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.

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.

Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils.

PubMed

Tian, Liyan; Guo, Qingjun; Zhu, Yongguan; He, Huijun; Lang, Yunchao; Hu, Jian; Zhang, Han; Wei, Rongfei; Han, Xiaokun; Peters, Marc; Yang, Junxing

2016-12-01

Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ 18 O P ) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L -1 NaHCO 3 (pH = 8.5), 0.1 mol L -1 NaOH and 1 mol L -1 HCl) of agricultural soils from the Beijing area. The δ 18 O P results of the water extracts and NaHCO 3 extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ 18 O P value of the water extracts and NaHCO 3 extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ 18 O P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ 18 O P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ 18 O p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.

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

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

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

2015-07-01

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

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.

Equilibrium Tin Isotope Fractionation during Metal-Sulfide-Silicate Differentiation: A Nuclear Resonant Inelastic X-ray Scattering Approach

NASA Astrophysics Data System (ADS)

Roskosz, M.; Amet, Q.; Fitoussi, C.; Laporte, D.; Hu, M. Y.; Alp, E. E.

2016-12-01

Metal-silicate differentiation was recently addressed through the insight of the isotopic composition of siderophile elements (mainly Fe, Si and Cr isotopes) of planetary and extraterrestrial bodies. A key limitation of this approach is however the knowledge of equilibrium fractionation factors between coexisting phases (metal alloys, silicates and sulfides) used to interpret data on natural samples. These properties are difficult to determine experimentally. In this context, tin is generally classified as a chalcophile element but it is also siderophile and volatile. We applied a synchrotron-based method to circumvent difficulties related to determination of equilibrium isotope fractionation. The nuclear resonant inelastic x-ray scattering (NRIXS) was used to measure the phonon excitation spectrum and then to derive the force constant and finally the fractionation factors of Sn-bearing geomaterials. Spectroscopic measurements were carried out at room pressure at Sector 30-ID (APS, USA). A range of Fe-Ni alloys, rhyolitic and basaltic glasses and iron sulfides containing isotopically enriched 119Sn were synthesized. The tin content and the redox conditions prevailing during the synthesis were varied. The data evaluation was carried out using PHOENIX and SciPhon programs. A strong effect of both the redox state and the tin content was measured. In addition, the composition of the silicate glasses was found to be another important factor determining the tin isotope metal-silicate-sulfide fractionation factors. Our results are consistent with trends previously observed in the case of iron isotopes [1,2]. We will discuss the implications of our experimental results in terms of tin isotope planetary signatures. References: [1] Dauphas et al. (2014), EPSL, 398, 127-140; [2] Roskosz et al. (2015), GCA, 169, 184-199.

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.

Solid-phase Microextraction (SPME) with Stable Isotope Calibration for Measuring Bioavailability of Hydrophobic Organic Contaminants

PubMed Central

Cui, Xinyi; Bao, Lianjun; Gan, Jay

2014-01-01

Solid-phase microextraction (SPME) is a biomimetic tool ideally suited for measuring bioavailability of hydrophobic organic compounds (HOCs) in sediment and soil matrices. However, conventional SPME sampling requires the attainment of equilibrium between the fiber and sample matrix, which may take weeks or months, greatly limiting its applicability. In this study, we explored the preloading of polydimethylsiloxane fiber with stable isotope labeled analogs (SI-SPME) to circumvent the need for long sampling time, and evaluated the performance of SI-SPME against the conventional equilibrium SPME (Eq-SPME) using a range of sediments and conditions. Desorption of stable isotope-labeled analogs and absorption of PCB-52, PCB-153, bifenthrin and cis-permethrin were isotropic, validating the assumption for SI-SPME. Highly reproducible preloading was achieved using acetone-water (1:4, v/v) as the carrier. Compared to Eq-SPME that required weeks or even months, the fiber concentrations (Cf) under equilibrium could be reliably estimated by SI-SPME in 1 d under agitated conditions or 20 d under static conditions in spiked sediments. The Cf values predicted by SI-SPME were statistically identical to those determined by Eq-SPME. The SI-SPME method was further applied successfully to field sediments contaminated with PCB 52, PCB 153, and bifenthrin. The increasing availability of stable isotope labeled standards and mass spectrometry nowadays makes SI-SPME highly feasible, allowing the use of SPME under non-equilibrium conditions with much shorter or flexible sampling time. PMID:23930601

Using Triple Oxygen Isotope Analyses of Biogenic Carbonate to Reconstruct Early Triassic Ocean Oxygen Isotopic Values and Temperatures

NASA Astrophysics Data System (ADS)

Gibbons, J. A.; Sharp, Z. D.; Atudorei, V.

2017-12-01

The calcite-water triple oxygen isotope fractionation is used to determine isotopic equilibrium and ancient ocean oxygen isotopic values and temperatures. Unlike conventional δ18O analysis where the formation water's isotopic value is assumed, paired δ17O-δ18O measurements allow for the water's isotopic composition to be calculated because there is only one unique solution for equilibrium fractionation using Δ17O-δ18O values (where Δ17O=δ17O-0.528δ18O). To a first approximation, the calcite-water equilibrium fractionation factor, θ (where θ=ln17α/ln18α), varies with temperature by 0.00001/°. The calcite-water equilibrium fractionation line was determined at two temperatures, 30° and 0°, by using modern carbonate samples that formed in ocean water with a δ18O value of 0‰. The θ values for the 30° and 0° samples are 0.52515 and 0.52486, respectively. Oxygen values were measured using complete fluorination in nickel tubes with BrF5 as the reaction reagent. We calibrated all oxygen values to the SMOW-SLAP scale by measuring SMOW, SLAP, San Carlos olivine, NBS-18, NBS-19, and PDB. The triple oxygen isotope calcite-water equilibrium fractionation line was applied to well preserved Early Triassic ammonite shells from the Western United States. Based on paired δ17O-δ18O measurements, the samples did not form in equilibrium with an ice-free ocean with an oxygen isotopic value of -1‰ or the modern ocean value of 0‰. Assuming the calcite is still primary and formed in equilibrium with the ocean water, our data indicate that the δ18O value of the ocean in the early Triassic was 3-5‰ lower than modern. Samples from the Smithian thermal maximum formed in water 10° warmer than samples from after the thermal maximum. Paired δ17O-δ18O measurements of pristine ancient carbonates may provide a better understanding of past ocean conditions during climate change events.

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Oxygen isotope geochemistry of the amphiboles: isotope effects of cation substitutions in minerals

NASA Astrophysics Data System (ADS)

Kohn, Matthew J.; Valley, John W.

1998-06-01

The occurrence of coexisting amphiboles in rocks and the likelihood of concurrent isotope closure allows equilibrium oxygen isotope fractionations among the amphiboles to be recovered from natural samples. Oxygen isotope analyses of mineral separates using laser fluorination show that coexisting amphiboles increasingly partition 18O in the order: hornblende ≪ gedrite < cummingtonite ≤ anthophyllite. The observed fractionations at ˜575°C are: Δ(Ged-Hbl) = 0.8‰, Δ(Cum-Hbl) = 0.9, Δ(Cum-Ged) = 0.2, Δ(Ath-Ged) = 0.3, and Δ(Ath-Hbl) > 0.9. Previously published data for hornblende, actinolite, glaucophane, and garnet show that Δ(Act-Hbl) ˜ 0.2, Δ(Gln-Grt) ≫ 1, and Δ(Hbl-Grt) ˜ 0. Thus, glaucophane strongly partitions 18O relative to the calcic amphiboles. The fractionation between two amphiboles of arbitrary composition can be predicted from the known fractionations for mica endmembers, pyroxene endmembers, and exchange components such as CaAl(NaSi) -1, NaAl(CaMg) -1, CaMg -1, MgFe -1, FeMn -1, KNa -1, KAl( Si) -1, and Fe 3+Al -1. Applications of the exchange component method reproduce measured amphibole fractionations to within ±0.1 to ±0.2‰, whereas other predictive methods cause misfit for typical metamorphic hornblende of ≥0.5‰ at 575°C. Although the isotope effects of cation exchanges may be small at high-T, they magnify dramatically for minerals formed in surficial, diagenetic, and low-T metamorphic environments. Different composition clays are predicted to have equilibrium δ 18O differences of 2-9‰. If the isotope fractionation can be determined for one mineral endmember, then calibrated exchanges allow accurate prediction of the isotope fractionations for intermediate compositions of most ortho-, ring-, chain-, and sheet-silicates.

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.

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

USGS Publications Warehouse

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

1976-01-01

Nine samples from the Monte Rosa Granite have been investigated by microscopic, X-ray, wet chemical, electron microprobe, stable isotope and Rb-Sr and K-Ar methods. Two mineral assemblages have been distinguished by optical methods and dated as Permian and mid-Tertiary by means of Rb-Sr age determinations. The Permian assemblage comprises quartz, orthoclase, oligoclase, biotite, and muscovite whereas the Alpine assemblage comprises quartz, microcline, albite+epidote or oligoclase, biotite, and phengite. Disequilibrium between the Permian and Alpine mineral assemblages is documented by the following facts: (i) Two texturally distinguishable generations of white K-mica are 2 M muscovite (Si=3.1-3.2) and 2 M or 3 T phengite (Si=3.3-3.4). Five muscovites show Permian Rb-Sr ages and oxygen isotope fractionations indicating temperatures between 520 and 560 ?? C; however, K-Ar ages are mixed or rejuvenated. Phengite always shows mid-Tertiary Rb-Sr ages, (ii) Two biotite generations can be recognized, although textural evidence is often ambiguous. Three out of four texturally old biotites show mid-Tertiary Rb-Sr cooling ages while the oxygen isotopic fractionations point to Permian, mixed or Alpine temperatures, (iii) Comparison of radiogenic and stable isotope relations indicates that the radiogenic isotopes in the interlayer positions of the micas were mobilized during Alpine time without recrystallization, that is, without breaking Al-O or Si-O bonds. High Ti contents in young muscovites and biotites also indicate that the octahedral (and tetrahedral) sites remained undisturbed during rejuvenation. (iv) 'Isotopic reversals' in the order of O18 enrichment between K-feldspar and albite exist. Arguments for equilibrium during Permian time are meagre because of Alpine overprinting effects. Texturally old muscovites show high temperatures and Permian Rb-Sr ages in concordancy with Rb-Sr whole rock ages. For the tectonically least affected samples, excellent concordance between quartz-muscovite and quartz-biotite 'Permian temperatures' implies oxygen isotope equilibrium in Permian time which was undisturbed during Alpine metamorphism. Arguments for equilibrium during the mid-Tertiary metamorphism are as follows: (i) Mid-Tertiary Rb-Sr mineral isochrons of up to six minerals exist, (ii) Oxygen isotope temperatures of coexisting Alpine phengites and biotites are concordant. The major factor for the adjustment of the Permian assemblages to Alpine conditions was the degree of Alpine tectonic overprinting rather than the maximum temperatures reached during the mid-Tertiary Alpine metamorphism. The lack of exchange with externally introduced fluid phases in the samples least affected by tectonism indicates that the Monte Rosa Granite 'stewed in its own juices'. This seems to be the major cause for the persistence of Permian ages and corresponding temperatures. ?? 1976 Springer-Verlag.

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.

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

ERIC Educational Resources Information Center

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

2017-01-01

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

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.

Solvent isotope-induced equilibrium perturbation for isocitrate lyase.

PubMed

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

2013-12-23

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

Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

USGS Publications Warehouse

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

2007-01-01

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

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.

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

USGS Publications Warehouse

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

2004-01-01

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

Combining stable isotope isotope geochemistry and carbonic anhydrase activity to trace vital effect in carbonate precipitation experiments

NASA Astrophysics Data System (ADS)

Thaler, C.; Ader, M.; Menez, B.; Guyot, F. J.

2013-12-01

Carbonates precipitated by skeleton-forming eukaryotic organisms are often characterized by non-equilibrium isotopic signatures. This specificity is referred to as the "vital effect" and can be used as an isotopic evidence to trace life. Combining stable isotope geochemistry and enzymology (using the enzyme carbonic anhydrase) we aim to demonstrate that prokaryotes are also able to precipitate carbonate with a non-equilibrium d18OCaCO3. Indeed, if in an biomineralization experiment carbonates are precipitated with a vital effect, the addition of carbonic anhydrase should drive the system to isotope equilibrium, And provide a comparison point to estimate the vital effect range. This protocol allowed us to identify a -20‰ vital effect for the d18O of carbonates precipitated by Sporosarcina pasteurii, a bacterial model of carbonatogen metabolisms. This approach is thus a powerfull tool for the understanding of microbe carbonatogen activity and will probably bring new insights into the understanding of bacterial activity in subsurface and during diagenesis.

Solvent Isotope-induced Equilibrium Perturbation for Isocitrate Lyase

PubMed Central

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

2014-01-01

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

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

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

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

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

Concentration effect on inter-mineral equilibrium isotope fractionation: insights from Mg and Ca isotopic systems

NASA Astrophysics Data System (ADS)

Huang, F.; Wang, W.; Zhou, C.; Kang, J.; Wu, Z.

2017-12-01

Many naturally occurring minerals, such as carbonate, garnet, pyroxene, and feldspar, are solid solutions with large variations in chemical compositions. Such variations may affect mineral structures and modify the chemical bonding environment around atoms, which further impacts the equilibrium isotope fractionation factors among minerals. Here we investigated the effects of Mg content on equilibrium Mg and Ca isotope fractionation among carbonates and Ca content on equilibrium Ca isotope fractionation between orthopyroxene (opx) and clinopyroxene (cpx) using first-principles calculations. Our results show that the average Mg-O bond length increases with decreasing Mg/(Mg+Ca) in calcite when it is greater than 1/48[1] and the average Ca-O bond length significantly decreases with decreasing Ca/(Ca+Mg+Fe) in opx when it ranges from 2/16 to 1/48[2]. Equilibrium isotope fractionation is mainly controlled by bond strengths, which could be measured by bond lengths. Thus, 103lnα26Mg/24Mg between dolomite and calcite dramatically increases with decreasing Mg/(Mg+Ca) in calcite [1] and it reaches a constant value when it is lower than 1/48. 103lnα44Ca/40Ca between opx and cpx significantly increases with decreasing Ca content in opx when Ca/(Ca+Mg+Fe) ranges from 2/16 to 1/48 [2]. If Ca/(Ca+Mg+Fe) is below 1/48, 103lnα44Ca/40Ca is not sensitive to Ca content. Based on our results, we conclude that the concentration effect on equilibrium isotope fractionation could be significant within a certain range of chemical composition of minerals, which should be a ubiquitous phenomenon in solid solution systems. [1] Wang, W., Qin, T., Zhou, C., Huang, S., Wu, Z., Huang, F., 2017. GCA 208, 185-197. [2] Feng, C., Qin, T., Huang, S., Wu, Z., Huang, F., 2014. GCA 143, 132-142.

Oxygen isotopes as a tracer of phosphate sources and cycling in aquatic systems (Invited)

NASA Astrophysics Data System (ADS)

Young, M. B.; Kendall, C.; Paytan, A.

2013-12-01

The oxygen isotopic composition of phosphate can provide valuable information about sources and processes affecting phosphorus as it moves through hydrologic systems. Applications of this technique in soil and water have become more common in recent years due to improvements in extraction methods and instrument capabilities, and studies in multiple aquatic environments have demonstrated that some phosphorus sources may have distinct isotopic compositions within a given system. Under normal environmental conditions, the oxygen-phosphorus bonds in dissolved inorganic phosphate (DIP) can only be broken by enzymatic activity. Biological cycling of DIP will bring the phosphate oxygen into a temperature-dependent equilibrium with the surrounding water, overprinting any existing isotopic source signals. However, studies conducted in a wide range of estuarine, freshwater, and groundwater systems have found that the phosphate oxygen is often out of biological equilibrium with the water, suggesting that it is common for at least a partial isotopic source signal to be retained in aquatic systems. Oxygen isotope analysis on various potential phosphate sources such as synthetic and organic fertilizers, animal waste, detergents, and septic/wastewater treatment plant effluents show that these sources span a wide range of isotopic compositions, and although there is considerable overlap between the source groups, sources may be isotopically distinct within a given study area. Recent soil studies have shown that isotopic analysis of phosphate oxygen is also useful for understanding microbial cycling across different phosphorus pools, and may provide insights into controls on phosphorus leaching. Combining stable isotope information from soil and water studies will greatly improve our understanding of complex phosphate cycling, and the increasing use of this isotopic technique across different environments will provide new information regarding anthropogenic phosphate inputs and controls on biological cycling within hydrologic systems.

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.

Equilibrium lithium isotope fractionation in Li-rich minerals

NASA Astrophysics Data System (ADS)

Liu, S.; Li, Y.; Liu, J.

2017-12-01

Lithium is the lightest alkali metal, and only exhibits +1 valence state in minerals. It is widely distributed on the Earth, and usually substitutes for Mg in silicate minerals. Li has two stable isotopes, 6Li and 7Li, with the relative abundances of 7.52% and 92.48%, respectively. The large mass difference between 6Li and 7Li could induce significant isotope fractionation in minerals. Li isotopes can provide an important geochemical tracer for mantle processes. However, the fractionation factors for Li in most minerals remain poorly known, which makes the geochemical implications of Li isotope fractionations in minerals difficult to assess. Here, we try to use the vibrational frequencies obtained by the first-principles methods based on density-functional theory to calculate the Li isotope fractionation parameters for amblygonite (LiAlPO4F), bikitaite (LiSi2AlO7H2), eucryptite (LiAlSiO4), lithiophilite (LiMnPO4), lithiophosphate (Li3PO4), montebrasite (LiAlPO5H), and spodumene (LiAlSi2O6) in the temperature range of 0-1200 ºC. For forsterite (Mg2SiO4) and diopside (CaMgSi2O6) in which Li takes the place of Mg, the equilibrium Li isotope fractionation between them also be studied. Our preliminary calculations show that the coordination number of Li seems to play an important role in controlling Li isotope fractionation in these minerals, and concentration of Li in forsterite and diopside seems to have great effects on Li isotope fractionation factors of them.

Sulphur isotope applications in two Philippine geothermal systems

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

Bayon, F.E.B.

1996-12-31

A general and very preliminary study of sulphur isotope geochemistry is presented in this paper. Data from the Mt. Apo and Palinpinon geothermal fields are used to demonstrate the use of sulphur isotopes in geothermometry and correlation of sulphur species. Sulphur and oxygen isotope geothermometers applied to Mt. Apo data show very good agreement with temperatures estimated using other established geothermometers, as well as bore measured temperatures. This signifies that sulphur isotopes in S-species in fluids of the Mt. Apo hydrothermal system are in equilibrium at drilled depths. In Palinpinon, on the other hand, temperature estimates from fluid and mineralmore » sulphur isotope geothermometry calculations do not agree with, and are commonly higher than, well measured temperatures and temperatures estimated from other geothermometers. Sulphur isotopes in the presently-exploited Palinpinon fluid are not in equilibrium, and sulphur isotope geothermometry may be reflective of isotopic equilibrium of the deeper portions of the hydrothermal system. Dissolved sulphate in both the Palinpinon and Mt. Apo geothermal fluids appear to originate from the disproportionation of magmatic SO{sub 2} at temperatures below 400{degrees}C. Hydrogen sulphide in well discharge fluids are dominantly directly derived from the magma, with a minor amount coming from SO{sub 2} disproportionation.« less

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

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

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

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

Empirical calibration of the clinopyroxene-garnet magnesium isotope geothermometer and implications

NASA Astrophysics Data System (ADS)

Li, Wang-Ye; Teng, Fang-Zhen; Xiao, Yilin; Gu, Hai-Ou; Zha, Xiang-Ping; Huang, Jian

2016-07-01

The large equilibrium Mg isotope fractionation between clinopyroxene and garnet observed in eclogites makes it a potential high-precision geothermometer, but calibration of this thermometer by natural samples is still limited. Here, we report Mg isotopic compositions of eclogite whole rocks as well as Mg and O isotopic compositions of clinopyroxene and garnet separates from 16 eclogites that formed at different temperatures from the Dabie orogen, China. The whole-rock δ26Mg values vary from -1.20 to +0.10 ‰. Among them, 11 samples display limited δ26Mg variations from -0.36 to -0.17 ‰, similar to those of their protoliths. The mineral separates exhibit very different δ26Mg values, from -0.39 to +0.39 ‰ for clinopyroxenes and from -1.94 to -0.81 ‰ for garnets. The clinopyroxene-garnet Mg isotope fractionation (Δ26Mgclinopyroxene-garnet = δ26Mgclinopyroxene-δ26Mggarnet) varies from 1.05 to 2.15 ‰. The clinopyroxene-garnet O isotope fractionation (Δ18Oclinopyroxene-garnet = δ18Oclinopyroxene-δ18Ogarnet) varies from -1.01 to +0.98 ‰. Equilibrium Mg isotope fractionation between clinopyroxene and garnet in the investigated samples is selected based on both the δ26Mgclinopyroxene versus δ26Mggarnet plot and the state of O isotope equilibrium between clinopyroxene and garnet. The equilibrium Δ26Mgclinopyroxene-garnet and corresponding temperature data obtained in this study, together with those available so far in literatures for natural eclogites, are used to calibrate the clinopyroxene-garnet Mg isotope thermometer. This yields a function of Δ26Mgclinopyroxene-garnet = (0.99 ± 0.06) × 106/ T 2, where T is temperature in Kelvin. The refined function not only provides the best empirically calibrated clinopyroxene-garnet Mg isotope thermometer for precise constraints of temperatures of clinopyroxene- and garnet-bearing rocks, but also has potential applications in high-temperature Mg isotope geochemistry.

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

NASA Astrophysics Data System (ADS)

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

2006-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-08-01

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

Pan-derived isotopic composition of atmospheric vapour in a Mediterranean wetland (Rhône River Delta, France).

PubMed

Vallet-Coulomb, Christine; Cartapanis, Olivier; Radakovitch, Olivier; Sonzogni, Corinne; Pichaud, Marc

2010-03-01

A continuous record of atmospheric vapour isotopic composition (delta(A)) can be derived from the isotope mass balance of a water body submitted to natural evaporation. In this paper, we present preliminary results of the application of this method to a drying evaporation pan, located in a Mediterranean wetland, during a two-month summer period. Results seem consistent with few atmospheric vapour data based on the assumption of isotopic equilibrium with precipitation, but we observed a shift between pan-derived delta(A) and the composition of vapour samples collected by cold trapping. These results suggest that further investigations are necessary to evaluate the effect of diurnal variations of atmospheric conditions on the applicability of the pan-evaporation method, and on the representative of grab atmospheric samples. We also propose a sensitivity analysis for evaluating the impact of the different measured components on delta(A) calculation, and show an improvement in the method efficiency as the pan is drying.

Oxygen isotope fractionation in the CaCO3-DIC-H2O system

NASA Astrophysics Data System (ADS)

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

2017-10-01

The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading to a relatively constant foraminifer calcite δ18O-temperature relationship (-0.21 ± 0.01‰/°C). The lower average coral δ18O data relative to foraminifers and other calcifiers is best explained by the precipitation of internal DIC derived from hydrated CO2 in a high-pH calcifying fluid and minimal subsequent DIC-H2O isotopic equilibration. This leads to a reduced and variable coral aragonite δ18O-temperature relationship (-0.11 to -0.22‰/°C). Together, the model presented here reconciles observations of oxygen isotope fractionation over a range of CaCO3-DIC-H2O systems.

Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite

NASA Astrophysics Data System (ADS)

Aufort, Julie; Ségalen, Loïc; Gervais, Christel; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne

2017-12-01

The stable isotope composition of biogenic apatite is an important geochemical marker that can record environmental parameters and is widely used to infer past climates, biomineralization processes, dietary preferences and habitat of vertebrates. In this study, theoretical equilibrium isotopic fractionation of oxygen, carbon and calcium in hydroxyapatite and carbonate-bearing hydroxyapatite is investigated using first-principles methods based on density-functional theory and compared to the theoretical isotopic fractionation properties of calcite, CO2 and H2O. Considering the variability of apatite crystal-chemistry, special attention is given to specific contributions of crystal sites to isotopic fractionation. Significant internal fractionation is calculated for oxygen and carbon isotopes in CO3 between the different structural sites occupied by carbonate groups in apatite (typically 7‰ for both 18O/16O and 13C/12C fractionation at 37 °C). Compared with calcite-water oxygen isotope fractionation, occurrence of A-type substitution in apatite structure, in addition to the main B-type substitution, could explain the larger temperature dependence of oxygen isotope fractionation measured at low temperature between carbonate in apatite and water. Theoretical internal fractionation of oxygen isotopes between carbonate and phosphate in B-type carbonated apatite (∼8‰ at 37 °C) is consistent with experimental values obtained from modern and well-preserved fossil bio-apatites. Concerning calcium, theoretical results suggest a small fractionation between apatite and calcite (-0.17‰ at 37 °C). Internal fractionation reaching 0.8‰ at 37 °C occurs between the two Ca sites in hydroxyapatite. Furthermore, the Ca isotopic fractionation properties of apatite are affected by the occurrence of carbonate groups, which could contribute to the variability observed on natural samples. Owing to the complexity of apatite crystal-chemistry and in light of the theoretical results, measurements of site-specific isotopic fractionation properties could improve our understanding and the interpretation of isotopic records in apatites.

Quantification of Labile Soil Mercury by Stable Isotope Dilution Techniques

NASA Astrophysics Data System (ADS)

Shetaya, Waleed; Huang, Jen-How; Osterwalder, Stefan; Alewell, Christine

2016-04-01

Mercury (Hg) is a toxic element that can cause severe health problems to humans. Mercury is emitted to the atmosphere from both natural and anthropogenic sources and can be transported over long distances before it is deposited to aquatic and terrestrial environments. Aside from accumulation in soil solid phases, Hg deposited in soils may migrate to surface- and ground-water or enter the food chain, depending on its lability. There are many operationally-defined extraction methods proposed to quantify soil labile metals. However, these methods are by definition prone to inaccuracies such as non-selectivity, underestimation or overestimation of the labile metal pool. The isotopic dilution technique (ID) is currently the most promising method for discrimination between labile and non-labile metal fractions in soil with a minimum disturbance to soil-solid phases. ID assesses the reactive metal pool in soil by defining the fraction of metal both in solid and solution phases that is isotopically-exchangeable known as the 'E-value'. The 'E-value' represents the metal fraction in a dynamic equilibrium with the solution phase and is potentially accessible to plants. This is carried out by addition of an enriched metal isotope to soil suspensions and quantifying the fraction of metal that is able to freely exchange with the added isotope by measuring the equilibrium isotopic ratio by ICP-MS. E-value (mg kg-1) is then calculated as follows: E-Value = (Msoil/ W) (CspikeVspike/ Mspike) (Iso1IAspike -Iso2IAspikeRss / Iso2IAsoil Rss - Iso1IAsoil) where M is the average atomic mass of the metal in the soil or the spike, W is the mass of soil (kg), Cspike is the concentration of the metal in the spike (mg L-1), Vspike is the volume of spike (L), IA is isotopic abundance, and Rss is the equilibrium ratio of isotopic abundances (Iso1:Iso2). Isotopic dilution has been successfully applied to determine E-values for several elements. However, to our knowledge, this method has not yet been applied to estimate the labile pool of mercury in contaminated soils. We performed a series of soil incubations spiked with 196Hg2+aiming at measuring and modelling the progressive assimilation of Hg ions into less labile forms. Soils with a wide range of characteristics are taken for our research purpose, inclusive of Hg concentrations ranging from 0.1 to 390 mg kg-1, pH between 3.5 - 7.5 and total organic carbon (TOC) between 2.5 - 8 %. In parallel, the labile pool of Hg estimated using ID will be compared with that determined using conventional extraction methods, e.g. sequential extraction procedures. These altogether allows us to answer (1) how the E-value of Hg in soils is comparable to those estimated based on selective extraction methods, (2) how the labile Hg correlates with the total soil Hg, soil pH and TOC, and (3) how the solubility of added Hg (e.g. via rainfall) decreased in soils of different properties during aging. The obtained results fills the knowledge gap concerning Hg biogeochemistry in the terrestrial environment and serves as a basis for estimating (and predicting) the risk of soil Hg diffusion from a point source to the adjacent environments.

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

NASA Technical Reports Server (NTRS)

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

1988-01-01

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

Equilibrium cycle pin by pin transport depletion calculations with DeCART

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

Kochunas, B.; Downar, T.; Taiwo, T.

As the Advanced Fuel Cycle Initiative (AFCI) program has matured it has become more important to utilize more advanced simulation methods. The work reported here was performed as part of the AFCI fellowship program to develop and demonstrate the capability of performing high fidelity equilibrium cycle calculations. As part of the work here, a new multi-cycle analysis capability was implemented in the DeCART code which included modifying the depletion modules to perform nuclide decay calculations, implementing an assembly shuffling pattern description, and modifying iteration schemes. During the work, stability issues were uncovered with respect to converging simultaneously the neutron flux,more » isotopics, and fluid density and temperature distributions in 3-D. Relaxation factors were implemented which considerably improved the stability of the convergence. To demonstrate the capability two core designs were utilized, a reference UOX core and a CORAIL core. Full core equilibrium cycle calculations were performed on both cores and the discharge isotopics were compared. From this comparison it was noted that the improved modeling capability was not drastically different in its prediction of the discharge isotopics when compared to 2-D single assembly or 2-D core models. For fissile isotopes such as U-235, Pu-239, and Pu-241 the relative differences were 1.91%, 1.88%, and 0.59%), respectively. While this difference may not seem large it translates to mass differences on the order of tens of grams per assembly, which may be significant for the purposes of accounting of special nuclear material. (authors)« less

First-principles investigation of vanadium isotope fractionation in solution and during adsorption

NASA Astrophysics Data System (ADS)

Wu, Fei; Qin, Tian; Li, Xuefang; Liu, Yun; Huang, Jen-How; Wu, Zhongqing; Huang, Fang

2015-09-01

Equilibrium fractionation factors of vanadium (V) isotopes among tri- (V(III)), tetra- (V(IV)) and penta-valent (V(V)) inorganic V species in aqueous system and during adsorption of V(V) to goethite are estimated using first-principles calculation. Our results highlight the dependence of V isotope fractionation on valence states and the chemical binding environment. The heavy V isotope (51V) is enriched in the main V species following a sequence of V(III) < V(IV) < V(V). According to our calculations, at 25 °C, the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V4+O(H2O)5]2+ (ln ⁡α V (V)- V (IV)) is 3.9‰, and the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V3+(OH)3(H2O)3] (ln ⁡α V (V)- V (III)) is 6.4‰. In addition, isotope fractionation between +5 valence species [V5+O2(OH)2]- and [V5+O2(H2O)4]+ is 1.5‰ at 25 °C, which is caused by their different bond lengths and coordination numbers (CN). Theoretical calculations also show that light V isotope (50V) is preferentially adsorbed on the surface of goethite. Our work reveals that V isotopes can be significantly fractionated in the Earth's surface environments due to redox reaction and mineral adsorption, indicating that V isotope data can be used to monitor toxic V(V) attenuation processes through reduction or adsorption in natural water systems. In addition, a simple mass balance model suggests that V isotope composition of seawater might vary with change of ambient oxygen levels. Thus our theoretical investigations imply a promising future for V isotopes as a potential new paleo-redox tracer.

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

Equilibrium stable-isotope fractionation of thallium and mercury

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2005-12-01

In this study first-principles quantum mechanical and empirical force-field models are used to estimate equilibrium mass-dependent isotopic fractionations among a variety of thallium and mercury compounds. High-precision MC-ICP-MS measurements have recently uncovered evidence of stable isotope fractionation for many elements, including 2-4‰ variability in the isotopic compositions of thallium[1] (atomic no. 81) and mercury[2] (atomic no. 80). The observed thallium- and mercury-isotope fractionations are remarkable, given that the magnitude of isotopic fractionation typically decreases as atomic number increases[3]. Stable isotope measurements could improve our understanding of geochemical and biogeochemical cycling of both elements, but little is known about the mechanisms driving these fractionations. A better understanding of the chemical processes controlling stable isotope compositions could help maximize the utility of these new geochemical tracers. Standard equilibrium stable isotope fractionation theory holds that the energy driving fractionation comes from isotopic effects on vibrational frequencies, which have generally not been measured. In the present study both quantum-mechanical and empirical force fields are used to estimate unknown frequencies. Results suggest that thallium and mercury fractionations of ≥ 0.5‰ are likely during the relevant redox reactions Tl+ ↔ Tl3+ and HgO ↔ Hg2+. Methyl-mercury and mercury-halide compounds like CH3HgCl will have ~ 1‰ higher 202Hg/198Hg than atomic vapor at room temperature. Fractionations between coexisting Hg2+ species appear to be much smaller, however. 205Tl/203Tl in Tl(H2O)_63+ is predicted to be ~0.5‰ higher than in coexisting Tl+-bearing substances. This result is in qualitative agreement with data from ferromanganese crusts [1], suggesting that Tl3+ in manganese-oxides will have higher 205Tl/203Tl than aqueous Tl+. Equilibrium fractionations for both elements are much smaller than the observed range of isotopic fractionations, however, which could point to a major role for kinetic-fractionation or Rayleigh-like distillation processes. Refs.: [1] Rehämper et al. (2002) EPSL 197:65. [2] Xie et al. (2005) J. Anal. Atomic Spectrom. 20:515. [3] Bigeleisen and Mayer (1947) J. Chem. Phys. 15:261.

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

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

Electroplating method for producing ultralow-mass fissionable deposits

DOEpatents

Ruddy, Francis H.

1989-01-01

A method for producing ultralow-mass fissionable deposits for nuclear reactor dosimetry is described, including the steps of holding a radioactive parent until the radioactive parent reaches secular equilibrium with a daughter isotope, chemically separating the daughter from the parent, electroplating the daughter on a suitable substrate, and holding the electroplated daughter until the daughter decays to the fissionable deposit.

Iron Isotopic Fractionation in Igneous Systems: Looking for Anharmonicity

NASA Astrophysics Data System (ADS)

Dauphas, N.; Roskosz, M.; Hu, M. Y.; Neuville, D. R.; Alp, E. E.; Hu, J.; Heard, A.; Zhao, J.

2017-12-01

Igneous rocks display variations in their Fe isotopic compositions that can be used to trace partial melting, magma differentiation, the origin of mineral zoning, and metasomatic processes. While tremendous progress has been made in our understanding of how iron isotopes can be fractionated at equilibrium or during diffusion, significant work remains to be done to establish equilibrium fractionation factors between phases relevant to igneous petrology. A virtue of iron isotope systematics is that iron possesses a Mössbauer isotope, 57Fe, and one can use the method of NRIXS to measure the force constant of iron bonds, from which beta-factors can be calculated. These measurements are done at a few synchrotron beamlines around the world, such as sector 3ID of the APS (Argonne). Tremendous insights have already been gained by applying this technique to Earth science materials. It was shown for instance that significant equilibrium fractionation exists between Fe2+ and Fe3+ at magmatic temperature, that the iron isotopic fractionation resulting from core formation must be small, and that iron isotopic fractionation is influenced by the polymerization of the melt. Combining NRIXS and ab initio studies, there are approximately 130 geologically-relevant solids and aqueous species for which beta-factors have been reported. A potential limitation of applying published NRIXS data to igneous petrology is that all the force constants have been measured at room temperature and the beta-factors are extrapolated to magmatic temperatures assuming that the systems are harmonic, which has never been demonstrated. One way to test this critical assumption is to measure the apparent force constant of iron bonds at various temperatures, so that the interatomic potential of iron bonds can be probed. A further virtue of NRIXS is that the data also allows us to derive the mean square displacement. If significant anharmonicity is present, it should be manifested as a decrease in the apparent force constant with increasing temperature and increasing mean square displacement. We have measured the Fe force constant of basalt glass and olivine using a wire furnace. At the conference, we will report on these experiments and will discuss some implications for igneous petrology.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Chapter 16Tracing Nitrogen Sources and Cycling in Catchments

USGS Publications Warehouse

Kendall, Carol

1998-01-01

This chapter focuses on the uses of isotopes to understand water chemistry.I Isotopic compositions generally cannot be interpreted successfully in the absence of other chemical and hydrologic data. The chapter focusses on uses of isotopes in tracing sources and cycling of nitrogen in the water-component of forested catchment, and on dissolved nitrate in shallow waters, nutrient uptake studies in agricultural areas, large-scale tracer experiments, groundwater contamination studies, food-web investigations, and uses of compound-specific stable isotope techniques. Shallow waters moving along a flowpath through a relatively uniform material and reacting with minerals probably do not achieve equilibrium but gradually approach some steady-state composition. The chapter also discusses the use of isotopic techniques to assess impacts of changes in land-management practices and land use on water quality. The analysis of individual molecular components for isotopic composition has much potential as a method for tracing the source, biogeochemistry, and degradation of organic liquids and gases because different materials have characteristic isotope spectrums or biomarkers.

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

NASA Astrophysics Data System (ADS)

Young, E. D.

2017-12-01

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

Stable carbon and sulfur isotopes as records of the early biosphere

NASA Technical Reports Server (NTRS)

Desmarais, David J.

1989-01-01

The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

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.

Multiple stable isotope fronts during non-isothermal fluid flow

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Latitudinal change in precipitation and water vapor isotopes over Southern ocean

NASA Astrophysics Data System (ADS)

Rahul, P.

2015-12-01

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

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

NASA Astrophysics Data System (ADS)

Sherman, David M.

2013-10-01

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

Site-Specific Carbon Isotopes in Organics

NASA Astrophysics Data System (ADS)

Piasecki, A.; Eiler, J. M.

2012-12-01

Natural organic molecules exhibit a wide range of internal site-specific isotope variation (i.e., molecules with same isotopic substitution type but different site). Such variations are generally unconstrained by bulk isotopic measurements. If known, site-specific variations might constrain temperatures of equilibrium, mechanisms of formation or consumption reactions, and possibly other details. For example, lipids can exhibit carbon isotope differences of up to 30‰ between adjacent carbon sites as a result of fractionations arising during decarboxylation of pyruvate and other steps in lipid biosynthesis(1). We present a method for site-specific carbon isotope analysis of propane, based on high-resolution, multi-collector gas source mass spectrometry, using a novel prototype instrument - the Thermo MAT 253 Ultra. This machine has an inlet system and electron bombardment ion source resembling those in conventional stable isotope gas source mass spectrometers, and the energy filter, magnet, and detector array resembling those in multi-collector ICPMS and TIMS. The detector array has 7 detector positions, 6 of which are movable, and each of which can collect ions with either a faraday cup (read through amplifiers ranging from 107-1012 ohms) or an SEM. High mass resolving power (up to 27,000, MRP = M/dM definition) is achieved through a narrow entrance slit, adjustable from 250 to 5 μm. Such resolution can cleanly separate isobaric interferences between isotopologues of organic molecules having the same cardinal mass (e.g., 13CH3 and 12CH2D). We use this technology to analyze the isotopologues and fragments of propane, and use such data to solve for the site-specific carbon isotope fractionation. By measuring isotopologues of both the one-carbon (13CH3) and the two-carbon (13C12CH4) fragment ion, we can solve for both bulk δ13C and the difference in δ13C between the terminal and central carbon position. We tested this method by analyzing mixtures between natural propane and labeled propane (13CH3-12CH2-12CH3). Results are consistent with the expected relative fractionations between the two fragments, indicating limited 'scrambling' of carbon positions of less than 2% in the source. The limits of precision of this method are currently ~0.5 ‰, sufficient to resolve known or suspected position-specific isotope effects in propane. We have explored the expected temperature-dependent equilibrium isotopic distributions of propane using density functional theory and quantum mechanical models of vibrational isotope effects. These models predict the homogeneous isotope exchange equilibria among the various isotopologues of propane, which include several of a wide range of effects that should be measurable by our methods. At 300 K we predict that the central carbon site is 15‰ higher in δ13C and 95 ‰ higher in δD than the terminal carbon site; similarly the molecule containing both a 13C and D in the central site is enriched by ~120 ‰ relative to a random isotopic distribution at 300 K. These predictions present targets for future experimental and empirical studies of the temperature dependence of isotopic ordering in propane. More generally, the methods we are developing for the study of intramolecular isotopic distributions in propane will serve as a model for future study of similar effects in other organic compounds. [1]DeNiro, Epstein (1977) Science Volume 197, 261-263.

First-principles Calculations of Equilibrium Calcium Isotope Fractionation among Ca-bearing Minerals

NASA Astrophysics Data System (ADS)

Zhou, C.; Wang, W.; Kang, J.; Wu, Z.; Huang, F.

2016-12-01

Calcium isotope fractionation factors of Ca-bearing minerals are investigated with the first principle calculations based on density functional theory (DFT). The sequence of heavy Ca isotope enrichment is forsterite > grossular > butschliite > lime > fluorite > tremolite diopside > anhydrite dolomite titanite > anorthite > perovskite gehlenite aragonite richterite > akermanite > oldhamite. This order is consistent with variation of Ca-O bond lengths, indicating that Ca-O bond energy plays an overwhelming role on the fractionations of Ca isotopes. Our study provides important insights into the Ca isotopic data of meteorites. Our calculation predicts that oldhamites (CaS) are enriched in light Ca isotopes relative to silicate phase if they are in equilibrium, contrast with the observations in Valdes et al (2014). Therefore, oldhamite and silicate phase in the meteorites should be in disequilibrium for Ca isotopes. Our results can also be used to understand Ca isotopic composition of the Moon. Δ44/40Ca between olivine (with CaO content of 2.48 wt%) and diopside is up to 0.41‰ and Δ44/40Cagrossular-diopside is 0.26‰ at 1500K. Feng et al. (2014) calculated that Δ44/40Ca between opx with CaO content of 1.74 wt% and cpx is about 0.27‰ at 1500 K. According to the Lunar Magma Ocean (LMO) model, the modern Moon is chemically stratified (Snyder et al., 1992; Elardo et al., 2011). Assuming that the lower cumulate and upper residual melt are in isotopic equilibrium during the evolution of Lunar Magma Ocean where the cumulate may be mainly composed of olivine and orthopyroxene or garnet/spinel, δ44/40Ca of the Moon could be underestimated by 0.05‰ to 0.25‰ if the shallow lunar samples are used to represent the bulk Moon.

Local equilibrium of mafic enclaves and granitoids of the Turtle pluton, southeast California: Mineral, chemical, and isotopic evidence

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

Allen, C.M.

Major element and trace element compositions of whole rocks, mineral compositions, and Rb-Sr isotopic compositions of enclave and host granitoid pairs from the Early Cretaceous, calc-alkaline Turtle pluton of southeastern California suggest that the local environmental profoundly affects some enclave types. In the Turtle pluton, where the source of fine-grained, mafic enclaves can be deduced to be magmatic by the presence of partially disaggregated basaltic dikes, mineral chemistry suggests partial or complete local equilibrium among mineral species in the enclave and its host granitoid. Because of local Rb-Sr isotopic equilibration between fine-grained enclaves and host granitoid, one cannot use Srmore » isotopes to distinguish an enclave source independent of its host rocks from an enclave source related to the enclosing pluton. However, preliminary Nd isotopic data suggest an independent, mantle source for enclaves.« less

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

PubMed

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

2017-01-01

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

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

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

USGS Publications Warehouse

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

2012-01-01

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

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

D/H isotopic fractionation effects in the H2-H2O system: An in-situ experimental study at supercritical water conditions

NASA Astrophysics Data System (ADS)

Foustoukos, D.; Mysen, B. O.

2011-12-01

Understanding the effect of temperature on the relative distribution of volatiles in supercritical aqueous solutions is important to constrain elemental and isotopic partitioning/fractionation effects in systems applicable to planetary interiors where the temperature-pressure conditions are often beyond existing experimental or theoretical datasets. For example, very little exists for the fundamental equilibria between H2, D2 and HD (H2 + D2 = 2HD), which, in turn, constrains the internal D/H isotope exchange and the evolution of HD in H2-containing systems such as H2-CH4 and H2-H2O. Theoretical calculations considering the partition functions of the molecules predict that with temperature increase, the equilibrium constant of this reaction approximates values that correspond to the stochastic distribution of species. These calculations consider pure harmonic vibrational frequencies, which, however, do not apply to the diatomic molecule of hydrogen, especially because anharmonic oscillations are anticipated to become stronger at high temperatures. Published experimental data have been limited to conditions lower than 468°C with large uncertainties at elevated temperatures. To address the lack of experimental data, a series of hydrothermal diamond anvil experiments has been conducted utilizing vibrational spectroscopy as a novel quantitative method to explore the relative distribution of H- and D-bearing volatiles in the H2-D2-D2O-H2O-Ti-TiO2 system. The fundamentals of this methodology are based on the distinct Raman frequency shift resulting from deuterium substitution in the H-H and O-H bonds. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (for 3-9hrs) at 600-800°C and pressures of 0.5-1 GPa, leading to formation of H2, D2, HD and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in-situ and in the quenched gas phase, indicate a significant deviation from the theoretical estimate of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy change for the 2HD=D2+H2 reaction, ΔHrx, approximates -3.1 kcal/mol, which differs greatly from the +0.2 kcal/mol predicted by statistical mechanics models. Similar differences in ΔHrx are observed for the isotope equilibrium reaction of 2HDO=H2O + D2O. The establishment of negative ΔHrx and the decrease of equilibrium constants with temperature increase are possibly triggered by dominant contribution of anharmonic vibrations or differences on the Henry Law constant between the H- and D-bearing species dissolved in supercritical fluids. The distinct Raman frequency shift due to deuterium isotopic substitutions demonstrated for H2 and H2O, would also be expected for other H-containing compounds such as, for example, CH4 and NH3. This approach to the experimental determination of isotopic equilibria may, therefore, provide ways to describe the equilibrium of isotope exchange reactions for which theoretical or experimental measurements are lacking and which are critical for evaluation of COHN fluid behavior in metamorphic and magmatic processes in the planetary interiors.

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.

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

NASA Astrophysics Data System (ADS)

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

2005-12-01

The enigma surrounding the `Dolomite Problem' is the relative abundance of dolomite in the geological record versus its very rare occurrence on the surface of the modern Earth despite a particularly favourable modern seawater chemistry. Recent studies of modern dolomite from hypersaline coastal lagoons in Brazil and Pleistocene dolomite from ODP cores collected during ODP Leg 201 on the Peru Margin suggest microbial mediation is an important factor [1]. Indeed, cultures of sulfate-reducing bacteria isolated from the lagoons mediate dolomite precipitation in the laboratory [2, 3]. In this study we report magnesium isotopic analyses of these modern microbial associated dolomites and ancient dolomites of a range of geological ages and environments. The application of stable magnesium isotopes to study dolomite formation and the nature of the processes involved represents a new frontier in isotope geochemistry. Highly accurate determination of the magnesium isotopic composition allows us to distinguish between kinetic and equilibrium isotope fractionation on the basis of the excess of 25Mg. A significant kinetic isotope fractionation is observed in laboratory cultures and surfical microbial mats from the Brazilian lagoons. Older dolomites (<3000 yrs.) taken from cores recovered from the lagoon are much closer to equilibrium. We interpret our data as evidencing an initial microbial mediated nucleation of dolomite that is a kinetic process and a subsequent inorganic addition of dolomite overprinting an equilibrium signature. This is in agreement with a previous major element and crystallographic study of the Brazilian dolomites [1]. The ancient dolomites analysed range in age from Neoproterozoic to Pleistocene and come from diverse geological environments including submarine diagenetic zones, platform carbonates and lagoonal environments. Magnesium isotopic analysis shows evidence of a varying component of kinetic fractionation, smaller than the kinetic end member as typified by the laboratory cultures. The ancient dolomites appear to evidence the same initial kinetic nucleation and subsequent equilibrium growth as the modern. In contrast, hydrothermal dolomite exhibits only equilibrium fractionation. Taken together, our results argue for a strong biological role in magnesium fixation into sedimentary dolomite in both the ancient and modern and suggest microbial processes are important in resolving the `Dolomite Problem'. References [1] Vasconcelos, C. and McKenzie, J.A., (1997), J. Sed. Res., 67, 378-390. [2] Vasconcelos, C., McKenzie, J.A., Bernasconi, S., Grujic, D. and Tien, A.J., (1995), Nature 377, 220-222. [3] Warthmann R., van Lith Y., Vasconcelos C., McKenzie J.A. and Karpoff A.M., (2000), Geology 28, 1091-1094.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

An accurate understanding of the relationships between the isotopic composition of liquid water and that of water vapor in the environment can help describe hydrologic processes across many scales. One such relationship is the isotopic equilibrium between falling raindrops and the surrounding vapor. The degree of equilibration is used to model the isotopic composition of precipitation in isotope-enable general circulation models and land-atmosphere exchange models. Although this equilibrium has been a topic of isotope hydrology research for more than four decades, few studies have included vapor measurements to validate modeling efforts. Recent advances in laser technology have allowed for in situ vapor measurements at high temporal resolution (e.g., >1 Hz). Here we present concomitant rain and vapor measurements for a series of 17 rain events during the 'Continental' rainy season (June through August) at Mpala Research Center in central Kenya. Rain samples (n=218) were collected at intervals of 2 to 35 minutes (median of 3 minutes) depending on the rain rate (0.4 to 10.5 mm/hr). The volume-weighted mean rain values for δ18O, δ2H and D-excess (δ2H - 8* δ18O) were 0.1 ‰, 10.7 ‰, and 10.1 ‰. These values are more enriched than the annual weighted means reported for the area (-2.2 ‰, -7.6 ‰, and 11.0 ‰, respectively). Vapor was measured continuously at ~2Hz (DLT-100, Los Gatos Research), with an inverted funnel intake 4m above the ground surface. The mean vapor isotopic composition during the rain events was -10.0 +/- 1.2 ‰ (1 σ) for δ18O and -73.9 +/- 7.0 ‰ for δ2H. The difference between the rain sample isotopic composition and that of liquid in isotopic equilibrium with the corresponding vapor at the ambient temperature was 0.8 +/- 2.2 ‰ for δ18O and 6.2 +/- 7.0 ‰ for δ2H. This disequilibrium was found to correlate with the natural log of rain rate (R2 of 0.26 for δ18O and 0.46 for δ2H), with lower rain rates having larger disequilibrium. There was also a temporal pattern in the disequilibrium for δ18O, with the first five rain events having significantly larger (p < 0.01) disequilibrium (4.4 ‰) than the subsequent rain events (0.6 ‰). The temporal pattern suggests that, in addition to the relationship with rain rate, there is some relationship between rain-vapor equilibrium and larger-scale controls such as vapor source region, precipitation recycling and air mass trajectory.

FE and MG Isotopic Analyses of Isotopically Unusual Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

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

2011-01-01

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

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

NASA Astrophysics Data System (ADS)

Pahlevan, K.; Karato, S. I.

2016-12-01

Models of the Moon-forming giant impact extensively melt and partially vaporize the silicate Earth and deliver a substantial mass of metal to the Earth's core. The subsequent evolution of the terrestrial magma ocean and overlying vapor atmosphere over the ensuing 105-6 years has been largely constrained by theoretical models with remnant signatures from this epoch proving somewhat elusive. We have calculated equilibrium hydrogen isotopic fractionation between the magma ocean and overlying steam atmosphere to determine the extent to which H isotopes trace the evolution during this epoch. By analogy with the modern silicate Earth, the magma ocean-steam atmosphere system is often assumed to be chemically oxidized (log fO2 QFM) with the dominant atmospheric vapor species taken to be water vapor. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also exhibit a much more reducing character (log fO2 IW) such that equilibration with the overlying atmosphere renders molecular hydrogen the dominant H-bearing vapor species. This variable - the redox state of the magma ocean - has not been explicitly included in prior models of the coupled evolution of the magma ocean-steam atmosphere system. We find that the redox state of the magma ocean influences not only the vapor speciation and liquid-vapor partitioning of hydrogen but also the equilibrium isotopic fractionation during the crystallization epoch. The liquid-vapor isotopic fractionation of H is substantial under reducing conditions and can generate measurable D/H signatures in the crystallization products but is largely muted in an oxidizing magma ocean and steam atmosphere. We couple equilibrium isotopic fractionation with magma ocean crystallization calculations to forward model the behavior of hydrogen isotopes during this epoch and find that the distribution of H isotopes in the silicate Earth immediately following crystallization represents an oxybarometer for the terrestrial magma ocean. Whether such endogenous isotopic heterogeneity would survive as an observable signature in the modern silicate Earth is an open question.

