Joseph L.; Gordon, Gwyneth W.; Romaniello, Stephen J.; Smith, Scott M.; Anbar, Ariel D.

2012-01-01

The ability to rapidly detect changes in bone mineral balance (BMB) would be of great value in the early diagnosis and evaluation of therapies for metabolic bone diseases such as osteoporosis and some cancers. However, measurements of BMB are hampered by difficulties with using biochemical markers to quantify the relative rates of bone resorption and formation and the need to wait months to years for altered BMB to produce changes in bone mineral density large enough to resolve by X-ray densitometry. We show here that, in humans, the natural abundances of Ca isotopes in urine change rapidly in response to changes in BMB. In a bed rest experiment, use of high-precision isotope ratio MS allowed the onset of bone loss to be detected in Ca isotope data after about 1 wk, long before bone mineral density has changed enough to be detectable with densitometry. The physiological basis of the relationship between Ca isotopes and BMB is sufficiently understood to allow quantitative translation of changes in Ca isotope abundances to changes in bone mineral density using a simple model. The rate of change of bone mineral density inferred from Ca isotopes is consistent with the rate observed by densitometry in long-term bed rest studies. Ca isotopic analysis provides a powerful way to monitor bone loss, potentially making it possible to diagnose metabolic bone disease and track the impact of treatments more effectively than is currently possible. PMID:22652567

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 appropriate experimental tests and combine them with micro- and nano-scale characterization, and to capture the critical processes in mathematical models. Some of the largest fractionation effects have been observed for silicate liquids, where both chemical and thermal diffusion generate large isotopic variations. Intake and transport of Ca in plants is also associated with substantial fractionation. Continuing work is beginning to place the fractionation into the context of global Ca cycles.« less

Using multiple isotopes to understand the source of ingredients used in golden beverages

NASA Astrophysics Data System (ADS)

Wynn, J. G.

2011-12-01

Traditionally, beer contains 4 simple ingredients: water, barley, hops and yeast. Each of these ingredients used in the brewing process contributes some combination of a number of "traditional" stable isotopes (i.e., isotopes of H, C, O, N and S) to the final product. As an educational exercise in an "Analytical Techniques in Geology" course, a group of students analyzed the isotopic composition of the gas, liquid and solid phases of a variety of beer samples collected from throughout the world (including other beverages). The hydrogen and oxygen isotopic composition of the water followed closely the isotopic composition of local meteoric water at the source of the brewery, although there is a systematic offset from the global meteoric water line that may be due to the effects of CO2-H2O equilibration. The carbon isotopic composition of the CO2 reflected that of the solid residue (the source of carbon used as a fermentation substrate), but may potentially be modified by addition of gas-phase CO2 from an inorganic source. The carbon isotopic composition of the solid residue similarly tracks that of the fermentation substrate, and may indicate some alcohol fermented from added sugars in some cases. The nitrogen isotopic composition of the solid residue was relatively constant, and may track the source of nitrogen in the barley, hops and yeast. Each of the analytical methods used is a relatively standard technique used in geological applications, making this a "fun" exercise for those involved, and gives the students hands-on experience with a variety of analytes from a non-traditional sample material.

Uranium Isotope Fractionation during Oxidation of Dissolved U(iv) and Synthetic Solid UO2

NASA Astrophysics Data System (ADS)

Wang, X.; Johnson, T. M.; Lundstrom, C. C.

2013-12-01

U isotopes (238U/235U) show promise as a tool for environmental monitoring of U contamination as well as a proxy for paleo-redox conditions. However, the isotopic fractionation mechanisms of U are still poorly understood. In groundwater systems, U(VI), a mobile contaminant, can be reduced to immobile U(IV) and thus remediated. Previous work shows that 238U/235U of the remaining U(VI) changes with the extent of reduction. Therefore, U(VI) isotope composition in groundwater can potentially be used to detect and perhaps quantify the extent of reduction. However, knowing if isotopic fractionation occurs during U(IV) oxidation is equally important. First, the reduced U(IV) (either solid or as dissolved organic complexes) potentially can be reoxidized to U(VI). If isotope fractionation occurs during oxidation, it would complicate the use of U isotope composition as a monitoring technique. Further, in natural weathering processes, U(IV) minerals are oxidized to form dissolved U(VI), which is carried to rivers and eventually to the ocean and deposited in marine sediments. The weathering cycle is thus sensitive to redox conditions, meaning the sedimentary U isotope record may serve as a paleoredox indicator, provided U isotope fractionation during oxidation and reduction are well known. We conducted experiments oxidizing 2 different U(IV) species by O2 and measuring isotopic fractionation factors. In one experiment, dissolved U(IV) in 0.1 N HCl (pH 1) was oxidized by entrained air. As oxidation proceeds at pH 1, the remaining dissolved U(IV) becomes progressively enriched in 238U in a linear trend, while the product U(VI) paralleled, but was offset to 1.0‰ lighter in 238U/235U. This linear progression of both remaining reactant and product suggests equilibrium fractionation during oxidation of dissolved U(IV) by O2. A second experiment oxidized synthetic, solid UO2 (in 20 mM NaHCO3, pH 7) with entrained air. The oxidative fractionation is very weak in this case with product U(VI) ~0.1‰ heavier than the remaining UO2. We attribute the lack of strong fractionation during oxidation of solid UO2 to a 'rind effect', where the surface layer must be completely oxidized before the next layer is exposed to oxidant. Hence, nearly complete, congruent conversion of each layer of U(IV) to U(VI) results in minimal isotope fractionation. A small amount of transient fractionation probably occurs initially, but this is quickly negated as the surface becomes isotopically fractionated. Interestingly, our measured ~0.1‰ U isotope fractionation during oxidation of solid U(IV) agrees with the natural observation that 238U/235U ratios in river water (mainly U(VI)) are ~0.1‰ greater than those in fresh continental rocks (primarily U(IV) minerals). Application of these results to natural settings should be done with caution, however. Oxidation of natural uraninite in continental rocks is a much slower process. If the U(VI) product and the U(IV) reactant remain in contact for long periods of time (e.g., months), they may evolve toward isotopic equilibrium. Measurements of 238U/235U in various natural weathering environments should be undertaken to examine this idea.

``Recycling'' Geophysics: Monitoring and Isotopic Analysis of Engineered Biological Systems

NASA Astrophysics Data System (ADS)

Doherty, R.; Singh, K. P.; Ogle, N.; Ntarlagiannis, D.

2010-12-01

The emerging sub discipline of biogeophysics has provoked debate on the mechanisms of microbial processes that may contribute to geophysical signatures. At field scales geophysical signatures are often non unique due to the many parameters (physical, chemical, and biological) that are involved. It may be easier to apply geophysical techniques such as electrodic potential (EP), self potential (SP) and induced polarization (IP) to engineered biological systems where there is a degree of control over the design of the physical and chemical domain. Here we present results of a column experiment that was designed to anaerobically biodegrade dissolved organic matter in landfill leachate. The column utilises a recycled porous media (concrete) to help sequester organic carbon. Electrodic potential, self potential and induced polarisation are used in conjunction with chemical and isotopic techniques to monitor the effectiveness of this approach. Preliminary carbon and oxygen isotopic analysis on concrete from the column in contact with leachate show isotopic enrichment suggesting abiotic precipitation of carbonates.

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

USGS Publications Warehouse

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

2016-01-01

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 CaSO4dissolution 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 provide important mechanistic details about the overall TSR process.

Potential use of stable isotope and fatty acid analyses for traceability of geographic origins of jumbo squid (Dosidicus gigas).

PubMed

Gong, Yi; Li, Yunkai; Chen, Xinjun; Chen, Ling

2018-04-15

Squid is an important seafood resource for Asian and European countries. With the continuous development of processed squid products, an effective traceability system has become increasingly prominent. Here, we attempt to trace the fishery products of the main target species, jumbo squid (Dosidicus gigas), by using biochemical tracers. Carbon and nitrogen isotope ratios (δ 13 C and δ 15 N values) and fatty acid profiles were identified in squid from three harvest locations in the eastern Pacific Ocean by isotope ratio mass spectrometry and gas chromatography/mass spectrometry, respectively. Comparative analysis was used to evaluate the geographic variations in tracers and to identify the suitable discriminatory variables among origins. Significant spatial variations were found in isotopic values and fatty acid profiles in squid muscle tissues, possibly because of different food availability and/or oceanographic conditions that each group experiences at a given location. The stepwise discriminant analysis indicated that δ 15 N, C16:1n7, C17:1n7, C18:2n6, C20:1 and C20:4n6 were effective variables at differentiating origin. Combined use of stable isotope ratios and fatty acid analyses could trace geographic origins of jumbo squid. This study provides an alternative approach for improving authenticity evaluation of commercial squid products. Copyright © 2018 John Wiley & Sons, Ltd.

Coal fly ash interaction with environmental fluids: Geochemical and strontium isotope results from combined column and batch leaching experiments

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

Brubaker, Tonya M; Stewart, Brian W; Capo, Rosemary C

2013-05-01

The major element and Sr isotope systematics and geochemistry of coal fly ash and its interactions with environmental waters were investigated using laboratory flow-through column leaching experiments (sodium carbonate, acetic acid, nitric acid) and sequential batch leaching experiments (water, acetic acid, hydrochloric acid). Column leaching of Class F fly ash samples shows rapid release of most major elements early in the leaching procedure, suggesting an association of these elements with soluble and surface bound phases. Delayed release of certain elements (e.g., Al, Fe, Si) signals gradual dissolution of more resistant silicate or glass phases as leaching continues. Strontium isotope resultsmore » from both column and batch leaching experiments show a marked increase in {sup 87}Sr/{sup 86}Sr ratio with continued leaching, yielding a total range of values from 0.7107 to 0.7138. For comparison, the isotopic composition of fluid output from a fly ash impoundment in West Virginia falls in a narrow range around 0.7124. The experimental data suggest the presence of a more resistant, highly radiogenic silicate phase that survives the combustion process and is leached after the more soluble minerals are removed. Strontium isotopic homogenization of minerals in coal does not always occur during the combustion process, despite the high temperatures encountered in the boiler. Early-released Sr tends to be isotopically uniform; thus the Sr isotopic composition of fly ash could be distinguishable from other sources and is a useful tool for quantifying the possible contribution of fly ash leaching to the total dissolved load in natural surface and ground waters.« less

N-loss isotope effects in the Peru oxygen minimum zone studied using a mesoscale eddy as a natural tracer experiment

NASA Astrophysics Data System (ADS)

Bourbonnais, Annie; Altabet, Mark A.; Charoenpong, Chawalit N.; Larkum, Jennifer; Hu, Haibei; Bange, Hermann W.; Stramma, Lothar

2015-06-01

Mesoscale eddies in Oxygen Minimum Zones (OMZs) have been identified as important fixed nitrogen (N) loss hotspots that may significantly impact both the global rate of N-loss as well as the ocean's N isotope budget. They also represent "natural tracer experiments" with intensified biogeochemical signals that can be exploited to understand the large-scale processes that control N-loss and associated isotope effects (ɛ; the ‰ deviation from 1 in the ratio of reaction rate constants for the light versus heavy isotopologues). We observed large ranges in the concentrations and N and O isotopic compositions of nitrate (NO3-), nitrite (NO2-), and biogenic N2 associated with an anticyclonic mode-water eddy in the Peru OMZ during two cruises in November and December 2012. In the eddy's center where NO3- was nearly exhausted, we measured the highest δ15N values for both NO3- and NO2- (up to ~70‰ and 50‰) ever reported for an OMZ. Correspondingly, N deficit and biogenic N2-N concentrations were also the highest near the eddy's center (up to ~40 µmol L-1). δ15N-N2 also varied with biogenic N2 production, following kinetic isotopic fractionation during NO2- reduction to N2 and, for the first time, provided an independent assessment of N isotope fractionation during OMZ N-loss. We found apparent variable ɛ for NO3- reduction (up to ~30‰ in the presence of NO2-). However, the overall ɛ for N-loss was calculated to be only ~13-14‰ (as compared to canonical values of ~20-30‰) assuming a closed system and only slightly higher assuming an open system (16-19‰). Our results were similar whether calculated from the disappearance of DIN (NO3- + NO2-) or from the appearance of N2 and changes in isotopic composition. Further, we calculated the separate ɛ values for NO3- reduction to NO2- and NO2- reduction to N2 of ~16-21‰ and ~12‰, respectively, when the effect of NO2- oxidation could be removed. These results, together with the relationship between N and O of NO3- isotopes and the difference in δ15N between NO3- and NO2-, confirm a role for NO2- oxidation in increasing the apparent ɛ associated with NO3- reduction. The lower ɛ for N-loss calculated in this study could help reconcile the current imbalance in the global N budget if representative of global OMZ N-loss.

Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria

PubMed Central

Navarrete, Jesica U.; Borrok, David M.; Viveros, Marian; Ellzey, Joanne T.

2011-01-01

Copper isotopes may prove to be a useful tool for investigating bacteria–metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ65Cu) to investigate Cu–bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5–6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ65Cusolution–solid = δ65Cusolution – δ65Cusolid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to –0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ65Cusolution–solid ranging from ~+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is shared by fungi, plants, and higher organisms, the influence of biological processes on the δ65Cu of natural waters and soils is probably considerable. PMID:21785492

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 chemistry’. PMID:29035266

Investigation of epi-thermal shape-parameter needed for precision analysis of activation

NASA Astrophysics Data System (ADS)

Elmaghraby, Elsayed K.

2017-06-01

The present work aims to expose factors that alter the isotope's effective resonance energy and its resonance integral in order to have consistency between the experimental observation of integral experiments and the prediction of the reaction rate. The investigation is based on disclosing the interference among resonances in Breit-Wigner and Reich-Moore representations to make the investigation of the statistical nature of resonances possible. The shape-parameter influence on the isotope's behavior in epi-thermal neutron field was investigated in the range from -0.1 to 0.1. Evaluated resonance data given in Evaluated Nuclear Data Files (ENDF/B VII.1) and temperature-dependent cross-sections of Point2015 are used. Only resolved resonances are considered in the present assessment. Tabulated values of resonance integrals and effective resonance energies with their moments are given for the majority of ENDF's isotopes. The reported data can be used, directly, to compute the integral parameters for any value of shape-parameter without the need to use numerical software tools. Correlations among effective resonance energy, experimental level spacing and resonance integral are discussed.

Low-temperature chemistry between water and hydroxyl radicals: H/D isotopic effects

NASA Astrophysics Data System (ADS)

Lamberts, T.; Fedoseev, G.; Puletti, F.; Ioppolo, S.; Cuppen, H. M.; Linnartz, H.

2016-01-01

Sets of systematic laboratory experiments are presented - combining Ultra High Vacuum cryogenic and plasma-line deposition techniques - that allow us to compare H/D isotopic effects in the reaction of H2O (D2O) ice with the hydroxyl radical OD (OH). The latter is known to play a key role as intermediate species in the solid-state formation of water on icy grains in space. The main finding of our work is that the reaction H2O + OD → OH + HDO occurs and that this may affect the HDO/H2O abundances in space. The opposite reaction D2O + OH → OD + HDO is much less effective, and also given the lower D2O abundances in space not expected to be of astronomical relevance. The experimental results are extended to the other four possible reactions between hydroxyl and water isotopes and are subsequently used as input for Kinetic Monte Carlo simulations. This way we interpret our findings in an astronomical context, qualitatively testing the influence of the reaction rates.

Massive isotopic effect in vacuum UV photodissociation of N2 and implications for meteorite data

PubMed Central

Chakraborty, Subrata; Muskatel, B. H.; Jackson, Teresa L.; Ahmed, Musahid; Levine, R. D.; Thiemens, Mark H.

2014-01-01

Nitrogen isotopic distributions in the solar system extend across an enormous range, from −400‰, in the solar wind and Jovian atmosphere, to about 5,000‰ in organic matter in carbonaceous chondrites. Distributions such as these require complex processing of nitrogen reservoirs and extraordinary isotope effects. While theoretical models invoke ion-neutral exchange reactions outside the protoplanetary disk and photochemical self-shielding on the disk surface to explain the variations, there are no experiments to substantiate these models. Experimental results of N2 photolysis at vacuum UV wavelengths in the presence of hydrogen are presented here, which show a wide range of enriched δ15N values from 648‰ to 13,412‰ in product NH3, depending upon photodissociation wavelength. The measured enrichment range in photodissociation of N2, plausibly explains the range of δ15N in extraterrestrial materials. This study suggests the importance of photochemical processing of the nitrogen reservoirs within the solar nebula. PMID:25267643

Electron Scattering from MERCURY-198 and Mercury -204.

NASA Astrophysics Data System (ADS)

Laksanaboonsong, Jarungsaeng

This experiment is the first electron scattering study on mercury isotopes. Electron scattering from ^{198}Hg and ^{204 }Hg has been performed at the NIKHEF-K Medium Energy Accelerator. Measured cross sections cover an effective momentum transfer range from 0.4 to 2.9 fm^ {-1}. Elastic cross sections were determined for scattering from both isotopes. Cross section for inelastic excitations in ^{198}Hg below 3 MeV were also determined. Measured cross sections were fit using DWBA phase shift codes to determine coefficients for Fourier-Bessel expansions of ground state and transition charge densities. Differences between the ground state charge densities of the two isotopes reveal the effect of the polarization of the proton core in response to the addition of neutrons. Spin and parity of several excited states of ^{198}Hg were determined. Extracted transition densities of these states show their predominantly collective nature. Charge densities for members of the ground state rotational band were compared with axially symmetric Hartree-Fock and geometrical model predictions.

Defining Uncertainty and Error in Planktic Foraminiferal Oxygen Isotope Measurements

NASA Astrophysics Data System (ADS)

Fraass, A. J.; Lowery, C.

2016-12-01

Foraminifera are the backbone of paleoceanography, and planktic foraminifera are one of the leading tools for reconstructing water column structure. Currently, there are unconstrained variables when dealing with the reproducibility of oxygen isotope measurements. This study presents the first results from a simple model of foraminiferal calcification (Foraminiferal Isotope Reproducibility Model; FIRM), designed to estimate the precision and accuracy of oxygen isotope measurements. FIRM produces synthetic isotope data using parameters including location, depth habitat, season, number of individuals included in measurement, diagenesis, misidentification, size variation, and vital effects. Reproducibility is then tested using Monte Carlo simulations. The results from a series of experiments show that reproducibility is largely controlled by the number of individuals in each measurement, but also strongly a function of local oceanography if the number of individuals is held constant. Parameters like diagenesis or misidentification have an impact on both the precision and the accuracy of the data. Currently FIRM is a tool to estimate isotopic error values best employed in the Holocene. It is also a tool to explore the impact of myriad factors on the fidelity of paleoceanographic records. FIRM was constructed in the open-source computing environment R and is freely available via GitHub. We invite modification and expansion, and have planned inclusions for benthic foram reproducibility and stratigraphic uncertainty.

Technical developments for an upgrade of the LEBIT Penning trap mass spectrometry facility for rare isotopes

NASA Astrophysics Data System (ADS)

Redshaw, M.; Barquest, B. R.; Bollen, G.; Bustabad, S. E.; Campbell, C. M.; Ferrer, R.; Gehring, A.; Kwiatkowski, A. A.; Lincoln, D. L.; Morrissey, D. J.; Pang, G. K.; Ringle, R.; Schwarz, S.

2011-07-01

The LEBIT (Low Energy Beam and Ion Trap) facility is the only Penning trap mass spectrometry (PTMS) facility to utilize rare isotopes produced via fast-beam fragmentation. This technique allows access to practically all elements lighter than uranium, and in particular enables the production of isotopes that are not available or that are difficult to obtain at isotope separation on-line facilities. The preparation of the high-energy rare-isotope beam produced by projectile fragmentation for low-energy PTMS experiments is achieved by gas stopping to slow down and thermalize the fast-beam ions, along with an rf quadrupole cooler and buncher and rf quadrupole ion guides to deliver the beam to the Penning trap. During its first phase of operation LEBIT has been very successful, and new developments are now underway to access rare isotopes even farther from stability, which requires dealing with extremely short lifetimes and low production rates. These developments aim at increasing delivery efficiency, minimizing delivery and measurement time, and maximizing use of available beam time. They include an upgrade to the gas-stopping station, active magnetic field monitoring and stabilization by employing a miniature Penning trap as a magnetometer, the use of stored waveform inverse Fourier transform (SWIFT) to most effectively remove unwanted ions, and charge breeding.

α -decay chains of superheavy nuclei with Z =125

NASA Astrophysics Data System (ADS)

Santhosh, K. P.; Nithya, C.

2018-04-01

The decay properties of the isotopes of Z =125 within the range 303 ≤ A ≤ 339 are investigated. The calculation of proton separation energies reveals that isotopes 125-309303 may decay through proton emission. Four different mass tables are used to show the sensitivity of the mass models used to calculate the Q values as well as the α-decay half-lives. α -decay chains are predicted by comparing the α half-lives calculated within the Coulomb and proximity potential model for deformed nuclei (CPPMDN) [Nucl. Phys. A 850, 34 (2011), 10.1016/j.nuclphysa.2010.12.002] with the spontaneous fission half-lives using the shell-effect-dependent formula [Phys. Rev. C 94, 054621 (2016), 10.1103/PhysRevC.94.054621]. It is seen that isotopes 125,311310 show 6α chains. 5α chains can be seen from isotopes 125-318312. Isotopes 125,320319 exhibit 2α chains and 323125 exhibits 1α chain. All the other isotopes, that is, 125 321 ,322 ,324 -339 may decay through spontaneous fission. The α half-lives using CPPMDN are compared with five other theoretical formalisms and are seen to be matching with each other. We hope that our studies will be helpful in designing future experiments to explore the island of stability.

Field-based stable isotope analysis of carbon dioxide by mid-infrared laser spectroscopy for carbon capture and storage monitoring.

PubMed

van Geldern, Robert; Nowak, Martin E; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A C; Jost, Hans-Jürg

2014-12-16

A newly developed isotope ratio laser spectrometer for CO2 analyses has been tested during a tracer experiment at the Ketzin pilot site (northern Germany) for CO2 storage. For the experiment, 500 tons of CO2 from a natural CO2 reservoir was injected in supercritical state into the reservoir. The carbon stable isotope value (δ(13)C) of injected CO2 was significantly different from background values. In order to observe the breakthrough of the isotope tracer continuously, the new instruments were connected to a stainless steel riser tube that was installed in an observation well. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10 day carbon stable isotope data set with 30 min resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within analytical precision. This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time stable isotope data directly in the field. The laser spectroscopy data revealed for the first time a prior to this experiment unknown, intensive dynamic with fast changing δ(13)C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The short-term variances as observed in this study might have been missed during previous works that applied laboratory-based IRMS analysis. The new technique could contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

Modeling nuclear field shift isotope fractionation in crystals

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2013-12-01

In this study nuclear field shift fractionations in solids (and chemically similar liquids) are estimated using calibrated density functional theory calculations. The nuclear field shift effect is a potential driver of mass independent isotope fractionation(1,2), especially for elements with high atomic number such as Hg, Tl and U. This effect is caused by the different shapes and volumes of isotopic nuclei, and their interactions with electronic structures and energies. Nuclear field shift isotope fractionations can be estimated with first principles methods, but the calculations are computationally difficult, limiting most theoretical studies so far to small gas-phase molecules and molecular clusters. Many natural materials of interest are more complex, and it is important to develop ways to estimate field shift effects that can be applied to minerals, solutions, in biomolecules, and at mineral-solution interfaces. Plane-wave density functional theory, in combination with the projector augmented wave method (DFT-PAW), is much more readily adapted to complex materials than the relativistic all-electron calculations that have been the focus of most previous studies. DFT-PAW is a particularly effective tool for studying crystals with periodic boundary conditions, and may also be incorporated into molecular dynamics simulations of solutions and other disordered phases. Initial calibrations of DFT-PAW calculations against high-level all-electron models of field shift fractionation suggest that there may be broad applicability of this method to a variety of elements and types of materials. In addition, the close relationship between the isomer shift of Mössbauer spectroscopy and the nuclear field shift isotope effect makes it possible, at least in principle, to estimate the volume component of field shift fractionations in some species that are too complex even for DFT-PAW models, so long as there is a Mössbauer isotope for the element of interest. Initial results will be presented for calculations of liquid-vapor fractionation of cadmium and mercury, which indicate an affinity for heavy isotopes in the liquid phase. In the case of mercury the results match well with recent experiments. Mössbauer-calibrated fractionation factors will also be presented for tin and platinum species. Platinum isotope behaviour in metals appears to particularly interesting, with very distinct isotope partitioning behaviour for iron-rich alloys, relative to pure platinum metal. References: 1) Bigeleisen, J. (1996) J. Am. Chem. Soc. 118, 3676-3680. 2) Nomura, M., Higuchi, N., Fujii, Y. (1996) J. Am. Chem. Soc. 118, 9127-9130.

Hydrogen isotope fractionation between C-H-O species in magmatic fluids

NASA Astrophysics Data System (ADS)

Foustoukos, D. I.; Mysen, B. O.

2012-12-01

Constraining the hydrogen isotope fractionation between H-bearing volatiles (e.g. H2, CH4, hydrocarbons, H2O) as function of temperature and pressure helps to promote our understanding of the isotopic composition of evolved magmatic fluids and the overall mantle-cycling of water and reduced C-O-H volatiles. To describe the thermodynamics of the exchange reactions between the different H/D isotopologues of H2 and CH4 under supercritical water conditions, a novel experimental technique has been developed by combining vibrational Raman spectroscopy with hydrothermal diamond anvil cell designs (HDAC), which offers a method to monitor the in-situ evolution of H/D containing species. To this end, the equilibrium relationship between H2-D2-HD in supercritical fluid was investigated at temperatures ranging from 300 - 800 oC and pressures ~ 0.3 - 1.3 GPa [1]. Experimental results obtained in-situ and ex-situ show a significant deviation from the theoretical values of the equilibrium constant predicted for ideal-gas reference state, and with an apparent negative temperature effect triggered by the enthalpy contributions due to mixing in supercritical water. Here, we present a series of HDAC experiments conducted to evaluate the role of supercritical water on the isotopic equilibrium between H/D methane isotopologues at 600 - 800 oC and 409 - 1622 MPa. In detail, tetrakis-silane (Si5C12H36) was reacted with H2O-D2O aqueous solution in the presence of either Ni or Pt metal catalyst, resulting to the formation of deuterated methane species such as CH3D, CHD3, CH2D2 and CD4. Two distinctly different set of experiments ("gas phase"; "liquid phase") were performed by adjusting the silane/water proportions. By measuring the relative intensities of Raman vibrational modes of species, experimental results demonstrate distinctly different thermodynamic properties for the CH4-CH3D-CHD3-CH2D2 equilibrium in gas and liquid-water-bearing systems. In addition, the D/H molar ratio of methane in the liquid is twice that recorded in the gas phase. Accordingly, condensed-phase isotope effects are inferred to govern the evolution of H/D isotopologues, induced by differences in the solubility of the isotopic molecules driven by excess energy/entropy developed during the mixing of non-polar species in the supercritical water structure. On the contrary, at such high temperatures/-pressures statistical thermodynamic models, based on the vibrational zero point energy distributions and high-temperature anharmonicity for isotopic molecules in ideal-gas reference state, predict minimal isotope exchange. Data, therefore, demonstrate that the solvation mechanism of H-D-bearing species in magmatic fluids can impose substantial D/H fractionation effects governing the δD composition of coexisting species even at lower-crust/upper-mantle temperature conditions. 1. Foustoukos D.I. and B.O. Mysen, (2012) D/H isotopic fractionation in the H2-H2O system at supercritical water conditions: Composition and hydrogen bonding effects, Geochim. Cosmochim. Acta, 86, 88-102.

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 frequency calculations of clusters derived from DFT structures vary by as much as 1.4‰. This suggests that the equilibrium fractionation factor for the bulk crystal can vary substantially, and that surface sorption can induce changes in αeq associated with gypsum precipitation. While we do not rule out the influence of kinetic isotope effects, our results clearly demonstrate that the mode of crystal growth can have a sizeable effect on the bulk fractionation factor (αs-f). Ultimately, our results suggest that the same mechanism by which organic molecules affect the morphology of a mineral can also impact the isotopic composition of the mineral. The results of our study provide valuable insight into the mechanism of Ca isotopic fractionation during gypsum precipitation. Our results are also important for establishing a framework for accurate interpretations of mineral-hosted Ca isotope records of the past, as we demonstrate a mechanistic pathway by which the biological and chemical environment can impact Ca isotopic fractionation during mineral precipitation.

Combining Solvent Isotope Effects with Substrate Isotope Effects in Mechanistic Studies of Alcohol and Amine Oxidation by Enzymes*

PubMed Central

Fitzpatrick, Paul F.

2014-01-01

Oxidation of alcohols and amines is catalyzed by multiple families of flavin-and pyridine nucleotide-dependent enzymes. Measurement of solvent isotope effects provides a unique mechanistic probe of the timing of the cleavage of the OH and NH bonds, necessary information for a complete description of the catalytic mechanism. The inherent ambiguities in interpretation of solvent isotope effects can be significantly decreased if isotope effects arising from isotopically labeled substrates are measured in combination with solvent isotope effects. The application of combined solvent and substrate (mainly deuterium) isotope effects to multiple enzymes is described here to illustrate the range of mechanistic insights that such an approach can provide. PMID:25448013

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 those observed for microbial biodegradation of the chlorinated ethenes suggest that there may be differences in the rate determining step for these two processes. Determining which steps are rate determining during degradation may allow optimization of contaminant remediation.

Proxies of Tropical Cyclone Isotope Spikes in Precipitation: Landfall Site Selection

NASA Astrophysics Data System (ADS)

Lawrence, J. R.; Maddocks, R.

2011-12-01

The human experience of climate change is not one of gradual changes in seasonal or yearly changes in temperature or rainfall. Despite that most paleoclimatic reconstructions attempt to provide just such information. Humans experience climate change on much shorter time scales. We remember hurricanes, weeks of drought or overwhelming rainy periods. Tropical cyclones produce very low isotope ratios in both rainfall and in atmospheric water vapor. Thus, climate proxies that potentially record these low isotope ratios offer the most concrete record of climate change to which humans can relate. The oxygen isotopic composition of tropical cyclone rainfall has the potential to be recorded in fresh water carbonate fossil material, cave deposits and corals. The hydrogen isotopic composition of tropical cyclone rainfall has the potential to be recorded in tree ring cellulose and organic matter in fresh water bodies. The Class of carbonate organisms known as Ostracoda form their carapaces very rapidly. Thus fresh water ephemeral ponds in the subtropics are ideal locations for isotopic studies because they commonly are totally dry when tropical cyclones make landfall. The other proxies suffer primarily from a dilution effect. The water from tropical cyclones is mixed with pre-existing water. In cave deposits tropical cyclone rains mix with soil and ground waters. In the near shore coral environment the rain mixes with seawater. For tree rings there are three sources of water: soil water, atmospheric water vapor that exchanges with leaf water and tropical cyclone rain. In lakes because of their large size rainfall runoff mixes with ground water and preexisting water in the lake. A region that shows considerable promise is Texas / Northeast Mexico. In a study of surface waters that developed from the passage of Tropical Storm Allison (2001) in SE Texas both the pond water and Ostracoda that bloomed recorded the low oxygen isotope signal of that storm (Lawrence et al, 2008). In 2010 rain from Hurricane Alex, Tropical Depression 2 and Tropical Storm Hermine flooded ephemeral ponds in south Texas. Isotopic analysis of water and fossil Ostracoda from ephemeral ponds in south Texas is planned. Cores (50 cm in length) were taken in one of these ponds where living Ostracoda were found and collected.

Experimentally determined sulfur isotope fractionation between metal and silicate and implications for planetary differentiation

NASA Astrophysics Data System (ADS)

Labidi, J.; Shahar, A.; Le Losq, C.; Hillgren, V. J.; Mysen, B. O.; Farquhar, J.

2016-02-01

The Earth's mantle displays a subchondritic 34S/32S ratio. Sulfur is a moderately siderophile element (i.e. iron-loving), and its partitioning into the Earth's core may have left such a distinctive isotope composition on the terrestrial mantle. In order to constrain the sulfur isotope fractionation occurring during core-mantle differentiation, high-pressure and temperature experiments were conducted with synthetic mixtures of metal and silicate melts. With the purpose to identify the mechanism(s) responsible for the S isotope fractionations, we performed our experiments in different capsules - namely, graphite and boron nitride capsules - and thus at different fO2, with varying major element chemistry of the silicate and metal fractions. The S isotope fractionations Δ34Smetal-silicate of equilibrated metal alloys versus silicate melts is +0.2 ± 0.1‰ in a boron-free and aluminum-poor system quenched at 1-1.5 GPa and 1650 °C. The isotope fractionation increases linearly with increasing boron and aluminum content, up to +1.4 ± 0.2‰, and is observed to be independent of the silicon abundance as well as of the fO2 over ∼3.5 log units of variations explored here. The isotope fractionations are also independent of the graphite or nitride saturation of the metal. Only the melt structural changes associated with aluminum and boron concentration in silicate melts have been observed to affect the strength of sulfur bonding. These results establish that the structure of silicate melts has a direct influence on the S2- average bonding strengths. These results can be interpreted in the context of planetary differentiation. Indeed, the structural environments of silicate evolve strongly with pressure. For example, the aluminum, iron or silicon coordination numbers increase under the effect of pressure. Consequently, based on our observations, the sulfur-bonding environment is likely to be affected. In this scheme, we tentatively hypothesize that S isotope fractionations between the silicate mantle and metallic core of terrestrial planetary bodies would depend on the average pressure at which their core-mantle differentiation occurred.

Interpreting the role of pH on stable isotopes in large benthic foraminifera

USGS Publications Warehouse

Robbins, Lisa L.; Knorr, P.O.; Wynn, J.G.; Hallock, P.; Harries, P.

2016-01-01

Large benthic foraminifera (LBF) are prolific producers of calcium carbonate sediments in shallow, tropical environments that are being influenced by ocean acidification (OA). Two LBF species, Amphistegina gibbosa (Order Rotaliida) with low-Mg calcite tests and Archaias angulatus (Order Miliolida) with high-Mg calcite tests, were studied to assess the effects of pH 7.6 on oxygen and carbon isotopic fractionation between test calcite and ambient seawater. The δ18O and δ13C values of terminal chambers and of whole adult tests of both species after 6 weeks were not significantly different between pH treatments of 8.0 and 7.6. However, tests of juveniles produced during the 6-week treatments showed significant differences between δ18O and δ13C values from control (pH 8.0) when compared with the treatment (pH 7.6) for both species. Although each individual's growth was photographed and measured, difficulty in distinguishing and manually extracting newly precipitated calcite from adult specimens likely confounded any differences in isotopic signals. However, juvenile specimens that resulted from asexual reproduction that occurred during the experiments did not contain old carbonate that could confound the new isotopic signals. These data reveal a potential bias in the design of OA experiments if only adults are used to investigate changes in test chemistries. Furthermore, the results reaffirm that different calcification mechanisms in these two foraminiferal orders control the fractionation of stable isotopes in the tests and will reflect decreasing pH in seawater somewhat differently. .

Experimental evidence for the absence of iron isotope fractionation between metal and silicate liquids at 1 GPa and 1250-1300 °C and its cosmochemical consequences

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Schmidt, Max W.; Bourdon, Bernard

2012-09-01

Iron isotope fractionation during metal-silicate differentiation has been proposed as a cause for differences in iron isotope compositions of chondrites, iron meteorites and the bulk silicate Earth. Stable isotope fractionation, however, rapidly decreases with increasing temperature. We have thus performed liquid metal-liquid silicate equilibration experiments at 1250-1300 °C and 1 GPa to address whether Fe isotope fractionation is resolvable at the lowest possible temperatures for magmatic metal-silicate differentiation. A centrifuging piston cylinder apparatus enabled quantitative metal-silicate segregation. Elemental tin or sulphur was used in the synthetic metal-oxide mixtures to lower the melting temperature of the metal. The analyses demonstrate that eight of the 10 experimental systems equilibrated in a closed isotopic system, as was assessed by varying run durations and starting Fe isotope compositions. Statistically significant iron isotope fractionation between quenched metals and silicates was absent in nine of the 10 experiments and all 10 experiments yield an average metal-silicate fractionation factor of 0.01 ± 0.04‰, independent of whether graphite or silica glass capsules were used. This implies that Fe isotopes do not fractionate during low pressure metal-silicate segregation under magmatic conditions. In large bodies such as the Earth, fractionation between metal and high pressure (>20 GPa) silicate phases may still be a possible process for equilibrium fractionation during metal-silicate differentiation. However, the 0.07 ± 0.02‰ heavier composition of bulk magmatic iron meteorites relative to the average of bulk ordinary/carbonaceous chondrites cannot result from equilibrium Fe isotope fractionation during core segregation. The up to 0.5‰ lighter sulphide than metal fraction in iron meteorites and in one ordinary chondrite can only be explained by fractionation during subsolidus processes.

Possibility for precise Weinberg-angle measurement in centrosymmetric crystals with axis

NASA Astrophysics Data System (ADS)

Mukhamedjanov, T. N.; Sushkov, O. P.

2006-03-01

We demonstrate that parity-nonconserving interaction due to the nuclear weak charge QW leads to a nonlinear magnetoelectric effect in centrosymmetric paramagnetic crystals. It is shown that the effect exists only in crystals with special symmetry axis k . Kinematically, the correlation (correction to energy) has the form HPNC∝QWE•[B×k](B•k) , where B and E are external magnetic and electric fields. This gives rise to the magnetic induction MPNC∝QW{k(B•[k×E])+[k×E](B•k)} . To be specific, we consider rare-earth-metal trifluorides and, in particular, dysprosium trifluoride which looks the most suitable for experiment. We estimate the optimal temperature for the experiment to be of a few kelvin. For the magnetic field B=1T and the electric field E=10kV/cm , the expected magnetic induction is 4πMPNC˜0.5×10-11G , six orders of magnitude larger than the best sensitivity currently under discussion. Dysprosium has several stable isotopes, and so comparison of the effects for different isotopes provides the possibility for precise measurement of the Weinberg angle.

Core formation conditons in planetesimals: constraints from isotope fractionation experiments.

NASA Astrophysics Data System (ADS)

Guignard, J.; Quitté, G.; Toplis, M. J.; Poitrasson, F.

2016-12-01

Planetesimals are small objects (10 to 1000 km) early accreted in the history of the solar system which show a wide variety of thermal history due to the initial amount of radiogenic elements [1] (26Al and 60Fe), from a simple metamorphism to a complete metal-silicate differentiation. Moreover, isotope compositions of siderophile element, e.g. Fe, Ni, and W in meteorites spread on a range that can be attributed to the process of core-mantle segregation. We therefore performed isotope fractionation experiments of nickel and tungsten between metal and silicate in a gas-mixing (CO-CO2) vertical furnace, at different temperatures (from 1270°C to 1600°C), oxygen fugacity (from IW+2 to IW-6) and annealing times (from 20 minutes to 48 hours). The starting silicate is an anorthite-diopside eutectic composition glass, synthesize from the respective oxides. The starting metal is either a nickel or tungsten wire according to the element to study. After each experiment, metal and silicate are mechanically separated and digested in acids. Nickel and Tungsten separation have been made according to the methods developed by [2] and [3] and isotopes measurements have been made using a high resolution MC-ICP-MS (Neptune; Thermofisher©). Results show evidence for a strong kinetic isotope fractionation during the first annealing times with a faster diffusion of lightest isotopes than heaviest. Similar mechanism has been already highlighted for iron isotope fractionation between silicate and metal [4]. Chemical and isotopic equilibrium is also reached in our experiments but the time required dependent on the conditions of temperature and oxygen fugacity. Therefore, at equilibrium, metal-silicate isotope fractionation has also been quantified as well its temperature dependence. These experimental data can be used in order to bring new constraints on the metal silicate segregation in the planetesimals early accreted. [1] Lee T., et al., GRL, 3, 41-44 (1976) [2] Quitté G., and Oberli F., JAAS, 21, 1249-1255 (2006) [3] Breton T., and Quitté G., JAAS, 29, 2284-2293 (2014) [4] Roskosz M., et al., EPSL, 248, 851-867 (2006)

Barium isotope fractionation during the experimental transformation of aragonite to witherite and of gypsum to barite, and the effect of ion (de)solvation.

PubMed

Böttcher, Michael E; Neubert, Nadja; von Allmen, Katja; Samankassou, Elias; Nägler, Thomas F

2018-06-01

In this study, we present the experimental results for stable barium (Ba) isotope fractionation ( 137 Ba/ 134 Ba) during the transformation of aragonite (CaCO 3 ) and gypsum (CaSO 4 ·2H 2 O) in Ba-bearing aqueous solution to witherite (BaCO 3 ) and barite (BaSO 4 ), respectively. The process was studied at three temperatures between 4 and 60 °C. In all cases, the transformation leads to a relative enrichment of the lighter 134 Ba isotope in the solid compared to the aqueous solution, with 137/134 Ba enrichment factors between -0.11 and -0.17 ‰ for BaCO 3 , and -0.21 and -0.26 ‰ for BaSO 4 . The corresponding mass-dependent 138/134 Ba enrichment factors are -0.15 to -0.23 ‰ for BaCO 3 , and -0.28 to -0.35 ‰ for BaSO 4 . The magnitude of isotope fractionation is within the range of recent reports for witherite and barite formation, as well as trace Ba incorporation into orthorhombic aragonite, and no substantial impact of temperature can be found between 4 and 80 °C. In previous studies, ion (de)solvation has been suggested to impact both the crystallization process of Ba-bearing solids and associated Ba isotope fractionation. Precipitation experiments of BaSO 4 and BaCO 3 using an methanol-containing aqueous solution indicate only a minor effect of ion and crystal surface (de)solvation on the overall Ba isotope fractionation process.

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

DOEpatents

Gold, Raymond; McElroy, William N.

1988-01-01

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

Experimental constraints on reconstruction of Archean seawater Ni isotopic composition from banded iron formations

NASA Astrophysics Data System (ADS)

Wang, Shui-Jiong; Wasylenki, Laura E.

2017-06-01

The Ni isotopic systematics in banded iron formations (BIFs) potentially recorded the Ni isotopic composition of ancient seawater over Precambrian geological history. However, the utility of BIFs as proxies requires quantitative knowledge of how Ni isotopes fractionated as dissolved Ni was initially incorporated into iron-rich sediments and how diagenesis may have affected the Ni isotopic systematics. Here we report results of synthesis experiments to investigate the behavior of Ni isotopes during Ni coprecipitation with ferrihydrite and then transformation of ferrihydrite to hematite. Ferrihydrite coprecipitation experiments at neutral pH demonstrated that the dissolved Ni was variably heavier than coprecipitated Ni (likely a mixture of surface-adsorbed and structurally incorporated Ni), with the isotope fractionation becoming larger as the fraction of Ni associated with solid increased (Δ60/58Nisolution-solid = +0.08 to +0.50‰). Further experiments at lower pH (3.7-6.7), in which structurally incorporated Ni likely dominated in solids, documented a decrease in Δ60/58Nisolution-solid from +0.44‰ to -0.18‰ as the pH decreased. The negative value for Δ60/58Nisolution-solid at low pH indicates the enrichment of heavier isotopes in incorporated Ni relative to dissolved and adsorbed Ni, possibly as a result of the presence of a small amount of tetrahedral Ni2+ in addition to octahedral Ni2+ in the ferrihydrite structure. The results of the ferrihydrite experiments thus reflect equilibrium isotope fractionation between three pools of Ni, with δ60/58Ni values in the order of incorporated > dissolved > adsorbed. Hematite was synthesized by transformation of Ni-bearing ferrihydrite in aqueous solution at ∼100 °C. A significant amount of Ni (up to 60%) was released (desorbed) from solids into solutions as pH dropped from ∼7 to 4.5-5.5 upon phase transformation. Rinsing of the synthesized hematite in 2 M acetic acid released only very small amounts of Ni (<4% of total Ni, presumably surface-adsorbed) that were isotopically heavier (δ60/58Ni = +0.11 ± 0.06‰) than the residues (presumably dominated by incorporated Ni), which had δ60/58Ni of -0.26 ± 0.07‰. The preference of lighter isotopes for the incorporated Ni relative to the surface-adsorbed Ni after phase transformation (most had been released into solution) is probably due to distortion of Nisbnd O octahedra in the hematite structure, with weaker Nisbnd O bond strengths on average. Hence, the more variable Δ60/58Nisolution-solid values (-0.04 to +0.77‰) observed in hematite experiments most likely reflect thermodynamically driven Rayleigh fractionation, with incorporated Ni unavailable to exchange with dissolved Ni due to continuous reduction in size of the highly reactive surface pool of Ni, through which all solid-solution exchange must occur. Overall, the synthesized hematite was isotopically lighter than the ferrihydrite by ∼0.08‰ in δ60/58Ni, which is however within the current analytical uncertainties (±0.09‰). This implies that earliest diagenesis of BIFs results in very limited change in the isotopic composition of solid-associated Ni. Our experimental results, although conducted in a very simple system that differs from Archean seawater, represent an important step toward reconstruction of the Ni isotopic composition of ancient seawater from Ni isotopic signatures in BIFs.

Isotope effects in photo dissociation of ozone with visible light

NASA Astrophysics Data System (ADS)

Früchtl, Marion; Janssen, Christof; Röckmann, Thomas

2014-05-01

Ozone (O3) plays a key role for many chemical oxidation processes in the Earth's atmosphere. In these chemical reactions, ozone can transfer oxygen to other trace gases. This is particularly interesting, since O3 has a very peculiar isotope composition. Following the mass dependent fractionation equation δ17O = 0.52 * δ18O, most fractionation processes depend directly on mass. However, O3 shows an offset to the mass dependent fractionation line. Processes, which show such anomalies, are termed mass independent fractionations (MIF). A very well studied example for a chemical reaction that leads to mass independent fractionation is the O3 formation reaction. To what degree O3 destruction reactions need to be considered in order to understand the isotope composition of atmospheric O3 is still not fully understood and an open question within scientific community. We set up new experiments to investigate the isotope effect resulting from photo dissociation of O3 in the Chappuis band (R1). Initial O3 is produced by an electric discharge. After photolysis O3 is collected in a cold trap at the triple point temperature of nitrogen (63K). O3 is then converted to O2 in order to measure the oxygen isotopes of O3 using isotope ratio mass spectrometry. To isolate O3 photo dissociation (R1) from O3 decomposition (R2) and secondary O3 formation (R3), we use varying amounts of carbon monoxide (CO) as O atom quencher (R4). In this way we suppress the O + O3 reaction (R3) and determine the isotope fractionation in R1 and R2 separately. We present first results on the isotope effects in O3 photo dissociation with visible light in the presence of different bath gases. Results are interpreted based on chemical kinetics modeling. (R1) O3 + hυ → O (3P) + O2 (R2) O3 + O (3P) → 2 O2 (R3) O + O2 + M → O3 + M (R4) O (3P) + CO + M → CO2 + M

A First Look at Oxygen and Silicon Isotope Variations in Diatom Silica from a Pliocene Antarctic Marine Sediment Core

NASA Astrophysics Data System (ADS)

Abbott, T.; Dodd, J. P.; Hackett, H.; Scherer, R. P.

2016-02-01

Coupled oxygen (δ18O) and silicon (δ30Si) isotope variations in diatom silica (opal-A) are increasingly used as a proxy to reconstruct paleoenvironmental conditions (water temperatures, water mass mixing, nutrient cycling) in marine environments. Diatom silica is a particularly significant paleoenvironmental proxy in high latitude environments, such as the Southern Ocean, where diatom blooms are abundant and diatom frustules are well preserved in the sediment. The Andrill-1B (AND-1B) sediment core from the Ross Sea (Antarctica) preserves several Pliocene ( 4.5 Ma) age diatomite units. Here we present preliminary δ18O and δ30Si values for a diatomite subunit in the AND-1B sediment core. Initial isotope values for the AND-1B diatoms silica record relatively high variability (range δ18O: 36.3‰ to 39.9‰) that could be interpreted as large-scale changes in the water temperature and/or freshwater mixing in the Ross Sea; however, a significant concern with marine sediment of this age is isotope fractionation during diagenesis and the potential formation of opal-CT lepispheres. The effects of clay contamination on the diatom silica δ18O values have been addressed through sample purification and quantified through chemical and physical analyses of the diatom silica. The isotopic effects of opal-CT are not as clearly understood and more difficult to physically separate from the primary diatom silica. In order to better understand the isotope variations in the AND-1B diatoms, we also evaluated silicon and oxygen isotope fractionation during the transition from opal-A to opal-CT in a controlled laboratory experiment. Opal-A from cultured marine diatoms (Thalassiosira weissflogii) was subjected to elevated temperatures (150°C) in acid digestion vessels for 4 weeks to initiate opal-CT precipitation. Quantifying the effects of opal-CT formation on δ18O and δ30Si variations in biogenic silica improves our understanding of the use of diatom silica isotope values a paleoenvironmental proxy throughout the Cenozoic.

The Isotopologue Record of Repeat Vital Effect Offenders: Tracking (Dis)equilibrium Effects in Sea Urchins and Nannofossil Using Clumped Isotopes

NASA Astrophysics Data System (ADS)

John, C. M.; Davies, A.; Drury, A. J.

2016-12-01

Vital effects vary between species and affect various isotopic systems in unequal proportion. The magnitude of the response of different isotopic systems might thus be key in understanding biologically-mediated disequilibrium, especially in groups that show a tendency to be "repeat offenders" with regards to vital effects. Here we present carbon, oxygen, and clumped isotope data from echinoderm calcite and nannofossil ooze, both of which exhibit strong vital effects in bulk isotopes. Our study is the first to investigate the clumped isotope (dis)equilibrium of echinoids. Results from two echinoids, three marine gastropods and a bivalve mollusk from modern beach deposits of Bali, Indonesia, highlight a significant offset in clumped isotopes of a regular echinoid test from expected values, interpreted as evidence of a similar "vital effect" as observed in surface corals. This is in contrast to the test of an irregular "sand dollar" echinoid, with clumped isotope values within error of expected sea surface temperature. Furthermore, data on the inter-skeletal variability in the clumped isotopic composition of two regular echinoid species shows that the spines of the echinoids are in equilibrium with seawater with respect to clumped isotopes, but the test is not. For the nannofossil material, no clumped isotope vital effects are observed, consistent with previously published studies but at odds with strong vital effects in carbon and oxygen isotopes, often correlated with cell-size. In addition, we reveal that the <63 micron fraction of deep-sea ooze could constitute useful material for clumped isotope studies. An intriguing result of our study is that vital effects are mostly absent in clumped isotopes, even in phylums known for important isotopic effects. It remains to be explained why some parts of the echinoids show clear vital effects, notably enrichment in clumped isotopes of urchin tests. Mechanisms that could explain this include pH effects during calcification. Rapid precipitation of calcite is however not considered as a likely mechanism as skeletal components with the largest growth rates show no clear clumped isotope vital effects.

Molybdenum isotope fractionation during adsorption to organic matter

NASA Astrophysics Data System (ADS)

King, E. K.; Perakis, S. S.; Pett-Ridge, J. C.

2018-02-01

Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2-170 h) and pH (2-7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (±0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

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 clumped-isotope effects. These isotopic signatures, manifest as either directly bound isotope ;clumps; or as features of a molecule's isotopic anatomy, are linked to molecular mechanisms and may eventually provide additional information about biogeochemical cycling on environmentally relevant spatial scales.

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.

Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

PubMed Central

Balci, Nurgul; Brunner, Benjamin; Turchyn, Alexandra V.

2017-01-01

Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62−) and elemental sulfur (S°) to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6) by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4) from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2). During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O) of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4), acid production, and mixed valence state sulfur species generated by the oxidation of the two different substrates suggests a metabolic flexibility in response to sulfur substrate availability. Our results demonstrate that microbial processing of mixed-valence-state sulfur species generates a significant sulfur isotope fractionation in acidic environments and oxidation of mixed-valence state sulfur species may produce sulfate with characteristic sulfur and oxygen isotope signatures. Elemental sulfur and tetrathionate are not only intermediate-valence state sulfur compounds that play a central role in sulfur oxidation pathways, but also key factors in shaping these isotope patterns. PMID:28861071

Calcium-aluminum-rich inclusions with fractionation and unidentified nuclear effects (FUN CAIs): II. Heterogeneities of magnesium isotopes and 26Al in the early Solar System inferred from in situ high-precision magnesium-isotope measurements

NASA Astrophysics Data System (ADS)

Park, Changkun; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.; Davis, Andrew M.; Bizzarro, Martin

2017-03-01

Calcium-aluminum-rich inclusions with isotopic mass fractionation effects and unidentified nuclear isotopic anomalies (FUN CAIs) have been studied for more than 40 years, but their origins remain enigmatic. Here we report in situ high precision measurements of aluminum-magnesium isotope systematics of FUN CAIs by secondary ion mass spectrometry (SIMS). Individual minerals were analyzed in six FUN CAIs from the oxidized CV3 carbonaceous chondrites Axtell (compact Type A CAI Axtell 2271) and Allende (Type B CAIs C1 and EK1-4-1, and forsterite-bearing Type B CAIs BG82DH8, CG-14, and TE). Most of these CAIs show evidence for excess 26Mg due to the decay of 26Al. The inferred initial 26Al/27Al ratios [(26Al/27Al)0] and the initial magnesium isotopic compositions (δ26Mg0) calculated using an exponential law with an exponent β of 0.5128 are (3.1 ± 1.6) × 10-6 and 0.60 ± 0.10‰ (Axtell 2271), (3.7 ± 1.5) × 10-6 and -0.20 ± 0.05‰ (BG82DH8), (2.2 ± 1.1) × 10-6 and -0.18 ± 0.05‰ (C1), (2.3 ± 2.4) × 10-5 and -2.23 ± 0.37‰ (EK1-4-1), (1.5 ± 1.1) × 10-5 and -0.42 ± 0.08‰ (CG-14), and (5.3 ± 0.9) × 10-5 and -0.05 ± 0.08‰ (TE) with 2σ uncertainties. We infer that FUN CAIs recorded heterogeneities of magnesium isotopes and 26Al in the CAI-forming region(s). Comparison of 26Al-26Mg systematics, stable isotope (oxygen, magnesium, calcium, and titanium) and trace element studies of FUN and non-FUN igneous CAIs indicates that there is a continuum among these CAI types. Based on these observations and evaporation experiments on CAI-like melts, we propose a generic scenario for the origin of igneous (FUN and non-FUN) CAIs: (i) condensation of isotopically normal solids in an 16O-rich gas of approximately solar composition; (ii) formation of CAI precursors by aggregation of these solids together with variable abundances of isotopically anomalous grains-possible carriers of unidentified nuclear (UN) effects; and (iii) melt evaporation of these precursors accompanied by crystallization under different temperatures and gas pressures, leading to the observed variations in mass-dependent isotopic fractionation (F) effects.

The Design and Use of Tungsten Coated TZM Molybdenum Tile Inserts in the DIII-D Tokamak Divertor

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

Murphy, Christopher; Nygren, R. E.; Chrobak, C P.

Future tokamak devices are envisioned to utilize a high-Z metal divertor with tungsten as theleading candidate. However, tokamak experiments with tungsten divertors have seen significantdetrimental effects on plasma performance. The DIII-D tokamak presently has carbon as theplasma facing surface but to study the effect of tungsten on the plasma and its migration aroundthe vessel, two toroidal rows of carbon tiles in the divertor region were modified with high-Zmetal inserts, composed of a molybdenum alloy (TZM) coated with tungsten. A dedicated twoweek experimental campaign was run with the high-Z metal inserts. One row was coated withtungsten containing naturally occurring levels ofmore » isotopes. The second row was coated withtungsten where the isotope 182W was enhanced from the natural level of 26% up to greater than90%. The different isotopic concentrations enabled the experiment to differentiate between thetwo different sources of metal migration from the divertor. Various coating methods wereexplored for the deposition of the tungsten coating, including chemical vapor deposition,electroplating, vacuum plasma spray, and electron beam physical vapor deposition. The coatingswere tested to see if they were robust enough to act as a divertor target for the experiment. Testsincluded cyclic thermal heating using a high power laser and high-fluence deuterium plasmabombardment. The issues associate with the design of the inserts (tile installation, thermal stress,arcing, leading edges, surface preparation, etc.), are reviewed. The results of the tests used toselect the coating method and preliminary experimental observations are presented.« less

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

NASA Astrophysics Data System (ADS)

Todd, E.; Stracke, A.

2013-12-01

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

What Mantle Processes Determine Isotopic

NASA Astrophysics Data System (ADS)

Tackley, P. J.; Xie, S.

2003-12-01

Isotopic measurements on Mid Ocean Ridge Basalts and Ocean Island Basalts indicate effective `ages' (from e.g., U-Pb or Sm-Nd systems) in the range 1-2 billion years- much less than the age of the Earth, even though melting should have been much more vigorous early on and skewed the mean time since melting to older values. This relatively young `age' has generally been explained in terms of stretching of heterogeneities by mantle convection, which might reduce them to dimensions too small to be individually distinguishable in short timescales of less than 1 Gyr. On the other hand, published numerical models that use tracers to track differentiated material (Christensen and Hofmann, 1994, Davies, 2002) suggest that Earth-like `ages' can be obtained without taking stretching-induced erasure of tracer signatures into account, although this might effectively happen if the lengthscale for sampling the isotope systems was large enough. In those models, the only explicit mechanism for resetting isotope systems was re-melting, but for this to explain the isotopic ages observed for basalts, the global rate of melting in the recent past would have had to be very much higher than present-day values. To investigate stretching vs. re-melting we have conducted numerical experiments of a cooling mantle with plate tectonics, differentiation and evolution of important isotopic systems. The time of last melting and the total strain is tracked on each tracer (in addition to isotopic information). The results confirm that a model matching today's crustal production rate and with a reasonable secular cooling history generates `ages' that are substantially larger than those observed, with the extent of crustal settling above the CMB making some difference but not enough. The effect of sampling lengthscale on observed `age' is also tested and found to be insufficient to explain the data. Thus, these results reaffirm the importance of stretching as a key mechanism for effectively deleting older heterogeneities. From analysis of strain vs. age and matching of the observed ages, it is estimated that erasure of heterogeneities occurs at strains of 103-104, somewhat larger than has often been assumed.

A modified procedure for measuring oxygen-18 content of nitrate

NASA Astrophysics Data System (ADS)

Ahmed, M. A.; Aly, A. I. M.; Abdel Monem, N.; Hanafy, M.; Gomaa, H. E.

2012-11-01

SummaryMass spectrometric analysis of O-isotopic composition of nitrate has many potential applications in studies of environmental processes. Through this work, rapid, reliable, precise, broadly applicable, catalyst-free, low-priced and less labor intensive procedure for measuring δ18O of nitrate using Isotope Ratio Mass Spectrometer has been developed and implemented. The conditions necessary to effect complete nitrate recovery and complete removal of other oxygen containing anions and dissolved organic carbon (DOC) without scarifying the isotopic signature of nitrate were investigated. The developed procedure consists of two main parts: (1) wet chemistry train for extraction and purification of nitrate from the liquid matrix; (2) off-line pyrolysis of extracted nitrate salt with activated graphite at 550 °C for 30 min. The conditions necessary to effect complete nitrate recovery and complete removal of other oxygen containing compounds were investigated. Dramatic reduction in processing times needed for analysis of δ18O of nitrate at natural abundance level was achieved. Preservation experiments revealed that chloroform (99.8%) is an effective preservative. Isotopic contents of some selected nitrate salts were measured using the modified procedure and some other well established methods at two laboratories in Egypt and Germany. Performance assessment of the whole developed analytical train was made using internationally distributed nitrate isotopes reference materials and real world sample of initial zero-nitrate content. The uncertainty budget was evaluated using the graphical nested hierarchal approach. The obtained results proved the suitability for handling samples of complicated matrices. Reduction of consumables cost by about 80% was achieved.

Bose-Fermi symmetry in the odd-even gold isotopes

NASA Astrophysics Data System (ADS)

Thomas, T.; Régis, J.-M.; Jolie, J.; Heinze, S.; Albers, M.; Bernards, C.; Fransen, C.; Radeck, D.

2014-05-01

In this work the results of an in-beam experiment on 195Au are presented, yielding new spins, multipole mixing ratios, and new low-lying states essential for the understanding of this nucleus. The positive-parity states from this work together with compiled data from the available literature for 185-199Au are compared to Interacting Boson Fermion Model calculations employing the Spin(6) Bose-Fermi symmetry. The evolution of the parameters for the τ splitting and the J splitting reveals a smooth behavior. Thereby, a common description based on the Bose-Fermi symmetry is found for 189-199Au. Furthermore, the calculated E2 transition strengths are compared to experimental values with fixed effective boson and fermion charges for all odd-even gold isotopes, emphasizing that the Spin(6) Bose-Fermi symmetry is valid for the gold isotopes.

Carbon Isotope Fractionation Effects During Degradation of Methyl Halides in Agricultural Soils

NASA Astrophysics Data System (ADS)

Miller, L. G.; Baesman, S. M.; Oremland, R. S.; Bill, M.; Goldstein, A. H.

2001-12-01

Fumigation of agricultural soils prior to planting row crops constitutes the largest anthropogenic source of methyl bromide (MeBr) to the atmosphere. Typically, more than 60% of the MeBr added is lost to the atmosphere during the 5-6 day fumigation period. The remainder is oxidized by bacteria or otherwise degraded in the soil. In experiments using washed cells of methylotrophic bacteria isolated from agricultural soil (strain IMB-1), oxidation of MeBr, methyl chloride (MeCl) and methyl iodide to CO2 resulted in large (up to 70‰ ) fractionation of stable carbon isotopes (Miller, et al. 2001). By contrast, fractionation measured in field soils using both in situ techniques and bottle incubations with MeBr was less than 35‰ . This discrepancy was initially attributed to the large transportation losses that occur without isotopic fractionation during field fumigation. However, this rationale cannot explain why bottle incubations with soil resulted in lower fractionation factors than incubations with bacterial cultures. We conducted additional laboratory bottle experiments to examine the biological and chemical controls of carbon isotope fractionation during degradation of MeBr and MeCl by soils and bacteria. Soils were collected from a strawberry field in Santa Cruz County, California within two weeks of the start of each experiment. The rate of removal of methyl halides from the headspace was greatest during incubations at soil moisture contents around 8%. Increasing the amount of soil and hence native bacteria in each bottle minimized the lag in uptake by up to several days. No lag was observed during incubations of soils with added IMB-1. Stable isotope fractionation factors were similar for degradation by live soil and live soil with added IMB-1. Heat-killed controls of cell cultures showed little uptake (<10% over 5 days) and no isotope fractionation. Heat-killed soil controls, by contrast, demonstrated significant loss of MeBr (20-30%) with isotope fractionation factors comparable to live soil. Loss of MeCl during the same time was lower (<10%) however isotope fractionation was comparable to live soil. Our results indicate that bacterial oxidation in soil rapidly consumes methyl halides but only partly controls the fractionation of carbon isotopes. Two chemical processes also act to remove MeBr in soil, hydrolysis and nucleophilic exchange with Cl-, both of which result in fractionation of carbon isotopes. Hydrolysis does not remove MeCl. It seems likely that fractionation in soil could result from a combination of biological and chemical processes, but since they all have sizeable fractionation factors associated with the removal of methyl halides, the relative rate of each process may not be as important as the total amount of methyl halide degraded. Attempts to constrain our understanding of atmospheric methyl halide budgets using stable isotope signatures of sources and sinks will have to rely on this type of information regarding the net isotopic impact of methyl halide uptake by soils. Miller, L.G., Kalin, R.M., McCauley, S.E., Hamilton, J.T.G., Harper, D.B., Millet, D.B., Oremland, R.S., and Goldstein, A.H. (2001) Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria, PNAS, vol. 98, 5833-5837.

Application of Stable Isotope-Assisted Metabolomics for Cell Metabolism Studies

PubMed Central

You, Le; Zhang, Baichen; Tang, Yinjie J.

2014-01-01

The applications of stable isotopes in metabolomics have facilitated the study of cell metabolisms. Stable isotope-assisted metabolomics requires: (1) properly designed tracer experiments; (2) stringent sampling and quenching protocols to minimize isotopic alternations; (3) efficient metabolite separations; (4) high resolution mass spectrometry to resolve overlapping peaks and background noises; and (5) data analysis methods and databases to decipher isotopic clusters over a broad m/z range (mass-to-charge ratio). This paper overviews mass spectrometry based techniques for precise determination of metabolites and their isotopologues. It also discusses applications of isotopic approaches to track substrate utilization, identify unknown metabolites and their chemical formulas, measure metabolite concentrations, determine putative metabolic pathways, and investigate microbial community populations and their carbon assimilation patterns. In addition, 13C-metabolite fingerprinting and metabolic models can be integrated to quantify carbon fluxes (enzyme reaction rates). The fluxome, in combination with other “omics” analyses, may give systems-level insights into regulatory mechanisms underlying gene functions. More importantly, 13C-tracer experiments significantly improve the potential of low-resolution gas chromatography-mass spectrometry (GC-MS) for broad-scope metabolism studies. We foresee the isotope-assisted metabolomics to be an indispensable tool in industrial biotechnology, environmental microbiology, and medical research. PMID:24957020

Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

NASA Astrophysics Data System (ADS)

Nielson, Kristine E.; Bowen, Gabriel J.

2010-03-01

Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles.

PubMed Central

Huang, T M; Hung, H C; Chang, T C; Chang, G G

1998-01-01

Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2, 4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (pi) for deuterium for the transition state (piT) increased when the pH of the solution was raised. At pL 11.0, the piT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles. PMID:9461520

Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles.

PubMed

Huang, T M; Hung, H C; Chang, T C; Chang, G G

1998-02-15

Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2, 4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (pi) for deuterium for the transition state (piT) increased when the pH of the solution was raised. At pL 11.0, the piT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles.

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 investigating the kinetics of equilibration of boron environment and isotopic composition are therefore required to refine our understanding of boron coprecipitation in carbonates and thus the theory behind the use of boron isotopes as an ocean pH proxy.

Calculation of gas-flow in plasma reactor for carbon partial oxidation

NASA Astrophysics Data System (ADS)

Bespala, Evgeny; Myshkin, Vyacheslav; Novoselov, Ivan; Pavliuk, Alexander; Makarevich, Semen; Bespala, Yuliya

2018-03-01

The paper discusses isotopic effects at carbon oxidation in low temperature non-equilibrium plasma at constant magnetic field. There is described routine of experiment and defined optimal parameters ensuring maximum enrichment factor at given electrophysical, gas-dynamic, and thermodymanical parameters. It has been demonstrated that at high-frequency generator capacity of 4 kW, supply frequency of 27 MHz and field density of 44 mT the concentration of paramagnetic heavy nuclei 13C in gaseous phase increases up to 1.78 % compared to 1.11 % for natural concentration. Authors explain isotopic effect decrease during plasmachemical separation induced by mixing gas flows enriched in different isotopes at the lack of product quench. With the help of modeling the motion of gas flows inside the plasma-chemical reactor based on numerical calculation of Navier-Stokes equation authors determine zones of gas mixing and cooling speed. To increase isotopic effects and proportion of 13C in gaseous phase it has been proposed to use quench in the form of Laval nozzle of refractory steel. The article represents results on calculation of optimal Laval Nozzle parameters for plasma-chemical reactor of chosen geometry of. There are also given dependences of quench time of products on pressure at the diffuser output and on critical section diameter. Authors determine the location of quench inside the plasma-chemical reactor in the paper.

Modeling experimental stable isotope results from CO2 adsorption and diffusion experiments

NASA Astrophysics Data System (ADS)

Larson, T. E.

2012-12-01

Transport of carbon dioxide through porous media can be affected by diffusion, advection and adsorption processes. Developing new tools to understand which of these processes dominates migration of CO2 or other gases in the subsurface is important to a wide range of applications including CO2 storage. Whereas advection rates are not affected by isotope substitution in CO2, adsorption and diffusion constants are. For example, differences in the binary diffusion constant calculated between C12O2-He and C13O2-He results in a carbon isotope fractionation whereby the front of the chromatographic peak is enriched in carbon-12 and the tail of the peak is enriched in carbon-13. Interestingly, adsorption is shown to have an opposite, apparent inverse affect whereby the lighter isotopologues of CO2 are preferentially retained by the chromatographic column and the heavier isotopologues are eluted first. This apparent inverse chromatographic effect has been ascribed to Van der Waals dispersion forces. Smaller molar volumes of the heavier isotopologues resulting from increased bond strength (shorter bond length) effectively decreases Van der Waals forces in heavier isotopologues compared to lighter isotopologues. Here we discuss the possible application of stable isotope values measured across chromatographic peaks to differentiate diffusion-dominated from adsorption-dominated transport processes for CO2. Separate 1-dimensional flow-through columns were packed with quartz and illite, and one remained empty. Dry helium was used as a carrier gas. Constant flow rate, temperature and column pressure were maintained. After background CO2 concentrations were minimized and constant, a sustained pulse of CO2 was injected at the head of the column and the effluent was sampled at 4 minute intervals for CO2 concentration, and carbon and oxygen isotope ratios. The quartz-sand packed and empty columns resulted in similar trends in concentration and isotope ratios whereby CO2 concentrations steadily increased and became constant after two pore volumes of CO2 flushed through the column. Carbon and oxygen isotope values of the front of the peak (first pore volume) are 2‰ and 5‰ lower than the injected CO2 values, respectively. These results are fit very well using a mass transfer model that only includes binary diffusion between CO2 and helium that account for isotope substitution in the reduced mass coefficient. In contrast to these diffusion-dominated systems, CO2 break through curves from the illite packed column show strong adsorption effects that include a +180‰ increase in the carbon isotope ratio at the front of the peak followed by a 20‰ decrease. Up to 20 pore volumes of CO2 were flushed through the column before the carbon and oxygen isotope values stabilized to their starting values. These adsorption effects cannot be modeled using mass isotope effects alone, and instead must include additional parameters such as volume effects. These results demonstrate the importance of understanding the isotopic effects of CO2 in different substrates, and potentially offers a tracer tool that can be used to quantify surface area, transport distance, and surface reactivity of CO2. Additional applications may include more affectively determining transfer rates of CO2 across low permeability zones.

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

Jamieson-Hanes, Julia H.; Shrimpton, Heather K.; Veeramani, Harish

A flow-through cell experiment was conducted to evaluate Zn isotope fractionation during ZnS precipitation under microbially-mediated sulfate-reducing conditions. Synthetic groundwater containing 0.90 mM Zn was pumped through a cell containing creek sediment that was biostimulated to promote sulfate reducing conditions. Real-time, in situ X-ray absorption spectroscopy (XAS) was applied at the Zn K-edge to collect spectra via a Kapton® window in the front of the cell over the course of the experiment. Aqueous effluent samples were collected and analysed to determine concentrations of anions and cations, and Zn isotope ratios. The flow rate was increased step-wise during the experiment tomore » modify the residence time and produce changes in the extent of sulfate reduction, which in turn controlled the extent of ZnS precipitation. Greater enrichment in the heavier isotope in the aqueous phase relative to the input solution was associated with more extensive Zn removal. A Rayleigh curve was fit to the isotope data, where ε = -0.27 ± 0.06‰ (2σ). Evaluation of Zn isotope fractionation under controlled flow conditions is critical to improve the efficacy of this powerful analytical technique when applied to natural systems or remediation projects in the field.« less

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.

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

USGS Publications Warehouse

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

2002-01-01

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

A free-air system for long-term stable carbon isotope labeling of adult forest trees

EPA Science Inventory

Stable carbon (C) isotopes, in particular employed in labeling experiments, are an ideal tool to broaden our understanding of C dynamics in trees and forest ecosystems. Here, we present a free-air exposure system, named isoFACE, designed for long-term stable C isotope labeling in...

Highly enriched multiply-labeled stable isotopic compounds as atmospheric tracers

DOEpatents

Goldblatt, M.; McInteer, B.B.

1974-01-29

Compounds multiply-labeled with stable isotopes and highly enriched in these isotopes are readily capable of detection in tracer experiments involving high dilutions. Thus, for example, /sup 13/C/sup 18/O/sub 2/ provides a useful tracer for following atmospheric pol lution produced as a result of fossil fuel burning. (Official Gazette)

Absence of fractionation of mercury isotopes during trophic transfer of methylmercury to freshwater fish in captivity

USGS Publications Warehouse

Kwon, Sae Yun; Blum, Joel D.; Carvan, Michael J.; Basu, Niladri; Head, Jessica A.; Madenjian, Charles P.; David, Solomon R.

2012-01-01

We performed two controlled experiments to determine the amount of mass-dependent and mass-independent fractionation (MDF and MIF) of methylmercury (MeHg) during trophic transfer into fish. In experiment 1, juvenile yellow perch (Perca flavescens) were raised in captivity on commercial food pellets and then their diet was either maintained on unamended food pellets (0.1 μg/g MeHg) or was switched to food pellets with 1.0 μg/g or 4.0 μg/g of added MeHg, for a period of 2 months. The difference in δ202Hg (MDF) and Δ199Hg (MIF) between fish tissues and food pellets with added MeHg was within the analytical uncertainty (δ202Hg, 0.07 ‰; Δ199Hg, 0.06 ‰), indicating no isotope fractionation. In experiment 2, lake trout (Salvelinus namaycush) were raised in captivity on food pellets and then shifted to a diet of bloater (Coregonus hoyi) for 6 months. The δ202Hg and Δ199Hg of the lake trout equaled the isotopic composition of the bloater after 6 months, reflecting reequilibration of the Hg isotopic composition of the fish to new food sources and a lack of isotope fractionation during trophic transfer. We suggest that the stable Hg isotope ratios in fish can be used to trace environmental sources of Hg in aquatic ecosystems.

Absence of fractionation of mercury isotopes during trophic transfer of methylmercury to freshwater fish in captivity

PubMed Central

Kwon, Sae Yun; Blum, Joel D; Carvan, Michael J; Basu, Niladri; Head, Jessica A; Madenjian, Charles P; David, Solomon R

2015-01-01

We performed two controlled experiments to determine the amount of mass-dependent and mass-independent fractionation (MDF and MIF) of methylmercury (MeHg) during trophic transfer into fish. In Experiment 1, juvenile yellow perch (Perca flavescens) were raised in captivity on commercial food pellets and then their diet was either maintained on un-amended food pellets (0.1 µg/g MeHg), or was switched to food pellets with 1.0 µg/g or 4.0 µg/g of added MeHg, for a period of 2 months. The difference in δ202Hg (MDF) and Δ199Hg (MIF) between fish tissues and food pellets with added MeHg were within the analytical uncertainty (δ202Hg; 0.07 ‰, Δ199Hg; 0.06 ‰) indicating no isotope fractionation. In Experiment 2, lake trout (Salvelinus namaycush) were raised in captivity on food pellets, and then shifted to a diet of bloater (Coregonus hoyi) for 6 months. The δ202Hg and Δ199Hg of the lake trout equaled the isotopic composition of the bloater after 6 months, reflecting re-equilibration of the Hg isotopic composition of the fish to new food sources and a lack of isotope fractionation during trophic transfer. We suggest that the stable Hg isotope ratios in fish can be used to trace environmental sources of Hg in aquatic ecosystems. PMID:22681311

Boron Isotopic Composition Correlates with Ultra-Structure in a - Sea Coral Lophelia Pertusa: Implications for Biomineralization and - PH

NASA Astrophysics Data System (ADS)

Blamart, D.; Rollion-Bard, C.; Meibom, A.; Cuif, J.; Juillet-Leclerc, A.; Dauphin, Y.; Douarin, M.

2007-12-01

The geochemistry (stable isotopes and trace elements) of biogenic carbonates has been widely used for more than fifty years to reconstruct past climatic variability. During this time, the studies were mainly based on bulk sampling limiting sometimes the interpretations of the geochemical data as paleoclimatic proxies. Recently, high spatial resolution sampling techniques, such as micro-mill and SIMS, have been employed in the study of C, O and B isotopic compositions and trace elements (Mg, Sr) in the skeletons of a variety of (deep-sea) coral species. These studies have documented dramatic 'vital effects' and uncovered a systematic relationship between skeletal ultra-structure and stable isotopic composition. The formation of skeleton corals follows a universal two-step growth process. At the tips of the skeletal structures, the mineralizing cell layer produces centers of calcification (COC) or, equivalently, Early Mineralization Zone (EMZ). These EMZ are subsequently overgrown by fibrous aragonite(FA) consisting of cyclically added layers. The EMZ are characterized by systematically lighter C and O isotopic compositions compared with the adjacent FA. A number of geochemical models have been proposed, in which this systematic stable isotopic difference between EMZ and FA is ascribed to a biologically induced variation in the pH of a proposed Extra-cytoplasmic Calcifying Fluid (ECF) reservoir. In these models, relatively high pH conditions during the formation of EMZ result in relatively light C and O isotopic compositions compared with FA, which form under generally lower pH conditions. A direct test of such models would be possible if the Boron isotopic composition, which is pH sensitive, of EMZ and FA could be measured. We performed ion microprobe d11B measurements for EMZ and FA in Lophelia pertusa, a deep-sea coral common in the North-East Atlantic Ocean. We observe a systematic difference in B isotopic composition between the EMZ and FA skeleton. In EMZ, the measured δ11B values are consistently low. Fibrous aragonite is characterized by systematically higher d11B values, but also display B isotopic heterogeneity associated with specific growth bands in the calyx wall. The magnitude of the observed B isotopic variations cannot be explained by changes in environmental conditions and are likely caused by biological processes involved in the biomineralization of new skeleton; i.e. 'vital' effects. The observed B isotopic variations are opposite to the predictions of geochemical models for vital effects. Our data indicate that pH variations are not responsible for the observed stable isotopic fractionations. Geochemical models therefore do not provide an adequate framework within which to understand coral skeletal formation. Without a better understanding of these processes, which require experiments, the use of B isotopic composition to reconstruct paleo-pH variations in the oceans must be considered problematic - at least as far as Lophelia pertusa is concerned.