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)

Ethane C-C clumping in natural gas : a proxy for cracking processes ?

NASA Astrophysics Data System (ADS)

Clog, M. D.; Ferreira, A. A.; Santos Neto, E. V.; Eiler, J. M.

2014-12-01

Ethane (C2H6) is the second-most abundant alkane in most natural gas reservoirs, and is used to produce ethylene for petrochemical industries. It is arguably the simplest molecule that can manifest multiple 13C substitutions. There are several plausible controls on Δ13C2H6in natural gas: thermodynamically controlled homogeneous isotope exchange reactions analogous to those behind carbonate clumped isotope thermometry; inheritance from larger biomolecules that undergo thermal degradation to produce natural gas; mixing of natural gases that differ markedly in bulk isotopic composition; diffusive fractionation; or combinations of these and/or other, less expected fractionations. There is little basis for predicting which of these will control isotopic variations among natural ethanes, but we think it likely that addition of this new isotopic proxy will reveal new insights into the natural chemistry of ethane. We have developed a method to measure the abundance of 13C2H6 in natural samples, using high-resolution mass spectrometry. We define Δ13C2H6 as 1000 . ((13C2H6/12C2H6)measured/(13C2H6/12C2H6)stochastic -1). We studied several suites of natural gas samples and experimentally produced or modified ethane. Natural ethanes, including closely related samples from a single natural gas field, exhibit surprisingly large ranges in Δ13C2H6 (4 ‰ overall; up to 3 ‰ in one gas field). Such ranges cannot be explained by thermodynamic equilibrium at a range of different temperatures, or by diffusive fractionation. Kinetic isotope effects associated with 'cracking' reactions, and/or inheritance of non-equilibrium carbon isotope structures from source organics are more likely causes. We observe a correlation between Δ13C2H6 and the concentration of alkanes other than methane in several suites of natural gases, suggesting the causes of clumped isotope variations are tied to the controls on gas wetness. An experiment examining ethane residual to high-temperature pyrolysis confirms this trend could be an isotopic fingerprint for ethane destruction.

Radiogenic ingrowth in systems with multiple reservoirs: applications to the differentiation of the mantle-crust system

NASA Astrophysics Data System (ADS)

Albarède, Francis

2001-06-01

Mantle isochrons such as those observed for oceanic basalts in the 207Pb/ 204Pb vs. 206Pb/ 204Pb diagram do not date discrete differentiation events but are often suggested to reflect a mean age of differentiation within the mantle-crust system. The present work deals with the isotopic aspects of radioactive decay of long-lived isotopes ( 87Rb, 147Sm, 176Lu) in systems with multiple reservoirs. For these isotopes, the probability of decay is small compared to the frequency of reservoir jumping. Consequently, a state of secular equilibrium exists for which changes in the nuclide abundances in each reservoir balance radioactive decay and ingrowth. Here a theory is presented that predicts the characteristic time to reach secular equilibrium (relaxation time) and the secular equilibrium properties of stable, radioactive, and daughter nuclides in a pair of reservoirs of constant mass. Expressions are derived for parent/daughter ratios, such as 87Rb/ 86Sr, and for isotopic ratios involving a daughter isotope, such as 87Sr/ 86Sr. It is shown that, at secular equilibrium, the reservoirs form linear arrays in isochron diagrams. The isochron slope and intercept reflect the relaxation time and have no significance of a mean age. The derived relationships are extended to an arbitrary number of reservoirs with constant mass. In the case of 87Rb, 147Sm, and 176Lu, the relaxation times of the mantle-crust system agree with each other (1.2±0.1 Gy). It is therefore likely that the Earth is at secular equilibrium for these nuclides and their daughter isotopes and that no memory of the initial differentiation of the Earth is preserved in the isotope composition of Sr, Nd, and Hf of modern basalts. The kappa conundrum is a straightforward consequence of Th and U having different relaxation times in the mantle-crust system. The 207Pb/ 204Pb and 4He/ 3He ratios are not at secular equilibrium, in contrast with 206Pb/ 204Pb and 208Pb/ 204Pb. The properties of oceanic basalts in terms of the last two ratios and the Nd and Hf secular evolution curves of mantle-derived material require the presence of deep hidden reservoirs that interacts with the depleted upper mantle. It is suggested that the most fertile lithospheric oceanic plates, in particular those loaded with plume heads, preferentially sink to the bottom of the mantle. The terrestrial mantle is therefore most likely chemically heterogeneous and models of Earth compositions based on a primitive lower mantle should be abandoned. In contrast, the transient-dominated 207Pb/ 204Pb and 4He/ 3He ratios can be used to model the early differentiation of the planet.

Development of a High-Resolution Laser Absorption Spectroscopy Method with Application to the Determination of Absolute Concentration of Gaseous Elemental Mercury in Air.

PubMed

Srivastava, Abneesh; Hodges, Joseph T

2018-06-05

Isotope dilution-cold-vapor-inductively coupled plasma mass spectrometry (ID-CV-ICPMS) has become the primary standard for measurement of gaseous elemental mercury (GEM) mass concentration. However, quantitative mass spectrometry is challenging for several reasons including (1) the need for isotopic spiking with a standard reference material, (2) the requirement for bias-free passive sampling protocols, (3) the need for stable mass spectrometry interface design, and (4) the time and cost involved for gas sampling, sample processing, and instrument calibration. Here, we introduce a high-resolution laser absorption spectroscopy method that eliminates the need for sample-specific calibration standards or detailed analysis of sample treatment losses. This technique involves a tunable, single-frequency laser absorption spectrometer that measures isotopically resolved spectra of elemental mercury (Hg) spectra of 6 1 S 0 ← 6 3 P 1 intercombination transition near λ = 253.7 nm. Measured spectra are accurately modeled from first-principles using the Beer-Lambert law and Voigt line profiles combined with literature values for line positions, line shape parameters, and the spontaneous emission Einstein coefficient to obtain GEM mass concentration values. We present application of this method for the measurement of the equilibrium concentration of mercury vapor near room temperature. Three closed systems are considered: two-phase mixtures of liquid Hg and its vapor and binary two-phase mixtures of Hg-air and Hg-N 2 near atmospheric pressure. Within the experimental relative standard uncertainty, 0.9-1.5% congruent values of the equilibrium Hg vapor concentration are obtained for the Hg-only, Hg-air, Hg-N 2 systems, in confirmation with thermodynamic predictions. We also discuss detection limits and the potential of the present technique to serve as an absolute primary standard for measurements of gas-phase mercury concentration and isotopic composition.

Detecting animal by-product intake using stable isotope ratio mass spectrometry (IRMS).

PubMed

da Silva, D A F; Biscola, N P; Dos Santos, L D; Sartori, M M P; Denadai, J C; da Silva, E T; Ducatti, C; Bicudo, S D; Barraviera, B; Ferreira, R S

2016-11-01

Sheep are used in many countries as food and for manufacturing bioproducts. However, when these animals consume animal by-products (ABP), which is widely prohibited, there is a risk of transmitting scrapie - a fatal prion disease in human beings. Therefore, it is essential to develop sensitive methods to detect previous ABP intake to select safe animals for producing biopharmaceuticals. We used stable isotope ratio mass spectrometry (IRMS) for 13 C and 15 N to trace animal proteins in the serum of three groups of sheep: 1 - received only vegetable protein (VP) for 89 days; 2 - received animal and vegetable protein (AVP); and 3 - received animal and vegetable protein with animal protein subsequently removed (AVPR). Groups 2 and 3 received diets with 30% bovine meat and bone meal (MBM) added to a vegetable diet (from days 16-89 in the AVP group and until day 49 in the AVPR group, when MBM was removed). The AVPR group showed 15 N equilibrium 5 days after MBM removal (54th day). Conversely, 15 N equilibrium in the AVP group occurred 22 days later (76th day). The half-life differed between these groups by 3.55 days. In the AVPR group, 15 N elimination required 53 days, which was similar to this isotope's incorporation time. Turnover was determined based on natural 15 N signatures. IRMS followed by turnover calculations was used to evaluate the time period for the incorporation and elimination of animal protein in sheep serum. The δ 13 C and δ 15 N values were used to track animal protein in the diet. This method is biologically and economically relevant for the veterinary field because it can track protein over time or make a point assessment of animal feed with high sensitivity and resolution, providing a low-cost analysis coupled with fast detection. Isotopic profiles could be measured throughout the experimental period, demonstrating the potential to use the method for traceability and certification assessments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ammonium stability and nitrogen isotope fractionations for NH4+-NH3(aq)-NH3(gas) systems at 20-70 °C and pH of 2-13: Applications to habitability and nitrogen cycling in low-temperature hydrothermal systems

NASA Astrophysics Data System (ADS)

Li, Long; Lollar, Barbara Sherwood; Li, Hong; Wortmann, Ulrich G.; Lacrampe-Couloume, Georges

2012-05-01

Ammonium/ammonia is an essential nutrient and energy source to support life in oceanic and terrestrial hydrothermal systems. Thus the stability of ammonium is crucial to determine the habitability or ecological structure in hydrothermal environments, but still not well understood. To date, the lack of constraints on nitrogen isotope fractionations between ammonium and ammonia has limited the application of nitrogen isotopes to trace (bio)geochemical processes in such environments. In this study, we carried out laboratory experiments to (1) examine the stability of ammonium in an ammonium sulfate solution under temperature conditions from 20 to 70 °C and pH from 2.1 to 12.6 and (2) determine nitrogen isotope fractionation between ammonium and ammonia. Our experimental results show that ammonium is stable under the experimental temperatures when pH is less than 6. In experiments with starting pH greater than 8, significant ammonium was lost as a result of dissociation of ammonium and degassing of ammonia product. Nitrogen concentrations in the fluids decreased by more than 50% in the first two hours, indicating extremely fast effusion rates of ammonia. This implies that ammonium at high pH fluids (e.g., Lost City Hydrothermal Vents, Oman ophiolite hyperalkaline springs) may not be stable. Habitable environments may be more favorable at the leading edge of a pH gradient toward more acidic conditions, where the fluid can efficiently trap any ammonia transferred from a high pH vent. Although modeling shows that high temperature, low pH hydrothermal vents (e.g., Rainbow hydrothermal vent) may have the capability to retain ammonium, their high temperatures may limit habitability. The habitable zone associated with such a hydrothermal vent is likely at the lower front of a temperature gradient. In contrast, modeling of ammonium in deep terrestrial systems, suggests that saline fracture waters in crystalline rocks such as described in the Canadian Shield and in the Witwatersrand Basin, South Africa may also provide habitable environments for life. The nitrogen isotope results of remaining ammonium from the partial dissociation experiments fit well with a batch equilibrium model, indicating equilibrium nitrogen isotope fractionations have been reached between ammonium and its dissociation product aqueous ammonia. Modeling yielded nitrogen isotope fractionations between ammonium and aqueous ammonia were 45.4‰ at 23 °C, 37.7‰ at 50 °C, and 33.5‰ at 70 °C, respectively. A relationship between nitrogen equilibrium isotope fractionation and temperature is determined for the experimental temperature range as: 103·lnα(aq)=25.94×{103}/{T}-42.25 Integrated with three previous theoretical estimates on nitrogen isotope equilibrium fractionations between ammonium and gaseous ammonia, we achieved three possible temperature-dependent nitrogen isotope equilibrium fractionation between aqueous ammonia and gaseous ammonia:

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.

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.

Copper isotope signatures in modern marine sediments

NASA Astrophysics Data System (ADS)

Little, Susan H.; Vance, Derek; McManus, James; Severmann, Silke; Lyons, Timothy W.

2017-09-01

The development of metal stable isotopes as tools in paleoceanography requires a thorough understanding of their modern marine cycling. To date, no Cu isotope data has been published for modern sediments deposited under low oxygen conditions. We present data encompassing a broad spectrum of hydrographic and redox regimes, including continental margin and euxinic (sulphide-containing) settings. Taken together with previously published data from oxic settings, these data indicate that the modern oceanic sink for Cu has a surprisingly homogeneous isotopic composition of about +0.3‰ (δ65Cu, relative to NIST SRM976). We suggest that this signature reflects one of two specific water-column processes: (1) an equilibrium isotope fractionation between soluble, isotopically heavy, Cu complexed to strong organic ligands and an isotopically light pool sorbed to particles that deliver Cu to the sediment, or (2) an equilibrium isotope fractionation between the same isotopically heavy ligand-bound pool and the particle reactive free Cu2+ species, with the latter being scavenged by particulates and thereby delivered to the sediment. An output flux of about +0.3‰ into sediments is isotopically light relative to the known inputs to the ocean (at around +0.6‰) and the seawater value of +0.6 to +0.9‰, suggesting the presence of an as yet unidentified isotopically light source of Cu to the oceans. We hypothesize that this source may be hydrothermal, or may result from the partial dissolution of continentally derived particles.

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

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

Nevinitsa, V. A., E-mail: Neviniza-VA@nrcki.ru; Dudnikov, A. A.; Blandinskiy, V. Yu.

2015-12-15

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

Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

2014-06-01

The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during uptake. However, Cu in Fe-Mn crusts is isotopically light (at ∼0.3 to 0.5‰) compared to the dissolved phase in seawater (at ∼0.9‰). We suggest that this is because dissolved Cu in the oceans is overwhelmingly complexed to strong organic ligands, which are better competitors for the heavy isotope.

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

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Carbon and oxygen isotope fractionation in non-marine ostracods: results from a 'natural culture' environment

NASA Astrophysics Data System (ADS)

Keatings, K. W.; Heaton, T. H. E.; Holmes, J. A.

2002-05-01

Carbon and oxygen isotope analysis of ostracods living in the near-constant conditions of spring-fed ponds in southern England allowed accurate determination of the ostracod's calcite-water 13C/12C and 18O/16O fractionations. The 13C/12C fractionations of two species, Candona candida and Pseudocandona rostrata, correspond to values expected for isotopic equilibrium with the pond's dissolved inorganic carbon at the measured temperature (11°C) and pH (6.9), whilst those of a third species, Herpetocypris reptans, would represent equilibrium at a slightly higher pH (7.1). The 18O/16O fractionations confirm two previous studies in being larger, by up to 3‰, than those 'traditionally' regarded as representing equilibrium. When the measured fractionations are considered in the context of more recent work, however, they can be explained in terms of equilibrium if the process of calcite formation at the ostracod lamella occurs at a relatively low pH (≤7) irrespective of the pH of the surrounding water. The pH of calcite formation, and therefore the calcite-water 18O/16O fractionation, may be species and stage (adult versus juvenile) specific, and related to the rate of calcification.

Process for recovering evolved hydrogen enriched with at least one heavy hydrogen isotope

DOEpatents

Tanaka, John; Reilly, Jr., James J.

1978-01-01

This invention relates to a separation means and method for enriching a hydrogen atmosphere with at least one heavy hydrogen isotope by using a solid titaniun alloy hydride. To this end, the titanium alloy hydride containing at least one metal selected from the group consisting of vanadium, chromium, manganese, molybdenum, iron, cobalt and nickel is contacted with a circulating gaseous flow of hydrogen containing at least one heavy hydrogen isotope at a temperature in the range of -20.degree. to +40.degree. C and at a pressure above the dissociation pressure of the hydrided alloy selectively to concentrate at least one of the isotopes of hydrogen in the hydrided metal alloy. The contacting is continued until equilibrium is reached, and then the gaseous flow is isolated while the temperature and pressure of the enriched hydride remain undisturbed selectively to isolate the hydride. Thereafter, the enriched hydrogen is selectively recovered in accordance with the separation factor (S.F.) of the alloy hydride employed.

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

PubMed

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

2016-04-22

Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr(3+), CrCl(2+) and CrCl2(+)) with equilibrium mass-dependent isotope fractionation spanning a range of ∼1‰/amu and consistent with theory. The heaviest isotopes partition into Cr(3+), intermediates in CrCl(2+) and the lightest in CrCl2(+)/CrCl3°. Thus, for a typical reported loss of ∼25% Cr (in the form of Cr(3+)) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected (53)Cr/(52)Cr (μ(53)Cr* of 5.2 ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr(3+) by >5 days exposure to HNO3H2O2 solutions at room temperature, resulting in >∼98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a chromatographic elution strategy that takes advantage of the slow reaction kinetics of de-chlorination of Cr in dilute HCl at room temperature. These procedures significantly improve cation chromatographic purification of Cr over previous methods and allow for high-purity Cr isotope analysis with a total recovery of >95%. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed Central

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

2016-01-01

Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr3+, CrCl2+ and CrCl2+) with equilibrium mass-dependent isotope fractionation spanning a range of ~1‰/amu and consistent with theory. The heaviest isotopes partition into Cr3+, intermediates in CrCl2+ and the lightest in CrCl2+/CrCl3°. Thus, for a typical reported loss of ~25% Cr (in the form of Cr3+) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected 53Cr/52Cr (μ53 Cr* of 5.2 ppm) and 54Cr/52Cr (μ54Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr3+ by >5 days exposure to HNO3 —H2O2 solutions at room temperature, resulting in >~98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a chromatographic elution strategy that takes advantage of the slow reaction kinetics of de-chlorination of Cr in dilute HCl at room temperature. These procedures significantly improve cation chromatographic purification of Cr over previous methods and allow for high-purity Cr isotope analysis with a total recovery of >95%. PMID:27036208

A test of the significance of intermolecular vibrational coupling in isotopic fractionation

DOE PAGES

Herman, Michael F.; Currier, Robert P.; Peery, Travis B.; ...

2017-07-15

Intermolecular coupling of dipole moments is studied for a model system consisting of two diatomic molecules (AB monomers) arranged co-linearly and which can form non-covalently bound dimers. The dipolar coupling is a function of the bond length in each molecule as well as of the distance between the centers-of-mass of the two molecules. The calculations show that intermolecular coupling of the vibrations results in an isotope-dependent modification of the AB-AB intermolecular potential. This in turn alters the energies of the low-lying bound states of the dimers, producing isotope-dependent changes in the AB-AB dimer partition function. Explicit inclusion of intermolecular vibrationalmore » coupling then changes the predicted gas-dimer isotopic fractionation. In addition, a mass dependence in the intermolecular potential can also result in changes in the number of bound dimer states in an equilibrium mixture. This in turn leads to a significant dimer population shift in the model monomer-dimer equilibrium system considered here. Finally, the results suggest that intermolecular coupling terms should be considered when probing the origins of isotopic fractionation.« less

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

NASA Astrophysics Data System (ADS)

Young, E. D.

2007-12-01

Laser ablation multiple-collector inductively coupled plasma-source mass spectrometry (LA-MC-ICPMS) is a rapid method for obtaining high-precision isotope ratio measurements in geological samples. The method has been used with success for measuring isotope ratios of numerous elements, including Pb, Hf, Mg, Si, and Fe in terrestrial and extraterrestrial samples. It fills the gap between the highest precision obtainable with acid digestion together with MC-ICPMS and thermal ionization mass spectrometry (TIMS) and the maximum spatial resolution afforded by secondary ion mass spectrometry (SIMS). Matrix effects have been shown to be negligible for Pb isotopic analysis by LA-MC-ICPMS (Simon et al., 2007). Glass standards NBS 610, 612, and 614 have Pb/matrix ratios spanning two orders of magnitude. Our sample-standard bracketing laser ablation technique gives accurate and precise 208Pb/206Pb and 207Pb/206Pb for these glasses. The accuracy is superior to that obtained when using Tl to correct for mass fractionation. Accuracy and precision (± 0.2 ‰) for Pb in feldspars is comparable to that for double-spike TIMS. Data like these have been used to distinguish distinct sources of magmas in the Long Valley silicic magma system. LA-MC-ICPMS analyses of Mg isotope ratios in calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrite meteorites have revealed a wealth of new information about the history of these objects. A byproduct of this work has been recognition of the importance of different mass fractionation laws among three isotopes of a given element. Kinetic and equilibrium processes define distinct fractionation laws. Reservoir effects can further modify these laws. The result is that the linear coefficient β that relates the logarithms of the ratios n2/n1 and n3/n1 (ni refers to the number of atoms of isotope i) of isotopes with masses m3 > m2 > m1 is not unique. Rather, it is process dependent. In the case of Mg, this coefficient ranges from 0.521 for single-step equilibrium processes to 0.510 or even lower for kinetic processes. Rayleigh fractionation involving a kinetic process with a single-step β of 0.510 produces an effective β of 0.512. Such differences in fractionation laws can be crucial for determining excesses or deficits in isotopes relative to mass fractionation. Contrary to some assertions, Si isotope ratios can be measured with high accuracy and precision using 193 nm excimer lasers with nanosecond pulse widths (Shahar and Young, 2007). Silicon isotope ratios in CAIs measured by 193 nm LA-MC-ICPMS have been combined with Mg isotope ratios to constrain the astrophysical environments in which these oldest solar system materials formed. Accuracy of the measurements was determined using gravimetric standards of various matrix compositions. The results establish that matrix effects for Si are below detection at the ± 0.2 ‰ precision of the laser ablation technique. High mass resolving power (m/Δ m ~ 9000) is necessary to obtain accurate Si isotope ratios by laser ablation. High-precision LA-MC-ICPMS measurements of 176Hf/177Hf in zircons can be obtained by normalizing to 179Hf/177Hf assuming an exponential fractionation law and no mass-dependent Hf, Lu, or Yb stable isotope fractionation. With corrections for interfering 176Lu and 176Yb precision for this method can be on the order of 0.3 epsilon (0.03 ‰). The approach has been used to infer the existence of continental crust on Earth 4.4 billion years before present (Harrison et al., 2005).

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.

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

PubMed

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

2011-03-01

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

Measuring volatile organic compounds and stable isotopes emitted from trees and soils of the Biosphere 2 Rainforest

NASA Astrophysics Data System (ADS)

Meraz, J. C.; Meredith, L. K.; Van Haren, J. L. M.; Volkmann, T. H. M.

2017-12-01

Rainforest trees and soils play an important role in volatile organic compound (VOC) emissions. It is known that many rainforest tree species emit these organic compounds, such as terpenes, which can have an impact on the atmosphere and can be indicative of their metabolic functions. Some VOCs also absorb infrared radiation at wavelengths at which water isotopes are measured with laser spectrometers. Normal concentrations are not high enough for ambient sampling, but increased concentrations resulting from soil and plant samples extracted using equilibrium methods affect observed isotope ratios. There is thus a need to characterize volatile emissions from soil and plant samples, and to develop better methods to account for VOC interference during water isotope measurements. In this study, we collected soil and leaf samples from plants of the Biosphere 2 Rainforest Biome, a mesocosm system created to stimulate natural tropical rainforest habitats . Volatile concentrations were measured using a Gasmet DX4015 FTIR analyzer and a custom sampling system with sulfur hexafluoride (SF6) used as a tracer gas to test for leakage, and a commercial laser spectrometer was used for isotopic analysis. We determined that the different types of tree species emit different kinds of VOCs, such as isoprenes, alcohols, and aldehydes, that will potentially have to be accounted for. This study will help build the understanding of which organic compounds are emitted and develop new methods to test for water isotopes and gas fluxes in clear and precise measures. Such measures can help characterize the functioning of environmental systems such as the Biosphere 2 Rainforest Biome.

Non-linear mixing effects on mass-47 CO2 clumped isotope thermometry: Patterns and implications.

PubMed

Defliese, William F; Lohmann, Kyger C

2015-05-15

Mass-47 CO(2) clumped isotope thermometry requires relatively large (~20 mg) samples of carbonate minerals due to detection limits and shot noise in gas source isotope ratio mass spectrometry (IRMS). However, it is unreasonable to assume that natural geologic materials are homogenous on the scale required for sampling. We show that sample heterogeneities can cause offsets from equilibrium Δ(47) values that are controlled solely by end member mixing and are independent of equilibrium temperatures. A numerical model was built to simulate and quantify the effects of end member mixing on Δ(47). The model was run in multiple possible configurations to produce a dataset of mixing effects. We verified that the model accurately simulated real phenomena by comparing two artificial laboratory mixtures measured using IRMS to model output. Mixing effects were found to be dependent on end member isotopic composition in δ(13)C and δ(18)O values, and independent of end member Δ(47) values. Both positive and negative offsets from equilibrium Δ(47) can occur, and the sign is dependent on the interaction between end member isotopic compositions. The overall magnitude of mixing offsets is controlled by the amount of variability within a sample; the larger the disparity between end member compositions, the larger the mixing offset. Samples varying by less than 2 ‰ in both δ(13)C and δ(18)O values have mixing offsets below current IRMS detection limits. We recommend the use of isotopic subsampling for δ(13)C and δ(18)O values to determine sample heterogeneity, and to evaluate any potential mixing effects in samples suspected of being heterogonous. Copyright © 2015 John Wiley & Sons, Ltd.

Toward a simple, repeatable, non-destructive approach to measuring stable-isotope ratios of water within tree stems

NASA Astrophysics Data System (ADS)

Raulerson, S.; Volkmann, T.; Pangle, L. A.

2017-12-01

Traditional methodologies for measuring ratios of stable isotopes within the xylem water of trees involve destructive coring of the stem. A recent approach involves permanently installed probes within the stem, and an on-site assembly of pumps, switching valves, gas lines, and climate-controlled structure for field deployment of a laser spectrometer. The former method limits the possible temporal resolution of sampling, and sample size, while the latter may not be feasible for many research groups. We present results from initial laboratory efforts towards developing a non-destructive, temporally-resolved technique for measuring stable isotope ratios within the xylem flow of trees. Researchers have used direct liquid-vapor equilibration as a method to measure isotope ratios of the water in soil pores. Typically, this is done by placing soil samples in a fixed container, and allowing the liquid water within the soil to come into isotopic equilibrium with the headspace of the container. Water can also be removed via cryogenic distillation or azeotropic distillation, with the resulting liquid tested for isotope ratios. Alternatively, the isotope ratios of the water vapor can be directly measured using a laser-based water vapor isotope analyzer. Well-established fractionation factors and the isotope ratios in the vapor phase are then used to calculate the isotope ratios in the liquid phase. We propose a setup which would install a single, removable chamber onto a tree, where vapor samples could non-destructively and repeatedly be taken. These vapor samples will be injected into a laser-based isotope analyzer by a recirculating gas conveyance system. A major part of what is presented here is in the procedure of taking vapor samples at 100% relative humidity, appropriately diluting them with completely dry N2 calibration gas, and injecting them into the gas conveyance system without inducing fractionation in the process. This methodology will be helpful in making temporally resolved measurements of the stable isotopes in xylem water, using a setup that can be easily repeated by other research groups. The method is anticipated to find broad application in ecohydrological analyses, and in tracer studies aimed at quantifying age distributions of soil water extracted by plant roots.

Separation of the isotopes of boron by chemical exchange reactions

DOEpatents

McCandless, Frank P.; Herbst, Ronald S.

1995-01-01

The isotopes of boron, .sup.10 B and .sup.11 B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF.sub.3 and a liquid BF.sub.3 . donor molecular addition complex formed between BF.sub.3 gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone.

Calculating Capstone Depleted Uranium Aerosol Concentrations from Beta Activity Measurements

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

Szrom, Fran; Falo, Gerald A.; Parkhurst, MaryAnn

2009-03-01

Beta activity measurements were used as surrogate measurements of uranium mass in aerosol samples collected during the field testing phase of the Capstone Depleted Uranium (DU) Aerosol Study. These aerosol samples generated by the perforation of armored combat vehicles were used to characterize the depleted uranium (DU) source term for the subsequent human health risk assessment (HHRA) of Capstone aerosols. Establishing a calibration curve between beta activity measurements and uranium mass measurements is straightforward if the uranium isotopes are in equilibrium with their immediate short-lived, beta-emitting progeny. For DU samples collected during the Capstone study, it was determined that themore » equilibrium between the uranium isotopes and their immediate short lived, beta-emitting progeny had been disrupted when penetrators had perforated target vehicles. Adjustments were made to account for the disrupted equilibrium and for wall losses in the aerosol samplers. Correction factors for the disrupted equilibrium ranged from 0.16 to 1, and the wall loss correction factors ranged from 1 to 1.92.« less

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

NASA Astrophysics Data System (ADS)

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

2014-06-01

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

Experimental, in-situ carbon solution mechanisms and isotope fractionation in and between (C-O-H)-saturated silicate melt and silicate-saturated (C-O-H) fluid to upper mantle temperatures and pressures

NASA Astrophysics Data System (ADS)

Mysen, Bjorn

2017-02-01

Our understanding of materials transport processes in the Earth relies on characterizing the behavior of fluid and melt in silicate-(C-O-H) systems at high temperature and pressure. Here, Raman spectroscopy was employed to determine structure of and carbon isotope partitioning between melts and fluids in alkali aluminosilicate-C-O-H systems. The experimental data were recorded in-situ while the samples were at equilibrium in a hydrothermal diamond anvil cell at temperatures and pressures to 825 °C and >1300 MPa, respectively. The carbon solution equilibrium in both (C-O-H)-saturated melt and coexisting, silicate-saturated (C-O-H) fluid is 2CO3 + H2O + 2Qn + 1 = 2HCO3 + 2Qn. In the Qn-notation, the superscript, n, is the number of bridging oxygen in silicate structural units. At least one oxygen in CO3 and HCO3 groups likely is shared with silicate tetrahedra. The structural behavior of volatile components described with this equilibrium governs carbon isotope fractionation factors between melt and fluid. For example, the ΔH equals 3.2 ± 0.7 kJ/mol for the bulk 13C/12C exchange equilibrium between fluid and melt. From these experimental data, it is suggested that at deep crustal and upper mantle temperatures and pressures, the δ13C-differences between coexisting silicate-saturated (C-O-H) fluid and (C-O-H)-saturated silicate melts may change by more than 100‰ as a function of temperature in the range of magmatic processes. Absent information on temperature and pressure, the use of carbon isotopes of mantle-derived magma to derive isotopic composition of magma source regions in the Earth's interior, therefore, should be exercised with care.

Contrasting Effects of Carbon and Sulfur on Fe-Isotope Fractionation between Metal and Silicate Melt during Planetary Core Formation

NASA Astrophysics Data System (ADS)

Elardo, S. M.; Shahar, A.

2015-12-01

There are numerous studies that show well-resolved Fe isotope fractionations in igneous materials from different planetary bodies. Potential explanations for these fractionations include a non-chondritic bulk planetary Fe isotopic composition, and equilibrium fractionation between Fe-alloys or minerals and silicate melts during planetary differentiation, mantle melting, or fractional crystallization. This is further complicated by the fact that these processes are not mutually exclusive, making the interpretation of Fe isotope data a complex task. Here we present new experimental results investigating the effect of C on Fe isotope fractionation between molten peridotite and an Fe-alloy. Experiments were conducted at 1 GPa and 1850° C for 0.5 - 3 hours on a mixture of an 54Fe-spiked peridotite and Fe-metal with and without Ni metal in an end-loaded piston cylinder at the Geophysical Laboratory. Carbon saturation was achieved with a graphite capsule, and resulted in C contents of the Fe-alloy in our experiments ranging from 3.8 - 4.9 wt. %. The metal and silicate phases from half of each experiment were separated manually and dissolved in concentrated acids. Iron was separated from matrix elements by anion exchange chromatagraphy. Iron-isotopic compositions were determined with the Nu Plasma II MC-ICP-MS at GL. The other half of each experiment was used for quantitative microbeam analysis. Equilibrium was assessed with a time series and the three-isotope exchange method. The Ni-free experiments resulted in no resolvable Fe isotope fractionation between the Fe-C-alloy and molten silicate. This is in contrast to the results of Shahar et al. (2015) which showed a fractionation for Δ57Fe of ~0.18 ‰ between a peridotite and an Fe-alloy with a similar S abundance to C in these experiments. The one experiment thus far that contained Ni (~4 wt. % in the alloy) showed a resolvable fractionation between the Fe-Ni-C alloy and silicate of ~0.10 ‰. Shahar et al. found a similar magnitude fractionation to our Ni bearing experiment in experiments with no C or S. The difference in temperature (1650° C in Shahar et al. vs. 1850° C here) may be partially responsible for these discrepancies. Ongoing experiments will further investigate the effects of C and other light elements on Fe isotope fractionation during core segregation.

Experimental design-based isotope-dilution SPME-GC/MS method development for the analysis of smoke flavouring products.

PubMed

Giri, Anupam; Zelinkova, Zuzana; Wenzl, Thomas

2017-12-01

For the implementation of Regulation (EC) No 2065/2003 related to smoke flavourings used or intended for use in or on foods a method based on solid-phase micro extraction (SPME) GC/MS was developed for the characterisation of liquid smoke products. A statistically based experimental design (DoE) was used for method optimisation. The best general conditions to quantitatively analyse the liquid smoke compounds were obtained with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre, 60°C extraction temperature, 30 min extraction time, 250°C desorption temperature, 180 s desorption time, 15 s agitation time, and 250 rpm agitation speed. Under the optimised conditions, 119 wood pyrolysis products including furan/pyran derivatives, phenols, guaiacol, syringol, benzenediol, and their derivatives, cyclic ketones, and several other heterocyclic compounds were identified. The proposed method was repeatable (RSD% <5) and the calibration functions were linear for all compounds under study. Nine isotopically labelled internal standards were used for improving quantification of analytes by compensating matrix effects that might affect headspace equilibrium and extractability of compounds. The optimised isotope dilution SPME-GC/MS based analytical method proved to be fit for purpose, allowing the rapid identification and quantification of volatile compounds in liquid smoke flavourings.

Isotopic exchange of carbon-bound hydrogen over geologic timescales

NASA Astrophysics Data System (ADS)

Sessions, Alex L.; Sylva, Sean P.; Summons, Roger E.; Hayes, John M.

2004-04-01

The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50-100°C) exchange likely occurs on timescales of 104 to 108 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (<1 Ma), cool sediments, but strong evidence for exchange in ancient (>350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity. Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ∼75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D2O indicate that the number of D atoms incorporated during structural rearrangements can be far less than the number of C-H bonds that are broken. Sample calculations indicate that, for steranes in immature sediments, the D/H ratio imparted by biosynthesis may be largely preserved in spite of significant structural changes.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Processes affecting the stable isotope composition of calcite during precipitation on the surface of stalagmites: Laboratory experiments investigating the isotope exchange between DIC in the solution layer on top of a speleothem and the CO2 of the cave atmosphere

NASA Astrophysics Data System (ADS)

Dreybrodt, Wolfgang; Hansen, Maximilian; Scholz, Denis

2016-02-01

We present a theoretical derivation of the exchange time, τex, needed to establish isotopic equilibrium between atmospheric CO2 in a cave and HCO3- dissolved in a thin water film covering the surface of a speleothem. The result is τex = τredex · [HCO3-]/ (KH · pCO2cave) , where τredex depends on the depth, a, of the water film and on temperature. [HCO3-] is the concentration of bicarbonate, pCO2cave the partial pressure of CO2, and KH is Henry's constant. To test the theory we prepared stagnant or flowing thin films of a NaHCO3 solution and exposed them at 20 °C to an CO2 containing atmosphere of pCO2 500, 12,500, or 25,000 ppmV and defined isotope composition. The δ13C and δ18O values of the DIC in the solution were measured as a function of the exposure time. For stagnant films with depths between 0.06 and 0.2 cm the δ13C values exhibit an exponential approach towards isotope equilibrium with the atmospheric CO2 with exchange time, τex. The δ18O values first evolve towards isotopic equilibrium with atmospheric CO2, reach a minimum value and then drift away from the isotopic equilibrium with atmospheric CO2 approaching a steady state caused by isotopic exchange of oxygen with water. The experimental findings are in satisfactory agreement with the theoretical predictions. To further investigate isotope evolution in cave analogue conditions, a water film containing 5 mmol/L of NaHCO3 with a depth of 0.013 cm flowing down an inclined borosilicate glass plate was exposed to an atmosphere with pCO2 = 500 ppmV at a temperature of 20 °C. The δ13C and δ18O values were measured as a function of flow (exposure) time, t. The isotope compositions in the DIC of the water film decrease linear in time by δDIC (t) =δDIC (0) - (δDIC (0) -δDIC (∞)) · t /τex where δDIC (0) is the initial isotope composition of dissolved inorganic carbon (DIC) in the water film and δDIC (∞) its final value. From these data an exchange time τex of ca. 7000 s was obtained, in satisfactory agreement with the theoretical predictions. The exchange times can be calculated by τex = τredex · [HCO3-]/ (KH · pCO2cave), where τredex is given by the theory as function of temperature and the depth, a, of the water film. This way it is possible to obtain exchange times for various conditions of stalagmite growth as they occur in caves.

Role of (n,2n) reactions in transmutation of long-lived fission products

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

Apse, V. A.; Kulikov, G. G., E-mail: ggkulikov@mephi.ru; Kulikov, E. G.

2016-12-15

The conditions under which (n,γ) and (n,2n) reactions can help or hinder each other in neutron transmutation of long-lived fission products (LLFPs) are considered. Isotopic and elemental transmutation for the main long-lived fission products, {sup 79}Se, {sup 93}Zr, {sup 99}Tc, {sup 107}Pd, {sup 126}Sn, {sup 129}I, and {sup 135}Cs, are considered. The effect of (n,2n) reactions on the equilibrium amount of nuclei of the transmuted isotope and the neutron consumption required for the isotope processing is estimated. The aim of the study is to estimate the influence of (n,2n) reactions on efficiency of neutron LLFP transmutation. The code TIME26 andmore » the libraries of evaluated nuclear data ABBN-93, JEF-PC, and JANIS system are applied. The following results are obtained: (1) The effect of (n,2n) reactions on the minimum number of neutrons required for transmutation and the equilibrium amount of LLFP nuclei is estimated. (2) It is demonstrated that, for three LLFP isotopes ({sup 126}Sn, {sup 129}I, and {sup 135}Cs), (n,γ) and (n,2n) reactions are partners facilitating neutron transmutation. The strongest effect of (n,2n) reaction is found for {sup 126}Sn transmutation (reduction of the neutron consumption by 49% and the equilibrium amount of nuclei by 19%).« less

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

NASA Astrophysics Data System (ADS)

Sade, Ziv; Halevy, Itay

2017-10-01

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

An improved CeO2 method for high-precision measurements of 17O/16O ratios for atmospheric carbon dioxide.

PubMed

Mahata, Sasadhar; Bhattacharya, Sourandra K; Wang, Chung-Ho; Liang, Mao-Chang

2012-09-15

The oxygen isotopic composition of carbon dioxide originating at the Earth's surface is modified in the stratosphere by interaction with ozone which has anomalous oxygen isotope ratio (Δ(17)O = 1000 * ln(1 + δ(17)O/1000) - 0.522 * 1000 * ln (1 + δ(18)O/1000) >0). The inherited anomaly provides a powerful tracer for studying biogeochemical cycles involving CO(2). However, the existing methods are either too imprecise or have difficulty in determining the small Δ(17)O variations found in the tropospheric CO(2). In this study an earlier published CeO(2) and CO(2) exchange method has been modified and improved for measuring the Δ(17)O values of atmospheric carbon dioxide with high precision. The CO(2) fraction from air samples was separated by cryogenic means and purified using gas chromatography. This CO(2) was first analyzed in an isotope ratio mass spectrometer, then artificially equilibrated with hot CeO(2) to alter its oxygen isotopes mass-dependently and re-analyzed. From these data the (17)O/(16)O and (18)O/(16)O ratios were calculated and the Δ(17)O value was determined. The validity of the method was established in several tests by using artificially prepared CO(2) with zero and non-zero Δ(17)O values. The published value of the CO(2)-H(2) O equilibrium slope was also reproduced. The CO(2)-CeO(2) equilibration method has been improved to measure the oxygen isotope anomaly (Δ(17)O value) of atmospheric CO(2) with an analytical precision of ±0.12‰ (2σ). Copyright © 2012 John Wiley & Sons, Ltd.

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).

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.

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.

Clumped isotope thermometry of calcite and dolomite in a contact metamorphic environment

NASA Astrophysics Data System (ADS)

Lloyd, Max K.; Eiler, John M.; Nabelek, Peter I.

2017-01-01

Clumped isotope compositions of slowly-cooled calcite and dolomite marbles record apparent equilibrium temperatures of roughly 150-200 °C and 300-350 °C, respectively. Because clumped isotope compositions are sensitive to the details of T-t path within these intervals, measurements of the Δ47 values of coexisting calcite and dolomite can place new constraints on thermal history of low-grade metamorphic rocks over a large portion of the upper crust (from ∼5 to ∼15 km depth). We studied the clumped isotope geochemistry of coexisting calcite and dolomite in marbles from the Notch Peak contact metamorphic aureole, Utah. Here, flat-lying limestones were intruded by a pluton, producing a regular, zoned metamorphic aureole. Calcite Δ47 temperatures are uniform, 156 ± 12 °C (2σ s.e.), across rocks varying from high-grade marbles that exceeded 500 °C to nominally unmetamorphosed limestones >5 km from the intrusion. This result appears to require that the temperature far from the pluton was close to this value; an ambient temperature just 20 °C lower would not have permitted substantial re-equilibration, and should have preserved depositional or early diagenetic Δ47 values several km from the pluton. Combining this result with depth constraints from overlying strata suggests the country rock here had an average regional geotherm of 22.3-27.4 °C/km from the late Jurassic Period until at least the middle Paleogene Period. Dolomite Δ47 in all samples above the talc + tremolite-in isograd record apparent equilibrium temperatures of 328-12+13 °C (1σ s.e.), consistent with the apparent equilibrium blocking temperature we expect for cooling from peak metamorphic conditions. At greater distances, dolomite Δ47 records temperatures of peak (anchi)metamorphism or pre-metamorphic diagenetic conditions. The interface between these domains is the location of the 330 °C isotherm associated with intrusion. Multiple-phase clumped isotope measurements are complemented by bulk δ13C and δ18O dolomite-calcite thermometry. These isotopic exchange thermometers are largely consistent with peak temperatures in all samples within 4 km of the contact, indicating that metamorphic recrystallization can occur even in samples too low-grade to produce growth of conventional metamorphic index minerals (i.e., talc and tremolite). Altogether, this work demonstrates the potential of these methods to quantify the conditions of metamorphism at sub-greenschist facies.

Separation of the isotopes of boron by chemical exchange reactions

DOEpatents

McCandless, F.P.; Herbst, R.S.

1995-05-30

The isotopes of boron, {sup 10}B and {sup 11}B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF{sub 3} and a liquid BF{sub 3} donor molecular addition complex formed between BF{sub 3} gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone. 1 Fig.

Oxygen isotope fractionation in the siderite-water system between 8.5 and 62 °C

NASA Astrophysics Data System (ADS)

van Dijk, Joep; Fernandez, Alvaro; Müller, Inigo A.; Lever, Mark; Bernasconi, Stefano M.

2018-01-01

The oxygen isotope composition of siderites can be used to deduce the temperature and/or oxygen isotope composition of the fluids from which they precipitated. Previous siderite-water oxygen isotope fractionation calibrations are not well constrained at temperatures below 33 °C where most of the siderite forms at the Earth's surface. Moreover, the few experimental low temperature calibration points available are possibly inaccurate as the corresponding siderites may not have formed in equilibrium with the solution. In this study, we synthesized siderite in the laboratory from 8.5 to 62 °C, using both active-degassing experiments and microbial cultures. We used the enzyme carbonic anhydrase, which significantly reduces the equilibration time of oxygen isotopes among all dissolved inorganic carbon (DIC) species and water to minimize siderite formation out of equilibrium. Our calibration is based on many more data points than previous calibrations and significantly reduces the uncertainty in siderite-water oxygen isotope fractionation in natural siderites formed at low temperatures. The best fit equation is 1000 * ln α = 19.67 ± 0.42(103/T) -36.27 ± 1.34 where α (1000+δ18Osiderite/1000+δ18Owater) is the fractionation factor and T is the temperature in Kelvin.

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

NASA Astrophysics Data System (ADS)

Gralher, Benjamin; Stumpp, Christine

2014-05-01

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

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.

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

PubMed Central

Yang, Sha; Liu, Yun

2015-01-01

The nuclear volume effects (NVEs) of Hg, Tl and Pb isotope systems are investigated with careful evaluation on quantum relativistic effects via the Dirac’s formalism of full-electron wave function. Equilibrium 202Hg/198Hg, 205Tl/203Tl, 207Pb/206Pb and 208Pb/206Pb isotope fractionations are found can be up to 3.61‰, 2.54‰, 1.48‰ and 3.72‰ at room temperature, respectively, larger than fractionations predicted by classical mass-dependent isotope fractionations theory. Moreover, the NVE can cause mass-independent fractionations (MIF) for odd-mass isotopes and even-mass isotopes. The plot of vs. for Hg-bearing species falls into a straight line with the slope of 1.66, which is close to previous experimental results. For the first time, Pb4+-bearing species are found can enrich heavier Pb isotopes than Pb2+-bearing species to a surprising extent, e.g., the enrichment can be up to 4.34‰ in terms of 208Pb/206Pb at room temperature, due to their NVEs are in opposite directions. In contrast, fractionations among Pb2+-bearing species are trivial. Therefore, the large Pb fractionation changes provide a potential new tracer for redox conditions in young and closed geologic systems. The magnitudes of NVE-driven even-mass MIFs of Pb isotopes (i.e., ) and odd-mass MIFs (i.e., ) are almost the same but with opposite signs. PMID:26224248

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.

Gluconeogenesis from labeled carbon: estimating isotope dilution

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

Kelleher, J.K.

1986-03-01

To estimate the rate of gluconeogenesis from steady-state incorporation of labeled 3-carbon precursors into glucose, isotope dilution must be considered so that the rate of labeling of glucose can be quantitatively converted to the rate of gluconeogenesis. An expression for the value of this isotope dilution can be derived using mathematical techniques and a model of the tricarboxylic acid (TCA) cycle. The present investigation employs a more complex model than that used in previous studies. This model includes the following pathways that may affect the correction for isotope dilution: 1) flux of 3-carbon precursor to the oxaloacetate pool via acetyl-CoAmore » and the TCA cycle; 2) flux of 4- or 5-carbon compounds into the TCA cycle; 3) reversible flux between oxaloacetate (OAA) and pyruvate and between OAA and fumarate; 4) incomplete equilibrium between OAA pools; and 5) isotope dilution of 3-carbon tracers between the experimentally measured pool and the precursor for the TCA-cycle OAA pool. Experimental tests are outlined which investigators can use to determine whether these pathways are significant in a specific steady-state system. The study indicated that flux through these five pathways can significantly affect the correction for isotope dilution. To correct for the effects of these pathways an alternative method for calculating isotope dilution is proposed using citrate to relate the specific activities of acetyl-CoA and OAA.« less

Iron isotopic systematics of pyroxenite xenoliths from North China Craton: implications for Melt-rock interaction in the sub-continental lithospheric mantle beneath eastern China

NASA Astrophysics Data System (ADS)

Zhao, X.; Cao, H.; Yu, H.; Huang, F.

2016-12-01

Iron isotope systems have become widely used tools in high temperature geochemistry and provide important constraints on mantle dynamics. Here, we report Fe isotopic data on a series of pyroxenite xenoliths from Hannuoba, North China Craton to further constrain the Fe isotopic composition of the mantle and investigate the behavior of Fe isotopes during mantle processes. These xenoliths range from Cr- pyroxenites, Al-pyroxenites to garnet pyroxenites, and are taken as physical evidence for different episodes of melt injection events. Our results show that both Cr- pyroxenites and Al-pyroxenites have a narrow range of Fe isotopes (δ57Fe=-0.01 to 0.09), similar to that reported typical mantle peridotites and they show equilibrium inter-mineral Fe isotope fractionation between coexisting mantle minerals. In contract, the garnet pyroxenites, which are products of reaction between a silicate melt and peridotite, exhibit larger Fe isotopic variations, with δ57Fe ranging from 0.08 to 0.30. The δ57Fe values of minerals in these garnet pyroxenites also vary widely from -0.25 to -0.03 in olivines, from -0.04 to 0.14 in orthopyroxenes, from -0.07 to 0.31 in clinopyroxenes, from 0.07 to 0.26 in spinels and from 0.30 to 0.39 in garnets. These observed data stand in marked contrast to the calculated equilibrium Fe isotope fractionation between coexisting mantle minerals at mantle temperature from theory, indicating disequilibrium isotope fractionation. The disequilibrium isotope fractionations between coexisting mantle minerals in garnet pyroxenites most likely reflect kinetic isotope fractionation during melt-peridotite interaction. In addition, the phlogopite clinopyroxenite with an apparent metasomatic overprint has the heaviest δ57Fe (as high as 1.00) but lightest δ26Mg (as low as -1.50) values of the investigated samples. Our study shows that mantle metasomatism plays an important role in producing Fe isotopic heterogeneity of the subcontinental mantle.

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.

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

Herman, Michael F.; Currier, Robert P.; Peery, Travis B.

Intermolecular coupling of dipole moments is studied for a model system consisting of two diatomic molecules (AB monomers) arranged co-linearly and which can form non-covalently bound dimers. The dipolar coupling is a function of the bond length in each molecule as well as of the distance between the centers-of-mass of the two molecules. The calculations show that intermolecular coupling of the vibrations results in an isotope-dependent modification of the AB-AB intermolecular potential. This in turn alters the energies of the low-lying bound states of the dimers, producing isotope-dependent changes in the AB-AB dimer partition function. Explicit inclusion of intermolecular vibrationalmore » coupling then changes the predicted gas-dimer isotopic fractionation. In addition, a mass dependence in the intermolecular potential can also result in changes in the number of bound dimer states in an equilibrium mixture. This in turn leads to a significant dimer population shift in the model monomer-dimer equilibrium system considered here. Finally, the results suggest that intermolecular coupling terms should be considered when probing the origins of isotopic fractionation.« less

Iron isotope fractionation among magnetite, pyrrhotite, chalcopyrite, rhyolite melt and aqueous fluid at magmatic-hydrothermal conditions

NASA Astrophysics Data System (ADS)

Bilenker, L. D.; Simon, A.; Lundstrom, C.; Gajos, N.

2012-12-01

Fractionation of non-traditional stable isotopes (NTSI) such as Fe in magmatic systems is a relatively understudied subject. The fractionation of Fe stable isotopes has been quantified in some natural igneous samples, but there is a paucity of experimental data that could provide further insight into the causative processes of the observed fractionation. Substantial experimental work has been performed at higher temperatures pertaining to the formation of chondrites and the Earth's core, but only a handful of studies have addressed crustal rocks. To fill this knowledge gap, we performed isothermal, isobaric experiments containing mineral (e.g., magnetite, Fe-sulfides) and fluid, or mineral, rhyolite melt, and fluid assemblages to quantify equilibrium fractionation factors (α). These data, to our knowledge, are the first data that quantify the effect of a fluid phase on iron isotope fractionation at conditions appropriate for evolving magmatic systems. Charges were run inside gold capsules held in a René-41 cold seal vessel, and heated to 400, 600, or 800°C at 150 MPa for mineral-fluid, and 800°C and 100 MPa for mineral-melt-fluid runs. Use of the René vessel fixed the fO2 at the NNO buffer, an oxidation state consistent with arc magmas. The isotopic compositions of the starting and quenched phases were obtained by using a Multi-Collector Plasma Mass Spectrometer (MC-ICP-MS). Equilibrium was assessed by performing time-series runs and the three-isotope method, used only once before in a similar Fe isotope study. Correlation between Fe isotope mass and oxidation state is also being explored. Magnetite-fluid results indicate enrichment of heavy Fe isotopes in the mineral relative to the fluid, consistent with measurements of felsic igneous rocks. Magnetite-melt-fluid relationships are also consistent with measurements of natural samples. In the latter assemblage, over the course of the run, the rhyolite melt becomes heavy relative to the fluid while magnetite takes on a heavier Fe isotope signature than the starting value. These data corroborate the hypothesis that fluid exsolution caused the isotopic patterns observed in highly-differentiated igneous rocks. Further, owing to the ubiquitous importance of melt degassing as a critical process for the formation of magmatic-hydrothermal ore deposits, these data may be potentially serve as an exploration tool. This work contributes to our overall understanding of igneous processes by elucidating the Fe isotope fingerprints observed in the field as well as develop the laboratory techniques needed to study NTSI fractionation in magmatic systems and build a reliable dataset for interpretation of natural systems.