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.

The Effect of Parasite Infection on Stable Isotope Turnover Rates of δ15N, δ13C and δ34S in Multiple Tissues of Eurasian Perch Perca fluviatilis.

PubMed

Yohannes, Elizabeth; Grimm, Claudia; Rothhaupt, Karl-Otto; Behrmann-Godel, Jasminca

2017-01-01

Stable isotope analysis of commercially and ecologically important fish can improve understanding of life-history and trophic ecology. However, accurate interpretation of stable isotope values requires knowledge of tissue-specific isotopic turnover that will help to describe differences in the isotopic composition of tissues and diet. We performed a diet-switch experiment using captive-reared parasite-free Eurasian perch (Perca fluviatilis) and wild caught specimens of the same species, infected with the pike tapeworm Triaenophorus nodulosus living in host liver tissue. We hypothesize that metabolic processes related to infection status play a major role in isotopic turnover and examined the influence of parasite infection on isotopic turn-over rate of carbon (δ13C), nitrogen (δ15N) and sulphur (δ34S) in liver, blood and muscle. The δ15N and δ13C turnovers were fastest in liver tissues, followed by blood and muscle. In infected fish, liver and blood δ15N and δ13C turnover rates were similar. However, in infected fish, liver and blood δ13C turnover was faster than that of δ15N. Moreover, in infected subjects, liver δ15N and δ13C turnover rates were three to five times faster than in livers of uninfected subjects (isotopic half-life of ca.3-4 days compared to 16 and 10 days, respectively). Blood δ34S turnover rate were about twice faster in non-infected individuals implying that parasite infection could retard the turnover rate of δ34S and sulphur containing amino acids. Slower turnover rate of essential amino acid could probably decrease individual immune function. These indicate potential hidden costs of chronic and persistent infections that may have accumulated adverse effects and might eventually impair life-history fitness. For the first time, we were able to shift the isotope values of parasites encapsulated in the liver by changing the dietary source of the host. We also report variability in isotopic turnover rates between tissues, elements and between infected and parasite-free individuals. These results contribute to our understanding of data obtained from field and commercial hatcheries; and strongly improve the applicability of the stable isotope method in understanding life-history and trophic ecology of fish populations.

The Effect of Parasite Infection on Stable Isotope Turnover Rates of δ15N, δ13C and δ34S in Multiple Tissues of Eurasian Perch Perca fluviatilis

PubMed Central

Yohannes, Elizabeth; Grimm, Claudia; Rothhaupt, Karl-Otto; Behrmann-Godel, Jasminca

2017-01-01

Stable isotope analysis of commercially and ecologically important fish can improve understanding of life-history and trophic ecology. However, accurate interpretation of stable isotope values requires knowledge of tissue-specific isotopic turnover that will help to describe differences in the isotopic composition of tissues and diet. We performed a diet-switch experiment using captive-reared parasite-free Eurasian perch (Perca fluviatilis) and wild caught specimens of the same species, infected with the pike tapeworm Triaenophorus nodulosus living in host liver tissue. We hypothesize that metabolic processes related to infection status play a major role in isotopic turnover and examined the influence of parasite infection on isotopic turn-over rate of carbon (δ13C), nitrogen (δ15N) and sulphur (δ34S) in liver, blood and muscle. The δ15N and δ13C turnovers were fastest in liver tissues, followed by blood and muscle. In infected fish, liver and blood δ15N and δ13C turnover rates were similar. However, in infected fish, liver and blood δ13C turnover was faster than that of δ15N. Moreover, in infected subjects, liver δ15N and δ13C turnover rates were three to five times faster than in livers of uninfected subjects (isotopic half-life of ca.3-4 days compared to 16 and 10 days, respectively). Blood δ34S turnover rate were about twice faster in non-infected individuals implying that parasite infection could retard the turnover rate of δ34S and sulphur containing amino acids. Slower turnover rate of essential amino acid could probably decrease individual immune function. These indicate potential hidden costs of chronic and persistent infections that may have accumulated adverse effects and might eventually impair life-history fitness. For the first time, we were able to shift the isotope values of parasites encapsulated in the liver by changing the dietary source of the host. We also report variability in isotopic turnover rates between tissues, elements and between infected and parasite-free individuals. These results contribute to our understanding of data obtained from field and commercial hatcheries; and strongly improve the applicability of the stable isotope method in understanding life-history and trophic ecology of fish populations. PMID:28046021

Experimentally determined isotope effect during Mg-Fe interdiffusion in olivine

NASA Astrophysics Data System (ADS)

Sio, C. K. I.; Roskosz, M.; Dauphas, N.; Bennett, N.; Mock, T. D.; Shahar, A.

2017-12-01

Isotopic fractionation provides the most direct means to investigate the nature of chemical zoning in minerals, which can be produced by either diffusive transport or crystal growth. Misinterpreting the nature of chemical zoning can result in erroneous conclusions regarding magmatic cooling rates and diffusion timescales. Isotopes are useful in this regard because the light isotopes diffuse faster than their heavier counterparts. As a result, isotopic fractionations should be associated with chemical zoning profiles if they are diffusion-driven. In contrast, little isotopic fractionation is associated with crystal growth during slow cooling at magmatic temperatures. The isotope effect for diffusion is described by β and is related to the mass (m) and diffusivity (D) of isotopes i and j of an element via: Di/Dj = (mj/mi)β. To model isotopic profiles, knowledge of β is required. Several estimates of β for Mg and Fe diffusion in olivine have been reported using natural samples but these estimates are uncertain because they depend on the choice of modeling parameters (Sio et al., 2013; Oeser et al., 2015; Collinet et al., 2017). We have experimentally determined β for Fe (βFe) in olivine as a function of crystallographic orientation, composition, and temperature. Thirty experiments have been conducted by juxtaposing crystallographically oriented olivine crystals to make Fo83.4-Fo88.8 and Fo88.8-Fo100 diffusion couples. These diffusion couples were annealed in a 1 atm gas mixing furnace at 1200 °C, 1300 °C or 1400 °C at QFM - 1.5 for up to 15 days. Chemical profiles were characterized using an electron microprobe and isotopic analyses were done using laser ablation MC-ICPMS. We found a crystallographic dependence of βFe for the Fo88.8-Fo100 couple where βFe [100] ≈ βFe [010] > βFe [001]. For the Fo83.4-Fo88.8 couple, βFe is 0.16 ± 0.09 (2σ) for all 3 major crystallographic axes. A temperature dependence of βFe could not be resolved. These experimentally determined β-values can be used in conjunction with the Mg-Fe diffusivities given in Dohmen and Chakraborty (2007) to simultaneously model the chemical-isotopic profiles of olivine to retrieve cooling and crystallization histories of magmatic rocks.

Potential of calcium isotopes to identify fractionations in vegetation: experimental approach

NASA Astrophysics Data System (ADS)

Cobert, F.; Schmitt, A.; Bourgade, P.; Stille, P.; Chabaux, F. J.; Badot, P.; Jaegler, T.

2010-12-01

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 cooccuring geochemical and biological processes 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, 5 (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 to be infinite. 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). Our results show, in accord with previously published field studies, that the bean organs are all enriched in the light 40Ca isotope compared to the nutritive solution (e.g. Wigand et al., 2005; Page et al., 2008; Cenki-Tok et al., 2009; Holmden and Bélanger, 2010). We identify two fractionation levels. The first occurs during the uptake of the nutrient elements by the lateral roots. This implies that the main mechanisms of light isotope enrichments in the plant are due to electrochemical gradient transport processes taking place at this interface. The second fractionation can be observed within the plant itself and is due to the nature of the considered organ itself. Indeed structural reservoirs (primary roots, stem, reproductive organs) incorporate more the light 40Ca isotope compared to the transfer reservoirs (lateral roots, xylem sap, leaves). This could be linked to ion-exchange reactions with the pectins in the cell walls of the conducting xylem. However, we also observe that bean organs from L4 experiment growing in nutrient solutions with lower Ca concentrations and low pH behave slightly differently and show reduced Ca isotopic fractionations compared with beans from the other experiments. All these results indicate that there is no simple correlation between Ca isotopic variations, Ca content and pH of the nutrient solution, and that also biological effects have to be involved. The data confirm the potential of the Ca isotopic system for tracing biological fractionations in natural ecosystems. Wiegand et al., (2005). Geophys. Res. Lett., 32, L11404 Page et al., (2008). Biogeochemistry, 88, 1-13 Cenki-Tok et al,. (2009). Geochim. Cosmochim. Acta, 73, 2215-2228 Holmden and Bélanger(2010). Geochim. Cosmochim. Acta, 74, 995-1015

Status of double beta decay experiments using isotopes other than 136Xe

NASA Astrophysics Data System (ADS)

Pandola, L.

2014-09-01

Neutrinoless double beta decay is a lepton-number violating process predicted by many extensions of the standard model. It is actively searched for in several candidate isotopes within many experimental projects. The status of the experimental initiatives which are looking for the neutrinoless double beta decay in isotopes other than 136Xe is reviewed, with special emphasis given to the projects that passed the R&D phase. The results recently released by the experiment GERDA are also summarized and discussed. The GERDA data give no positive indication of neutrinoless double beta decay of 76Ge and disfavor in a model-independent way the long-standing observation claim on the same isotope. The lower limit reported by GERDA for the half-life of neutrinoless double beta decay of 76Ge is T1/20ν > 2.1 ṡ1025 yr (90% C.L.), or T1/20ν > 3.0 ṡ1025 yr, when combined with the results of other 76Ge predecessor experiments.

Mass-independent fractionation of mercury isotopes during photochemical reduction in freshwater systems

NASA Astrophysics Data System (ADS)

Rose, C. H.; Bergquist, B. A.; Blum, J. D.

2009-12-01

Mercury is a globally distributed environmental toxin. Both inorganic and methylated species have severe detrimental effects on humans and animals, but it is methyl mercury (MeHg) that bioaccumulates in food webs and results in significant human exposure via fish consumption. Photochemical reduction of aqueous Hg species to dissolved gaseous Hg(0) can result in a net transfer of Hg from aquatic systems to the atmosphere, making it unavailable for methylation. In addition, photo-reduction of MeHg is an alternative fate to bioaccumulation for this powerful neurotoxin. Both mass-dependent isotope fractionation (MDF) and mass-independent fractionation (MIF) are observed in natural samples. MIF is the deviation in isotope ratios from those predicted by MDF based on 202Hg/198Hg. Bergquist and Blum 2007 showed that aqueous photo-reduction of Hg2+ and MeHg in the presence of dissolved natural organic matter results not only in Rayleigh-type MDF but also significant MIF, with the odd isotopes 199Hg and 201Hg being preferentially retained in the reactant (soluble) phase. Berquist and Blum 2007 also observed that the ratio of the MIF for the odd isotopes was different for each of the photo-reduction pathways (MeHg versus Hg2+) and suggested this ratio could be unique to certain pathways, which might allow identification of photo-reduction among other pathways in natural samples. They also suggested that the magnitude of MIF might relate quantitatively to the amount of photo-reduction Hg undergoes in aqueous systems. To better understand the causes of MIF and its capacity along with MDF as a tool for tracing photo-reduction of Hg, further experiments mimicking the freshwater photo-reduction of Hg2+ and MeHg were carried out. Each species was photo-reduced in the presence of Suwannee River Fulvic Acid with different portions of the electromagnetic spectrum blocked by filters. Bergquist and Blum 2007 suggested the magnetic isotope effect (MIE) as the cause of the MIF they observed. The MIE should be expressed during reactions involving excited radical pair intermediates and therefore should be affected by the wavelengths of light available for radical production. Experiments were performed (1) under full spectrum, (2) with over 90 percent of UVB rays blocked and (3) with over 95 percent of both UVA and UVB rays blocked. These experiments were run simultaneously under natural sunlight. The Hg2+ full spectrum experiments showed an 84 percent loss of Hg2+ to Hg vapor, which was larger than the 77 percent loss of the UVB blocked reactor and the 14 percent loss of the UVA and UVB blocked reactor. Significant differences in isotope ratios were also observed, and initial results suggest that MIF may be most sensitive to UVA. Since radical production is key to the MIE, this suggests that the UVA region may be most important to producing Hg radicals. In contrast, the losses in all three MeHg reservoirs were similar suggesting that the UVA and UVB portions of the spectrum are not critical in MeHg photo-reduction.

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

PubMed

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

2016-10-04

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

Physical and Biological Carbon Isotope Fractionation in Methane During Gas-Push-Pull-Tests

NASA Astrophysics Data System (ADS)

Gonzalez-Gil, G.; Schroth, M. H.; Gomez, K.; Zeyer, J.

2005-12-01

Stable isotope analyses have become a common tool to assess microbially-mediated processes in subsurface environments. We investigated if stable carbon isotope analysis can be used as a tool to complement gas push-pull tests (GPPTs), a novel technique that was recently developed and tested for the in-situ quantification of CH4 oxidation in soils. During a GPPT a gas mixture containing CH4, O2 and nonreactive tracer gases is injected into the soil, where CH4 is oxidized by indigenous microorganisms. Thereafter, a blend of injected gas mixture and soil air is extracted from the same location, and CH4 oxidation is quantified from an analysis of extracted CH4 and tracer gases. To assess the magnitude of physical isotope fractionation due to molecular diffusion during GPPTs, we conducted laboratory experiments in the absence of microbial activity in a 1m-high, 1m-diameter tank filled with dry sand. During the GPPTs' extraction phase, the isotopic composition of methane was analyzed. Results indicated strong carbon isotope fractionation (>20 per mil) during GPPTs. To assess the combined effect of physical and biological isotope fractionation, numerical simulations of GPPTs were conducted in which microbial CH4 isotope fractionation was simulated using first-order rate constants and microbial kinetic isotope fractionation factors previously reported for methane oxidation in landfill environments. Results of these simulations indicated that for small CH4 oxidation rates, overall isotope fractionation in CH4 is dominated by physical fractionation. Conversely, for high CH4 oxidation rates, overall fractionation is dominated by biological fractionation. Thus, CH4 isotope fractionation data alone from a single GPPT cannot be used to assess microbial CH4 oxidation. However, biological fractionation may be quantified if physical fractionation due to diffusion is known. This can be achieved by conducting two sequential GPPTs, with microbial activity being inhibited in the second test.

Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

NASA Astrophysics Data System (ADS)

Migeon, Valérie; Bourdon, Bernard; Pili, Eric; Fitoussi, Caroline

2018-06-01

As an attempt to prevent illicit trafficking of nuclear materials, it is critical to identify the origin and transformation of uranium materials from the nuclear fuel cycle based on chemical and isotope tracers. The potential of molybdenum (Mo) isotopes as tracers is considered in this study. We focused on leaching, the first industrial process used to release uranium from ores, which is also known to extract Mo depending on chemical conditions. Batch experiments were performed in the laboratory with pH ranging from 0.3 to 5.5 in sulfuric acid. In order to span a large range in uranium and molybdenum yields, oxidizers such as nitric acid, hydrogen peroxide and manganese dioxide were also added. An enrichment in heavy Mo isotopes is produced in the solution during leaching of a granitic uranium ore, when Mo recovery is not quantitative. At least two Mo reservoirs were identified in the ore: ∼40% as Mo oxides soluble in water or sulfuric acid, and ∼40% of Mo hosted in sulfides soluble in nitric acid or hydrogen peroxide. At pH > 1.8, adsorption and/or precipitation processes induce a decrease in Mo yields with time correlated with large Mo isotope fractionations. Quantitative models were used to evaluate the relative importance of the processes involved in Mo isotope fractionation: dissolution, adsorption, desorption, precipitation, polymerization and depolymerization. Model best fits are obtained when combining the effects of dissolution/precipitation, and adsorption/desorption onto secondary minerals. These processes are inferred to produce an equilibrium isotope fractionation, with an enrichment in heavy Mo isotopes in the liquid phase and in light isotopes in the solid phase. Quantification of Mo isotope fractionation resulting from uranium leaching is thus a promising tool to trace the origin and transformation of nuclear materials. Our observations of Mo leaching are also consistent with observations of natural Mo isotope fractionation taking place during chemical weathering in terrestrial environments where the role of secondary processes such as adsorption is significant.

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.

Initial results from the Caltech/DRSI balloon-borne isotope experiment

NASA Technical Reports Server (NTRS)

Schindler, S. M.; Buffington, A.; Christian, E. C.; Grove, J. E.; Lau, K. H.; Stone, E. C.; Rasmussen, I. L.; Laursen, S.

1985-01-01

The Caltech/DSRI balloonborne High Energy Isotope Spectrometer Telescope (HEIST) was flown successfully from Palestine, Texas on 14 May, 1984. The experiment was designed to measure cosmic ray isotopic abundances from neon through iron, with incident particle energies from approx. 1.5 to 2.2 GeV/nucleon depending on the element. During approximately 38 hours at float altitude, 100,000 events were recorded with Z or = 6 and incident energies approx. 1.5 GeV/nucleon. We present results from the ongoing data analysis associated with both the preflight Bevalac calibration and the flight data.

Initial results from the Caltech/DSRI balloon-borne isotope experiment

NASA Technical Reports Server (NTRS)

Schindler, S. M.; Buffington, A.; Christian, E. C.; Grove, J. E.; Lau, K. H.; Stone, E. C.; Rasmussen, I. L.; Laursen, S.

1985-01-01

The Caltech/DSRI balloon-borne High Energy Isotope Spectrometer Telescope (HEIST) was flown successfully from Palestine, Texas on 14 May 1984. The experiment was designed to measure cosmic ray isotopic abundances from neon through iron, with incident particle energies from approximately 1.5 to 2.2 GeV/nucleon, depending on the element. During approximately 38 hours at float altitude, 10 to the 5th events were recorded with Z or = 6 and incident energies 1.5 GeV/nucleon. We present results from the ongoing data analysis associated with both the pre-flight Bevalac calibration and the flight data.

Isotope Inversion Experiment evaluating the suitability of calibration in surrogate matrix for quantification via LC-MS/MS-Exemplary application for a steroid multi-method.

PubMed

Suhr, Anna Catharina; Vogeser, Michael; Grimm, Stefanie H

2016-05-30

For quotable quantitative analysis of endogenous analytes in complex biological samples by isotope dilution LC-MS/MS, the creation of appropriate calibrators is a challenge, since analyte-free authentic material is in general not available. Thus, surrogate matrices are often used to prepare calibrators and controls. However, currently employed validation protocols do not include specific experiments to verify the suitability of a surrogate matrix calibration for quantification of authentic matrix samples. The aim of the study was the development of a novel validation experiment to test whether surrogate matrix based calibrators enable correct quantification of authentic matrix samples. The key element of the novel validation experiment is the inversion of nonlabelled analytes and their stable isotope labelled (SIL) counterparts in respect to their functions, i.e. SIL compound is the analyte and nonlabelled substance is employed as internal standard. As a consequence, both surrogate and authentic matrix are analyte-free regarding SIL analytes, which allows a comparison of both matrices. We called this approach Isotope Inversion Experiment. As figure of merit we defined the accuracy of inverse quality controls in authentic matrix quantified by means of a surrogate matrix calibration curve. As a proof-of-concept application a LC-MS/MS assay addressing six corticosteroids (cortisol, cortisone, corticosterone, 11-deoxycortisol, 11-deoxycorticosterone, and 17-OH-progesterone) was chosen. The integration of the Isotope Inversion Experiment in the validation protocol for the steroid assay was successfully realized. The accuracy results of the inverse quality controls were all in all very satisfying. As a consequence the suitability of a surrogate matrix calibration for quantification of the targeted steroids in human serum as authentic matrix could be successfully demonstrated. The Isotope Inversion Experiment fills a gap in the validation process for LC-MS/MS assays quantifying endogenous analytes. We consider it a valuable and convenient tool to evaluate the correct quantification of authentic matrix samples based on a calibration curve in surrogate matrix. Copyright © 2016 Elsevier B.V. All rights reserved.

Self-diffusion in 69Ga121Sb/71Ga123Sb isotope heterostructures

NASA Astrophysics Data System (ADS)

Bracht, H.; Nicols, S. P.; Haller, E. E.; Silveira, J. P.; Briones, F.

2001-05-01

Gallium and antimony self-diffusion experiments have been performed in undoped 69Ga121Sb/71Ga123Sb isotope heterostructures at temperatures between 571 and 708 °C under Sb- and Ga-rich ambients. Ga and Sb profiles measured with secondary ion mass spectrometry reveal that Ga diffuses faster than Sb by several orders of magnitude. This strongly suggests that the two self-atom species diffuse independently on their own sublattices. Experimental results lead us to conclude that Ga and Sb diffusion are mediated by Ga vacancies and Sb interstitials, respectively, and not by the formation of a triple defect proposed earlier by Weiler and Mehrer [Philos. Mag. A 49, 309 (1984)]. The extremely slow diffusion of Sb up to the melting temperature of GaSb is proposed to be a consequence of amphoteric transformations between native point defects which suppress the formation of those native defects which control Sb diffusion. Preliminary experiments exploring the effect of Zn indiffusion at 550 °C on Ga and Sb diffusion reveal an enhanced intermixing of the Ga isotope layers compared to undoped GaSb. However, under the same conditions the diffusion of Sb was not significantly affected.

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence.

PubMed

Berhanu, Tesfaye A; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S K; Johnson, Matthew S; Savarino, Joël

2014-06-28

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ((15)N, (17)O, and (18)O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ(15)N, δ(18)O, and Δ(17)O). From these measurements an average photolytic isotopic fractionation of (15)ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of (15)ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of (14)NO3 (-) and (15)NO3 (-) in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well reproduced the values obtained in the laboratory study. These cross sections can be used in isotopic models to reproduce the stable isotopic composition of nitrate found in Antarctic snow profiles.

Simultaneous measurement of sulfur and lead isotopes in sulfides using nanosecond laser ablation coupled with two multi-collector inductively coupled plasma mass spectrometers

NASA Astrophysics Data System (ADS)

Yuan, Honglin; Liu, Xu; Chen, Lu; Bao, Zhian; Chen, Kaiyun; Zong, Chunlei; Li, Xiao-Chun; Qiu, Johnson Wenhong

2018-04-01

We herein report the coupling of a nanosecond laser ablation system with a large-scale multi-collector inductively coupled plasma mass spectrometer (Nu1700 MC-ICPMS, NP-1700) and a conventional Nu Plasma II MC-ICPMS (NP-II) for the simultaneous laser ablation and determination of in situ S and Pb isotopic compositions of sulfide minerals. We found that the required aerosol distribution between the two spectrometers depended on the Pb content of the sample. For example, for a sulfide containing 100-3000 ppm Pb, the aerosol was distributed between the NP-1700 and the NP-II spectrometers in a 1:1 ratio, while for lead contents >3000 and <100 ppm, these ratios were 5:1 and 1:3, respectively. In addition, S isotopic analysis showed a pronounced matrix effect, so a matrix-matched external standard was used for standard-sample bracketing correction. The NIST NBS 977 (NBS, National Bureau of Standards; NIST, National Institute of Standards & Technology) Tl (thallium) dry aerosol internal standard and the NIST SRM 610 (SRM, standard reference material) external standard were employed to obtain accurate results for the analysis of Pb isotopes. In tandem experiments where airflow conditions were similar to those employed during stand-alone analyses, small changes in the aerosol carrier gas flow did not significantly influence the accurate determination of S and Pb isotope ratios. In addition, careful optimization of the flow ratio of the aerosol carrier (He) and makeup (Ar) gases to match stand-alone analytical conditions allowed comparable S and Pb isotope ratios to be obtained within an error of 2 s analytical uncertainties. Furthermore, the results of tandem analyses obtained using our method were consistent with those of previously reported stand-alone techniques for the S and Pb isotopes of chalcopyrite, pyrite, galena, and sphalerite, thus indicating that this method is suitable for the simultaneous analysis of S and Pb isotopes of natural sulfide minerals, and provides an effective tool to determine S and Pb isotope compositions of sulfides formed through multi-stage deposition routes.

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

NASA Astrophysics Data System (ADS)

Berhanu, Tesfaye A.; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S. K.; Johnson, Matthew S.; Savarino, Joël

2014-06-01

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate (15N, 17O, and 18O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ15N, δ18O, and Δ17O). From these measurements an average photolytic isotopic fractionation of 15ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of 15ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of 14NO3- and 15NO3- in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well reproduced the values obtained in the laboratory study. These cross sections can be used in isotopic models to reproduce the stable isotopic composition of nitrate found in Antarctic snow profiles.

Molybdenum isotope fractionation during adsorption to organic matter

USGS Publications Warehouse

King, Elizabeth K.; Perakis, Steven; Pett-Ridge, Julie C.

2018-01-01

Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2–170 h) and pH (2–7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (± 0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

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‰ (2σ). Equilibrium Si isotope fractionation for Fe-Si gel systems is significantly larger in magnitude than estimates of a near-zero solid-aqueous fractionation factor between pure Si gel and aqueous Si, indicating a major influence of Fe atoms on Si-O bonds, and hence the isotopic properties, of Fe-Si gel. Larger Si isotope fractionation in the Fe(II)-bearing systems may be caused by incorporation of Fe(II) into the solid structure, which may further weaken Fe-Si bonds and thus change the Si isotope fractionation factor. The relatively large Si isotope fractionation for Fe-Si gel, relative to pure Si gel, provides a new explanation for the observed contrast in δ30Si values in the Precambrian BIFs and cherts, as well as an explanation for the relatively negative δ30Si values in BIFs, in contrast to previous proposals that the more negative δ30Si values in BIFs reflect hydrothermal sources of Si or sorption to Fe oxides/hydroxides.

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

USGS Publications Warehouse

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

2008-01-01

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

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

NASA Technical Reports Server (NTRS)

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

2011-01-01

One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II? quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Investigation into the Feasibility of Highly Enriched Uranium Detection by External Neutron Stimulation (Expanded Study)

DTIC Science & Technology

2006-05-01

26 1.10.1 Radiation Isotope Detector Operation ...... 27 1.10.2 HEU Counts in Radioisotope with 1 kg HEU.. 27 1.10.3 Radiation Isotope ...REACTOR GRADE PLUTONIUM ........... 173 10.2 GAMMA EMITTING ISOTOPES IN CARGO MATERIAL ............. 177 10.3 MCNP ANALYSIS OF GAMMA TRANSPORT FROM A...experiment at USNA using a germanium detector .......................... 31 1-13 Counts in the radiation isotope detector versus counting time for 1

Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

USGS Publications Warehouse

Coleman, D.D.; Risatti, J.B.; Schoell, M.

1981-01-01

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted. We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both 13C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26??C than at 11.5??C. The change in ??D relative to the change in ??13C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway. The change in the ??D value for the residual methane was from 8 to 14 times greater than the change in the ??13C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria. ?? 1981.

Linking low-level stable isotope fractionation to expression of the cytochrome P450 monooxygenase-encoding ethB gene for elucidation of methyl tert-butyl ether biodegradation in aerated treatment pond systems.

PubMed

Jechalke, Sven; Rosell, Mònica; Martínez-Lavanchy, Paula M; Pérez-Leiva, Paola; Rohwerder, Thore; Vogt, Carsten; Richnow, Hans H

2011-02-01

Multidimensional compound-specific stable isotope analysis (CSIA) was applied in combination with RNA-based molecular tools to characterize methyl tertiary (tert-) butyl ether (MTBE) degradation mechanisms occurring in biofilms in an aerated treatment pond used for remediation of MTBE-contaminated groundwater. The main pathway for MTBE oxidation was elucidated by linking the low-level stable isotope fractionation (mean carbon isotopic enrichment factor [ε(C)] of -0.37‰ ± 0.05‰ and no significant hydrogen isotopic enrichment factor [ε(H)]) observed in microcosm experiments to expression of the ethB gene encoding a cytochrome P450 monooxygenase able to catalyze the oxidation of MTBE in biofilm samples both from the microcosms and directly from the ponds. 16S rRNA-specific primers revealed the presence of a sequence 100% identical to that of Methylibium petroleiphilum PM1, a well-characterized MTBE degrader. However, neither expression of the mdpA genes encoding the alkane hydroxylase-like enzyme responsible for MTBE oxidation in this strain nor the related MTBE isotope fractionation pattern produced by PM1 could be detected, suggesting that this enzyme was not active in this system. Additionally, observed low inverse fractionation of carbon (ε(C) of +0.11‰ ± 0.03‰) and low fractionation of hydrogen (ε(H) of -5‰ ± 1‰) in laboratory experiments simulating MTBE stripping from an open surface water body suggest that the application of CSIA in field investigations to detect biodegradation may lead to false-negative results when volatilization effects coincide with the activity of low-fractionating enzymes. As shown in this study, complementary examination of expression of specific catabolic genes can be used as additional direct evidence for microbial degradation activity and may overcome this problem.

Linking Low-Level Stable Isotope Fractionation to Expression of the Cytochrome P450 Monooxygenase-Encoding ethB Gene for Elucidation of Methyl tert-Butyl Ether Biodegradation in Aerated Treatment Pond Systems▿ †

PubMed Central

Jechalke, Sven; Rosell, Mònica; Martínez-Lavanchy, Paula M.; Pérez-Leiva, Paola; Rohwerder, Thore; Vogt, Carsten; Richnow, Hans H.

2011-01-01

Multidimensional compound-specific stable isotope analysis (CSIA) was applied in combination with RNA-based molecular tools to characterize methyl tertiary (tert-) butyl ether (MTBE) degradation mechanisms occurring in biofilms in an aerated treatment pond used for remediation of MTBE-contaminated groundwater. The main pathway for MTBE oxidation was elucidated by linking the low-level stable isotope fractionation (mean carbon isotopic enrichment factor [ɛC] of −0.37‰ ± 0.05‰ and no significant hydrogen isotopic enrichment factor [ɛH]) observed in microcosm experiments to expression of the ethB gene encoding a cytochrome P450 monooxygenase able to catalyze the oxidation of MTBE in biofilm samples both from the microcosms and directly from the ponds. 16S rRNA-specific primers revealed the presence of a sequence 100% identical to that of Methylibium petroleiphilum PM1, a well-characterized MTBE degrader. However, neither expression of the mdpA genes encoding the alkane hydroxylase-like enzyme responsible for MTBE oxidation in this strain nor the related MTBE isotope fractionation pattern produced by PM1 could be detected, suggesting that this enzyme was not active in this system. Additionally, observed low inverse fractionation of carbon (ɛC of +0.11‰ ± 0.03‰) and low fractionation of hydrogen (ɛH of −5‰ ± 1‰) in laboratory experiments simulating MTBE stripping from an open surface water body suggest that the application of CSIA in field investigations to detect biodegradation may lead to false-negative results when volatilization effects coincide with the activity of low-fractionating enzymes. As shown in this study, complementary examination of expression of specific catabolic genes can be used as additional direct evidence for microbial degradation activity and may overcome this problem. PMID:21148686

Fingerprinting Bacterial and Fungal Manganese Oxidation via Stable Oxygen Isotopes of Manganese Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Wankel, S. D.; Hansel, C. M.

2016-12-01

Manganese (Mn) oxides are a ubiquitous mineralogical component of surface Earth and Mars. Mn(III/IV) oxides are potent environmental sorbents and oxidants that play a crucial role in the fate of organic matter. The processes by which Mn(II) oxidation occurs in natural systems are poorly understood, but a number of studies have implicated microogranisms as the primary agents of Mn(II) oxidation in terrestrial and marine environments. The ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides transcends the boundaries of biological domain, with an abundance of well-characterized prokaryotes as well as eukaryotic fungi with the ability to oxidize Mn(II) to Mn(III/IV) oxides. Biological Mn(II) oxidation proceeds directly through enzymatic activity or indirectly through the production of reactive oxygen species. Building upon earlier research suggesting that stable oxygen isotope fractionation could be used to fingerprint unique Mn(II)-oxidizing organisms or distinct oxidation pathways, here we use culture-based studies of Mn(II)-oxidizing bacteria and fungi to determine the kinetic oxygen isotope effects associated with Mn(II) oxidation. Since the oxygen molecules in Mn(III/IV) oxides are comprised of oxygen from both precursor water and molecular oxygen, we used a two-fold approach to constrain isotope fractionation with respect to each oxygen source. We used open system oxidation experiments using oxygen-18 labeled water in parallel with closed system Rayleigh distillation oxidation experiments to fully constrain isotope fractionation associated with oxygen atom incorporation during Mn(II) oxidation. Our results suggest commonalities among fractionation factors from groups of Mn(II)-oxidizing organisms that have similar oxidation mechanisms. These results suggest that stable oxygen isotopes of Mn(III/IV) oxides have the potential to distinguish between Mn(II) oxidation pathways in nature, providing a way to determine which groups of Mn(II) oxidizers may be active in present and past surface Earth environments.

Lead Isotopes in Olivine-Phyric Shergottite Tissint: Implications for the Geochemical Evolution of the Shergottite Source Mantle

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Simon, J. I.; Jones, J. H.; Yokoyama, T.

2015-01-01

Geochemically-depleted shergottites are basaltic rocks derived from a martian mantle source reservoir. Geochemical evolution of the martian mantle has been investigated mainly based on the Rb-Sr, Sm-Nd, and Lu-Hf isotope systematics of the shergottites [1]. Although potentially informative, U-Th- Pb isotope systematics have been limited because of difficulties in interpreting the analyses of depleted meteorite samples that are more susceptible to the effects of near-surface processes and terrestrial contamination. This study conducts a 5-step sequential acid leaching experiment of the first witnessed fall of the geochemically-depleted olivinephyric shergottite Tissint to minimize the effect of low temperature distrubence. Trace element analyses of the Tissint acid residue (mostly pyroxene) indicate that Pb isotope compositions of the residue do not contain either a martian surface or terrestrial component, but represent the Tissint magma source [2]. The residue has relatively unradiogenic initial Pb isotopic compositions (e.g., 206Pb/204Pb = 10.8136) that fall within the Pb isotope space of other geochemically-depleted shergottites. An initial µ-value (238U/204Pb = 1.5) of Tissint at the time of crystallization (472 Ma [3]) is similar to a time-integrated mu- value (1.72 at 472 Ma) of the Tissint source mantle calculated based on the two-stage mantle evolution model [1]. On the other hand, the other geochemically-depleted shergottites (e.g., QUE 94201 [4]) have initial µ-values of their parental magmas distinctly lower than those of their modeled source mantle. These results suggest that only Tissint potentially reflects the geochemical signature of the shergottite mantle source that originated from cumulates of the martian magma ocean

Silicon Isotopes doping experiments to measure quartz dissolution and precipitation rates at equilibrium and test the principle of detailed balance

NASA Astrophysics Data System (ADS)

Zhu, C.; Rimstidt, J. D.; Liu, Z.; Yuan, H.

2016-12-01

The principle of detailed balance (PDB) has been a cornerstone for irreversible thermodynamics and chemical kinetics for a long time, and its wide application in geochemistry has mostly been implicit and without experimental testing of its applicability. Nevertheless, many extrapolations based on PDB without experimental validation have far reaching impacts on society's mega environmental enterprises. Here we report an isotope doping method that independently measures simultaneous dissolution and precipitation rates and can test this principle. The technique reacts a solution enriched in a rare isotope of an element with a solid having natural isotopic abundances (Beck et al., 1992; Gaillardet, 2008; Gruber et al., 2013). Dissolution and precipitation rates are found from the changing isotopic ratios. Our quartz experiment doped with 29Si showed that the equilibrium dissolution rate remains unchanged at all degrees of undersaturation. We recommend this approach to test the validity of using the detailed balance relationship in rate equations for other substances.

Coupling experimental and field-based approaches to decipher carbon sources in the shell of the great scallop, Pecten maximus (L.)

NASA Astrophysics Data System (ADS)

Marchais, V.; Richard, J.; Jolivet, A.; Flye-Sainte-Marie, J.; Thébault, J.; Jean, F.; Richard, P.; Paulet, Y.-M.; Clavier, J.; Chauvaud, L.

2015-11-01

This research investigated how the carbon isotopic composition of food source (δ13Cfood) and dissolved inorganic carbon (δ13CDIC) influences the carbon isotopic composition of Pecten maximus shells (δ13Cshell) under both experimental and natural conditions. The objectives are to better understand the relationship between P. maximus and its environment, and to specifically distinguish conditions under which calcification is influenced by respired CO2 derived from food sources versus conditions in which calcification uses inorganic carbon from seawater. Laboratory experiment investigated carbon incorporation into shell carbonates by maintaining scallops under conditions where the stable carbon isotopic composition of food sources was considerably depleted (-54‰), relative to values observed in the natural environment (-21‰). Laboratory experiment ran for 78 days under three temperature conditions, 15 °C, 21 °C and 25 °C. A survey of the environmental parameters and stable carbon isotopic composition into shell carbonate of natural population of P. maximus was also realized during the same year in the Bay of Brest, France. Data collected from both laboratory experiment and the natural environment confirmed that both δ13CDIC and δ13Cfood influence δ13Cshell values and that organic carbon incorporation (CM) averages about 10% (4.3-6.8% under experimental conditions and 1.9-16.6% in the natural environment). The shift in stable carbon isotopic composition from the uptake of depleted food sources under experimental conditions realized a marked divergence in the predicted equilibrium between calcium carbonate and ambient bicarbonate, relative to the natural environment. This offset was 1.7 ± 0.6‰ for scallops in their natural environment and 2.5 ± 0.5 and 3.2 ± 0.9‰ for scallops under experimental conditions at water temperatures of 15 °C and 21 °C, respectively. The offset of 3‰ for scallops subjected to laboratory experiment could not be explained in light of growth rate but may be related to food supply and/or temperature. Food source and temperature effects may also explain the annual variation observed in CM values measured from scallops in their natural environment. CM estimation from the natural population of P. maximus varied seasonally from around 2% at the end of winter, to 12% in summer. The seasonal variation resembles variability in the carbon isotopic composition of the food sources throughout the year with an exception at the end of winter.