Carbon isotope exchange between CO2 and CH4 in hydrothermal fluids from the Tuscan-Roman and Campanian degassing systems (central-southern Italy)

NASA Astrophysics Data System (ADS)

Tassi, F.; Fiebig, J.; Nocentini, M.; Vaselli, O.

2010-12-01

The carbon isotope composition in CO2 and CH4 are commonly used as exploration tools and diagnostic indicators to investigate the origin of endogenous gases. At temperature <200 °C both proportions and isotope ratios of these two gases are considered to be largely controlled by processes (i.e. bacterial activity, thermal hydrolysis, and cracking of organic matter) that are mainly dictated by kinetics. Recent investigations on abiogenic generation of CH4 suggest that at temperatures as low as 100 °C, CH4 production from CO2 has halftimes in the order of 1 year. The present work is based on the d13C-CO2 and d13C-CH4 values of more than 83 gas discharges from the Tuscan-Roman and Campanian degassing systems (central-southern Italy). The main aims are to i) investigate the processes regulating the chemical and isotopic compositions of CO2 and CH4 and ii) verify the use of the CO2-CH4 carbon isotopic equilibrium for evaluating the temperature of deep hydrothermal reservoirs. Our results show that the d13C-CH4 values, with few exceptions related to local production of biogenic CH4 at shallow depth, are > -40 ‰ V-PDB. The most intriguing feature of the measured d13C-CH4 values is that they progressively decrease from the peri-Tyrrhenian area, where productive geothermal systems and active volcanoes are located, to East, i.e. approaching the CH4-rich reservoirs that mark the Adriatic side of the Italian peninsula. The d13C-CO2 values are substantially spanning from a thermometamorphic to a mantle degassing CO2 and do not show any preferential spatial distribution. Secondary carbon isotope fractionation caused by interaction with relatively shallow aquifers may contribute to the scatter of d13C-CO2 values, considering the high solubility of CO2 in liquid water. However, the CO2-CH4 isotopic compositions of fluids from the high temperature geothermal systems characterizing the Tyrrhenian coast of central-southern Italy, i.e. Larderello, Mt. Amiata, Manziana and Phlegrean Fields, provide apparent equilibrium temperatures in the range of those directly measured in production wells and/or estimated on the basis of the CH4-CO2 chemical geothermometer. These results are consistent with the fact that the carbon isotopic equilibrium in the CO2-CH4 system has to be preceded by that of the chemical exchange because the latter has a kinetic rate 400 times faster than the isotopic partitioning. The observed agreement between measured and/or inferred aquifer temperatures with apparent carbon isotopic equilibration supports recent findings that CO2 and CH4 can attain carbon isotopic equilibrium in high-enthalpy hydrothermal systems. The d13C-CH4 values of gas discharges located eastward, toward the Appennine sedimentary chain, are likely produced by mixing of high temperature fluids from the geothermal areas and a relatively cold deep aquifer characterized by biogenic CH4: The higher distance from the geothermal-volcanic systems, the higher fraction of low temperature fluids.

Equilibrium 2H/1H fractionation in organic molecules: III. Cyclic ketones and hydrocarbons

NASA Astrophysics Data System (ADS)

Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A.

2013-04-01

Quantitative interpretation of stable hydrogen isotope ratios (2H/1H) in organic compounds is greatly aided by knowledge of the relevant equilibrium fractionation factors (ɛeq). Previous efforts have combined experimental measurements and hybrid Density Functional Theory (DFT) calculations to accurately predict equilibrium fractionations in linear (acyclic) organic molecules (Wang et al., 2009a,b), but the calibration produced by that study is not applicable to cyclic compounds. Here we report experimental measurements of equilibrium 2H/1H fractionation in six cyclic ketones, and use those data to evaluate DFT calculations of fractionation in diverse monocyclic and polycyclic compounds commonly found in sedimentary organic matter and petroleum. At 25, 50, and 75 °C, the experimentally measured ɛeq values for secondary and tertiary Hα in isotopic equilibrium with water are in the ranges of -130‰ to -150‰ and +10‰ to -40‰ respectively. Measured data are similar to DFT calculations of ɛeq for axial Hα but not equatorial Hα. In tertiary Cα positions with methyl substituents, this can be understood as a result of the methyl group forcing Hα atoms into a dominantly axial position. For secondary Cα positions containing both axial and equatorial Hα atoms, we propose that axial Hα exchanges with water significantly faster than the equatorial Hα does, due to the hyperconjugation-stabilized transition state. Interconversion of axial and equatorial positions via ring flipping is much faster than isotopic exchange at either position, and as a result the steady-state isotopic composition of both H's is strongly weighted toward that of axial Hα. Based on comparison with measured ɛeq values, a total uncertainty of 10-30‰ remains for theoretical ɛeq values. Using DFT, we systematically estimated the ɛeq values for individual H positions in various cyclic structures. By summing over all individual H positions, the molecular equilibrium fractionation was estimated to be -75‰ to -95‰ for steroids, -90‰ to -105‰ for hopanoids, and -65‰ to -100‰ for typical cycloparaffins between 0 and 100 °C relative to water. These are distinct from the typical biosynthetic fractionations of -150‰ to -300‰, but are similar to equilibrium fractionations for linear hydrocarbons (Wang et al., 2009b). Thus post-burial H exchange will generally remove the ˜50-100‰ biosynthetic fractionations between cyclic isoprenoid and n-alkyl lipid molecules, which can be used to evaluate the extent of H exchange in sedimentary organic matter and oils.

Triple Oxygen Isotope Constraints on Seawater δ18O and Temperature

NASA Astrophysics Data System (ADS)

Hayles, J.; Shen, B.; Homann, M.; Yeung, L.

2017-12-01

One point of contention among geoscientists is whether the 18O/16O ratio of seawater is roughly constant, or if it varies considerably throughout geologic time. On one hand, the oxygen isotope composition of the ocean is thought to be well buffered by high- and low-temperature interactions between seawater and seafloor rocks. If these interactions do not vary on billion-year timescales, the oxygen-isotope compositions of marine sedimentary rocks mostly relate to changes in seawater temperature and global ice volume. On the other hand, long-term cooling of the planetary interior would alter these water-rock interactions leading to a secular change in the oxygen isotope composition of seawater. Models suggest that this secular change would enrich seawater with heavy oxygen isotopes over time. In this study, we present new, high precision, triple-oxygen-isotope (18O/16O, 17O/16O) analyses of marine chert samples from 3.45 Ga to 460Ma. The results of these analyses are paired with a new theoretical quartz-water equilibrium curve and a simplified seawater model to provide possible pairings of δ'18O and Δ'17O for the water which these samples could have formed in equilibrium with. Analysis of the new sample data, in addition to published chert triple oxygen isotope compositions, shows a general trend of older chert samples being progressively incompatible with waters possessing a modern-like seawater triple oxygen isotope composition. Implications on constraining the secular evolution of seawater δ18O and temperature will be discussed.

Recent terebratulide brachiopods: Do they faithfully record oceanographic conditions throughout ontogeny?

NASA Astrophysics Data System (ADS)

Kercher, P.; Carlson, S. J.

2012-12-01

Brachiopods have commonly been used to infer secular changes in ocean chemistry over the Phanerozoic Eon since Lowenstam (1961) concluded that Recent brachiopod calcite was precipitated in equilibrium with seawater. In order to infer paleoenvironmental conditions with confidence, however, the impact of potential kinetic and metabolic fractionation effects on the final isotopic signature, as it varies among individuals, must be determined. In this study, we analyzed the oxygen and carbon isotopic composition of closely spaced (~2/mm) samples of calcite along growth transects from individuals of the rhynchonelliform brachiopod, Laqueus californianus. By combining local oceanographic information with knowledge of brachiopod shell structure and growth patterns through ontogeny, in individuals of different ages from the same locality that died simultaneously, we can address the fidelity of brachiopod shell calcite as both an environmental proxy and a recorder of biological activity among conspecific individuals, in real time. This is an essential, but largely ignored, component in the paleoenvironmental interpretation of brachiopod shell calcite. In May 2011, more than 75 live L. californianus specimens were collected by Dr. J. Barry at Monterey Bay Aquarium Research Institute (MBARI) from Monterey Bay at 160 m water depth (36.7322N, 121.9739W) and generously given to us for use in this study. The specimens range in length from 5.75 to 46.16 mm, representing a range of ontogenetic ages. Water temperatures at 160 m range annually from 8C in the spring/summer upwelling season to 10C during the winter, while salinity fluctuates from 33.76 ppt in the winter to 34.11 ppt in the summer. Daily temperature and salinity data collected by MBARI over three decades allow us to calculate approximate equilibrium calcite values. We use these values to evaluate the claim that brachiopods mineralize in isotopic equilibrium with seawater throughout their lifespan with minimal intraspecific variation. We also use the MBARI data to correlate annual temperature fluctuations with δ18O trends within the calcite to estimate ontogenetic ages and growth rates. Full-grown adults were 10-11 years old when collected live, and grow an average of about 4 mm/year over their lifespan, growing faster before sexual maturity and slowing down after. The early results of the ontogenetic sampling tracts indicate calcite δ18O and δ13C values are strongly positively correlated. This relationship suggests kinetic fractionation effects are likely influencing the isotopic composition of the shells. Cyclic isotopic fluctuations are also recorded, in accordance with seasonal temperature oscillations in Monterey Bay, apparent even at 160 m depth. In most of the specimens, the amplitudes of the isotopic fluctuations exceed those of the predicted equilibrium values. Furthermore, our data support the claim made by other researchers that the outer primary layer of the shell is significantly depleted in both oxygen and carbon isotopes, below the range of equilibrium calcite. Isotopic oscillations across individuals align reasonably well both with each other and with ambient water temperature patterns. These results suggest that intraspecific variability is low in L. californianus and that these organisms are recording their environment similarly.

Study of the isotopic features of Swan bands in comets

NASA Technical Reports Server (NTRS)

Krishna Swamy, K. S.

1987-01-01

It is shown from a detailed statistical equilibrium calculation of the (C-12)(C-13) molecule that the interpretation of the observed intensities of Swan bands of the normal and the isotopic molecule of C2 in terms of the abundance ratio of C-12 and C-13 is a reasonable one. The synthetic profile of some isotopic features in the (0.0) Swan band is compared with the observed profiles for comet West.

Characterization of calcium isotopes in natural and synthetic barite

USGS Publications Warehouse

Griffith, E.M.; Schauble, E.A.; Bullen, T.D.; Paytan, A.

2008-01-01

The mineral barite (BaSO4) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (??44/40Ca = -2.01 ?? 0.15???) but are different from hydrothermal and cold seep barite samples (??44/40Ca = -4.13 to -2.72???). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, ??44/40Ca = -3.42 to -2.40???. Temperature, saturation state, a Ba2 + / a SO42 -, and aCa2+/aBa2+ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower 44Ca/40Ca than calcite, by -9??? at 0 ??C and -8??? at 25 ??C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower ??44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca2+ substitution for Ba2+ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca2+ and other elements in inorganic and biogenic minerals. ?? 2008 Elsevier Ltd.

Trapped ion system for sympathetic cooling and non-equilibrium dynamics

NASA Astrophysics Data System (ADS)

Doret, Charlie; Jubin, Sierra; Stevenson, Sarah

2017-04-01

Atomic systems are superbly suited to the study of non-equilibrium dynamics. These systems' exquisite isolation from environmental perturbations leads to long relaxation times that enable exploration of far-from-equilibrium phenomena. We present progress towards trapping chains of multiple co-trapped calcium isotopes geared towards measuring thermal equilibration and sympathetic cooling rates. We also discuss plans for future experiments in non-equilibrium statistical mechanics, including exploration of the quantum-to-classical crossover between ballistic transport and diffusive, Fourier's Law conduction. This work is supported by Cottrell College Science Award from the Research Corporation for Science Advancement and by Williams College.

Integrating Stable Isotope - Reactive Transport Model Approach for Assessment of Chlorinated Solvent Degradation

DTIC Science & Technology

2016-06-01

Dehalococcoides species require molecular hydrogen as the immediate electron donor. In the microcosm, H2 was produced by fermentation of lactate. It was...superimposed depletion upon H2/H2O equilibrium rather than being tied to the H isotope composition of the fermentation substrate (see Kuder et al., 2013 for more

Hydrogen and Oxygen Stable Isotope Fractionation in Body Fluid Compartments of Dairy Cattle According to Season, Farm, Breed, and Reproductive Stage

PubMed Central

Abeni, Fabio; Petrera, Francesca; Capelletti, Maurizio; Dal Prà, Aldo; Bontempo, Luana; Tonon, Agostino; Camin, Federica

2015-01-01

Environmental temperature affects water turnover and isotope fractionation by causing water evaporation from the body in mammals. This may lead to rearrangement of the water stable isotope equilibrium in body fluids. We propose an approach to detect possible variations in the isotope ratio in different body fluids on the basis of different homoeothermic adaptations in varying reproductive stages. Three different reproductive stages (pregnant heifer, primiparous lactating cow, and pluriparous lactating cow) of two dairy cattle breeds (Italian Friesian and Modenese) were studied in winter and summer. Blood plasma, urine, faecal water, and milk were sampled and the isotope ratios of H (2H/1H) and O (18O/16O) were determined. Deuterium excess and isotope-fractionation factors were calculated for each passage from plasma to faeces, urine and milk. The effects of the season, reproductive stages and breed on δ 2H and δ 18O were significant in all the fluids, with few exceptions. Deuterium excess was affected by season in all the analysed fluids. The correlations between water isotope measurements in bovine body fluids ranged between 0.6936 (urine-milk) and 0.7848 (urine-plasma) for δ 2H, and between 0.8705 (urine-milk) and 0.9602 (plasma-milk) for δ 18O. The increase in both isotopic δ values in all body fluids during summer is representative of a condition in which fractionation took place as a consequence of a different ratio between ingested and excreted water, which leads to an increased presence of the heavy isotopes. The different body water turnover between adult lactating cattle and non-lactating heifers was confirmed by the higher isotopic δ for the latter, with a shift in the isotopic equilibrium towards values more distant from those of drinking water. PMID:25996911

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

NASA Astrophysics Data System (ADS)

Deng, Yuying; Li, Yingzhou; Li, Long

2018-04-01

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

Geochemistry of reduced gas related to serpentinization of the Zambales ophiolite, Philippines

USGS Publications Warehouse

Abrajano, T.A.; Sturchio, N.C.; Kennedy, B.M.; Lyon, G.L.; Muehlenbachs, K.; Böhlke, J.K.

1990-01-01

Methane-hydrogen gas seeps with mantle-like C and noble gas isotopic characteristics issue from partially serpentinized ultramafic rocks in the Zambales ophiolite, Philippines. New measurements of noble gas and 14C isotope abundances, rock/mixed-volatile equilibrium calculations, and previous chemical and isotopic data suggest that these reduced gases are products of periodotite hydration. The gas seeps are produced in rock-dominated zones of serpentinization, and similar gases may be ubiquitous in ultramafic terranes undergoing serpentinization.

Experimental determination of the Mo isotope fractionation factor between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, R. C.; Burkhardt, C.; Schmidt, M. W.; Bourdon, B.

2011-12-01

The conditions and chemical consequences of core formation have mainly been reconstructed from experimentally determined element partition coefficients between metal and silicate liquids. However, first order questions such as the mode of core formation or the nature of the light element(s) in the Earth's core are still debated [1]. In addition, the geocentric design of most experimental studies leaves the conditions of core formation on other terrestrial planets and asteroids even more uncertain than for Earth. Through mass spectrometry, records of mass-dependent stable isotope fractionation during high-temperature processes such as metal-silicate segregation are detectable. Stable isotope fractionation may thus yield additional constrains on core formation conditions and its consequences for the chemical evolution of planetary objects. Experimental investigations of equilibrium mass-dependent stable isotope fractionation have shown that Si isotopes fractionate between metal and silicate liquids at temperatures of 1800°C and pressures of 1 GPa, while Fe isotopes leave no resolvable traces of core formation processes [2,3]. Molybdenum is a refractory and siderophile trace element in the Earth, and thus much less prone to complications arising from mass balancing core and mantle and from potential volatile behaviour than other elements. To determine equilibrium mass-dependent Mo isotope fractionation during metal-silicate segregation, we have designed piston cylinder experiments with a basaltic silicate composition and an iron based metal with ~8 wt% Mo, using both graphite and MgO capsules. Metal and silicate phases are completely segregated by the use of a centrifuging piston cylinder at ETH Zurich, thus preventing analysis of mixed metal and silicate signatures. Molybdenum isotope compositions were measured using a Nu Instruments 1700 MC-ICP-MS at ETH Zurich. To ensure an accurate correction of analytical mass fractionation a 100Mo-97Mo double spike was admixed before chemical purification. Initial results provide an equilibrium 98Mo/95Mo isotope fractionation factor between metal and silicate liquids of -0.18±0.10% (2σ) at 1400°C and 1 GPa. Although the relative mass difference of these Mo isotopes is smaller than for Fe isotopes, this result implies that metal-silicate segregation may have led to mass-dependent stable Mo isotope fractionation, as opposed to Fe isotopes. A possible explanation is that the bonding environment of Mo may counterbalance its relatively small mass separation. At reducing conditions, Mo occurs in 4+ valence state in silicates [4] and thus its bond strength difference between metal and silicate may be more similar to that of Si than Fe. Stable Mo isotopes may thus become an important tool for constraining the conditions of core formation in asteroids and terrestrial planets. [1] Rubie et al. (2011) EPSL 301, 31-42. [2] Shahar et al. (2009) EPSL 288, 228-234. [3] Poitrasson et al. (2009) EPSL 278, 376-385. [4] Farges et al. (2006) Can. Min. 44, 731-753.

Application and validation of isotope dilution method (IDM) for predicting bioavailability of hydrophobic organic contaminants in soil.

PubMed

Wang, Jie; Taylor, Allison; Schlenk, Daniel; Gan, Jay

2018-05-01

Risk assessment of hydrophobic organic contaminants (HOCs) using the total chemical concentration following exhaustive extraction may overestimate the actual availability of HOCs to non-target organisms. Existing methods for estimating HOC bioavailability in soil have various operational limitations. In this study, we explored the application of isotope dilution method (IDM) to quantify the accessible fraction (E) of DDTs and PCBs in both historically-contaminated and freshly-spiked soils. After addition of 13 C or deuterated analogues to a soil sample, the phase distribution of isotope-labeled and native chemicals reached an apparent equilibrium within 48 h of mixing. The derived E values in the three soils ranged from 0.19 to 0.82, depending on the soil properties and also the contact time of HOCs (i.e., aging). The isotope dilution method consistently predicted greater accumulation into earthworm (Eisenia fetida) than that by polyethylene (PE) or solid phase microextraction (SPME) sampler, likely because desorption in the gut enhanced bioavailability of soil-borne HOCs. A highly significant linear regression (R 2  = 0.91) was found between IDM and 24-h Tenax desorption, with a slope statistically identical to 1. The IDM-derived accessible concentration (C e ) was further shown to accurately predict tissue residues in earthworm exposed in the same soils. Given the relatively short duration and simple steps, IDM has the potential to be readily adopted for measuring HOC bioaccessibility in soil and for improving risk assessment and evaluation of remediation efficiency. Copyright © 2018 Elsevier Ltd. All rights reserved.

How to explain Si isotopes of chert?

NASA Astrophysics Data System (ADS)

Liu, Y.

2016-12-01

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

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

Aggarwal, J.K.; Palmer, M.R.

Boron isotope ratios have been determined in a variety of different geothermal waters from hydrothermal systems across Iceland. Isotope ratios from the high temperature meteoric water recharged systems reflect the isotope ratio of the host rocks without any apparent fractionation. Seawater recharged geothermal systems exhibit more positive {delta}{sup 11}B values than the meteoric water recharged geothermal systems. Water/rock ratios can be assessed from boron isotope ratios in the saline hydrothermal systems. Low temperature hydrothermal systems also exhibit more positive {delta}{sup 11}B than the high temperature systems, indicating fractionation of boron due to adsorption of the lighter isotope onto secondary minerals.more » Fractionation of boron in carbonate deposits may indicate the level of equilibrium attained within the systems.« less

Biological forcing controls the chemistry of the coral exoskeleton

NASA Astrophysics Data System (ADS)

Meibom, A.; Mostefaoui, S.; Cuif, J.; Yurimoto, H.; Dauphin, Y.; Houlbreque, F.; Dunbar, R.; Constantz, B.

2006-12-01

A multitude of marine organisms produce calcium carbonate skeletons that are used extensively to reconstruct water temperature variability of the tropical and subtropical oceans - a key parameter in global climate-change models. Such paleo-climate reconstructions are based on the notion that skeletal oxygen isotopic composition and certain trace-element abundances (e.g., Sr/Ca and Mg/Ca ratios) vary in response to changes in the water temperature. However, it is a fundamental problem that poorly understood biological processes introduce large compositional deviations from thermodynamic equilibrium and hinder precise calibrations of many paleo-climate proxies. Indeed, the role of water temperature in controlling the composition of the skeleton is far from understood. We have studied trace-element abundances as well as oxygen and carbon isotopic compositions of individual skeletal components in the zooxanthellate and non-zooxanthellate corals at ultra-structural, i.e. micrometer to sub-micrometer length scales. From this body of work we draw the following, generalized conclusions: 1) Centers of calcification (COC) are not in equilibrium with seawater. Notably, the Sr/Ca ratio is higher than expected for aragonite equilibrium with seawater at the temperature at which the skeleton was formed. Furthermore, the COC are further away from equilibrium with seawater than fibrous skeleton in terms of stable isotope composition. 2) COC are dramatically different from the fibrous aragonite skeleton in terms of trace element composition. 3) Neither trace element nor stable isotope variations in the fibrous (bulk) part of the skeleton are directly related to changes in SST. In fact, changes in SST can have very little to do with the observed compositional variations. 4) Trace element variations in the fibrous (bulk) part of the skeleton are not related to the activity of zooxanthellae. These observations are directly relevant to the issue of biological versus non-biological control over skeleton composition and will be discussed.

Tracing the sources and cycling of phosphorus in river sediments using oxygen isotopes: Methodological adaptations and first results from a case study in France.

PubMed

Pistocchi, Chiara; Tamburini, Federica; Gruau, Gerard; Ferhi, André; Trevisan, Dominique; Dorioz, Jean-Marcel

2017-03-15

An essential aspect of eutrophication studies is to trace the ultimate origin of phosphate ions (P-PO 4 ) associated with the solid phase of river sediments, as certain processes can make these ions available for algae. However, this is not a straightforward task because of the diversity of allochthonous and autochthonous sources that can supply P-PO 4 to river sediments as well as the existence of in-stream processes that can change the speciation of these inputs and obscure the original sources. Here, we present the results of a study designed to explore the potentials, limitations and conditions for the use of the oxygen isotope composition of phosphate (δ 18 Op) extracted from river sediments for this type of tracing. We first tested if the method commonly applied to soils to purify P-PO 4 and to measure their δ 18 Op concentrations could be adapted to sediments. We then applied this method to a set of sediments collected in a river along a gradient of anthropogenic pressure and compared their isotopic signatures with those from samples that are representative of the potential P-PO 4 inputs to the river system (soils and riverbank material). The results showed that following some adaptations, the purification method could be successfully transposed to river sediments with a high level of P-PO 4 purification (>97%) and high δ 18 Op measurement repeatability and accuracy (<0.4‰). The values for the potential allochthonous sources varied from 11.8 to 18.3‰, while the δ 18 Op value for the river sediments ranged from 12.2 to 15.8‰. Moreover, a sharp increase (>3‰) in the sediment δ 18 Op value immediately downstream from the discharge point revealed the strong impact of municipal wastewater. The calculation of the theoretical equilibrium δ 18 O p values using the river water temperature and δ 18 O w showed that the downstream sediments were in equilibrium, which was not the case for the upstream sediments. This difference could be related to the contrast between the short residence time of the transfer system in the catchment head, which can preserve the isotopic variability of the source materials, and the longer residence times and higher P bioavailability in the lower catchment, possibly fostering the recycling of P-PO 4 by the biota and the equilibration of the oxygen isotope signature in P-PO 4 . These results demonstrate the potential of the isotopic approach to assess the sources and in-stream turnover of sedimentary P in river systems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Light charged clusters emitted in 32 MeV/nucleon Xe,124136+Sn,112124 reactions: Chemical equilibrium and production of 3He and 6He

NASA Astrophysics Data System (ADS)

Bougault, R.; Bonnet, E.; Borderie, B.; Chbihi, A.; Dell'Aquila, D.; Fable, Q.; Francalanza, L.; Frankland, J. D.; Galichet, E.; Gruyer, D.; Guinet, D.; Henri, M.; La Commara, M.; Le Neindre, N.; Lombardo, I.; Lopez, O.; Manduci, L.; Marini, P.; Pârlog, M.; Roy, R.; Saint-Onge, P.; Verde, G.; Vient, E.; Vigilante, M.; Indra Collaboration

2018-02-01

Background: The isovector part of the nuclear equation of state remains partly unknown and is the subject of many studies. The degree of equilibration between the two main collision partners in heavy ion reactions may be used to study the equation of state since it is connected to isospin (N /Z ) transport properties of nuclear matter. Purpose: We aim to test chemical equilibrium attainment by measuring isotopic characteristics of emitted elements as a function of impact parameter. Method: We study four Xe,124136+Sn,112124 reactions at 32 MeV/nucleon. The data were acquired with the INDRA detector at the GANIL (Caen, France) facility. Combined (projectile+target) systems are identical for two studied reactions, therefore it is possible to study the path towards chemical equilibrium from different neutron to proton ratio (N /Z ) entrance channels. The study is limited to identified isotopes detected in the forward part of the center of mass in order to focus on the evolution of projectile-like fragment isotopic content and the benefit of excellent detection performances of the forward part of the apparatus. Results: Light charged particle productions, multiplicities, and abundance ratios dependence against impact parameter are studied. It is measured to almost identical mean characteristics for the two 124Xe+124Sn and 136Xe+112Sn systems for central collisions. Comparing all four studied systems it is shown that mean values evolve from projectile N /Z to projectile+target N /Z dependence. Those identical mean characteristics concern all light charged particles except 3He whose mean behavior is strongly different. Conclusions: Our inclusive analysis (no event selection) shows that N /Z equilibration between the projectile-like and the target-like is realized to a high degree for central collisions. The light charged particle production mean value difference between 124Xe+124Sn and 136Xe+112Sn systems for central collisions is of the order of a few %. This slight difference could be explained by pre-equilibrium particle emission whose intensity may differ for the two reactions. This point is demonstrated using 3He mean characteristics whose production takes place before chemical equilibrium attainment. The realized N /Z balance between projectile-like and target-like does not imply a pure two-body mechanism. Indeed a midrapidity production of light charged particle does exist and its N /Z is different as compared to the projectile-like one: it is n enriched. This point is touched using 6He midrapidity production which is favored by the drift phenomenon.

Detection of phosphohydrolytic enzyme activity through the oxygen isotope composition of dissolved phosphate

NASA Astrophysics Data System (ADS)

Colman, A. S.

2016-02-01

Phosphohydrolytic enzymes play an important role in phosphorus remineralization. As they release phosphate (Pi) from various organophosphorus compounds, these enzymes facilitate the transfer of oxygen atoms from water to the phosphoryl moieties. Most such enzymatic reactions impart a significant isotopic fractionation to the oxygen transferred. If this reaction occurs within a cell, then the resultant oxygen isotope signal is overprinted by continued recycling of the Pi. However, if this reaction occurs extracellularly, then the isotopic signal will be preserved until the Pi is transported back into a cell. Thus, the oxygen isotope composition of Pi (δ18Op) in an aquatic ecosystem can serve as a useful indicator of the mechanisms by which P is remineralized. We develop a time-dependent model illustrating the sensitivity of the δ18O of dissolved phosphate to various modes of P remineralization. The model is informed by cell lysis experiments that reveal the relative proportions of P­i that are directly liberated from cytosol vs. regenerated from co-liberated dissolved organic phosphorus compounds via extracellular hydrolysis. By incorporating both cellular uptake and release fluxes of P, we show that the degree of isotopic disequilibrium in an aquatic ecosystem can be a strong indicator of P remineralization mode. Apparent oxygen isotope equilibrium between Pi and water arises in this model as a steady-state scenario in which fractionation upon cellular uptake of Pi counterbalances the hydrolytic source flux of disequilibrated Pi. Low and high rates of extracellular phosphohydrolase activity are shown to produce steady-state δ18Op values that are respectively above or below thermodynamic equilibrium compositions.

Carbon isotope constraints on degassing of carbon dioxide from Kilauea Volcano

USGS Publications Warehouse

Gerlach, T.M.; Taylor, B.E.

1990-01-01

We examine models for batch-equilibrium and fractional-equilibrium degassing of CO2 from magma at Kilauea Volcano. The models are based on 1. (1) the concept of two-stage degassing of CO2 from magma supplied to the summit chamber, 2. (2) C isotope data for CO2 in eruptive and noneruptive (quiescent) gases from Kilauea and 3. (3) data for the isotopic fractionation of C between CO2 and C dissolved in tholeiitic basalt melt. The results of our study indicate that 1. (1) both eruptive and noneruptive degassing of CO2 most closely approach a batch equilibrium process, 2. (2) the ??13C of parental magma supplied to the summit chamber is in the range -4.1 to-3.4??? and 3. (3) the ??13C of melt after summit chamber degassing is in the range -7 to -8???, depending upon the depth of equilibration. We also present ??13C data for CO2 in eruptive gases from the current East Rift Zone eruption. These are the first C isotope data for CO2 in high-temperature (>900??C) eruptive gases from Kilauea; they have a mean ??13C value of -7.82 ?? 0.24??? and are similar to those predicted for the melt after summit chamber degassing. The minor role played by fractional degassing of ascending magma at Kilauea means that exsolved CO2 tends to remain entrained in and coherent with its host melt during ascent from both mantle source regions and crustal magma reservoirs. This has important implications for magma dynamics at Kilauea. ?? 1990.

13C-18O isotope signatures and ‘clumped isotope’ thermometry in foraminifera and coccoliths

NASA Astrophysics Data System (ADS)

Tripati, Aradhna K.; Eagle, Robert A.; Thiagarajan, Nivedita; Gagnon, Alexander C.; Bauch, Henning; Halloran, Paul R.; Eiler, John M.

2010-10-01

Accurate constraints on past ocean temperatures and compositions are critical for documenting climate change and resolving its causes. Most proxies for temperature are not thermodynamically based, appear to be subject to biological processes, require regional calibrations, and/or are influenced by fluid composition. As a result, their interpretation becomes uncertain when they are applied in settings not necessarily resembling those in which they were empirically calibrated. Independent proxies for past temperature could provide an important means of testing and/or expanding on existing reconstructions. Here we report measurements of abundances of stable isotopologues of calcitic and aragonitic benthic and planktic foraminifera and coccoliths, relate those abundances to independently estimated growth temperatures, and discuss the possible scope of equilibrium and kinetic isotope effects. The proportions of 13C- 18O bonds in these samples exhibits a temperature dependence that is generally similar to that previously been reported for inorganic calcite and other biologically precipitated carbonate-containing minerals (apatite from fish, reptile, and mammal teeth; calcitic brachiopods and molluscs; aragonitic coral and mollusks). Most species that exhibit non-equilibrium 18O/ 16O (δ 18O) and 13C/ 12C (δ 13C) ratios are characterized by 13C- 18O bond abundances that are similar to inorganic calcite and are generally indistinguishable from apparent equilibrium, with possible exceptions among benthic foraminiferal samples from the Arctic Ocean where temperatures are near-freezing. Observed isotope ratios in biogenic carbonates can be explained if carbonate minerals generally preserve a state of ordering that reflects the extent of isotopic equilibration of the dissolved inorganic carbon species.

Oxygen isotope heterogeneity and disequilibria of olivine crystals in large volume Holocene basalts from Iceland: Evidence for magmatic digestion and erosion of Pleistocene hyaloclastites

NASA Astrophysics Data System (ADS)

Bindeman, Ilya; Gurenko, Andrey; Sigmarsson, Olgeir; Chaussidon, Marc

2008-09-01

This work considers petrogenesis of the largest Holocene basaltic fissure eruptions of Iceland, which are also the largest in the world: Laki (1783-84 AD, 15 km 3), Eldgjá (934 AD, 18 km 3), Veidivötn (900, 1480 AD, multiple eruptions, >2 km 3), Núpahraun (ca. 4000 BP, >1 km 3) and Thjórsárhraun (ca 8000 BP, >20 km 3). We present oxygen isotope laser fluorination analyses of 55 individual and bulk olivine crystals, coexisting individual and bulk plagioclase phenocrysts, and their host basaltic glasses with average precision of better than 0.1‰ (1SD). We also report O isotope analyses of cores and rims of 61 olivine crystals by SIMS with average precision on single spots of 0.24‰ (1SD) in 13 samples coupled with electron microprobe data for major and trace elements in these olivines. Within each individual sample, we have found that basaltic glass is relatively homogeneous with respect to oxygen isotopes, plagioclase phenocrysts exhibit crystal to crystal variability, while individual olivines span from the values in equilibrium with the low-δ 18O matrix glass to those being three permil higher in δ 18O than the equilibrium. Olivine cores with maximum value of 5.2‰ are found in many of these basalts and suggest that the initial magma was equilibrated with normal-δ 18O mantle. No olivines or their intracrystalline domains are found with bulk or spot value higher than those found in MORB olivines. The δ 18O variability of 0.3-3‰ exists for olivine grains from different lavas, and variable core-to-rim oxygen isotopic zoning is present in selected olivine grains. Many olivines in the same sample are not zoned, while a few grains are zoned with respect to oxygen isotopes and exhibit small core-to-core variations in Fe-Mg, Ni, Mn, Ca. Grains that are zoned in both Mg# and δ 18O exhibit positive correlation of these two parameters. Electron microprobe analysis shows that most olivines equilibrated with the transporting melt, and thin Fe-richer rim is present around many grains, regardless of the degree of olivine-melt oxygen isotope disequilibrium. The preservation of isotopic and compositional zoning in selected grains, and subtle to severe Δ 18O (melt-olivine) and Δ 18O (plagioclase-olivine) disequilibria suggests rather short crystal residence times of years to centuries. Synglacially-altered upper crustal, tufaceous hyaloclastites of Pleistocene age serve as a viable source for low-δ 18O values in Holocene basalts through assimilation, mechanical and thermal erosion, and devolatilization of stoped blocks. Cumulates formed in response to cooling during assimilation, and xenocrysts derived from hyaloclastites, contribute to the diverse δ 18O crystalline cargo. The magma plumbing systems under each fissure are likely to include a network of interconnected dikes and sills with high magma flow rates that contribute to the efficacy of magmatic erosion of large quantities (10-60% mass) of hyaloclastites required by isotopic mass balance. Olivine diversity and the pervasive lack of phenocryst-melt oxygen isotopic equilibrium suggest that a common approach of analyzing bulk olivine for oxygen isotopes, as a proxy for the basaltic melt or to infer mantle δ 18O value, needs to proceed with caution. The best approach is to analyze olivine crystals individually and demonstrate their equilibrium with matrix.

Nuclear Reaction Rates and the Production of Light P-Process Isotopes in Fast Expansions of Proton-Rich Matter

NASA Astrophysics Data System (ADS)

Jordan, G. C., IV; Meyer, B. S.

2004-09-01

We study nucleosynthesis in rapid expansions of proton-rich matter such as might occur in winds from newly-born neutron stars. For rapid enough expansion, the system fails to maintain an equilibrium between neutrons and protons and the abundant 4He nuclei. This leads to production of quite heavy nuclei early in the expansion. As the temperature falls, the system attempts to re-establish the equilibrium between free nucleons and 4He. This causes the abundance of free neutrons to drop and the heavy nuclei to disintegrate. If the disintegration flows quench before the nuclei reach the iron group, a distribution of p-process nuclei remains. We briefly discuss the possibility of this process as the mechanism of production of light p-process isotopes (specifically 92Mo, 94Mo, 96Ru, and 98Ru), and we provide a qualitative assessment of the impact of nuclear reaction rates of heavy, proton rich isotopes on the production of these astrophysically important nuclides.

The new high-resolution IRMS MAT253 ULTRA at Utrecht University

NASA Astrophysics Data System (ADS)

Röckmann, Thomas; Hofmann, Magdalena; Paul, Dipayan; Popa, Elena; Adnew, Getachew

2017-04-01

In 2016, the new high-resolution, multi-collector isotope ratio mass spectrometer MAT253 ULTRA [1] was installed at Utrecht University. This instrument is designed to reach a mass resolving power of 20,000 to 40,000 (M/ΔM). The ion currents are detected with a variable multi-collector unit that allows to register up to 9 ion currents simultaneously with Faraday cups and ion counters. The width of the entrance slit can be varied between 5 and 250μm so that the instrument can be operated under low, medium and high mass resolution, and an optimum balance between resolution and sensitivity can be selected for the respective applications. The central field of application of the new IRMS at Utrecht University is the measurement of multiply substituted isotopologues (clumped isotopes) in atmospheric trace compounds (e.g. 13CDH3, 13C18O16O, 18O18O, 15N14N18O) [1-7]. It is known from thermodynamics that the zero point energy of a chemical bond usually decreases when multiple heavy isotopes clump together in a molecule, and this effect depends on temperature [7]. Therefore, the abundance of clumped isotopes can be used as temperature indicator under thermodynamical equilibrium conditions. However, in the atmosphere, many reactions are controlled kinetically. It has been shown recently for a few examples that negative clumping signatures (anti-clumping) can be produced under non-equilibrium conditions [3,4]. In addition, based on purely statistical reasons, anti-clumping signatures will be produced in any molecule that contains indistinguishable atoms, which originate from isotopically distinct reservoir [5,6]. Thus, the investigation of multiply substituted isotopologues is expected to generate novel isotope signatures that can complement conventional stable isotope analysis in atmospheric science. We will present data on the performance of the MAT 253 ULTRA instrument and first scientific applications to atmospheric research. 1. Eiler, J.M., et al., A high-resolution gas-source isotope ratio mass spectrometer, Int. J. Mass Spect., 2013. 335: 45- 56. 2. Young, E.D., et al., A large-radius high-mass-resolution multiple-collector isotope ratio mass spectrometer for analysis of rare isotopologues of O2, N2, CH4 and other gases, Int. J. Mass Spect., 2016. 401: 1-10. 3. Wang, D.T., et al., Nonequilibrium clumped isotope signals in microbial methane, Science, 2015. 348: 428-431. 4. Yeung, L.Y., et al., Biological signatures in clumped isotopes of O2, Science, 2015. 348: 431-434. 5. Yeung, L.Y., Combinatorial effects on clumped isotopes and their significance in biogeochemistry, Geochim. Cosmochim. Act., 2016: doi:10.1016/j.gca.2015.09.020. 6. Röckmann, T., et al., Statistical clumped isotope signatures Scientific reports, 2016. 6: 31947; doi: 10.1038/srep31947. 7. Wang, Z.G., et al., Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases, Geochim. Cosmochim. Act., 2004. 68: 4779-4797.

Calculation of boron-isotope fractionation between B(OH) 3(aq) and B(OH)4-(aq)

NASA Astrophysics Data System (ADS)

Rustad, James R.; Bylaska, Eric J.; Jackson, Virgil E.; Dixon, David A.

2010-05-01

Density functional and correlated molecular orbital calculations (MP2) are carried out on B(OH) 3· nH 2O clusters ( n = 0, 6, 32), and B(OH)4-· nH 2O ( n = 0, 8, 11, 32) to estimate the equilibrium distribution of 10B and 11B isotopes between boric acid and borate in aqueous solution. For the large 32-water clusters, multiple conformations are generated from ab initio molecular dynamics simulations to account for the effect of solvent fluctuations on the isotopic fractionation. We provide an extrapolated value of the equilibrium constant α34 for the isotope exchange reaction 10B(OH) 3(aq) + 11B(OH)4- (aq) = 11B(OH) 3(aq) + 11B(OH)4- (aq) of 1.026-1.028 near the MP2 complete basis set limit with 32 explicit waters of solvation. With some exchange-correlation functionals we find potentially important contributions from a tetrahedral neutral B(OH) 3·H 2O Lewis acid-base complex. The extrapolations presented here suggest that DFT calculations give a value for 10 3ln α34 about 15% higher than the MP2 calculations.

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.

99 Tc NMR determination of the oxygen isotope content in 18 O-enriched water.

PubMed

Tarasov, Valerii P; Kirakosyan, Gayana А; German, Konstantin E

2018-03-01

99 Tc NMR has been suggested as an original method of evaluating the content of oxygen isotopes in oxygen-18-enriched water, a precursor for the production of radioisotope fluorine-18 used in positron emission tomography. To this end, solutions of NH 4 TcO 4 or NaTcO 4 (up to 0.28 mol/L) with natural abundance of oxygen isotopes in virgin or recycled 18 O-enriched water have been studied by 99 Tc NMR. The method is based on 16 O/ 17 O/ 18 O intrinsic isotope effects in the 99 Tc NMR chemical shifts, and the statistical distribution of oxygen isotopes in the coordination sphere of TcO 4 - and makes it possible to quantify the composition of enriched water by measuring the relative intensities of the 99 Tc NMR signals of the Tc 16 O 4-n 18 O n - isotopologues. Because the oxygen exchange between TcO 4 - and enriched water in neutral and alkaline solutions is characterized by slow kinetics, gaseous HCl was bubbled through a solution for a few seconds to achieve the equilibrium distribution of oxygen isotopes in the Tc coordination sphere without distortion of the oxygen composition of the water. Pertechnetate ion was selected as a probe due to its high stability in solutions and the significant 99 Tc NMR shift induced by a single 16 O→ 18 O substitution (-0.43 ± 0.01 ppm) in TcO 4 - and spin coupling constant 1 J( 99 Tc- 17 O) (131.46 Hz) favourable for the observation of individual signals of Tc 16 O 4-n 18 O n - isotopologues. Copyright © 2017 John Wiley & Sons, Ltd.

Pseudo-equilibrium geometry of HNO determined by an E-Band CP-FTmmW spectrometer

DOE PAGES

Zaleski, Daniel P.; Prozument, Kirill

2017-05-16

An E-Band (60–90 GHz) chirped-pulse Fourier transform millimeter-wave spectrometer has been constructed for eventual kinetics and dynamics studies. The performance of the spectrometer is demonstrated with the molecule nitroxyl (HNO). Using the new spectrometer and by passing isotopically labelled methyl nitrite (CH 3ONO) through a pyrolysis nozzle, the spectra of minor isotopologues of HNO have been obtained. The observations on the isotopologues identified here, H 15NO, HN 18O, and D 15NO, have been combined with the earlier isotopic observations, HNO and DNO, to create a global r m (1) HNO geometry that approximates an equilibrium structure. Furthermore, the results aremore » compared to high-level ab initio calculations.« less

Pseudo-equilibrium geometry of HNO determined by an E-Band CP-FTmmW spectrometer

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

Zaleski, Daniel P.; Prozument, Kirill

An E-Band (60–90 GHz) chirped-pulse Fourier transform millimeter-wave spectrometer has been constructed for eventual kinetics and dynamics studies. The performance of the spectrometer is demonstrated with the molecule nitroxyl (HNO). Using the new spectrometer and by passing isotopically labelled methyl nitrite (CH 3ONO) through a pyrolysis nozzle, the spectra of minor isotopologues of HNO have been obtained. The observations on the isotopologues identified here, H 15NO, HN 18O, and D 15NO, have been combined with the earlier isotopic observations, HNO and DNO, to create a global r m (1) HNO geometry that approximates an equilibrium structure. Furthermore, the results aremore » compared to high-level ab initio calculations.« less

Fluid heterogeneity during granulite facies metamorphism in the Adirondacks: stable isotope evidence

USGS Publications Warehouse

Valley, J.W.; O'Neil, J.R.

1984-01-01

The preservation of premetamorphic, whole-rock oxygen isotope ratios in Adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived, hot CO2-H2O fluids during granulite facies metamorphism. This conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations. The data suggest that these rocks were not an open system during metamorphism; that fluid/rock ratios were in many instances between 0.0 and 0.1; that externally derived fluids, as well as fluids derived by metamorphic volatilization, rose along localized channels and were not pervasive; and thus that no single generalization can be applied to metamorphic fluid conditions in the Adirondacks. Analyses of 3 to 4 coexisting minerals from Adirondack marbles show that isotopic equilibrium was attained at the peak of granulite and upper amphibolite facies metamorphism. Thus the isotopic compositions of metamorphic fluids can be inferred from analyses of carbonates and fluid budgets can be constructed. Carbonates from the granulite facies are on average, isotopically similar to those from lower grade or unmetamorphosed limestones of the same age showing that no large isotopic shifts accompanied high grade metamorphism. Equilibrium calculations indicate that small decreases in ??18O, averaging 1 permil, result from volatilization reactions for Adirondack rock compositions. Additional small differences between amphibolite and granulite facies marbles are due to systematic lithologie differences. The range of Adirondack carbonate ??18O values (12.3 to 27.2) can be explained by the highly variable isotopic compositions of unmetamorphosed limestones in conjunction with minor 18O and 13C depletions caused by metamorphic volatilization suggesting that many (and possibly most) marbles have closely preserved their premetamorphic isotopic compositions. Such preservation is particularly evident in instances of high ??18O calcites (25.0 to 27.2), low ??18O wollastonites (-1.3 to 3.5), and sharp gradients in ??18O (18 permil/15m between marble and anorthosite, 8 permil/25 m in metasediments, and 6 permil/1 m in skarn). Isotopic exchange is seen across marble-anorthosite and marble-granite contacts only at the scale of a few meters. Small (<5 m) marble xenoliths are in approximate exchange equilibrium with their hosts, but for larger xenoliths and layers of marble there is no evidence of exchange at distances greater than 10 m from meta-igneous contacts. ?? 1984 Springer-Verlag.

Predicting equilibrium uranium isotope fractionation in crystals and solution

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2015-12-01

Despite the rapidly growing interest in using 238U/235U measurements as a proxy for changes in oxygen abundance in surface and near-surface environments, the present theoretical understanding of uranium isotope fractionation is limited to a few simple gas-phase molecules and analogues of dissolved species (e.g., 1,2,3). Understanding uranium isotope fractionation behavior in more complicated species, such as crystals and adsorption complexes, will help in the design and interpretation of experiments and field studies, and may suggest other uses for 38U/235U measurements. In this study, a recently developed first-principles method for estimating the nuclear volume component of field shift fractionation in crystals and complex molecular species (4) is combined with mass-dependent fractionation theory to predict equilibrium 38U/235U fractionations in aqueous and crystalline uranium compounds, including uraninite (UO2). The nuclear field shift effect, caused by the interaction of electrons with the finite volume of the positive charge distribution in uranium nuclei, is estimated using Density Functional Theory and the Projector Augmented Wave method (DFT-PAW). Tests against relativistic electronic structure calculations and Mössbauer isomer shift data indicate that the DFT-PAW method is reasonably accurate, while being much better suited to models of complex and crystalline species. Initial results confirm previous predictions that the nuclear volume effect overwhelms mass depdendent fractionation in U(VI)-U(IV) exchange reactions, leading to higher 238U/235U in U(IV) species (i.e., for UO2 xtal vs. UO22+aq, ln αNV ≈ +1.8‰ , ln αMD ≈ -0.8‰, ln αTotal ≈ +1.0‰ at 25ºC). UO2 and U(H2O)94+, are within ~0.4‰ of each other, while U(VI) species appear to be more variable. This suggests that speciation is likely to significantly affect natural uranium isotope fractionations, in addition to oxidation state. Tentatively, it appears that uranyl-type (UO22+-bearing) structures will tend to have higher 238U/235U than uranate-type structures that lack strong U=O bonds. References: 1. Bigeleisen (1996) JACS 118:3676; 2. Schauble (2006) Eos 87:V21B-0570; 3. Abe et al. (2008) J Chem Phys 128:144309, 129:164309, & Abe et al. (2010) J Chem Phys 133:044309; 4. Schauble (2013) PNAS 110:17714.

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.

Constraints on the origin of Os-isotope disequilibrium in included and interstitial sulfides in mantle peridotites: Implications for the interpretation of Os-isotope signatures in MORB and Abyssal Peridotites

NASA Astrophysics Data System (ADS)

Lassiter, J. C.

2016-12-01

The use of isotope variations in basalts to probe the composition and evolution of the mantle is predicated on the assumption of local (i.e., grain-scale) isotopic equilibrium during mantle melting (Hofmann & Hart, 1978). However, several studies report Os-isotope disequilibrium in distinct populations of sulfides in some peridotites. In principle, grain-scale isotopic heterogeneity could reflect variable radiogenic ingrowth in ancient sulfides with variable Re/Os, or partial re-equilibration of low-Re/Os sulfides with high-Re/Os silicate phases along grain boundaries during mantle melting (e.g., Alard et al., 2005). Both cases require that sulfides fail to maintain isotopic equilibrium with neighboring phases over geologically long ( Ga) time scales. The preservation of Os-isotope disequilibrium in peridotites has been ascribed to the armoring effect of low-[Os] silicates, which limit diffusive exchange between isolated Os-rich phases. This raises the prospect that peridotite-derived melts may not inherit the Os-isotope composition of their source. The timescale required for diffusive equilibration between separate sulfide grains or between Os-rich sulfides and Os-poor silicates is a function of average sulfide size and spacing, Os diffusivity in armoring silicate minerals, and Os partitioning between silicate and sulfide phases. For typical sulfide abundances and sizes in mantle peridotites, neighboring sulfides are expected to re-equilibrate in less than a few 10s of m.y. at adiabatic mantle temperatures, even for very high (>106) sulfide/silicate KD values. Maintenance of disequilibrium requires very large sulfides (>100 um) separated by several mm and diffusion rates (D < 10-20 m2/s) slower than for most other elements in olivine. Equilibration timescales between sulfides and surrounding silicates are similar, so that large-scale isotopic disequilibrium between sulfides and silicates is also unlikely within the convecting mantle. Instead, observed grain-scale Os-isotope disequilibrium in mantle peridotites likely reflects recent sulfide metasomatism linked to interaction with eclogite- or pyroxenite-derived melts. Interstitial sulfides with radiogenic Os-isotopes provide further evidence for a role of eclogite melting in MORB genesis.

Resolved 12CH2D2 and 13CH3D in CH4 as Sensitive Indicators of Disequilibrium and Equilibrium during Microbial Methane Cycling

NASA Astrophysics Data System (ADS)

Ash, J. L.; Egger, M.; Slomp, C. P.; Kohl, I. E.; Treude, T.; Rumble, D.; Young, E. D.

2016-12-01

The ability to measure the relative concentrations of at least two doubly-substituted rare isotopologues of gases with biogeochemical relevance provides new constraints on sources and sinks of these gases. In particular, as shown recently for O2, the use of two independent, rare isotopologues allows for detection of thermodynamic intra-species equilibrium and disequilibrium. Here, we report the first measurements of fully resolved 13CH3D and 12CH2D2 from natural samples of microbial methane gas. A suite of sedimentary methane samples from the Bornholm Basin in the Baltic Sea was collected during IODP Exp. 347. Sample depths range from 2-20 meters below seafloor (mbsf). Methane concentrations decrease with depth, and mcrA (a marker for methanogenesis and methanotropy) is present throughout. See Figure. Both Δ13CH3D and Δ12CH2D2 increase with depth as methane concentrations decrease with the shallowest samples exhibiting disequilibrium by up to 2‰ in Δ13CH3D and 13‰ in Δ12CH2D2 while the deepest samples approach isotopic thermodynamic equilibrium (marked by grey bars in Figure). The Fe-mediated anaerobic oxidation of methane (Fe-AOM) has been inferred in these sediments by geochemical modeling . Slow methane cycling by methanogensis and methanotrophy is likely responsible for the approach to isotopic bond order equilibrium in CH4 with depth, consistent with Fe-AOM. While axenic culturing experiments generate methane with large deficits in 12CH2D2 (reported at this meeting), these data from the Baltic Sea demonstrate that isotopic equilibrium can be achieved during microbial recycling of methane. In the absence of Δ12CH2D2, the Δ13CH3D values alone could be misinterpreted as representing gradients in temperature due perhaps to exothermic organic matter degradation. The combination of both mass-18 rare isotopologues of methane provides the means to distinguish equilibrium from disequilibrium and probe microbial methane cycling even where Δ13CH3D suggests reasonable temperatures.