CO2-dependent carbon isotope fractionation in the dinoflagellate Alexandrium tamarense

NASA Astrophysics Data System (ADS)

Wilkes, Elise B.; Carter, Susan J.; Pearson, Ann

2017-09-01

The carbon isotopic composition of marine sedimentary organic matter is used to resolve long-term histories of pCO2 based on studies indicating a CO2-dependence of photosynthetic carbon isotope fractionation (εP). It recently was proposed that the δ13C values of dinoflagellates, as recorded in fossil dinocysts, might be used as a proxy for pCO2. However, significant questions remain regarding carbon isotope fractionation in dinoflagellates and how such fractionation may impact sedimentary records throughout the Phanerozoic. Here we investigate εP as a function of CO2 concentration and growth rate in the dinoflagellate Alexandrium tamarense. Experiments were conducted in nitrate-limited chemostat cultures. Values of εP were measured on cells having growth rates (μ) of 0.14-0.35 d-1 and aqueous carbon dioxide concentrations of 10.2-63 μmol kg-1 and were found to correlate linearly with μ/[CO2(aq)] (r2 = 0.94) in accord with prior, analogous chemostat investigations with eukaryotic phytoplankton. A maximum fractionation (εf) value of 27‰ was characterized from the intercept of the experiments, representing the first value of εf determined for an algal species employing Form II RubisCO-a structurally and catalytically distinct form of the carbon-fixing enzyme. This value is larger than theoretical predictions for Form II RubisCO and not significantly different from the ∼25‰ εf values observed for taxa employing Form ID RubisCO. We also measured the carbon isotope contents of dinosterol, hexadecanoic acid, and phytol from each experiment, finding that each class of biomarker exhibits different isotopic behavior. The apparent CO2-dependence of εP values in our experiments strengthens the proposal to use dinocyst δ13C values as a pCO2 proxy. Moreover, the similarity between the εf value for A. tamarense and the consensus value of ∼25‰ indicates that the CO2-sensitivity of carbon isotope fractionation saturates at similar CO2 levels across all three ecologically prominent clades of eukaryotic phytoplankton. This continuity of εf across taxa may help to explain why there is no coherent signature of phytoplankton evolutionary succession in Phanerozoic carbon isotope records.

Isotope production and target preparation for nuclear astrophysics data

NASA Astrophysics Data System (ADS)

Schumann, Dorothea; Dressler, Rugard; Maugeri, Emilio Andrea; Heinitz, Stephan

2017-09-01

Targets are in many cases an indispensable ingredient for successful experiments aimed to produce nuclear data. With the recently observed shift to study nuclear reactions on radioactive targets, this task can become extremely challenging. Concerted actions of a certain number of laboratories able to produce isotopes and manufacture radioactive targets are urgently needed. We present here some examples of successful isotope and target production at PSI, in particular the production of 60Fe samples used for half-life measurements and neutron capture cross section experiments, the chemical processing and fabrication of lanthanide targets for capture cross section experiments at n_TOF (European Organization for Nuclear Research (CERN), Switzerland) as well as the recently performed manufacturing of highly-radioactive 7Be targets for the measurement of the 7Be(n,α)4He cross section in the energy range of interest for the Big-Bang nucleosynthesis contributing to the solving of the cosmological Li-problem. The two future projects: "Determination of the half-life and experiments on neutron capture cross sections of 53Mn" and "32Si - a new chronometer for nuclear dating" are briefly described. Moreover, we propose to work on the establishment of a dedicated network on isotope and target producing laboratories.

Changes in the mean square charge radii and electromagnetic moments of neutron-deficient Bi isotopes

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

Barzakh, A. E., E-mail: barzakh@mail.ru; Batist, L. Kh.; Fedorov, D. V.

In-source laser spectroscopy experiments for neutron deficient bismuth isotopes at the 306.77 nm atomic transition were carried out at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility of Petersburg Nuclear Physics Institute (PNPI). New data on isotope shifts and hyperfine structure for {sup 189–198,} {sup 211}Bi isotopes and isomers were obtained. The changes in the mean-square charge radii and the magnetic moment values were deduced. Marked deviation from the nearly spherical behavior for ground states of bismuth isotopes at N < 109 is demonstrated, in contrast to the lead and thallium isotopic chains. The big isomer shift between Imore » = 1/2 (intruder) and I = 9/2 (normal) states for odd Bi isotopes (A = 193, 195, 197) was found.« less

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

NASA Technical Reports Server (NTRS)

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

2010-01-01

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V-PDB) apparent isotopic fractionation accompanies the pyrolysis extractions. We postulate that this isotope offset could be the result of incomplete thermal desorption during pyrolysis. We are continuing to investigate the reliability of this pyrolysis technique for correcting carbon isotope measurements of mineral surface catalyzed organic compounds.

Quantum tunneling of thermal protons through pristine graphene.

PubMed

Poltavsky, Igor; Zheng, Limin; Mortazavi, Majid; Tkatchenko, Alexandre

2018-05-28

Engineering of atomically thin membranes for hydrogen isotope separation is an actual challenge which has a broad range of applications. Recent experiments [M. Lozada-Hidalgo et al., Science 351, 68 (2016)] unambiguously demonstrate an order-of-magnitude difference in permeabilities of graphene-based membranes to protons and deuterons at ambient conditions, making such materials promising for novel separation technologies. Here we demonstrate that the permeability mechanism in such systems changes from quantum tunneling for protons to quasi-classical transport for heavier isotopes. Quantum nuclear effects exhibit large temperature and mass dependence, modifying the Arrhenius activation energy and Arrhenius prefactor for protons by more than 0.5 eV and by seven orders of magnitude correspondingly. Our findings not only shed light on the separation process for hydrogen isotope ions passing through pristine graphene but also offer new insights for controlling ion transport mechanisms in nanostructured separation membranes by manipulating the shape of the barrier and transport process conditions.

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

Production of Radioactive Beams on the Proton Dripline Using MARS at Texas A&M

NASA Astrophysics Data System (ADS)

Roundey, Rebekah; Roeder, Brian; Youngs, Michael

2017-09-01

Exotic nuclei near the proton dripline are of interest for research in nuclear astrophysics, especially in the study of the r-p process. A 58Ni on Ni reaction at higher energies has been shown to successfully populate isotopes on the dripline, but this reaction has not previously been used at the Cyclotron Institute. In this experiment, a 58Ni beam at 36 MeV/u was impinged on Nickel and Beryllium targets to determine which isotopes could be produced. The resulting fragments were measured with two Silicon detectors in order to determine energy loss and production rates for each isotope. The effects of the different targets and the presence of a Carbon stripper foil on production rates will be presented and compared with simulations from the LISE++ program. Funded by a NSF REU Grant (PHY-1659847) and a DOE Grant (DE-FG02-93ER40773).

Isotopic composition of cosmic ray nitrogen at 1.5 GeV/amu

NASA Technical Reports Server (NTRS)

Dwyer, R.; Meyer, P.

1975-01-01

For any location, the earth's magnetic field acts as a filter for incoming cosmic rays, allowing only particles above a certain rigidity. The relative isotopic composition of abundant elements can be measured with a detector sensitive to the velocity of particles in the penumbra of the earth's magnetic field. In this paper, the nitrogen velocity spectrum is compared with that of carbon plus oxygen as a reference, since in this case Z-dependent effects are minimal. The form of the energy spectrum of carbon, nitrogen, and oxygen, needed for proper correction, was measured in the same experiment. The results were obtained using a scintillator-Cerenkov counter telescope with a geometric factor of 0.25 sq in sr, flown twice on high-altitude balloons from Palestine, Texas, obtaining an exposure factor of 20 sq m sr hr. Results are presented on the isotopic composition of nitrogen at about 1.5GeV/amu.

Testing plant use of mobile vs immobile soil water sources using stable isotope experiments.

PubMed

Vargas, Ana I; Schaffer, Bruce; Yuhong, Li; Sternberg, Leonel da Silveira Lobo

2017-07-01

We tested for isotope exchange between bound (immobile) and mobile soil water, and whether there is isotope fractionation during plant water uptake. These are critical assumptions to the formulation of the 'two water worlds' hypothesis based on isotope profiles of soil water. In two different soil types, soil-bound water in two sets of 19-l pots, each with a 2-yr-old avocado plant (Persea americana), were identically labeled with tap water. After which, one set received isotopically enriched water whereas the other set received tap water as the mobile phase water. After a dry down period, we analyzed plant stem water as a proxy for soil-bound water as well as total soil water by cryogenic distillation. Seventy-five to 95% of the bound water isotopically exchanged with the mobile water phase. In addition, plants discriminated against 18 O and 2 H during water uptake, and this discrimination is a function of the soil water loss and soil type. The present experiment shows that the assumptions for the 'two water worlds' hypothesis are not supported. We propose a novel explanation for the discrepancy between isotope ratios of the soil water profile and other water compartments in the hydrological cycle. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

A method for screening of plant species for space use

NASA Technical Reports Server (NTRS)

Goeschl, J. D.; Sauer, R. L.; Scheld, H. W.

1986-01-01

A cost-effective methodology which monitors numerous dynamic aspects of carbon assimilation and allocation kinetics in live, intact plants is discussed. Analogous methods can apply to nitrogen uptake and allocation. This methodology capitalizes on the special properties of the short-lived, positron-gamma emitting isotope C-11 especially when applied as CO2-11 in a special extended square wave (ESW) pattern. The 20.4 minute half-life allows for repeated or continuous experiments on the same plant over periods of minutes, hours, days, or weeks. The steady-state isotope equilibrium approached during the ESW experiments, and the parameters which can be analyzed by this technique are also direct results of that short half-life. Additionally, the paired .511 MeV gamma rays penetrate any amount of tissue and their 180 deg opposite orientation provides good collimation and allows coincidence counting which nearly eliminates background.

Multiple stable oxygen isotopic studies of atmospheric sulfate: A new quantitative way to understand sulfate formation processes in the atmosphere

NASA Astrophysics Data System (ADS)

Lee, Charles Chi-Woo

2000-11-01

Sulfate is an important trace species in the Earth's atmosphere because of its roles in numerous atmospheric processes. In addition to its inherent light-scattering properties, sulfate can serve as cloud condensation nucleus (CCN), affecting cloud formation as well as microphysical properties of clouds. Consequently, atmospheric sulfate species influence the global radiative energy balance. Sulfate is known to increase acidity of rainwater with negative consequences in both natural and urban environments. In addition, aerosol sulfate (<=2.5 μm) is respirable and poses a threat to human health as a potential carrier of toxic pollutants through the respiratory tract. Despite intense investigative effort, uncertainty regarding the relative significance of gas and aqueous phase oxidation pathways still remains. Acquisition of such information is important because the lifetime and transport of S(IV) species and sulfate aerosols are influenced by the oxidative pathways. In addition, sulfate formation processes affect the aerosol size distribution, which ultimately influences radiative properties of atmospheric aerosols. Therefore, the budgetary information of the sulfur cycle, as well as the radiative effects of sulfate on global climate variation, can be attained from better quantitative understanding of in situ sulfate formation processes in the atmosphere. Multiple stable oxygen isotopic studies of atmospheric sulfate are presented as a new tool to better comprehend the atmospheric sulfate formation processes. Coupled with isotopic studies, 35S radioactivity measurements have been utilized to assess contribution of sulfate from high altitude air masses. Atmospheric sulfate (aerosols and rainwater) samples have been collected from diverse environments. Laboratory experiments of gas and aqueous phase S(IV) oxidation by various oxidants, as well as biomass burning experiments, have also been conducted. The main isotopic results from these studies are as follows: (1)Atmospheric (aerosol and rainwater) sulfate has a mass independent oxygen isotopic composition; (2)Aqueous phase S(IV) oxidation by atmospheric ozone and hydrogen peroxide are the source of the mass independent anomaly in atmospheric sulfate; (3)The mass independent oxygen isotopic anomaly appears to enhance with increasing altitude, suggesting a stratospheric contribution; (4)Primary sulfate from biomass burning has a mass dependent oxygen isotopic composition.

Assessing the Impact of Sublimation on the Stable Water Isotope Signal of Surface Ice

NASA Astrophysics Data System (ADS)

Dennis, D. P.; Ehrenfeucht, S.; Marchant, D. R.

2017-12-01

Sublimation is often a significant, if not the dominant, mechanism for ablation in polar and high elevation glacial systems. Previous field studies on firn and ice have suggested that sublimation can enrich the stable water isotope (δD and δ18O) signatures of these exposed materials. Several additional studies have attempted to replicate this effect through laboratory experiments. However, neither the magnitude of alteration caused by sublimation nor the maximum depth at which ice is affected are well-constrained. The effect of sublimation-induced alteration on the original meteoric signal relative to other post-depositional processes is additionally unknown. Here, we present the results of an experimental study on the effect of sublimation on stable water isotope ratios in surface ice. Using high-resolution data, we attempt to assess the suitability of δD and δ18O in near-surface and exposed ice for use as paleoclimate proxies. This type of analysis is particularly useful for future studies of ice from hyper-arid polar regions like the Antarctic McMurdo Dry Valleys, and may be extended to icy planetary bodies, including surface ice on Mars.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Berninger, Ulf-Niklas; Pérez-Fernàndez, Andrea; Chmeleff, Jérôme; Mavromatis, Vasileios

2018-04-01

This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The δ26Mg composition of the fluid was up to ∼0.35‰ heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 °C. The δ26Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system from external chemical input and/or the existence of a yet to be defined dissolution/precipitation inhibition mechanism.

Platinum isotopes in iron meteorites: Galactic cosmic ray effects and nucleosynthetic homogeneity in the p-process isotope 190Pt and the other platinum isotopes

NASA Astrophysics Data System (ADS)

Hunt, Alison C.; Ek, Mattias; Schönbächler, Maria

2017-11-01

Platinum isotopes are sensitive to the effects of galactic cosmic rays (GCR), which can alter isotope ratios and mask nucleosynthetic isotope variations. Platinum also features one p-process isotope, 190Pt, which is very low abundance and therefore challenging to analyse. Platinum-190 is relevant for early solar-system chronology because of its decay to 186Os. Here, we present new Pt isotope data for five iron meteorite groups (IAB, IIAB, IID, IIIAB and IVA), including high-precision measurements of 190Pt for the IAB, IIAB and IIIAB irons, determined by multi-collector ICPMS. New data are in good agreement with previous studies and display correlations between different Pt isotopes. The slopes of these correlations are well-reproduced by the available GCR models. We report Pt isotope ratios for the IID meteorite Carbo that are consistently higher than the predicted effects from the GCR model. This suggests that the model predictions do not fully account for all the GCR effects on Pt isotopes, but also that the pre-atmospheric radii and exposure times calculated for Carbo may be incorrect. Despite this, the good agreement of relative effects in Pt isotopes with the predicted GCR trends confirms that Pt isotopes are a useful in-situ neutron dosimeter. Once GCR effects are accounted for, our new dataset reveals s- and r-process homogeneity between the iron meteorite groups studied here and the Earth. New 190Pt data for the IAB, IIAB and IIIAB iron meteorites indicate the absence of GCR effects and homogeneity in the p-process isotope between these groups and the Earth. This corresponds well with results from other heavy p-process isotopes and suggests their homogenous distribution in the inner solar system, although it does not exclude that potential p-process isotope variations are too diluted to be currently detectable.

The isotopic imprint of fixed nitrogen elimination in the redox transition zone of Lake Lugano, Switzerland

NASA Astrophysics Data System (ADS)

Wenk, Christine; Blees, Jan; Niemann, Helge; Zopfi, Jakob; Schubert, Carsten J.; Veronesi, Mauro; Simona, Marco; Koba, Keisuke; Lehmann, Moritz F.

2010-05-01

Nitrogen (N) loading in lakes from natural and anthropogenic sources is partially mitigated by microbially mediated processes that take place in redox transition zones (RTZ) in the water column and in sediments. However, the role of lakes as a terrestrial sink of fixed N is still poorly constrained. Furthermore, modes of suboxic N2 (and N2O) production other than canonical denitrification (e.g. anaerobic ammonium oxidation, or anammox) have barely been investigated in lakes, and the microbial communities involved in N transformations in lacustrine RTZ are mostly unknown. The isotopic composition of dissolved nitrogen species can serve as a reliable indicator of N-transformations in aquatic environments. However, the successful application of N (and O) isotope measurements in natural systems requires a solid understanding of the various N-transformation-specific isotope effects. The deep, south-alpine Lake Lugano, with a permanent chemocline in its North Basin, is an excellent model system for a biogeochemically dynamic lake, in which to study N isotope ratio variations associated with fixed N elimination and regeneration processes. We present the first comprehensive dataset of hydrochemical parameters (including N2/Ar and dissolved N2O concentrations), natural abundance stable isotope ratios of dissolved inorganic nitrogen (DIN) compounds (nitrate, nitrite, ammonium, dinitrogen, nitrous oxide), and the isotopomeric composition of water column N2O for the North Basin of Lake Lugano. Isotopic data will be integrated with molecular microbiological phylogenetic analyses and results from incubation experiments with 15N-labeled N-substrates. Strong gradients in DIN concentrations, as well as in the N and O isotope (and isotopomeric) compositions of nitrate and N2O towards the redox-transition zone indicate nitrate reduction, occurring with a high community N-fractionation. The site preference of N2O isotopomers above the chemocline indicates that the N2O is not only produced by denitrification. Furthermore, the ratio of nitrate N versus O isotope enrichment is 0.6, significantly lower than the ratio expected for sole water column denitrification. Ammonium concentrations in the hypolimnion constantly decrease to 0µM at about 20m below the oxycline, suggesting that anammox, the anaerobic oxidation of ammonium, takes place below the RTZ. First results from 16S rDNA analysis confirmed the presence of anammox bacteria (Candidatus ‘Kuenenia') in the water column. Further phylogenetic and isotope-labeling experiments will provide more information on the spatial and seasonal distribution of anammox bacteria in the water column, on the quantitative partitioning between the candidate N elimination processes, and thus likely on the N isotope fractionation of single N transformation pathways.

Li diffusion and the effect of local structure on Li mobility in Li2O-SiO2 glasses.

PubMed

Bauer, Ute; Welsch, Anna-Maria; Behrens, Harald; Rahn, Johanna; Schmidt, Harald; Horn, Ingo

2013-12-05

Aimed to improve the understanding of lithium migration mechanisms in ion conductors, this study focuses on Li dynamics in binary Li silicate glasses. Isotope exchange experiments and conductivity measurements were carried out to determine self-diffusion coefficients and activation energies for Li migration in Li2Si3O7 and Li2Si6O13 glasses. Samples of identical composition but different isotope content were combined for diffusion experiments in couples or triples. Diffusion profiles developed between 511 and 664 K were analyzed by femtosecond laser ablation combined with multiple collector inductively coupled plasma mass spectrometry (fs LA-MC-ICP-MS) and secondary ion mass spectrometry (SIMS). Analyses of diffusion profiles and comparison of diffusion data reveal that the isotope effect of lithium diffusion in silicate glasses is rather small, consistent with classical diffusion behavior. Ionic conductivity of glasses was measured between 312 and 675 K. The experimentally obtained self-diffusion coefficient, D(IE), and ionic diffusion coefficient, D(σ), derived from specific DC conductivity provided information about correlation effects during Li diffusion. The D(IE)/D(σ) is higher for the trisilicate (0.27 ± 0.05) than that for the hexasilicate (0.17 ± 0.02), implying that increasing silica content reduces the efficiency of Li jumps in terms of long-range movement. This trend can be rationalized by structural concepts based on nuclear magnetic resonance (NMR) and Raman spectroscopy as well as molecular dynamic simulations, that is, lithium is percolating in low-dimensional, alkali-rich regions separated by a silica-rich matrix.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Malic enzyme: Tritium isotope effects with alternative dinucleotide substrates and divalent metal ions

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

Karsten, W.E.; Harris, B.G.; Cook, P.F.

1992-01-01

The NAD-malic enzyme from Ascaris suum catalyzes the divalent metal ion dependent oxidative decarboxylation of L-malate to yield pyruvate, carbon dioxide and NADH. Multiple isotope effect studies suggest a stepwise chemical mechanism with hydride transfer from L-malate to NAD occurring first to form oxalacetate, followed by decarboxylation. Utilizing L-malate-2-T, tritium V/K isotope effects have been determined for the hydride transfer step using a variety of alternative dinucleotide substrates and divalent metal ions. Combination of these data with deuterium isotope effects data and previously determined [sup 13]C isotope effects has allowed the calculation of intrinsic isotope effects for the malic enzymemore » catalyzed reaction. The identity of both the dinucleotide substrate and divalent metal ion has an effect of the size of the intrinsic isotope effect for hydride transfer.« less

Compound-specific carbon isotope analysis of instantaneous gas generated from shaly coal during hydrous pyrolysis

NASA Astrophysics Data System (ADS)

Tsai, Wen-Yu; Sun, Chih-Hsien; Huang, Wuu-Liang

2010-05-01

Isotopes of natural gases have provided important information for indicating their maturation, origins and influencing factors during the generation processes. In order to distinguish compositions of gas generated at different intervals of maturities, the present study investigates the variation of compound-specific carbon isotope (CSI) ratios of hydrocarbon gases from a shaly coal by instantaneous hydrous pyrolysis, during which the earlier generated gas was evacuated before the start of next maturation stage. The experiments were conducted at ten different maturity stages (0.65 to 2.02 % Ro) from a terrestrial shaly coal with 0.48 % Ro. The gas products were analyzed by GC-IR-MS. The results show that, in general, the δ13C values of methane (C1), ethane (C2), propane (C3) slightly increase, then decrease and finally increase with increasing maturities. This reverse phenomenon indicates the heterogeneous and complex compositions of the kerogen. The isotope compositions of gases exhibit three distinct clusters in natural gas plot of δ13C values versus 1/n (where n is carbon number of the gaseous molecule), corresponding to three different groups of maturity stages. By linking the same maturity stage of δ13C values, all lines show nearly parallel in each group with consistently reverse trend of δ13C3 < δ13C2 > δ13C1. These three distinct clusters were also observed in the cross plotting of iC4/nC4 versus iC5/nC5 isomer ratios. This may imply that the kerogen is composed of three discrete structural domains which were progressively cracked at three major groups of maturity stages. The reverse trend was inconsistent with data for gas collected cumulatively in most prior pyrolysis experiments and the linear relationship predicted from kinetic isotope effect (KIE) model. Although the non-linear relationship or reverse trend, δ13C3 < δ13C2, was also reported for some natural gases, it was interpreted as a result of mixing from different source rocks or other processes. Our results, however, suggest that this non-linear relationship or reverse phenomenon can also be attributed to the mixing of gases generated from different maturity stages solely from a single source formation. Therefore, our results provide a new interpretation for the variation of isotope data of the cumulative and instantaneous gases in hydrous pyrolysis experiments and isotope variation in natural gas.

Soil tension mediates isotope fractionation during soil water evaporation

NASA Astrophysics Data System (ADS)

Gaj, Marcel; McDonnell, Jeffrey

2017-04-01

Isotope tracing of the water cycle is increasing in its use and usefulness. Many new studies are extracting soil waters and relating these to streamflow, groundwater recharge and plant transpiration. Nevertheless, unlike isotope fractionation factors from open water bodies, soil water fractionation factors are poorly understood and until now, only empirically derived. In contrast to open water evaporation where temperature, humidity and vapor pressure gradient define fractionation (as codified in the well-known Craig and Gordon model), soil water evaporation includes additionally, fractionation by matrix effects. There is yet no physical explanation of kinetic and equilibrium fraction from soil water within the soil profile. Here we present a simple laboratory experiment with four admixtures of soil grain size (from sand to silt to clay). Oven-dried samples were spiked with water of known isotopic composition at different soil water contents. Soils were then stored in sealed bags and the headspace filled with dry air and allowed to equilibrate for 24hours. Isotopic analysis of the headspace vapor was done with a Los Gatos Inc. water vapor isotope analyzer. Soil water potential of subsamples were measured with a water potential meter. We show for the first time that soil tension controls isotope fractionation in the resident soil water. Below a Pf 3.5 the δ-values of 18O and 2H of the headspace vapor is more positive and increases with increasing soil water potential. Surprisingly, we find that the relationship between soil tension and equilibrium fractionation is independent of soil type. However, δ-values of each soil type plot along a distinct evaporation line. These results indicate that equilibrium fractionation is affected by soil tension in addition to temperature. Therefore, at high soil water tension (under dry conditions) equilibrium fractionation is not consistent with current empirical formulations that ignore these effects. These findings may have implications for plant water uptake studies since plant root water uptake imparts tension to extract water from the soil matrix. Since this is the same physical force as soil water potential, root water uptake at high soil water potential might cause fractionation of soil water. Our work is ongoing to examine these knock-on effects.

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. coli (e.g. membranes, cytosol, etc.), including the catalytic metal atoms within CdCA. These experiments allow isotopic exchange reactions to be observed in biological systems at an unparalleled resolution, demonstrating that isotopic fractionation can occur, in vivo, on length scales as small as a few Å. We will explore future applications of this technique using the marine geochemistry of Cd as a case study. This experimental approach has great promise for studying the individual isotopic biosignatures of other biochemical reactions, in particular those which may have been active during early Earth History.

Intramolecular isotope distributions reveal lower than expected increases in photosynthesis over the past 200 years

NASA Astrophysics Data System (ADS)

Ehlers, Ina; Augusti, Angela; Köhler, Iris; Zuidema, Pieter; Robertson, Iain; Nilsson, Mats; Schleucher, Jürgen

2015-04-01

The ability of the biosphere to act as CO2 sink through photosynthesis strongly influences future atmospheric CO2 concentrations and crop productivity. However, plant responses to increasing atmospheric CO2 are poorly understood, in particular on time scales of decades that are most relevant for the global carbon cycle. Most plants in the global terrestrial vegetation and most crops use the C3 photosynthetic pathway. Photorespiration is a side reaction of C3 photosynthesis that reduces CO2 assimilation in all C3 plants. By studying intramolecular isotope distributions (isotopomer abundances) in century-long archives of plant material, we reconstruct how the atmospheric CO2 increase since industrialization has changed the ratio of photorespiration to photosynthesis. For 12 tree species from five continents, we observe that the CO2 increase has reduced the photorespiration / photosynthesis ratio. However, the observed reduction is on average 50 % smaller than expected from CO2 manipulation experiments. This apparent discrepancy is explained by results from a factorial CO2 / temperature manipulation experiment, which shows that isotopomers reflect the integrated effect of CO2 and temperature on the photorespiration / photosynthesis ratio. Thus, the 50 % smaller suppression of photorespiration in trees is explained by increases in leaf temperature of 2 ° C, due to global warming and a possible contribution of reduced transpirational cooling due to stomatal closure. Previous studies of long-term effects of increasing CO2 on trees have measured 13C fractionation of leaf gas exchange (Δ13C) in tree-ring series. In several studies a discrepancy was observed: strong historic increases in photosynthesis are estimated, but increases in biomass are not observed. The temperature influence revealed by our isotopomer data resolves this discrepancy; the lower estimate of CO2 fertilization has major implications for the future role of forests as CO2 sink and for vegetation-climate interactions. Isotopomer abundances reflect metabolic regulation, because enzyme isotope effects alter the isotope abundance in individual intramolecular positions. Thus, isotopomers of long-lived metabolites of historic plant material are the first tool to connect plant ecophysiology with paleo research. Another strength is that ratios of isotopomers are independent of source isotopic signatures (δ13C of CO2 and δD of water). Thus, isotopomer ratios and source isotopic signatures are orthogonal signals of plant processes and of environmental changes, respectively. Glucose has seven deuterium- and six 13C isotopomers, each influenced by specific fractionation mechanisms, therefore several climatic and/or physiological signals may be retrieved from just one metabolite.

Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream

PubMed Central

Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken

2016-01-01

ABSTRACT Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ15NNO2− and δ18ONO2−, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of “Candidatus Nitrosocaldus.” The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ18O value of nitrite produced from ammonia oxidation varied with the δ18O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ18ONO2− in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. IMPORTANCE Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of the rate of ammonia oxidation. The discovery of ammonia-oxidizing archaea (AOA) in marine and terrestrial environments has transformed the concept that ammonia oxidation is operated only by bacterial species, suggesting that AOA play a significant role in the global nitrogen cycle. However, the archaeal contribution to ammonia oxidation in the global biosphere is not yet completely understood. This study successfully identified key factors controlling nitrogen and oxygen isotopic ratios of nitrite produced from thermophilic Thaumarchaeota and elucidated the applicability and its limit of nitrite isotopes as a geochemical clock of ammonia oxidation rate in nature. Oxygen isotope analysis in this study also provided new biochemical information on archaeal ammonia oxidation. PMID:27208107

Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream.

PubMed

Nishizawa, Manabu; Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken

2016-08-01

Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ(15)NNO2- and δ(18)ONO2-, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of "Candidatus Nitrosocaldus." The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ(18)O value of nitrite produced from ammonia oxidation varied with the δ(18)O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ(18)ONO2- in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of the rate of ammonia oxidation. The discovery of ammonia-oxidizing archaea (AOA) in marine and terrestrial environments has transformed the concept that ammonia oxidation is operated only by bacterial species, suggesting that AOA play a significant role in the global nitrogen cycle. However, the archaeal contribution to ammonia oxidation in the global biosphere is not yet completely understood. This study successfully identified key factors controlling nitrogen and oxygen isotopic ratios of nitrite produced from thermophilic Thaumarchaeota and elucidated the applicability and its limit of nitrite isotopes as a geochemical clock of ammonia oxidation rate in nature. Oxygen isotope analysis in this study also provided new biochemical information on archaeal ammonia oxidation. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Experimental Constraints on Fe Isotope Fractionation in Carbonatite Melt Systems

NASA Astrophysics Data System (ADS)

Stuff, M.; Schuessler, J. A.; Wilke, M.

2015-12-01

Iron isotope data from carbonatite rocks show the largest variability found in igneous rocks to date [1]. Thus, stable Fe isotopes are promising tracers for the interaction of carbonate and silicate magmas in the mantle, particularly because their fractionation is controlled by oxidation state and bonding environment. The interpretation of Fe isotope data from carbonatite rocks remains hampered, since Fe isotope fractionation factors between silicate and carbonate melts are unknown and inter-mineral fractionation can currently only be assessed by theoretical calculations [1;2]. We present results from equilibration experiments in three natrocarbonatite systems between immiscible silicate and carbonate melts, performed at 1200°C and 0.7 GPa in an internally heated gas pressure vessel at intrinsic redox conditions. The Fe isotope compositions of the silicate melt (sil.m.), quenched to a glass, and the carbonate melt (carb.m.), forming fine-grained quench crystals, were analysed by solution MC-ICP-MS. Our first data indicate a remarkable fractionation of Δ56Fesil.m.‒carb.m.= 0.29 ±0.07 ‰ near equilibrium. At short run durations, even stronger fractionation up to Δ56Fesil.m.‒carb.m. = 0.41 ±0.07 ‰ occurs, due to kinetic effects. Additionally, Δ56Fesil.m.‒carb.m. changes with bulk chemical composition, likely reflecting considerable differences between the studied systems in terms of the Fe3+/Fe2+-ratios in the two immiscible liquids. Our findings provide experimental support for a carbonatite genesis model, in which extremely negative δ56Fe values in carbonatites result from differentiation processes, such as liquid immiscibility [1]. This effect can be enhanced by disequilibrium during fast ascent of carbonatite magmas. Their sensitivity to chemical and redox composition makes Fe isotopes a potential tool for constraining the original compositions of carbonatite magmas. [1] Johnson et al. (2010) Miner. Petrol. 98, 91-110. [2] Polyakov & Mineev (2000) Geochim. Cosmochim. Acta 64, 849-865.

Effects of nitrate and water on the oxygen isotopic analysis of barium sulfate precipitated from water samples

USGS Publications Warehouse

Hannon, Janet E.; Böhlke, John Karl; Mroczkowski, Stanley J.

2008-01-01

BaSO4 precipitated from mixed salt solutions by common techniques for SO isotopic analysis may contain quantities of H2O and NO that introduce errors in O isotope measurements. Experiments with synthetic solutions indicate that δ18O values of CO produced by decomposition of precipitated BaSO4 in a carbon reactor may be either too low or too high, depending on the relative concentrations of SO and NO and the δ18O values of the H2O, NO, and SO. Typical δ18O errors are of the order of 0.5 to 1‰ in many sample types, and can be larger in samples containing atmospheric NO, which can cause similar errors in δ17O and Δ17O. These errors can be reduced by (1) ion chromatographic separation of SO from NO, (2) increasing the salinity of the solutions before precipitating BaSO4 to minimize incorporation of H2O, (3) heating BaSO4under vacuum to remove H2O, (4) preparing isotopic reference materials as aqueous samples to mimic the conditions of the samples, and (5) adjusting measured δ18O values based on amounts and isotopic compositions of coexisting H2O and NO. These procedures are demonstrated for SO isotopic reference materials, synthetic solutions with isotopically known reagents, atmospheric deposition from Shenandoah National Park, Virginia, USA, and sulfate salt deposits from the Atacama Desert, Chile, and Mojave Desert, California, USA. These results have implications for the calibration and use of O isotope data in studies of SO sources and reaction mechanisms.

Stable Carbon Isotope Evidence and Quantification of Reductive Dechlorination of Chlorinated Ethenes at Kelly AFB, TX

NASA Astrophysics Data System (ADS)

Morrill, P.; Lacrampe-Couloume, G.; Slater, G.; Sleep, B.; Edwards, E.; McMaster, M.; Major, D.; Sherwood Lollar, B.

2002-12-01

Cis-1, 2-dichloroethene (cDCE) was the primary volatile organic compound (VOC) after biostimulation of a perchloroethene (PCE) plume in a pilot test at Kelly Air Force Base (AFB) in San Antonio Texas. A stable natural microbial consortium, KB-1, shown in laboratory experiments to reduce chlorinated ethenes to non-toxic ethene was added in a pilot test area (PTA). After the addition of KB-1 stable carbon isotope values were measured for each chlorinated ethene to verify the occurrence of reductive dechlorination and quantify the extent of cDCE degradation. After bioaugmentation with KB-1, PCE, TCE and cDCE concentrations declined, while VC concentrations increased and subsequently decreased, as ethene became the dominant transformation product measured. Shifts in carbon isotopic values up to 2.7 permil, 6.4 permil, 10.9 permil and 10.6 permil were observed for PCE, TCE, cDCE and VC respectively. These isotopic shifts are consistent with the effects of biodegradation observed during laboratory and field studies. Most notably, isotopic enrichment trends characteristic of reductive dechlorination were detectable in the parent compounds before measurable concentrations of daughter products VC and ethene were produced. These results illustrate the advantage of using the more sensitive compound specific isotope analysis to confirm degradation in addition to the traditional method of monitoring the appearance of degradation products. Fractionation factors obtained from laboratory studies were used in conjunction with isotope data measured in the field to estimate the extent of cDCE degraded. It is estimated that within a 44 day period, 37 to 48 percent of the cDCE was reductively dechlorinated. Independent biodegradation estimates using data from a bromide tracer test, a groundwater flow model, and concentration analyses were all in good agreement with the isotope degradation estimate.

Predicting rates of isotopic turnover across the animal kingdom: a synthesis of existing data.

PubMed

Thomas, Stephen M; Crowther, Thomas W

2015-05-01

The stable isotopes of carbon ((12)C, (13)C) and nitrogen ((14)N, (15)N) represent powerful tools in food web ecology, providing a wide range of dietary information in animal consumers. However, identifying the temporal window over which a consumer's isotopic signature reflects its diet requires an understanding of elemental incorporation, a process that varies from days to years across species and tissue types. Though theory predicts body size and temperature are likely to control incorporation rates, this has not been tested empirically across a morphologically and phylogenetically diverse range of taxa. Readily available estimates of this relationship would, however, aid in the design of stable isotope food web investigations and improve the interpretation of isotopic data collected from natural systems. Using literature-derived turnover estimates from animal species ranging in size from 1 mg to 2000 kg, we develop a predictive tool for stable isotope ecologists, allowing for estimation of incorporation rates in the structural tissues of entirely novel taxa. In keeping with metabolic scaling theory, we show that isotopic turnover rates of carbon and nitrogen in whole organisms and muscle tissue scale allometrically with body mass raised approximately to the power -0.19, an effect modulated by body temperature. This relationship did not, however, apply to incorporation rates in splanchnic tissues, which were instead dependent on the thermoregulation tactic employed by an organism, being considerably faster in endotherms than ectotherms. We believe the predictive turnover equations we provide can improve the design of experiments and interpretation of results obtained in future stable isotopic food web studies. © 2014 The Authors. Journal of Animal Ecology © 2014 British Ecological Society.

The evolution of Carbon isotopes in calcite in the presence of cyanobacteria

NASA Astrophysics Data System (ADS)

Grimm, Christian; Mavromatis, Vasileios; Pokrovsky, Oleg S.; Oelkers, Eric H.

2016-04-01

Stable isotopic compositions in carbonates are widely used as indicators of environmental conditions prevailing during mineral formation. This reconstruction is substantially based on the assumption that there is no change in the mineral composition over geological time. However, recent experimental studies have shown that carbon and magnesium isotopes in hydrous Mg-carbonates undergo continuous re-equilibration with the ambient solution even after mineral precipitation stopped ([1] and [2], respectively). To verify whether this holds true for anhydrous Ca-bearing carbonates which readily form at earth's surface environments, a series of batch system calcite precipitation experiments were performed in the presence of actively growing cyanobacteria Synechococcus sp. The bacteria were grown at ambient temperature in a BG11 culture medium (SIGMA C3061) and continuous stirring, air-bubbling and illumination. Calcite precipitation was initiated by the addition of 8.5mM CaCl2 and 0-50 mM NaHCO3 or NaHCO3-Na2CO3 mixtures. The presence of cyanobacteria is on one hand promoting CaCO3 formation due to increasing pH resulting from photosynthesis. On the other hand, actively growing cyanobacteria drastically change carbon isotope signature of the aqueous fluid phase by preferably incorporating the lighter 12C isotope into biomass [1]. This study explores the effect of continuously changing carbon isotope compositions in dissolved inorganic carbon (DIC) on precipitated calcite which is in chemical equilibrium with the ambient fluid phase. [1] Mavromatis et al. (2015). The continuous re-equilibration of carbon isotope compositions of hydrous Mg-carbonates in the presence of cyanobacteria. Chem. Geol. 404, 41-51 [2] Mavromatis et al. (2012). Magnesium isotope fractionation during hydrous magnesium carbonate precipitation with and without cyanobacteria. Geochim. Cosmochim. Acta 76, 161-174

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.

Feasibility of two low-cost organic substrates for inducing denitrification in artificial recharge ponds: Batch and flow-through experiments

NASA Astrophysics Data System (ADS)

Grau-Martínez, Alba; Torrentó, Clara; Carrey, Raúl; Rodríguez-Escales, Paula; Domènech, Cristina; Ghiglieri, Giorgio; Soler, Albert; Otero, Neus

2017-03-01

Anaerobic batch and flow-through experiments were performed to assess the capacity of two organic substrates to promote denitrification of nitrate-contaminated groundwater within managed artificial recharge systems (MAR) in arid or semi-arid regions. Denitrification in MAR systems can be achieved through artificial recharge ponds coupled with a permeable reactive barrier in the form of a reactive organic layer. In arid or semi-arid regions, short-term efficient organic substrates are required due to the short recharge periods. We examined the effectiveness of two low-cost, easily available and easily handled organic substrates, commercial plant-based compost and crushed palm tree leaves, to determine the feasibility of using them in these systems. Chemical and multi-isotopic monitoring (δ15NNO3, δ18ONO3, δ34SSO4, δ18OSO4) of the laboratory experiments confirmed that both organic substrates induced denitrification. Complete nitrate removal was achieved in all the experiments with a slight transient nitrite accumulation. In the flow-through experiments, ammonium release was observed at the beginning of both experiments and lasted longer for the experiment with palm tree leaves. Isotopic characterisation of the released ammonium suggested ammonium leaching from both organic substrates at the beginning of the experiments and pointed to ammonium production by DNRA for the palm tree leaves experiment, which would only account for a maximum of 15% of the nitrate attenuation. Sulphate reduction was achieved in both column experiments. The amount of organic carbon consumed during denitrification and sulphate reduction was 0.8‰ of the total organic carbon present in commercial compost and 4.4% for the palm tree leaves. The N and O isotopic fractionation values obtained (εN and εO) were - 10.4‰ and - 9.0‰ for the commercial compost (combining data from both batch and column experiments), and - 9.9‰ and - 8.6‰ for the palm tree column, respectively. Both materials showed a satisfactory capacity for denitrification, but the palm tree leaves gave a higher denitrification rate and yield (amount of nitrate consumed per amount of available C) than commercial compost

Volume Measurements of Laser-generated Pits for in Situ Geochronology Using KArLE (Potassium-Argon Laser Experiment)

NASA Technical Reports Server (NTRS)

French, R. A.; Cohen, B. A.; Miller, J. S.

2014-01-01

KArLE (Potassium-­-Argon Laser Experiment) has been developed for in situ planetary geochronology using the K - Ar (potassium-­-argon) isotope system, where material ablated by LIBS (Laser-­-Induced Breakdown Spectroscopy) is used to calculate isotope abundances. We are determining the accuracy and precision of volume measurements of these pits using stereo and laser microscope data to better understand the ablation process for isotope abundance calculations. If a characteristic volume can be determined with sufficient accuracy and precision for specific rock types, KArLE will prove to be a useful instrument for future planetary rover missions.

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

Walker, J.F.; Johnson, L.; Simpson, N.B.

In arctic tundra soil N is highly limiting, N mineralization is slow and organic N greatly exceeds inorganic N. We studied the effects of fungistatics (azoxystrobin [Quadris{reg_sign}] or propiconazole [Tilt{reg_sign}]) on the fungi isolated from ericaceous plant roots in vitro. In addition to testing the phytotoxicity of the two fungistatics we also tested their effects on growth and nitrogen uptake of an ericaceous plant (Vaccinium uliginosum) in a closed Petri plate system without root-associated fungi. Finally, to evaluate the fungistatic effects in an in vivo experiment we applied fungistatics and nitrogen isotopes to intact tundra soil cores from Toolik Lake,more » Alaska, and examined the ammonium-N and glycine-N use by Vaccinium vitis-idaea with and without fungistatics. The experiments on fungal pure cultures showed that Tilt{reg_sign} was more effective in reducing fungal colony growth in vitro than Quadris{reg_sign}, which was highly variable among the fungal strains. Laboratory experiments aiming to test the fungistatic effects on plant performance in vitro showed that neither Quadris{reg_sign} nor Tilt{reg_sign} affected V. uliginosum growth or N uptake. In this experiment V. uliginosum assimilated more than an order of magnitude more ammonium-N than glycine-N. The intact tundra core experiment provided contrasting results. After 10 wk of fungistatic application in the growth chamber V. vitis-idaea leaf %N was 10% lower and the amount of leaf {sup 15}N acquired was reduced from labeled ammonium (33%) and glycine (40%) during the 4 d isotope treatment. In contrast to the in vitro experiment leaf {sup 15}N assimilation from glycine was three times higher than from {sup 15}NH{sub 4} in the treatments that received no-fungistatics. We conclude that the function of the fungal communities is essential to the acquisition of N from organic sources and speculate that N acquisition from inorganic sources is mainly inhibited by competition with complex soil microbial communities.« less

Stable isotope fractionation of selenium by natural microbial consortia

USGS Publications Warehouse

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

2003-01-01

The mobility and bioavailability of Se depend on its redox state, and reduction of Se oxyanions to less mobile, reduced species controls transport of this potentially toxic element in the environment. Stable isotope fractionation of Se is currently being developed as an indicator of Se immobilization through reduction. In this study, Se isotope fractionation resulting from reduction of Se(VI) and Se(IV) oxyanions by natural microbial consortia was measured in sediment slurry experiments under nearly natural conditions, with no substrate added. Experiments were conducted with a wide range of initial Se concentrations and with sediment and water from three locations with contrasting environmental settings. The products of Se(VI) and Se(IV) reduction were enriched in the lighter isotopes relative to the reactants. Shifts of -2.60/00 to -3.10/00 and -5.50/00 to -5.70/00, respectively, were observed in the 80Se/76Se ratio. These isotopic fractionations did not depend significantly on initial Se concentrations, which were varied from 22 μg/l to 8 mg/l, or on geochemical differences among the sediments. These results provide estimates of Se isotope fractionation in organic-rich wetland environments but may not be appropriate for substrate-poor aquifers and marine sediments.

Carbon isotope equilibration during sulphate-limited anaerobic oxidation of methane

NASA Astrophysics Data System (ADS)

Yoshinaga, Marcos Y.; Holler, Thomas; Goldhammer, Tobias; Wegener, Gunter; Pohlman, John W.; Brunner, Benjamin; Kuypers, Marcel M. M.; Hinrichs, Kai-Uwe; Elvert, Marcus

2014-03-01

Collectively, marine sediments comprise the largest reservoir of methane on Earth. The flux of methane from the sea bed to the overlying water column is mitigated by the sulphate-dependent anaerobic oxidation of methane by marine microbes within a discrete sedimentary horizon termed the sulphate-methane transition zone. According to conventional isotope systematics, the biological consumption of methane leaves a residue of methane enriched in 13C (refs , , ). However, in many instances the methane within sulphate-methane transition zones is depleted in 13C, consistent with the production of methane, and interpreted as evidence for the intertwined anaerobic oxidation and production of methane. Here, we report results from experiments in which we incubated cultures of microbial methane consumers with methane and low levels of sulphate, and monitored the stable isotope composition of the methane and dissolved inorganic carbon pools over time. Residual methane became progressively enriched in 13C at sulphate concentrations above 0.5 mM, and progressively depleted in 13C below this threshold. We attribute the shift to 13C depletion during the anaerobic oxidation of methane at low sulphate concentrations to the microbially mediated carbon isotope equilibration between methane and carbon dioxide. We suggest that this isotopic effect could help to explain the 13C-depletion of methane in subseafloor sulphate-methane transition zones.

Oxygen isotope ratios of PO4: An inorganic indicator of enzymatic activity and P metabolism and a new biomarker in the search for life

PubMed Central

Blake, Ruth E.; Alt, Jeffrey C.; Martini, Anna M.

2001-01-01

The distinctive relations between biological activity and isotopic effect recorded in biomarkers (e.g., carbon and sulfur isotope ratios) have allowed scientists to suggest that life originated on this planet nearly 3.8 billion years ago. The existence of life on other planets may be similarly identified by geochemical biomarkers, including the oxygen isotope ratio of phosphate (δ18Op) presented here. At low near-surface temperatures, the exchange of oxygen isotopes between phosphate and water requires enzymatic catalysis. Because enzymes are indicative of cellular activity, the demonstration of enzyme-catalyzed PO4–H2O exchange is indicative of the presence of life. Results of laboratory experiments are presented that clearly show that δ18OP values of inorganic phosphate can be used to detect enzymatic activity and microbial metabolism of phosphate. Applications of δ18Op as a biomarker are presented for two Earth environments relevant to the search for extraterrestrial life: a shallow groundwater reservoir and a marine hydrothermal vent system. With the development of in situ analytical techniques and future planned sample return strategies, δ18Op may provide an important biosignature of the presence of life in extraterrestrial systems such as that on Mars. PMID:11226207

Oxygen isotope ratios of PO4: an inorganic indicator of enzymatic activity and P metabolism and a new biomarker in the search for life.

PubMed

Blake, R E; Alt, J C; Martini, A M

2001-02-27

The distinctive relations between biological activity and isotopic effect recorded in biomarkers (e.g., carbon and sulfur isotope ratios) have allowed scientists to suggest that life originated on this planet nearly 3.8 billion years ago. The existence of life on other planets may be similarly identified by geochemical biomarkers, including the oxygen isotope ratio of phosphate (delta(18)O(p)) presented here. At low near-surface temperatures, the exchange of oxygen isotopes between phosphate and water requires enzymatic catalysis. Because enzymes are indicative of cellular activity, the demonstration of enzyme-catalyzed PO(4)-H(2)O exchange is indicative of the presence of life. Results of laboratory experiments are presented that clearly show that delta(18)O(P) values of inorganic phosphate can be used to detect enzymatic activity and microbial metabolism of phosphate. Applications of delta(18)O(p) as a biomarker are presented for two Earth environments relevant to the search for extraterrestrial life: a shallow groundwater reservoir and a marine hydrothermal vent system. With the development of in situ analytical techniques and future planned sample return strategies, delta(18)O(p) may provide an important biosignature of the presence of life in extraterrestrial systems such as that on Mars.

A novel membrane inlet mass spectrometer method to measure ¹⁵NH4₄⁺ for isotope-enrichment experiments in aquatic ecosystems.

PubMed

Yin, Guoyu; Hou, Lijun; Liu, Min; Liu, Zhanfei; Gardner, Wayne S

2014-08-19

Nitrogen (N) pollution in aquatic ecosystems has attracted much attention over the past decades, but the dynamics of this bioreactive element are difficult to measure in aquatic oxygen-transition environments. Nitrogen-transformation experiments often require measurement of (15)N-ammonium ((15)NH4(+)) ratios in small-volume (15)N-enriched samples. Published methods to determine N isotope ratios of dissolved ammonium require large samples and/or costly equipment and effort. We present a novel ("OX/MIMS") method to determine N isotope ratios for (15)NH4(+) in experimental waters previously enriched with (15)N compounds. Dissolved reduced (15)N (dominated by (15)NH4(+)) is oxidized with hypobromite iodine to nitrogen gas ((29)N2 and/or (30)N2) and analyzed by membrane inlet mass spectrometry (MIMS) to quantify (15)NH4(+) concentrations. The N isotope ratios, obtained by comparing the (15)NH4(+) to total ammonium (via autoanalyzer) concentrations, are compared to the ratios of prepared standards. The OX/MIMS method requires only small sample volumes of water (ca. 12 mL) or sediment slurries and is rapid, convenient, accurate, and precise (R(2) = 0.9994, p < 0.0001) over a range of salinities and (15)N/(14)N ratios. It can provide data needed to quantify rates of ammonium regeneration, potential ammonium uptake, and dissimilatory nitrate reduction to ammonium (DNRA). Isotope ratio results agreed closely (R = 0.998, P = 0.001) with those determined independently by isotope ratio mass spectrometry for DNRA measurements or by ammonium isotope retention time shift liquid chromatography for water-column N-cycling experiments. Application of OX/MIMS should simplify experimental approaches and improve understanding of N-cycling rates and fate in a variety of freshwater and marine environments.

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.

Position-specific isotope modeling of organic micropollutants transformations through different reaction pathways

NASA Astrophysics Data System (ADS)

Jin, Biao; Rolle, Massimo

2016-04-01

Organic compounds are produced in vast quantities for industrial and agricultural use, as well as for human and animal healthcare [1]. These chemicals and their metabolites are frequently detected at trace levels in fresh water environments where they undergo degradation via different reaction pathways. Compound specific stable isotope analysis (CSIA) is a valuable tool to identify such degradation pathways in different environmental systems. Recent advances in analytical techniques have promoted the fast development and implementation of multi-element CSIA. However, quantitative frameworks to evaluate multi-element stable isotope data and incorporating mechanistic information on the degradation processes [2,3] are still lacking. In this study we propose a mechanism-based modeling approach to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. We validate the proposed approach with the concentration and multi-element isotope data of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model precisely captures the dual element isotope trends characteristic of different reaction pathways and their range of variation consistent with observed multi-element (C, N) bulk isotope fractionation. The proposed approach can also be used as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. [1] Schwarzenbach, R.P., Egli, T., Hofstetter, T.B., von Gunten, U., Wehrli, B., 2010. Global Water Pollution and Human Health. Annu. Rev. Environ. Resour. doi:10.1146/annurev-environ-100809-125342. [2] Jin, B., Haderlein, S.B., Rolle, M., 2013. Integrated carbon and chlorine isotope modeling: Applications to chlorinated aliphatic hydrocarbons dechlorination. Environ. Sci. Technol. 47, 1443-1451. doi:10.1021/es304053h. [3] Jin, B., Rolle, M., 2014. Mechanistic approach to multi-element isotope modeling of organic contaminant degradation. Chemosphere 95, 131-139. doi:10.1016/j.chemosphere.2013.08.050.

Feeding strategies for groundwater enhanced biodenitrification in an alluvial aquifer: chemical, microbial and isotope assessment of a 1D flow-through experiment.

PubMed

Vidal-Gavilan, G; Carrey, R; Solanas, A; Soler, A

2014-10-01

Nitrate-removal through enhanced in situ biodenitrification (EISB) is an existing alternative for the recovery of groundwater quality, and is often suggested for use in exploitation wells pumping at small flow-rates. Innovative approaches focus on wider-scale applications, coupling EISB with water-management practices and new monitoring tools. However, before this approach can be used, some water-quality issues such as the accumulation of denitrification intermediates and/or of reduced compounds from other anaerobic processes must be addressed. With such a goal, a flow-through experiment using 100mg-nitrate/L groundwater was built to simulate an EISB for an alluvial aquifer. Heterotrophic denitrification was induced through the periodic addition of a C source (ethanol), with four different C addition strategies being evaluated to improve the quality of the denitrified water. Chemical, microbial and isotope analyses of the water were performed. Biodenitrification was successfully stimulated by the daily addition of ethanol, easily achieving drinking water standards for both nitrate and nitrite, and showing an expected linear trend for nitrogen and oxygen isotope fractionation, with a εN/εO value of 1.1. Nitrate reduction to ammonium was never detected. Water quality in terms of remaining C, microbial counts, and denitrification intermediates was found to vary with the experimental time, and some secondary microbial respiration processes, mainly manganese reduction, were suspected to occur. Carbon isotope composition from the remaining ethanol also changed, from an initial enrichment in (13)C-ethanol compared to the value of the injected ethanol (-30.6‰), to a later depletion, achieving δ(13)C values well below the initial isotope composition (to a minimum of -46.7‰). This depletion in the heavy C isotope follows the trend of an inverse fractionation. Overall, our results indicated that most undesired effects on water quality may be controlled through the optimization of the C/N ratio determined from the amounts of injected ethanol vs. the amount of nitrate in groundwater, with a smaller C/N ratio causing a lower level of undesired impurities. Furthermore, the authors suggest that the biofilm life-time has a direct effect on microbial population and hence affects biodenitrification performance, influencing the accumulation of nitrite over time. Copyright © 2014 Elsevier B.V. All rights reserved.

Metabolism: Part II. The Tricarboxylic Acid (TCA), Citric Acid, or Krebs Cycle.

ERIC Educational Resources Information Center

Bodner, George M.

1986-01-01

Differentiates the tricarboxylic acid (TCA) cycle (or Krebs cycle) from glycolysis, and describes the bridge between the two as being the conversion of pyruvate into acetyl coenzyme A. Discusses the eight steps in the TCA cycle, the results of isotopic labeling experiments, and the net effects of the TCA cycle. (TW)

Racemization of alanine by the alanine racemases from Salmonella typhimurium and Bacillus stearothermophilus: energetic reaction profiles

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

Faraci, W.S.; Walsh, C.T.

1988-05-03

Alanine racemases are bacterial pyridoxal 5'-phosphate (PLP) dependent enzymes providing D-alanine as an essential building block for biosynthesis of the peptidoglycan layer of the cell wall. Two isozymic alanine racemases, encoded by the dadB gene and the alr gene, from the Gram-negative mesophilic Salmonella typhimurium and one from the Gram-positive thermophilic Bacillus stearothermophilus have been examined for the racemization mechanism. Substrate deuterium isotope effects and solvent deuterium isotope effects have been measured in both L ..-->.. D and D..-->.. L directions for all three enzymes to assess the degree to which abstraction of the ..cap alpha..-proton or protonation of substratemore » PLP carbanion is limiting in catalysis. Additionally, experiments measuring internal return of ..cap alpha..-/sup 3/H from substrate to product and solvent exchange/substrate conversion experiments in /sup 3/H/sub 2/O have been used with each enzyme to examine the partitioning of substrate PLP carbanion intermediates and to obtain the relative heights of kinetically significant energy barriers in alanine racemase catalysis.« less

Discrimination factors of carbon and nitrogen stable isotopes in meerkat feces

PubMed Central

2017-01-01

Stable isotope analysis of feces can provide a non-invasive method for tracking the dietary habits of nearly any mammalian species. While fecal samples are often collected for macroscopic and genetic study, stable isotope analysis can also be applied to expand the knowledge of species-specific dietary ecology. It is somewhat unclear how digestion changes the isotope ratios of animals’ diets, so more controlled diet studies are needed. To date, most diet-to-feces controlled stable isotope experiments have been performed on herbivores, so in this study I analyzed the carbon and nitrogen stable isotope ratios in the diet and feces of the meerkat (Suricata suricatta), a small omnivorous mammal. The carbon trophic discrimination factor between diet and feces (Δ13Cfeces) is calculated to be 0.1 ± 1.5‰, which is not significantly different from zero, and in turn, not different than the dietary input. On the other hand, the nitrogen trophic discrimination factor (Δ15Nfeces) is 1.5 ± 1.1‰, which is significantly different from zero, meaning it is different than the average dietary input. Based on data generated in this experiment and a review of the published literature, carbon isotopes of feces characterize diet, while nitrogen isotope ratios of feces are consistently higher than dietary inputs, meaning a discrimination factor needs to be taken into account. The carbon and nitrogen stable isotope values of feces are an excellent snapshot of diet that can be used in concert with other analytical methods to better understand ecology, diets, and habitat use of mammals. PMID:28626611

Isotope Effect in Ozone Formation: Assessing the Relationship Between Photon Energy and Stabilization

NASA Astrophysics Data System (ADS)

Gardner, D. A.; Chakraborty, S.; Thiemens, M. H.

2016-12-01

While it has been found that the isotopic fractionation of oxygen during processes such as evaporation or precipitation happens mass-dependently (i.e. δ17O = 0.52δ18O), it was discovered in the 1980's that during ozone (O3) formation, fractionation occurs mass-independently (i.e. δ17O = δ18O). The purpose of this series of photolysis experiments was to assess the relationship between incoming photon energy and anomalous oxygen enrichment during the formation of ozone from molecular oxygen, a topic that has not yet been explored in detail, to our knowledge. A UV lamp emitting wavelengths of 184.9 and 253.7 nm was used to photolyze molecular oxygen in a vacuum chamber to form ozone. The ozone was separated from unreacted oxygen by trapping ozone with liquid nitrogen in the reaction chamber finger. After the untrapped oxygen was evacuated, the ozone was collected in a sample tube with molecular sieve, which allows the ozone to break down to molecular oxygen. In these experiments, mass-spectroscopy was performed on molecular oxygen to measure the isotopic composition (δ17O and δ18O). A limited number of experiments were performed using two different collection methods: collection immediately following formation and collection at the end of photon exposure, allowing a certain amount of ozone to dissociate and recycle. We compared the enrichments of against in ozone from the two above mentioned cases. In the former case, the enrichment in δ17O and δ18O follow a linear relationship of 0.92 (normalized to starting composition), consistent with literature data. Whereas for the latter case, the measured slope value was 0.83. The individual δ17O and δ18O values were also relatively higher compared to the first case. Differences for these two cases may arise due to the additional contribution from ozone dissociation (follow a nearly mass-dependent slope, i.e. 0.5) in the second case. More experiments are underway in an attempt to understand the stabilization step of ozone formation (i.e. energy dependence) and associated isotope effect. Results from different photon energies (e.g. 116.5, 121.6, and 123.6 nm) from different UV lamps will be presented in the meeting.

Alpha heating and isotopic mass effects in JET plasmas with sawteeth

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

Budny, R. V.; Team, JET

2016-02-09

The alpha heating experiment in the Joint European Torus (JET) 1997 DTE1 campaign is re-examined. Several effects correlated with tritium content and thermal hydrogenic isotopic mass < A> weaken the conclusion that alpha heating was clearly observed. These effects delayed the occurrence of significant sawtooth crashes allowing the electron and ion temperatures T e and T i to achieve higher values. Under otherwise equal circumstances T e and T i were typically higher for discharges with higher < A >, and significant scaling of T i, T e, and total stored energy with < A > were observed. The highermore » T i led to increased ion–electron heating rates with magnitudes comparable to those computed for alpha electron heating. Rates of other heating/loss processes also had comparable magnitudes. Simulations of T e assuming the observed scaling of T i are qualitatively consistent with the measured profiles, without invoking alpha heating« 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 relate molecular mechanisms to signals observable at environmentally relevant spatial scales.

Study of the 249-251Cf + 48Ca reactions: recent results and outlook

NASA Astrophysics Data System (ADS)

Voinov, A. A.; Oganessian, Yu Ts; Abdullin, F. Sh; Brewer, N. T.; Dmitriev, S. N.; Grzywacz, R. K.; Hamilton, J. H.; Itkis, M. G.; Miernik, K.; Polyakov, A. N.; Roberto, J. B.; Rykaczewski, K. P.; Sabelnikov, A. V.; Sagaidak, R. N.; Shirokovsky, I. V.; Shumeiko, M. V.; Stoyer, M. A.; Subbotin, V. G.; Sukhov, A. M.; Tsyganov, Yu S.; Utyonkov, V. K.; Vostokin, G. K.

2018-02-01

Experiment aiming at the synthesis of heavy isotopes of Z=118 (Og) using beam of 48Ca and a target of 249-251Cf was undertaken in October 2015 - April 2016 employing the Dubna Gas-Filled Recoil Separator (FLNR JINR). The target of mixed isotopes of 249-251Cf (50.7% of 249Cf, 12.9% of 250Cf, and 36.4% of 251Cf) was irradiated by 48Ca ions at two beam energies of 252 and 258 MeV with the corresponding accumulated beam doses of 1.6×1019 and 1.1×1019. A single event observed at lower beam energy was assigned to the isotope 294Og, the product of the reaction 249Cf(48Ca, 3n); its decay pattern and the observed radioactive properties of the nuclides in the decay chain reproduce in full those observed for 294Og in our earlier experiments of 2002-2005 and 2012. At higher beam energy we observed no decay chains that could be attributed to the isotopes of Og. The possibility of renewal of this experiment in the future is discussed.

Production of radioactive isotopes through cosmic muon spallation in KamLAND

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

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

2010-02-15

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

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

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

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

2009-06-30

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

Isotopic studies of metabolic systems by mass spectrometry: using Pascal's triangle to produce biological standards with fully controlled labeling patterns.

PubMed

Millard, Pierre; Massou, Stéphane; Portais, Jean-Charles; Létisse, Fabien

2014-10-21

Mass spectrometry (MS) is widely used for isotopic studies of metabolism in which detailed information about biochemical processes is obtained from the analysis of isotope incorporation into metabolites. The biological value of such experiments is dependent on the accuracy of the isotopic measurements. Using MS, isotopologue distributions are measured from the quantitative analysis of isotopic clusters. These measurements are prone to various biases, which can occur during the experimental workflow and/or MS analysis. The lack of relevant standards limits investigations of the quality of the measured isotopologue distributions. To meet that need, we developed a complete theoretical and experimental framework for the biological production of metabolites with fully controlled and predictable labeling patterns. This strategy is valid for different isotopes and different types of metabolisms and organisms, and was applied to two model microorganisms, Pichia augusta and Escherichia coli, cultivated on (13)C-labeled methanol and acetate as sole carbon source, respectively. The isotopic composition of the substrates was designed to obtain samples in which the isotopologue distribution of all the metabolites should give the binomial coefficients found in Pascal's triangle. The strategy was validated on a liquid chromatography-tandem mass spectrometry (LC-MS/MS) platform by quantifying the complete isotopologue distributions of different intracellular metabolites, which were in close agreement with predictions. This strategy can be used to evaluate entire experimental workflows (from sampling to data processing) or different analytical platforms in the context of isotope labeling experiments.

Atomic and Molecular Beam Scattering: Characterizing Structure and Dynamics of Hybrid Organic-Semiconductor Interfaces and Introducing Novel Isotope Separation Techniques

NASA Astrophysics Data System (ADS)

Nihill, Kevin John

This thesis details a range of experiments and techniques that use the scattering of atomic beams from surfaces to both characterize a variety of interfaces and harness mass-specific scattering conditions to separate and enrich isotopic components in a mixture of gases. Helium atom scattering has been used to characterize the surface structure and vibrational dynamics of methyl-terminated Ge(111), thereby elucidating the effects of organic termination on a rigid semiconductor interface. Helium atom scattering was employed as a surface-sensitive, non-destructive probe of the surface. By means of elastic gas-surface diffraction, this technique is capable of providing measurements of atomic spacing, step height, average atomic displacement as a function of surface temperature, gas-surface potential well depth, and surface Debye temperature. Inelastic time-of-flight studies provide highly resolved energy exchange measurements between helium atoms and collective lattice vibrations, or phonons; a collection of these measurements across a range of incident kinematic parameters allowed for a thorough mapping of low-energy phonons (e.g., the Rayleigh wave) across the surface Brillouin zone and subsequent comparison with complementary theoretical calculations. The scattering of molecular beams - here, hydrogen and deuterium from methyl-terminated Si(111) - enables the measurement of the anisotropy of the gas-surface interaction potential through rotationally inelastic diffraction (RID), whereby incident atoms can exchange internal energy between translational and rotational modes and diffract into unique angular channels as a result. The probability of rotational excitations as a function of incident energy and angle were measured and compared with electronic structure and scattering calculations to provide insight into the gas-surface interaction potential and hence the surface charge density distribution, revealing important details regarding the interaction of H2 with an organic-functionalized semiconductor interface. Aside from their use as probes for surface structure and dynamics, atomic beam sources are also demonstrated to enable the efficient separation of gaseous mixtures of isotopes by means of diffraction and differential condensation. In the former method, the kinematic conditions for elastic diffraction result in an incident beam of natural abundance neon diffracting into isotopically distinct angles, resulting in the enrichment of a desired isotope; this purification can be improved by exploiting the difference in arrival times of the two isotopes at a given final angle. In the latter method, the identical incident velocities of coexpanded isotopes lead to minor but important differences in their incident kinetic energies, and thus their probability of adsorbing on a sufficiently cold surface, resulting in preferential condensation of a given isotope that depends on the energy of the incident beam. Both of these isotope separation techniques are made possible by the narrow velocity distribution and velocity seeding effect offered only by high-Mach number supersonic beam sources. These experiments underscore the utility of supersonically expanded atomic and molecular beam sources as both extraordinarily precise probes of surface structure and dynamics and as a means for high-throughput, non-dissociative isotopic enrichment methods.

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.

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 not only limits diatom growth, but also affects the Zn uptake physiology of diatoms. Uptake of heavy isotopes occurs under Fe-limiting conditions that drive extremely low Zn uptake rates. On the other hand, more rapid Zn uptake rates result in biomass that is indistinguishable from the external bioavailable free Zn pool. These experimental results can, in principle, explain the range of Zn isotopic compositions found in the real surface ocean, given the geographically variable interplay between Fe-limitation, Zn uptake rates, and the degree of organic complexation of oceanic Zn.

Experimental determination of iron isotope fractionations among Fe aq 2 + -FeSaq-Mackinawite at low temperatures: Implications for the rock record

NASA Astrophysics Data System (ADS)

Wu, Lingling; Druschel, Greg; Findlay, Alyssa; Beard, Brian L.; Johnson, Clark M.

2012-07-01

The Fe isotope fractionation factors among aqueous ferrous iron (Fe aq 2 +), aqueous FeS clusters (FeSaq), and nanoparticulate mackinawite under neutral and mildly acidic and alkaline pH conditions have been determined using the three-isotope method. Combined voltammetric analysis and geochemical modeling were used to determine the Fe speciation in the experimental systems. The equilibrium 56Fe/54Fe fractionation factor at 20 °C and pH 7 has been determined to be -0.32 ± 0.29 (2σ)‰ between Fe aq 2 + (minor FeSaq also present in the experiment) and mackinawite. This fractionation factor was essentially constant when pH was changed to 6 or 8. When equal molarity of HS- and Fe aq 2 + were added to the system, however, the isotopic fractionation at pH 7 changed to -0.64 ± 0.36 (2σ)‰, correlating with a significant increase in the proportion of FeHS+ and FeSaq. These results highlight a more important role of aqueous Fe-S speciation in the equilibrium Fe isotope fractionation factor than recognized in previous studies. The isotopic fractionation remained constant when temperature was increased from 20 °C to 35 °C for fractionation factors between Fe aq 2 + , and mackinawite and between dominantly FeHS+ and mackinawite. Synthesis experiments similar to those of Butler et al. (2005) and Guilbaud et al. (2010) at pH 4 show consistent results: over time, the aqueous Fe-mackinawite fractionation decreases but even after 38 days of aging the fractionation factor is far from the equilibrium value inferred using the three-isotope method. In contrast, at near-neutral pH the fractionation factor for the synthesis experiment reached the equilibrium value in 38 days. These differences are best explained by noting that at low pH the FeS mackinawite particles coarsen more rapidly via particle aggregation, which limits isotopic exchange, whereas at higher pH mackinawite aggregation is limited, and Fe isotope exchange occurs more rapidly, converging on the equilibrium value. These results suggest that mackinawite formed in natural environments at near-neutral or alkaline pH are unlikely to retain kinetic isotope fractionations, but are more likely to reflect equilibrium isotope compositions. This in turn has important implications for interpreting iron isotope compositions of Fe sulfides in natural systems.

Adsorption isotope effects of water on mesoporous silica and alumina with implications for the land-vegetation-atmosphere system

NASA Astrophysics Data System (ADS)

Lin, Ying; Horita, Juske; Abe, Osamu

2018-02-01

Soil water dynamics within a vadose (unsaturated) zone is a key component in the hydrologic cycle, especially in arid regions. In applying the Craig-Gordon evaporation model to obtain isotopic compositions of soil water and the evaporated vapor in land-surface models (LSMs), it has been assumed that the equilibrium isotope fractionation factors between soil water and water vapor, α(2H) and α(18O), are identical to those between liquid and vapor of bulk water. Isotope effects in water condensation arise from intermolecular hydrogen bonding in the condensed phase and the appearance of hindered rotation/translation. Hydrogen bonding between water molecules and pore surface hydroxyl groups influences adsorption isotope effects. To test whether equilibrium fractionation factors between soil water and water vapor are identical to those between liquid and vapor of bulk water and to evaluate the influence of pore size and chemical composition upon adsorption isotope effects, we extended our previous experiments of a mesoporous silica (15 nm) to two other mesoporous materials, a silica (6 nm) and an alumina (5.8 nm). Our results demonstrated that α(2H) and α(18O) between adsorbed water and water vapor are 1.057 and 1.0086 for silica (6 nm) and 1.041 and 1.0063 for alumina (5.8 nm), respectively, at saturation pressure (po), which are smaller than 1.075 and 1.0089, respectively, between liquid and vapor phases of free water at 30 °C and that the differences exaggerate at low water contents. However, the profiles of α values with relative pressures (p/po) for these three materials differ due to the differences in chemical compositions and pore sizes. Empirical formula relating α(2H) and α(18O) values to the proportions of filled pores (f) are developed for potential applications to natural soils. Our results from triple oxygen isotope analyses demonstrated that the isotope fractionation does not follow a canonical law. For the silica (15 nm), fractionation exponents (17θ) are 0.5361 ± 0.0018 and 0.5389 ± 0.0016 at p/po = 0.72 and 0.77, respectively. For the silica (6 nm), 17θ values are 0.5330 ± 0.0011 at p/po = 0.65 and 0.5278 ± 0.0010 at p/po = 0.81. For the alumina (5.8 nm), 17θ value is 0.5316 ± 0.0015 at p/po = 0.78. These values are greater than or equal to that of liquid-vapor equilibrium of bulk water (0.529 ± 0.001).

Impact of diagenetic alteration on sea urchin (Echinodermata) magnesium isotope signatures: Comparison of experimental and fossil data

NASA Astrophysics Data System (ADS)

Riechelmann, Sylvia; Mavromatis, Vasileios; Buhl, Dieter; Dietzel, Martin; Hoffmann, René; Jöns, Niels; Eisenhauer, Anton; Immenhauser, Adrian

2017-04-01

Due to their thermodynamically instable high-Mg calcite mineralogy, the skeletal elements of echinoderms are often regarded as unreliable archives of Phanerozoic marine climate dynamics. Nevertheless, traditional and non-traditional isotope and elemental proxy data from echinoderms have been used to reconstruct global changes in palaeoseawater composition (Sandberg-cycles). Recently, these data and the interpretation have been controversially discussed in context with ancient seawater properties. This paper tests the sensitivity of echinoderm skeletal hardparts, specifically sea urchin spines to diagenetic alteration based on magnesium isotope data. We apply a dual approach by: (i) performing hydrothermal alteration experiments using meteoric, marine, and burial reactive fluids; and (ii) comparing these data with fossil sea urchin hardparts. The degree of alteration of experimentally altered and fossil sea urchin hardparts is assessed by a combination of optical (fluorescence, cathodoluminescence (CL), scanning electron microscopy (SEM)) and geochemical tools (elemental distribution, carbon, oxygen and magnesium isotopes). Although initial fluid chemistry of the experiments did not allow the detection of diagenetic overprint by elemental distribution (Fe, Mn) and cathodoluminescence, other tools such as fluorescence, SEM, delta18O, Mg concentration and delta26Mg display alteration effects, which respond to differential fluid temperature, chemistry, and experiment duration time. At experiments run under meteoric conditions with no Mg in the initial fluid, the solid is enriched in the heavier Mg isotopomer due to preferential dissolution of the lighter isotope. In contrast, initial burial and marine fluids have medium to high Mg concentrations. There, the Mg concentration and the delta26Mg values of the altered sea urchin spines increase. Fossil sea urchin hardparts display partly very strong diagenetic overprint as observed by their elemental distribution, cathodoluminescence, delta18O, Mg elemental concentration and delta26Mg. The absence of luminescence might indicate both well-preserved sea urchin spines, but also the secondary enrichment of quenching elements such as iron along diagenetic pathways. The relation between Mg concentration and delta26Mg of the experimentally altered sea urchin spines is in agreement with observations from fossil spines, which also display a 26Mg-enrichment of the solid phase. There, it seems that with increasing degree of alteration, an increase in Mg concentration and delta26Mg occurs. Hence, the experiments performed in this study seem to reflect diagenetic processes under natural conditions. However, the patterns observed are complicated by the interplay of kinetic and thermodynamic processes and the presence of variable amounts of water soluble and water insoluble organic matter within these biominerals. Due to (i) a natural inter- and intra-species variability of the Mg concentration and Mg isotopic composition throughout the echinoderm skeleton and (ii) the fractionation of Mg isotopes during the transformation of ACC as a precursor phase to calcite, the use of delta26Mg values of sea urchin hardparts as a proxy for past seawater delta26Mg is deemed unsuitable. In general, the data shown here are considered significant for those aiming to reconstruct palaeoenvironmental parameters based on echinoderm archives.

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

NASA Astrophysics Data System (ADS)

Fu, Q.; Socki, R. A.; Niles, P. B.

2010-12-01

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 °C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the δ13C values of CH4 and C2H6 were -50.3‰ and -39.3‰ (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a δ13C value of -19.2‰, which was 3.2‰ heavier than its source, formic acid. The δ13C difference between CO2 and CH4 was 31.1‰, which was higher than the value of 9.4‰ calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1‰) observed in similar experiments previously performed at 400 °C and 50 MPa with longer reaction times. CH4 is 11.0‰ less enriched in 13C than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer-Tropsch-type (FTT) synthesis in a gas phase. The observed increase of δ13C values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

NASA Technical Reports Server (NTRS)

Fu, Qi; Socki, R. A.; Niles, P. B.

2010-01-01

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer- Tropsch-type (FTT) synthesis in a gas phase. The observed increase of (sigma)C-13 values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.

Vegetation effects on event water dynamics - Insights from in-situ stable isotope observations and dye patterns

NASA Astrophysics Data System (ADS)

Volkmann, Till; Haberer, Kristine; Gessler, Arthur; Weiler, Markus

2014-05-01

The predicted changes of climate and land-use could have drastic effects on the water balance of ecosystems, particularly under frequent drought and subsequent rewetting conditions. Yet, inference of these effects and related consequences for the structure and functioning of ecosystems, groundwater recharge, leaching of nutrients and pollutants, drinking water availability, and the water cycle is currently impeded by gaps in our understanding of the manifold interactions between vegetation and soil water dynamics. While plants require water and nutrients, they also exert, for instance, important below-ground controls on the distribution and movement of water and chemicals in the rooted soil horizons via uptake and redistribution of water, modification of soil hydraulic properties, and formation of conduits for rapid preferential water flow. This work aims to contribute to fill existing gaps by assessing the effects of different plant types and their rooting systems on the soil water dynamics. Therefore, we conducted artificial drought and subsequent rewetting experiments using isotopically and dye (Brilliant Blue FCF) labeled water on plots of various surface cover (bare soil, grass, beech, oak, vine) established on relatively homogeneous luvisol on loess in southwestern Germany. Detailed insight into the short-term dynamics of event water infiltration and root uptake during the field experiments was facilitated by the application of novel techniques for high-frequency in-situ monitoring of stable isotope signatures in pore and transpiration water using commercial laser-based spectrometers, augmenting conventional observations of soil physicochemical states (soil water content, matric potential, electrical conductivity). The temporal point information is complemented by dye staining profiles, providing a detailed picture of spatial infiltration patterns, and by root density observations. The results of the experiments allow for a comprehensive spatiotemporal characterization of the effects of differing vegetation cover and rooting systems on infiltration, preferential flow path characteristics, and water storage in the rooted soil horizons. This will contribute to an improved ability to estimate environmental change impacts on the fate of water, nutrients, and pollutants in this critical zone and associated feedbacks within the soil-vegetation-atmosphere system.

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.

Shape evolution for neutron-deficient bismuth isotopes studied by resonance laser ionization spectroscopy

NASA Astrophysics Data System (ADS)

Molkanov, P. L.; Barzakh, A. E.; Fedorov, D. V.; Ivanov, V. S.; Moroz, F. V.; Orlov, S. Yu.; Panteleev, V. N.; Seliverstov, M. D.; Volkov, Yu. M.

2017-11-01

In-source laser spectroscopy experiments for bismuth isotopes at the 306.77 nm atomic transition has been carried out at the IRIS (Investigation of Radioactive Isotopes at Synchrocyclotron) facility of Petersburg Nuclear Physics Institute. New data on isotope shifts for 189-198,211Bi isotopes and isomers have been obtained. The changes in the mean-square charge radii were deduced. The large isomer shift has been observed for the intruder isomer states of Bi with spin I = 1/2 ( A = 193, 195, 197). This testifies to the shape coexistence in these nuclei with the intruder isomer states more deformed than the ground states. Marked deviation from the nearly spherical behavior for ground states of the even-neutron Bi isotopes at N < 109 is demonstrated, in contrast to the Pb and Tl isotopic chains.