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.

Oxygen and carbon isotope ratios of hydrothermal minerals from Yellowstone drill cores

USGS Publications Warehouse

Sturchio, N.C.; Keith, T.E.C.; Muehlenbachs, K.

1990-01-01

Oxygen and carbon isotope ratios were measured for hydrothermal minerals (silica, clay and calcite) from fractures and vugs in altered rhyolite, located between 28 and 129 m below surface (in situ temperatures ranging from 81 to 199??C) in Yellowstone drill holes. The purpose of this study was to investigate the mechanism of formation of these minerals. The ??18O values of the thirty-two analyzed silica samples (quartz, chalcedony, ??-cristobalite, and ??-cristobalite) range from -7.5 to +2.8???. About one third of the silica 7samples have ??18O values that are consistent with isotopic equilibrium with present thermal waters; most of the other silica samples appear to have precipitated from water enriched in 18O (up to 4.7???) relative to present thermal water, assuming precipitation at present in situ temperatures. Available data on fluid-inclusion homogenization temperatures in hydrothermal quartz indicate that silica precipitation occurred mostly at temperatures above those measured during drilling and imply that 15O enrichments in water during silica precipitation were generally larger than those estimated from present conditions. Similarly, clay minerals (celadonite and smectite) have ??18O values higher (by 3.5 to 7.9???) than equilibrium values under present conditions. In contrast, all eight analyzed calcite samples are close to isotopic equilibrium with present thermal waters. The frequent incidence of apparent 18O enrichment in thermal water from which the hydrothermal minerals precipitated may indicate that a higher proportion of strongly 18O-enriched deep hydrothermal fluid once circulated through shallow portions of the Yellowstone system, or that a recurring transient 18O-enrichment effect occurs at shallow depths and is caused either by sudden decompressional boiling or by isotopic exchange at low water/rock ratios in new fractures. The mineralogy and apparent 18O enrichments of hydrothermal fracture-filling minerals are consistent with deposition during transient boiling or rock-water exchange (fracturing) events. ?? 1990.

Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variation Seen in Cryogenic Laboratory Studies of Carbonate Salts

NASA Technical Reports Server (NTRS)

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

2013-01-01

The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average delta13C(DIC-CARB) values of 20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = 13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of 35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = 34%0 ] at 0degC. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the relative paucity of carbonate minerals in the martian crust.

Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Liu, Yun

2011-12-01

With a growing interest in small 17O-anomaly, there is a pressing need for the precise ratio, ln 17α/ln 18α, for a particular mass-dependent fractionation process (MDFP) (e.g., for an equilibrium isotope exchange reaction). This ratio (also denoted as " θ") can be determined experimentally, however, such efforts suffer from the demand of well-defined process or a set of processes in addition to high precision analytical capabilities. Here, we present a theoretical approach from which high-precision ratios for MDFPs can be obtained. This approach will complement and serve as a benchmark for experimental studies. We use oxygen isotope exchanges in equilibrium processes as an example. We propose that the ratio at equilibrium, θE ≡ ln 17α/ln 18α, can be calculated through the equation below: θa-bE=κa+(κa-κb){ln18βb}/{ln18α} where 18βb is the fractionation factor between a compound "b" and the mono-atomic ideal reference material "O", 18αa-b is the fractionation factor between a and b and it equals to 18βa/ 18βb and κ is a new concept defined in this study as κ ≡ ln 17β/ln 18β. The relationship between θ and κ is similar to that between α and β. The advantages of using κ include the convenience in documenting a large number of θ values for MDFPs and in estimating any θ values using a small data set due to the fact that κ values are similar among O-bearing compounds with similar chemical groups. Frequency scaling factor, anharmonic corrections and clumped isotope effects are found insignificant to the κ value calculation. However, the employment of the rule of geometric mean (RGM) can significantly affect the κ value. There are only small differences in κ values among carbonates and the structural effect is smaller than that of chemical compositions. We provide κ values for most O-bearing compounds, and we argue that κ values for Mg-bearing and S-bearing compounds should be close to their high temperature limitation (i.e., 0.5210 for Mg and 0.5159 for S). We also provide θ values for CO 2(g)-water, quartz-water and calcite-water oxygen isotope exchange reactions at temperature from 0 to 100 °C.

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.

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.

Biotic and abiotic pathways of phosphorus cycling in minerals and sediments: insights from oxygen isotopes in phosphate

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

Jaisi, Deb P.; Kukkadapu, Ravi K.; Stout, Lisa M.

2011-07-06

A key question to address in the development of oxygen isotope ratios in phosphate (18Op) as a tracer of biogeochemical cycling of phosphorus in ancient and modern environments is the nature of isotopic signatures associated with uptake and cycling of mineral-bound phosphate by microorganisms. Here we present experimental results aimed at understanding the biotic and abiotic pathway of P cycling during biological uptake of phosphate sorbed to ferrihydrite and the selective uptake of specific sedimentary phosphate phases by Escherichia coli, Vibrio fischeri and Marinobacter aquaeolei. Results indicate that a significant fraction of ferrihydrite-bound phosphate is biologically available. The fraction ofmore » phosphate taken up by E. coli attained an equilibrium isotopic composition in a short time (<50 hrs) due to efficient O-isotope exchange between phosphate and water (biotic pathway). The difference in isotopic composition between newly equilibrated aqueous and residual sorbed phosphate promoted the exchange of intact phosphate radicals (abiotic pathway) so that this difference gradually became negligible. In sediment containing different P phases, E. coli and V. fischeri ‘extracted’ loosely sorbed phosphate first while M. aquaeolei preferred iron-oxide bound phosphate. Each bacterium imprinted a biotic isotopic signature on each P phase that it took up and cycled. For example, the 18Op value of the sorbed phosphate phase shifted gradually towards equilibrium isotopic composition and the value of Fe oxide-bound phosphate showed slight changes at first, but when new iron oxides were formed, co-precipitated/occluded phosphate retained 18O values of aqueous phosphate at that time. Concentrations and isotopic compositions of authigenic and detrital phosphates did not change, suggesting that these phosphate phases were not utilized by bacteria. These findings support burgeoning applications of 18Op as a tracer of phosphorus cycling in sediments, soils and aquatic environments and as an indicator of paleo- environmental conditions.« less

Chemical and oxygen isotopic properties of ordinary chondrites (H5, L6) from Oman: Signs of isotopic equilibrium during thermal metamorphism

NASA Astrophysics Data System (ADS)

Ali, Arshad; Nasir, Sobhi J.; Jabeen, Iffat; Al Rawas, Ahmed; Banerjee, Neil R.; Osinski, Gordon R.

2017-10-01

Mean bulk chemical data of recently found H5 and L6 ordinary chondrites from the deserts of Oman generally reflect isochemical features which are consistent with the progressive thermal metamorphism of a common, unequilibrated starting material. Relative differences in abundances range from 0.5-10% in REE (Eu = 14%), 6-13% in siderophile elements (Co = 48%), and >10% in lithophile elements (exceptions are Ba, Sr, Zr, Hf, U = >30%) between H5 and L6 groups. These differences may have accounted for variable temperature conditions during metamorphism on their parent bodies. The CI/Mg-normalized mean abundances of refractory lithophile elements (Al, Ca, Sm, Yb, Lu, V) show no resolvable differences between H5 and L6 suggesting that both groups have experienced the same fractionation. The REE diagram shows subtle enrichment in LREE with a flat HREE pattern. Furthermore, overall mean REE abundances are 0.6 × CI with enriched La abundance ( 0.9 × CI) in both groups. Precise oxygen isotope compositions demonstrate the attainment of isotopic equilibrium by progressive thermal metamorphism following a mass-dependent isotope fractionation trend. Both groups show a slope-1/2 line on a three-isotope plot with subtle negative deviation in Δ17O associated with δ18O enrichment relative to δ17O. These deviations are interpreted as the result of liberation of water from phyllosilicates and evaporation of a fraction of the water during thermal metamorphism. The resultant isotope fractionations caused by the water loss are analogous to those occurring between silicate melt and gas phase during CAI and chondrule formation in chondrites and are controlled by cooling rates and exchange efficiency.

The stable isotopes of site wide waters at an oil sands mine in northern Alberta, Canada

NASA Astrophysics Data System (ADS)

Baer, Thomas; Barbour, S. Lee; Gibson, John J.

2016-10-01

Oil sands mines have large disturbance footprints and contain a range of new landforms constructed from mine waste such as shale overburden and the byproducts of bitumen extraction such as sand and fluid fine tailings. Each of these landforms are a potential source of water and chemical release to adjacent surface and groundwater, and consequently, the development of methods to track water migration through these landforms is of importance. The stable isotopes of water (i.e. 2H and 18O) have been widely used in hydrology and hydrogeology to characterize surface water/groundwater interactions but have not been extensively applied in mining applications, or specifically to oil sands mining in northern Alberta. A prerequisite for applying these techniques is the establishment of a Local Meteoric Water Line (LMWL) to characterize precipitation at the mine sites as well as the development of a 'catalogue' of the stable water isotope signatures of various mine site waters. This study was undertaken at the Mildred Lake Mine Site, owned and operated by Syncrude Canada Ltd. The LMWL developed from 2 years (2009/2012) of sample collection is shown to be consistent with other LMWLs in western Canada. The results of the study highlight the unique stable water isotope signatures associated with hydraulically placed tailings (sand or fluid fine tailings) and overburden shale dumps relative to natural surface water and groundwater. The signature associated with the snow melt water on reclaimed landscapes was found to be similar to ground water recharge in the region. The isotopic composition of the shale overburden deposits are also distinct and consistent with observations made by other researchers in western Canada on undisturbed shales. The process water associated with the fine and coarse tailings streams has highly enriched 2H and 18O signatures. These signatures are developed through the non-equilibrium fractionation of imported fresh river water during evaporation from cooling towers used within the raw water process circuit. This highly fractionated surface water eventually becomes part of the recycled tailings water circuit, and as a consequence it undergoes further non-equilibrium fractionation as a result of surface evaporation, leading to additional enrichment along local evaporation lines.

Backbone dynamics of a model membrane protein: measurement of individual amide hydrogen-exchange rates in detergent-solubilized M13 coat protein using /sup 13/C NMR hydrogen/deuterium isotope shifts

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

Henry, G.D.; Weiner, J.H.; Sykes, B.D.

Hydrogen-exchange rates have been measured for individual assigned amide protons in M13 coat protein, a 50-residue integral membrane protein, using a /sup 13/C nuclear magnetic resonance (NMR) equilibrium isotope shift technique. The locations of the more rapidly exchanging amides have been determined. In D/sub 2/O solutions, a peptide carbonyl resonance undergoes a small upfield isotope shift (0.08-0.09 ppm) from its position in H/sub 2/O solutions; in 1:1 H/sub 2/O/D/sub 2/O mixtures, the carbonyl line shape is determined by the exchange rate at the adjacent nitrogen atom. M13 coat protein was labeled biosynthetically with /sup 13/C at the peptide carbonyls ofmore » alanine, glycine, phenylalanine, proline, and lysine, and the exchange rates of 12 assigned amide protons in the hydrophilic regions were measured as a function of pH by using the isotope shift method. This equilibrium technique is sensitive to the more rapidly exchanging protons which are difficult to measure by classical exchange-out experiments. In proteins, structural factors, notably H bonding, can decrease the exchange rate of an amide proton by many orders of magnitude from that observed in the freely exposed amides of model peptides such as poly(DL-alanine). With corrections for sequence-related inductive effects, the retardation of amide exchange in sodium dodecyl sulfate solubilized coat protein has been calculated with respect to poly(DL-alanine). The most rapidly exchanging protons, which are retarded very little or not at all, are shown to occur at the N- and C-termini of the molecule. A model of the detergent-solubilized coat protein is constructed from these H-exchange data which is consistent with circular dichroism and other NMR results.« less

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

NASA Astrophysics Data System (ADS)

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

2006-05-01

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

Isotopic composition of Mg and Fe in garnet peridotites from the Kaapvaal and Siberian cratons

NASA Astrophysics Data System (ADS)

An, Yajun; Huang, Jin-Xiang; Griffin, W. L.; Liu, Chuanzhou; Huang, Fang

2017-03-01

We present Mg and Fe isotopic data for whole rocks and separated minerals (olivine, clinopyroxene, orthopyroxene, garnet, and phlogopite) of garnet peridotites that equilibrated at depths of 134-186 km beneath the Kaapvaal and Siberian cratons. There is no clear difference in δ26Mg and δ56Fe of garnet peridotites from these two cratons. δ26Mg of whole rocks varies from -0.243‰ to -0.204‰ with an average of -0.225 ± 0.037‰ (2σ, n = 19), and δ56Fe from -0.038‰ to 0.060‰ with an average of -0.003 ± 0.068‰ (2σ, n = 19). Both values are indistinguishable from the fertile upper mantle, indicating that there is no significant Mg-Fe isotopic difference between the shallow and deep upper mantle. The garnet peridotites from ancient cratons show δ26Mg similar to komatiites and basalts, further suggesting that there is no obvious Mg isotopic fractionation during different degrees of partial melting of deep mantle peridotites and komatiite formation. The precision of the Mg and Fe isotope data (⩽±0.05‰ for δ26Mg and δ56Fe, 2σ) allows us to distinguish inter-mineral isotopic fractionations. Olivines are in equilibrium with opx in terms of Mg and Fe isotopes. Garnets have the lowest δ26Mg and δ56Fe among the coexisting mantle minerals, suggesting the dominant control of crystal structure on the Mg-Fe isotopic compositions of garnets. Elemental compositions and mineralogy suggest that clinopyroxene and garnet were produced by later metasomatic processes as they are not in chemical equilibrium with olivine or orthopyroxene. This is consistent with the isotopic disequilibrium of Mg and Fe isotopes between orthopyroxene/olivine and garnet/clinopyroxene. Combined with one sample showing slightly heavy δ26Mg and much lighter δ56Fe, these disequilibrium features in the garnet peridotites reveal kinetic isotopic fractionation due to Fe-Mg inter-diffusion during reaction between peridotites and percolating melts in the Kaapvaal craton.

Gallium isotope fractionation during Ga adsorption on calcite and goethite

NASA Astrophysics Data System (ADS)

Yuan, Wei; Saldi, Giuseppe D.; Chen, JiuBin; Vetuschi Zuccolini, Marino; Birck, Jean-Louis; Liu, Yujie; Schott, Jacques

2018-02-01

Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △71Gasolid-solution up to -1.27‰ and -0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for 'closed system' equilibrium and 'Rayleigh fractionation' models indicates that the experimental data are consistent with a 'closed system' equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga-O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH)4- to 6 and 1.94 Å in the >Ca-O-GaOH(OH2)4+ surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH)20 surface complexes (Ga-O distances of 1.96-1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH)4- is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga-O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its geochemical analog aluminum.

Study of evaporating the irradiated graphite in equilibrium low-temperature plasma

NASA Astrophysics Data System (ADS)

Bespala, E. V.; Novoselov, I. Yu.; Pavlyuk, A. O.; Kotlyarevskiy, S. G.

2018-01-01

The paper describes a problem of accumulation of irradiated graphite due to operation of uranium-graphite nuclear reactors. The main noncarbon contaminants that contribute to the overall activity of graphite elements are iso-topes 137Cs, 60Co, 90Sr, 36Cl, and 3H. A method was developed for processing of irradiated graphite ensuring the volu-metric decontamination of samples. The calculation results are presented for equilibrium composition of plasma-chemical reactions in systems "irradiated graphite-argon" and "irradiated graphite-helium" for a wide range of tem-peratures. The paper describes a developed mathematical model for the process of purification of a porous graphite surface treated by equilibrium low-temperature plasma. The simulation results are presented for the rate of sublimation of radioactive contaminants as a function of plasma temperature and plasma flow velocity when different plasma-forming gases are used. The extraction coefficient for the contaminant 137Cs from the outer side of graphite pores was calculated. The calculations demonstrated the advantages of using a lighter plasma forming gas, i.e., helium.

Prediction of equilibrium distributions of isotopologues for methane, ethane and propane using density functional theory

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Peterson, Brian; Eiler, John

2016-10-01

Many previous studies have examined abundances of deuterium (D) and 13C within small organic molecules. Recent advances in analytical instrumentation add the abilities to measure site-specific and multiply substituted isotopologues of natural organics. Here we perform first-principles calculations of the equilibrium distributions of 13C and D in the volatile alkanes (including both single and multiple substitutions), as a guide to the interpretation of current measurements and as a basis for anticipating isotope effects that might be examined with future analytical techniques. The models we present illustrate several common themes of the isotopic structures of the small alkanes, including; temperature dependent enrichment of clumped isotope species, with amplitudes in the order D-D > 13C-D > 13C-13C; similarity in strength of such clumped isotope effects between different molecules (e.g., 13C-D clumping is ∼5‰ enriched at 300 K in methane, ethane and propane); a ∼10× contrast between the amplitudes of stronger adjacent substitution of two heavy isotopes vs. weaker non-adjacent substitution; temperature-dependent site-specific fractionation of D and 13C into interior positions of molecules relative to terminal methyl groups; and a relatively simple additive effect to the overall amplitude of enrichment when clumped and site specific effects combine in the same isotopologue. We suggest that the most promising tools suggested by our results are isotopic thermometers based on site-specific distribution of deuterium, which exhibits strong (∼100‰), highly temperature dependent fractionation between methyl groups and methylene carbon positions in propane (and likely other larger n-alkanes).

Development of a model using the MATLAB System identification toolbox to estimate (222)Rn equilibrium factor from CR-39 based passive measurements.

PubMed

Abo-Elmagd, M; Sadek, A M

2014-12-01

Can and Bare method is a widely used passive method for measuring the equilibrium factor F through the determination of the track density ratio between bare (D) and filtered (Do) detectors. The dimensions of the used diffusion chamber are altering the deposition ratios of Po-isotopes on the chamber walls as well as the ratios of the existing alpha emitters in air. Then the measured filtered track density and therefore the resultant equilibrium factor is changed according to the diffusion chamber dimensions. For this reason, high uncertainty was expected in the measured F using different diffusion chambers. In the present work, F is derived as a function of both track density ratio (D/Do) and the dimensions of the used diffusion chambers (its volume to the total internal surface area; V/A). The accuracy of the derived formula was verified using the black-box modeling technique via the MATLAB System identification toolbox. The results show that the uncertainty of the calculated F by using the derived formula of F (D/Do, V/A) is only 5%. The obtained uncertainty ensures the quality of the derived function to calculate F using diffusion chambers with wide range of dimensions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Stable C, O and clumped isotope systematics and 14C geochronology of carbonates from the Quaternary Chewaucan closed-basin lake system, Great Basin, USA: Implications for paleoenvironmental reconstructions using carbonates

NASA Astrophysics Data System (ADS)

Hudson, Adam M.; Quade, Jay; Ali, Guleed; Boyle, Douglas; Bassett, Scott; Huntington, Katharine W.; De los Santos, Marie G.; Cohen, Andrew S.; Lin, Ke; Wang, Xiangfeng

2017-09-01

Isotopic compositions of lacustrine carbonates are commonly used for dating and paleoenvironmental reconstructions. Here we use carbonate δ13C and δ18O, clumped (Δ47), and 14C compositions to better understand the carbonate isotope system in closed-basin lakes and trace the paleohydrologic and temperature evolution in the Chewaucan closed-basin lake system, northern Great Basin, USA, over the Last Glacial/Holocene transition. We focus on shorezone tufas to establish that they form in isotopic equilibrium with lake water and DIC, they can be dated reliably using 14C, and their clumped isotope composition can be used to reconstruct past lake temperature. Calculations of the DIC budget and reservoir age for the lake indicate residence time is short, and dominated by exchange with atmospheric CO2 at all past lake levels. Modern lake DIC and shorezone tufas yield δ13C and 14C values consistent with isotopic equilibrium with recent fossil fuel and bomb-influenced atmospheric CO2, supporting these calculations. δ13C values of fossil tufas are also consistent with isotopic equilibrium with pre-industrial atmospheric CO2 at all shoreline elevations. This indicates that the 14C reservoir effect for this material is negligible. Clumped isotope (Δ47) results indicate shorezone tufas record mean annual lake temperature. Modern (average 13 ± 2 °C) and 18 ka BP-age tufas (average 6 ± 2 °C) have significantly different temperatures consistent with mean annual temperature lowering of 7 ± 3 °C (1 SE) under full glacial conditions. For shorezone tufas and other lake carbonates, including spring mounds, mollusk shells, and ostracod tests, overall δ13C and δ18O values co-vary according to the relative contribution of spring and lacustrine end member DIC and water compositions in the drainage system, but specific isotope values depend strongly upon sample context and are not well correlated with past lake depth. This contrasts with the interpretation that carbonate isotopes in closed-basin lake systems reflect changes in DIC and water budgets connected to higher or lower lake volumes. Instead, a small overlapping range of isotope compositions characterize multiple lake levels, so that none can be identified uniquely by isotope composition alone. Relative to other lake carbonates, δ13C and δ18O values for ostracods in Ana River Canyon deposits are very strongly influenced by Ana River water, suggesting low lake level and volume characterized Summer Lake for most of the past 100,000 years. Coupled with sedimentologic observations, the Ana River deposits thus suggest dry conditions like today are close to the mean climate state in the northern Great Basin. By contrast, basin-integrating highstands such as that dating to ∼14 ka BP, during the last glacial termination, are hydrologically unique and short-lived. Overall, our results indicate carbonate isotope records must account for the specific geochemical and hydrologic characteristics of lake system in order to provide robust paleoenvironmental reconstructions.

Stable C, O and clumped isotope systematics and 14C geochronology of carbonates from the Quaternary Chewaucan closed-basin lake system, Great Basin, USA: Implications for paleoenvironmental reconstructions using carbonates

USGS Publications Warehouse

Hudson, Adam; Quade, Jay; Ali, Guleed; Boyle, Douglas P.; Bassett, Scott; Huntington, Katharine W.; De los Santos, Marie G.; Cohen, Andrew S.; Lin, Ke; Wang, Xiangfeng

2017-01-01

Isotopic compositions of lacustrine carbonates are commonly used for dating and paleoenvironmental reconstructions. Here we use carbonate δ13C and δ18O, clumped (Δ47), and 14C compositions to better understand the carbonate isotope system in closed-basin lakes and trace the paleohydrologic and temperature evolution in the Chewaucan closed-basin lake system, northern Great Basin, USA, over the Last Glacial/Holocene transition. We focus on shorezone tufas to establish that they form in isotopic equilibrium with lake water and DIC, they can be dated reliably using 14C, and their clumped isotope composition can be used to reconstruct past lake temperature. Calculations of the DIC budget and reservoir age for the lake indicate residence time is short, and dominated by exchange with atmospheric CO2 at all past lake levels. Modern lake DIC and shorezone tufas yield δ13C and 14C values consistent with isotopic equilibrium with recent fossil fuel and bomb-influenced atmospheric CO2, supporting these calculations. δ13C values of fossil tufas are also consistent with isotopic equilibrium with pre-industrial atmospheric CO2 at all shoreline elevations. This indicates that the 14C reservoir effect for this material is negligible. Clumped isotope (Δ47) results indicate shorezone tufas record mean annual lake temperature. Modern (average 13 ± 2 °C) and 18 ka BP-age tufas (average 6 ± 2 °C) have significantly different temperatures consistent with mean annual temperature lowering of 7 ± 3 °C (1 SE) under full glacial conditions. For shorezone tufas and other lake carbonates, including spring mounds, mollusk shells, and ostracod tests, overall δ13C and δ18O values co-vary according to the relative contribution of spring and lacustrine end member DIC and water compositions in the drainage system, but specific isotope values depend strongly upon sample context and are not well correlated with past lake depth. This contrasts with the interpretation that carbonate isotopes in closed-basin lake systems reflect changes in DIC and water budgets connected to higher or lower lake volumes. Instead, a small overlapping range of isotope compositions characterize multiple lake levels, so that none can be identified uniquely by isotope composition alone. Relative to other lake carbonates, δ13C and δ18O values for ostracods in Ana River Canyon deposits are very strongly influenced by Ana River water, suggesting low lake level and volume characterized Summer Lake for most of the past 100,000 years. Coupled with sedimentologic observations, the Ana River deposits thus suggest dry conditions like today are close to the mean climate state in the northern Great Basin. By contrast, basin-integrating highstands such as that dating to ∼14 ka BP, during the last glacial termination, are hydrologically unique and short-lived. Overall, our results indicate carbonate isotope records must account for the specific geochemical and hydrologic characteristics of lake system in order to provide robust paleoenvironmental reconstructions.

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).

Phosphorus cycling in forest ecosystems: insights from oxygen isotopes in phosphate

NASA Astrophysics Data System (ADS)

Pistocchi, Chiara; Tamburini, Federica; Bünemann, Else; Frossard, Emmanuel

2015-04-01

The current view on the phosphorus (P) cycle in forest ecosystems relies mostly on measurements and correlations of pools, and to a lower extent on measurement of fluxes. We have no direct insight into the processes phosphate goes through at the ecosystem level, and into the relative importance of organic and mineral pools in sustaining P nutrition of trees. The analysis of oxygen isotopes associated to P (18Op) is expected to bring this type of information. The German Priority Program SPP 1685 aims to test the overall hypothesis that the P-depletion of soils drives forest ecosystems from P acquiring systems (efficient mobilization of P from the mineral phase) to P recycling systems (highly efficient cycling of P). Our contribution to this project will consist in studying the relative importance of biological and geochemical processes in controlling the P cycle in temperate beech forest ecosystems in Germany along a gradient of decreasing soil P availability. We will follow the fate of phosphate from litter fall to the uptake of P by plants via P release by decomposition of organic matter or after release from P-containing minerals, by using a multi-isotope approach (O in water and phosphate plus 33P). To address our research question we will rely on measurements in experimental forest sites and on laboratory incubations of the organic layer or the mineral soil. We present here the first results issued from the 2014 sampling on three study sites, where we characterized the P pools in surface soil horizons by a sequential extraction (modified after Tiessen and Moir, 2007) and we analysed the 18Op of the resin extractable- and microbial-P fractions. Contrary to what was previously found (e.g. Tamburini et al. 2012) the isotopic composition of these fractions in most of the samples does not reflect the equilibrium value (as the result of the dominance of the pyrophosphatase activity on the other enzymatic processes, Blake et al. 2005). Depending on the P availability in the soil, deviations from the equilibrium are more or less pronounced. We hypothesized that the 18Op is the result of other processes such the mineralization of organic P by phosphatases. These first results of 18Op on forest soils are suggesting that isotopic equilibrium driven by biological cycling (pyrophosphatase) is not always overprinting other processes. In addition, together with information on P speciation/concentration, 18Op seems to provide direct insights on P cycling at the ecosystem level. Blake R.E., Neil J.R.O., Surkov A.V. (2005) Biogeochemical cycling of phosphorus: insights from oxygen isotope effects of phosphoenzymes. American Journal of Science 305: 596-620 Moir J.O., Tiessen H. Characterization of available P by sequential extraction. Soil Sampling and Methods of Analysis, Second Edition. Ed. by M.R. Carter and E.G. Gregorich CRC Press 2007 Tamburini F., Pfahler V, Bünemann E.K., Guelland K., Bernasconi S.M., Frossard E. (2012) Oxygen Isotopes Unravel the Role of Microorganisms in Phosphate Cycling in Soils. Environmental Science & Technology 46: 5956-5962

Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems

USGS Publications Warehouse

Young, M.B.; McLaughlin, K.; Kendall, C.; Stringfellow, W.; Rollog, M.; Elsbury, K.; Donald, E.; Paytan, A.

2009-01-01

The oxygen isotopic composition of dissolved inorganic phosphate (δ18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source δ18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for δ18O p to be a useful tool for source tracking, the δ18Op of phosphate sources must be distinguishable from one another; however, the δ18Op of potential sources has not been well characterized. We measured the δ18O p of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of δ18Op values (from +8.4 to +24.9‰) for the various sources, and statistically significant differences were found between several of the source types. δ18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in δ18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and δ18Op can be used for identifying phosphate sources to aquatic systems.

Theoretical estimates of equilibrium 13C-18O clumping in carbonates and organic acids

NASA Astrophysics Data System (ADS)

Schauble, E. A.; Eiler, J. M.

2004-12-01

The development of techniques for measuring small gas-phase molecules containing more than one rare stable isotope (e.g., 13C18O16O) at natural, ppm-level abundances1,2 has made it possible to track sources and sinks of atmospheric gases from a new perspective. Similar measurements of 13C-18O clumping in ancient samples could improve our understanding of ancient climates, if the abundances of `clumped' rare stable isotopes in materials that retain isotopic signatures over geologic time can be measured with sufficient precision. This theoretical study estimates the abundances of such 13C-18O `clumps' in carbonates and organic acids and discusses their potential applications. Accompanying abstracts by Eiler et al. and Ghosh et al. will present the analytical methods and some initial data for carbonate minerals to examine the applicability of our theoretical models. Equilibrium isotopic speciations in carbonate minerals and organic acids are calculated from the reduced partition function ratios of isotopically substituted crystals and molecules. Vibrational frequencies used as input for these calculations come from ab initio force fields, determined using density functional theory. Our calculations indicate that carbonate minerals, including calcite, dolomite, and aragonite, when equilibrated at earth-surface temperatures, will have a slight overabundance of CO32- groups containing both 13C and 18O (i.e., 13C18O16O22-) relative to what would be expected if carbon and oxygen isotopes were distributed randomly in the crystal lattice. Calcite and dolomite crystals are predicted to have 0.4‰ excesses of 13C18O16O22- at 298 K; in aragonite the excess will be about 0.05‰ larger. The excesses are smaller for crystals formed or equilibrated at higher temperatures, decreasing by 0.003\\permil/oC at room temperature and essentially disappearing at temperatures of 1000 K or higher. Similarly, there is an excess of both 13C18O16OH and 13C16O18OH groups in organic acids like formic acid (HCOOH) and pyruvic acid (CH3COCOOH) that equilibrate at low temperatures. For gas-phase carboxylic acids, 13C-18O clumping in the COOH group is strongest at the C=O double bond, with an 1.0-1.1‰ excess at room temperature. The C-O-H subgroup has an ~0.4‰ 13C-18O excess, and thus the average anomaly for the whole COOH group is 0.7-0.8\\permil. As with carbonate minerals, these excesses decrease at higher temperatures. The magnitude of 13C-18O clumping in carboxylic acid is similar to gas-phase CO2 1,2,3, while in carbonate minerals the effect is about one-half as large. The temperature sensitivity of these isotopic clumping effects suggests that measurements of abundances of 13C-18O bonds in carbonates and organic acids could be useful for paleothermometry. The clumping equilibrium is an internal property of each phase, so temperature information can be obtained even when the isotopic composition of the fluid phase from which a sample precipitated is unknown. Clumping effects may also be able to distinguish pristine, unaltered sedimentary and biogenic carbonates and organic deposits from those that have undergone post-depositional diagenesis or metamorphism, even in samples that have not suffered extensive open-system exchange. Refs: 1Eiler et al. 2004, GCA in press; 2Schauble et al. in prep.; 3Wang et al. 2004, GCA in press.

Self-diffusion of magnesium in spinel and in equilibrium melts - Constraints on flash heating of silicates

NASA Technical Reports Server (NTRS)

Sheng, Y. J.; Wasserburg, G. J.; Hutcheon, I. D.

1992-01-01

An isotopic tracer is used to measure Mg self-diffusion in spinel and coexisting melt at bulk chemical equilibrium. The diffusion coefficients were calculated from the measured isotope profiles using a model that includes the complementary diffusion of Mg-24, Mg-25, and Mg-26 in both phases with the constraint that the Mg content of each phase is constant. The activation energy and preexponential factor for Mg self-diffusion in spinel are, respectively, 384 +/- 7 kJ and 74.6 +/- 1.1 sq cm/s. These data indicate Mg diffusion in spinel is much slower than previous estimates. The activation energy for Mg self-diffusion in coexisting melt is 343 +/- 25 kJ and the preexponential factor is 7791.9 +/- 1.3 sq cm/s. These results are used to evaluate cooling rates of plagioclase-olivine inclusions (POIs) in the Allende meteorite. Given a maximum melting temperature for POIs of about 1500 C, these results show that a 1-micron radius spinel would equilibrate isotopically with a melt within about 60 min.

Mass fractionation processes of transition metal isotopes

NASA Astrophysics Data System (ADS)

Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

2002-06-01

Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

Dating human skeletal remains: investigating the viability of measuring the equilibrium between 210Po and 210Pb as a means of estimating the post-mortem interval.

PubMed

Swift, B

1998-11-30

Estimating the post-mortem interval in skeletal remains is a notoriously difficult task; forensic pathologists often rely heavily upon experience in recognising morphological appearances. Previous techniques have involved measuring physical or chemical changes within the hydroxyapatite matrix, radiocarbon dating and 90Sr dating, though no individual test has been advocated. Within this paper it is proposed that measuring the equilibrium between two naturally occurring radio-isotopes, 210Po and 210Pb, and comparison with post-mortem examination samples would produce a new method of dating human skeletal remains. Possible limitations exist, notably the effect of diagenesis, time limitations and relative cost, though this technique could provide a relatively accurate means of determining the post-mortem interval. It is therefore proposed that a large study be undertaken to provide a calibration scale against which bones uncovered can be dated.

Chromium isotopic anomalies in the Allende meteorite

NASA Technical Reports Server (NTRS)

Papanastassiou, D. A.

1986-01-01

Abundances of the chromium isotopes in terrestrial and bulk meteorite samples are identical to 0.01 percent. However, Ca-Al-rich inclusions from the Allende meteorite show endemic isotopic anomalies in chromium which require at least three nucleosynthetic components. Large anomalies at Cr-54 in a special class of inclusions are correlated with large anomalies at Ca-48 and Ti-50 and provide strong support for a component reflecting neutron-rich nucleosynthesis at nuclear statistical equilibrium. This correlation suggests that materials from very near the core of an exploding massive star may be injected into the interstellar medium.

Modeling the thermal unfolding 2DIR spectra of a β-hairpin peptide based on the implicit solvent MD simulation.

PubMed

Wu, Tianmin; Yang, Lijiang; Zhang, Ruiting; Shao, Qiang; Zhuang, Wei

2013-07-25

We simulated the equilibrium isotope-edited FTIR and 2DIR spectra of a β-hairpin peptide trpzip2 at a series of temperatures. The simulation was based on the configuration distributions generated using the GB(OBC) implicit solvent model and the integrated tempering sampling (ITS) technique. A soaking procedure was adapted to generate the peptide in explicit solvent configurations for the spectroscopy calculations. The nonlinear exciton propagation (NEP) method was then used to calculate the spectra. Agreeing with the experiments, the intensities and ellipticities of the isotope-shifted peaks in our simulated signals have the site-specific temperature dependences, which suggest the inhomogeneous local thermal stabilities along the peptide chain. Our simulation thus proposes a cost-effective means to understand a peptide's conformational change and related IR spectra across its thermal unfolding transition.

Iron Isotope Constraints on Planetesimal Core Formation

NASA Astrophysics Data System (ADS)

Jordan, M.; Young, E. D.

2016-12-01

The prevalence of iron in both planetary cores and silicate mantles renders the element a valuable tool for understanding core formation. Magmatic iron meteorites exhibit an enrichment in 57Fe/54Fe relative to chondrites and HED meteorites. This is suggestive of heavy Fe partitioning into the cores of differentiated bodies. If iron isotope fractionation accompanies core formation, we can elucidate details about the history of accretion for planetary bodies as well as their compositions and relative core sizes. The equilibrium 57Fe/54Fe between metal and silicate is necessary for understanding observed iron isotope compositions and placing constraints on core formation. We measure this fractionation in two Aubrite meteorites, Norton County and Mount Egerton, which have known temperatures of equilibration and equilibrated silicon isotopes. Iron was purified using ion-exchange chromatography. Data were collected on a ThermoFinnigan NeptuneTM multiple-collector inductively coupled plasma-source mass spectrometer (MC-ICP-MS) run in wet plasma mode. The measured fractionation Δ57Femetal-silicate is 0.08‰ ± 0.039 (2 SE) for Norton County and 0.09‰ ± 0.019 (2 SE) for Mount Egerton, indicating that the heavy isotopes of Fe partition into the metallic phase. These rocks are in isotopic equilibrium at a temperature of 1130 K and 1200 K ± 80 K, respectively. The concentration of the heavy isotopes of iron in the metallic phase is consistent with recent experimental studies. Using our measured metal-silicate Fe isotope fractionation and the resulting temperature calibration, while taking into account impurities in the metallic phase and temperatures of equilibration, determine that core formation could explain the observed difference between magmatic iron meteorites and chondrites if parent bodies have small cores. In order to verify that Rayleigh distillation during fractional crystallization was not a cause of iron isotope fractionation in iron meteorites, we measured iron isotope ratios in a suite of iron meteorites representing a large range of degrees of fractional crystallization. We find no clear variation in 57Fe/54Fe among these samples.

Chemical and isotopic fractionations by evaporation and their cosmochemical implications

NASA Astrophysics Data System (ADS)

Ozawa, Kazuhito; Nagahara, Hiroko

2001-07-01

A kinetic model for evaporation of a multi-component condensed phase with a fixed rate constant of the reaction is developed. A binary system with two isotopes for one of the components undergoing simple thermal histories (e.g., isothermal heating) is investigated in order to evaluate the extent of isotopic and chemical fractionations during evaporation. Diffusion in the condensed phase and the effect of back reaction from ambient gas are taken into consideration. Chemical and isotopic fractionation factors and the Péclet number for evaporation are the three main parameters that control the fractionation. Dust enrichment factor (η), the ratio of the initial dust quantity to that required for attainment of gas-dust equilibrium, is critical when back reactions become significant. Dust does not reach equilibrium with gas at η < 1. Notable chemical and isotopic fractionations usually take place under these conditions. There are two circumstances in which isotopic fractionation of a very volatile element does not accompany chemical fractionation during isothermal heating. One is free evaporation when diffusion in the condensed phase is very slow (η = 0), and the other is evaporation in the presence of ambient gas (η > 0). In the former case, a quasi-steady state in the diffusion boundary layer is maintained for isotopic fractionation but not for chemical fractionation. In the latter case, the back reaction brings the strong isotopic fractionation generated in the earlier stage of evaporation back to a negligibly small value in the later stage before complete evaporation. The model results are applied to cosmochemical fractionation of volatile elements during evaporation from a condensed phase that can be regarded as a binary solution phase. The wide range of potassium depletion without isotopic fractionation in various types of chondrules (Alexander et al., 2000) is explained by instantaneous heating followed by cooling in a closed system with various degrees of dust enrichment (η = 0.001-10) and cooling rates of less than ˜5°C/min. The extent of decoupling between isotopic and chemical fractionations of various elements in chondrules and matrix minerals may constrain the time scale and the conditions of heating and cooling processes in the early solar nebula.

Rb-Sr And Sm-Nd Ages, and Petrogenesis of Depleted Shergottite Northwest Africa 5990

NASA Technical Reports Server (NTRS)

Shih, C. Y.; Nyquist, L. E.; Reese, Y.; Irving, A. J.

2011-01-01

Northwest Africa (NWA) 5990 is a very fresh Martian meteorite recently found on Hamada du Draa, Morocco and was classified as an olivine-bearing diabasic igneous rock related to depleted shergottites [1]. The study of [1] also showed that NWA 5990 resembles QUE 94201 in chemical, textural and isotopic aspects, except QUE 94201 contains no olivine. The depleted shergottites are characterized by REE patterns that are highly depleted in LREE, older Sm-Nd ages of 327-575 Ma and highly LREE-depleted sources with Nd= +35+48 [2-7]. Age-dating these samples by Sm-Nd and Rb-Sr methods is very challenging because they have been strongly shocked and contain very low abundances of light rare earth elements (Sm and Nd), Rb and Sr. In addition, terrestrial contaminants which are commonly present in desert meteorites will compromise the equilibrium of isotopic systems. Since NWA 5990 is a very fresh meteorite, it probably has not been subject to significant desert weathering and thus is a good sample for isotopic studies. In this report, we present Rb-Sr and Sm-Nd isotopic results for NWA 5990, discuss the correlation of the determined ages with those of other depleted shergottites, especially QUE 94201, and discuss the petrogenesis of depleted shergottites.

Thermal equilibration of iron meteorite and pallasite parent bodies recorded at the mineral scale by Fe and Ni isotope systematics

NASA Astrophysics Data System (ADS)

Chernonozhkin, Stepan M.; Weyrauch, Mona; Goderis, Steven; Oeser, Martin; McKibbin, Seann J.; Horn, Ingo; Hecht, Lutz; Weyer, Stefan; Claeys, Philippe; Vanhaecke, Frank

2017-11-01

In this work, a femtosecond laser ablation (LA) system coupled to a multi-collector inductively coupled plasma-mass spectrometer (fs-LA-MC-ICP-MS) was used to obtain laterally resolved (30-80 μm), high-precision combined Ni and Fe stable isotope ratio data for a variety of mineral phases (olivine, kamacite, taenite, schreibersite and troilite) composing main group pallasites (PMG) and iron meteorites. The stable isotopic signatures of Fe and Ni at the mineral scale, in combination with the factors governing the kinetic or equilibrium isotope fractionation processes, are used to interpret the thermal histories of small differentiated asteroidal bodies. As Fe isotopic zoning is only barely resolvable within the internal precision level of the isotope ratio measurements within a single olivine in Esquel PMG, the isotopically lighter olivine core relative to the rim (Δ56/54Ferim-core = 0.059‰) suggests that the olivines were largely thermally equilibrated. The observed hint of an isotopic and concentration gradient for Fe of crudely similar width is interpreted here to reflect Fe loss from olivine in the process of partial reduction of the olivine rim. The ranges of the determined Fe and Ni isotopic signatures of troilite (δ56/54Fe of -0.66 to -0.09‰) and schreibersite (δ56/54Fe of -0.48 to -0.09‰, and δ62/60Ni of -0.64 to +0.29‰) may result from thermal equilibration. Schreibersite and troilite likely remained in equilibrium with their enclosing metal to temperatures significantly below their point of crystallization. The Ni isotopic signatures of bulk metal and schreibersite correlate negatively, with isotopically lighter Ni in the metal of PMGs and isotopically heavier Ni in the metal of the iron meteorites analyzed. As such, the light Ni isotopic signatures previously observed in PMG metal relative to chondrites may not result from heterogeneity in the Solar Nebula, but rather reflect fractionation in the metal-schreibersite system. Comparison between the isotope ratio profiles of Fe and Ni determined across kamacite-taenite interfaces (Δ56/54Fekam-tae = -0.51 to -0.69‰ and Δ62/60Nikam-tae = +1.59 to +2.50‰) and theoretical taenite sub-solidus diffusive isotopic zoning broadly constrain the cooling rates of Esquel, CMS 04071 PMGs and Udei Station IAB to between ∼25 and 500 °C/Myr.

Isotopic Exchange of Deuterium Between Hydrogen and Water in Vapor Phase. Report No. 56; INTERCAMBIO ISOTOPICO DE DEUTERIO ENTRE EL HIDROGENO Y EL AGUA EN FASE VAPOR. INFORME NO. 56

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

Baran, W.J.; Cretella, R.F.

1961-01-01

The design is described of a device for the measurement of catalytic activities of the isotopic exchange reaction, H/sub 2/O (v) + HD in equilibrium HDO (v) + H/sub 2/, and to determine experimentally the kinetics for the interpretation of the results for the optimum conditions for the reaction. (tr- auth)

A new method of tree xylem water extraction for isotopic analysis

NASA Astrophysics Data System (ADS)

Gierke, C.; Newton, B. T.

2011-12-01

The Sacramento Mountain Watershed Study in the southern Sacramento Mountains of New Mexico is designed to assess the forest restoration technique of tree thinning in mountain watersheds as an effective method of increasing local and regional groundwater recharge. The project is using a soil water balance approach to quantify the partitioning of local precipitation within this watershed before and after thinning trees. Understanding what sources trees extract their water from (e.g. shallow groundwater, unsaturated fractured bedrock, and soils) is difficult due to a complex hydrologic system and heterogeneous distribution of soil thicknesses. However, in order to accurately quantify the soil water balance and to assess how thinning trees will affect this water balance, it is important determine the sources from which trees extract their water. We plan to use oxygen and hydrogen stable isotopic analysis of various end member waters to identify these different sources. We are in the process of developing a new method of determining the isotopic composition of tree water that has several advantages over conventional methods. Within the tree there is the xylem which transports water from the roots to the leaves and the phloem which transports starches and sugars in a water media throughout the tree. Previous studies have shown that the isotopic composition of xylem water accurately reflects that of source water, while phloem water has undergone isotopic fractionation during photosynthesis and metabolism. The distillation of water from twigs, which is often used to extract tree water for isotopic analysis, is very labor intensive. Other disadvantages to distillation methods include possible fractionation due to phase changes and the possible extraction of fractionated phloem waters. Employing a new mixing method, the composition of the twig water (TW) can be determined by putting twigs of unknown isotopic water composition into waters of known compositions or initial waters (IW), allowing diffusive processes to proceed to equilibrium, measuring the composition of the resulting mixture or final water (FW) then, solving a simple mixing equation. To evaluate this method, we collected several twig samples from Douglas Firs in the Sacramento Mountains. Twig water was prepared for isotopic analysis both by cryogenic distillation and the mixing method. Soil in close proximity to these trees was also sampled and water was extracted by cryogenic distillation. Preliminary results show that the isotopic composition of distilled twig water and soil waters plot to the right of the local meteoric water line (LMWL) suggesting that trees are extracting shallow evaporated soil water. Twig water obtained from the mixing method plot near the LMWL within the range expected for local snow melt, suggesting a possibly deeper non-evaporated source. In general, distillation values are approximately 4% heavier with respect to delta 18O than waters obtained from the mixing method. It is possible that this difference is due to the contribution of the fractionated water of the twig phloem that is released during the distillation process. This difference is quite significant and can lead to very different interpretations. These results are being addressed with additional experiments.

Carbon and oxygen isotopic disequilibrium during calcification of Globigerina bulloides in the Southern ocean

NASA Astrophysics Data System (ADS)

K, P.; Ghosh, P.; N, A.

2015-12-01

Oxygen and carbon isotopes in planktonic foraminifera Globigerina bulloides recovered from the water column of 0-1000 m depth across the meridional transect i.e. 10°N to 53°S of Indian ocean were compared with the available data from the core-top samples across the same transect. We also recorded in situ temperatures of the water column based on probe (CTD) profiles. The δ18O and δ13C values measured in the core top samples matches with the tow results. The equilibrium δ18O of calcite calculated from known temperature and δ18O of water column allowed us to compare the observed δ18O of formaminieral shell with the expected equilibrium values. Our comparison of carbonate composition in the samples between 10°N till 40°S showed excellent match with the expected equilibrium δ18O values established from the water collected at depth range of ~75-200m, however beyond 40°S the disequilibrium was pronounced with heavier δ18O (enriched by ~1.5‰) recorded in the carbonate as compared with the expected equilibrium δ18O values established from water. This observation was further verified with δ13C measurement of shell carbonates comparing with the equilibrium δ13C of calcite calculated with known temperature and δ13C of dissolved inorganic carbon in the water column. The δ13C of the shell carbonate was found heavier as compared to the expected equilibrium δ13C. Both δ18O and δ13C showed simultaneous enrichment signature in the region beyond 40°S suggesting role of processes such as leaching along with dissolution of shell carbonate in a relatively acidic condition.

Non-destructive in-situ method and apparatus for determining radionuclide depth in media

DOEpatents

Xu, X. George; Naessens, Edward P.

2003-01-01

A non-destructive method and apparatus which is based on in-situ gamma spectroscopy is used to determine the depth of radiological contamination in media such as concrete. An algorithm, Gamma Penetration Depth Unfolding Algorithm (GPDUA), uses point kernel techniques to predict the depth of contamination based on the results of uncollided peak information from the in-situ gamma spectroscopy. The invention is better, faster, safer, and/cheaper than the current practice in decontamination and decommissioning of facilities that are slow, rough and unsafe. The invention uses a priori knowledge of the contaminant source distribution. The applicable radiological contaminants of interest are any isotopes that emit two or more gamma rays per disintegration or isotopes that emit a single gamma ray but have gamma-emitting progeny in secular equilibrium with its parent (e.g., .sup.60 Co, .sup.235 U, and .sup.137 Cs to name a few). The predicted depths from the GPDUA algorithm using Monte Carlo N-Particle Transport Code (MCNP) simulations and laboratory experiments using .sup.60 Co have consistently produced predicted depths within 20% of the actual or known depth.

Neodymium and strontium isotopic dating of diagenesis and low-grade metamorphism of argillaceous sediments

NASA Astrophysics Data System (ADS)

Schaltegger, Urs; Stille, Peter; Rais, Naoual; Piqué, Alain; Clauer, Norbert

1994-03-01

The behaviour of the Rb-Sr and Sm-Nd isotopic systems with increasing degree of Hercynian metamorphic overprint was studied along a transect in Cambrian shales of northwestern Morocco. Clay fractions of < 0.2 to 2-6 μm size from five samples were investigated, representing a range from nonmetamorphic to epizonal metamorphic conditions. The samples were washed in cold l N HC1 prior to digestion to separate soluble/exchangeable Rb, Sr, Sm, and Nd from amounts of these elements fixed in the crystallographic sites of the minerals and to analyze both components separately. The results reveal that the Rb-Sr isotopic system is dominated by Sr hosted by clay mineral phases (both detrital and authigenic illite and chlorite) and carbonate-hosted soluble Sr. Isotopic homogenization of Sr occurred during Hercynian metamorphism, yielding ages between 309 and 349 Ma. The Sm-Nd isotopic system, on the other hand, is dominated by cogenetic apatite and Fe oxide/ hydroxide, both having high contents of leachable REEs. The leachates yield a Sm-Nd isochron age of 523 ± 72 Ma, indicating diagenetic equilibrium between apatite and Fe-oxide/hydroxide. Fine-grained clay fractions of < 0.2 μm size plot onto this reference line, suggesting isotopic equilibrium with the leachates. Size fractions > 0.2 μm show inheritance of a detrital Nd component. The study demonstrates that the diagenesis of the investigated argillaceous sediments can be dated by the Sm-Nd chronometer in authigenic cement phases. The isotopic system of these minerals (apatite, Fe hydroxide/oxide) was homogenized during authigenic mineral growth in a sediment that was flushed by diagenetic fluids and had abundant primary or secondary interconnected pore space. The Hercynian metamorphic overprint caused partial isotopic rehomogenization of the adsorbed and clay-hosted portion of the Sr as well as of the carbonate-hosted Sr. The Sm-Nd system in the cement phases survived this metamorphism. This results in decoupling of the two isotopic systems and allows the dating of diagenesis on the one hand (Sm-Nd) and metamorphism on the other hand (Rb-Sr).

Pressure-dependent boron isotopic fractionation observed by column chromatography

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Predictions and Verification of an Isotope Marine Boundary Layer Model

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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.

A stochastic modeling of isotope exchange reactions in glutamine synthetase

NASA Astrophysics Data System (ADS)

Kazmiruk, N. V.; Boronovskiy, S. E.; Nartsissov, Ya R.

2017-11-01

The model presented in this work allows simulation of isotopic exchange reactions at chemical equilibrium catalyzed by a glutamine synthetase. To simulate the functioning of the enzyme the algorithm based on the stochastic approach was applied. The dependence of exchange rates for 14C and 32P on metabolite concentration was estimated. The simulation results confirmed the hypothesis of the ascertained validity for preferred order random binding mechanism. Corresponding values of K0.5 were also obtained.

Isotopic composition of water in a deep unsaturated zone beside a radioactive-waste disposal area near Beatty, Nevada

USGS Publications Warehouse

Stonestrom, David A.; Prudic, David E.; Striegl, Robert G.; Morganwalp, David W.; Buxton, Herbert T.

1999-01-01

The isotopic composition of water in deep unsaturated zones is of interest because it provides information relevant to hydrologic processes and contaminant migration. Profiles of oxygen-18 (18O), deuterium (D), and tritium (3H) from a 110-meter deep unsaturated zone, together with data on the isotopic composition of ground water and modern-day precipitation, are interpreted in the context of water-content, water-potential, and pore-gas profiles. At depths greater than about three meters, water vapor and liquid water are in approximate equilibrium with respect to D and 18O. The vapor-phase concentrations of D and 18O have remained stable through repeated samplings. Vapor-phase 3H concentrations have generally increased with time, requiring synchronous sampling of liquid and vapor to assess equilibrium. Below 30 meters, concentrations of D and 18O in pore water become approximately equal to the composition of ground water, which is isotopically lighter than modern precipitation and has a carbon-14 (14C) concentration of about 26 percent modern carbon. These data indicate that net gradients driving fluxes of water, gas, and heat are directed upwards for undisturbed conditions at the Amargosa Desert Research Site (ADRS). Superimposed on the upward-directed flow field, tritium is migrating away from waste in response to gradients in tritium concentrations.

Oxygen and hydrogen isotopic composition of the fluid during formation of anthophyllite metaultramafic rocks in the Sysert metamorphic complex, central Urals

NASA Astrophysics Data System (ADS)

Murzin, V. V.

2014-12-01

The oxygen (δ18O) and hydrogen (δD) isotopic composition of H2O-bearing minerals was studied for the ore-bearing amphibole metaultramafic rocks, which are the products of the early regional (435 ± 44 Ma) and late local (260 ± 6 Ma) silicic metasomatose in the Sysert metamorphic complex. The gold-sulfide mineralization of the Karas'evogorskoe deposit and anthophyllite-asbestos bodies of the Tersut deposit are related to the regional and local metasomatose combined with plagiogranitization and potassium granitization, respectively. The H2O-bearing minerals of metasomatites (anthophyllite, tremolite, talc) of the Karas'evogorskoe and Tersut deposits are characterized by heavier δ18O (9.8 to 12.2 and 7.6 to 9.4‰, respectively) and lighter ·D (87 to -91 and -56 to -67‰, respectively) values. The calculated isotopic composition of the fluid in equilibrium with these minerals indicates a heterogeneous source of water for the fluids related to the formation of metasomatites and the metamorphic origin of fluids. During the regional metasomatose, this fluid was a result of equilibrium of the deep fluid with volcanosedimentary rocks enriched in the heavy oxygen isotope. At the local metasomatose, the metamorphic fluid was formed by interaction of magmatic water produced by potassium granitization with ultramafic rocks.

Towards Non-Equilibrium Dynamics with Trapped Ions

NASA Astrophysics Data System (ADS)

Silbert, Ariel; Jubin, Sierra; Doret, Charlie

2016-05-01

Atomic systems are superbly suited to the study of non-equilibrium dynamics. These systems' exquisite isolation from environmental perturbations leads to long relaxation times that enable exploration of far-from-equilibrium phenomena. One example of particular relevance to experiments in trapped ion quantum information processing, metrology, and precision spectroscopy is the approach to thermal equilibrium of sympathetically cooled linear ion chains. Suitable manipulation of experimental parameters permits exploration of the quantum-to-classical crossover between ballistic transport and diffusive, Fourier's Law conduction, a topic of interest not only to the trapped ion community but also for the development of microelectronic devices and other nanoscale structures. We present progress towards trapping chains of multiple co-trapped calcium isotopes geared towards measuring thermal equilibration and discuss plans for future experiments in non-equilibrium statistical mechanics. This work is supported by Cottrell College Science Award from the Research Corporation for Science Advancement and by Williams College.

Using Isotopic Age of Water as a Constraint on Model Identification at a Critical Zone Observatory

NASA Astrophysics Data System (ADS)

Duffy, C.; Thomas, E.; Bhatt, G.; George, H.; Boyer, E. W.; Sullivan, P. L.

2016-12-01

This paper presents an ecohydrologic model constrained by comprehensive space and time observations of water and stable isotopes of oxygen and hydrogen for an upland catchment, the Susquehanna/Shale Hills Critical Zone Observatory (SSH_CZO). The paper first develops the theoretical basis for simulation of flow, isotope ratios and "age" as water moves through the canopy, to the unsaturated and saturated zones and finally to an intermittent stream. The model formulation demonstrates that the residence time and age of environmental tracers can be directly simulated without knowledge of the form of the underlying residence time distribution function and without the addition of any new physical parameters. The model is used to explore the observed rapid attenuation of event and seasonal isotopic ratios in precipitation over the depth of the soil zone and the impact of decreasing hydraulic conductivity with depth on the dynamics of streamflow and stream isotope ratios. The results suggest the importance of mobile macropore flow on recharge to groundwater during the non-growing cold-wet season. The soil matrix is also recharged during this season with a cold-season isotope signature. During the growing-dry season, root uptake and evaporation from the soil matrix along with a declining water table provides the main source of water for plants and determines the growing season signature. Flow path changes during storm events and transient overland flow is inferred by comparing the frequency distribution of groundwater and stream isotope histories with model results. Model uncertainty is evaluated for conditions of matrix-macropore partitioning and heterogeneous variations in conductivity with depth. The paper concludes by comparing the fully dynamical model with the simplified mixing model form in dynamic equilibrium. The comparison illustrates the importance of system memory on the time scales for flow and mixing processes and the limitations of the dynamic equilibrium assumption on estimated age and residence time.

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

PubMed

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

2015-05-26

The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

Kimball, Justine; Eagle, Robert; Dunbar, Robert

Here, deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C 18O 16O 2 inmore » carbonate minerals, analyzed in CO 2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ 47 values. We analyzed Δ 47 in live-collected aragonitic scleractinian ( Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ 47 values were compared to in situ temperatures, and the relationship between Δ 47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ 47–temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ 47–temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO 2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect high-Mg and aragonite crystals attaining nominal mineral equilibrium clumped isotope signatures due to conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological “vital effect” influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological vital effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO 2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ 47 is a subject that warrants further investigation.« less

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

DOE PAGES

Kimball, Justine; Eagle, Robert; Dunbar, Robert

2016-12-12

Here, deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C 18O 16O 2 inmore » carbonate minerals, analyzed in CO 2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ 47 values. We analyzed Δ 47 in live-collected aragonitic scleractinian ( Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ 47 values were compared to in situ temperatures, and the relationship between Δ 47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ 47–temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ 47–temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO 2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect high-Mg and aragonite crystals attaining nominal mineral equilibrium clumped isotope signatures due to conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological “vital effect” influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological vital effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO 2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ 47 is a subject that warrants further investigation.« less

Oxygen and carbon isotope disequilibria in Galapagos corals: isotopic thermometry and calcification physiology

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

McConnaughey, T.A.

1986-01-01

Biological carbonate skeletons are built largely from carbon dioxide, which reacts to form carbonate ion within thin extracellular solutions. The light isotopes of carbon and oxygen react faster than the heavy isotopes, depleting the resulting carbonate ions in /sup 13/C and /sup 18/O. Calcium carbonate precipitation occurs sufficiently fast that the skeleton remains out of isotopic equilibrium with surrounding fluids. This explanation for isotopic disequilibrium in biological carbonates was partially simulated in vitro, producing results similar to those seen in non-photosynthetic corals. Photosynthetic corals have higher /sup 13/C//sup 12/C ratios due to the preferential removal of /sup 12/C (as organicmore » carbon) from the reservoir of dissolved inorganic carbon. The oxygen isotopic variations in corals can be used to reconstruct past sea surface temperatures to an accuracy of about 0.5/sup 0/C. The carbon isotopic content of photosynthetic corals provides an indication of cloudiness. Using isotopic data from Galapagos corals, it was possible to construct proxy histories of the El Nino phenomenon. The physiology of skeletogenesis appears to be surprisingly similar in calcium carbonate, calcium phosphate, and silica precipitating systems.« less

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

USGS Publications Warehouse

Bullen, Thomas D.; Baskaran, Mark

2011-01-01

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

Oxygen and carbon isotopic growth record in a reef coral from the florida keys and a deep-sea coral from blake plateau

USGS Publications Warehouse

Emiliani, C.; Harold, Hudson J.; Shinn, E.A.; George, R.Y.

1978-01-01

Carbon and oxygen isotope analysis through a 30-year (1944 to 1974) growth of Montastrea annularis from Hen and Chickens Reef (Florida Keys) shows a strong yearly variation in the abundances of both carbon-13 and oxygen-18 and a broad inverse relationship between the two isotopes. Normal annual dense bands are formed during the summer and are characterized by heavy carbon and light oxygen. "Stress bands" are formed during particularly severe winters and are characterized by heavy carbon and heavy oxygen. The isotopic effect of Zooxanthellae metabolism dominates the temperature effect on the oxygen-18/oxygen-16 ratio. The isotopic results on the deep-sea solitary coral Bathypsammia tintinnabulum, where Zooxanthellae are nonexistent, indicates that the abundance of the heavy isotopes carbon-13 and oxygen-18 is inversely related to the growth rate, with both carbon and oxygen approaching equilibrium values with increasing skeletal age.

Oxygen isotope fractionation between analcime and water - An experimental study

NASA Technical Reports Server (NTRS)

Karlsson, Haraldur R.; Clayton, Robert N.

1990-01-01

The oxygen isotope fractionation between analcime and water is studied to test the feasibility of using zeolites as low-temperature thermometers. The fractionation of oxygen isotopes between natural analcime and water is determined at 300, 350, and 400 C, and at fluid pressures ranging from 1.5 to 5.0 kbar. Also, isotope ratios for the analcime framework, the channel water, and bulk water are obtained. The results suggest that the channel water is depleted in O-18 relative to bulk water by a constant value of about 5 percent, nearly independent of temperature. The analcime-water fractionation curve is presented, showing that the exchange has little effect on grain morphology and does not involve recrystallization. The exchange is faster than any other observed for a silicate. The exchange rates suggest that zeolites in active high-temperature geothermal areas are in oxygen isotopic equilibrium with ambient fluids. It is concluded that calibrated zeolites may be excellent low-temperature oxygen isotope geothermometers.

Modeling tritium transport through a deep unsaturated zone in an arid environment

USGS Publications Warehouse

Mayers, C.J.; Andraski, Brian J.; Cooper, C.A.; Wheatcraft, S.W.; Stonestrom, David A.; Michel, R.L.

2005-01-01

Understanding transport of tritium (3H) in unsaturated zones is critical to evaluating options for waste isolation. Tritium typically is a large component of low-level radioactive waste (LLRW). Studies at the U.S. Geological Survey's Amargosa Desert Research Site (ADRS) in Nevada investigate 3H transport from a closed LLRW facility. Two boreholes are 100 and 160 m from the nearest waste trench and extend to the water table at 110 m. Soil-water vapor samples from the deep boreholes show elevated levels of 3H at all depths. The objectives of this study were to (i) test source thermal and gas-advection mechanisms driving 3H transport and (ii) evaluate model sensitivity to these mechanisms and to selected physical and hydraulic properties including porosity, tortuosity, and anisotropy. A two-dimensional numerical model incorporated a non-isothermal, heterogeneous domain of the unsaturated zone and instantaneous isotopic equilibrium. The TOUGH2 code was used; however, it required modification to account for temperature dependence of both the Henry's law equilibrium constant and isotopic fractionation with respect to tritiated water. Increases in source temperature, pressure, and porosity enhanced 3H migration, but failed to match measured 3H distributions. All anisotropic simulations with a source pressure component resembled, in shape, the upper portion of the 3H distribution of the nearest borehole. Isotopic equilibrium limited migration of 3H, while effects of radioactive decay were negligible. A 500 Pa pressure increase above ambient pressure in conjunction with a high degree of anisotropy (1:100) was necessary for simulated 3H transport to reach the nearest borehole.

Re-Os isotopic systematics in chromitites from the Stillwater Complex, Montana, USA

NASA Astrophysics Data System (ADS)

Marcantonio, Franco; Zindler, Alan; Reisberg, Laurie; Mathez, E. A.

1993-08-01

New Re-Os isotopic data on chromitites of the Stillwater Complex demonstrate isotopic equilibrium between cumulate chromite and whole rock. Initial osmium isotopic ratios for the chromitites, chosen for their freshness, are consistent with derivation from a mantle-derived magma that suffered little or no interaction with the continental crust prior to crystallization. Molybdenite, separated from a sample of the G-chromitite, yields a Re-Os age of 2740 Ma, indistinguishable from the age of the intrusion. The presence of molybdenite documents rhenium, and probably osmium, mobilization by hydrothermal fluids that permeated the intrusion shortly after crystallization. Initial osmium isotopic variability observed in chromitites and other rocks from the Stillwater Complex could result from interaction with these fluids. In this context, there is no compelling reason to call on assimilation of crust by mantle-derived magma to explain the osmium or neodymium isotopic variability. Although osmium isotopic systematics have been affected by hydrothermal processes, Re-Os results demonstrate that more than 95 percent of the osmium, and by inference other PGEs in the Stillwater Complex, derive from the mantle.

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

NASA Astrophysics Data System (ADS)

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

2003-12-01

In mature oceanic lithosphere, formed at mid-ocean ridges, residual mantle peridotites and associated magmatic crust are, in principle, linked by a cogenetic relationship, because the times of asthenospheric mantle melting and magmatic crust production are assumed to be roughly coheval. This implies that oceanic peridotites and associated magmatic rocks should have similar isotopic compositions. Few isotope studies have been devoted to test this assumption. At mid-ocean ridges, similar Nd isotopic compositions in basalts and abyssal peridotites have been found by Snow et al. (1994), thus indicating that oceanic peridotites are indeed residues of MORB melting. By contrast, Salters and Dick (2002) have documented Nd isotope differences between abyssal peridotites and associated basalts, with peridotites showing higher 143Nd/144Nd values, and they concluded that an enriched pyroxenitic source component is required to explain the low end of the 143Nd/144Nd variation of the basalts. Here we present Sm/Nd isotope data on ophiolitic mantle peridotites and intruded gabbroic rocks from Mt.Maggiore (Corsica, France), interpreted as lithosphere remnants of the Jurassic Ligurian Tethys ocean. The peridotites are residual after low-degree (<10%) fractional melting. In places, spinel peridotites grade to plagioclase-rich impregnated peridotites. Clinopyroxene separates from both spinel- and plagioclase- peridotites display high 147Sm/144Nd (0.49-0.59) and 143Nd/144Nd (0.513367-0.513551) ratios, consistent with their depleted signature. The associated gabbros have Nd isotopic compositions typical of MORB (143Nd/144Nd = 0.51312-0.51314). Sm/Nd data on plag, whole rock and cpx from an olivine gabbro define an internal isochron with an age of 162 +/- 10 Ma, and an initial epsilon Nd value (9.0) indicating a MORB-type source. In the Sm-Nd isochron diagram, the peridotite data also conform to the above linear array, their initial (160 Ma) epsilon Nd values varying in the range 7.6-8.9. Sm/Nd isotopic compositions of the peridotites are therefore consistent with a Jurassic age of melting and melt impregnation, and point to isotopic compositional similarities between depleted peridotites and associated magmatic rocks. In a regional geodynamic context, Sm/Nd isotope data for the Mt.Maggiore gabbro-peridotite association represent the first record of the attainment of a mature oceanic stage of the Ligurian Tethys ocean. Also, the data presented provide striking evidence of the existence of isotopic equilibrium between melts and their mantle residue. References Snow et al. (1994), Nature 371, 57-60. Salters and Dick (2002), Nature 418,68-72.

Oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system up to 0.7 mol/kg ionic strength at 25 °C

USGS Publications Warehouse

Kim, Sang-Tae; Gebbinck, Christa Klein; Mucci, Alfonso; Coplen, Tyler B.

2014-01-01

To investigate the oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system, witherite (BaCO3) was precipitated quasi-instantaneously and quantitatively from Na-Cl-Ba-CO2 solutions of seawater-like ionic strength (I = 0.7 mol/kg) at two pH values (~7.9 and ~10.6) at 25 °C. The oxygen isotope composition of the witherite and the dissolved inorganic carbon speciation in the starting solution were used to estimate the oxygen isotope fractionations between HCO3¯ and H2O as well as between CO3 2 and H2O. Given the analytical error on the oxygen isotope composition of the witherite and uncertainties of the parent solution pH and speciation, oxygen isotope fractionation between NaHCO3° and HCO3¯, as well as between NaCO3¯ and CO3 2, is negligible under the experimental conditions investigated. The influence of dissolved NaCl concentration on the oxygen isotope fractionation in the aragonite-CO2-H2O-NaCl system also was investigated at 25 °C. Aragonite was precipitated from Na-Cl-Ca-Mg-(B)-CO2 solutions of seawater-like ionic strength using passive CO2 degassing or constant addition methods. Based upon our new experimental observations and published experimental data from lower ionic strength solutions by Kim et al. (2007b), the equilibrium aragonite-water oxygen isotope fractionation factor is independent of the ionic strength of the parent solution up to 0.7 mol/kg. Hence, our study also suggests that the aragonite precipitation mechanism is not affected by the presence of sodium and chloride ions in the parent solution over the range of concentrations investigated.

Analysis of positional isotope exchange in ATP by cleavage of the beta P-O gamma P bond. Demonstration of negligible positional isotope exchange by myosin.

PubMed

Dale, M P; Hackney, D D

1987-12-15

A method for analysis of positional isotope exchange (PIX) during ATP in equilibrium with HOH oxygen exchange is presented that uses a two-step degradation of ATP resulting in cleavage of the beta P-O gamma P bond. This cleavage yields Pi derived from the gamma-phosphoryl of ATP that contains all four of the gamma oxygens. Both PIX between the beta,gamma-bridge and beta-nonbridge positions and washout of the gamma-nonbridge oxygens can be simultaneously followed by using ATP labeled with 17O at the beta-nonbridge positions and 18O at the beta,gamma-bridge and gamma-nonbridge positions. Application of this method to ATP in equilibrium with HOH exchange during single turnovers of myosin indicates that the bulk of the ATP undergoes rapid washout of gamma-nonbridge oxygens in the virtual absence of PIX. At 25 degrees C with subfragment 1 the scrambling rate is at the limit of detectability of approximately 0.001 s-1, which is 50-fold slower than the steady-state rate. This corresponds to a probability of scrambling for the beta-oxygens of bound ADP of 1 in 10,000 for each cycle of reversible hydrolysis of bound ATP. A fraction of the ATP, however, does not undergo rapid washout. With myosin and stoichiometric ATP at 0 degrees C, this fraction corresponds to 10% of the ATP remaining at 36 s, or 2% of the initial ATP, and an equivalent level of ATP is found that does not bind irreversibly to myosin in a cold chase experiment. A significant level of apparent PIX is observed with subfragment 1 in the fraction that resists washout, and this apparent PIX is shown to be due to contaminant adenylate kinase activity. This apparent PIX due to adenylate kinase provides a possible explanation for the PIX observed by Geeves et al. [Geeves, M. A., Webb, M. R., Midelfort, C. F., & Trentham, D. R. (1980) Biochemistry 19, 4748-4754] with subfragment 1.

Calcium and Oxygen Isotopic Composition of Calcium Carbonates

NASA Astrophysics Data System (ADS)

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

2016-04-01

Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40Ca. On the other hand, 40Ca may desorb more easily, especially if the bond strength is lower as in the case of aragonite. For kinetic oxygen isotopic fractionation, the faster deprotonation of HC16O3- and the faster incorporation of C16O32- at the surfaces causes a smaller enrichment of 18O in all three polymorphs, which will be preserved at higher precipitation rates. In consequence to the different behavior of calcium and oxygen isotopes, they can be useful for multiproxy applications. Thereby calcium isotopes can be used to identify kinetic effects, especially if both aragonite and calcite, can be analyzed in one sample. Oxygen isotopes are more strongly related to temperature. [1]A. Niedermayr, S.J. Köhler and M. Dietzel (2013), Chemical Geology, 340, 105-120.

Isotopic Abundances as Tracers of the Processes of Lunar Formation

NASA Astrophysics Data System (ADS)

Pahlevan, K.

2011-12-01

Ever since Apollo, isotopic abundances have been used as tracers to study lunar formation, in particular, to study the sources of the lunar material. In the last decade, however, a number of isotopic similarities have been observed between the lunar samples and the Earth's mantle such that these two reservoirs are now known to be indistinguishable from one another to high precision for a variety of isotopic tracers. This occurs against the backdrop of a Solar System that exhibits widespread heterogeneity with respect to these tracers, a situation that strongly argues that the source of the lunar material is the silicate Earth. To reconcile this observation with the fact that the Moon is thought to result from the collision of two isotopically distinct planetary bodies, a scenario has emerged in which the material from the Moon-forming impactor and the proto-Earth are homogenized in the aftermath of the giant impact. This takes place via turbulent mixing in the time after the giant impact but before lunar accretion while the Earth-Moon system exists in the form of a continuous, high-temperature fluid. Importantly, this high-temperature phase of the evolution occurs in the presence of at least two phases (liquid + vapor) making possible chemical and isotopic fractionation. While equilibrium isotopic fractionation tends to zero at high temperatures, and the post giant impact environment experiences some of the highest temperatures encountered in the Earth sciences, there are several factors that nevertheless make equilibrium isotope effects important probes of this early evolution. (1) Because the vaporization of silicates involves decomposition reactions, the bonding environment for elements in the liquid is often very different from that in the vapor. This difference makes the magnitude of isotopic fractionation intrinsically large, even at the relevant temperatures. (2) Since the isotopic composition of a silicate liquid and co-existing vapor are distinctly different, if the Moon preferentially forms from the liquid or vapor relative to the Earth, mass-dependent isotopic differences at the planetary scale may arise. The large density contrast between liquid and vapor makes phase separation possible. (3) The precision with which planetary isotopic compositions can be determined has increased such that measurements are sensitive to even small degrees of high-temperature phase separation. Using thermodynamic models of silicate liquids to determine the partial vaporization behavior of the major elements, we will present calculations of isotopic fractionation due to liquid-vapor separation for the elements iron, magnesium, silicon, and oxygen. Improvements in analytical precision have largely settled the question of the source of the lunar material - the Earth's mantle - and isotopic measurements are now beginning to yield insight into the high-temperatures processes operating during lunar formation.

Fractionation of Cu and Mo isotopes caused by vapor-liquid partitioning, evidence from the Dahutang W-Cu-Mo ore field

NASA Astrophysics Data System (ADS)

Yao, Junming; Mathur, Ryan; Sun, Weidong; Song, Weile; Chen, Huayong; Mutti, Laurence; Xiang, Xinkui; Luo, Xiaohong

2016-05-01

The study presents δ65Cu and δ97Mo isotope values from cogenetic chalcopyrite and molybdenite found in veins and breccias of the Dahutang W-Cu-Mo ore field in China. The samples span a 3-4 km range. Both isotopes show a significant degree of fractionation. Cu isotope values in the chalcopyrite range from -0.31‰ to +1.48‰, and Mo isotope values in the molybdenite range from -0.03‰ to +1.06‰. For the cogenetic sulfide veined samples, a negative slope relationship exists between δ65Cu and δ97Mo values, which suggest a similar fluid history. Rayleigh distillation models the vein samples' change in isotope values. The breccia samples do not fall on the trend, thus indicating a different source mineralization event. Measured fluid inclusion and δD and δ18O data from cogenetic quartz indicate changes in temperature, and mixing of fluids do not appear to cause the isotopic shifts measure. Related equilibrium processes associated with the partitioning of metal between the vapor-fluid in the hydrothermal system could be the probable cause for the relationship seen between the two isotope systems.

The Sima de los Huesos hominids date to beyond U/Th equilibrium (>350 kyr) and perhaps to 400-500 kyr: New radiometric dates

USGS Publications Warehouse

Bischoff, J.L.; Shamp, D.D.; Aramburu, Arantza; Arsuaga, J.L.; Carbonell, E.; Bermudez de Castro, Jose Maria

2003-01-01

The Sima de los Huesos site of the Atapuerca complex near Burgos, Spain contains the skeletal remains of at least 28 individuals in a mud breccia underlying an accumulation of the Middle Pleistocene cave bear (U. deningeri). Earlier dating estimates of 200 to 320 kyr were based on U-series and ESR methods applied to bones, made inaccurate by unquantifiable uranium cycling. We report here on a new discovery within the Sima de los Huesos of human bones stratigraphically underlying an in situ speleothem. U-series analyses of the speleothem shows the lower part to be at isotopic U/Th equilibrium, translating to a firm lower limit of 350 kyr for the SH hominids. Finite dates on the upper part suggest a speleothem growth rate of c. 1 cm/32 kyr. This rate, along with paleontological constraints, place the likely age of the hominids in the interval of 400 to 600 kyr. ?? 2002 Elsevier Science Ltd. All rights reserved.

Diffusion model validation and interpretation of stable isotopes in river and lake ice

USGS Publications Warehouse

Ferrick, M.G.; Calkins, D.J.; Perron, N.M.; Cragin, J.H.; Kendall, C.

2002-01-01

The stable isotope stratigraphy of river- and lake-ice archives winter hydroclimatic conditions, and can potentially be used to identify changing water sources or to provide important insights into ice formation processes and growth rates. However, accurate interpretations rely on known isotopic fractionation during ice growth. A one-dimensional diffusion model of the liquid boundary layer adjacent to an advancing solid interface, originally developed to simulate solute rejection by growing crystals, has been used without verification to describe non-equilibrium fractionation during congelation ice growth. Results are not in agreement, suggesting the presence of important uncertainties. In this paper we seek validation of the diffusion model for this application using large-scale laboratory experiments with controlled freezing rates and frequent sampling. We obtained consistent, almost constant, isotopic boundary layer thicknesses over a representative range of ice growth rates on both quiescent and well-mixed water. With the 18O boundary layer thickness from the laboratory, the model successfully quantified reduced river-ice growth rates relative to those of a nearby lake. These results were more representative and easier to obtain than those of a conventional thermal ice-growth model. This diffusion model validation and boundary layer thickness determination provide a powerful tool for interpreting the stable isotope stratigraphy of floating ice. The laboratory experiment also replicated successive fractionation events in response to a freeze-thaw-refreeze cycle, providing a mechanism for apparent ice fractionation that exceeds equilibrium. Analysis of the composition of snow ice and frazil ice in river and lake cores indicated surprising similarities between these ice forms. Published in 2002 by John Wiley & Sons, Ltd.

Discriminating trpzip2 and trpzip4 peptides’ folding landscape using the two-dimensional infrared spectroscopy: A simulation study

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

Wu, Tianmin; Zhang, Ruiting; Li, Huanhuan

2014-02-07

We analyzed, based on the theoretical spectroscopic modeling, how the differences in the folding landscapes of two β-hairpin peptides trpzip2 and trpzip4 are reflected in their thermal unfolding infrared measurements. The isotope-edited equilibrium FTIR and two dimensional infrared spectra of the two peptides were calculated, using the nonlinear exciton propagation method, at a series of temperatures. The spectra calculations were based on the configuration distributions generated using the GB{sup OBC} implicit solvent MD simulation and the integrated tempering sampling technique. Conformational analysis revealed the different local thermal stabilities for these two peptides, which suggested the different folding landscapes. Our studymore » further suggested that the ellipticities of the isotope peaks in the coherent IR signals are more sensitive to these local stability differences compared with other spectral features such as the peak intensities. Our technique can thus be combined with the relevant experimental measurements to achieve a better understanding of the peptide folding behaviors.« less

Assessing bioavailability of DDT and metabolites in marine sediments using solid-phase microextraction with performance reference compounds.

PubMed

Bao, Lian-Jun; Jia, Fang; Crago, J; Zeng, Eddy Y; Schlenk, D; Gan, Jay

2013-09-01

Solid-phase microextraction (SPME) has often been used to estimate the freely dissolved concentration (Cfree ) of organic contaminants in sediments. A significant limitation in the application of SPME for Cfree measurement is the requirement for attaining equilibrium partition, which is often difficult for strongly hydrophobic compounds such as DDT. A method was developed using SPME with stable isotope-labeled analogues as performance reference compounds (PRCs) to measure Cfree of DDT and metabolites (DDTs) in marine sediments. Six (13) C-labeled or deuterated PRCs were impregnated into polydimethylsiloxane (PDMS) fiber before use. Desorption of PRCs from PDMS fibers and absorption of DDTs from sediment were isotropic in a range of sediments evaluated ex situ under well-mixed conditions. When applied to a historically contaminated marine sediment from a Superfund site, the PRC-SPME method yielded Cfree values identical to those found by using a conventional equilibrium SPME approach (Eq-SPME), whereas the time for mixing was reduced from 9 d to only 9 h. The PRC-SPME method was further evaluated against bioaccumulation of DDTs by Neanthes arenaceodentata in the contaminated sediment with or without amendment of activated carbon or sand. Strong correlations were consistently found between the derived equilibrium concentrations on the fiber and lipid-normalized tissue residues for DDTs in the worms. Results from the present study clearly demonstrated the feasibility of coupling PRCs with SPME sampling to greatly shorten sampling time, thus affording much improved flexibility in the use of SPME for bioavailability evaluation. Copyright © 2013 SETAC.

Assessing Bioavailability of DDT and Metabolites in Marine Sediments using Solid-Phase Microextraction with Performance Reference Compounds

PubMed Central

Bao, Lian-Jun; Jia, Fang; Crago, J.; Zeng, Eddy Y.; Schlenk, D.; Gan, Jay

2014-01-01

Solid-phase microextraction (SPME) has often been used to estimate the freely dissolved concentration (Cfree) of organic contaminants in sediments. A significant limitation in the application of SPME for Cfree measurement is the requirement for attaining equilibrium partition, which is often difficult for strongly hydrophobic compounds such as DDT. A method was developed using SPME with stable isotope-labeled analogues as performance reference compounds (PRCs) to measure Cfree of DDT and metabolites (DDTs) in marine sediments. Six 13C-labeled or deuterated PRCs were impregnated into polydimethylsiloxane (PDMS) fiber before use. Desorption of PRCs from PDMS fibers and absorption of DDTs from sediment were isotropic in a range of sediments evaluated ex situ under well-mixed conditions. When applied to a historically contaminated marine sediment from a Superfund site, the PRC-SPME method yielded Cfree values identical to those found by using a conventional equilibrium SPME approach (Eq-SPME), wherease the time for mixing was reduced from 9 d to only 9 h. The PRC-SPME method was further evaluated against bioaccumulation of DDTs by Neanthes arenaceodentata in the contaminated sediment with or without amendment of activated carbon or sand. Strong correlations were consistently found between the derived equilibrium concentrations on the fiber and lipid-normalized tissue residues for DDTs in the worms. Results from the present study clearly demonstrated the feasibility of coupling PRCs with SPME sampling to greatly shorten sampling time, thus affording much improved flexibility in the use of SPME for bioavailability evaluation. Environ Toxicol Chem 2013;32:1946–1953. PMID:23661411

Position-Specific Hydrogen and Carbon Isotope Fractionations of Light Hydrocarbons by Quantitative NMR

NASA Astrophysics Data System (ADS)

Liu, C.; Mcgovern, G. P.; Horita, J.

2015-12-01

Traditional isotope ratio mass spectrometry methods to measure 2H/1H and 13C/12C ratios of organic molecules only provide average isotopic values of whole molecules. During the measurement process, valuable information of position-specific isotope fractionations (PSIF) between non-equivalent H and C positions is lost, which can provide additional very useful information about the origins and history of organic molecules. Quantitative nuclear magnetic resonance (NMR) spectrometry can measure 2H and 13C PSIF of organic molecules without destruction. The 2H and 13C signals from different positions of a given molecule show up as distinctive peaks in an NMR spectrum, and their peak areas are proportional to the 2H and 13C populations at each position. Moreover, quantitative NMR can be applied to a wide variety of organic molecules. We have been developing quantitative NMR methods to determine 2H and 13C PSIF of light hydrocarbons (propane, butane and pentane), using J-Young and custom-made high-pressure NMR cells. With careful conditioning of the NMR spectrometer (e.g. tuning, shimming) and effective 1H -13C decoupling, precision of ± <10‰ (2H) and ± <1‰ (13C) can be readily attainable after several hours of acquisition. Measurement time depends on the relaxation time of interested nucleus and the total number of scans needed for high signal-to-noise ratios. Our data for commercial, pure hydrocarbon samples showed that 2H PSIF in the hydrocarbons can be larger than 60‰ and that 13C PSIF can be as large as 15‰. Comparison with theoretical calculations indicates that the PSIF patterns of some hydrocarbon samples reflect non-equilibrium processes in their productions.

Clumped Isotope Thermometry Reveals Variations in Soil Carbonate Seasonal Biases Over >4 km of Relief in the Semi-Arid Andes of Central Chile

NASA Astrophysics Data System (ADS)

Burgener, L. K.; Huntington, K. W.; Hoke, G. D.; Schauer, A. J.; Ringham, M. C.; Latorre Hidalgo, C.; Díaz, F.

2015-12-01

The application of carbonate clumped isotope thermometry to soil carbonates has the potential to shed new light on questions regarding terrestrial paleoclimate. In order to better utilize this paleoclimate tool, outstanding questions regarding seasonal biases in soil carbonate formation and the relationship between soil carbonate formation temperatures (T(Δ47)) and surface temperatures must be resolved. We address these questions by comparing C, O, and clumped isotope data from Holocene/modern soil carbonates to modern meteorological data. The data were collected along a 170 km transect with >4 km of relief in central Chile (~30°S). Previous studies have suggested that soil carbonates should record a warm season bias and form in isotopic equilibrium with soil water and soil CO2. We identify two discrete climate zones separated by the local winter snow line (~3200 m). Below this boundary, precipitation falls as rain and soil carbonate T(Δ47) values at depths >40 cm resemble summer soil temperatures; at higher elevations, precipitation falls as snow and T(Δ47) values resemble mean annual soil temperatures. Soil carbonates from the highest sample site (4700 m), which is devoid of vegetation and located near perennial snow fields, yield anomalous δ18O, δ13C, and T(Δ47) values, indicative of kinetic isotope effects that we attribute to cryogenic carbonate formation. Our results suggest that soil carbonates from depths <40 cm are affected by large, high frequency variations in temperature and precipitation, and should not be used as paleotemperature proxies. These findings (1) highlight the role of soil moisture in modulating soil carbonate formation and the resulting T(Δ47) values, (2) underscore the importance of understanding past soil moisture conditions when attempting to reconstruct paleotemperatures using carbonate clumped isotope thermometry, and (3) suggest that soil carbonates from high elevation or high latitude sites may form under non-equilibrium conditions.

Heterogeneous distribution of Zn stable isotopes in mice and applications to medical sciences

NASA Astrophysics Data System (ADS)

Moynier, F.; Fujii, T.; Shaw, A.; Le Borgne, M.

2013-12-01

Zinc is required for the function of more than 300 enzymes involved in many metabolic pathways, and is a vital micronutrient for living organisms. To investigate if Zn isotopes could be used to better understand metal homeostasis, as well as a biomarker for diseases, we assessed the distribution of natural Zn isotopes in various mouse tissues. We found that, with respect to Zn isotopes, most mouse organs are isotopically distinct and that the total range of variation within one mouse encompasses the variations observed in the Earth's crust. Therefore, biological activity must have a major impact on the distribution of Zn isotopes in inorganic materials. The most striking aspect of the data is that red blood cells and bones are enriched by ~0.5 per mil in 66Zn relative to 64Zn when compared to serum, and up to ~1 per mil when compared to the brain and liver. This fractionation is well explained by the equilibrium distribution of isotopes between different bonding environments of Zn in different organs. Differences in gender and genetic background did not appear to affect the isotopic distribution of Zn. Together, these results suggest that potential use of Zn isotopes as a tracer for dietary Zn, and for detecting disturbances in Zn metabolism due to pathological conditions.

Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water

NASA Astrophysics Data System (ADS)

Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

2016-04-01

Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the oxygen isotope composition of ambient CO2. This non-destructive approach was tested through laboratory incubations of air-dried soils that were re-wetted with water of known isotopic composition. Performance was assessed by comparing estimates of the soil water oxygen isotope composition derived from open chamber flux measurements with those measured in the irrigation water and soil water extracted following incubations. The influence of soil pH and bovine carbonic anhydrase additions on these estimates was also investigated. Coherent values were found between the soil water composition estimates obtained from the dual steady state approach and those measured for irrigation waters. Estimates of carbonic anhydrase activity made using this approach also reflected well artificial increases to the concentration of carbonic anhydrase and indicated that this activity was sensitive to soil pH.

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

PubMed

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

2012-07-14

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

Morphology Controls on Calcite Recrystallization.

PubMed

Heberling, Frank; Paulig, Leonie; Nie, Zhe; Schild, Dieter; Finck, Nicolas

2016-11-01

Environmental scientists and geoscientists working in different fields regard the reactivity of calcite and corresponding changes in its trace elemental- or isotopic composition from diametrically opposed points of view. As one extreme, calcite based environmental remediation strategies rely on the fast recrystallization of calcite and the concurrent uptake and immobilization of pollutants. Paleo-ecological investigations denote the other extreme, and rely on the invariability of calcite composition over geological periods of time. We use long-term radiotracer experiments to quantify recrystallization rates of seven types of calcite powder with diverse morphology and particle size distribution. On the one hand our results demonstrate the long-term metastability of calcite with equilibrated crystal surfaces even at isotopic dis-equilibrium. On the other hand, we document the extremely high reactivity and interfacial free energy of freshly ground, rough calcite. Our results indicate that bulk calcite recrystallization is an interfacial free energy driven Ostwald-ripening process, in which particle roughness effects dominate over the effect of crystal habitus and particle size. We confirm that the dynamic equilibrium exchange of crystal constituents between kink sites involves an activation barrier of about 25 kJ/mol. At room temperature the equilibrium exchange is limited to a near surface region and proceeds at a rate of (3.6 ± 1.4)·10 -13 mol/(m 2 ·s).

Equilibrium Temperature Profiles within Fission Product Waste Forms

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

Kaminski, Michael D.

2016-10-01

We studied waste form strategies for advanced fuel cycle schemes. Several options were considered for three waste streams with the following fission products: cesium and strontium, transition metals, and lanthanides. These three waste streams may be combined or disposed separately. The decay of several isotopes will generate heat that must be accommodated by the waste form, and this heat will affect the waste loadings. To help make an informed decision on the best option, we present computational data on the equilibrium temperature of glass waste forms containing a combination of these three streams.

Iron isotopic fractionation between silicate mantle and metallic core at high pressure

PubMed Central

Liu, Jin; Dauphas, Nicolas; Roskosz, Mathieu; Hu, Michael Y.; Yang, Hong; Bi, Wenli; Zhao, Jiyong; Alp, Esen E.; Hu, Justin Y.; Lin, Jung-Fu

2017-01-01

The +0.1‰ elevated 56Fe/54Fe ratio of terrestrial basalts relative to chondrites was proposed to be a fingerprint of core-mantle segregation. However, the extent of iron isotopic fractionation between molten metal and silicate under high pressure–temperature conditions is poorly known. Here we show that iron forms chemical bonds of similar strengths in basaltic glasses and iron-rich alloys, even at high pressure. From the measured mean force constants of iron bonds, we calculate an equilibrium iron isotope fractionation between silicate and iron under core formation conditions in Earth of ∼0–0.02‰, which is small relative to the +0.1‰ shift of terrestrial basalts. This result is unaffected by small amounts of nickel and candidate core-forming light elements, as the isotopic shifts associated with such alloying are small. This study suggests that the variability in iron isotopic composition in planetary objects cannot be due to core formation. PMID:28216664

Carbon isotopic evidence for photosynthesis in Early Cambrian oceans

NASA Astrophysics Data System (ADS)

Surge, Donna M.; Savarese, Michael; Dodd, J. Robert; Lohmann, Kyger C.

1997-06-01

Were the first metazoan reefs ecologically similar to modern tropical reefs, enabling them to persist under oligotrophic conditions? We tested the hypothesis of ecological similarity by employing a geochemical approach. Petrography, cathodoluminescence, trace elements, and stable isotope analyses of primary precipitates of the Lower Cambrian Ajax Limestone, South Australia, indicate preservation of original C isotopic composition. All primary carbonate components exhibit C isotopic values similar to the composition of inorganically precipitated fibrous marine cements, suggesting that archaeocyaths and the calcimicrobe Epiphyton precipitated skeletal carbonate in equilibrium with ambient seawater in the absence of vital effects. Such data do not support the contention that archaeocyaths possessed photosymbionts. However, a +0.55‰ shift in δ13C occurs in reefs developed under shallower-water conditions relative to deeper reefs. This shift suggests the stratification of primary production in Early Cambrian oceans. The pattern is similar to that seen in the modern ocean, whereby significant photosynthesis modulates the C isotopic composition of the photic zone.

Non-traditional stable isotope behaviors in immiscible silica-melts in a mafic magma chamber.

PubMed

Zhu, Dan; Bao, Huiming; Liu, Yun

2015-12-01

Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ(57)Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ(57)Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ(57)Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted.

Monitoring of tritium

DOEpatents

Corbett, James A.; Meacham, Sterling A.

1981-01-01

The fluid from a breeder nuclear reactor, which may be the sodium cooling fluid or the helium reactor-cover-gas, or the helium coolant of a gas-cooled reactor passes over the portion of the enclosure of a gaseous discharge device which is permeable to hydrogen and its isotopes. The tritium diffused into the discharge device is radioactive producing beta rays which ionize the gas (argon) in the discharge device. The tritium is monitored by measuring the ionization current produced when the sodium phase and the gas phase of the hydrogen isotopes within the enclosure are in equilibrium.

β-Decay Half-Lives of 110 Neutron-Rich Nuclei across the N=82 Shell Gap: Implications for the Mechanism and Universality of the Astrophysical r Process.

PubMed

Lorusso, G; Nishimura, S; Xu, Z Y; Jungclaus, A; Shimizu, Y; Simpson, G S; Söderström, P-A; Watanabe, H; Browne, F; Doornenbal, P; Gey, G; Jung, H S; Meyer, B; Sumikama, T; Taprogge, J; Vajta, Zs; Wu, J; Baba, H; Benzoni, G; Chae, K Y; Crespi, F C L; Fukuda, N; Gernhäuser, R; Inabe, N; Isobe, T; Kajino, T; Kameda, D; Kim, G D; Kim, Y-K; Kojouharov, I; Kondev, F G; Kubo, T; Kurz, N; Kwon, Y K; Lane, G J; Li, Z; Montaner-Pizá, A; Moschner, K; Naqvi, F; Niikura, M; Nishibata, H; Odahara, A; Orlandi, R; Patel, Z; Podolyák, Zs; Sakurai, H; Schaffner, H; Schury, P; Shibagaki, S; Steiger, K; Suzuki, H; Takeda, H; Wendt, A; Yagi, A; Yoshinaga, K

2015-05-15

The β-decay half-lives of 110 neutron-rich isotopes of the elements from _{37}Rb to _{50}Sn were measured at the Radioactive Isotope Beam Factory. The 40 new half-lives follow robust systematics and highlight the persistence of shell effects. The new data have direct implications for r-process calculations and reinforce the notion that the second (A≈130) and the rare-earth-element (A≈160) abundance peaks may result from the freeze-out of an (n,γ)⇄(γ,n) equilibrium. In such an equilibrium, the new half-lives are important factors determining the abundance of rare-earth elements, and allow for a more reliable discussion of the r process universality. It is anticipated that universality may not extend to the elements Sn, Sb, I, and Cs, making the detection of these elements in metal-poor stars of the utmost importance to determine the exact conditions of individual r-process events.

Isotope fractionation during the anaerobic consumption of acetate by methanogenic and sulfate-reducing microorganisms

NASA Astrophysics Data System (ADS)

Gövert, D.; Conrad, R.

2009-04-01

During the anaerobic degradation of organic matter in anoxic sediments and soils acetate is the most important substrate for the final step in production of CO2 and/or CH4. Sulfate-reducing bacteria (SRB) and methane-producing archaea both compete for the available acetate. Knowledge about the fractionation of 13C/12C of acetate carbon by these microbial groups is still limited. Therefore, we determined carbon isotope fractionation in different cultures of acetate-utilizing SRB (Desulfobacter postgatei, D. hydrogenophilus, Desulfobacca acetoxidans) and methanogens (Methanosarcina barkeri, M. acetivorans). Including literature values (e.g., Methanosaeta concilii), isotopic enrichment factors (epsilon) ranged between -35 and +2 permil, possibly involving equilibrium isotope effects besides kinetic isotope effects. The values of epsilon were dependent on the acetate-catabolic pathway of the particular microorganism, the methyl or carboxyl position of acetate, and the relative availability or limitation of the substrate acetate. Patterns of isotope fractionation in anoxic lake sediments and rice field soil seem to reflect the characteristics of the microorganisms actively involved in acetate catabolism. Hence, it might be possible using environmental isotopic information to determine the type of microbial metabolism converting acetate to CO2 and/or CH4.

U, Th, and Pb isotopes in hot springs on the Juan de Fuca Ridge

NASA Technical Reports Server (NTRS)

Chen, J. H.

1987-01-01

Concentrations and isotopic compositions of U, Th, and Pb in three hydrothermal fluids from the Juan de Fuca Ridge were determined from samples obtained by the Alvin submersible. The samples were enriched in Pb and Th relative to deep-sea water, and were deficient in U. No clear relationship with Mg was found, suggesting nonideal mixing between the hot hydrothermal fluids and the cold ambient seawater. Values for U-234/U-238 have a seawater signature, and show a U-234 enrichment relative to the equilibrium value. The Pb isotopic composition has a uniform midocean ridge basalt signature, and it is suggested that Pb in these fluids may represent the best average value of the local oceanic crust.

STABLE ISOTOPE GEOCHEMISTRY OF THERMAL FLUIDS FROM LASSEN VOLCANIC NATIONAL PARK, CALIFORNIA.

USGS Publications Warehouse

Janik, Cathy J.; Nehring, Nancy L.; Truesdell, Alfred H.

1983-01-01

In the Lassen vapor-dominated geothermal system, surface manifestations of thermal fluids at high elevations (1800-2500 m) include superheated and drowned fumaroles, steam-heated acid-sulfate hot springs, and low-chloride bicarbonate springs. Neutral high-chloride hot water discharges at lower elevations. Deuterium and oxygen-18 data establish genetic connections between these fluids and with local meteoric waters. Steam from the highest temperature fumarole at Bumpass Hell and water from the highest chloride hot spring have isotopic compositions corresponding to vapor-liquid equilibrium at 235 degree C. Carbon and sulfur isotope data suggest that the CO//2 and H//2S in the system did not entirely originate from magmatic sources, but probably include contributions from thermal metamorphism of marine sedimentary rocks. Observations suggest that carbon and sulfur isotope variations are useful indicators of gas reactions and flow paths in geothermal systems. Refs.

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

NASA Astrophysics Data System (ADS)

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

2011-06-01

In this paper we present the first detailed geochemical study of the world-famous actively forming Pamukkale and Karahayit travertines (Denizli Basin, SW-Turkey) and associated thermal waters. Sampling was performed along downstream sections through different depositional environments (vent, artificial channel and lake, terrace-pools and cascades of proximal slope, marshy environment of distal slope). δ 13C travertine values show significant increase (from + 6.1‰ to + 11.7‰ PDB) with increasing distance from the spring orifice, whereas the δ 18O travertine values show only slight increase downstream (from - 10.7‰ to - 9.1‰ PDB). Mainly the CO 2 outgassing caused the positive downstream shift (~ 6‰) in the δ 13C travertine values. The high δ 13C values of Pamukkale travertines located closest to the spring orifice (not affected by secondary processes) suggest the contribution of CO 2 liberated by thermometamorphic decarbonation besides magmatic sources. Based on the gradual downstream increase of the concentration of the conservative Na +, K +, Cl -, evaporation was estimated to be 2-5%, which coincides with the moderate effect of evaporation on the water isotope composition. Stable isotopic compositions of the Pamukkale thermal water springs show of meteoric origin, and indicate a Local Meteoric Water Line of Denizli Basin to be between the Global Meteoric Water Line (Craig, 1961) and Western Anatolian Meteoric Water Line (Şimşek, 2003). Detailed evaluation of several major and trace element contents measured in the water and in the precipitated travertine along the Pamukkale MM section revealed which elements are precipitated in the carbonate or concentrated in the detrital minerals. Former studies on the Hungarian Egerszalók travertine (Kele et al., 2008a, b, 2009) had shown that the isotopic equilibrium is rarely maintained under natural conditions during calcite precipitation in the temperature range between 41 and 67 °C. In this paper, besides the detailed geochemical analyses along downstream sections, we present new evidences of non-equilibrium calcite-water fractionation in lower temperature range (13.3 to 51.3 °C). Our measurements and calculations on natural hot water travertine precipitations at Pamukkale and Egerszalók revealed that the δ 18O travertine is equal with the δ 18O HCO3 at the orifice of the thermal springs, which means that practically there is no oxygen isotope fractionation between these two phases. High rate of CO 2 degassing with rapid precipitation of carbonate could be responsible for this as it was theoretically supposed by O'Neil et al. (1969). Thus, for the determination of the deposition temperature of a fossil travertine deposit we propose to use the water-bicarbonate oxygen isotope equilibrium fractionation instead of the water-travertine fractionation, which can result 8-9 °C difference in the calculated values. Our study is the first detailed empirical proof of O'Neil's hypothesis on a natural carbonate depositing system. The presented observations can be used to identify more precisely the deposition temperature of fossil travertines during paleoclimate studies.

A Sr and Mg isotopic study of soil and stream waters along an erosional gradient, Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Rosen, V. B.; Maher, K.; Kouba, C. M.; Weinman, B. A.; Yoo, K.; Mudd, S. M.

2012-12-01

Since chemical weathering rates are proposed to regulate atmospheric CO2 concentrations and by extension global temperature over geologic timescales, understanding the relationship between chemical weathering rates and physical erosion is crucial to accurately interpreting Earth's climate history. The rate of supply of fresh minerals to the weathering zone is known to be an important control on chemical weathering rates. However, the consequences of physical erosion on the isotopic composition of weathering-derived solutes are more difficult to assess. This study capitalizes on a series of granitic hillslope transects with different erosion rates but similar climate, vegetation, and bedrock, in order to assess the consequences of erosion on the Sr and Mg isotopic composition of solutes. Reactive transport model simulations of varying complexity have been used to complement the field measurements and to analyze the sensitivity of fluid isotopic compositions to changes in key parameters such as erosion rate, flow rate, and biological cycling. The three hillslopes in the Feather River Basin, California reflect different degrees of channel erosion at their bases—BRC is a hillslope with active channel incision (60% average slope, below the knickpoint), FTA is a hillslope reflecting the transition between the relict and modern-day incising areas (50% average slope, at the knickpoint), and POMD is a 30% average hillslope in the relict landscape above the knickpoint. We measured the major element compositions, as well as the Sr and Mg isotopic compositions of soil water leaches (deionized water leaches), lysimeters, stream waters, and groundwaters by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The 87Sr/86Sr values of soil and stream waters show minimal variation (0.7042 to 0.7046) as a function of soil depth, erosion rate, or sampling season despite abundant radiogenic biotite in the profiles. These results agree with the reactive transport model predictions at high erosion rates, and suggest that soil residence times and isotopic equilibrium times are too short for biotite weathering to influence the solute isotopic composition. In contrast, model results for δ26Mg of the soil waters and minerals suggest that the Mg isotopic composition of the solute changes as a function of erosion rate because of shorter isotopic equilibrium length scales at higher erosion rates. The isotopic reactive transport modeling, combined with hillslope depth profiles and stream water analyses, provides a useful approach for linking the isotopic composition of solutes to erosion rates. This study may provide insights into past and present riverine isotopic compositions, and contribute to our understanding of how surface processes have influenced past atmospheric conditions.

Carbon isotope turnover as a measure of arrival time in migratory birds

USGS Publications Warehouse

Oppel, Steffen; Powell, Abby N.