Cenozoic climate evolution in Asian region and its influence on isotopic composition of precipitation

NASA Astrophysics Data System (ADS)

Botsyun, Svetlana; Donnadieu, Yannick; Sepulchre, Pierre; Risi, Camille; Fluteau, Frédéric

2015-04-01

The evolution of Asian climate during the Cenozoic as well as the onset of monsoon systems in this area is highly debated. Factors that control climate include the geographical position of continents, the land-sea distribution and altitude of orogens. In tern, several climatic parameters such as air temperature, precipitation amount and isotopic fractionation through mass-dependent processes impact precipitation δ18O lapse rate. Stable oxygen paleoaltimetry is considered to be a very efficient and widely applied technique, but the link between stable oxygen composition of precipitation and climate is not well established. To quantify the influence of paleogeography changes on climate and precipitation δ18O over Asia, the atmospheric general circulation model LMDZ-iso, with embedded stable oxygen isotopes, was used. For more realistic experiments, sea surface temperatures were calculated with the fully coupled model FOAM. Various scenarios of TP growth have been applied together with Paleocene, Eocene, Oligocene and Miocene boundary conditions. The results of our numerical modelling show a significant influence of paleogeography changes on the Asian climate. The retreat of the Paratethys ocean, the changes in latitudinal position of India, and the height of the Tibetan Plateau most likely control precipitation patterns over Asia and cause spatial and temporal isotopic variations linked with the amount effect. Indian Ocean currents restructuring during the Eocene induces a substantial warming over Asian continent. The adiabatic and non-adiabatic temperature effects explain some of δ18O signal variations. We highlight the importance of these multiple factor on paleoelevations estimates derived using oxygen stable isotopes.

Magnesium isotope fractionation in biogenic and abiogenic carbonates: implications for paleoenvironmental proxies

NASA Astrophysics Data System (ADS)

Saenger, Casey; Wang, Zhengrong

2014-04-01

Geochemical variations in marine biogenic carbonates that are preserved in the geological record serve as proxies of past environmental change. However, interpreting most proxies is complicated by biologically-mediated vital effects, highlighting the need to develop new tools for reconstructing paleoenvironmental change. Recently, magnesium (Mg) isotope variability in carbonates has been explored extensively to determine its utility as a paleoenvironmental proxy. We review the results of these works, which have yielded valuable information on the factors affecting Mg isotope fractionation between carbonates and solution (Δ26Mgcarb-sol) in biogenic and abiogenic carbonate minerals. Strong evidence exists for a mineralogical control on Δ26Mgcarb-sol, with the negative offset from 0‰ following the sequence aragonite < dolomite < magnesite < calcite. Abiogenic carbonates precipitated from solutions with relatively high Mg/Ca ratios (>˜3 mol/mol) and saturation states (Ω >˜3) that are similar to seawater suggest that Δ26Mgcarb-sol has a temperature dependence of ˜0.01‰ °C-1 and is insensitive to precipitation rate. In contrast, a significant precipitation rate dependence is observed in calcites precipitated from solutions with relatively low Mg/Ca ratios (<˜3 mol/mol) and saturation states (Ω <˜3). This difference likely reflects varying mineral growth mechanisms and we discuss the degree to which Δ26Mgcarb-sol may be affected by factors such as fluid inclusions, amorphous calcium carbonate precursors, ion attachment/detachment kinetics, surface entrapment and Mg speciation. High-Mg calcite organisms, which likely precipitate from relatively unmodified seawater, also exhibit a temperature dependence of ˜0.01‰ °C-1, albeit sometimes with a systematic offset toward smaller fractionations. In contrast, strong vital effects in low-Mg calcite organisms, which exclude Mg from their calcifying fluids, lead to Δ26Mgcarb-sol values that exhibit no clear temperature dependence and are offset from abiogenic experiments. The majority of biogenic aragonites have Δ26Mgcarb-sol values that are slightly more positive than those in abiogenic experiments, but bivalves and one sclerosponge species can exhibit significantly larger fractionations. Although vital effects and analytical uncertainties will limit Δ26Mgcarb-sol paleotemperature reconstructions to anomalies of at least ±10 °C, Mg isotope variability in biogenic carbonates may be a useful proxy for the Mg isotope composition of seawater, which reflects continental weathering, dolomitization and hydrothermal activity.

Effect of 3-nitrooxypropanol on methane and hydrogen emissions, methane isotopic signature, and ruminal fermentation in dairy cows.

PubMed

Lopes, J C; de Matos, L F; Harper, M T; Giallongo, F; Oh, J; Gruen, D; Ono, S; Kindermann, M; Duval, S; Hristov, A N

2016-07-01

The objective of this crossover experiment was to investigate the effect of a methane inhibitor, 3-nitrooxypropanol (3NOP), on enteric methane emission, methane isotopic composition, and rumen fermentation and microbial profile in lactating dairy cows. The experiment involved 6 ruminally cannulated late-lactation Holstein cows assigned to 2 treatments: control and 3NOP (60 mg/kg of feed dry matter). Compared with the control, 3NOP decreased methane emission by 31% and increased hydrogen emission from undetectable to 1.33 g/d. Methane emissions per kilogram of dry matter intake and milk yield were also decreased 34% by 3NOP. Milk production and composition were not affected by 3NOP, except milk fat concentration was increased compared with the control. Concentrations of total VFA and propionate in ruminal fluid were not affected by treatment, but acetate concentration tended to be lower and acetate-to-propionate ratio was lower for 3NOP compared with the control. The 3NOP decreased the molar proportion of acetate and increase those of propionate, butyrate, valerate, and isovalerate. Deuterium-to-hydrogen ratios of methane and the abundance of (13)CH3D were similar between treatments. Compared with the control, minor (4‰) depletion in the (13)C/(12)C ratio was observed for 3NOP. Genus composition of methanogenic archaea (Methanobrevibacter, Methanosphaera, and Methanomicrobium) was not affected by 3NOP, but the proportion of methanogens in the total cell counts tended to be decreased by 3NOP. Prevotella spp., the predominant bacterial genus in ruminal contents in this experiment, was also not affected by 3NOP. Compared with the control, Ruminococcus and Clostridium spp. were decreased and Butyrivibrio spp. was increased by 3NOP. This experiment demonstrated that a substantial inhibition of enteric methane emission by 3NOP in dairy cows was accompanied with increased hydrogen emission and decreased acetate-to-propionate ratio; however, neither an effect on rumen archaeal community composition nor a significant change in the isotope composition of methane was observed. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

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

PubMed

Varga, Matthew J; Schwartz, Steven D

2016-04-12

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

Isotope and multiband effects in layered superconductors.

PubMed

Bussmann-Holder, Annette; Keller, Hugo

2012-06-13

In this review we consider three classes of superconductors, namely cuprate superconductors, MgB(2) and the new Fe based superconductors. All of these three systems are layered materials and multiband compounds. Their pairing mechanisms are under discussion with the exception of MgB(2), which is widely accepted to be a 'conventional' electron-phonon interaction mediated superconductor, but extending the Bardeen-Cooper-Schrieffer (BCS) theory to account for multiband effects. Cuprates and Fe based superconductors have higher superconducting transition temperatures and more complex structures. Superconductivity is doping dependent in these material classes unlike in MgB(2) which, as a pure compound, has the highest values of T(c) and a rapid suppression of superconductivity with doping takes place. In all three material classes isotope effects have been observed, including exotic ones in the cuprates, and controversial ones in the Fe based materials. Before the area of high-temperature superconductivity, isotope effects on T(c) were the signature for phonon mediated superconductivity-even when deviations from the BCS value to smaller values were observed. Since the discovery of high T(c) materials this is no longer evident since competing mechanisms might exist and other mediating pairing interactions are discussed which are of purely electronic origin. In this work we will compare the three different material classes and especially discuss the experimentally observed isotope effects of all three systems and present a rather general analysis of them. Furthermore, we will concentrate on multiband signatures which are not generally accepted in cuprates even though they are manifest in various experiments, the evidence for those in MgB(2), and indications for them in the Fe based compounds. Mostly we will consider experimental data, but when possible also discuss theoretical models which are suited to explain the data.

You are not always what we think you eat: selective assimilation across multiple whole-stream isotopic tracer studies

Treesearch

W. K. Dodds; S. M. Collins; S. K. Hamilton; J. L. Tank; S. Johnson; J. R. Webster; K. S. Simon; M. R. Whiles; H. M. Rantala; W. H. McDowell; S. D. Peterson; T. Riis; C. L. Crenshaw; S. A. Thomas; P. B. Kristensen; B. M. Cheever; A. S. Flecker; N. A. Griffiths; T. Crowl; E. J. Rosi-Marshall; R. El-Sabaawi; E. Martí

2014-01-01

Analyses of 21 15N stable isotope tracer experiments, designed to examine food web dynamics in streams around the world, indicated that the isotopic composition of food resources assimilated by primary consumers (mostly invertebrates) poorly reflected the presumed food sources. Modeling indicated that consumers assimilated only 33–50% of the N...

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

Application of Fe Isotopes to the Search for Life and Habitable Planets

NASA Technical Reports Server (NTRS)

Johnson, Clark M.; Beard, Brian L.; Nealson, Kenneth L.

2001-01-01

The relatively new field of Fe isotope geochemistry can make important contributions to tracing the geochemical cycling of Fe, which bears on issues such as metabolic processing of Fe, surface redox conditions, and development of planetary atmospheres and biospheres. It appears that Fe isotope fractionation in nature and the lab spans about 4 per mil (%) in Fe-56/Fe-54, and although this range is small, our new analytical methods produce a precision of +/- 0.05% on sample sizes as small as 100 ng (10(exp -7) g); this now provides us with a sufficient "signal-to-noise" ratio to make this isotope system useful. We review our work in three areas: 1) the terrestrial and lunar rock record, 2) experiments on inorganic fractionation, and 3) experiments involving biological processing of Fe. Additional information is contained in the original extended abstract.

On the influence of anharmonicity on the isotope effect

NASA Astrophysics Data System (ADS)

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

1991-12-01

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

Isotope effects on the optical spectra of semiconductors

NASA Astrophysics Data System (ADS)

Cardona, Manuel; Thewalt, M. L. W.

2005-10-01

Since the end of the cold war, macroscopic amounts of separated stable isotopes of most elements have been available “off the shelf” at affordable prices. Using these materials, single crystals of many semiconductors have been grown and the dependence of their physical properties on isotopic composition has been investigated. The most conspicuous effects observed have to do with the dependence of phonon frequencies and linewidths on isotopic composition. These affect the electronic properties of solids through the mechanism of electron-phonon interaction, in particular, in the corresponding optical excitation spectra and energy gaps. This review contains a brief introduction to the history, availability, and characterization of stable isotopes, including their many applications in science and technology. It is followed by a concise discussion of the effects of isotopic composition on the vibrational spectra, including the influence of average isotopic masses and isotopic disorder on the phonons. The final sections deal with the effects of electron-phonon interaction on energy gaps, the concomitant effects on the luminescence spectra of free and bound excitons, with particular emphasis on silicon, and the effects of isotopic composition of the host material on the optical transitions between the bound states of hydrogenic impurities.

Disentangling effects of growth and nutritional status on seabird stable isotope ratios

USGS Publications Warehouse

Sears, J.; Hatch, Shyla A.; O'Brien, D. M.

2009-01-01

A growing number of studies suggest that an individual's physiology affects its carbon and nitrogen stable isotope signatures, obscuring a signal often assumed to be only a reflection of diet and foraging location. We examined effects of growth and moderate food restriction on red blood cell (RBC) and feather ??15N and ??13C in rhinoceros auklet chicks (Cerorhinca monocerata), a piscivorous seabird. Chicks were reared in captivity and fed either control (75 g/day; n = 7) or ~40% restricted (40 g/day; n = 6) amounts of high quality forage fish. We quantified effects of growth on isotopic fractionation by comparing ??15N and ??13C in control chicks to those of captive, non-growing subadult auklets (n = 11) fed the same diet. To estimate natural levels of isotopic variation, we also collected blood from a random sample of free-living rhinoceros auklet adults and chicks in the Gulf of Alaska (n = 15 for each), as well as adult feather samples (n = 13). In the captive experiment, moderate food restriction caused significant depletion in ??15N of both RBCs and feathers in treatment chicks compared to control chicks. Growth also induced depletion in RBC ??15N, with chicks exhibiting lower ??15N when they were growing the fastest. As growth slowed, ??15N increased, resulting in an overall pattern of enrichment over the course of the nestling period. Combined effects of growth and restriction depleted ??15N in chick RBCs by 0.92???. We propose that increased nitrogen-use efficiency is responsible for 15N depletion in both growing and food-restricted chicks. ??15N values in RBCs of free-ranging auklets fell within a range of only 1.03???, while feather ??15N varied widely. Together, our captive and field results suggest that both growth and moderate food restriction can affect stable isotope ratios in an ecologically meaningful way in RBCs although not feathers due to greater natural variability in this tissue. ?? 2008 Springer-Verlag.

Can Biomass Burning Explain Isotopically Light Fe in Marine Aerosols?

NASA Astrophysics Data System (ADS)

Sherry, A. M.; Anbar, A. D.; Herckes, P.; Romaniello, S. J.

2016-02-01

Iron (Fe) is an important micronutrient that limits primary productivity in large parts of the ocean. In these regions, atmospheric aerosol deposition is an important source of Fe to the surface ocean and thus has a critical impact on ocean biogeochemistry. Fe-bearing aerosols originate from many sources with potentially distinct Fe isotopic compositions. Consequently, Fe isotopes may provide a new tool to trace the sources of aerosol Fe to the oceans. Mead et al. (2013) first discovered that Fe in the fine fraction of Bermuda aerosols is often isotopically lighter than Fe from known anthropogenic and crustal sources. 1 These authors suggested that this light isotopic signature was likely the result of biomass burning, since Fe in plants is the only known source of isotopically light Fe. More recently, Conway et al. found that Fe in the soluble fraction of aerosols collected during 2010-2011 North Atlantic GEOTRACES cruises also showed light isotope values, which they likewise attributed to biomass burning.2 These studies are further supported by new modeling work which suggests that biomass burning aerosols should contribute significant amounts of soluble Fe to tropical and southern oceans.3To test if biomass burning releases aerosols with a light Fe isotope composition, we are conducting lab-scale biomass burning experiments using natural samples of vegetation and leaf litter. Burn aerosols were collected on cellulose filters, then digested and analyzed for trace metal concentrations using inductively-coupled mass spectrometry (ICP-MS). Fe isotopes were determined by using multiple collector ICP-MS following separation and purification of Fe using anion exchange chromatography. We will discuss metal concentration and isotope data from these experiments with implications for the interpretation of Fe isotope signals in aerosol samples. 1Mead, C et al. GRL, 2013, 40, 5722-5727. 2 Conway, T et al. Goldschmidt Abs 2015 593. 3Ito, A. ES&T Lett, 2015, 2, 70-75.

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.

Isotopically Enriched C-13 Diamond Anvil as a Stress Sensor in High Pressure Experiments

NASA Astrophysics Data System (ADS)

Vohra, Yogesh; Qiu, Wei; Kondratyev, Andreiy; Velisavljevic, Nenad; Baker, Paul

2004-03-01

The conventional high pressure diamond anvils were modified by growing an isotopically pure C-13 diamond layer by microwave plasma chemical vapor deposition using methane/hydrogen/oxygen chemistry. The isotopically pure C-13 nature of the culet of the diamond anvil was confirmed by the Raman spectroscopy measurements. This isotopically engineered diamond anvil was used against a natural abundance diamond anvil for high pressure experiments in a diamond anvil cell. Spatial resolved Raman spectroscopy was used to measure the stress induced shift in the C-13 layer as well as the undelying C-12 layer to ultra high pressures. The observed shift and splitiing of the diamond first order Raman spectrum was correlated with the stress distribution in the diamond anvil cell. The experimental results will be compared with the finite element modeling results using NIKE-2D software in order to create a mathematical relationship between sets of the following parameters: vertical (z axis) distance; horizontal (r axis) distance; max shear stress, and pressure. The isotopically enriched diamond anvils offer unique opportunities to measure stress distribution in the diamond anvil cell devices.

Laboratory investigations of stable carbon and oxygen isotope ratio data enhance monitoring of CO2 underground

NASA Astrophysics Data System (ADS)

Barth, Johannes A. C.; Myrttinen, Anssi; Becker, Veith; Nowak, Martin; Mayer, Bernhard

2014-05-01

Stable carbon and oxygen isotope data play an important role in monitoring CO2 in the subsurface, for instance during carbon capture and storage (CCS). This includes monitoring of supercritical and gaseous CO2 movement and reactions under reservoir conditions and detection of potential CO2 leakage scenarios. However, in many cases isotope data from field campaigns are either limited due to complex sample retrieval or require verification under controlled boundary conditions. Moreover, experimentally verified isotope fractionation factors are also accurately known only for temperatures and pressures lower than commonly found in CO2 reservoirs (Myrttinen et al., 2012). For this reason, several experimental series were conducted in order to investigate effects of elevated pressures, temperatures and salinities on stable carbon and oxygen isotope changes of CO2 and water. These tests were conducted with a heateable pressure device and with glass or metal gas containers in which CO2 reacted with fluids for time periods of hours to several weeks. The obtained results revealed systematic differences in 13C/12C-distributions between CO2 and the most important dissolved inorganic carbon (DIC) species under reservoir conditions (CO2(aq), H2CO3 and HCO3-). Since direct measurements of the pH, even immediately after sampling, were unreliable due to rapid CO2 de-gassing, one of the key results of this work is that carbon isotope fractionation data between DIC and CO2 may serve to reconstruct in situ pH values. pH values reconstructed with this approach ranged between 5.5 and 7.4 for experiments with 60 bars and up to 120 °C and were on average 1.4 pH units lower than those measured with standard pH electrodes directly after sampling. In addition, pressure and temperature experiments with H2O and CO2 revealed that differences between the oxygen isotope ratios of both phases depended on temperature, water-gas ratios as well as salt contents of the solutions involved. Such systematic knowledge of the extent of oxygen isotope fractionation between H2O and CO2 can help to reconstruct equilibration times, fluid-CO2 ratios as well as temperature and salinity conditions. Isotope results from systematic laboratory studies and the information they provide for assessing in situ reservoir conditions can be transferred to field applications concerning integrity of CO2 reservoirs. They can also apply to natural systems and other industrial uses that involve monitoring of gases in the subsurface under similar pressure and temperature conditions. Reference: Myrttinen, A., Becker, V., Barth, J.A.C., 2012. A review of methods used for equilibrium isotope fractionation investigations between dissolved inorganic carbon and CO2. Earth-Science Reviews, 115(3): 192-199.

Stable sulfur isotope partitioning during simulated petroleum formation as determined by hydrous pyrolysis of Ghareb Limestone, Israel

USGS Publications Warehouse

Amrani, A.; Lewan, M.D.; Aizenshtat, Zeev

2005-01-01

Hydrous pyrolysis experiments at 200 to 365??C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2 S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2??? in 34S during thermal maturation compared with the initial ??34S values. The ??34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1??? of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21??? lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the ??34S-enriched secondary pyrite decomposes above 300??C resulting in a corresponding decrease in the ??34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen ??34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and ??34S of each phase including the H2S(gas). H2S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite. Copyright ?? 2005 Elsevier Ltd.

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste

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

Wimmer, Bernhard, E-mail: bernhard.wimmer@ait.ac.at; Hrad, Marlies; Huber-Humer, Marion

Highlights: ► The isotopic signature of δ{sup 13}C-DIC of leachates is linked to the reactivity of MSW. ► Isotopic signatures of leachates depend on aerobic/anaerobic conditions in landfills. ► In situ aeration of landfills can be monitored by isotope analysis in leachate. ► The isotopic analysis of leachates can be used for assessing the stability of MSW. ► δ{sup 13}C-DIC of leachates helps to define the duration of landfill aftercare. - Abstract: Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated themore » isotopic signatures of δ{sup 13}C, δ{sup 2}H and δ{sup 18}O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25 year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration. We found significant differences in the δ{sup 13}C-value of the dissolved inorganic carbon (δ{sup 13}C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ{sup 13}C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ{sup 13}C-DIC of −20‰ to −25‰. The production of methane under anaerobic conditions caused an increase in δ{sup 13}C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ{sup 13}C-DIC of about −20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation–reduction status of MSW landfills. Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration.« less

2015 DOE Final UF Report. Effects of Warming the Deep Soil and Permafrost on Ecosystem Carbon Balance in Alaskan Tundra. A Coupled Measurement and Modeling Approach

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

Schuur, Edward

2015-06-11

The major research goal of this project was to understand and quantify the fate of carbon stored in permafrost ecosystems using a combination of field and laboratory experiments to measure isotope ratios and C fluxes in a tundra ecosystem exposed to experimental warming. Field measurements centered on the establishment of a two-factor experimental warming using a snow fence and open top chambers to increase winter and summer temperatures alone, and in combination, at a tundra field site at the Eight Mile Lake watershed near Healy, Alaska. The objective of this experimental warming was to significantly raise air and deep soilmore » temperatures and increase the depth of thaw beyond that of previous warming experiments. Detecting the loss and fate of the old permafrost C pool remains a major challenge. Because soil C has been accumulating in these ecosystems over the past 10,000 years, there is a strong difference between the radiocarbon isotopic composition of C deep in the soil profile and permafrost compared to that near the soil surface. This large range of isotopic variability is unique to radiocarbon and provides a valuable and sensitive fingerprint for detecting the loss of old soil C as permafrost thaws.« less

Iron oxides stimulate sulfate-driven anaerobic methane oxidation in seeps

DOE PAGES

Sivan, Orit; Antler, Gilad; Turchyn, Alexandra V.; ...

2014-09-22

Seep sediments are dominated by intensive microbial sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Through geochemical measurements of incubation experiments with methane seep sediments collected from Hydrate Ridge, we provide insight into the role of iron oxides in sulfate-driven AOM. Seep sediments incubated with 13C-labeled methane showed co-occurring sulfate reduction, AOM, and methanogenesis. The isotope fractionation factors for sulfur and oxygen isotopes in sulfate were about 40‰ and 22‰, respectively, reinforcing the difference between microbial sulfate reduction in methane seeps versus other sedimentary environments (for example, sulfur isotope fractionation above 60‰ in sulfate reduction coupled to organicmore » carbon oxidation or in diffusive sedimentary sulfate–methane transition zone). The addition of hematite to these microcosm experiments resulted in significant microbial iron reduction as well as enhancing sulfate-driven AOM. The magnitude of the isotope fractionation of sulfur and oxygen isotopes in sulfate from these incubations was lowered by about 50%, indicating the involvement of iron oxides during sulfate reduction in methane seeps. The similar relative change between the oxygen versus sulfur isotopes of sulfate in all experiments (with and without hematite addition) suggests that oxidized forms of iron, naturally present in the sediment incubations, were involved in sulfate reduction, with hematite addition increasing the sulfate recycling or the activity of sulfur-cycling microorganisms by about 40%. Furthermore, these results highlight a role for natural iron oxides during bacterial sulfate reduction in methane seeps not only as nutrient but also as stimulator of sulfur recycling.« less

Carbon and hydrogen isotopic effects of stomatal density in Arabidopsis thaliana

NASA Astrophysics Data System (ADS)

Lee, Hyejung; Feakins, Sarah J.; Sternberg, Leonel da S. L.

2016-04-01

Stomata are key gateways mediating carbon uptake and water loss from plants. Varied stomatal densities in fossil leaves raise the possibility that isotope effects associated with the openness of exchange may have mediated plant wax biomarker isotopic proxies for paleovegetation and paleoclimate in the geological record. Here we use Arabidopsis thaliana, a widely used model organism, to provide the first controlled tests of stomatal density on carbon and hydrogen isotopic compositions of cuticular waxes. Laboratory grown wildtype and mutants with suppressed and overexpressed stomatal densities allow us to directly test the isotope effects of stomatal densities independent of most other environmental or biological variables. Hydrogen isotope (D/H) measurements of both plant waters and plant wax n-alkanes allow us to directly constrain the isotopic effects of leaf water isotopic enrichment via transpiration and biosynthetic fractionations, which together determine the net fractionation between irrigation water and n-alkane hydrogen isotopic composition. We also measure carbon isotopic fractionations of n-alkanes and bulk leaf tissue associated with different stomatal densities. We find offsets of +15‰ for δD and -3‰ for δ13C for the overexpressed mutant compared to the suppressed mutant. Since the range of stomatal densities expressed is comparable to that found in extant plants and the Cenozoic fossil record, the results allow us to consider the magnitude of isotope effects that may be incurred by these plant adaptive responses. This study highlights the potential of genetic mutants to isolate individual isotope effects and add to our fundamental understanding of how genetics and physiology influence plant biochemicals including plant wax biomarkers.

Experimental identification of Ca isotopic fractionations in higher plants

NASA Astrophysics Data System (ADS)

Cobert, Florian; Schmitt, Anne-Désirée; Bourgeade, Pascale; Labolle, François; Badot, Pierre-Marie; Chabaux, François; Stille, Peter

2011-10-01

Hydroponic experiments have been performed in order to identify the co-occurring geochemical and biological processes affecting the Ca isotopic compositions within plants. To test the influence of the Ca concentration and pH of the nutritive solution on the Ca isotopic composition of the different plant organs, four experimental conditions were chosen combining two different Ca concentrations (5 and 60 ppm) and two pHs (4 and 6). The study was performed on rapid growing bean plants in order to have a complete growth cycle. Several organs (root, stem, leaf, reproductive) were sampled at two different growth stages (10 days and 6 weeks of culture) and prepared for Ca isotopic measurements. The results allow to identify three Ca isotopic fractionation levels. The first one takes place when Ca enters the lateral roots, during Ca adsorption on cation-exchange binding sites in the apoplasm. The second one takes place when Ca is bound to the polygalacturonic acids (pectins) of the middle lamella of the xylem cell wall. Finally, the last fractionation occurs in the reproductive organs, also caused by cation-exchange processes with pectins. However, the cell wall structures of these organs and/or number of available exchange sites seem to be different to those of the xylem wall. These three physico-chemical fractionation mechanisms allow to enrich the organs in the light 40Ca isotope. The amplitude of the Ca isotopic fractionation within plant organs is highly dependent on the composition of the nutritive solution: low pH (4) and Ca concentrations (5 ppm) have no effect on the biomass increase of the plants but induce smaller fractionation amplitudes compared to those obtained from other experimental conditions. Thus, Ca isotopic signatures of bean plants are controlled by the external nutritive medium. This study highlights the potential of Ca isotopes to be applied in plant physiology (to identify Ca uptake, circulation and storage mechanisms within plants) and in biogeochemistry (to identify Ca recycling, Ca content and pH evolutions in soil solutions through time).

Carbon and hydrogen isotope fractionation under continuous light: implications for paleoenvironmental interpretations of the High Arctic during Paleogene warming.

PubMed

Yang, Hong; Pagani, Mark; Briggs, Derek E G; Equiza, M A; Jagels, Richard; Leng, Qin; Lepage, Ben A

2009-06-01

The effect of low intensity continuous light, e.g., in the High Arctic summer, on plant carbon and hydrogen isotope fractionations is unknown. We conducted greenhouse experiments to test the impact of light quantity and duration on both carbon and hydrogen isotope compositions of three deciduous conifers whose fossil counterparts were components of Paleogene Arctic floras: Metasequoia glyptostroboides, Taxodium distichum, and Larix laricina. We found that plant leaf bulk carbon isotopic values of the examined species were 1.75-4.63 per thousand more negative under continuous light (CL) than under diurnal light (DL). Hydrogen isotope values of leaf n-alkanes under continuous light conditions revealed a D-enriched hydrogen isotope composition of up to 40 per thousand higher than in diurnal light conditions. The isotope offsets between the two light regimes is explained by a higher ratio of intercellular to atmospheric CO(2) concentration (C (i)/C (a)) and more water loss for plants under continuous light conditions during a 24-h transpiration cycle. Apparent hydrogen isotope fractionations between source water and individual lipids (epsilon(lipid-water)) range from -62 per thousand (Metasequoia C(27) and C(29)) to -87 per thousand (Larix C(29)) in leaves under continuous light. We applied these hydrogen fractionation factors to hydrogen isotope compositions of in situ n-alkanes from well-preserved Paleogene deciduous conifer fossils from the Arctic region to estimate the deltaD value in ancient precipitation. Precipitation in the summer growing season yielded a deltaD of -186 per thousand for late Paleocene, -157 per thousand for early middle Eocene, and -182 per thousand for late middle Eocene. We propose that high-latitude summer precipitation in this region was supplemented by moisture derived from regionally recycled transpiration of the polar forests that grew during the Paleogene warming.

Chromium isotope fractionation in ferruginous sediments

NASA Astrophysics Data System (ADS)

Bauer, Kohen W.; Gueguen, Bleuenn; Cole, Devon B.; Francois, Roger; Kallmeyer, Jens; Planavsky, Noah; Crowe, Sean A.

2018-02-01

Ferrous Fe is a potent reductant of Cr(VI), and while a number of laboratory studies have characterized Cr isotope fractionation associated with Cr(VI) reduction by ferrous iron, the expression of this fractionation in real-world ferrous Fe-rich environments remains unconstrained. Here we determine the isotope fractionation associated with Cr(VI) reduction in modern ferrous Fe-rich sediments obtained from the previously well studied Lake Matano, Indonesia. Whole core incubations demonstrate that reduction of Cr(VI) within ferruginous sediments provides a sink for Cr(VI) leading to Cr(VI) concentration gradients and diffusive Cr(VI) fluxes across the sediment water interface. As reduction proceeded, Cr(VI) remaining in the overlying lake water became progressively enriched in the heavy isotope (53Cr), increasing δ53Cr by 2.0 ± 0.1‰ at the end of the incubation. Rayleigh distillation modelling of the evolution of Cr isotope ratios and Cr(VI) concentrations in the overlying water yields an effective isotope fractionation of εeff = 1.1 ± 0.2‰ (53Cr/52Cr), whereas more detailed diagenetic modelling implies an intrinsic isotope fractionation of εint = 1.80 ± 0.04‰. Parallel slurry experiments performed using anoxic ferruginous sediment yield an intrinsic isotope fractionation of εint = 2.2 ± 0.1‰. These modelled isotope fractionations are corroborated by direct measurement of the δ53Cr composition on the upper 0.5 cm of Lake Matano sediment, revealing an isotopic offset from the lake water of Δ53Cr = 0.21-1.81‰. The data and models reveal that effective isotope fractionations depend on the depth at which Cr(VI) reduction takes place below the sediment water interface-the deeper the oxic non-reactive zone, the smaller the effective fractionation relative to the intrinsic fractionation. Based on the geochemistry of the sediment we suggest the electron donors responsible for reduction are a combination of dissolved Fe(II) and 0.5 M HCl extractable (solid phase) Fe(II). Our results are in line with the range of intrinsic fractionation factors observed for such phases in previous laboratory studies. We suggest that intrinsic isotope fractionations of around 1.8‰, may be broadly characteristic of ferruginous environments, but we note that the partitioning of ferrous Fe between dissolved and solid phases may modulate this value. These results indicate that seawater δ53Cr is only captured with high-fidelity by ferruginous sediments when oxygen penetration, and therefore the upper boundary of the zone of Cr(VI) reduction, extends to more than 10 cm below the sediment-water-interface, as can be the case in sediments deposited below oligotrophic waters. In more productive regions, with thinner oxic zones, ferruginous sediments would record δ53Cr as much as 1.8‰ lower than seawater δ53Cr. This implies that a range of sediment δ53Cr compositions, that include that of the igneous silicate earth (ISE), are possible even when seawater is isotopically heavier than the ISE.

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.

The reduction and oxidation of ceria: A natural abundance triple oxygen isotope perspective

NASA Astrophysics Data System (ADS)

Hayles, Justin; Bao, Huiming

2015-06-01

Ceria (CeO2) is a heavily studied material in catalytic chemistry for use as an oxygen storage medium, oxygen partial pressure regulator, fuel additive, and for the production of syngas, among other applications. Ceria powders are readily reduced and lose structural oxygen when subjected to low pO2 and/or high temperature conditions. Such dis-stoichiometric ceria can then re-oxidize under higher pO2 and/or lower temperature by incorporating new oxygen into the previously formed oxygen site vacancies. Despite extensive studies on ceria, the mechanisms for oxygen adsorption-desorption, dissociation-association, and diffusion of oxygen species on ceria surface and within the crystal structure are not well known. We predict that a large kinetic oxygen isotope effect should accompany the release and incorporation of ceria oxygen. As the first attempt to determine the existence and the degree of the isotope effect, this study focuses on a set of simple room-temperature re-oxidation experiments that are also relevant to a laboratory procedure using ceria to measure the triple oxygen isotope composition of CO2. Triple-oxygen-isotope labeled ceria powders are heated at 700 °C and cooled under vacuum prior to exposure to air. By combining results from independent experimental sets with different initial oxygen isotope labels and using a combined mass-balance and triangulation approach, we have determined the isotope fractionation factors for both high temperature reduction in vacuum (⩽10-4 mbar) and room temperature re-oxidation in air. Results indicate that there is a 1.5‰ ± 0.8‰ increase in the δ18O value of ceria after being heated in vacuum at 700 °C for 1 h. When the vacuum is broken at room temperature, the previously heated ceria incorporates 3-19% of its final structural oxygen from air, with a δ18O value of 2.1-4.1+7.7 ‰ for the incorporated oxygen. The substantial incorporation of oxygen from air supports that oxygen mobility is high in vacancy-rich ceria during re-oxidation at room temperature. The quantified oxygen isotope fractionation factors are consistent with the direct involvement of O2 in the rate limiting step for ceria reoxidation in air at room temperature. While additional parameters may reduce some of the uncertainties in our approach, this study demonstrates that isotope effects can be an encouraging tool for studying oxygen transport kinetics in ceria and other oxides. In addition, our finding warns of the special cares and limits in using ceria as an exchange medium for laboratory triple oxygen isotope analysis of CO2 or other oxygen-bearing gases.

From Mars Meteorites to Laboratory Investigations: Understanding Heterogeneous Photochemical Transformations Using Oxygen Triple Isotope Anomalies of Carbonates

NASA Astrophysics Data System (ADS)

Shaheen, R.; Smirnova, V.; Jackson, T. L.; Mang, L.; Thiemens, M. H.

2016-12-01

The planet Mars is unique in our solar system with a positive O-isotope anomaly observed in its bulk silicate and carbonates minerals ranging from 0.3 to 0.6 ‰. The carbonate isotopic signature can be used to reveal its origin, past history and atmosphere-hydrosphere-geosphere-interactions. Ozone is a powerful natural tracer of photochemical processes in Earth's atmosphere. It possess the highest enrichment in heavy isotopes δ17O ≈ δ18O (70-150‰) and oxygen isotopic anomaly (Δ17O = 30-40‰). The oxygen isotopic anomaly from ozone is transferred to other oxygen carrying molecules in the atmosphere through different mechanisms. Laboratory experiments were conducted with the JSC-Mars Simulant and iron oxide to investigate how this anomaly can be transferred to water and minerals under conditions similar to present day Mars. Three sets of laboratory experiments (O3-H2O-UV-minerals; O2-H2O-UV-minerals; O3-H2O-minerals) were performed. The oxygen triple isotopic analysis of product mineral carbonates formed from adsorbed CO2 reaction showed an oxygen isotopic anomaly (Δ17O = 0.4-3‰). The oxygen triple isotopic composition of water at photochemical equilibrium shifted towards ozone with Δ17O = 9‰ indicating reaction of ozone with water vapor via electronically excited oxygen atoms and transfer of the anomaly via hydroxyl radicals. HOx (HO, HO2) are extremely reactive and have very short life time (< μs), however, our data indicate that its signature is preserved through surficial interactions with adsorbed CO2 on mineral surfaces. Hydroxyl radicals may have played a significant role in heterogeneous photochemical transformations on mineral dust in the atmosphere of Mars and transfer of ozone anomaly to water and other oxygen bearing minerals through surficial reactions. Series of experiments were performed to constrain the amount of H2O required to preserve the oxygen isotope anomaly observed in carbonate minerals in the Martian meteorites. These observation will help refine Mars photochemistry models and also to constrain the past hydrological cycle and its coupling with the regolith. The observed inverse correlation between ozone and water vapor also suggests a dynamic role of hydroxyl radical chemistry in the atmosphere of Mars.

Chromium Isotope Behaviour During Aerobic Microbial Reduction Activities

NASA Astrophysics Data System (ADS)

Zhang, Q.; Amor, K.; Porcelli, D.; Thompson, I.

2014-12-01

Microbial activity is a very important, and possibly even the dominant, reduction mechanism for many metals in natural water systems. Isotope fractionations during microbial metal reduction can reflect one major mechanism in metal cycling in the environment, and isotopic signatures can be used to identify and quantify reduction processes during biogeochemical cycling in the present environment as well as in the past. There are many Cr (VI)-reducing bacteria that have been discovered and isolated from the environment, and Cr isotopes were found to be fractionated during microbial reduction processes. In this study, Cr reduction experiments have been undertaken to determine the conditions under which Cr is reduced and the corresponding isotope signals that are generated. The experiments have been done with a facultative bacteria Pseudomonas fluorescens LB 300, and several parameters that have potential impact on reduction mechanisms have been investigated. Electron donors are important for bacteria growth and metabolism. One factor that can control the rate of Cr reduction is the nature of the electron donor. The results show that using citrate as an electron donor can stimulate bacteria reduction activity to a large extent; the reduction rate is much higher (15.10 mgˑL-1hour-1) compared with experiments using glucose (6.65 mgˑL-1ˑhour-1), acetate (4.88 mgˑL-1hour-1) or propionate (4.85 mgˑL-1hour-1) as electron donors. Groups with higher electron donor concentrations have higher reduction rates. Chromium is toxic, and when increasing Cr concentrations in the medium, the bacteria reduction rate is also higher, which reflects bacteria adapting to the toxic environment. In the natural environment, under different pH conditions, bacteria may metabolise in different ways. In our experiments with pH, bacteria performed better in reducing Cr (VI) when pH = 8, and there are no significant differences between groups with pH = 4 or pH = 6. To investigate this further, Cr isotope determinations will be presented, which are essential in better understanding bacterial reducing activities under different environmental conditions and can also provide important background information for interpreting Cr isotope fractionations in natural environment, and using Cr isotopes to identify reduction by microbial activity.