2009-01-01

Arrival time on breeding or non-breeding areas is of interest in many ecological studies exploring fitness consequences of migratory schedules. However, in most field studies, it is difficult to precisely assess arrival time of individuals. Here, we use carbon isotope turnover in avian blood as a technique to estimate arrival time for birds switching from one habitat or environment to another. Stable carbon isotope ratios (δ13C) in blood assimilate to a new equilibrium following a diet switch according to an exponential decay function. This relationship can be used to determine the time a diet switch occurred if δ13C of both the old and new diet are known. We used published data of captive birds to validate that this approach provides reliable estimates of the time since a diet switch within 1–3 weeks after the diet switch. We then explored the utility of this technique for King Eiders (Somateria spectabilis) arriving on terrestrial breeding grounds after wintering and migration at sea. We estimated arrival time on breeding grounds in northern Alaska (95% CI) from red blood cell δ13C turnover to be 4–9 June. This estimate overlapped with arrival time of birds from the same study site tracked with satellite transmitters (5–12 June). Therefore, we conclude that this method provides a simple yet reliable way to assess arrival time of birds moving between isotopically distinct environments.

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.

Seasonal Changes in the Isotopic Compositions and Sinking Fluxes of Euthecosomatous Pteropod Shells in the Sargasso Sea

NASA Astrophysics Data System (ADS)

Fabry, V. J.; Deuser, W. G.

1992-04-01

Seasonal variations in the oxygen and carbon isotopic compositions and fluxes of five euthecosomatous pteropods were determined from a 14-month series of sediment trap deployments in the Sargasso Sea. Medium and large shell sizes of Styliola subula, Clio pyramidata, Limacina inflata, Creseis acicula, and Cuvierina columnella were collected throughout the sampling period. Comparisons of the δ18O of shell samples with the vertical and temporal variations in the calculated δ18O of aragonite in equilibrium with seawater suggest that these pteropods deposited the bulk of their shell mass at the following depths: S. subula and L. inflata at 50 m, C. pyramidata at 75 m, C. acicula in the upper 25 m, and C. columnella at 50-75 m. Although several of these species undergo diel vertical migration of several hundred meters in this region, the estimated depths of calcification match the upper parts of the species' vertical ranges, where the mean populations occur only at night. In all species, seasonal changes in the δ18O of shells were closely coupled to those of equilibrium δ18O for aragonite, suggesting that most of the shell mass of these individuals was formed within several months. Flux-weighted, mean δ18O values for the species reveal that seasonal variations in the sinking fluxes of shells would not affect the isotopic compositions of shell accumulations in Bermuda Rise sediments. Carbon and oxygen isotopes were positively correlated in all species except C. columnella, which suggests that temperature may influence the δ13C of the shells of these species.

Carbon isotope exchange in the system CO 2-CH 4 at elevated temperatures

NASA Astrophysics Data System (ADS)

Horita, Juske

2001-06-01

Carbon isotope exchange was investigated for the system CO 2-CH 4 at 150 to 600°C in the presence of several potential catalysts by use of isotopically normal or 13C-enriched gases. Silica gel, graphite, molecular sieve Linde 4A, magnetite, and hematite oxidized small amounts of CH 4 in starting CO 2-CH 4 mixtures to CO and CO 2 but failed to enhance the net rate of carbon isotope exchange between CO 2 and CH 4, even after 169 to 1833 h at 400 to 500°C. In contrast, several commercial transition-metal catalysts (Ni, Pd, Rh, and Pt) promoted reactions significantly toward chemical and isotopic equilibrium. With the Ni catalyst, the attainment of carbon isotopic equilibrium between CO 2 and CH 4 was demonstrated for the first time at temperatures from 200 to 600°C by complete isotopic reversal from opposite directions. The experimentally determined carbon isotope fractionation factors between CO 2 and CH 4 (10 3lnα) were similar to, but slightly greater than (0.7-1.1‰, 0.89‰ on average), those of statistical-mechanical calculations by Richet et al. (1977). The experimental results can be described by the following equation between 200 and 600°C only: 10 3lnα(CO 2-CH 4) = 26.70 - 49.137(10 3/T) + 40.828(10 6/T 2) - 7.512(10 9/T 3) (T = 473.15-873.15 K, 1σ = ±0.14‰, n = 44). Alternatively, an equation generated by fitting Richet et al. (1977) data in the temperature range from 0 to 1300°C can be modified by adding +0.89‰ to its constant; 10 3lnα(CO 2-CH 4) = 0.16 + 11.754(10 6/T 2) - 2.3655(10 9/T 3) + 0.2054(10 12/T 4) (T = 273-1573 K, 1σ = ±0.21‰, n = 44). This and other recent experimental studies in the literature demonstrate that transition metals, which are widespread in many natural materials, can catalyze reactions among natural gases at relatively low temperatures (≤200°C). The role of natural catalysts, "geocatalysts," in the abiogenic formation of methane, hydrocarbons, and simple organic compounds has important implications, ranging from the exploration of hydrocarbon resources to prebiotic organic synthesis.

Oxygen isotopes in nitrate: New reference materials for 18O:17O:16O measurements and observations on nitrate-water equilibration

USGS Publications Warehouse

Böhlke, J.K.; Mroczkowski, S.J.; Coplen, T.B.

2003-01-01

Despite a rapidly growing literature on analytical methods and field applications of O isotope-ratio measurements of NO3− in environmental studies, there is evidence that the reported data may not be comparable because reference materials with widely varying δ18O values have not been readily available. To address this problem, we prepared large quantities of two nitrate salts with contrasting O isotopic compositions for distribution as reference materials for O isotope-ratio measurements: USGS34 (KNO3) with low δ18O and USGS35 (NaNO3) with high δ18O and ‘mass-independent’ δ17O. The procedure used to produce USGS34 involved equilibration of HNO3 with 18O-depleted meteoric water. Nitric acid equilibration is proposed as a simple method for producing laboratory NO3− reference materials with a range of δ18O values and normal (mass-dependent) 18O:17O:16O variation. Preliminary data indicate that the equilibrium O isotope-fractionation factor (α) between [NO3−] and H2O decreases with increasing temperature from 1.0215 at 22°C to 1.0131 at 100°C. USGS35 was purified from the nitrate ore deposits of the Atacama Desert in Chile and has a high 17O:18O ratio owing to its atmospheric origin. These new reference materials, combined with previously distributed NO3− isotopic reference materials IAEA-N3 (=IAEA-NO-3) and USGS32, can be used to calibrate local laboratory reference materials for determining offset values, scale factors, and mass-independent effects on N and O isotope-ratio measurements in a wide variety of environmental NO3− samples. Preliminary analyses yield the following results (normalized with respect to VSMOW and SLAP, with reproducibilities of ±0.2–0.3‰, 1σ): IAEA-N3 has δ18O = +25.6‰ and δ17O = +13.2‰; USGS32 has δ18O = +25.7‰; USGS34 has δ18O = −27.9‰ and δ17O = −14.8‰; and USGS35 has δ18O = +57.5‰ and δ17O = +51.5‰.

Nitrogen isotope effects induced by anammox bacteria

PubMed Central

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

2013-01-01

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

The oceanic budgets of nickel and zinc isotopes: the importance of sulfidic environments as illustrated by the Black Sea

PubMed Central

Little, Susan H.; Archer, Corey; Cameron, Vyllinniskii; Andersen, Morten B.; Rijkenberg, Micha J. A.; Lyons, Timothy W.

2016-01-01

Isotopic data collected to date as part of the GEOTRACES and other programmes show that the oceanic dissolved pool is isotopically heavy relative to the inputs for zinc (Zn) and nickel (Ni). All Zn sinks measured until recently, and the only output yet measured for Ni, are isotopically heavier than the dissolved pool. This would require either a non-steady-state ocean or other unidentified sinks. Recently, isotopically light Zn has been measured in organic carbon-rich sediments from productive upwelling margins, providing a potential resolution of this issue, at least for Zn. However, the origin of the isotopically light sedimentary Zn signal is uncertain. Cellular uptake of isotopically light Zn followed by transfer to sediment does not appear to be a quantitatively important process. Here, we present Zn and Ni isotope data for the water column and sediments of the Black Sea. These data demonstrate that isotopically light Zn and Ni are extracted from the water column, probably through an equilibrium fractionation between different dissolved species followed by sequestration of light Zn and Ni in sulfide species to particulates and the sediment. We suggest that a similar, non-quantitative, process, operating in porewaters, explains the Zn data from organic carbon-rich sediments. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035259

Problem-Based Test: Replication of Mitochondrial DNA during the Cell Cycle

ERIC Educational Resources Information Center

Setalo, Gyorgy, Jr.

2013-01-01

Terms to be familiar with before you start to solve the test: cell cycle, generation time, S-phase, cell culture synchronization, isotopic pulse-chase labeling, density labeling, equilibrium density-gradient centrifugation, buoyant density, rate-zonal centrifugation, nucleoside, nucleotide, kinase enzymes, polymerization of nucleic acids,…

Experimental Determination of Isotopic Fractionation of Chromium(III) During Oxidation by Manganese Oxides

NASA Astrophysics Data System (ADS)

Bain, D. J.; Bullen, T. D.

2004-12-01

In environmental conditions, chromium (Cr) exists in either the immobile, micronutrient trivalent form (Cr(III)) or the mobile, toxic hexavalent (Cr(VI)) form. Cr(VI) quickly reduces upon encountering Fe(II) or soil organic material (SOM). Therefore, it is often assumed that human Cr additions to terrestrial systems will impact localized areas and natural sources pose minimal threat to human or ecosystem health. However, oxidation and mobilization of Cr(III) by common manganese (Mn) oxides is less understood, especially in field settings. Moreover, Cr(VI)'s anionic form should enhance mobility through Fe- and SOM-poor soil and saprolite matrices. The variety of redox environments along a flowpath makes Cr source identification difficult with only concentration and speciation data. However, Cr has four stable isotopes (50, 52, 53, and 54), and characteristic fractionations during redox transformations might allow clarification of sources and flowpaths. For example, Cr(VI) reduction by a variety of reductants discriminates against heavy Cr, resulting in an increasingly heavy Cr(VI) fraction as reduction proceeds (α Cr(III)-Cr(VI) ˜ 0.996). Measurement of isotopic fractionation in other environmental Cr transformations, including oxidation, is necessary to understand Cr fate and transport. Recent estimates of isotopic fractionation between Cr aqueous species based on theoretical considerations indicate that at equilibrium α Cr(III)-Cr(VI) ˜ 0.994. To test this theoretical prediction, we are assessing the isotopic variability of aqueous Cr during oxidation of Cr(III) on MnO2 materials such as birnessite in laboratory experiments. Initial results indicate that the isotopic composition of the product Cr(VI) ranges from -2.50 to +0.71 ‰ δ 53Cr, suggesting an important role for kinetic isotope effects during the initial oxidation process. Large fluctuations in isotopic composition continue after dissolved Cr(VI) and Cr(III) ratios stabilize and net Cr(VI) production rates are very slow. Moreover, the Cr(VI) isotopic composition fluctuates between heavy and light compositions several times over the course of reaction. Overall, however, the long term trend appears to be toward the equilibrium fractionation predicted by theory. This adds further credence to hypothesized multiple oxidation pathways existing in the system and suggests that multiple processes with off-setting fractionations are driving the system. If these results are representative of natural systems, environmental Cr samples that have been oxidized or been oxidized/reduced multiple times along a flowpath, will have isotopic compositions that vary widely, depending predominantly on sample collection time. In turn, this suggests that Cr isotopic compositions alone will not clarify Cr fate and transport, especially at larger scales (e.g., catchments), and other geochemical and hydrologic constraints will be required.

D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

NASA Astrophysics Data System (ADS)

Foustoukos, Dionysis I.; Mysen, Bjorn O.

2012-06-01

A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the O-D⋯O environment. This difference allows enhanced gas solubility in the denser and more polar H2O clusters, and thus, affects the D/H exchange between the H2-D2 volatiles and the coexisting H2O-D2O mixtures. The proposed role of temperature in promoting differences in the density and polarity of hydrogen-bonded OHO and ODO molecules may be explained with isotope-specific molar volume effects similar to those suggested to account for the hydrogen isotope fractionation between H2O and hydroxide mineral phases (e.g. brucite) across large pressure intervals.

Condensation and Evaporation of Solar System Materials

NASA Astrophysics Data System (ADS)

Davis, A. M.; Richter, F. M.

2003-12-01

It is widely believed that the materials making up the solar system were derived from a nebular gas and dust cloud that went through an early high-temperature stage during which virtually all of the material was in the gas phase. At one time, it was thought that the entire inner solar nebula was hot, but it is now believed that most material was processed through regions where high temperatures were achieved. Certainly some material, such as presolar grains (cf., Mendybaev et al., 2002a), has never been exposed to high temperatures. As the system cooled, solids and perhaps liquids began to condense, but at some point the partially condensed materials became isolated from the remaining gas. Various lines of evidence support this view. At the largest scale, there is the observation that the Earth, Moon, Mars, and all chondritic meteorites except for the CI chondrites are depleted to varying degrees in the abundances of moderately volatile elements relative to bulk solar system composition. The CI chondrites reflect the bulk composition of the solar system for all but hydrogen, carbon, nitrogen, oxygen, and the rare gases, the most volatile elements (see Chapter 1.03; Palme et al., 1988; McDonough and Sun, 1995; Humayun and Cassen, 2000). The depletions in moderately volatile elements are, to a significant degree, correlated with condensation temperature, suggesting progressive removal of gas as condensation proceeded ( Cassen, 1996). Additional observations that can be explained by partial condensation are that various particularly primitive components of meteorites (e.g., calcium-, aluminum-rich refractory inclusions, and certain metal grains) have mineralogy and/or details of their chemical composition that are remarkably similar to what is calculated for equilibrium condensates from a solar composition gas. For example, the calcium-, aluminum-rich inclusions (CAIs) in chondritic meteorites have compositions very similar to that calculated for the first 5% of total condensable matter (see Chapter 1.08; Grossman, 1973; Wänke et al., 1974; Grossman and Ganapathy, 1976; Grossman et al., 1977), where CI chondrites are taken to represent total condensable matter.Elemental abundance patterns ordered by volatility certainly could have been produced by partial condensation, but they could also have been caused by partial evaporation. The relative importance of these opposite processes is still subject to debate and uncertainty. It should be remembered that condensation calculations typically assume chemical equilibrium in a closed system, in which case the system has no memory of the path by which it arrived at a given state, and thus the chemical and isotopic composition of the condensed phase cannot be used to distinguish between partial condensation and partial evaporation. Humayun and Clayton (1995) have taken a somewhat different view by arguing that condensation and evaporation are distinguishable, in that evaporation, but not condensation, will produce isotopically fractionated residues. With this idea in mind, they carefully measured the potassium isotopic compositions of a broad range of solar system materials with different degrees of potassium depletion and found them to be indistinguishable. This they took as evidence that evaporation could not have been a significant process in determining the diverse elemental abundance patterns of the various solar system materials they measured, because had evaporation been important in fractionating potassium it would have also fractionated the potassium isotopes. We will qualify this line of reasoning by arguing that evaporation and condensation can under certain conditions produce isotopically fractionated condensed phases (i.e., that partial evaporation can produce isotopically heavy residues and that partial condensation can produce isotopically light condensates) but that under other conditions both can produce elemental fractionations without significant isotopic fractionation. The absence of isotopic fractionation in a volatile element-depleted condensed phase is more a measure of the degree to which the system maintained thermodynamic equilibrium than a diagnostic of whether the path involved condensation or evaporation.The pervasive volatile element depletion of inner solar system planets and the asteroidal parent bodies of most meteorites is a major, but by no means the only reason to consider evaporation and condensation processes in the early history of the solar system. Chondrules appear to have been rapidly heated and then cooled over a period of minutes to hours (see Chapter 1.07). If this occurred in a gas of solar composition under nonequilibrium conditions, chondrules should have partially evaporated and an isotopic fractionation record should remain. The absence of such effects can be used to chonstrain the conditions of chondrule formation (e.g., Alexander et al., 2000; Alexander and Wang, 2001). There is good petrologic, chemical, and isotopic evidence suggesting that certain solar system materials such as the coarse-grained CAIs are likely evaporation residues. For example, the type B CAIs are often found to have correlated enrichments in the heavy isotopes of silicon and magnesium ( Figure 1), and these isotopic fractionations are very much like those of evaporation residues produced in laboratory experiments. Condensation also appears to be a major control of elemental zoning patterns in metal grains in CH chondrites (Meibom et al., 1999, 2001; Campbell et al., 2001; Petaev et al., 2001; Campbell et al., 2002). A more contemporary example is the isotopic and chemical compositions of deep-sea spherules that have been significantly affected by evaporative loss during atmospheric entry ( Davis et al., 1991a; Davis and Brownlee, 1993; Herzog et al., 1994, 1999; Xue et al., 1995; Alexander et al., 2002). (7K)Figure 1. Isotopic mass fractionation effects in CAIs. Most coarse-grained CAIs have enrichments of a few ‰ amu-1 in magnesium and silicon, whereas "fractionation and unknown nuclear" (FUN) CAIs are isotopically heavier. The volatile element depletion patterns of planetary size objects and the chemical and isotopic composition of numerous smaller objects such as chondrules and CAIs provide the motivation to consider evaporation and condensation process in the early solar system. The key point is that the processes that led to chondrules and planets appear to have occurred under conditions very close to equilibrium, whereas the processes that led to CAIs involved significant departures from equilibrium.

Modelling and intepreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2012-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, droplet size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

Modelling and interpreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2013-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed-phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters, including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, particle size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

Chromatographic hydrogen isotope separation

DOEpatents

Aldridge, Frederick T.

1981-01-01

Intermetallic compounds with the CaCu.sub.5 type of crystal structure, particularly LaNiCo.sub.4 and CaNi.sub.5, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation colum. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale mutli-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen can produce large quantities of heavy water at an effective cost for use in heavy water reactors.

Modeling Chemical and Isotopic Variations in Lab Formed Hydrothermal Carbonates

NASA Technical Reports Server (NTRS)

Niles, P. B.; Leshin, L. A.; Golden, D. C.; Socki, R. A.; Guan, Y.; Ming, D. W.

2005-01-01

Chemical and mineralogical data (e.g. [1]) from Mars suggest that the history of liquid water on the planet was more sporadic in nature than long-lived. The non-equilibrium chemical and isotopic compositions of the carbonates preserved in the martian meteorite ALH84001 are direct evidence of ancient secondary minerals that have not undergone significant diagenesis or stabilization processes typical of long-lived aqueous systems on Earth. Thus secondary minerals and sediments on Mars may primarily record the characteristics of the aqueous environment in which they formed without being significantly overprinted by subsequent diagenetic processes during burial.

Chromatographic hydrogen isotope separation

DOEpatents

Aldridge, F.T.

Intermetallic compounds with the CaCu/sub 5/ type of crystal structure, particularly LaNiCo/sub 4/ and CaNi/sub 5/, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation column. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale multi-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen cn produce large quantities of heavy water at an effective cost for use in heavy water reactors.

Reconstruction of Late Quaternary Climate in Central Europe - A Comparison of Stable Isotope and Trace Element Variations in Speleothems From Different Cave Systems in Germany.

NASA Astrophysics Data System (ADS)

Nordhoff, P.; Wiegand, B.; Simon, K.; Rosendahl, W.; Hansen, B. T.; Kempe, S.

2003-12-01

Speleothems (stalagmites, stalactites, flowstones) are important archives for Late Quaternary continental climatic and paleo-environmental reconstruction. Speleothems form when calcium carbonate precipitates from solutions seeping into caves hosted e.g. in limestone or dolomite complexes. Information of past climate variability and changes in local environmental conditions can be obtained from signatures of the stable isotopes of oxygen and carbon as well as trace element pattern recorded in speleothems. Reconstruction of paleo-temperature and past environmental conditions from stable isotopes, however, require isotopic equilibrium between the drip water and the precipitating calcium carbonate. Results from Dietzel et al. (1992) and Johnson and Ingram (2001) indicate that the formation of modern travertine and speleothem calcite occurs under isotopic equilibrium. Factors that influence the stable oxygen and carbon isotope composition during speleothem precipitation include e.g. the moisture source and precipitation, photosynthetic pathways, the bedrock proportion, and the drip rate. This often leads to a situation with several variables. However, a specific interpretation is possible when dealing with environments where only one of the factors is dominant, or specific settings are assumed to be invariant, or further proxies like trace element variations help to define the frame conditions during speleothem formation. Concentrations of trace elements (e.g. Sr, Mg) which are co-precipitated with calcite are related to changes in the composition of the solution and strongly depend on the dissolution/precipitation dynamics along drip water flow paths. In a multiproxy approach they are a valuable tool for the interpretation of the recorded stable isotope variations. We present first results from different cave systems located in the Swabian Alps and the Harz Mountains (Germany). Our study includes a high-resolution multiproxy approach, using U/Th-TIMS data, stable oxygen/carbon isotope data, and geochemical compositions of speleothems, covering ages from the Late Pleistocene to the Early Holocene. The results are compared to geochemical data from host rocks, soil zones, cave sediments, drip water compositions, and recent calcium carbonate precipitates. Understanding the response of a cave system to the actual climatic, hydrologic and environmental regimen is a main requirement for the interpretation of "paleo-information" conserved in speleothems in order to lead to a coherent picture of past continental climate dynamics. References: Dietzel M., Usdowski E., and Hoefs J., (1992): Applied Geochemistry 7: 177-184. Johnson, K.R. and Ingram, B.L. (2001): Abstract volume, 4th Internat. Symp. On Applied Isotope Geochemistry, Pacific Groove, USA: 70-72.

Equilibrium chemical vapor deposition growth of Bernal-stacked bilayer graphene.

PubMed

Zhao, Pei; Kim, Sungjin; Chen, Xiao; Einarsson, Erik; Wang, Miao; Song, Yenan; Wang, Hongtao; Chiashi, Shohei; Xiang, Rong; Maruyama, Shigeo

2014-11-25

Using ethanol as the carbon source, self-limiting growth of AB-stacked bilayer graphene (BLG) has been achieved on Cu via an equilibrium chemical vapor deposition (CVD) process. We found that during this alcohol catalytic CVD (ACCVD) a source-gas pressure range exists to break the self-limitation of monolayer graphene on Cu, and at a certain equilibrium state it prefers to form uniform BLG with a high surface coverage of ∼94% and AB-stacking ratio of nearly 100%. More importantly, once the BLG is completed, this growth shows a self-limiting manner, and an extended ethanol flow time does not result in additional layers. We investigate the mechanism of this equilibrium BLG growth using isotopically labeled (13)C-ethanol and selective surface aryl functionalization, and results reveal that during the equilibrium ACCVD process a continuous substitution of graphene flakes occurs to the as-formed graphene and the BLG growth follows a layer-by-layer epitaxy mechanism. These phenomena are significantly in contrast to those observed for previously reported BLG growth using methane as precursor.

Non-traditional stable isotope behaviors in immiscible silica-melts in a mafic magma chamber

PubMed Central

Zhu, Dan; Bao, Huiming; Liu, Yun

2015-01-01

Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ57Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ57Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ57Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted. PMID:26620121

Modelling deuterium release from tungsten after high flux high temperature deuterium plasma exposure

NASA Astrophysics Data System (ADS)

Grigorev, Petr; Matveev, Dmitry; Bakaeva, Anastasiia; Terentyev, Dmitry; Zhurkin, Evgeny E.; Van Oost, Guido; Noterdaeme, Jean-Marie

2016-12-01

Tungsten is a primary candidate for plasma facing materials for future fusion devices. An important safety concern in the design of plasma facing components is the retention of hydrogen isotopes. Available experimental data is vast and scattered, and a consistent physical model of retention of hydrogen isotopes in tungsten is still missing. In this work we propose a model of non-equilibrium hydrogen isotopes trapping under fusion relevant plasma exposure conditions. The model is coupled to a diffusion-trapping simulation tool and is used to interpret recent experiments involving high plasma flux exposures. From the computational analysis performed, it is concluded that high flux high temperature exposures (T = 1000 K, flux = 1024 D/m2/s and fluence of 1026 D/m2) result in generation of sub-surface damage and bulk diffusion, so that the retention is driven by both sub-surface plasma-induced defects (bubbles) and trapping at natural defects. On the basis of the non-equilibrium trapping model we have estimated the amount of H stored in the sub-surface region to be ∼10-5 at-1, while the bulk retention is about 4 × 10-7 at-1, calculated by assuming the sub-surface layer thickness of about 10 μm and adjusting the trap concentration to comply with the experimental results for the integral retention.

Triple oxygen isotope composition of photosynthetic oxygen

NASA Astrophysics Data System (ADS)

van der Meer, Anne; Kaiser, Jan

2013-04-01

The measurement of biological production rates is essential for our understanding how marine ecosystems are sustained and how much CO2 is taken up through aquatic photosynthesis. Traditional techniques to measure marine production are laborious and subject to systematic errors. A biogeochemical approach based on triple oxygen isotope measurements in dissolved oxygen (O2) has been developed over the last few years, which allows the derivation of gross productivity integrated over the depth of the mixed layer and the time-scale of O2 gas exchange (Luz and Barkan, 2000). This approach exploits the relative 17O/16O and 18O/16O isotope ratio differences of dissolved O2 compared to atmospheric O2 to work out the rate of biological production. Two parameters are key for this calculation: the isotopic composition of dissolved O2 in equilibrium with air and the isotopic composition of photosynthetic oxygen. Recently, a controversy has emerged in the literature over these parameters (Kaiser, 2011) and one of the goals of this research is to provide additional data to resolve this controversy. In order to obtain more information on the isotopic signature of biological oxygen, laboratory experiments have been conducted to determine the isotopic composition of oxygen produced by different phytoplankton cultures.

Ultra-Sensitive Elemental Analysis Using Plasmas 4.Application of Inductively Coupled Plasma Mass Spectrometry to the Study of Environmental Radioactivity

NASA Astrophysics Data System (ADS)

Yoshida, Satoshi

Applications of inductively coupled plasma mass spectrometry (ICP-MS) to the determination of long-lived radionuclides in environmental samples were summarized. In order to predict the long-term behavior of the radionuclides, related stable elements were also determined. Compared with radioactivity measurements, the ICP-MS method has advantages in terms of its simple analytical procedures, prompt measurement time, and capability of determining the isotope ratio such as240Pu/239Pu, which can not be separated by radiation. Concentration of U and Th in Japanese surface soils were determined in order to determine the background level of the natural radionuclides. The 235U/238U ratio was successfully used to detect the release of enriched U from reconversion facilities to the environment and to understand the source term. The 240Pu/239Pu ratios in environmental samples varied widely depending on the Pu sources. Applications of ICP-MS to the measurement of I and Tc isotopes were also described. The ratio between radiocesium and stable Cs is useful for judging the equilibrium of deposited radiocesium in a forest ecosystem.

Experimental calibration of silicon and oxygen isotope fractionations between quartz and water at 250°C by in situ microanalysis of experimental products and application to zoned low δ 30Si quartz overgrowths

DOE PAGES

Pollington, Anthony D.; Kozdon, Reinhard; Anovitz, Lawrence M.; ...

2015-12-01

The interpretation of silicon isotope data for quartz is hampered by the lack of experimentally determined fractionation factors between quartz and fluid. Further, there is a large spread in published oxygen isotope fractionation factors at low temperatures, primarily due to extrapolation from experimental calibrations at high temperature. We report the first measurements of silicon isotope ratios from experimentally precipitated quartz and estimate the equilibrium fractionation vs. dissolved silica using a novel in situ analysis technique applying secondary ion mass spectrometry to directly analyze experimental products. These experiments also yield a new value for oxygen isotope fractionation. Quartz overgrowths up tomore » 235 μm thick were precipitated in silica–H 2O–NaOH–NaCl fluids, at pH 12–13 and 250 °C. At this temperature, 1000lnα 30Si(Qtz–fluid) = 0.55 ± 0.10‰ and 1000lnα 18O(Qtz–fluid) = 10.62 ± 0.13‰, yielding the relations 1000lnα 30Si(Qtz–fluid) = (0.15 ± 0.03) * 10 6/T 2 and 1000lnα 18O(Qtz–fluid) = (2.91 ± 0.04) * 10 6/T 2 when extended to zero fractionation at infinite temperature. Values of δ 30Si(Qtz) from diagenetic cement in sandstones from the basal Cambrian Mt. Simon Formation in central North America range from 0 to ₋5.4‰. Paired δ 18O and δ 30Si values from individual overgrowths preserve a record of Precambrian weathering and fluid transport. In conclusion, the application of the experimental quartz growth results to observations from natural sandstone samples suggests that precipitation of quartz at low temperatures in nature is dominated by kinetic, rather than equilibrium, processes.« less

Sulfur isotopic disequilibrium and fluid-rock interaction during metamorphism of sulfidic black shales from the Waterville-Augusta area, Maine, USA

USGS Publications Warehouse

Oliver, N.H.S.; Hoering, T.C.; Johnson, T.W.; Rumble, D.; Shanks, Wayne C.

1992-01-01

Sulfur isotope ratios of pyrite (py) and pyrrhotite (po) from regionally metamorphosed graphitic sulfidic schists and related rocks from south-central Maine, USA, were analysed using SO2 and SF6 techniques. There is a broad range in ??34S values for both pyrite and pyrrhotite at most outcrops, up to 8%. and overall the values are isotopically light, averaging ~ -27??? for the entire data set, suggesting that the rocks have not been grossly isotopically disturbed by regional metamorphism from their inferred organic-rich sedimentary origins. At all temperatures from chlorite to sillimanite grades, sulfide analysed from veins and blebs within the schists show predominantly disequilibrium fractionations ranging from ??34Spy-po -3.0 to +3.5???, as do matrix sulfides from rocks that attained temperatures 500??C do matrix pyrite-pyrrhotite pairs with polygonal or aligned granoblastic microstructures approach isotopic equilibrium at millimeter to centimeter scales, suggesting that the process that favoured equilibration was recrystallization accompanying metamorphism and deformation. This disequilibrium may be a function of preferential interaction of one of the phases with an infiltrating fluid, but the lack of any systematic trends in the data, particularly with both negative and positive ??34Spy-po at some outcrops, does not permit ready identification of fluid sources, fluxes, or compositions. By combining published fluid fluxes for the area and a knowledge of the mass of sulfur contained in the rocks and the inferred infiltrating fluid, it appears that sulfur should have been homogenized over at least 10's to 1000's of meters, if equilibrium had been attained between rock sulfides and an infiltrating fluid of constant composition. That this did not occur was probably due to lack of equilibration between sulfides and the fluid but may also have arisen because of channelling of fluid flow along rather than across layers, or a lack of fluid infiltration through this unit. ?? 1992.

Stable Isotope Anatomy of Tropical Cyclone Ita, North-Eastern Australia, April 2014

PubMed Central

Munksgaard, Niels C.; Zwart, Costijn; Kurita, Naoyuki; Bass, Adrian; Nott, Jon; Bird, Michael I.

2015-01-01

The isotope signatures registered in speleothems during tropical cyclones (TC) provides information about the frequency and intensity of past TCs but the precise relationship between isotopic composition and the meteorology of TCs remain uncertain. Here we present continuous δ18O and δ2H data in rainfall and water vapour, as well as in discrete rainfall samples, during the passage of TC Ita and relate the evolution in isotopic compositions to local and synoptic scale meteorological observations. High-resolution data revealed a close relationship between isotopic compositions and cyclonic features such as spiral rainbands, periods of stratiform rainfall and the arrival of subtropical and tropical air masses with changing oceanic and continental moisture sources. The isotopic compositions in discrete rainfall samples were remarkably constant along the ~450 km overland path of the cyclone when taking into account the direction and distance to the eye of the cyclone at each sampling time. Near simultaneous variations in δ18O and δ2H values in rainfall and vapour and a near-equilibrium rainfall-vapour isotope fractionation indicates strong isotopic exchange between rainfall and surface inflow of vapour during the approach of the cyclone. In contrast, after the passage of spiral rainbands close to the eye of the cyclone, different moisture sources for rainfall and vapour are reflected in diverging d-excess values. High-resolution isotope studies of modern TCs refine the interpretation of stable isotope signatures found in speleothems and other paleo archives and should aim to further investigate the influence of cyclone intensity and longevity on the isotopic composition of associated rainfall. PMID:25742628

Understanding Copper Isotope Behavior in the High Temperature Magmatic-Hydrothermal Porphyry Environment

NASA Astrophysics Data System (ADS)

Gregory, Melissa J.; Mathur, Ryan

2017-11-01

Copper stable isotope geochemistry has the potential to constrain aspects of ore deposit formation once variations in the isotopic data can be related to the physiochemical conditions during metal deposition. This study presents Cu isotope ratios for samples from the Pebble porphyry Cu-Au-Mo deposit in Alaska. The δ65Cu values for hypogene copper sulfides range from -2.09‰ to 1.11‰ and show linear correlations with the δ18O isotope ratios calculated for the fluid in equilibrium with the hydrothermal alteration minerals in each sample. Samples with sodic-potassic, potassic, and illite alteration display a negative linear correlation between the Cu and O isotope results. This suggests that fractionation of Cu isotopes between the fluid and precipitating chalcopyrite is positive as the hydrothermal fluid is evolving from magmatic to mixed magmatic-meteoric compositions. Samples with advanced argillic alteration display a weak positive linear correlation between Cu and O isotope results consistent with small negative fluid-chalcopyrite Cu isotope fractionation during fluid evolution. The hydrothermal fluids that formed sodic-potassic, potassic, and illite alteration likely transported Cu as CuHS0. Hydrothermal fluids that resulted in advanced argillic alteration likely transport Cu as CuCl2-. The pH conditions also control Cu isotope fractionation, consistent with previous experimental work. Larger fractionation factors were found between fluids and chalcopyrite precipitating under neutral conditions contrasting with small fractionation factors calculated between fluids and chalcopyrite precipitating under acidic conditions. Therefore, this study proposes that hydrothermal fluid compositions and pH conditions are related to Cu isotope variations in high temperature magmatic-hydrothermal deposits.

Statistical analysis of experimental multifragmentation events in 64Zn+112Sn at 40 MeV/nucleon

NASA Astrophysics Data System (ADS)

Lin, W.; Zheng, H.; Ren, P.; Liu, X.; Huang, M.; Wada, R.; Chen, Z.; Wang, J.; Xiao, G. Q.; Qu, G.

2018-04-01

A statistical multifragmentation model (SMM) is applied to the experimentally observed multifragmentation events in an intermediate heavy-ion reaction. Using the temperature and symmetry energy extracted from the isobaric yield ratio (IYR) method based on the modified Fisher model (MFM), SMM is applied to the reaction 64Zn+112Sn at 40 MeV/nucleon. The experimental isotope distribution and mass distribution of the primary reconstructed fragments are compared without afterburner and they are well reproduced. The extracted temperature T and symmetry energy coefficient asym from SMM simulated events, using the IYR method, are also consistent with those from the experiment. These results strongly suggest that in the multifragmentation process there is a freezeout volume, in which the thermal and chemical equilibrium is established before or at the time of the intermediate-mass fragments emission.

Stable isotope deltas: Tiny, yet robust signatures in nature

USGS Publications Warehouse

Brand, Willi A.; Coplen, Tyler B.

2012-01-01

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

On the electron-induced isotope fractionation in low temperature (32)O(2)/(36)O(2) ices--ozone as a case study.

PubMed

Sivaraman, B; Mebel, A M; Mason, N J; Babikov, D; Kaiser, R I

2011-01-14

The formation of six ozone isotopomers and isotopologues, (16)O(16)O(16)O, (18)O(18)O(18)O, (16)O(16)O(18)O, (18)O(18)O(16)O, (16)O(18)O(16)O, and (18)O(16)O(18)O, has been studied in electron-irradiated solid oxygen (16)O(2) and (18)O(2) (1 ∶ 1) ices at 11 K. Significant isotope effects were found to exist which involved enrichment of (18)O-bearing ozone molecules. The heavy (18)O(18)O(18)O species is formed with a factor of about six higher than the corresponding (16)O(16)O(16)O isotopologue. Likewise, the heavy (18)O(18)O(16)O species is formed with abundances of a factor of three higher than the lighter (16)O(16)O(18)O counterpart. No isotope effect was observed in the production of (16)O(18)O(16)O versus(18)O(16)O(18)O. Such studies on the formation of distinct ozone isotopomers and isotopologues involving non-thermal, non-equilibrium chemistry by irradiation of oxygen ices with high energy electrons, as present in the magnetosphere of the giant planets Jupiter and Saturn, may suggest that similar mechanisms may contribute to the (18)O enrichment on the icy satellites of Jupiter and Saturn such as Ganymede, Rhea, and Dione. In such a Solar System environment, energetic particles from the magnetospheres of the giant planets may induce non-equilibrium reactions of suprathermal and/or electronically excited atoms under conditions, which are quite distinct from isotopic enrichments found in classical, thermal gas phase reactions.

COORDINATED ANALYSES OF PRESOLAR GRAINS IN THE ALLAN HILLS 77307 AND QUEEN ELIZABETH RANGE 99177 METEORITES

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

Nguyen, Ann N.; Nittler, Larry R.; Alexander, Conel M. O'D.

2010-08-10

We report the identification of presolar silicates ({approx}177 ppm), presolar oxides ({approx}11 ppm), and one presolar SiO{sub 2} grain in the Allan Hills (ALHA) 77307 chondrite. Three grains having Si-isotopic compositions similar to SiC X and Z grains were also identified, though the mineral phases are unconfirmed. Similar abundances of presolar silicates ({approx}152 ppm) and oxides ({approx}8 ppm) were also uncovered in the primitive CR chondrite Queen Elizabeth Range (QUE) 99177, along with 13 presolar SiC grains and one presolar silicon nitride. The O-isotopic compositions of the presolar silicates and oxides indicate that most of the grains condensed in low-massmore » red giant and asymptotic giant branch stars. Interestingly, unlike presolar oxides, few presolar silicate grains have isotopic compositions pointing to low-metallicity, low-mass stars (Group 3). The {sup 18}O-rich (Group 4) silicates, along with the few Group 3 silicates that were identified, likely have origins in supernova outflows. This is supported by their O- and Si-isotopic compositions. Elemental compositions for 74 presolar silicate grains were determined by scanning Auger spectroscopy. Most of the grains have non-stoichiometric elemental compositions inconsistent with pyroxene or olivine, the phases commonly used to fit astronomical spectra, and have comparable Mg and Fe contents. Non-equilibrium condensation and/or secondary alteration could produce the high Fe contents. Transmission electron microscopic analysis of three silicate grains also reveals non-stoichiometric compositions, attributable to non-equilibrium or multistep condensation, and very fine scale elemental heterogeneity, possibly due to subsequent annealing. The mineralogies of presolar silicates identified in meteorites thus far seem to differ from those in interplanetary dust particles.« less

Chemical and isotopic equilibrium between CO 2 and CH 4 in fumarolic gas discharges: Generation of CH 4 in arc magmatic-hydrothermal systems

NASA Astrophysics Data System (ADS)

Fiebig, Jens; Chiodini, Giovanni; Caliro, Stefano; Rizzo, Andrea; Spangenberg, Jorge; Hunziker, Johannes C.

2004-05-01

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH 4) within two subduction-related magmatic-hydrothermal environments. Apparent temperatures derived from carbon isotope partitioning between CH 4 and CO 2 of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H 2O-H 2-CO 2-CO-CH 4 geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH 4, CO 2 and H 2O implying that carbon isotope partitioning between CO 2 and CH 4 in both systems is controlled by aquifer temperature. N 2/ 3He and CH 4/ 3He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH 4 may have been primarily generated through the reduction of CO 2 by H 2 in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH 4 and subsequent re-equilibration with co-existing CO 2 cannot be ruled out entirely. CO 2/ 3He ratios and δ 13C CO 2 values imply that the evolved CO 2 either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH 4 during thermometamorphism.

Using oxygen isotopes of phosphate to trace phosphorus sources and cycling in lake Erie

USGS Publications Warehouse

Elsbury, K.E.; Paytan, A.; Ostrom, N.E.; Kendall, C.; Young, M.B.; McLaughlin, K.; Rollog, M.E.; Watson, S.

2009-01-01

Water samples collected during three sampling trips to Lake Erie displayed oxygen isotopic values of dissolved phosphate (??18O p) that were largely out of equilibrium with ambient conditions, indicating that source signatures may be discerned. ??18O p values in the Lake ranged from +10??? to +17???, whereas the equilibrium value was expected to be around +14???. The riverine weighted average ??18Op value was +11??? and may represent one source of phosphate to the Lake. The lake ?? 18Op values indicated that there must be one or more as yet uncharacterized source(s) of phosphate with a high ?? 18Op value. Potential sources other than rivers are not yet well-characterized with respect to ??18O of phosphate, but we speculate that a likely source may be the release of phosphate from sediments under reducing conditions created during anoxic events in the hypolimnion of the central basin of Lake Erie. Identifying potential phosphorus sources to the Lake is vital for designing effective management plans for reducing nutrient inputs and associated eutrophication. ?? 2009 American Chemical Society.

The formation of weathering products on the LEW 85320 ordinary chondrite - Evidence from carbon and oxygen stable isotope compositions and implications for carbonates in SNC meteorites

NASA Technical Reports Server (NTRS)

Grady, Monica M.; Wright, I. P.; Pillinger, C. T.; Gibson, E. K., Jr.

1989-01-01

Isotopic analysis of nesquehonite recovered from the surface of the LEW 85320 H5 ordinary chondrite shows that the delta C-13 and delta O-18 values of the two generations of bicarbonate (Antarctic and Texas) are different: delta C-13 = + 7.9 per mil and + 4.2 per mil; delta O-18 = + 17.9 per mil and + 12.1 per mil, respectively. Carbon isotopic compositions are consistent with equilibrium formation from atmospheric carbon dioxide at - 2 + or - 4 C (Antarctic) and + 16 + or - 4 C (Texas). Oxygen isotopic data imply that the water required for nesquehonite precipitation was derived from atmospheric water vapor or glacial meltwater which had locally exchanged with silicates, either in the meteorite or in underlying bedrock. Although carbonates with similar delta C-13 values have been identified in the SNC meteorites EETA 79001 and Nakhla, petrographic and temperature constraints argue against their simply being terrestrial weathering products.

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

DOE PAGES

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

2016-07-22

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

The isotope composition of selenium in chondrites constrains the depletion mechanism of volatile elements in solar system materials

NASA Astrophysics Data System (ADS)

Vollstaedt, Hauke; Mezger, Klaus; Leya, Ingo

2016-09-01

Solar nebula processes led to a depletion of volatile elements in different chondrite groups when compared to the bulk chemical composition of the solar system deduced from the Sun's photosphere. For moderately-volatile elements, this depletion primarily correlates with the element condensation temperature and is possibly caused by incomplete condensation from a hot solar nebula, evaporative loss from the precursor dust, and/or inherited from the interstellar medium. Element concentrations and interelement ratios of volatile elements do not provide a clear picture about responsible mechanisms. Here, the abundance and stable isotope composition of the moderately- to highly-volatile element Se are investigated in carbonaceous, ordinary, and enstatite chondrites to constrain the mechanism responsible for the depletion of volatile elements in planetary bodies of the inner solar system and to define a δ 82 / 78 Se value for the bulk solar system. The δ 82 / 78 Se of the studied chondrite falls are identical within their measurement uncertainties with a mean of - 0.20 ± 0.26 ‰ (2 s.d., n = 14, relative to NIST SRM 3149) despite Se abundance depletions of up to a factor of 2.5 with respect to the CI group. The absence of resolvable Se isotope fractionation rules out a kinetic Rayleigh-type incomplete condensation of Se from the hot solar nebula or partial kinetic evaporative loss on the precursor material and/or the parent bodies. The Se depletion, if acquired during partial condensation or evaporative loss, therefore must have occurred under near equilibrium conditions to prevent measurable isotope fractionation. Alternatively, the depletion and cooling of the nebula could have occurred simultaneously due to the continuous removal of gas and fine particles by the solar wind accompanied by the quantitative condensation of elements from the pre-depleted gas. In this scenario the condensation of elements does not require equilibrium conditions to avoid isotope fractionation. The results further suggest that the processes causing the high variability of Se concentrations and depletions in ordinary and enstatite chondrites did not involve any measurable isotope fractionation. Different degrees of element depletions and isotope fractionations of the moderately-volatile elements Zn, S, and Se in ordinary and enstatite chondrites indicate that their volatility is controlled by the thermal stabilities of their host phases and not by the condensation temperature under canonical nebular conditions.

Crystallization history of enriched shergottites from Fe and Mg isotope fractionation in olivine megacrysts

NASA Astrophysics Data System (ADS)

Collinet, Max; Charlier, Bernard; Namur, Olivier; Oeser, Martin; Médard, Etienne; Weyer, Stefan

2017-06-01

Martian meteorites are the only samples available from the surface of Mars. Among them, olivine-phyric shergottites are basalts containing large zoned olivine crystals with highly magnesian cores (Fo 70-85) and rims richer in Fe (Fo 45-60). The Northwest Africa 1068 meteorite is one of the most primitive "enriched" shergottites (high initial 87Sr/86Sr and low initial ε143Nd). It contains olivine crystals as magnesian as Fo 77 and is a major source of information to constrain the composition of the parental melt, the composition and depth of the mantle source, and the cooling and crystallization history of one of the younger magmatic events on Mars (∼180 Ma). In this study, Fe-Mg isotope profiles analyzed in situ by femtosecond-laser ablation MC-ICP-MS are combined with compositional profiles of major and trace elements in olivine megacrysts. The cores of olivine megacrysts are enriched in light Fe isotopes (δ56FeIRMM-14 = -0.6 to -0.9‰) and heavy Mg isotopes (δ26MgDSM-3 = 0-0.2‰) relative to megacryst rims and to the bulk martian isotopic composition (δ56Fe = 0 ± 0.05‰, δ26Mg = -0.27 ± 0.04‰). The flat forsterite profiles of megacryst cores associated with anti-correlated fractionation of Fe-Mg isotopes indicate that these elements have been rehomogenized by diffusion at high temperature. We present a 1-D model of simultaneous diffusion and crystal growth that reproduces the observed element and isotope profiles. The simulation results suggest that the cooling rate during megacryst core crystallization was slow (43 ± 21 °C/year), and consistent with pooling in a deep crustal magma chamber. The megacryst rims then crystallized 1-2 orders of magnitude faster during magma transport toward the shallower site of final emplacement. Megacryst cores had a forsterite content 3.2 ± 1.5 mol% higher than their current composition and some were in equilibrium with the whole-rock composition of NWA 1068 (Fo 80 ± 1.5). NWA 1068 composition is thus close to a primary melt (i.e. in equilibrium with the mantle) from which other enriched shergottites derived.

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.

Relationship between δ 18O values for skeletal apatite from reindeer and foxes and yearly mean δ 18O values of environmental water

NASA Astrophysics Data System (ADS)

Iacumin, Paola; Longinelli, Antonio

2002-07-01

The oxygen isotope composition of bone and tooth phosphate of 50 fox specimens and 30 reindeer specimens from various locations with different climatic and environmental conditions was measured. The existing relationship between these values and the mean oxygen isotope composition of local meteoric water has been calculated. In the case of foxes, specimens belonging to two genera ( Vulpes and Alopex) and three different species were measured. The samples fit a straight line whose equation can be used for paleoclimatological studies either in Arctic or in temperate regions. For reindeer ( Rangifer), a relatively large range of isotopic values was obtained from each location, suggesting imperfect equilibrium conditions with environmental water. The calculated equation can be used for semi-quantitative information on local paleowaters at high latitudes only.

Stable Isotopes, Multidisciplinary Studies, and the Leadership of J.G. Liou in UHP Metamorphism

NASA Astrophysics Data System (ADS)

Rumble, D.

2005-12-01

J.G. Liou has played a crucial role in improving knowledge of UHP metamorphism by leading multi-disciplinary, multi-institutional teams of researchers and by encouraging new investigators and providing them access to samples. Stable isotope geochemistry has made important contributions to understanding UHP metamorphism including: (1) The discovery of O- and H-isotope signatures of meteoric water in UHP rocks from China and Kazakhstan demonstrates that their protoliths originated at or near Earth's surface in a cold climate(a); (2) The mapping of contiguous tracts of outcrops extending over distances of 100 km where both eclogites and their wall rocks retain unusually low d18O and dD is consistent with the subduction and exhumation of UHP slabs as coherent structural units(b); (3) Analysis of samples from the Chinese Continental Scientific Drilling project reveals not only that UHP metamorphic rocks have not exchanged O-isotopes with mantle rocks while they were buried in the upper mantle but also that garnet peridotite slabs from the mantle have not exchanged with crustal wall rocks(c). Recent advances have resulted from multidisciplinary geochemical investigations. The analysis of zircons for both d18O and U-Pb established the age of cold climate, meteoric water alteration of protoliths to be Neoproterozoic for UHP rocks from Dabie and Sulu, China(d). Thus, O-isotopes plus age dating raises the possibility that evidence of snowball Earth conditions has been preserved in an unlikely host: UHP metamorphic rocks. A comparison of U-Pb, Sm-Nd, and Rb-Sr isotope data with analyses for d18O in coexisting minerals shows that discordant age dates correlate with mineral pairs that are not in O-isotope exchange equilibrium(e). It may be seen that multidisciplinary geochemical investigations provide mutually reinforcing data that greatly strengthens interpretations. New discoveries of de novo microdiamonds accompanied by multiphase mineral inclusions in UHP metamorphosed crustal rocks raise exciting possibilities for future stable isotope research on their origin(f). Micron-scale analytical techniques including ion microprobe, "Nano-SIMS", and UV-laser ablation, should be applied to the mineral assemblages to determine whether parent fluids were super-critical C-O-H fluids or carbonate-rich melts. (a) Geochim.Cosmochim.Acta (GCA) 59, 2859; Euro.J.Mineral 8, 317; GCA 61, 1658.(b) GCA 62, 3307.(c) Amer.Mineral. 90, 857.(d) GCA 66, 2299; GCA 68, 4145.(e) GCA 66, 625.(f) J.Metamorph.Geol. 21, 425.

New insight on Li and B isotope fractionation during serpentinization derived from batch reaction investigations

NASA Astrophysics Data System (ADS)

Hansen, Christian T.; Meixner, Anette; Kasemann, Simone A.; Bach, Wolfgang

2017-11-01

Multiple batch experiments (100 °C, 200 °C; 40 MPa) were conducted, using Dickson-type reactors, to investigate Li and B partitioning and isotope fractionation between rock and water during serpentinization. We reacted fresh olivine (5 g; Fo90; [B] = <0.02 μg/g; δ11BOlivine -14‰; [Li] = 1.7 μg/g; δ7LiOlivine = +5.3‰) with seawater-like fluids (75 ml, 3.2 wt.% NaCl) adjusted with respect to their Li (0.2, 0.5 μg/ml; and δ7LiFluid +55‰) and B (∼10 μg/ml and δ11BFluid -0.3‰) characteristics. At 200 °C a reaction turnover of about 70% and a serpentinization mineral assemblage matching equilibrium thermodynamic computational results (EQ3/6) developed after 224 days runtime. Characterization of concomitant fluid samples indicated a distinct B incorporation into solid phases ([B]final_200 °C = 55.61 μg/g; DS/FB200 °C = 13.42) and a preferential uptake of the lighter 10B isotope (Δ11BS-F = -3.46‰). Despite a low reaction turnover at 100 °C (<12%), considerable amounts of B were again incorporated into solid phases ([B]final_100 °C = 25.33 μg/g; DS/FB100 °C = 24.2) with even a larger isotope fractionation factor (Δ11BS-F = -9.97‰). While magnitude of isotope fraction appears anti-correlated with temperature, we argue for an overall attenuation of the isotopic effect through changes in B speciation in saline solutions (NaB(OH)4(aq) and B(OH)3Cl-) as well as variable B fixation and fractionation for different serpentinization product minerals (brucite, chrysotile). Breakdown of the Li-rich olivine and limited Li incorporation into product mineral phases resulted in an overall lower Li content of the final solid phase assemblage at 200 °C ([Li]final_200 °C = 0.77 μg/g; DS/FLi200 °C = 1.58). First order changes in Li isotopic compositions were defined by mixing of two isotopically distinct sources i.e. the fresh olivine and the fluid rather than by equilibrium isotope fraction. At 200 °C primary olivine is dissolved, releasing its Li budget into the fluid which shifts towards a lower δ7LiF of +38.62‰. Newly formed serpentine minerals (δ7LiS = +30.58‰) incorporate fluid derived Li with a minor preference of the 6Li isotope. At 100 °C Li enrichment of secondary phases exceeded Li release by olivine breakdown ([Li]final_100 °C = 2.10 μg/g; DS/FLi100 °C = 11.3) and it was accompanied by preferential incorporation of heavier 7Li isotope that might be due to incorporation of a 7Li enriched fluid fraction into chrysotile nanotubes.