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

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

Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joël

2014-06-28

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. [“Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry,” J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ({sup 15}N, {sup 17}O, and {sup 18}O) provide additional information concerning post-depositional processes. Here, we present results frommore » studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ{sup 15}N, δ{sup 18}O, and Δ{sup 17}O). From these measurements an average photolytic isotopic fractionation of {sup 15}ε = (−15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of {sup 15}ε = (−47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from −40 to −74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of {sup 14}NO{sub 3}{sup −} and {sup 15}NO{sub 3}{sup −} in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well reproduced the values obtained in the laboratory study. These cross sections can be used in isotopic models to reproduce the stable isotopic composition of nitrate found in Antarctic snow profiles.« less

Mass-dependent and Mass-independent Sulphur Isotope Fractionation Accompanying Thermal- and Photo-chemical Decomposition of Sulphur Bearing Organic Compounds

NASA Astrophysics Data System (ADS)

Oduro, Harry; Izon, Gareth; Ono, Shuhei

2014-05-01

The bimodal S-isotope record, specifically the transition from mass independent (MIF) to mass dependent fractionation (MDF), is perhaps the most widely cited line of evidence for an irreversible rise in atmospheric oxygen at ca. 2.4Ga. The production and preservation of S-MIF, manifested in both Δ33S and Δ36S, within the geological record are linked to atmospheric O2 via a number of arguments. However, to date, the only mechanism capable of generating S-MIF consistent with the Archaean sedimentary records involves gas-phase ultraviolet irradiation of SO21 photolysis. More recently, Δ33S S-MIF trends have been reported from en vitro thermochemical sulphate reduction (TSR) experiments, prompting authors to question the importance of S-MIF as a proxy for Earth oxidation2. Importantly, whilst emerging TSR experiments3,4 affirm the reported Δ33S trends2, these experiments fail to identify correlated S-MIF between Δ33S and Δ36S values3,4. Realization that S-MIF is confined to Δ33S during TSR, precludes TSR as a mechanism responsible for the origin of the Archaean S-MIF record but strongly suggests the effect originating from a magnetic isotope effect (MIE) associated with 33S nucleus3,4. Clearly, photochemical and thermochemical processes impart different Δ36S/Δ33S trends with significant variation in δ34S; however, a complete experimental elucidation of mechanisms responsible for the S-MIF and S-MIE signatures is lacking. Interestingly, a complete understanding of the S-isotope chemistry during thermal- and photo-chemical decomposition may reveal wavelength and thermal dependence archived in the sedimentary record. Here we extend the experimental database to explore the magnitude and sign of Δ36S/Δ33S and δ34S produced during both photo- and thermochemical processes. Here the organic sulphur compounds (OSC) utilized in these experiments carries diagnostic Δ36S/Δ33S patterns that differ from those reported from photolysis experiment SO2 and from the Archaean sedimentary record. Further thermal decomposition of several sulphur containing compounds with; 1) an aliphatic-S (e.g., diphenyl disulphide), 2) tri-substituted aromatic-S (trithiane), and S-amino acids (e.g., cysteine, methionine, taurine, and glutathionine) were tested for four S-isotope fractionation under vacuum. Among these, aromatic trithiane produced anomalous 33S up to 1.3‰, indicating thermal decomposition through radical chemistry, producing S-MIE. While taurine with sulphonic acid (R-SO2OH) functional groups yielded S-MDF up to 15‰ (between the AVS and the residual OSC), which is consistent with estimated zero-point energy shifts for thiol (R-SH), and thiyl (R-S-CH3) groups of cysteine and methionine, respectively. These results suggest that OSC might undergo either thermal or photochemical decomposition and the S-MIF, S-MDF, and S-MIE signatures may be archived in the geologic record. The emerging mechanisms responsible for these isotope signals and their implications will be discussed in more detail. Ultimately this work offers a framework where these signals can be used as a diagnostic marker to distinguish between thermo- and photochemical processes. References: 1. Farquhar et al., Science 2000 2. Watanabe et al., Science 2010; 3. Oduro et al., PNAS 2011; 4. Kopf and Ono, GCA 2012.

Investigating the Mechanism of Heteroaromatic Decarboxylation Using Solvent Kinetic Isotope Effects and Eyring Transition-State Theory

ERIC Educational Resources Information Center

Mundle, Scott O. C.; Opinska, Liliana Guevara; Kluger, Ronald; Dicks, Andrew P.

2011-01-01

An upper-level mechanistic organic experiment is outlined where undergraduates measure kinetic rate constants for decarboxylation of pyrrole-2-carboxylic acid by the initial-rates method. UV spectroscopy is used to monitor reactant disappearance in both hydrochloric acid and deuterium chloride at different temperatures. Individual data are pooled…

Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

ERIC Educational Resources Information Center

Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon

2014-01-01

An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D[subscript 2]O and a catalytic amount of H[subscript 2]SO[subscript 4]. The resulting labeled product is characterized by [superscript 1]H NMR. Students also…

Testing the Late-Veneer hypothesis with selenium isotopes

NASA Astrophysics Data System (ADS)

Labidi, J.; Koenig, S.; Bennett, N.; Kurzawa, T.; Aierken, E.; Shahar, A.; Schoenberg, R.

2016-12-01

Selenium (Se) is a siderophile element displaying an excess abundance in Earth's mantle compared to experimental predictions [1], which may be attributed to the Late-Veneer. As Se is also volatile, testing the late-veneer addition of Se can constrain the origin of other volatile elements on Earth. Here we combine high-precision Se isotope measurements of metal-silicate partitioning experiments and chondrites to assess whether planetary differentiation could leave a measurable Se isotopic signature on planetary mantles. We performed Se isotopic measurements of 5 metal-silicate partitioning experiments and 20 chondrites of all major classes. Experiments were conducted at 1 GPa and 1650 C for 1 to 4 hours using the piston-cylinder apparatus at Carnegie's Geophysical Laboratory. After wet chemistry, data were obtained on a ThermoFisher Scientific™ NeptunePlus MC-ICP-MS at the University of Tübingen with a 74Se/77Se double spike technique. δ82/76Se values are given relative to NIST SRM-3149 and the external reproducibility calculated from duplicate meteorite analyses is ≤ 0.1‰ (2 s.d.). Chondrites vary over a 0.8‰ range of δ82/76Se values. CIs and CMs show evidence for heavier 82Se/76Se ratios, likely due to mixing processes in the proto-planetary nebula. When these isotopically heavier meteorites are excluded, remaining chondrites have δ82/76Se values varying over a 0.3‰ range, within uncertainty of previous results [2]. We suggest that these chondrites may be used to estimate a δ82/76Se value of bulk planets. At the conditions of our experiments, the partition coefficients for Se log Dmetal-silicate range from 0.7±0.1 to 1.9±0.1, consistent with previous work [1]. A small but resolvable Se isotopic fractionation was observed: 82Se/76Se ratios were enriched by ≤ 0.5‰ in the silicates relative to the metals. Thus, given current uncertainties for Se isotopic measurements, marginal differences between planetary mantles and chondrites may be resolved. [1] Rose-Weston et al. 2009, GCA, 73(15), 4598-4615. [2] Vollstaedt et al. 2016, 450, 372-380.

Isotopic fractionation of gases during its migration: experiments and 2D numerical simulation

NASA Astrophysics Data System (ADS)

Kara, S.; Prinzhofer, A.

2003-04-01

Several works have been developed in the last decade on the experimental isotope fractionation of gases during migration (Prinzhofer et al., 1997 and Zhang &Krooss, 2001 among others). We add to these results new experiments on diffusion of CO_2, which becomes currently a crucial subject for environmental purpose. Our experiments showed that transport by diffusion of CO_2 through a water saturated shale induces a significant and systematic carbon isotopic fractionation with heavier (13C enriched) CO_2 migrating first. In all experiments, significant isotope fractionation was found but still remains without quantitative interpretation. To interpret these data, we developed a 2D numerical model at the pore scale. The general principle of this model is the study of transport by water solubilization/diffusion of gas in a capillary saturated with water with two different media : a mobile zone representing free water and a immobile zone representing bounded water. The model takes also into account solubilization coefficients of gas in water, as well as the migration distance and the volume of upstream and downstream reservoirs. Using our numerical model, we could reproduce the evolution of isotopic fractionations and the velocity of CO_2 migration versus the production factor F (proportion of diffused gas). We determined some physical parameters of the porous medium (bentonite) which are not directly measurable at the present time. Furthermore, we used these parameters to reproduce the curves of isotopic fractionation obtained by Pernaton (1998) on methane migration with the same porous rock. We used also a modified version of this model with infinite reservoirs to reproduce the curves of isotopic fractionation of Zhang &Krooss (2001). Application of this model to geological scale is under progress, in order to implement it into sedimentary basins modelling. REFERENCES: Zhang T. and Krooss M. (2001). Geochim. Cosmochim. Acta, Vol. 65, No.16, pp. 2723-2742. Pernaton E. (1998) PhD. Thesis, Université de Paris VII, 272 pp. Prinzhofer A. and Pernaton E. (1997) Chem. Geol., vol. 142, 193-200.

Introduction to chemistry and applications in nature of mass independent isotope effects special feature.

PubMed

Thiemens, Mark H

2013-10-29

Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented.

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.

Amino Acid Isotopic Trophic Enrichment in Mesozooplankton: Is Alanine a Better Predictor of Protistan Grazer Steps?

NASA Astrophysics Data System (ADS)

Decima, M.; Landry, M. R.; Bradley, C. J.; Fogel, M. L.

2016-02-01

Food-web studies within marine environments are increasingly reliant upon results from compound-specific isotope analysis of amino acids (CSIA-AA). The approach is advantageous because it allows consumer trophic positions to be estimated without sampling the dynamic primary producers. The baseline signal in the source AA phenylalanine is preserved, and a constant enrichment in glutamic acid at each trophic step is assumed, regardless of consumer type or diet. However, a number of recent studies challenge the assumption of universal and invariant isotopic fractionation of glutamic acid for all trophic levels, as well as its specific applicability to the main grazers in the ocean: the protistan microzooplankton. We present results from both laboratory and field studies that further explore this issue. Experiments include six 2-stage chemostats, using two different microzooplankton-phytoplankton pairs and one copepod-phytoplankton pair, and one 3-stage experiment using a copepod-microzooplankton-phytoplankton chain. We confirm previous observations of negligible fractionation of glutamic acid in protistan consumers when nutrients are limiting. In contrast, a consistent trophic enrichment effect was observed for alanine, with increasing δ15N values by trophic level for both metazoan and protistan consumers. A re-analysis of published CSIA-AA data of zooplankton species show that an index using alanine and phenylalanine gives trophic level estimates closer to expected given current understanding of the linkages within microbial food webs. Our results examine the details of isotopic fractionation of alanine within defined food chains and generally support its potential use as a trophic level indicator that includes the protistan contribution to mesozooplankton diet.

Investigating the behaviour of Mg isotopes during the formation of clay minerals

NASA Astrophysics Data System (ADS)

Wimpenny, Joshua; Colla, Christopher A.; Yin, Qing-Zhu; Rustad, James R.; Casey, William H.

2014-03-01

We present elemental and isotopic data detailing how the Mg isotope system behaves in natural and experimentally synthesized clay minerals. We show that the bulk Mg isotopic composition (δ26Mg) of a set of natural illite, montmorillonite and kaolinite spans a 2‰ range, and that their isotopic composition depends strongly on a balance between the relative proportions of structural and exchangeable Mg. After acid leaching, these natural clays become relatively enriched in isotopically heavy Mg by between 0.2‰ and 1.6‰. Results of exchange experiments indicate that the Mg that has adsorbed to interlayer spaces and surface charged sites is relatively enriched in isotopically light Mg compared to the residual clay. The isotopic composition of this exchangeable Mg (-1.49‰ to -2.03‰) is characteristic of the isotopic composition of Mg found in many natural waters. Further experiments with an isotopically characterized MgCl2 solution shows that the clay minerals adsorb this exchangeable Mg with little or no isotopic fractionation, although we cannot discount the possibility that the uptake of exchangeable Mg does so with a slight preference for 24Mg. To characterize the behaviour of Mg isotopes during clay mineral formation we synthesized brucite (Mg(OH)2), which we consider to be a good analogue for the incorporation of Mg into the octahedral sheet of Mg-rich clay minerals or into the brucitic layer of clays such as chlorite. In our experiment the brucite mineral becomes enriched in the heavy isotopes of Mg while the corresponding solution is always relatively enriched in isotopically light Mg. The system reaches a steady state after 10 days with a final fractionation factor (αsolid-solution) of 1.0005 at near-neutral pH. This result is consistent with the general consensus that secondary clay minerals preferentially take up isotopically heavy Mg during their formation. However our results also show that exchangeable Mg is an important component within bulk clay minerals and can have an important influence over the bulk clay δ26Mg value. Modeling shows that in certain soils or sediments where the percentage of exchangeable Mg is >30% and the isotopic composition of the exchangeable Mg is around -2‰, the generation of bulk δ26Mg values of <-0.5‰ is likely. On a broader scale, Mg-rich minerals such as smectite and illite are likely to impart a stronger control over the Mg budget in clay rich sediments, and their high structural Mg component is likely to result in bulk sediment δ26Mg values that are closer in composition to the UCC. Despite this, results of modeling, together with experimental observation suggests that the uptake of exchangeable Mg into these clay rich sediments could cause a decrease in the bulk δ26Mg value by up to ˜0.3-0.4‰. This should be accounted for when assessing the δ26Mg value of sediments on a crustal scale.

Ultrafiltration by a compacted clay membrane. I - Oxygen and hydrogen isotopic fractionation. II - Sodium ion exclusion at various ionic strengths.

NASA Technical Reports Server (NTRS)

Coplen, T. B.; Hanshaw, B. B.

1973-01-01

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 by 0.8% relative to the residual solution. No additional isotopic fractionation due to a salt-filtering mechanism was observed at NaCl concentrations up to 0.01N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

SIMS chemical and isotopic analysis of impact features from LDEF experiments AO187-1 and AO187-2

NASA Technical Reports Server (NTRS)

Stadermann, Frank J.; Amari, Sachiko; Foote, John; Swan, Pat; Walker, Robert M.; Zinner, Ernst

1995-01-01

Previous secondary ion mass spectrometry (SIMS) studies of extended impact features from LDEF capture cell experiment AO187-2 showed that it is possible to distinguish natural and man-made particle impacts based on the chemical composition of projectile residues. The same measurement technique has now been applied to specially prepared gold target impacts from experiment AO187-1 in order to identify the origins of projectiles that left deposits too thin to be analyzed by conventional energy-dispersive x-ray (EDX) spectroscopy. The results indicate that SIMS may be the method of choice for the analysis of impact deposits on a variety of sample surfaces. SIMS was also used to determine the isotopic compositions of impact residues from several natural projectiles. Within the precision of the measurements all analyzed residues show isotopically normal compositions.

Temperature dependence of the isotope chemistry of the heavy elements.

PubMed Central

Bigeleisen, J

1996-01-01

The temperature coefficient of equilibrium isotope fractionation in the heavy elements is shown to be larger at high temperatures than that expected from the well-studied vibrational isotope effects. The difference in the isotopic behavior of the heavy elements as compared with the light elements is due to the large nuclear isotope field shifts in the heavy elements. The field shifts introduce new mechanisms for maxima, minima, crossovers, and large mass-independent isotope effects in the isotope chemistry of the heavy elements. The generalizations are illustrated by the temperature dependence of the isotopic fractionation in the redox reaction between U(VI) and U(IV) ions. PMID:8790340

BIODEGRADATION OF FLUORANTHENE AS MONITORED USING STABLE CARBON ISOTOPES

EPA Science Inventory

The measurement of stable isotope ratios of carbon (d13C values) was investigated as a viable technique to monitor the intrinsic bioremediation of polycyclic aromatic hydrocarbons (PAHs). Biometer-flask experiments were conducted in which the bacterium, Sphingomonas paucimobilis,...

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.

Magnesium isotope fractionation in bacterial mediated carbonate precipitation experiments

NASA Astrophysics Data System (ADS)

Parkinson, I. J.; Pearce, C. R.; Polacskek, T.; Cockell, C.; Hammond, S. J.

2012-12-01

Magnesium is an essential component of life, with pivotal roles in the generation of cellular energy as well as in plant chlorophyll [1]. The bio-geochemical cycling of Mg is associated with mass dependant fractionation (MDF) of the three stable Mg isotopes [1]. The largest MDF of Mg isotopes has been recorded in carbonates, with foraminiferal tests having δ26Mg compositions up to 5 ‰ lighter than modern seawater [2]. Magnesium isotopes may also be fractionated during bacterially mediated carbonate precipitation and such carbonates are known to have formed in both modern and ancient Earth surface environments [3, 4], with cyanobacteria having a dominant role in carbonate formation during the Archean. In this study, we aim to better constrain the extent to which Mg isotope fractionation occurs during cellular processes, and to identify when, and how, this signal is transferred to carbonates. To this end we have undertaken biologically-mediated carbonate precipitation experiments that were performed in artificial seawater, but with the molar Mg/Ca ratio set to 0.6 and with the solution spiked with 0.4% yeast extract. The bacterial strain used was marine isolate Halomonas sp. (gram-negative). Experiments were run in the dark at 21 degree C for two to three months and produced carbonate spheres of various sizes up to 300 μm in diameter, but with the majority have diameters of ~100 μm. Control experiments run in sterile controls (`empty` medium without bacteria) yielded no precipitates, indicating a bacterial control on the precipitation. The carbonate spheres are produced are amenable to SEM, EMP and Mg isotopic analysis by MC-ICP-MS. Our new data will shed light on tracing bacterial signals in carbonates from the geological record. [1] Young & Galy (2004). Rev. Min. Geochem. 55, p197-230. [2] Pogge von Strandmann (2008). Geochem. Geophys. Geosys. 9 DOI:10.1029/2008GC002209. [3] Castanier, et al. (1999). Sed. Geol. 126, 9-23. [4] Cacchio, et al. (2003). Geomicrobiol. J. 20, 85-98.

Effects of must concentration techniques on wine isotopic parameters.

PubMed

Guyon, Francois; Douet, Christine; Colas, Sebastien; Salagoïty, Marie-Hélène; Medina, Bernard

2006-12-27

Despite the robustness of isotopic methods applied in the field of wine control, isotopic values can be slightly influenced by enological practices. For this reason, must concentration technique effects on wine isotopic parameters were studied. The two studied concentration techniques were reverse osmosis (RO) and high-vacuum evaporation (HVE). Samples (must and extracted water) have been collected in various French vineyards. Musts were microfermented at the laboratory, and isotope parameters were determined on the obtained wine. Deuterium and carbon-13 isotope ratios were studied on distilled ethanol by nuclear magnetic resonance (NMR) and isotope ratio mass spectrometry (IRMS), respectively. The oxygen-18 ratio was determined on extracted and wine water using IRMS apparatus. The study showed that the RO technique has a very low effect on isotopic parameters, indicating that this concentration technique does not create any isotopic fractionation, neither at sugar level nor at water level. The effect is notable for must submitted to HVE concentration: water evaporation leads to a modification of the oxygen-18 ratio of the must and, as a consequence, ethanol deuterium concentration is also modified.

Stable carbon isotope fractionation by sulfate-reducing bacteria

NASA Technical Reports Server (NTRS)

Londry, Kathleen L.; Des Marais, David J.

2003-01-01

Biogeochemical transformations occurring in the anoxic zones of stratified sedimentary microbial communities can profoundly influence the isotopic and organic signatures preserved in the fossil record. Accordingly, we have determined carbon isotope discrimination that is associated with both heterotrophic and lithotrophic growth of pure cultures of sulfate-reducing bacteria (SRB). For heterotrophic-growth experiments, substrate consumption was monitored to completion. Sealed vessels containing SRB cultures were harvested at different time intervals, and delta(13)C values were determined for gaseous CO(2), organic substrates, and products such as biomass. For three of the four SRB, carbon isotope effects between the substrates, acetate or lactate and CO(2), and the cell biomass were small, ranging from 0 to 2 per thousand. However, for Desulfotomaculum acetoxidans, the carbon incorporated into biomass was isotopically heavier than the available substrates by 8 to 9 per thousand. SRB grown lithoautotrophically consumed less than 3% of the available CO(2) and exhibited substantial discrimination (calculated as isotope fractionation factors [alpha]), as follows: for Desulfobacterium autotrophicum, alpha values ranged from 1.0100 to 1.0123; for Desulfobacter hydrogenophilus, the alpha value was 0.0138, and for Desulfotomaculum acetoxidans, the alpha value was 1.0310. Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO(2) resulted in biomass with a delta(13)C composition intermediate to that of the substrates. The extent of fractionation depended on which enzymatic pathways were used, the direction in which the pathways operated, and the growth rate, but fractionation was not dependent on the growth phase. To the extent that environmental conditions affect the availability of organic substrates (e.g., acetate) and reducing power (e.g., H(2)), ecological forces can also influence carbon isotope discrimination by SRB.

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

PubMed

Höhener, Patrick; Yu, Xianjing

2012-03-15

Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by "heavy divided by light", carbon enrichment factors for equilibrium sorption were derived which ranged from -0.13±0.04‰ (benzene) to -0.52±0.19‰ (trichloroethene at 5-15 °C). Hydrogen enrichment factors for sorption of 14 different compounds were between -2.4 and -9.2‰. For perdeuterated hydrocarbons the predicted enrichment factors ranged from -19±5.4‰ (benzene) to -64±30‰ (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for (13)C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants. Copyright © 2011 Elsevier B.V. All rights reserved.

The Effect of Protein Mass Modulation on Human Dihydrofolate Reductase

PubMed Central

Francis, Kevin; Sapienza, Paul J.; Lee, Andrew L.; Kohen, Amnon

2016-01-01

Dihydrofolate reductase (DHFR) from Escherichia coli has long served as a model enzyme with which to elucidate possible links between protein dynamics and the catalyzed reaction. Such physical properties of its human counterpart have not been rigorously studied so far, but recent computer-based simulations suggest that these two DHFRs differ significantly in how closely coupled the protein dynamics and the catalyzed C-H→C hydride transfer step are. To test this prediction, two contemporary probes for studying the effect of protein dynamics on catalysis were combined here: temperature dependence of intrinsic kinetic isotope effects (KIEs) that are sensitive to the physical nature of the chemical step, and protein mass-modulation that slows down fast dynamics (femto- to picosecond timescale) throughout the protein. The intrinsic H/T KIEs of human DHFR, like those of E. coli DHFR, are shown to be temperature-independent in the range from 5–45 °C, indicating fast sampling of donor and acceptor distances (DADs) at the reaction’s transition state (or tunneling ready state – TRS). Mass modulation of these enzymes through isotopic labeling with 13C, 15N, and 2H at nonexchangeable hydrogens yield an 11% heavier enzyme. The additional mass has no effect on the intrinsic KIEs of the human enzyme. This finding indicates that the mass-modulation of the human DHFR affects neither DAD distribution nor the DAD’s conformational sampling dynamics. Furthermore, reduction in the enzymatic turnover number and the dissociation rate constant for the product indicate that the isotopic substitution affects kinetic steps that are not the catalyzed C-H→C hydride transfer. The findings are discussed in terms of fast dynamics and their role in catalysis, the comparison of calculations and experiments, and the interpretation of isotopically-modulated heavy enzymes in general. PMID:26813442

Sulfur and oxygen isotope fractionation during benzene, toluene, ethyl benzene, and xylene degradation by sulfate-reducing bacteria.

PubMed

Knöller, Kay; Vogt, Carsten; Richnow, Hans-Herrmann; Weise, Stephan M

2006-06-15

We examined the oxygen and sulfur isotope fractionation of sulfate during anaerobic degradation of toluene by sulfate-reducing bacteria in culture experiments with Desulfobacula toluolica as a type strain and with an enrichment culture Zz5-7 obtained from a benzene, toluene, ethylbenzene, and xylene (BTEX)-contaminated aquifer. Sulfur isotope fractionation can show considerable variation upon sulfate reduction and may react extremely sensitively to changes in environmental conditions. In contrast, oxygen isotope fractionation seems to be less sensitive to environmental changes. Our results clearly indicate that oxygen isotope fractionation is dominated by isotope exchange with ambient water. To verify our experimental results and to test the applicability of oxygen and sulfur isotope investigations under realistic field conditions, we evaluated isotope data from two BTEX-contaminated aquifers presented in the recent literature. On a field scale, bacterial sulfate reduction may be superimposed by processes such as dispersion, adsorption, reoxidation, or mixing. The dual isotope approach enables the identification of such sulfur transformation processes. This identification is vital for a general qualitative evaluation of the natural attenuation potential of the contaminated aquifer.

The carbon and oxygen isotope records of reef-dwelling foraminifers subjected to five varied pCO2 seawater

NASA Astrophysics Data System (ADS)

Hikami, M.; Ishimura, T.; Suzuki, A.; Nojiri, Y.; Kawahata, H.

2013-12-01

Ocean acidification (OA) in response to rising atmospheric pCO2 is generally expected to reduce rates of calcification by reef calcifying organisms, with potentially severe implications for coral reef ecosystems. Reef dwelling foraminifera is one of the most important primary and carbonate producers in coral reef environments. Their shells are composed of high-Mg calcite and they are host to algal endosymbionts. In our previous culture experiment with two algal reef dwelling foraminifers, Amphisorus kudakajimensis and Calcarina gaudichaudii in the seawater of five different pCO2 conditions, net calcification of A. kudakajimensis was reduced under higher pCO2, whereas net calcification of C. gaudichaudii showed continued increasing trend with pCO2. These contrasting responses between the two species are possibly due to differences in calcification mechanisms and to links between calcification by the foraminifers and photosynthesis by the algal endosymbionts. But the factors affecting these calcification mechanisms are poorly understood. In this study, to get a better understanding of the effect of OA on their calcification, we cultured three reef dwelling foraminifers: Amphisorus hemprichii, belong to imperforate species, Baculogypsina sphaerulata, and C. gaudichaudii belong to perforate species, in the seawater of five different pCO2 conditions and we address the response of carbon and oxygen isotopes of the carbonate shells of foraminifers. The oxygen isotope ratio of cultured foraminiferal tests under five varied pCO2 seawater indicated no significant correlation to pCO2 values. On the other hand, the carbon isotope ratio of foraminiferal tests indicated heavy trend with rising pCO2 in all species. Alteration of carbonate chemistry result from ocean acidification may be effect strongly on carbon isotope composition relate to metabolic system (i.e. photosynthesis and respiration). In perforate species, both of oxygen and carbon isotope ratio were lighter than that in imperforate. For oxygen isotope ratio variation possibility among species would be caused by their Mg-content concentration in calcite shells. The distinct difference in the level of carbon isotope ratio between pure calcite and perforate foraminifera might be influenced by the degree of dependency on metabolic CO2 used for shell construction. The imperforate species would use most carbon derived from bicarbonate ion of seawater directly because the carbon isotope ratio of shell is almost same to that of pure calcite. Therefore, oxygen and carbon isotope ratio of foraminiferal test have the potential to reveal calcification mechanism of two species.

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.

Cryogenic Carbonate Formation on Mars: Clues from Stable Isotope Variations Seen in Experimental Studies

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Niles, Paul B.; Fu, Qi; Gibson, Everett K., Jr.

2010-01-01

Discoveries of large deposits of sedimentary materials on the planet Mars by landers and orbiters have confirmed the widely held hypothesis that water has played a crucial role in the development of the martian surface. Recent studies have indicated that both water ice and liquid water may have been present and in the case of water ice perhaps is still present on or near the surface of Mars. However, there remains much controversy about the prevailing atmospheric conditions and climate of Mars during its history and whether liquid water existed on the martian surface simply during discrete geological events or whether this water was present over relatively much longer geologic time periods. The recent identification of Ca-rich carbonate by the Phoenix lander as well as its measurement of the isotopic composition of atmospheric CO2 has shown the importance of understanding the carbonates on Mars as an important sink of atmospheric carbon. This work compliments that of our past experiments where we produced cryogenic calcite in open containers, as analogs for terrestrial aufeis formation, and as a means for evaluating the fractionation of C-13 in CO2 during bicarbonate freezing [13]. Unlike our previous experiments in which carbonates were grown in ambient laboratory condition in open containers (atmospheric pressure and composition), this work attempts to quantify the amount of delta C-13 enrichment possible in both fluids and secondary carbonates formed from freezing of bicarbonate fluids under martian-like atmospheric conditions. Morphologic textures of produced carbonates in these experiments are also examined under SEM in order to identify the effect that the cryogenic freezing process has on the mineral's mineralogy. Understanding the role of kinetic isotope fractionation during formation of carbonates under martian-like conditions will aid in our ability to quantify the isotopic composition of the carbonate sink furthering our ability to model the climate history of Mars.

DISPERSION OF RADIOACTIVE ISOTOPES IN THE SOIL BY EARTHWORMS (in Russian)

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

Peredel'skii, A.A.; Shain, S.S.; Karavyanskii, N.S.

1960-11-01

The effects of earthworms on the distribution and migration of radioisotopes in contaminated earth were investigated. Data on the mean Ca/sup 45/ and Sr/sup 90/ activity of a single worm and its coprolith in contaminated soil are tabulated. It is shown that the specific radioactivity in the earthworm quickly reaches a maximum and remains unchanged during further inhabitance in the contuminated soil. The specific activity of the earthworm can reach that of the soil; however, after leaving the contuminated area, the activity is rapidly reduced in the worm. The specific activity of the earthworm coprolith is close to that ofmore » the body; sometimes it exceeds the activity of both the body and the soil due to uptake of organic material of higher radioactivity. The experiment shows that the influence of earthworms on dissemination of shont-lifs isotopes is negligible but that with long-life isotopes it may be more noticeable. (R.V.J.)« less

Towards Time-Scaling of Mixing for the Campanian Ignimbrite: Systemic Variation in Sr-Isotopic Composition from Mixing Experiments

NASA Astrophysics Data System (ADS)

de Campos, Cristina; Civetta, Lucia; Perugini, Diego; Dingwell, Donald B.

2010-05-01

Eruptions in the Campi Flegrei caldera, the most dangerous volcanic setting in Europe, are thought to be triggered by short-term pre-eruptive mixing of trachytic to trachydacitic resident and new basaltic, trachyandesitic (=shoshonitic) magma, in shallow magma chambers (e. g. Arienzo et al, 2008, Bull. Volcanol.). Previous geochemical and volcanological data on the Campanian Ignimbrite, (>150 km3, 39 Ma), in Campi Flegrei, point towards a layered reservoir, which evolved from the replenishment of the magma chamber with shoshonitic magma and short-term pre-eruptive mixing between a trachytic and a phonolitic trachytic magma. With the purpose to experimentally study the mobility and homogenization of Rb-Sr isotopes in this system, we performed mixing experiments using natural phonolitic trachytic (end-member A - S. Nicola type) and trachytic (end-member B - Mondragone-type) samples, representing the two end-members involved in the origin of the Campanian Ignimbrite. Resultant glasses from a time series, ranging from 1-hour up to 1-week, under constant flow velocity (0.5 rotations per minute; after De Campos et al., 2008. Chem. Geol.), have been analysed with respect to the Rb- and Sr-systematics. Our results reveal a progressive homogenization of the contrasting Sr-isotopes towards a hybrid value. With increasing experimental duration a clear decrease in the standard deviation of isotopic ratios has been observed, reflecting progressive isotopic homogenization. Our results also support the effectiveness of mixing in the Campi Flegrei reservoirs, in liquidus, under high temperature, before the onset of fractional crystallization. Since different eruptive events from Campi Flegrei can be well characterized by means of isotopic composition, the main goal for the present study will be to use experimental data and numerical modeling in order to estimate time scales of mixing associated with the eruption of the Campanian Ignimbrite, and then compare them to the several other volcanic events in Campi Flegrei. The results to be presented will be corrected according to the recently developed numerical modeling by Perugini et al. (in print, Bull. Volcanol.).

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste.

PubMed

Wimmer, Bernhard; Hrad, Marlies; Huber-Humer, Marion; Watzinger, Andrea; Wyhlidal, Stefan; Reichenauer, Thomas G

2013-10-01

Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated the isotopic signatures of δ(13)C, δ(2)H and δ(18)O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration. We found significant differences in the δ(13)C-value of the dissolved inorganic carbon (δ(13)C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ(13)C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ(13)C-DIC of -20‰ to -25‰. The production of methane under anaerobic conditions caused an increase in δ(13)C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ(13)C-DIC of about -20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation-reduction status of MSW landfills. Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Early diagenesis and organic matter preservation--A molecular stable isotope perspective

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

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

1992-01-01

Through new developments in stable isotope capability, gas chromatography coupled to a stable isotope ratio mass spectrometer (GC/IRMS), the molecular pathways of the diagenetic reactions can be observed on the components themselves. The authors report the results of laboratory-controlled degradation experiments of fresh organic substrates. Isotopically resolvable materials were used. Seagrass showed slight enrichments in [delta]N-15 with little change in [delta]C-13 following four weeks of decomposition. During that period the identifiable amino acid content decreased by approx. 50% for each amino acid. Mixtures of marine sediment with the same seagrass showed enrichments in nitrogen with associated depletions in carbon isotopicmore » compositions over the same time span. Control experiments on the sediments without added fresh seagrass showed no change in isotopic content. These changes are attributed to hydrolysis, deamination and decarboxylation reactions. Isotopic fractionations of similar size and direction have been observed in laboratory studies on peptide hydrolysis and natural samples of particulate organic materials. At the molecular level, using GC/IRMS, certain amino acids are seen to decrease in C-13 content while others become increasingly enriched in C-13. Similar reactions are seen in carbohydrates. The molecular isotope approach indicates that the process of diagenesis and preservation is significantly more complex than simple breakdown and loss. A large portion of the organic matter eventually preserved in organic-rich deposits can be attributed to new production in the deposit.« less

Introduction to Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

PubMed Central

Thiemens, Mark H.

2013-01-01

Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented. PMID:24167299

Chemical and isotopic measurements of micrometeoroids by secondary ion mass spectrometry (A0187-2)

NASA Technical Reports Server (NTRS)

Foote, J. H.; Swan, P. D.; Walker, R. M.; Zinner, E. K.; Bahr, D.; Fechtig, H.; Jessberger, E.; Igenbergs, E.; Kreitmayr, U.; Kuczera, H.

1984-01-01

The objective of this experiment is to measure the chemical and isotopic composition of interplanetary dust particles of mass greater than 10 to the minus 10 power G for most of thermator elements expected to be present.

Uses of Radioactive Isotopes in Industry; APLICACIONES DE LOS ISOTOPOS RADIACTIVOS EN LA INDUSTRIA

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

Plata, A.; del Val Cob, M.; Gamboya, J.M.

1962-01-01

A list of some of the most important problems in industry that were approached by the use of radioactive isotopes is presented. The list was compiled through the experience galned in revising for several years important scientific journals and other sources of information on this subject. The classification of industries was done in an arbitrary way, choosing those isotope uses that have reached a higher degree of development. (auth)

A Multi-Proxy Paradigm in the Pursuit of Ocean Paleoredox

NASA Astrophysics Data System (ADS)

Anbar, A. D.; Duan, Y.; Kendall, B.; Reinhard, C.; Severmann, S.; Lyons, T. W.

2011-12-01

The geologic record provides abundant evidence for variations in ocean oxygenation throughout Earth history. Expansion of ocean anoxic zones is expected in the future as a consequence of global climate change, with attendant effects on global nutrient inventories, carbon cycling and fluxes of trace greenhouse gases to the atmosphere. Therefore, studying ancient ocean redox variations not only teaches us about the history of the Earth system, but also provides insights into how the system may respond to analogous human perturbations. However, the extent, duration, causes, and consequences of most past variations are poorly understood. This problem motivates the development of paleoredox proxies, including novel stable isotope systems such as Mo, Fe, U and Tl. Experience with these emerging isotope systems demonstrates great promise but also many challenges. The Mo isotope system is illustrative. To first order, the geochemical cycling and isotope systematics of this element are straightforward, making it a useful proxy. However, critical unresolved issues include: (a) uncertainties in the ocean inputs through time; (b) ambiguities about fractionation mechanisms; (c) inadequate understanding of how modern analogs map to ancient systems. Similar challenges confront all the novel isotope systems. The way forward requires integration of multiple isotopic proxies, as well as information gleaned from careful analyses of element concentrations. For example, an episode of Mo enrichment in the 2.5 Ga Mt. McRae Shale is generally interpreted as resulting from buildup of Mo in seawater due to oxidative weathering. This enrichment is therefore thought to indicate a "whiff" of O2 in the environment prior to the Great Oxidation Event that began at 2.4 Ga. Molybdenum isotopes are consistent with this interpretation. However, Mo enrichment due to enhanced input from low-T hydrothermal sources in an anoxic regime cannot be completely excluded given the current state of knowledge of Mo isotope systematics from such sources. By considering sedimentary Fe enrichments together with Fe isotopes, we find that the Mo enrichment correlates with the telltale signature of a shelf-to-basin Fe redox "shuttle". Uranium isotopes also exhibit variations indicative of redox transformations. This multi-proxy dataset therefore paints a robust picture of trace metal redox cycling consistent with the "whiff" interpretation.

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.

Nuclear applications of inorganic mass spectrometry.

PubMed

De Laeter, John

2010-01-01

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

Experimental Constraints on Reconstruction of Archean Seawater Ni Isotopic Composition from Banded Iron Formations

NASA Astrophysics Data System (ADS)

Wang, S.; Wasylenki, L.

2016-12-01

Ni isotope systematics in banded iron formations (BIFs) potentially recorded the Ni isotopic composition of ancient seawater during the Precambrian Eon[1]. The use of BIFs as seawater proxies requires knowing how Ni isotopes fractionated during initial incorporation into iron-rich sediments and during early diagenesis. We conducted experiments to investigate Ni isotope behavior during coprecipitation with ferrihydrite and transformation of ferrihydrite to hematite. Ferrihydrite synthesis at neutral pH demonstrated that dissolved Ni was variably heavier than coprecipitated Ni (Δ60/58Ni = +0.08 to +0.50 ‰), in contrast to the constant offset observed earlier during adsorption to pre-existing ferrihydrite[2]. Experiments at lower pH (<7) yielded negative values of Δ60/58Ni ( -0.18 ‰), suggesting enrichment in heavier isotopes of structurally incorporated Ni relative to dissolved and adsorbed Ni, possibly due to the presence of a small amount of highly fractionated tetrahedral Ni2+ in the ferrihydrite structure. We model our results as equilibrium fractionation among three pools of Ni with systematically varied proportions. We synthesized hematite by transforming Ni-bearing ferrihydrite in aqueous solution at 100 °C and observed significant Ni release from solids (up to 60 %) as pH dropped from 7 to 4.5 - 5.5 during phase transformation. Rinsing hematite with acetic acid released very little Ni (presumably surface-adsorbed) compared to the amounts remaining in solid residues (presumably incorporated). We infer that Δ60/58Ni values (-0.04 to +0.77 ‰) observed in hematite experiments likely reflect Rayleigh fractionation between incorporated and dissolved Ni. The final hematite was slightly lighter than the ferrihydrite had been (by 0.08 ‰), indicating that this phase transformation results in very limited change in Ni isotopic composition, given current analytical uncertainty of ± 0.09 ‰. [1] Wasylenki and Wang (2016) Goldschmidt; [2] Wasylenki et al. (2015) ChemGeol.

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.

The identification of meteorite inclusions with isotope anomalies

NASA Technical Reports Server (NTRS)

Papanastassiou, D. A.; Brigham, C. A.