Role of isotope mass and evidence of fluctuating zonal flows during the L–H transition in the TJ-II stellarator

NASA Astrophysics Data System (ADS)

Losada, U.; Estrada, T.; Liu, B.; van Milligen, B.; Cheng, J.; Silva, C.; Pastor, I.; Fontdecaba, J. M.; Hidalgo, C.; TJ-II team1, the

2018-07-01

Mean radial electric fields as well as low frequency Zonal Flow-like global oscillations in radial electric field have been identified during the low to high (L–H) transition in Hydrogen and Deuterium dominated plasmas in the stellarator TJ-II. No evidence of isotope effect on the L–H transition dynamics was observed in the investigated TJ-II plasma scenarios. These observations emphasize the critical role of both zero frequency (equilibrium) and low frequency varying large-scale flows for stabilizing turbulence during the triggering of the L–H transition in magnetically confined toroidal plasmas.

Nickel and chromium isotopes in Allende inclusions

NASA Technical Reports Server (NTRS)

Birck, J. L.; Lugmair, G. W.

1988-01-01

High-precision nickel and chromium isotopic measurements were carried out on nine Allende inclusions. It is found that Ni-62, Ni-64, excesses are present in at least three of the samples. The results suggest that the most likely mechanism for the anomalies is a neutron-rich statistical equilibrium process. An indication of elevated Ni-60 is found in almost every inclusion measured. This effect is thought to be related to the decay of now extinct Fe-60. An upper limit of 1.6 X 10 to the -6th is calculated for the Fe-60/Fe-56 ratio at the time these Allende inclusions crystallized.

Thermophysiology of Tyrannosaurus rex: Evidence from Oxygen Isotopes.

PubMed

Barrick, R E; Showers, W J

1994-07-08

The oxygen isotopic composition of vertebrate bone phosphate (delta(p)) is related to ingested water and to the body temperature at which the bone forms. The delta(p) is in equilibrium with the individual's body water, which is at a physiological steady state throughout the body. Therefore, intrabone temperature variation and the mean interbone temperature differences of well-preserved fossil vertebrates can be determined from the deltap variation. Values of delta(p) from a well-preserved Tyrannosaurus rex suggest that this species maintained homeothermy with less than 4 degrees C of variability in body temperature. Maintenance of homeothermy implies a relatively high metabolic rate that is similar to that of endotherms.

Tungsten species in natural ferromanganese oxides related to its different behavior from molybdenum in oxic ocean

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Takahashi, Yoshio; Marcus, Matthew A.; Uruga, Tomoya; Tanida, Hajime; Terada, Yasuko; Usui, Akira

2013-04-01

The tungsten (W) species in marine ferromanganese oxides were investigated by wavelength dispersive XAFS method. We found that the W species are in distorted Oh symmetry in natural ferromanganese oxides. The host phase of W is suggested to be Mn oxides by μ-XRF mapping. We also found that the W species forms inner-sphere complexes in hexavalent state and distorted Oh symmetry on synthetic ferrihydrite, goethite, hematite, and δ-MnO2. The molecular-scale information of W indicates that the negatively-charged WO42- ion mainly adsorbs on the negatively-charged Mn oxides phase in natural ferromanganese oxides due to the strong chemical interaction. In addition, preferential adsorption of lighter W isotopes is expected based on the molecular symmetry of the adsorbed species, implying the potential significance of the W isotope systems similar to Mo. Adsorption experiments of W on synthetic ferrihydrite and δ-MnO2 were also conducted. At higher equilibrium concentration, W exhibits behaviors similar to Mo on δ-MnO2 due to their formations of inner-sphere complexes. On the other hand, W shows a much larger adsorption on ferrihydrite than Mo. This is due to the formation of the inner- and outer-sphere complexes for W and Mo on ferrihydrite, respectively. Considering the lower equilibrium concentration such as in oxic seawater, however, the enrichment of W into natural ferromanganese oxides larger than Mo may be controlled by the different stabilities of their inner-sphere complexes on the Mn oxides. These two factors, (i) the stability of inner-sphere complexes on the Mn oxides and (ii) the mode of attachment on ferrihydrite (inner- or outer-sphere complex), are the causes of the different behaviors of W and Mo on the surface of the Fe/Mn (oxyhydr)oxides.

Clumped isotope composition of cold-water corals: A role for vital effects?

NASA Astrophysics Data System (ADS)

Spooner, Peter T.; Guo, Weifu; Robinson, Laura F.; Thiagarajan, Nivedita; Hendry, Katharine R.; Rosenheim, Brad E.; Leng, Melanie J.

2016-04-01

The carbonate clumped isotope thermometer is a promising tool for determining past ocean temperatures. It is based on the temperature dependence of rare isotopes 'clumping' into the same carbonate ion group in the carbonate mineral lattice. The extent of this clumping effect is independent of the isotope composition of the water from which carbonate precipitates, providing unique advantages over many other paleotemperature proxies. Existing calibrations of this thermometer in cold-water and warm-water corals suggest clumped isotope 'vital effects' are negligible in cold-water corals but may be significant in warm-water corals. Here, we test the calibration of the carbonate clumped isotope thermometer in cold-water corals with a recently collected and well characterised sample set spanning a range of coral genera (Balanophyllia, Caryophyllia, Dasmosmilia, Desmophyllum, Enallopsammia and Javania). The clumped isotope compositions (Δ47) of these corals exhibit systematic dependences on their growth temperatures, confirming the basis of the carbonate clumped isotope thermometer. However, some cold-water coral genera show Δ47 values that are higher than the expected equilibrium values by up to 0.05‰ (equivalent to underestimating temperature by ∼9 °C) similar to previous findings for some warm-water corals. This finding suggests that the vital effects affecting corals Δ47 are common to both warm- and cold-water corals. By comparison with models of the coral calcification process we suggest that the clumped isotope offsets in these genera are related to the kinetic isotope effects associated with CO2 hydration/hydroxylation reactions in the corals' calcifying fluid. Our findings complicate the use of the carbonate clumped isotope thermometer in corals, but suggest that species- or genus-specific calibrations could be useful for the future application of this paleotemperature proxy.

Evaluation of Pleistocene groundwater flow through fractured tuffs using a U-series disequilibrium approach, Pahute Mesa, Nevada, USA

USGS Publications Warehouse

Paces, James B.; Nichols, Paul J.; Neymark, Leonid A.; Rajaram, Harihar

2013-01-01

Groundwater flow through fractured felsic tuffs and lavas at the Nevada National Security Site represents the most likely mechanism for transport of radionuclides away from underground nuclear tests at Pahute Mesa. To help evaluate fracture flow and matrix–water exchange, we have determined U-series isotopic compositions on more than 40 drill core samples from 5 boreholes that represent discrete fracture surfaces, breccia zones, and interiors of unfractured core. The U-series approach relies on the disruption of radioactive secular equilibrium between isotopes in the uranium-series decay chain due to preferential mobilization of 234U relative to 238U, and U relative to Th. Samples from discrete fractures were obtained by milling fracture surfaces containing thin secondary mineral coatings of clays, silica, Fe–Mn oxyhydroxides, and zeolite. Intact core interiors and breccia fragments were sampled in bulk. In addition, profiles of rock matrix extending 15 to 44 mm away from several fractures that show evidence of recent flow were analyzed to investigate the extent of fracture/matrix water exchange. Samples of rock matrix have 234U/238U and 230Th/238U activity ratios (AR) closest to radioactive secular equilibrium indicating only small amounts of groundwater penetrated unfractured matrix. Greater U mobility was observed in welded-tuff matrix with elevated porosity and in zeolitized bedded tuff. Samples of brecciated core were also in secular equilibrium implying a lack of long-range hydraulic connectivity in these cases. Samples of discrete fracture surfaces typically, but not always, were in radioactive disequilibrium. Many fractures had isotopic compositions plotting near the 230Th-234U 1:1 line indicating a steady-state balance between U input and removal along with radioactive decay. Numerical simulations of U-series isotope evolution indicate that 0.5 to 1 million years are required to reach steady-state compositions. Once attained, disequilibrium 234U/238U and 230Th/238U AR values can be maintained indefinitely as long as hydrological and geochemical processes remain stable. Therefore, many Pahute Mesa fractures represent stable hydrologic pathways over million-year timescales. A smaller number of samples have non-steady-state compositions indicating transient conditions in the last several hundred thousand years. In these cases, U mobility is dominated by overall gains rather than losses of U.

Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

NASA Astrophysics Data System (ADS)

Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

2015-12-01

Chondrichthyan teeth (sharks, rays, and chimaeras) are mineralized in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are generally consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the hybodont shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

Stable isotopes of pedogenic carbonates from the Somma-Vesuvius area, southern Italy, over the past 18 kyr: palaeoclimatic implications

NASA Astrophysics Data System (ADS)

Zanchetta, G.; di Vito, M.; Fallick, A. E.; Sulpizio, R.

2000-12-01

Stable isotopes were measured in the carbonate and organic matter of palaeosols in the Somma-Vesuvius area, southern Italy in order to test whether they are suitable proxy records for climatic and ecological changes in this area during the past 18000 yr. The ages of the soils span from ca. 18 to ca. 3 kyr BP. Surprisingly, the Last Glacial to Holocene climate transition was not accompanied by significant change in 18O of pedogenic carbonate. This could be explained by changes in evaporation rate and in isotope fractionation between water and precipitated carbonate with temperature, which counterbalanced the expected change in isotope composition of meteoric water. Because of the rise in temperature and humidity and the progressive increase in tree cover during the Holocene, the Holocene soil carbonates closely reflect the isotopic composition of meteoric water. A cooling of about 2°C after the Avellino eruption (3.8 ka) accounts for a sudden decrease of about 1 in 18O of pedogenic carbonate recorded after this eruption. The 13C values of organic matter and pedogenic carbonate covary, indicating an effective isotope equilibrium between the organic matter, as the source of CO2, and the pedogenic carbonate. Carbon isotopes suggest prevailing C3 vegetation and negligible mixing with volcanogenic or atmospheric CO2.

Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

NASA Astrophysics Data System (ADS)

Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

2015-08-01

Chondrichthyan teeth (sharks, rays and chimaeras) are mineralised in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered as a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the primitive shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

Isotopic Randomness and Maxwell's Demon

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

2005-03-01

Isotopic disorder in crystals can lead to suppression of thermal conductivity, mobility variations and (weak) Anderson localization on isotopic fluctuations. The latter (AAB, J.ChemPhys.1984) is akin to polaron effect (self-localization due polarization). Possibility of isotopic patterning (IP) increases near melting point (thermally activated isotopic hopping swaps). Crystal near melting threshold become “informationally sensitive” as if its IP is operated by some external Maxwell’s Demon, MD (AAB, URAM J, 2002). At this state short range (e.g. electrostatic inverse square) forces evolve into long-range interactions (due to divergence of order parameter) and information sensitivity can be further amplified by (say) a single fast electron (e.g. beta-particle from decay of 14-C or other radioactive isotope) which may result in cascade of impact ionization events and (short time-scale) enhancement of screening by impact-generated non-equilibrium (non-thermal) electrons. In this state informationally driven (MD-controlled) IP (Eccles effect) can result in decrease of positional entropy signifying emergence of physical complexity out of pure information, similar to peculiar “jinni effect” on closed time loops in relativistic cosmology (R.J.Gott, 2001) or Wheeler’s “it from bit” metaphor. By selecting special IP, MD modifies ergodicity principle in favor of info rich states.

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.

Theoretical estimates of equilibrium sulfur isotope effects in aqueous sulfur systems: Highlighting the role of isomers in the sulfite and sulfoxylate systems

NASA Astrophysics Data System (ADS)

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

2016-12-01

We present theoretical calculations for all three isotope ratios of sulfur (33S/32S, 34S/32S, 36S/32S) at the B3LYP/6-31+G(d,p) level of theory for aqueous sulfur compounds modeled in 30-40H2O clusters spanning the range of sulfur oxidation state (Sn, n = -2 to +6) for estimating equilibrium fractionation factors in aqueous systems. Computed 34β values based on major isotope (34S/32S) reduced partition function ratios (RPFRs) scale to a first order with sulfur oxidation state and coordination, where 34β generally increase with higher oxidation state and increasing coordination of the sulfur atom. Exponents defining mass dependent relationships based on β values (x/34κ = ln(xβ)/ln(34β), x = 33 or 36) conform to tight ranges over a wide range of temperature for all aqueous compounds (33/34κ ≈ 0.5148-0.5159, 36/34κ ≈ 1.89-1.90 from T ⩾ 0 °C). The exponents converge near a singular value for all compounds at the high temperature limit (33/34κT→∞ = 0.51587 ± 0.00003 and 36/34κT→∞ = 1.8905 ± 0.0002; 1 s.d. of all computed compounds), and typically follow trends based on oxidation state and coordination similar to those seen in 34β values at lower temperatures. Theoretical equilibrium fractionation factors computed from these β-values are compared to experimental constraints for HSO3-T(aq)/SO2(g, aq), SO2(aq)/SO2(g), H2S(aq)/H2S(g), H2S(aq)/HS-(aq), SO42-(aq)/H2ST(aq), S2O32-(aq) (intramolecular), and S2O32-(aq)/H2ST(aq), and generally agree within a reasonable estimation of uncertainties. We make predictions of fractionation factors where other constraints are unavailable. Isotope partitioning of the isomers of protonated compounds in the sulfite and sulfoxylate systems depend strongly on whether protons are bound to either sulfur or oxygen atoms. The magnitude of the HSO3-T/SO32- major isotope (34S/32S) fractionation factor is predicted to increase with temperature from 0 to 70 °C due to the combined effects of the large magnitude (HS)O3-/SO32- fractionation factor (1000ln34α(HS)bisulfite-sulfite = 19.9‰, 25 °C) relative to the (HO)SO2-/SO32- fractionation factor (1000ln34α(HO)bisulfite-sulfite = -2.2‰, 25 °C), and the increased stability of the (HS)O3- isomer with increasing temperature. We argue that isomerization phenomenon should be considered in models of the sulfur cycle, including models that describe the overall sulfur isotope fractionations associated with microbial metabolism (e.g., microbial sulfate reduction).

Origin of temporal compositional trends in monogenetic vent eruptions: Insights from the crystal cargo in the Papoose Canyon sequence, Big Pine Volcanic Field, CA

NASA Astrophysics Data System (ADS)

Gao, Ruohan; Lassiter, John C.; Ramirez, Gabrielle

2017-01-01

Many monogenetic vents display systematic temporal-compositional variations over the course of eruption. Previous studies have proposed that these trends may reflect variable degrees of crustal assimilation, or melting and mixing of heterogeneous mantle source(s). Discrimination between these two endmember hypotheses is critical for understanding the plumbing systems of monogenetic volcanoes, which pose a significant volcanic hazard in many areas. In this study, we examine the Papoose Canyon (PC) monogenetic vent in the Big Pine Volcanic Field (BPVF), which had been well characterized for temporal-compositional variations in erupted basalts. We present new major and trace element and Sr-Nd-Pb-O isotopic data from the PC "crystal cargo" (phenocrysts and xenoliths). Comparison of "crystal cargo" and host basalt provides new constraints on the history of magma storage, fractionation, and crustal contamination that are obscured in the bulk basalts due to pre- and syn-eruptive magma mixing processes. The abundances of phenocrysts and ultramafic xenoliths in the PC sequence decrease up-section. Olivine and clinopyroxene phenocrysts span a wide range of Mg# (77-89). The majority of phenocrysts are more evolved than olivine or clinopyroxene in equilibrium with their host basalts (Mg# = 68- 71, equilibrium Fo ≈ 85- 89). In addition, the ultramafic xenoliths display cumulate textures. Olivine and clinopyroxene from ultramafic xenoliths have Mg# (73-87) similar to the phenocrysts, and lower than typical mantle peridotites. Sr-Nd-Pb isotope compositions of the xenoliths are similar to early PC basalts. Finally, many clinopyroxene phenocrysts and clinopyroxene in xenoliths have trace element abundances in equilibrium with melts that are more enriched than the erupted basalts. These features suggest that the phenocrysts and xenoliths derive from melt that is more fractionated and enriched than erupted PC basalts. Pressure constraints suggest phenocrysts and ultramafic xenoliths crystallized at ∼5-7 kbar, corresponding to mid-crust depths. Correlations between HFSE depletion and Sr-Nd-Pb isotopic compositions, high δ18 O values in olivines, and radiogenic Os isotopic compositions in whole rocks also suggest incorporation of a crustally contaminated component. We propose that the phenocrysts and ultramafic xenoliths derive from melts that ponded and fractionated and assimilated continental crust, possibly in mid-crustal sills. These melts were drained and mixed with more primitive melts as the eruption began, and the temporal-compositional trends and decreasing crystal phase abundances reflect gradual deflation and exhaustion of these sills as the eruption progressed. The isotopic variations in the PC sequence span much of the compositional range observed in the BPVF. Evidence for variable crustal contamination of PC basalts suggests that much of the isotopic variation observed in the BPVF may also reflect crustal contamination rather than mantle source heterogeneity as previously proposed. In addition, evidence of pre-eruptive magma ponding and fractionation, if applicable to other monogenetic vents, may have significant implications for monitoring and hazard assessment of monogenetic volcano fields.

Large sulfur isotope fractionations in Martian sediments at Gale crater

NASA Astrophysics Data System (ADS)

Franz, H. B.; McAdam, A. C.; Ming, D. W.; Freissinet, C.; Mahaffy, P. R.; Eldridge, D. L.; Fischer, W. W.; Grotzinger, J. P.; House, C. H.; Hurowitz, J. A.; McLennan, S. M.; Schwenzer, S. P.; Vaniman, D. T.; Archer, P. D., Jr.; Atreya, S. K.; Conrad, P. G.; Dottin, J. W., III; Eigenbrode, J. L.; Farley, K. A.; Glavin, D. P.; Johnson, S. S.; Knudson, C. A.; Morris, R. V.; Navarro-González, R.; Pavlov, A. A.; Plummer, R.; Rampe, E. B.; Stern, J. C.; Steele, A.; Summons, R. E.; Sutter, B.

2017-09-01

Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA’s Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in 34S. Measured values of δ34S range from -47 +/- 14‰ to 28 +/- 7‰, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

Stable water isotopologue ratios in fog and cloud droplets of liquid clouds are not size-dependent

USGS Publications Warehouse

Spiegel, J.K.; Aemisegger, F.; Scholl, M.; Wienhold, F.G.; Collett, J.L.; Lee, T.; van Pinxteren, D.; Mertes, S.; Tilgner, A.; Herrmann, H.; Werner, Roland A.; Buchmann, N.; Eugster, W.

2012-01-01

In this work, we present the first observations of stable water isotopologue ratios in cloud droplets of different sizes collected simultaneously. We address the question whether the isotope ratio of droplets in a liquid cloud varies as a function of droplet size. Samples were collected from a ground intercepted cloud (= fog) during the Hill Cap Cloud Thuringia 2010 campaign (HCCT-2010) using a three-stage Caltech Active Strand Cloud water Collector (CASCC). An instrument test revealed that no artificial isotopic fractionation occurs during sample collection with the CASCC. Furthermore, we could experimentally confirm the hypothesis that the δ values of cloud droplets of the relevant droplet sizes (μm-range) were not significantly different and thus can be assumed to be in isotopic equilibrium immediately with the surrounding water vapor. However, during the dissolution period of the cloud, when the supersaturation inside the cloud decreased and the cloud began to clear, differences in isotope ratios of the different droplet sizes tended to be larger. This is likely to result from the cloud's heterogeneity, implying that larger and smaller cloud droplets have been collected at different moments in time, delivering isotope ratios from different collection times.

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.

Mechanism of α-ketol-type rearrangement of benzoin derivatives under basic conditions.

PubMed

Karino, Masahiro; Kubouchi, Daiki; Hamaoka, Kazuki; Umeyama, Shintaro; Yamataka, Hiroshi

2013-07-19

The mechanism of base-catalyzed rearrangement of ring-substituted benzoins in aqueous methanol was examined by kinetic and product analyses. Substituent effects on the rate and equilibrium constants revealed that the kinetic process has a different electron demand compared to the equilibrium process. Reactions in deuterated solvents showed that the rate of H/D exchange of the α-hydrogen is similar to the overall rate toward the equilibrium state. A proton-inventory experiment using partially deuterated solvents showed a linear dependence of the rate on the deuterium fraction of the solvent, indicating that only one deuterium isotope effect contributes to the overall rate process. All these results point to a mechanism in which the rearrangement is initiated by the rate-determining α-hydrogen abstraction rather than a mechanism with initial hydroxyl hydrogen abstraction as in the general α-ketol rearrangement.

Temperature and vital effect controls on Bamboo coral (Isididae) isotopegeochemistry: A test of the "lines method"

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

Hill, T M; Spero, H J; Guilderson, T P

Deep-sea bamboo corals hold promise as long-term climatic archives, yet little information exists linking bamboo coral geochemistry to measured environmental parameters. This study focuses on a suite of 10 bamboo corals collected from the Pacific and Atlantic basins (250-2136 m water depth) to investigate coral longevity, growth rates, and isotopic signatures. Calcite samples for stable isotopes and radiocarbon were collected from the base the corals, where the entire history of growth is recorded. In three of the coral specimens, samples were also taken from an upper branch for comparison. Radiocarbon and growth band width analyses indicate that the skeletal calcitemore » precipitates from ambient dissolved inorganic carbon and that the corals live for 150-300 years, with extension rates of 9-128 {micro}m/yr. A linear relationship between coral calcite {delta}{sup 18}O and {delta}{sup 13}C indicates that the isotopic composition is influenced by vital effects ({delta}{sup 18}O:{delta}{sup 13}C slope of 0.17-0.47). As with scleractinian deep-sea corals, the intercept from a linear regression of {delta}{sup 18}O versus {delta}{sup 13}C is a function of temperature, such that a reliable paleotemperature proxy can be obtained, using the 'lines method.' Although the coral calcite {delta}{sup 18}O:{delta}{sup 13}C slope is maintained throughout the coral base ontogeny, the branches and central cores of the bases exhibit {delta}{sup 18}O:{delta}{sup 13}C values that are shifted far from equilibrium. We find that a reliable intercept value can be derived from the {delta}{sup 18}O:{delta}{sup 13}C regression of multiple samples distributed throughout one specimen or from multiple samples within individual growth bands.« less

Identification of sulfur sources and isotopic equilibria in submarine hot-springs using multiple sulfur isotopes

NASA Astrophysics Data System (ADS)

McDermott, Jill M.; Ono, Shuhei; Tivey, Margaret K.; Seewald, Jeffrey S.; Shanks, Wayne C.; Solow, Andrew R.

2015-07-01

Multiple sulfur isotopes were measured in metal sulfide deposits, elemental sulfur, and aqueous hydrogen sulfide to constrain sulfur sources and the isotopic systematics of precipitation in seafloor hydrothermal vents. Areas studied include the Eastern Manus Basin and Lau Basin back-arc spreading centers and the unsedimented basalt-hosted Southern East Pacific Rise (SEPR) and sediment-hosted Guaymas Basin mid-ocean ridge spreading centers. Chalcopyrite and dissolved hydrogen sulfide (H2S) δ34S values range from -5.5‰ to +5.6‰ in Manus Basin samples, +2.4‰ to +6.1‰ in Lau Basin samples, and +3.7‰ to +5.7‰ in SEPR samples. Values of δ34S for cubic cubanite and H2S range from -1.4‰ to +4.7‰ in Guaymas Basin samples. Multiple sulfur isotope systematics in fluid-mineral pairs from the SEPR and Lau Basin show that crustal host rock and thermochemical reduction of seawater-derived dissolved sulfate (SO4) are the primary sources of sulfur in mid-ocean ridge and some back-arc systems. At PACMANUS and SuSu Knolls hydrothermal systems in the Eastern Manus Basin, a significant contribution of sulfur is derived from disproportionation of magmatic sulfur dioxide (SO2), while the remaining sulfur is derived from crustal host rocks and SO4 reduction. At the sedimented Guaymas Basin hydrothermal system, sulfur sources include crustal host rock, reduced seawater SO4, and biogenic sulfide. Vent fluid flow through fresher, less-mature sediment supplies an increased quantity of reactant organic compounds that may reduce 34S-enriched SO4, while fluid interaction with more highly-altered sediments results in H2S characterized by a small, but isotopically-significant input of 34S-depleted biogenic sulfides. Near-zero Δ33S values in all samples implicate the abiotic processes of SO4 reduction and leaching of host rock as the major contributors to sulfur content at a high temperature unsedimented mid-ocean ridge and at a back-arc system. Δ33S values indicate that SO2 disproportionation is an additional process that contributes sulfur to a different back-arc system and to acid spring-type hydrothermal fluid circulation. At the sedimented Guaymus Basin, near-zero Δ33S values are also observed, despite negative δ34S values that indicate inputs of biogenic pyrite for some samples. In contrast with previous studies reporting isotope disequilibrium between H2S and chalcopyrite, the δ34S values of chalcopyrite sampled from the inner 1-2 mm of a chimney wall are within ±1‰ of δ34S values for H2S in the paired vent fluid, suggesting equilibrium fluid-mineral sulfur isotope exchange at 300-400 °C. Isotopic equilibrium between hydrothermal fluid H2S and precipitating chalcopyrite implies that sulfur isotopes in the chalcopyrite lining across a chimney wall may accurately record past hydrothermal activity.

Isotopic constraints on ice age fluids in active geothermal systems: Reykjanes, Iceland

NASA Astrophysics Data System (ADS)

Pope, Emily C.; Bird, Dennis K.; Arnórsson, Stefán; Fridriksson, Thráinn; Elders, Wilfred A.; Fridleifsson, Gudmundur Ó.

2009-08-01

The Reykjanes geothermal system is located on the landward extension of the Mid-Atlantic Ridge in southwest Iceland, and provides an on-land proxy to high-temperature hydrothermal systems of oceanic spreading centers. Previous studies of elemental composition and salinity have shown that Reykjanes geothermal fluids are likely hydrothermally modified seawater. However, δD values of these fluids are as low as -23‰, which is indicative of a meteoric water component. Here we constrain the origin of Reykjanes hydrothermal solutions by analysis of hydrogen and oxygen isotope compositions of hydrothermal epidote from geothermal drillholes at depths between 1 and 3 km. δDEPIDOTE values from wells RN-8, -9, -10 and -17 collectively range from -60 to -78‰, and δ18OEPIDOTE in these wells are between -3.0 and 2.3‰. The δD values of epidote generally increase along a NE trend through the geothermal field, whereas δ18O values generally decrease, suggesting a southwest to northeast migration of the geothermal upflow zone with time that is consistent with present-day temperatures and observed hydrothermal mineral zones. For comparative analysis, the meteoric-water dominated Nesjavellir and Krafla geothermal systems, which have a δDFLUID of ˜ -79‰ and -89‰, respectively, show δDEPIDOTE values of -115‰ and -125‰. In contrast, δDEPIDOTE from the mixed meteoric-seawater Svartsengi geothermal system is -68‰; comparable to δDEPIDOTE from well RN-10 at Reykjanes. Stable isotope compositions of geothermal fluids in isotopic equilibrium with the epidotes at Reykjanes are computed using published temperature dependent hydrogen and oxygen isotope fractionation curves for epidote-water, measured isotope composition of the epidotes and temperatures approximated from the boiling point curve with depth. Calculated δD and δ18O of geothermal fluids are less than 0‰, suggesting that fluids of meteoric or glacial origin are a significant component of the geothermal solutions. Additionally, δDFLUID values in equilibrium with geothermal epidote are lower than those of modern-day fluids, whereas calculated δ18OFLUID values are within range of the observed fluid isotope composition. We propose that modern δDEPIDOTE and δDFLUID values are the result of diffusional exchange between hydrous alteration minerals that precipitated from glacially-derived fluids early in the evolution of the Reykjanes system and modern seawater-derived geothermal fluids. A simplified model of isotope exchange in the Reykjanes geothermal system, in which the average starting δDROCK value is -125‰ and the water to rock mass ratio is 0.25, predicts a δDFLUID composition within 1‰ of average measured values. This model resolves the discrepancy between fluid salinity and isotope composition of Reykjanes geothermal fluids, explains the observed disequilibrium between modern fluids and hydrothermal epidote, and suggests that rock-fluid interaction is the dominant control over the evolution of fluid isotope composition in the hydrothermal system.

The source of phosphate in the oxidation zone of ore deposits: Evidence from oxygen isotope compositions of pyromorphite

NASA Astrophysics Data System (ADS)

Burmann, Fabian; Keim, Maximilian F.; Oelmann, Yvonne; Teiber, Holger; Marks, Michael A. W.; Markl, Gregor

2013-12-01

Pyromorphite (Pb5[PO4]3Cl) is an abundant mineral in oxidized zones of lead-bearing ore deposits and due to its very low solubility product effectively binds Pb during supergene alteration of galena (PbS). The capacity of a soil or near-surface fluid to immobilize dissolved Pb depends critically on the availability of phosphate in this soil or fluid. Potential phosphorus sources in soil include (i) release during biological processes, i.e. leaching from litter/lysis of microbial cells (after intracellular enzyme activity) in soil and hydrolysis from soil organic matter by extracellular enzymes and (ii) inorganic phosphate from the dissolution of apatite in the adjacent basement rocks. Intracellular enzyme activity in plants/microorganisms associated with kinetic fractionation produces an oxygen isotope composition distinctly different from inorganic processes in soil. This study presents the first oxygen isotope data for phosphate (δ18OP) in pyromorphite and a comprehensive data set for apatite from crystalline rocks. We investigated 38 pyromorphites from 26 localities in the Schwarzwald (Southwest Germany) and five samples from localities outside the Schwarzwald in addition to 12 apatite separates from gneissic and granitic host rocks. Pyromorphites had δ18OP values between +10‰ and +19‰, comparable to literature data on δ18OP in the readily available P fraction in soil (resin-extractable P) from which minerals potentially precipitate in soils. δ18OP values below the range of equilibrium isotope fractionation can be attributed either to apatites that formed geochemically (δ18OP of apatites:+6‰ to +9‰) or less likely to biological processes (extracellular enzyme activity). However, for most of our samples isotopic equilibrium with ambient water was indicated, which suggests biological activity. Therefore, we conclude that the majority of pyromorphites in oxidized zones of ore bodies formed from biologically cycled phosphate. This study highlights that biological activity and Pb mobilization are intimately connected: in humid regions with high biological activity in soil, Pb might be precipitated rapidly due to biologically-released phosphate, whereas Pb will be released to the environment from ore deposits or mine dumps much more easily in arid regions with low biological activity, because pyromorphite cannot form due to limited supply of phosphorus. Phosphate from magmatic, metamorphic or sedimentary rocks: The most important phosphate-bearing mineral in such rocks is apatite (Ca5[(PO4)3(F,Cl,OH)]). In magmatic and metamorphic rocks it generally occurs as fluorapatite (Piccoli and Candela, 2002; Filippelli, 2008), whereas sedimentary rocks may also contain considerable amounts of carbonate-fluorapatite. Phosphorites are present in the geological record since the Lower Proterozoic (Cook and McElhinny, 1979; Shemesh et al., 1983). Alteration with low-pH fluids can dissolve apatite and thereby release geochemical phosphate (Filippelli, 2008). Low pH values may be attained by dissolution of atmospheric CO2 or by reaction with sulfides present in the rocks or in adjacent ore deposits. Phosphate of organic origin, such as from plants, animals or microorganisms: Phosphorus is required in most biological systems, as it is an essential element in major organic molecules such as adenosine triphosphate in the energy cycle, or in phospholipids, which form cell walls (Bucher, 2007; Filippelli, 2008). Organisms take up phosphorus as dissolved inorganic phosphate and cycle it through metabolic processes (intracellular enzyme activity). Once entering the soil, the organic material is decomposed by extracellular enzyme activity (hydrolysis of ester bonds) and phosphate is being released (Bünemann et al., 2011). Phosphate of anthropogenic origin: Since phosphate is a limiting factor in organism growth, it is an important ingredient of fertilizers in the agricultural industry. Also, phosphate can be found as ingredients in detergents, toothpaste and as a release of waste water treatment plants (Young et al., 2009). Anthropogenic effects will not be discussed further in the following. On this basis, we consider three different cases of pyromorphite formation as illustrated on the conceptual scheme of Fig. 1. Case 1: Pyromorphite grown recently (within the last hundreds of years) on rock surfaces in former mines. Both, phosphate released geochemically from igneous rocks and phosphate released biologically during leaching from litter/lysis of microbial cells and soil organic matter decomposition are possible sources. Case 2: Pyromorphite formation on mine dumps, below vegetation (recent, during tens to hundreds of years). Based on the specific setting of these samples investigated here (they were found exclusively below a large fern; see more details in the section on sample description), biologically-mediated P release provides the phosphate for pyromorphite growth. Case 3: Pyromorphite growth in the oxidized zones of ore bodies prior to human interference. Most samples of our study belong to this case.Phosphorus generally forms very strong covalent bonds (Huminicki and Hawthorne, 2002) and there is only negligible exchange of oxygen isotopes between phosphate and ambient water under most near-surface conditions without biological activity (Winter et al., 1940; Longinelli, 1965). The only important exchange of oxygen isotopes between phosphate and ambient water involves biological activity and the oxygen isotope composition of phosphate (δ18OP) may be modified by different enzymatic/cellular processes. Once phosphate is taken up by organisms, intracellular pyrophosphatase mediates internal P cycling. This is associated with a temperature-dependent equilibrium isotope fractionation due to the reversible exchange of O atoms between the phosphate molecule and cell water. As a result the δ18OP is equilibrated with the ambient water, and the equilibrium temperature can be calculated following the revised empirical equation from Longinelli and Nuti (1973) presented by Puceat et al. (2010): T(°C)=118.7-4.22[(δ18OP+(22.6-δ18ONBS120c))-δ18OW] where T is the temperature of the ambient water, δ18OP is the oxygen isotope composition of the phosphate at equilibrium conditions, δ18ONBS120c is the oxygen isotope composition of reference material NBS120c according to Vennemann et al. (2002) and δ18OW is the oxygen isotope composition of the ambient water. Knowledge of the δ18OP of ambient water and its temperature renders it possible to calculate a theoretical equilibrium value for δ18OP. If phosphate is again released from organisms into the soil, it will reflect the δ18OP of the cell-internal P cycling. In addition, extracellular enzymes are released in soil if the demand for P requires the hydrolysis of organic P in soil (McGill and Cole, 1981). Extracellular enzymes also transfer O atoms from water to phosphate and thus, change δ18OP. The associated isotopic fractionation factors vary between -10‰ (enzyme: 5‧-nucleotidase) and -30‰ (enzyme: alkaline phosphatase; Liang and Blake, 2006, 2009). All recent publications on δ18OP of phosphate in the readily available P fraction in soil (resin P) showed δ18OP values in the range calculated for isotopic equilibrium fractionation irrespective of environmental conditions (parent material, climate, biome). At most 20% down to 0% of the measured δ18OP fell outside the calculated isotopic equilibrium range (Angert et al., 2011, 2012; Tamburini et al., 2012). We therefore infer a dominant role of intracellular enzyme activity for δ18OP values in resin P in soil.Theoretical calculations by Lecuyer et al. (1999) imply that oxygen isotope exchange between phosphate and water can also occur in the absence of biological activity. An extrapolation of their equations to temperatures of 10 °C shows, however, that it takes more than 6000 years to exchange 10% of the phosphate oxygen (Colman et al., 2005). Traditionally, the oxygen isotope composition of phosphate has been used as a tool for determining paleotemperatures (e.g., Longinelli, 1984), but recent studies suggested to test its suitability for tracing phosphate sources in aquatic systems (Gruau et al., 2005; Elsbury et al., 2009; Young et al., 2009). Most of these studies deal with short-term ecological cycles and therefore the inorganic exchange of oxygen is negligible. However, this effect has to be considered for processes that happen in geological timescales.Due to the low phosphate concentrations in natural waters (Blake et al., 2005) and the low solubility product of pyromorphite, it is reasonable to assume almost all phosphate to precipitate as pyromorphite without any fractionation. Accordingly, the δ18OP of pyromorphite reflects the oxygen isotope composition of the dissolved phosphate in the water from which it precipitated and records the source, if this phosphate was not modified during fluid transport.Different phosphate reservoirs differ in their oxygen-isotope composition and with more and more data available it is possible to discriminate between different sources. Data for phosphates in aquatic systems are provided by Young et al. (2009): Phosphates of anthropogenic origin (fertilizers and the corresponding processing stages, detergents and toothpaste) show δ18OP values between +13.3‰ and +22.3‰, for phosphates from organic sources (vegetation leachate and animal waste) values between +14.2‰ and +23.1‰ are reported and a range between +8.4‰ and +14.2‰ is covered by phosphates of waste water treatment plants. For terrestrial ecosystems, Tamburini et al. (2012) reported δ18OP values between +4.5‰ and +31.4‰ with most data falling in the range of +12.4‰ to +31.4‰ for phosphate in plants (N = 11). Microbial phosphate in soil covered a range of +11‰ to +19‰. Resin-extractable P in soil as the readily available P fraction in soil from which P-containing minerals would precipitate, showed a range of 14.5-20.0‰ (Angert et al., 2011, 2012; Weiner et al., 2011; Tamburini et al., 2012). Additionally, Tamburini et al., 2012 reported values for apatite, most likely from the metamorphosed granitic bedrock, to be about +7‰. This is consistent with theoretical considerations by Shemesh et al. (1983) and with data from a gabbro (+4.1‰) and a tonalite (+6.7‰) reported by Taylor and Epstein (1962). Mizota et al. (1992) analyzed δ18OP of apatites from carbonatites, volcanic ashes and hydrothermal vugs covering a range of +0.2 to +12.2‰ (N = 10), whereas phosphate from phosphorites have higher values of up to +20‰ (e.g., Shemesh et al. (1983).This study investigates the oxygen isotope composition of phosphate in pyromorphite and in apatite from crystalline rocks. To evaluate possible phosphate sources, the results will be checked for isotopic equilibrium with different ambient waters and possible phosphate sources will be discussed.

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Bringing organic carbon isotopes and phytoliths to the table as additional constraints on paleoelevation

NASA Astrophysics Data System (ADS)

Sheldon, N. D.; Cotton, J. M.; Hren, M. T.; Hyland, E. G.; Smith, S. Y.; Strömberg, C. A. E.

2015-12-01

A commonly used tool in paleotectonic and paleoaltimetry studies is the oxygen isotopic composition of authigenic carbonates formed that formed in lakes or soils, with both spatial (e.g., shoreline to mountain top) or temporally resolved records potentially providing constraints. However, in many cases there is a substantial spread in the oxygen isotope data for a given time period, often to the point of allowing for essentially any interpretation of the data depending upon how they have been used by the investigator. One potential way of distinguishing between different potential paleotectonic or paleoaltimetric interpretations is to use carbon isotope and plant microfossil (phytolith) analyses from the same paleosols to screen the oxygen isotope data by looking for evidence of evaporative enrichment. For example, if both inorganic (carbonate) and organic carbon isotopes are measured from the same paleosol, then in it possible to determine if the two isotope record equilibrium conditions or if they record disequilibrium driven by kinetic effects. In the former case, the oxygen isotope results can be considered reliable whereas in the latter case, the oxygen isotope results can be considered unreliable and could be culled from the interpretation. Similarly, because the distribution of C4 plants varies as a function of temperature and elevation, the presence/absence or abundance of C4 plant phytoliths, or of carbon isotope compositions that require a component of C4 vegetation can also be used to constrain paleoelevation by providing a maximum elevation constraint. Worked examples will include the late Miocene-Pliocene of Catamarca, Argentina, where phytoliths and organic carbon isotopes provide a maximum elevation constraint and can be used to demonstrate that oxygen isotopes do not provide a locally useful constraint on paleoelevation, and Eocene-Miocene of southwestern Montana where organic matter and phytoliths can be used to select between different potential uplift histories as indicated by pedogenic carbonate oxygen isotope data.

Evaluation of new geological reference materials for uranium-series measurements: Chinese Geological Standard Glasses (CGSG) and macusanite obsidian.

PubMed

Denton, J S; Murrell, M T; Goldstein, S J; Nunn, A J; Amato, R S; Hinrichs, K A

2013-10-15

Recent advances in high-resolution, rapid, in situ microanalytical techniques present numerous opportunities for the analytical community, provided accurately characterized reference materials are available. Here, we present multicollector thermal ionization mass spectrometry (MC-TIMS) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) uranium and thorium concentration and isotopic data obtained by isotope dilution for a suite of newly available Chinese Geological Standard Glasses (CGSG) designed for microanalysis. These glasses exhibit a range of compositions including basalt, syenite, andesite, and a soil. Uranium concentrations for these glasses range from ∼2 to 14 μg g(-1), Th/U weight ratios range from ∼4 to 6, (234)U/(238)U activity ratios range from 0.93 to 1.02, and (230)Th/(238)U activity ratios range from 0.98 to 1.12. Uranium and thorium concentration and isotopic data are also presented for a rhyolitic obsidian from Macusani, SE Peru (macusanite). This glass can also be used as a rhyolitic reference material, has a very low Th/U weight ratio (around 0.077), and is approximately in (238)U-(234)U-(230)Th secular equilibrium. The U-Th concentration data agree with but are significantly more precise than those previously measured. U-Th concentration and isotopic data agree within estimated errors for the two measurement techniques, providing validation of the two methods. The large (238)U-(234)U-(230)Th disequilibria for some of the glasses, along with the wide range in their chemical compositions and Th/U ratios should provide useful reference points for the U-series analytical community.

The smallest Gliders in the Ocean- Temperature Recordings from Pteropods using SIMS

NASA Astrophysics Data System (ADS)

Keul, N.; Orland, I. J.; Valley, J. W.; Kozdon, R.; deMenocal, P. B.

2016-02-01

During the last few decades, the development, refinement and application of geochemical methods have lead to the establishment of new proxies to estimate global change. The oxygen isotope composition of carbonate shells formed by marine organisms is a widely used proxy for past ocean temperatures. Secondary ion mass spectrometry (SIMS) is a high spatial-resolution in situ technique, allowing oxygen isotope measurements on very small samples (down to 3 μm spot size). Pteropods are pelagic mollusks, producing shells made out of aragonite, which is more soluble than calcite in seawater, making them one of the first responders to climate change. They calcify closely at the aragonite- seawater equilibrium and are therefor ideal candidates to reconstruct temperatures based on their d18O. The oxygen isotopic composition of pteropod shells from sediment traps, net tows and a culture study from the Fram Strait will be presented. Specimens travelled in the Westspitsbergen Current prior to sinking into the sediment. During this transport specimens continue to grow, sequentially adding aragonite to the shell. We show that when using traditional (whole shell) δ18O measurements, the isotopic signatures of whole shells reflect the latitudinal gradient. Combining this with SIMS-derived δ18O measurements on individual shell parts, however, reveals that this is only half the story: Comparing δ18O of earlier (produced further South) and later shell parts (produced further North) shows that pteropods calcify in sequentially shallower water depths, overriding the latitudinal South to North temperature gradient. Combining traditional and novel δ18O measurements can potentially not only allow the reconstruction of temperature/ global warming, but also to assess ecological key parameters, such as habitat depth, at the same time.

Studying Antarctic Ordinary Chondrite (OC) and Miller Range (MIL) Nakhlite Meteorites to Assess Carbonate Formation on Earth and Mars

NASA Astrophysics Data System (ADS)

Evans, Michael Ellis

Carbonates are found in meteorites collected from Antarctica. The stable isotope composition of these carbonates records their formation environment on either Earth or Mars. The first research objective of this dissertation is to characterize the delta18O and delta 13C values of terrestrial carbonates formed on Ordinary Chondrites (OCs) collected in regions near known martian meteorites. The second objective is to characterize the delta18O and delta13C values of martian carbonates from Nakhlites collected from the Miller Range (MIL). The third objective is to assess environmental changes on Mars since the Noachian period. The OCs selected had no pre-terrestrial carbonates so any carbonates detected are presumed terrestrial in origin. The study methodology is stepped extraction of CO2 created from phosphoric acid reaction with meteorite carbonate. Stable isotope results show that two distinct terrestrial carbonate species (Ca-rich and Fe/Mg-rich) formed in Antarctica on OCs from a thin-film of meltwater containing dissolved CO2. Carbon isotope data suggests the terrestrial carbonates formed in equilibrium with atmospheric CO2 delta 13C = -7.5‰ at >15°C. The wide variation in delta 18O suggests the carbonates did not form in equilibrium with meteoric water alone, but possibly formed from an exchange of oxygen isotopes in both water and dissolved CO2. Antarctica provides a model for carbonate formation in a low water/rock ratio, near 0°C environment like modern Mars. Nakhlite parent basalt formed on Mars 1.3 billion years ago and the meteorites were ejected by a single impact approximately 11 million years ago. They traveled thru space before eventually falling to the Earth surface 10,000-40,000 years ago. Nakhlite samples for this research were all collected from the Miller Range (MIL) in Antarctica. The Nakhlite stable isotope results show two carbonate species (Ca-rich and Fe/Mg-rich) with a range of delta18O values that are similar to the terrestrial OC carbonates. The Nakhlite carbonates have distinctly different, heavier delta13C values from a presumed martian carbon reservoir. These carbonates cannot form in equilibrium at 15°C with the modern Mars atmospheric CO2 (measured by the Curiosity rover) delta13C = 46‰, but may reflect kinetic carbonate formation from a high pH fluid. Alternatively, the Nakhlite carbonates may have formed with a lighter, early Amazonian atmosphere of delta 13C ≈ 30‰. Assuming the martian carbonates formed in a thin-film environment like the OC terrestrial carbonates, an oxygen mixing model predicts early Amazonian martian meteoric water delta18O = -30‰.

Molten salt reactor neutronics and fuel cycle modeling and simulation with SCALE

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

Betzler, Benjamin R.; Powers, Jeffrey J.; Worrall, Andrew

Current interest in advanced nuclear energy and molten salt reactor (MSR) concepts has enhanced interest in building the tools necessary to analyze these systems. A Python script known as ChemTriton has been developed to simulate equilibrium MSR fuel cycle performance by modeling the changing isotopic composition of an irradiated fuel salt using SCALE for neutron transport and depletion calculations. Some capabilities in ChemTriton that have improved, include a generic geometry capable of modeling multi-zone and multi-fluid systems, enhanced time-dependent feed and separations, and a critical concentration search. Although more generally applicable, the capabilities developed to date are illustrated in thismore » paper in three applied problems: (1) simulating the startup of a thorium-based MSR fuel cycle (a likely scenario requires the first of these MSRs to be started without available 233U); (2) determining the effect of the removal of different fission products on MSR operations; and (3) obtaining the equilibrium concentration of a mixed-oxide light-water reactor fuel in a two-stage fuel cycle with a sodium fast reactor. Moreover, the third problem is chosen to demonstrate versatility in an application to analyze the fuel cycle of a non-MSR system. During the first application, the initial fuel salt compositions fueled with different sources of fissile material are made feasible after (1) removing the associated nonfissile actinides after much of the initial fissile isotopes have burned and (2) optimizing the thorium concentration to maintain a critical configuration without significantly reducing breeding capability. In the second application, noble metal, volatile gas, and rare earth element fission products are shown to have a strong negative effect on criticality in a uranium-fueled thermal-spectrum MSR; their removal significantly increases core lifetime (by 30%) and fuel utilization. In the third application, the fuel of a mixed-oxide light-water reactor approaches an equilibrium composition after 20 depletion steps, demonstrating the potential for the longer time scales required to achieve equilibrium for solid-fueled systems over liquid fuel systems. This time to equilibrium can be reduced by starting with an initial fuel composition closer to that of the equilibrium fuel, reducing the need to handle time-dependent fuel compositions.« less

Molten salt reactor neutronics and fuel cycle modeling and simulation with SCALE

DOE PAGES

Betzler, Benjamin R.; Powers, Jeffrey J.; Worrall, Andrew

2017-03-01

Current interest in advanced nuclear energy and molten salt reactor (MSR) concepts has enhanced interest in building the tools necessary to analyze these systems. A Python script known as ChemTriton has been developed to simulate equilibrium MSR fuel cycle performance by modeling the changing isotopic composition of an irradiated fuel salt using SCALE for neutron transport and depletion calculations. Some capabilities in ChemTriton that have improved, include a generic geometry capable of modeling multi-zone and multi-fluid systems, enhanced time-dependent feed and separations, and a critical concentration search. Although more generally applicable, the capabilities developed to date are illustrated in thismore » paper in three applied problems: (1) simulating the startup of a thorium-based MSR fuel cycle (a likely scenario requires the first of these MSRs to be started without available 233U); (2) determining the effect of the removal of different fission products on MSR operations; and (3) obtaining the equilibrium concentration of a mixed-oxide light-water reactor fuel in a two-stage fuel cycle with a sodium fast reactor. Moreover, the third problem is chosen to demonstrate versatility in an application to analyze the fuel cycle of a non-MSR system. During the first application, the initial fuel salt compositions fueled with different sources of fissile material are made feasible after (1) removing the associated nonfissile actinides after much of the initial fissile isotopes have burned and (2) optimizing the thorium concentration to maintain a critical configuration without significantly reducing breeding capability. In the second application, noble metal, volatile gas, and rare earth element fission products are shown to have a strong negative effect on criticality in a uranium-fueled thermal-spectrum MSR; their removal significantly increases core lifetime (by 30%) and fuel utilization. In the third application, the fuel of a mixed-oxide light-water reactor approaches an equilibrium composition after 20 depletion steps, demonstrating the potential for the longer time scales required to achieve equilibrium for solid-fueled systems over liquid fuel systems. This time to equilibrium can be reduced by starting with an initial fuel composition closer to that of the equilibrium fuel, reducing the need to handle time-dependent fuel compositions.« less

[Distribution of 137Cs, 90Sr and their chemical analogues in the components of an above-ground part of a pine in a quasi-equilibrium condition].

PubMed

Mamikhin, S V; Manakhov, D V; Shcheglov, A I

2014-01-01

The additional study of the distribution of radioactive isotopes of caesium and strontium and their chemical analogues in the above-ground components of pine in the remote from the accident period was carried out. The results of the research confirmed the existence of analogy in the distribution of these elements on the components of this type of wood vegetation in the quasi-equilibrium (relatively radionuclides) condition. Also shown is the selective possibility of using the data on the ash content of the components of forest stands of pine and oak as an information analogue.

Non-equilibrium effects on the chemistry of nebular condensates - Implications for the planets and asteroids

NASA Technical Reports Server (NTRS)

Blander, M.

1979-01-01

Kinetic effects, for example nucleation constraints and slow reactions, should have been important in nebular condensation. Consideration of these effects leads to the prediction of pressure-dependent compositions and physical properties of nebular condensates which is consistent with (1) the differences between different classes of chondritic meteorites, (2) some of the differences between planets, and (3) the presence of oxidized iron on the moon and in the eucrite parent body (presumably an asteroid) despite the low abundance of volatiles. Diffusion effects appear to be important for understanding oxygen isotope anomalies in refractory inclusions in Allende. The consideration of kinetic effects leads to more information concerning nebular processes than if equilibrium is assumed.

Isotopic studies of mariposite-bearing rocks from the south- central Mother Lode, California.

USGS Publications Warehouse

Kistler, R.W.; Dodge, F.C.W.; Silberman, M.L.

1983-01-01

Gold-bearing vein formation in the Mother Lode belt of the study area apparently occurred during the Early Cretaceous between 127 and 108 m.y. B.P. The hydrothermal fluids that carried the gold precipitated quartz and mariposite at approx 320oC, similar to the T of precipitation of gold-bearing quartz veins in the Allegheny district. The O- and H-isotopic composition calculated for the fluid indicate that it was similar to formation water or was metamorphic in origin. If the carbonate in the veins was in isotopic equilibrium with this same fluid, it apparently precipitated at a higher T of approx 400oC. The Sr in the carbonate is much less radiogenic than that in any known marine carbonate, but is similar in isotopic composition to that in metamorphosed mafic volcanic rocks of the general region. These mafic rocks could have been the source for the Sr in the hydrothermal veins. This observation supports the contention that the gold-mariposite-quartz-carbonate rocks were formed as an alteration product of serpentinite and other mafic igneous rocks.-A.P.