1989-01-01

Ca-Al refractory inclusions with characteristic chemical and mineralogical compositions show an enhanced occurrence of 20 pct of isotope anomalies reflecting unknown nucleosynthetic effects for O and Mg. The anomalies are characterized by large isotope fractionation in Mg, apparent deficits in Mg-26/Mg-24, and large correlated effects for isotopes of Ca, Ti, and Cr. These isotope patterns define exotic components depleted in the most neutron-rich isotopes of Ca, Ti, and Cr, or components depleted in isotopes produced in explosive O and Si burning. An opaque assemblage within one of the inclusions yields isotope anomalies in Cr similar to the bulk inclusion and must be intrinsically part of the inclusion and not a trapped, foreign grain aggregate.

Preliminary Study: Application of Off-Axis ICOS to Determine Stable Carbon Isotope in Dissolved Inorganic Carbon

NASA Astrophysics Data System (ADS)

Kim, Y. T.; Lee, J. M.; Hwang, J. H.; Piao, J.; Woo, N. C.

2015-12-01

CO2 is one of the major causes for global climate change. Because stable carbon isotope ratio is used to trace carbon source, several analytical techniques likes IRMS (Isotope Ratio Mass Spectrometry) and LAS (Laser Absorption Spectrometry) were extensively used. Off-axis ICOS, a kind of LAS, has merits on long-term stability and field application, therefore it is widely being used in CCS (Carbon Capture and Storage) field. The aim of this study is to extend the application scope of OA-ICOS to determine dissolved inorganic carbon (DIC). Because OA-ICOS showed dependence of δ13C on CO2 concentration, data processing is required. We tested CO2 Carbon Isotope Analyzer (CCIA-36-EP, Los Gatos Research) with both reference gas (δ13C= -28.28‰) and aqueous solutions prepared by dissolving sodium bicarbonate standards (δ13C= -12.26‰ and +3.96‰). The differences of δ13C between reference and measurement values are plotted by CO2 concentrations, then compared. At first, we checked the similarity between our curve pattern for reference gas and Guillon's research (δ13C= -43.99‰) by other Analyzer. To analyze aqueous samples, more errors can be caused than gas analysis. The carbon isotope fractionation occurs during dissolving standard reagents and extracting DIC as CO2 gas form. This effect is mixed with CO2 concentration dependence effect, therefore the curve patterns are different with that for reference gas. Our experiments are done for various δ13C values. It could be an important point to use OA-ICOS to analyze DIC, too.

Why is Mineral-Associated Organic Matter Enriched in 15N? Evidence from Grazed Pasture Soil

NASA Astrophysics Data System (ADS)

Baisden, W. T.; Wells, N. S.; Mudge, P. L.; Clough, T. J.; Schipper, L. A.; Ghani, A.; Stevenson, B.

2014-12-01

Throughout the scientific literature, measurements across soil depth and density fractions suggest that, with few exceptions, mineral-associated organic matter (OM) has higher δ15N than non-mineral-associated OM. This implies that the δ15N difference between N inputs and mineral-stabilized OM may characterize the microbial processes involved in stabilization and mineral association. Yet current understanding of observed N isotope fractionation in terrestrial ecosystems suggests the large isotope effects are expressed during inorganic N transformations from NH4 to gaseous loss pathways of NH3 volatilization and denitrification. How can the relative importance of N isotope fractionation during OM stabilization versus loss pathways be resolved? We recently examined N isofluxes when a temporary nitrogen excess is created by urine deposition in a New Zealand dairy pasture. We found that the N isotopic composition of volatilized NH3, and NO3 available for leaching or denitrification could not be linked back to the added N using Rayleigh distillation models. Instead, the results imply that the added N was immobilized, and the N available for losses was increasingly derived from mineralization of organic matter during the course of the experiment. These results are consistent with recent evidence of enhanced OM mineralization in urine patches, understanding of N isotope mass balances and long-standing evidence that gross mineralization and immobilization fluxes greatly exceed net mineralization and nitrification, except at very high N saturation. These results suggest that where 15N enrichment occurs due to fractionating loss pathways, the isotope effects are primarily transmitted to immobilized N, forming 15N enriched stabilized OM. This further explains earlier findings that the δ15N of soil OM represents an integrated indicator of losses, reflecting the intensity and duration of pastoral agriculture. We suggest that development of an indicator based on δ15N in mineral-associated OM might relate mineralization rates to the δ15N of stabilized or immobilized N.

Online stable isotope analysis of dissolved organic carbon size classes using size exclusion chromatography coupled to an isotope ratio mass spectrometer.

PubMed

Malik, Ashish; Scheibe, Andrea; LokaBharathi, P A; Gleixner, Gerd

2012-09-18

Stable isotopic content of dissolved organic carbon (δ(13)C-DOC) provides valuable information on its origin and fate. In an attempt to get additional insights into DOC cycling, we developed a method for δ(13)C measurement of DOC size classes by coupling high-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) to online isotope ratio mass spectrometry (IRMS). This represents a significant methodological contribution to DOC research. The interface was evaluated using various organic compounds, thoroughly tested with soil-water from a C3-C4 vegetation change experiment, and also applied to riverine and marine DOC. δ(13)C analysis of standard compounds resulted in excellent analytical precision (≤0.3‰). Chromatography resolved soil DOC into 3 fractions: high molecular weight (HMW; 0.4-10 kDa), low molecular weight (LMW; 50-400 Da), and retained (R) fraction. Sample reproducibility for measurement of δ(13)C-DOC size classes was ±0.25‰ for HMW fraction, ± 0.54‰ for LMW fraction, and ±1.3‰ for R fraction. The greater variance in δ(13)C values of the latter fractions was due to their lower concentrations. The limit of quantification (SD ≤0.6‰) for each size fraction measured as a peak is 200 ng C (2 mg C/L). δ(13)C-DOC values obtained in SEC mode correlated significantly with those obtained without column in the μEA mode (p < 0.001, intercept 0.17‰), which rules out SEC-associated isotopic effects or DOC loss. In the vegetation change experiment, fractions revealed a clear trend in plant contribution to DOC; those in deeper soils and smaller size fractions had less plant material. It was also demonstrated that the technique can be successfully applied to marine and riverine DOC without further sample pretreatment.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

A novel design for a dual stable isotope continuous labeling chamber: results on labeling efficiency and C and N allocation in Andropogon gerardii

NASA Astrophysics Data System (ADS)

Soong, J.; Stewart, C.; Reuss, D.; Pinney, C.; Cotrufo, F. M.

2010-12-01

The use of stable isotope enriched plant material can provide an unobstructed method of studying ecosystem nutrient dynamics between plants, soil, and atmosphere. However, the production of uniformly labeled perennial plant material is challenging due to plant physiological constraints and the mechanics of building and operating an isotope labeling system. In this study we present the design of a novel dual 13C and 15N continuous isotope labeling chamber located at Colorado State University. The chamber is equipped with automatic controls for CO2 concentration, temperature, and humidity, and has successfully been used to grow and label the tallgrass perennial Andropogon gerardii in pots from rhizomes. Three different nitrogen fertilization levels were applied to assess how substrate availability may alter growth and overall performance in the system. The efficiency of the 13C and 15N labeling chamber, its design and overall performance, as well as a full C, N, 13C, and 15N budget of the aboveground biomass, belowground biomass, and soil will be presented. Solid samples were analyzed on an EA-IRMS, while air samples from the chamber were analyzed using a precon-GC-IRMS system. The dual stable isotope labeled A. gerardii produced from this chamber will be used in a decomposition experiment to quantify the relative contribution of aboveground litter derived C to soil respiration, dissolved organic carbon, and various soil organic matter pools. Based on the results of our A. gerardii 13C and 15N labeling experiment we believe that this chamber design can be used to successfully produce dual stable isotope labeled plants for a wide variety of terrestrial nutrient flux experiments.

Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

NASA Technical Reports Server (NTRS)

Mahaffy, P.; Niemann, Hasso (Technical Monitor)

2001-01-01

Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

The impact of Tibet and the Andes on the climate and isotopic composition of precipitation

NASA Astrophysics Data System (ADS)

Battisti, D. S.; Ding, Q.; Liu, X.; Roe, G.

2012-12-01

We summarize modeling and theoretical evidence for the impact of the high topography in Tibet and the Andes on the climate and the isotopic (δ18O) composition of precipitation, regionally and globally. Tibet controls the seasonal cycle of precipitation over eastern China, mainly via dynamical processes, and has little to no impact on the Indian and southeast Asian monsoons. Tibet is also responsible for the northwesterly winds and extraordinary cold winters in northern China, and contributes to the mid-winter suppression of storminess in the western and central Pacific. The Andes greatly shape the climatological precipitation over South America, and are an important contributor to the annual cycle in sea surface temperature, precipitation and atmospheric circulation throughout the eastern half of the tropical Pacific. We have performed a series of numerical experiments with the isotope-enabled ECHAM 4.6 atmospheric general circulation model to illuminate the impact of the Andes and Tibet on the regional distribution of oxygen isotopes in precipitation. Experiments to be discussed include a world without an elevated Andes circa 12 million years BP, and a series of experiments that prescribed a plausible evolution of the continental geometry and topography for the past 50 million years in and around the Indian Ocean basin. In the latter case, additional idealized experiments are performed to illuminate the separate impacts of topography and continental configuration.

Formation of nonextractable soil residues: A stable isotope approach

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

Richnow, H.H.; Eschenback, A.; Mahro, B.

1999-11-01

Stable carbon isotopic measurements were employed to characterize the transformation of a {sup 13}C-labeled polycyclic aromatic hydrocarbon (PAH), anthracene, in a closed soil bioreactor system. The {sup 13}C-label was used to calculate a carbon mass balance including mineralization and the formation of nonextractable soil-bound residues. Similar results were obtained from {sup 13}C-labeled carbon and {sup 14}C-labeled carbon mass balance calculations for separate batch experiments with labeled anthracene. In concentration ranges typical for real PAH-contaminated sites, the sensitivity of the {sup 13}C tracer method meets the requirements of classical radiotracer experiments. Therefore, the authors balancing method based on stable isotope-labeled chemicalsmore » may supplement or substitute radiotracer experiments under many circumstances. One major advantage of using stable isotope-labeled tracers is the possible application in transformation studies where the use of radioactive substances is of environmental concern. The transformation of {sup 13}C-labeled PAH into nonextractable residues clearly depends on the metabolic activity of the soil microflora and occurs during an early phase of biodegradation. Successive contamination of the soil by anthracene leads to a progressive adaptation of the microflora to a complete mineralization of anthracene in the soil. The extent of residue formation is controlled by the capability of the microflora to degrade the contaminant. Results of long-term experiments indicate that nonextractable residues are relatively stable over time.« less

Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method

NASA Astrophysics Data System (ADS)

Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

2018-04-01

Isotope ratio monitoring by 13C NMR spectrometry (irm-13C NMR) provides the complete 13C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13C natural abundance values (50‰), irm-13C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13C NMR. Until now, the conventional strategy to determine the position-specific abundance xi relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1H NMR pulse sequence (named DWET) with a 13C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T1, which forms a serious limitation for irm-13C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T1 variations. Their performance is evaluated on the determination of the 13C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm-13C NMR since it is now possible to perform isotopic analysis with high relaxing agent concentrations, leading to a strong reduction of the overall experiment time.

Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model

NASA Astrophysics Data System (ADS)

Hansen, Maximilian; Scholz, Denis; Froeschmann, Marie-Louise; Schöne, Bernd R.; Spötl, Christoph

2017-08-01

Speleothem stable carbon isotope (δ13C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ13C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gaseous CO2 and the DIC in thin solution films. The model considers all parameters affecting carbon isotope exchange, such as diffusion into, out of and within the film, the chemical reactions occurring within the film as well as the dependence of diffusion and the reaction rates on isotopic mass and temperature. To verify the model, we conducted laboratory experiments under completely controlled, cave-analogue conditions at three different temperatures (10, 20, 30 °C). We exposed thin (≈0.1 mm) films of a NaHCO3 solution with four different concentrations (1, 2, 5 and 10 mmol/l, respectively) to a nitrogen atmosphere containing a specific amount of CO2 (1000 and 3000 ppmV). The experimentally observed temporal evolution of the pH and δ13C values of the DIC is in good agreement with the model predictions. The carbon isotope exchange times in our experiments range from ca. 200 to ca. 16,000 s and strongly depend on temperature, film thickness, atmospheric pCO2 and the concentration of DIC. For low pCO2 (between 500 and 1000 ppmV, as for strongly ventilated caves), our time constants are substantially lower than those derived in a previous study, suggesting a potentially stronger influence of carbon isotope exchange on speleothem δ13C values. However, this process should only have an influence in case of very long drip intervals and slow precipitation rates.

Small (13)C/(12)C fractionation contrasts with large enantiomer fractionation in aerobic biodegradation of phenoxy acids.

PubMed

Qiu, Shiran; Gözdereliler, Erkin; Weyrauch, Philip; Lopez, Eva C Magana; Kohler, Hans-Peter E; Sørensen, Sebastian R; Meckenstock, Rainer U; Elsner, Martin

2014-05-20

Phenoxy acid herbicides are important groundwater contaminants. Stable isotope analysis and enantiomer analysis are well-recognized approaches for assessing in situ biodegradation in the field. In an aerobic degradation survey with six phenoxyacetic acid and three phenoxypropionic acid-degrading bacteria we measured (a) enantiomer-specific carbon isotope fractionation of MCPP ((R,S)-2-(4-chloro-2-methylphenoxy)-propionic acid), DCPP ((R,S)-2-(2,4-dichlorophenoxy)-propionic acid), and 4-CPP ((R,S)-2-(4-chlorophenoxy)-propionic acid); (b) compound-specific isotope fractionation of MCPA (4-chloro-2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid); and (c) enantiomer fractionation of MCPP, DCPP, and 4-CPP. Insignificant or very slight (ε = -1.3‰ to -2.0‰) carbon isotope fractionation was observed. Equally small values in an RdpA enzyme assay (εea = -1.0 ± 0.1‰) and even smaller fractionation in whole cell experiments of the host organism Sphingobium herbicidovorans MH (εwc = -0.3 ± 0.1‰) suggest that (i) enzyme-associated isotope effects were already small, yet (ii) further masked by active transport through the cell membrane. In contrast, enantiomer fractionation in MCPP, DCPP, and 4-CPP was pronounced, with enantioselectivities (ES) of -0.65 to -0.98 with Sphingomonas sp. PM2, -0.63 to -0.89 with Sphingobium herbicidovorans MH, and 0.74 to 0.97 with Delftia acidovorans MC1. To detect aerobic biodegradation of phenoxypropionic acids in the field, enantiomer fractionation seems, therefore, a stronger indicator than carbon isotope fractionation.

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.

Effect of a Jurassic oceanic anoxic event on belemnite ecology and evolution

PubMed Central

Ullmann, Clemens Vinzenz; Thibault, Nicolas; Ruhl, Micha; Hesselbo, Stephen P.; Korte, Christoph

2014-01-01

The Toarcian oceanic anoxic event (T-OAE; ∼183 million y ago) is possibly the most extreme episode of widespread ocean oxygen deficiency in the Phanerozoic, coinciding with rapid atmospheric pCO2 increase and significant loss of biodiversity in marine faunas. The event is a unique past tipping point in the Earth system, where rapid and massive release of isotopically light carbon led to a major perturbation in the global carbon cycle as recorded in organic and inorganic C isotope records. Modern marine ecosystems are projected to experience major loss in biodiversity in response to enhanced ocean anoxia driven by anthropogenic release of greenhouse gases. Potential consequences of this anthropogenic forcing can be approximated by studying analog environmental perturbations in the past such as the T-OAE. Here we present to our knowledge the first organic carbon isotope record derived from the organic matrix in the calcite rostra of early Toarcian belemnites. We combine both organic and calcite carbon isotope analyses of individual specimens of these marine predators to obtain a refined reconstruction of the early Toarcian global exogenic carbon cycle perturbation and belemnite paleoecology. The organic carbon isotope data combined with measurements of oxygen isotope values from the same specimens allow for a more robust interpretation of the interplay between the global carbon cycle perturbation, environmental change, and biotic response during the T-OAE. We infer that belemnites adapted to environmental change by shifting their habitat from cold bottom waters to warm surface waters in response to expanded seafloor anoxia. PMID:24982187

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.

Selfing results in inbreeding depression of growth but not of gas exchange of surviving adult black spruce trees

Treesearch

Kurt Johnsen; John E. Major; Chris A. Maier

2003-01-01

Summary In most tree species, inbreeding greatly reduces seed production, seed viability, survival and growth. In a previous large-scale quantitative analysis of a black spruce (Picea mariana (Mill.) B.S.P.) diallel experiment, selfing had large deleterious effects on growth but no impact on stable carbon isotope discrimination (an...

EFFECTS OF CLIMATE CHANGE ON LABILE AND STRUCTURAL CARBON IN DOUGLAS-FIR NEEDLES AS ESTIMATED BY DELTA 13C AND C AREA MEASUREMENTS

EPA Science Inventory

Isotopic measurements may provide new insights into levels in leaves of labile and structural carbon (C) under climate change. In a 4-year climate change experiment using Pseudotsuga menziesii (Douglas-fir) seedlings and a 2x2 factorial design in enclosed chambers (n=3), atmosph...

Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: interaction of seawater with fayalite and magnetite at 200–350°C

USGS Publications Warehouse

Shanks, Wayne C.; Bischoff, James L.; Rosenbauer, Robert J.

1981-01-01

Systematics of sulfur isotopes in the 250 and 350°C experiments indicate that isotopic equilibrium is reached, and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H2S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur.

Isotope dilution gas chromatography with mass spectrometry for the analysis of 4-octyl phenol, 4-nonylphenol, and bisphenol A in vegetable oils.

PubMed

Wu, Pinggu; Zhang, Liqun; Yang, Dajin; Zhang, Jing; Hu, Zhengyan; Wang, Liyuan; Ma, Bingjie

2016-03-01

By the combination of solid-phase extraction as well as isotope dilution gas chromatography with mass spectrometry, a sensitive and reliable method for the determination of endocrine-disrupting chemicals including bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils was established. The application of a silica/N-(n-propyl)ethylenediamine mixed solid-phase extraction cartridge achieved relatively low matrix effects for bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils. Experiments were designed to evaluate the effects of derivatization, and the extraction parameters were optimized. The estimated limits of detection and quantification for bisphenol A, 4-octylphenol, and 4-nonylphenol were 0.83 and 2.5 μg/kg, respectively. In a spiked experiment in vegetable oils, the recovery of the added bisphenol A was 97.5-110.3%, recovery of the added 4-octylphenol was 64.4-87.4%, and that of 4-nonylphenol was 68.2-89.3%. This sensitive method was then applied to real vegetable oil samples from Zhejiang Province of China, and none of the target compounds were detected. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron-catalyzed halogenation of alkanes: modeling of nonheme halogenases by experiment and DFT calculations.

PubMed

Comba, Peter; Wunderlich, Steffen

2010-06-25

When the dichloroiron(II) complex of the tetradentate bispidine ligand L=3,7-dimethyl-9-oxo-2,4-bis(2-pyridyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate methyl ester is oxidized with H(2)O(2), tBuOOH, or iodosylbenzene, the high-valent Fe=O complex efficiently oxidizes and halogenates cyclohexane. Kinetic D isotope effects and the preference for the abstraction of tertiary over secondary carbon-bound hydrogen atoms (quantified in the halogenation of adamantane) indicate that C-H activation is the rate-determining step. The efficiencies (yields in stoichiometric and turnover numbers in catalytic reactions), product ratios (alcohol vs. bromo- vs. chloroalkane), and kinetic isotope effects depend on the oxidant. These results suggest different pathways with different oxidants, and these may include iron(IV)- and iron(V)-oxo complexes as well as oxygen-based radicals.

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.

Geological controls on isotopic signatures of streamflow: results from a nested catchment experiment in Luxembourg (Europe)

NASA Astrophysics Data System (ADS)

Pfister, Laurent; McDonnell, Jeffrey J.; Hissler, Christophe; Martinez-Carreras, Nuria; Gourdol, Laurent; Klaus, Julian; François Iffly, Jean; Barnich, François; Stewart, Mike K.

2014-05-01

Controls of geology and topography on hydrological metrics, like summer low flow (Grant and Tague, 2004) or dynamic storage (Sayama et al., 2011), have been identified in nested catchment experiments. However, most tracer-based studies on streamflow generation have been carried out in small (10 km2) homogenous catchments (Klaus and McDonnell, 2013). The controlling effects of catchment physiography on how catchments store and release water, and how this eventually controls stream isotope behaviour over a large range of scale are poorly understood. Here, we present results from a nested catchment analysis in the Alzette River basin (Luxembourg, Europe). Our hydro-climatological network consists of 16 recording streamgauges and 21 pluviographs. Catchment areas range from 0.47 to 285 km2, with clean and mixed combinations of distinct geologies ranging from schists to marls, sandstone, dolomite and limestone. Our objective was to identify geological controls on (i) winter runoff ratios, (ii) maximum storage and (iii) isotopic signatures in streamflow. For each catchment we determined average runoff ratios from winter season precipitation-discharge double-mass curves. Maximum catchment storage was based on the dynamic storage change approach of Sayama et al. (2011). Changes in isotopic signatures of streamflow were documented along individual catchment flow duration curves. We found strong correlations between average winter runoff ratios, maximum storage and the prevailing geological settings. Catchments with impermeable bedrock (e.g. marls or schists) were characterised by small storage potential and high average filling ratios. As a consequence, these catchments also exhibited the highest average runoff ratios. In catchments underlain by permeable bedrock (e.g. sandstone), storage potential was significantly higher and runoff ratios were considerably smaller. The isotopic signatures of streamflow showed large differences between catchments. In catchments dominated by permeable bedrock, isotopic signatures of streamflow remained stable throughout the entire flow duration curve consistent with a large storage and mixing potential. On less permeable bedrock substrate, we have observed that isotopic signatures in streamflow were much more variable, due to reduced storage volume and comparatively smaller mixing potential. Other metrics such as catchment size and flowpath length exerted a smaller secondary control on isotopic signatures of streamflow in the Alzette River sub-basins. Tague, C., Grant, G.E., 2004. A geological framework for interpreting the low-flow regimes of Cascade streams, Willamette River Basin, Oregon. Water Resources Research, 40(4), doi:10.1029/2003WR002629 Sayama, T., McDonnell, J.J., Dhakal, A., Sullivan, K., 2011. How much water can a watershed store ? Hydrological Processes 25, 3899-3908. Klaus, J., McDonnell, J.J., 2013. Hydrograph separation using stable isotopes: Review and evaluation. Journal of Hydrology 505, 47-64.

Feasibility of two low-cost organic substrates for inducing denitrification in artificial recharge ponds: Batch and flow-through experiments.

PubMed

Grau-Martínez, Alba; Torrentó, Clara; Carrey, Raúl; Rodríguez-Escales, Paula; Domènech, Cristina; Ghiglieri, Giorgio; Soler, Albert; Otero, Neus

2017-03-01

Anaerobic batch and flow-through experiments were performed to assess the capacity of two organic substrates to promote denitrification of nitrate-contaminated groundwater within managed artificial recharge systems (MAR) in arid or semi-arid regions. Denitrification in MAR systems can be achieved through artificial recharge ponds coupled with a permeable reactive barrier in the form of a reactive organic layer. In arid or semi-arid regions, short-term efficient organic substrates are required due to the short recharge periods. We examined the effectiveness of two low-cost, easily available and easily handled organic substrates, commercial plant-based compost and crushed palm tree leaves, to determine the feasibility of using them in these systems. Chemical and multi-isotopic monitoring (δ 15 N NO3 , δ 18 O NO3 , δ 34 S SO4 , δ 18 O SO4 ) of the laboratory experiments confirmed that both organic substrates induced denitrification. Complete nitrate removal was achieved in all the experiments with a slight transient nitrite accumulation. In the flow-through experiments, ammonium release was observed at the beginning of both experiments and lasted longer for the experiment with palm tree leaves. Isotopic characterisation of the released ammonium suggested ammonium leaching from both organic substrates at the beginning of the experiments and pointed to ammonium production by DNRA for the palm tree leaves experiment, which would only account for a maximum of 15% of the nitrate attenuation. Sulphate reduction was achieved in both column experiments. The amount of organic carbon consumed during denitrification and sulphate reduction was 0.8‰ of the total organic carbon present in commercial compost and 4.4% for the palm tree leaves. The N and O isotopic fractionation values obtained (ε N and ε O ) were -10.4‰ and -9.0‰ for the commercial compost (combining data from both batch and column experiments), and -9.9‰ and -8.6‰ for the palm tree column, respectively. Both materials showed a satisfactory capacity for denitrification, but the palm tree leaves gave a higher denitrification rate and yield (amount of nitrate consumed per amount of available C) than commercial compost. Copyright © 2017 Elsevier B.V. All rights reserved.

Isotope scattering and phonon thermal conductivity in light atom compounds: LiH and LiF

DOE PAGES

Lindsay, Lucas R.

2016-11-08

Engineered isotope variation is a pathway toward modulating lattice thermal conductivity (κ) of a material through changes in phonon-isotope scattering. The effects of isotope variation on intrinsic thermal resistance is little explored, as varying isotopes have relatively small differences in mass and thus do not affect bulk phonon dispersions. However, for light elements isotope mass variation can be relatively large (e.g., hydrogen and deuterium). Using a first principles Peierls-Boltzmann transport equation approach the effects of isotope variance on lattice thermal transport in ultra-low-mass compound materials LiH and LiF are characterized. The isotope mass variance modifies the intrinsic thermal resistance viamore » modulation of acoustic and optic phonon frequencies, while phonon-isotope scattering from mass disorder plays only a minor role. This leads to some unusual cases where values of isotopically pure systems ( 6LiH, 7Li 2H and 6LiF) are lower than the values from their counterparts with naturally occurring isotopes and phonon-isotope scattering. However, these differences are relatively small. The effects of temperature-driven lattice expansion on phonon dispersions and calculated κ are also discussed. This work provides insight into lattice thermal conductivity modulation with mass variation and the interplay of intrinsic phonon-phonon and phonon-isotope scattering in interesting light atom systems.« less

Carbon dioxide in the atmosphere: isotopic exchange with ozone and its use as a tracer in the middle atmosphere

NASA Technical Reports Server (NTRS)

Yung, Y. L.; Lee, A. Y.; Irion, F. W.; DeMore, W. B.; Wen, J.

1997-01-01

Atmospheric heavy ozone is enriched in the isotopes 18O and 17O. The magnitude of this enhancement, of the order of 100%, is very large compared with that commonly known in atmospheric chemistry and geochemistry. The heavy oxygen atom in heavy ozone is therefore useful as a tracer of chemical species and pathways that involve ozone or its derived products. As a test of the isotopic exchange reactions, we successfully carry out a series of numerical experiments to simulate the results of the laboratory experiments performed by Wen and Thiemens [1993] on ozone and CO2. A small discrepancy between the experimental and the model values for 17O exchange is also revealed. The results are used to compute the magnitude of isotopic exchange between ozone and carbon dioxide via the excited atom O(1D) in the middle atmosphere. The model for 18O is in good agreement with the observed values.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been widely used as refrigerants, propellants, solvents, foaming agents and are important intermediates in the production of anesthetics and other fluorinated compounds. Due to their ozone depletion potential, production was banned for most uses under the Montreal Protocol (1987) and its amendments and atmospheric mixing ratios have started to decrease. In addition to the atmosphere, CFCs and HCFCs have been detected in groundwater, and emissions from various sources such as landfill sites are still ongoing. Previous studies have shown that both abiotic and biotic transformation of CFCs may occur under certain conditions. To investigate degradation that may take place in soils and groundwaters, a purge and trap method (P&T) has been developed to measure the stable carbon isotopic composition of CFCs and HCFCs extracted from waters. A set of pure phase working standards (HCFC-22, CFC-11, CFC-113) has been prepared offline and characterized by sealed tube combustion dual inlet mass spectrometry. Comparison between isotopic standards and CFCs extracted by our method demonstrates the sample P&T extraction steps do not induce significant δ13C fractionation (lt;0.5 per mill). Standards characterized by continuous flow CSIA (compound specific isotope analysis) after extraction agree with offline characterized values. Evaporation experiments were carried out to investigate any isotope effects due to volatile loss that might occur either due to sampling methods or sample handling in the lab. Monitoring δ13C values during progressive evaporation showed small isotopic fractionation associated with evaporation. Enrichment factors, obtained from Rayleigh plots, showed inverse isotope fractionation i.e depletion in 13C in the remaining compound. Notably, this effect is in the opposite direction to the fractionation (13C enrichment) that is likely to be associated with abiotic or biotic transformation effects. This bodes well for the use of CSIA to identify and monitor transformation in the field as any isotopic effects due to volatile loss would only result in a conservative estimate of transformation but not confuse the degradation signal. As a result, enrichment factors in field samples might be underestimated and lead to a more conservative estimate of degradation at contaminated sites. CFCs from several suppliers were characterized to investigate δ13C variation between sources and between different CFC compounds. Significant differences were observed between all measured compounds. However for each compound, δ13C values determined in this study were similar to ranges reported previously for other pure phase CFCs - suggesting a consistent range of source signatures may exist for each compound. As a last step of method evaluation, water samples from a contaminated industrial site were measured. This first preliminary field data will be discussed in comparison to pure phase compounds and with respect to potential degradation.

Analysis of High Frequency Site-Specific Nitrogen and Oxygen Isotopic Composition of Atmospheric Nitrous Oxide at Mace Head, Ireland

NASA Astrophysics Data System (ADS)

McClellan, M. J.; Harris, E. J.; Olszewski, W.; Ono, S.; Prinn, R. G.

2014-12-01

Atmospheric nitrous oxide (N2O) significantly impacts Earth's climate due to its dual role as an inert potent greenhouse gas in the troposphere and as a reactive source of ozone-destroying nitrogen oxides in the stratosphere. However, there remain significant uncertainties in the global budget of this gas. The marked spatial divide in its reactivity means that all stages in the N2O life cycle—emission, transport, and destruction—must be examined to understand the overall effect of N2O on climate. Source and sink processes of N2O lead to varying concentrations of N2O isotopologues (14N14N16O, 14N15N16O, 15N14N16O, and 14N14N18O being measured) due to preferential isotopic production and elimination in different environments. Estimation of source and sink fluxes can be improved by combining isotopically resolved N2O observations with simulations using a chemical transport model with reanalysis meteorology and treatments of isotopic signatures of specific surface sources and stratospheric intrusions. We present the first few months of site-specific nitrogen and oxygen isotopic composition data from the Stheno-TILDAS instrument (Harris et al, 2013) at Mace Head, Ireland and compare these to results from MOZART-4 (Model for Ozone and Related Chemical Tracers, version 4) chemical transport model runs including N2O isotopic fractionation processes and reanalysis meterological fields (NCEP/NCAR, MERRA, and GEOS-5). This study forms the basis for future inverse modeling experiments that will improve the accuracy of isotopically differentiated N2O emission and loss estimates. Ref: Harris, E., D. Nelson, W. Olszewski, M. Zahniser, K. Potter, B. McManus, A. Whitehill, R. Prinn, and S. Ono, Development of a spectroscopic technique for continuous online monitoring of oxygen and site-specific nitrogen isotopic composition of atmospheric nitrous oxide, Analytical Chemistry, 2013; DOI: 10.1021/ac403606u.

Isotope effects associated with the anaerobic oxidation of sulfite and thiosulfate by the photosynthetic bacterium, Chromatium vinosum

NASA Technical Reports Server (NTRS)

Fry, B.; Gest, H.; Hayes, J. M.

1985-01-01

The purple photosynthetic bacterium Chromatium vinosum, strain D, catalyzes several oxidations of reduced sulfur compounds under anaerobic conditions in the light: e.g., sulfide --> sulfur --> sulfate, sulfite --> sulfate, and thiosulfate --> sulfur + sulfate. Here it is shown that no sulfur isotope effect is associated with the last of these processes; isotopic compositions of the sulfur and sulfate produced can differ, however, if the sulfane and sulfonate positions within the thiosulfate have different isotopic compositions. In the second process, an observed change from an inverse to a normal isotope effect during oxidation of sulfite may indicate the operation of 2 enzymatic pathways. In contrast to heterotrophic anaerobic reduction of oxidized sulfur compounds, anaerobic oxidations of inorganic sulfur compounds by photosynthetic bacteria are characterized by relatively small isotope effects.

The evolution of 17O-excess in surface water of the arid environment during recharge and evaporation.

PubMed

Surma, J; Assonov, S; Herwartz, D; Voigt, C; Staubwasser, M

2018-03-21

This study demonstrates the potential of triple O-isotopes to quantify evaporation with recharge on a salt lake from the Atacama Desert, Chile. An evaporative gradient was found in shallow ponds along a subsurface flow-path from a groundwater source. Total dissolved solids (TDS) increased by 177 g/l along with an increase in δ 18 O by 16.2‰ and in δD by 65‰. 17 O-excess decreased by 79 per meg, d-excess by 55‰. Relative humidity (h), evaporation over inflow (E/I), the isotopic composition of vapor ( * R V ) and of inflowing water ( * R WI ) determine the isotope distribution in 17 O-excess over δ 18 O along a well-defined evaporation curve as the classic Craig-Gordon model predicts. A complementary on-site simple (pan) evaporation experiment over a change in TDS, δ 18 O, and 17 O-excess by 392 g/l, 25.0‰, and -130 per meg, respectively, was used to determine the effects of sluggish brine evaporation and of wind turbulence. These effects translate to uncertainty in E/I rather than h. The local composition of * R V relative to * R WI pre-determines the general ability to resolve changes in h. The triple O-isotope system is useful for quantitative hydrological balancing of lakes and for paleo-humidity reconstruction, particularly if complemented by D/H analysis.

Dual isotope plots reflect transformation pathways of pesticides: Potential to assess pesticide fate and elucidate transformation mechanisms

NASA Astrophysics Data System (ADS)

Meyer, Armin; Penning, Holger; Sorensen, Sebastian; Aamand, Jens; Elsner, Martin

2010-05-01

The degradation of pesticides in deeper soil layers and groundwater is of growing interest, because they have repeatedly been found in drinking water supply wells and may pose a risk to future water resources. Current assessment schemes face a common problem, however: natural degradation often cannot be reliably assessed by concentration measurements alone, since mass balances are difficult to establish and transformation cannot be distinguished from sorption or dilution. Even detection of metabolites may only give an incomplete picture. When several transformation pathways occur, some metabolites may be degraded or form bound residues so that the associated pathways may be missed. Our research shows that dual isotope plots derived from compound specific isotope analysis offer a novel approach to give additional, complementary insight into the natural degradation of pesticides. Detection of metabolites is not required, since the isotope fractionation can be fully observed in the pesticide itself. Specifically, different initial biotransformation reactions of the phenylurea herbicide isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) in pure culture experiments with bacterial and fungal strains showed strongly pathway-dependent isotope fractionation. When analyzing isotopic changes in different parts of the isoproturon molecule, hydroxylation of the isopropyl group by fungi was found to be associated with C and H isotope fractionation. In contrast, hydrolysis by Arthrobacter globiformis D47 caused strong C and N isotope fractionation, albeit in a different manner than abiotic hydrolysis so that isotope measurements can distinguish between both modes of transformation. Likewise, we observed highly pathway-dependent C and N isotope fractionation of atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine). Desalkylation of atrazine by Rhodococcus sp. strain NI86/21 resulted in enrichment of both 13-C and 15-N in atrazine, whereas hydrolysis to hydroxyatrazine by Chelatobacter heintzii, Pseudomonas sp. ADP and Arthrobacter aurescens TC1 gave enrichment of 13-C, but depletion of 15-N. Comparison with abiotic reference experiments provided novel insight into the underlying enzymatic transformation mechanisms. Our investigations show how characteristic isotope patterns may significantly add to the present understanding of the environmental fate of pesticides.

Stable Carbon Isotopic Signatures of Abiotic Organics from Hydrothermal Synthesis Experiments

NASA Technical Reports Server (NTRS)

Stern, Jennifer C.; Summers, David P.; Kubo, Mike; Yassar, Saima

2006-01-01

Stable carbon isotopes can be powerful biogeochemical markers in the study of life's origins. Biogenic carbon fixation produces organics that are depleted in C-13 by about -20 to -30%0. Less attention has been paid to the isotopic signatures of abiotic processes. The possibility of abiotic processes producing organics with morphologies and isotopic signatures in the biogenic range has been at the center of recent debate over the Earth's earliest microfossils. The abiotic synthesis of organic compounds in hydrothermal environments is one possible source of endogenous organic matter to the prebiotic earth. Simulated hydrothermal settings have been shown to synthesize, among other things, single chain amphiphiles and simple lipids from a mix of CO, CO2, and H2. A key characteristic of these amphiphilic molecules is the ability to self-assemble in aqueous phases into more organized structures called vesicles, which form a selectively permeable boundary and serve the function of containing and concentrating other organic molecules. The ability to form cell like structures also makes these compounds more likely to be mistaken for biogenic. Hydrothermal simulation experiments were conducted from oxalic or formic acid in water at 175 C for 72 hr. The molecular and isotopic composition of the products of these reactions were determined and compared to biogenic fractionations . Preliminary results indicate isotopic fractionation during abiotic hydrocarbon synthesis in hydrothermal environments is on par with biological carbon fixation.

Mass-independent fractionation of oxygen isotopes during H2O2 formation by gas-phase discharge from water vapour

NASA Astrophysics Data System (ADS)

Velivetskaya, Tatiana A.; Ignatiev, Alexander V.; Budnitskiy, Sergey Y.; Yakovenko, Victoria V.; Vysotskiy, Sergey V.

2016-11-01

Hydrogen peroxide is an important atmospheric component involved in various gas-phase and aqueous-phase transformation processes in the Earth's atmosphere. A study of mass-independent 17O anomalies in H2O2 can provide additional insights into the chemistry of the modern atmosphere and, possibly, of the ancient atmosphere. Here, we report the results of laboratory experiments to study the fractionation of three oxygen isotopes (16O, 17O, and 18O) during H2O2 formation from products of water vapour dissociation. The experiments were carried out by passing an electrical discharge through a gaseous mixture of helium and water at atmospheric pressure. The effect of the presence of O2 in the gas mixture on the isotopic composition of H2O2 was also investigated. All of the experiments showed that H2O2 produced under two different conditions (with or without O2 added in the gas mixtures) was mass-independently fractionated (MIF). We found a positive MIF signal (∼1.4‰) in the no-O2 added experiments, and this signal increased to ∼2.5‰ once O2 was added (1.6% mixing ratio). We suggest that if O2 concentrations are very low, the hydroxyl radical recombination reaction is the dominant pathway for H2O2 formation and is the source of MIF in H2O2. Although H2O2 formation via a hydroxyl radical recombination process is limited in the modern atmosphere, it would be possible in the Archean atmosphere when O2 was a trace constituent, and H2O2 would be mass-independently fractionated. The anomalous 17O excess, which was observed in H2O2 produced by spark discharge experiments, may provide useful information about the radical chemistry of the ancient atmosphere and the role of H2O2 in maintaining and controlling the atmospheric composition.

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.