Pteropods are excellent recorders of surface temperature and carbonate ion concentration.

PubMed

Keul, N; Peijnenburg, K T C A; Andersen, N; Kitidis, V; Goetze, E; Schneider, R R

2017-10-03

Pteropods are among the first responders to ocean acidification and warming, but have not yet been widely explored as carriers of marine paleoenvironmental signals. In order to characterize the stable isotopic composition of aragonitic pteropod shells and their variation in response to climate change parameters, such as seawater temperature, pteropod shells (Heliconoides inflatus) were collected along a latitudinal transect in the Atlantic Ocean (31° N to 38° S). Comparison of shell oxygen isotopic composition to depth changes in the calculated aragonite equilibrium oxygen isotope values implies shallow calcification depths for H. inflatus (75 m). This species is therefore a good potential proxy carrier for past variations in surface ocean properties. Furthermore, we identified pteropod shells to be excellent recorders of climate change, as carbonate ion concentration and temperature in the upper water column have dominant influences on pteropod shell carbon and oxygen isotopic composition. These results, in combination with a broad distribution and high abundance, make the pteropod species studied here, H. inflatus, a promising new proxy carrier in paleoceanography.

Survival of nature's rarest isotope {sup 180}Ta under stellar conditions

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

Mohr, P.; Kaeppeler, F.; Gallino, R.

2007-01-15

The nucleosynthesis of nature's rarest isotope {sup 180}Ta depends sensitively on the temperature of the astrophysical environment because of depopulation of the long-living isomeric state via intermediate states to the short-living ground state by thermal photons. Reaction rates for this transition have been measured in the laboratory. These ground state rates underestimate the stellar rates dramatically because under stellar conditions intermediate states are mainly populated by excitations from thermally excited states in {sup 180m}Ta. Full thermalization of {sup 180}Ta is already achieved for typical s-process temperatures around kT=25 keV. Consequently, for the survival of {sup 180}Ta in the s-process fastmore » convective mixing is required which has to transport freshly synthesized {sup 180}Ta to cooler regions. In supernova explosions {sup 180}Ta is synthesized by photon- or neutrino-induced reactions at temperatures above T{sub 9}=1 in thermal equilibrium; independent of the production mechanism, freeze-out from thermal equilibrium occurs at kT{approx_equal}40 keV, and only 35{+-}4% of the synthesized {sup 180}Ta survive in the isomeric state.« less

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.

Reduction of Thermal Conductivity by Nanoscale 3D Phononic Crystal

PubMed Central

Yang, Lina; Yang, Nuo; Li, Baowen

2013-01-01

We studied how the period length and the mass ratio affect the thermal conductivity of isotopic nanoscale three-dimensional (3D) phononic crystal of Si. Simulation results by equilibrium molecular dynamics show isotopic nanoscale 3D phononic crystals can significantly reduce the thermal conductivity of bulk Si at high temperature (1000 K), which leads to a larger ZT than unity. The thermal conductivity decreases as the period length and mass ratio increases. The phonon dispersion curves show an obvious decrease of group velocities in 3D phononic crystals. The phonon's localization and band gap is also clearly observed in spectra of normalized inverse participation ratio in nanoscale 3D phononic crystal. PMID:23378898

Determination of uranium isotopes in food and environmental samples by different techniques: a comparison.

PubMed

Forte, M; Rusconi, R; Margini, C; Abbate, G; Maltese, S; Badalamenti, P; Bellinzona, S

2001-01-01

The uranium concentration in 59 samples of bottled and tap water, mainly from northern Italy, was measured by different techniques. Results obtained by inductively coupled plasma mass spectrometry (ICP-MS), semiconductor alpha spectrometry and low level liquid scintillation counting with alpha/beta discrimination (LSC) have been compared. High resolution gamma spectrometry and semiconductor alpha spectrometry have been used to analyse uranium in a variety of organic and inorganic samples. Isotopic secular equilibrium in the 238U series may be lacking or hidden by auto-absorption phenomena, so caution should be used in evaluating gamma spectrometry data. Alpha spectrometry has also been used to ascertain the possible pollution from depleted uranium in the environment.

Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

2018-04-01

Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy Fe isotopes compositions of the sulfides from the SMAR may suggest the equilibrium fractionation process under high temperature conditions. The red Fe oxides are enriched in heavy Fe isotopes, indicating that the oxidative weathering processes result in the occurrence of significant Fe-isotope fractionation and the preferential enrichment of heavy Fe isotopes in the oxidation product.

Methods for Estimating Adsorbed Uranium(VI) and Distribution Coefficients of Contaminated Sediments

USGS Publications Warehouse

Kohler, M.; Curtis, G.P.; Meece, D.E.; Davis, J.A.

2004-01-01

Assessing the quantity of U(VI) that participates in sorption/desorption processes in a contaminated aquifer is an important task when investigating U migration behavior. U-contaminated aquifer sediments were obtained from 16 different locations at a former U mill tailings site at Naturita, CO (U.S.A.) and were extracted with an artificial groundwater, a high pH sodium bicarbonate solution, hydroxylamine hydrochloride solution, and concentrated nitric acid. With an isotopic exchange method, both a KD value for the specific experimental conditions as well as the total exchangeable mass of U(VI) was determined. Except for one sample, KD values determined by isotopic exchange with U-contaminated sediments that were in equilibrium with atmospheric CO2 agreed within a factor of 2 with KD values predicted from a nonelectrostatic surface complexation model (NEM) developed from U(VI) adsorption experiments with uncontaminated sediments. The labile fraction of U(VI) and U extracted by the bicarbonate solution were highly correlated (r2 = 0.997), with a slope of 0.96 ?? 0.01. The proximity of the slope to one suggests that both methods likely access the same reservoir of U(VI) associated with the sediments. The results indicate that the bicarbonate extraction method is useful for estimating the mass of labile U(VI) in sediments that do not contain U(IV). In-situ KD values calculated from the measured labile U(VI) and the dissolved U(VI) in the Naturita alluvial aquifer agreed within a factor of 3 with in-situ K D values predicted with the NEM and groundwater chemistry at each well.

Investigating understory flora species as an isotope proxy for atmospheric water vapor

NASA Astrophysics Data System (ADS)

Rambo, J. P.; Lai, C.; Farlin, J. P.

2011-12-01

An understanding of stable isotope variation in leaf water is useful in quantifying water fluxes through different pathways. Little is known about species specific variations of leaf water 18O and 2H enrichment and their interactions with atmospheric water vapor in understory flora. Toward this end, we measured stable 18O and 2H signatures of leaf water and atmospheric water vapor in an old growth forest in the Pacific Northwest. A LGR off-axis cavity-enhanced absorption spectroscopy analyzer was used to measure hourly 18O/16O and 2H/1H ratios of atmospheric water vapor (δ18Ov and δ2Hv) at 3 canopy heights (1m aboveground, mid- and above-canopy). By employing a routine, in-situ calibration, we were able to account for the concentration and temperature dependency from the instrument-reported δ18Ov and δ2Hv values using a single reference water. By using a 3-point calibration procedure we were able to produce accurate (±0.2% for δ18Ov, ±0.5% for δ2Hv) and precise (±0.3% for δ18Ov, ±3.0% for δ2Hv) measurements on the VSMOW scale. During our sampling campaign we observed large variations ranging from -175.0% to -125.1% for δ2Hv and -23.9% to -13.5% for δ18Ov. Leaf tissue of four dominant understory plant species were sampled every 2 hours over a three day period. Previous studies showed that leaf water becomes isotopically enriched from evaporative fractionation during the day, and then returns to an isotopic equilibrium with atmospheric water vapor during nighttime, reaching a complete equilibrium at pre-dawn in wet environments (i.e. Amazon forests). This diurnal pattern in leaf water isotope ratios was ubiquitous in terrestrial ecosystems, however, leading to the potential of using this plant-based signature as a proxy to infer δ18Ov and δ2Hv in remote locations. In the present study we investigate how leaf water of understory flora and atmospheric water vapor interact in a temperate forest.

Unraveling climatic changes from intra-profile variation in oxygen and hydrogen isotopic composition of goethite and kaolinite in laterites: An integrated study from Yaou, French Guiana

NASA Astrophysics Data System (ADS)

Girard, Jean-Pierre; Freyssinet, Philippe; Chazot, Gilles

2000-02-01

An integrated study of O and H isotopes in the lateritic profile of Yaou, French Guiana, was undertaken to investigate the usefulness of stable isotopes as tracers of climatic changes in continental environments. The studied profile is composed of a 27 m thick saprolite, mostly developed in the past under wet-and-dry tropical climate in association with a duricrust, overlain by a 3 m thick yellow latosol formed more recently under present equatorial hot and humid climate. δ 18O-δD values determined for weathering goethite (pseudomorphs after pyrite) and kaolinite (microcrystalline clay groundmass) throughout the 30 m deep profile reflect formation temperatures consistent with present (25°C) and realistic past climatic temperatures (20°C-30°C), indicating that weathering minerals formed in isotopic equilibrium with their genetic environment and were not subjected to significant isotope exchange after formation. A distinct shift downward (2‰ for δ 18O, 15‰ for δD) from low to high δ 18O-δD values occurs around 20 m depth in the saprolite. It is interpreted as recording the change from the past tropical to the present equatorial climate. Goethite and kaolinite in the 5-10 m thick saprolite interval immediately above the active basement weathering front are in isotopic equilibrium with modern water and must have formed under present equatorial-humid conditions. In contrast, goethite and kaolinite found higher up in the saprolite and in the duricrust formed in the past under tropical wet and dry climate from waters distinctly depleted in 18O and D relative to modern water. The marked depletion of paleo-meteoric water at Yaou most likely reflects a more contrasted or "monsoonal" character of the ancient tropical climate. The present study shows that ancient weathering minerals in lateritic profiles preserve their δ 18O-δD values and carry a time signal. The time signal is best expressed in minerals formed rapidly at the weathering front and not subjected to post-formational remobilization, such as the goethite pseudomorphs after pyrite occurring at Yaou. Groundmass kaolinite is more susceptible to partial remobilization, through successive dissolution-precipitation reactions, which may obliterate the paleoclimatic signal. Unraveling the climatic record carried by weathering minerals in old soil systems is greatly enhanced by studying both oxygen and hydrogen isotopic compositions.

Phosphorus dynamics in soils irrigated with reclaimed waste water or fresh water - A study using oxygen isotopic composition of phosphate

USGS Publications Warehouse

Zohar, I.; Shaviv, A.; Young, M.; Kendall, C.; Silva, S.; Paytan, A.

2010-01-01

Transformations of phosphate (Pi) in different soil fractions were tracked using the stable isotopic composition of oxygen in phosphate (??18Op) and Pi concentrations. Clay soil from Israel was treated with either reclaimed waste water (secondary, low grade) or with fresh water amended with a chemical fertilizer of a known isotopic signature. Changes of ??18Op and Pi within different soil fractions, during a month of incubation, elucidate biogeochemical processes in the soil, revealing the biological and the chemical transformation impacting the various P pools. P in the soil solution is affected primarily by enzymatic activity that yields isotopic equilibrium with the water molecules in the soil solution. The dissolved P interacts rapidly with the loosely bound P (extracted by bicarbonate). The oxides and mineral P fractions (extracted by NaOH and HCl, respectively), which are considered as relatively stable pools of P, also exhibited isotopic alterations in the first two weeks after P application, likely related to the activity of microbial populations associated with soil surfaces. Specifically, isotopic depletion which could result from organic P mineralization was followed by isotopic enrichment which could result from preferential biological uptake of depleted P from the mineralized pool. Similar transformations were observed in both soils although transformations related to biological activity were more pronounced in the soil treated with reclaimed waste water compared to the fertilizer treated soil. ?? 2010 Elsevier B.V.

The Sensitivity of Atmospheric Water Isotopes to Entrainment and Precipitation Efficiency in a Bulk Plume Model of Convection

NASA Astrophysics Data System (ADS)

Duan, S.; Wright, J. S.; Romps, D. M.

2016-12-01

Atmospheric water isotopes have been proposed as potentially powerful constraints on the physics of convective clouds and parameterizations of convective processes in models. We have previously derived an analytical model of water vapor (H2O) and one of its heavy isotopes (HDO) in convective environments based on a bulk-plume convective water budget in radiative convective equilibrium. This analytical model provides a useful starting point for examining the joint responses of water vapor and its isotopic composition to changes in convective parameters; however, certain idealistic assumptions are required to make the model analytically solvable. Here, we develop a more flexible numerical framework that enables a wider range of model configurations and includes additional isotopic tracers. This model provides a bridge between Rayleigh distillation, which is simple but inflexible, and more complicated convection schemes and cloud resolving models, which are more realistic but also more difficult to perturb and interpret. Application of realistic in-cloud water profiles in our model produces vertical distributions of δD that qualitatively match satellite observations from the Tropospheric Emission Spectrometer (TES). We test the sensitivity of water vapor and its isotopic composition to a wide range of perturbations in the model parameters and their vertical profiles. In this presentation, we focus especially on establishing constraints for convective entrainment and precipitation efficiency. We conclude by discussing the potential application of this model as part of a larger water isotope toolkit for use with offline diagnostics provided by reanalyses and GCMs.

Planetary and meteoritic Mg/Si and δ30 Si variations inherited from solar nebula chemistry

NASA Astrophysics Data System (ADS)

Dauphas, Nicolas; Poitrasson, Franck; Burkhardt, Christoph; Kobayashi, Hiroshi; Kurosawa, Kosuke

2015-10-01

The bulk chemical compositions of planets are uncertain, even for major elements such as Mg and Si. This is due to the fact that the samples available for study all originate from relatively shallow depths. Comparison of the stable isotope compositions of planets and meteorites can help overcome this limitation. Specifically, the non-chondritic Si isotope composition of the Earth's mantle was interpreted to reflect the presence of Si in the core, which can also explain its low density relative to pure Fe-Ni alloy. However, we have found that angrite meteorites display a heavy Si isotope composition similar to the lunar and terrestrial mantles. Because core formation in the angrite parent-body (APB) occurred under oxidizing conditions at relatively low pressure and temperature, significant incorporation of Si in the core is ruled out as an explanation for this heavy Si isotope signature. Instead, we show that equilibrium isotopic fractionation between gaseous SiO and solid forsterite at ∼1370 K in the solar nebula could have produced the observed Si isotope variations. Nebular fractionation of forsterite should be accompanied by correlated variations between the Si isotopic composition and Mg/Si ratio following a slope of ∼1, which is observed in meteorites. Consideration of this nebular process leads to a revised Si concentration in the Earth's core of 3.6 (+ 6.0 / - 3.6) wt% and provides estimates of Mg/Si ratios of bulk planetary bodies.

Stable water isotopic composition of the Antarctic subglacial Lake Vostok: implications for understanding the lake's hydrology.

PubMed

Ekaykin, Alexey A; Lipenkov, Vladimir Y; Kozachek, Anna V; Vladimirova, Diana O

2016-01-01

We estimated the stable isotopic composition of water from the subglacial Lake Vostok using two different sets of samples: (1) water frozen on the drill bit immediately after the first lake unsealing and (2) water frozen in the borehole after the unsealing and re-drilled one year later. The most reliable values of the water isotopic composition are: -59.0 ± 0.3 ‰ for oxygen-18, -455 ± 1 ‰ for deuterium and 17 ± 1 ‰ for d-excess. This result is also confirmed by the modelling of isotopic transformations in the water which froze in the borehole, and by a laboratory experiment simulating this process. A comparison of the newly obtained water isotopic composition with that of the lake ice (-56.2 ‰ for oxygen-18, -442.4 ‰ for deuterium and 7.2 ‰ for d-excess) leads to the conclusion that the lake ice is very likely formed in isotopic equilibrium with water. In turn, this means that ice is formed by a slow freezing without formation of frazil ice crystals and/or water pockets. This conclusion agrees well with the observed physical and chemical properties of the lake's accreted ice. However, our estimate of the water's isotopic composition is only valid for the upper water layer and may not be representative for the deeper layers of the lake, so further investigations are required.

Mass transfer and carbon isotope evolution in natural water systems

USGS Publications Warehouse

Wigley, T.M.L.; Plummer, Niel; Pearson, F.J.

1978-01-01

This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

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.

Measuring U-series Disequilibrium in Weathering Rinds to Study the Influence of Environmental Factors to Weathering Rates in Tropical Basse-Terre Island (French Guadeloupe)

NASA Astrophysics Data System (ADS)

Guo, J.; Ma, L.; Sak, P. B.; Gaillardet, J.; Chabaux, F. J.; Brantley, S. L.

2015-12-01

Chemical weathering is a critical process to global CO2 consumption, river/ocean chemistry, and nutrient import to biosphere. Weathering rinds experience minimal physical erosion and provide a well-constrained system to study the chemical weathering process. Here, we applied U-series disequilibrium dating method to study weathering advance rates on the wet side of Basse-Terre Island, French Guadeloupe, aiming to understand the role of the precipitation in controlling weathering rates and elucidate the behavior and immobilization mechanisms of U-series isotopes during rind formation. Six weathering clasts from 5 watersheds with mean annual precipitation varying from 2000 to 3000 mm/yr were measured for U-series isotope ratios and major element compositions on linear core-to-rind transects. One sample experienced complete core-to-rind transformation, while the rest clasts contain both rinds and unweathered cores. Our results show that the unweathered cores are under U-series secular equilibrium, while all the rind materials show significant U-series disequilibrium. For most rinds, linear core-to-rind increases of (230Th/232Th) activity ratios suggest a simple continuous U addition history. However, (234U/238U) and (238U/232Th) trends in several clasts show evidences of remobilization of Uranium besides the U addition, complicating the use of U-series dating method. The similarity between U/Th ratios and major elements trends like Fe, Al, P in some transects and the ongoing leaching experiments suggest that redox and organic colloids could control the mobilization of U-series isotopes in the rinds. Rind formation ages and weathering advance rate (0.07-0.29mm/kyr) were calculated for those rinds with a simple U-addition history. Our preliminary results show that local precipitation gradient significantly influenced the weathering advance rate, revealing the potential of estimating weathering advance rates at a large spatial scale using the U-series dating method.

Mercury emissions and stable isotopic compositions at Vulcano Island (Italy)

NASA Astrophysics Data System (ADS)

Zambardi, T.; Sonke, J. E.; Toutain, J. P.; Sortino, F.; Shinohara, H.

2009-01-01

Sampling and analyses methods for determining the stable isotopic compositions of Hg in an active volcanic system were tested and optimized at the volcanic complex of Vulcano (Aeolian Islands, Italy). Condensed gaseous fumarole Hg (fum)T, plume gaseous elemental Hg (g)0 and plume particulate Hg (p)II were obtained at fumaroles F0, F5, F11, and FA. The average total Hg emissions, based on Hg T/SO 2 in condensed fumarolic gases and plumes, range from 2.5 to 10.1 kg y - 1 , in agreement with published values [Ferrara, R., Mazzolai, B., Lanzillotta, E., Nucaro, E., Pirrone, N., 2000. Volcanoes as emission sources of atmospheric mercury in the Mediterranean Basin. Sci. Total Environ. 259(1-3), 115-121; Aiuppa, A., Bagnato, E., Witt, M.L.I., Mather, T.A., Parello, F., Pyle, D.M., Martin, R.S., 2007. Real-time simultaneous detection of volcanic Hg and SO 2 at La Fossa Crater, Vulcano (Aeolian Islands, Sicily). Geophys. Res. Lett. 34(L21307).]. Plume Hg (p)II increases with distance from the fumarole vent, at the expense of Hg (g)0 and indicates significant in-plume oxidation and condensation of fumarole Hg (fum)T. Relative to the NIST SRM 3133 Hg standard, the stable isotopic compositions of Hg are δ 202Hg (fum)T = - 0.74‰ ± 0.18 (2SD, n = 4) for condensed gaseous fumarole Hg (fum)T, δ 202Hg (g)0 = - 1.74‰ ± 0.36 (2SD, n = 1) for plume gaseous elemental Hg (g)0 at the F0 fumarole, and δ 202Hg (p)II = - 0.11‰ ± 0.18 (2SD, n = 4) for plume particulate Hg (p)II. The enrichment of Hg (p)II in the heavy isotopes and Hg (g)0 in the light isotopes relative to the total condensed fumarolic Hg (fum)T gas complements the speciation data and demonstrates a gas-particle fractionation occurring after the gas expulsion in ambient T° atmosphere. A first order Rayleigh equilibrium condensation isotope fractionation model yields a fractionation factor α cond-gas of 1.00135 ± 0.00058.

Oxygen isotope activities and concentrations in aqueous salt solutions at elevated temperatures: Consequences for isotope geochemistry

USGS Publications Warehouse

Truesdell, A.H.

1974-01-01

Studies of the effect of dissolved salts on the oxygen isotope activity ratio of water have been extended to 275??C. Dehydrated salts were added to water of known isotope composition and the solutions were equilibrated with CO2 which was sampled for analysis. For comparison similar studies were made using pure water. Results on water nearly coincide with earlier calculations. Salt effects diminish with increasing temperature only for solutions of MgCl2 and LiCl. Other salt solutions show complex behavior due to the temperature-dependent formation of ion pairs of changing character. Equilibrium fractionations (103 ln ??) between 1 molal solutions and pure water at 25, 100, and 275??C are: NaCl 0.0, -1.5, +1.0; KCl 0.0, -1.0, +2.0; LiCl -1.0, -0.6, -0.5; CaCl2 -0.4, -1.8, +0.8; MgCl2 -1.1, -0.7, -0.3; MgSO4 -1.1, +0.1, -; NaF (0.8 m) 0.0, -1.5, -0.3; and NH4Cl (0.55 m) 0.0, -1.2, -1.3. These effects are significant in the isotope study of hot saline fluids responsible for ore deposition and of fluids found in certain geothermal systems. Minor modification of published isotope geothermometers may be required. ?? 1974.

Sharpening the U-Th Chronometer: Progress and Outlook

NASA Astrophysics Data System (ADS)

McLean, N. M.; Condon, D. J.; Henderson, G. M.; Richards, D. A.; Noble, S.; Mason, A.

2013-12-01

Uranium is incorporated into a variety of natural materials when they form, including carbonates like speleothems and corals. The two most abundant naturally occurring uranium isotopes, 238U and 235U, decay to 206Pb and 207Pb over long timescales with half-lives of 4.5 and 0.7 billion years respectively, but transition through several intermediate daughter isotopes with shorter half-lives first. Fractionation between these daughter isotopes, including 234U, 230Th, and 231Pa, and their parent isotopes, followed by their time-dependent return to secular equilibrium over the course of up to ~800 kyr, forms the basis for U-series geochronology, and allows speleothems and corals to be precisely dated. These carbonates often additionally incorporate chemical and isotopic signatures (e.g., trace elements, δ18O and δ13C) from the environment in which they form, and thus are some of the best dated paleoclimate archives, offering clues about past and future conditions for life on Earth. Over the past decade, the analytical precision of U-series isotope measurements has improved dramatically, largely due to the steadily increasing sensitivity of multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Analytical uncertainties in U-Th dates now approach or are better than 0.1% (2σ), for instance ×100 years for a speleothem or coral that is 130 kyr old (Cheng et al., 2013). However, the accuracy of U-series dates also depends on the accuracy of tracer calibrations, reference solutions and data reduction protocols, which has not kept pace in many laboratories. This means that dates measured in different labs, while impressively precise, may not be directly comparable. To address issues of inter-laboratory bias and improve the accuracy and inter-comparability of U-Th dates, we have instigated work in three related directions. First, we report on the mixing of three synthetic U-Th age solutions, created by combining high-purity mono-isotopic solutions to mimic the isotopic composition of commonly analyzed materials. These age solutions will form the basis for an inter-laboratory comparison and serve as international reference materials for assessing long-term reproducibility. Second is the creation of several U-Th gravimetric solutions, which can be used to calibrate the mixed 229Th-236U×233U tracers used in the community without having to rely on materials assumed to be in secular equilibrium. Tracers calibrated against these solutions, and therefore U-Th dates measured with these tracers, will be fully metrologically traceable. Finally, we report progress on and important considerations in developing data reduction and uncertainty propagation protocols for calculating U-Th dates and constructing and interpreting U-Th age models. Reference: Cheng et al. (2013) EPSL 371-372, 82-91

Isotopic fractionation of volatile species during bubble growth in magmas

NASA Astrophysics Data System (ADS)

Watson, E. B.

2016-12-01

Bubbles grow in decompressing magmas by simple expansion and also by diffusive supply of volatiles to the bubble/melt interface. The latter phenomenon is of significant geochemical interest because diffusion can fractionate isotopes, raising the possibility that the isotopic character of volatile components in bubbles may not reflect that of volatiles dissolved in the host melt over the lifetime of a bubble—even in the complete absence of equilibrium vapor/melt isotopic fractionation. None of the foregoing is conceptually new, but recent experimental studies have established the existence of isotope mass effects on diffusion in silicate melts for several elements (Li, Mg, Ca, Fe), and this finding has now been extended to the volatile (anionic) element chlorine (Fortin et al. 2016; this meeting). Knowledge of isotope mass effects on diffusion of volatile species opens the way for quantitative models of diffusive fractionation during bubble growth. Significantly different effects are anticipated for "passive" volatiles (e.g., noble gases and Cl) that are partitioned into existing bubbles but play little role in nucleation and growth, as opposed to "active" volatiles whose limited solubilities lead to bubble nucleation during magma decompression. Numerical solution of the appropriate diffusion/mass-conservation equations reveals that the isotope effect on passive volatiles partitioned into bubbles growing at a constant rate in a static system depends (predictably) upon R/D, Kd and D1/D2 (R = growth rate; D = diffusivity; Kd = bubble/melt partition coefficient; D1/D2 = diffusivity ratio of the isotopes of interest). Constant R is unrealistic, but other scenarios can be explored by including the solubility and EOS of an "active" volatile (e.g., CO2) in numerical simulations of bubble growth. For plausible decompression paths, R increases exponentially with time—leading, potentially, to larger isotopic fractionation of species partitioned into the growing bubble.

Intra-event isotope and raindrop size data of tropical rain reveal effects concealed by event averaged data

NASA Astrophysics Data System (ADS)

Managave, S. R.; Jani, R. A.; Narayana Rao, T.; Sunilkumar, K.; Satheeshkumar, S.; Ramesh, R.

2016-08-01

Evaporation of rain is known to contribute water vapor, a potent greenhouse gas, to the atmosphere. Stable oxygen and hydrogen isotopic compositions (δ18O and, δD, respectively) of precipitation, usually measured/presented as values integrated over rain events or monthly mean values, are important tools for detecting evaporation effects. The slope ~8 of the linear relationship between such time-averaged values of δD and δ18O (called the meteoric water line) is widely accepted as a proof of condensation under isotopic equilibrium and absence of evaporation of rain during atmospheric fall. Here, through a simultaneous investigation of the isotopic and drop size distributions of seventeen rain events sampled on an intra-event scale at Gadanki (13.5°N, 79.2°E), southern India, we demonstrate that the evaporation effects, not evident in the time-averaged data, are significantly manifested in the sub-samples of individual rain events. We detect this through (1) slopes significantly less than 8 for the δD-δ18O relation on intra-event scale and (2) significant positive correlations between deuterium excess ( d-excess = δD - 8*δ18O; lower values in rain indicate evaporation) and the mass-weighted mean diameter of the raindrops ( D m ). An estimated ~44 % of rain is influenced by evaporation. This study also reveals a signature of isotopic equilibration of rain with the cloud base vapor, the processes important for modeling isotopic composition of precipitation. d-excess values of rain are modified by the post-condensation processes and the present approach offers a way to identify the d-excess values least affected by such processes. Isotope-enabled global circulation models could be improved by incorporating intra-event isotopic data and raindrop size dependent isotopic effects.

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.

Multiple isotope analyses of the pike tapeworm Triaenophorus nodulosus reveal peculiarities in consumer-diet discrimination patterns.

PubMed

Behrmann-Godel, J; Yohannes, E

2015-03-01

Previous studies of dietary isotope discrimination have led to the general expectation that a consumer will exhibit enriched stable isotope levels relative to its diet. Parasite-host systems are specific consumer-diet pairs in which the consumer (parasite) feeds exclusively on one dietary source: host tissue. However, the small numbers of studies previously carried out on isotopic discrimination in parasite-host (ΔXP-HT) systems have yielded controversial results, showing some parasites to be isotopically depleted relative to their food source, while others are enriched or in equilibrium with their hosts. Although the mechanism for these deviations from expectations remains to be understood, possible influences of specific feeding niche or selection for only a few nutritional components by the parasite are discussed. ΔXP-HT for multiple isotopes (δ13C, δ15N, δ34S) were measured in the pike tapeworm Triaenophorus nodulosus and two of its life-cycle fish hosts, perch Perca fluviatilis and pike Esox lucius, within which T. nodulosus occupies different feeding locations. Variability in the value of ΔXP-HT calculated for the parasite and its different hosts indicates an influence of feeding location on isotopic discrimination. In perch liver ΔXP-HT was relatively more negative for all three stable isotopes. In pike gut ΔXP-HT was more positive for δ13C, as expected in conventional consumer-diet systems. For parasites feeding on pike gut, however, the δ15N and δ34S isotope values were comparable with those of the host. We discuss potential causes of these deviations from expectations, including the effect of specific parasite feeding niches, and conclude that ΔXP-HT should be critically evaluated for trophic interactions between parasite and host before general patterns are assumed.

Biomedical silver-109m isotope generator

DOEpatents

Wanek, Philip M.; Steinkruger, Frederick J.; Moody, David C.

1987-01-01

A method, composition of matter, and apparatus for producing substantially pure Ag-109m for use in biomedical imaging techniques. Cd-109, which decays with a half-life of 453 days to Ag-109m is loaded onto an ion exchange column consisting of particulate tin phosphate. After secular equilibrium is reached in about ten minutes, Ag-109m may be selectively eluted from the column by means of a physiologically acceptable aqueous buffered eluent solution of sodium thiosulfate, and either ascorbic acid or dextrose. The breakthrough of toxic Cd-109 is on the order of 1.times.10.sup.-7, which is sufficiently low to permit administration of the Ag-109m-containing eluate, with but a minor pH adjustment, directly to a human patient within a matter of seconds.

Biomedical silver-109m isotope generator

DOEpatents

Wanek, P.M.; Steinkruger, F.J.; Moody, D.C.

1985-03-05

A method, composition of matter, and apparatus for producing substantially pure Ag-109m for use in biomedical imaging techniques. Cd-109, which decays with a half-life of 453 days to Ag-109m, is loaded onto an ion exchange column consisting of particulate tin phosphate. After secular equilibrium is reached in about ten minutes, Ag-109m may be selectively eluted from the column by means of a physiologically acceptable aqueous buffered eluent solution of sodium thiosulfate, and either ascorbic acid or dextrose. The breakthrough of toxic Cd-109 is on the order of 1 x 10-7, which is sufficiently low to permit administration of the Ag-109m-containing eluate, with but a minor pH adjustment, directly to a human patient within a matter of seconds. 1 fig.

Method for production of an isotopically enriched compound

DOEpatents

Watrous, Matthew G.

2012-12-11

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

Study report on a double isotope method of calcium absorption

NASA Technical Reports Server (NTRS)

1978-01-01

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

Origin of sulfur for elemental sulfur concentration in salt dome cap rocks, Gulf Coast Basin, USA

NASA Astrophysics Data System (ADS)

Hill, J. M.; Kyle, R.; Loyd, S. J.

2017-12-01

Calcite cap rocks of the Boling and Main Pass salt domes contain large elemental sulfur accumulations. Isotopic and petrographic data indicate complex histories of cap rock paragenesis for both domes. Whereas paragenetic complexity is in part due to the open nature of these hydrodynamic systems, a comprehensive understanding of elemental sulfur sources and concentration mechanisms is lacking. Large ranges in traditional sulfur isotope compositions (δ34S) among oxidized and reduced sulfur-bearing phases has led some to infer that microbial sulfate reduction and/or influx of sulfide-rich formation waters occurred during calcite cap rock formation. Ultimately, traditional sulfur isotope analyses alone cannot distinguish among local microbial or exogenous sulfur sources. Recently, multiple sulfur isotope (32S, 33S, 34S, 36S) studies reveal small, but measurable differences in mass-dependent behavior of microbial and abiogenic processes. To distinguish between the proposed sulfur sources, multiple-sulfur-isotope analyses have been performed on native sulfur from the Boling and Main Pass cap rocks. Similarities or deviations from equilibrium relationships indicate which pathways were responsible for native sulfur precipitation. Pathway determination provides insight into Gulf Coast cap rock development and potentially highlights the conditions that led to anomalous sulfur enrichment in Boling and Main Pass Domes.

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.

Monitoring water stable isotope composition in soils using gas-permeable tubing and infrared laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Rothfuss, Youri; Vereecken, Harry; Brüggemann, Nicolas

2013-04-01

The water stable isotopologues 1H2H16O and 1H218O are powerful tracers of processes occurring in nature. Their slightly different masses as compared to the most abundant water isotopologue (1H216O) affect their thermodynamic (e.g. during chemical equilibrium reactions or physical phase transitions with equilibration) and kinetic (liquid and vapor phases transport processes and chemical reactions without equilibration) properties. This results in measurable differences of the isotopic composition of water within or between the different terrestrial ecosystem compartments (i.e. sub-soil, soil, surface waters, plant, and atmosphere). These differences can help addressing a number of issues, among them water balance closure and flux partitioning from the soil-plant-atmosphere continuum at the field to regional scales. In soils particularly, the isotopic composition of water (δ2H and δ18O) provides qualitative information about whether water has only infiltrated or already been re-evaporated since the last rainfall event or about the location of the evaporation front. From water stable isotope composition profiles measured in soils, it is also possible, under certain hypotheses, to derive quantitative information such as soil evaporation flux and the identification of root water uptake depths. In addition, water stable isotopologues have been well implemented into physically based Soil-Vegetation-Atmosphere Transfer models (e.g. SiSPAT-Isotope; Soil-Litter iso; TOUGHREACT) and have demonstrated their potential. However, the main disadvantage of the isotope methodology is that, contrary to other soil state variables that can be monitored over long time periods, δ2H and δ18O are typically analyzed following destructive sampling. Here, we present a non-destructive method for monitoring soil liquid water δ2H and δ18O over a wide range of water availability conditions and temperatures by sampling and measuring water vapor equilibrated with soil water using gas-permeable polypropylene tubing and a cavity ring-down laser absorption spectrometer. By analyzing water vapor δ2H and δ18O sampled with the tubing from a fine sand for temperatures ranging between 8-24° C, we demonstrate that (i) our new method is capable of monitoring δ2H and δ18O in soils online with high precision and, after calibration, also with high accuracy, (ii) our sampling protocol enabled detecting changes of δ2H and δ18O following non-fractionating addition and removal of liquid water and water vapor of different isotopic compositions, and (iii) the time needed for the tubing to monitor these changes is compatible with the observed variations of δ2H and δ18O in soils under natural conditions.

Lithium and carbon isotopes in river catchment: combined tracers to constrain chemical weathering processes

NASA Astrophysics Data System (ADS)

Rad, S.; Rive, K.; Assayag, N.; Dictor, M.; Garcin, M.

2012-12-01

Water-rock interactions produced in river catchment are accompanied by fractionation or changes in stable isotopes such as H, Li, C and O during chemical weathering processes. Li is a fluid-mobile element that tends to preferentially partition into the fluid phase during water-rock interaction. The relative mass difference between the two isotopes is considerable, generating large mass dependent fractionation during chemical weathering processes. The CO2 dissolves into the water providing the main acid that attack the rock during chemical weathering. Carbon stable isotopes and concentration of Dissolved Inorganic Carbon (DIC) in the river catchment can be used to determine the origin and consumption rates of CO2. In the present work, stable isotopes were analyzed in Allier River, one of the major river basins of France. The lithology is dominated by granite rocks within current upstream, while it is mainly basaltic and Oligocene sediments in the downstream with hydrothermal manifestations. We propose a new isotopic approach by combining δ7Li and δ13CDIC analyses in river catchment waters. A first method has been applied to volcanic tropical environments with Li concentrations correlated to δ13CDIC (Rad et al., 2011). Here, we have completed this approach by lithium isotopes. Water samples were collected during several field trips. Our results show a large variation in Li isotopes and C isotopes within the catchment from 3.3 ‰ to 30.3 ‰ and from -17.9‰ to -3.5‰, respectively. Chemical weathering rates linearly increase from upstream to downstream over 400km distance, whereas Li isotope signatures decrease and global C signature increases. This is due to low water-rock interaction dominated in upstream, whereas the downstream is punctually impacted by hydrothermalism. From Li and C isotopes, our results show 4 groups reflecting different chemical weathering processes: the first group with high fractionation of Li and C, for Li, the heavy lithium partitioned into surface waters, leaving lighter lithium behind in the weathered products, the signature of C is mainly due to organic matter or partially due to biochemical interaction with assimilation of CO2 by microorganism. The second group involves atmospheric equilibrium with CO2 degassing with organic origin or "cold" CO2 degassing with important fraction of Li. The third group present high fractionation of C, reflecting presence of superficial C with organic origin, with low fractionation of Li underling the hydrothermalism impact. Finally a fourth group with low fractionation mainly due to high temperature water-rock interaction. Therefore, the combination of the two tracers, Li and C isotopes, offers a powerful tool to discriminate chemical weathering processes from sources of alteration during water-rock interactions under multi-lithology terrains. Reference: Rad, S., Rivé, K., Allègre, C.J., 2011. Weathering regime associated with subsurface circulation on volcanic islands. Aquat. Geochem. 17, 3, 221-241.

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.

Testing the Limits to Accurate Comminution Dates: A Progress Report

NASA Astrophysics Data System (ADS)

Piccione, G.; Blackburn, T.; Edwards, G. H.

2017-12-01

The ability to resolve the timing of fine particle production holds potential for contributing to several Earth Science sub-disciplines including glaciology, eolian and fluvial geomorphology, soil production, and fault dynamics. A relatively new geochronologic tool, U-series comminution dating, has shown potential to directly date the timing of particle comminution. This system's sensitivity to particle size arises from a physical disequilibrium in the 238U decay chain generated by the ejected loss of intermediate daughter products (e.g. 234U). It is the goal of this ongoing study to develop and test analytical procedures to improve the accuracy of comminution dating. In the geologic settings explored by previous studies, comminution dates integrate both the time of particle transport and time since deposition. To better test the accuracy of comminution dates, our study focuses on settings where silt has experienced little to no transport time, specifically, glacial moraines in the Eastern Sierras and Rock Avalanches in the San Gabriel Mountains, both locations with existing independent geochronologic constraints. Previous studies demonstrate the dependency of U-series comminution date on grain size and shape. Here we show that mineralogy of samples also plays a role, possibly controlled by the uranium content and crystal bond strength. To separate samples by size and mineralogy, we use dry sonic-sieving, density and magnetic separation. Non-detrital materials deposited on the rim of comminuted grains have an isotopic composition that is unrelated to the isotopic evolution since comminution and therefore must be removed through a multi-step leaching procedure. Leaching is complicated by the fact that areas within the comminuted crystal that have experienced physical fractionation are contained within damaged zones and are prone to being leached themselves, which removes areas of interest from the crystal. We present progress made on a sample processing method developed to alleviate complications that affect comminution age measurements. Initial 234U/238U measurements for untreated silt from an 800ka Sierran glacial till are up to 6% above secular equilibrium, while samples processed with this method have measured ratios as low as 3% below secular equilibrium.

Trace element abundances in megacrysts and their host basalts - Constraints on partition coefficients and megacryst genesis

NASA Technical Reports Server (NTRS)

Irving, A. J.; Frey, F. A.

1984-01-01

Rare earth and other trace element abundances are determined in megacrysts of clinopyroxene, orthopyroxene, amphibole, mica, anorthoclase, apatite and zircon, as well as their host basalts, in an effort to gather data on mineral/melt trace element partitioning during the high pressure petrogenesis of basic rocks. Phase equilibria, major element partitioning and isotopic ratio considerations indicate that while most of the pyroxene and amphibole megacrysts may have been in equilibrium with their host magmas at high pressures, mica, anorthoclase, apatite, and zircon megacrysts are unlikely to have formed in equilibrium with their host basalts. It is instead concluded that they were precipitated from more evolved magmas, and have been mixed into their present hosts.

Kinetic and equilibrium lithium acidities of arenes: theory and experiment.

PubMed

Streitwieser, Andrew; Shah, Kamesh; Reyes, Julius R; Zhang, Xingyue; Davis, Nicole R; Wu, Eric C

2010-08-26

Kinetic acidities of arenes, ArH, measured some time ago by hydrogen isotope exchange kinetics with lithium cyclohexylamide (LiCHA) in cyclohexylamine (CHA) show a wide range of reactivities that involve several electronic mechanisms. These experimental reactivities give an excellent Brønsted correlation with equilibrium lithium ion pair acidities (pK(Li)) derived as shown recently from computations of ArLi.2E (E = dimethyl ether). The various electronic mechanisms are well modeled by ab initio HF calculations with modest basis sets. Additional calculations using NH(3) as a model for CHA further characterize the TS of the exchange reactions. The slopes of Brønsted correlations of ion pair systems can vary depending on the nature of the ion pairs.

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

ERIC Educational Resources Information Center

Heald, Emerson F.

1978-01-01

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

Growth versus metabolic tissue replacement in mouse tissues determined by stable carbon and nitrogen isotope analysis

NASA Astrophysics Data System (ADS)

Macavoy, S. E.; Jamil, T.; Macko, S. A.; Arneson, L. S.

2003-12-01

Stable isotope analysis is becoming an extensively used tool in animal ecology. The isotopes most commonly used for analysis in terrestrial systems are those of carbon and nitrogen, due to differential carbon fractionation in C3 and C4 plants, and the approximately 3‰ enrichment in 15N per trophic level. Although isotope signatures in animal tissues presumably reflect the local food web, analysis is often complicated by differential nutrient routing and fractionation by tissues, and by the possibility that large organisms are not in isotopic equilibrium with the foods available in their immediate environment. Additionally, the rate at which organisms incorporate the isotope signature of a food through both growth and metabolic tissue replacement is largely unknown. In this study we have assessed the rate of carbon and nitrogen isotopic turnover in liver, muscle and blood in mice following a diet change. By determining growth rates, we were able to determine the proportion of tissue turnover caused by growth versus that caused by metabolic tissue replacement. Growth was found to account for approximately 10% of observed tissue turnover in sexually mature mice (Mus musculus). Blood carbon was found to have the shortest half-life (16.9 days), followed by muscle (24.7 days). Liver carbon turnover was not as well described by the exponential decay equations as other tissues. However, substantial liver carbon turnover was observed by the 28th day after diet switch. Surprisingly, these tissues primarily reflect the carbon signature of the protein, rather than carbohydrate, source in their diet. The nitrogen signature in all tissues was enriched by 3 - 5‰ over their dietary protein source, depending on tissue type, and the isotopic turnover rates were comparable to those observed in carbon.

Modeling radium distribution in coastal aquifers during sea level changes: The Dead Sea case

USGS Publications Warehouse

Kiro, Yael; Yechieli, Yoseph; Voss, Clifford I.; Starinsky, Abraham; Weinstein, Yishai

2012-01-01

We present a new approach to studying the behavior of radium isotopes in a coastal aquifer. In order to simulate radium isotope distributions in the dynamic flow field of the Dead Sea aquifer, a multi-species density dependent flow model (SUTRA-MS) was used. Field data show that the activity of 226Ra decreases from 140 to 60 dpm/L upon entering the aquifer from the Dead Sea, and then further decreases linearly due to mixing with Ra-poor fresh water. On the other hand, an increase is observed in the activity of the shorter-lived isotopes (up to 52 dpm/L 224Ra and 31 dpm/L 223Ra), which are relatively low in Dead Sea water (up to 2.5 dpm/L 224Ra and 0.5 dpm/L 223Ra). The activities of the short lived radium isotopes also decrease with decreasing salinity, which is due to the effect of salinity on the adsorption of radium. The relationship between 224Ra and salinity suggests that the adsorption partition coefficient (K) is linearly related to salinity. Simulations of the steady-state conditions, show that the distance where equilibrium activity is attained for each radium isotope is affected by the isotope half-life, K and the groundwater velocity, resulting in a longer distance for the long-lived radium isotopes. K affects the radium distribution in transient conditions, especially that of the long-lived radium isotopes. The transient conditions in the Dead Sea system, with a 1 m/yr lake level drop, together with the radium field data, constrains K to be relatively low (226Ra cannot be explained by adsorption, and it is better explained by removal via coprecipitation, probably with barite or celestine.

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

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

δ15N values of atmospheric N species simultaneously collected using sector-based samplers distant from sources - Isotopic inheritance and fractionation

NASA Astrophysics Data System (ADS)

Savard, Martine M.; Cole, Amanda; Smirnoff, Anna; Vet, Robert

2017-08-01

The nitrogen isotope ratios (δ15N) of atmospheric N species are commonly suggested as indicators of N emission sources. Therefore, numerous research studies have developed analytical methodologies and characterized primary (gases) and secondary emission products (mostly precipitation and aerosols) from various emitters. These previous studies have generally collected either reduced or oxidized N forms, and sampled them separately prior to determining their δ15N values. Distinctive isotopic signals have been reported for emissions from various sources, and seasonality of the δ15N values has been frequently attributed to shifts in relative contributions from sources with different isotopic signals. However, theoretical concepts suggest that temperature effects on isotopic fractionation may also affect the δ15N values of atmospheric reaction products. Here we use a sector-based multi-stage filter system to simultaneously collect seven reduced and oxidized N species downwind from five different source types in Alberta, Canada. We report δ15N values obtained with a state-of-the-art gold-furnace pre-concentrator online with an isotope ratio mass spectrometer (IRMS) to provide representative results even for oxidized-N forms. We find that equilibrium isotope effects and their temperature dependence play significant roles in determining the δ15N values of the secondary emission products. In the end, seasonal δ15N changes here are mainly caused by temperature effects on fractionation, and the δ15N values of only two N species from one source type can be retained as potential fingerprints of emissions.

The record of mantle heterogeneity preserved in Earth's oceanic crust

NASA Astrophysics Data System (ADS)

Burton, K. W.; Parkinson, I. J.; Schiano, P.; Gannoun, A.; Laubier, M.

2017-12-01

Earth's oceanic crust is produced by melting of the upper mantle where it upwells beneath mid-ocean ridges, and provides a geographically widespread elemental and isotopic `sample' of Earth's mantle. The chemistry of mid-ocean ridge basalts (MORB), therefore, holds key information on the compositional diversity of the upper mantle, but the problem remains that mixing and reaction during melt ascent acts to homogenise the chemical variations they acquire. Nearly all isotope and elemental data obtained thus far are for measurements of MORB glass, and this represents the final melt to crystallise, evolving in an open system. However, the crystals that are present are often not in equilibrium with their glass host. Melts trapped in these minerals indicate that they crystallised from primitive magmas that possess diverse compositions compared to the glass. Therefore, these melt inclusions preserve information on the true extent of the mantle that sources MORB, but are rarely amenable to precise isotope measurement. An alternative approach is to measure the isotope composition of the primitive minerals themselves. Our new isotope data indicates that these minerals crystallised from melts with significantly different isotope compositions to their glass host, pointing to a mantle source that has experienced extreme melt depletion. These primitive minerals largely crystallised in the lower oceanic crust, and our preliminary data for lower crustal rocks and minerals shows that they preserve a remarkable range of isotope compositions. Taken together, these results indicate that the upper mantle sampled by MORB is extremely heterogeneous, reflecting depletion and enrichment over much of Earth's geological history.

delta18O variations in the Halimeda of Virgin Islands sands: evidence of cool water in the northeast Carribean, late Holocene

USGS Publications Warehouse

Holmes, Charles W.

1983-01-01

Halimeda segments from carbonate sands on the Virgin Islands platform have delta 18 O versus PDB isotopic values ranging from -0.3% to -1.3% (x = -0.9%). Modern Halimeda segments from the same area have a measured delta18 O ranging from -2.0% to -2.5% PDB (x = -2.15%), and the carbonate skeleton appears to have formed in isotopic equilibrium with the oceanic waters on the platform. Biologic and geochemical data indicate that the sand deposits have accumulated under physical and chemical conditions similar to the modern shelf environment. 14 C data suggest that the sand was deposited over an approximate 5800-year span, centering about 4000 years B.P. The average isotopic difference of 1.25% between the Holocene and modern carbonate indicates that the late Holocene Halimeda lived in waters approximately 4 degrees cooler than the present.

U-Th-Pb, Rb-Sr, and Sm-Nd isotopic systematics of lunar troctolitic cumulate 76535 - Implications on the age and origin of this early lunar, deep-seated cumulate

NASA Technical Reports Server (NTRS)

Premo, Wayne R.; Tatsumoto, M.

1992-01-01

The U-Th-Pb, Rb-Sr, and Sm-Nd isotopic systematics of four lightly leached residues of pristine, high-Mg, troctolitic cumulate 76535 were analyzed in order to determine their ages and magma sources. The data indicate that the cumulate was in isotopic equilibrium with a fluid or magma characterized by a high U-238/Pb-204 (mu) value of 600 at 4.236 Ga. Two and three stage Pb evolution calculations define even greater source mu values of about 1000, assuming low lunar initial mu values between 5 and 40 prior to about 4.43 Ga. These results are similar to mu values for KREEP sources and are also consistent with values from 78235, suggesting that at least some high-Mg suite rocks were derived from magma sources with high-mu values similar to KREEP, and support that idea that these rocks postdate primary lunar differentiation and formation of ferroan anorthosites.

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.

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.

How well does CO emission measure the H2 mass of MCs?

NASA Astrophysics Data System (ADS)

Szűcs, László; Glover, Simon C. O.; Klessen, Ralf S.

2016-07-01

We present numerical simulations of molecular clouds (MCs) with self-consistent CO gas-phase and isotope chemistry in various environments. The simulations are post-processed with a line radiative transfer code to obtain 12CO and 13CO emission maps for the J = 1 → 0 rotational transition. The emission maps are analysed with commonly used observational methods, I.e. the 13CO column density measurement, the virial mass estimate and the so-called XCO (also CO-to-H2) conversion factor, and then the inferred quantities (I.e. mass and column density) are compared to the physical values. We generally find that most methods examined here recover the CO-emitting H2 gas mass of MCs within a factor of 2 uncertainty if the metallicity is not too low. The exception is the 13CO column density method. It is affected by chemical and optical depth issues, and it measures both the true H2 column density distribution and the molecular mass poorly. The virial mass estimate seems to work the best in the considered metallicity and radiation field strength range, even when the overall virial parameter of the cloud is above the equilibrium value. This is explained by a systematically lower virial parameter (I.e. closer to equilibrium) in the CO-emitting regions; in CO emission, clouds might seem (sub-)virial, even when, in fact, they are expanding or being dispersed. A single CO-to-H2 conversion factor appears to be a robust choice over relatively wide ranges of cloud conditions, unless the metallicity is low. The methods which try to take the metallicity dependence of the conversion factor into account tend to systematically overestimate the true cloud masses.

A novel technique to determine cobalt exchangeability in soils using isotope dilution.

PubMed

Wendling, Laura A; Kirby, Jason K; McLaughlin, Michael J

2008-01-01

The environmental risk posed by Co contamination is largely a function of its oxidation state. Our objective was to assess the potential biological availability of Co and the reactions and fate of soluble Co(II) after addition to soils with varying physical and chemical characteristics. A potential risk in quantifying exchangeable Co in soils using isotope dilution techniques is the possible presence of two species of Co in soil solution and adsorbed on soil solid phases [Co(II) and Co(III)], coupled with the possibility that when an isotope of Co is added it may undergo a change in oxidation state during the measurement phase. In this study, we have utilized an isotope dilution technique with cation exchange and high-performance liquid chromatography-inductively coupled plasma-mass spectrometry to determine the isotopically exchangeable Co fraction in several soils with varying characteristics such as differing Al, Fe, and Mn oxide content; pH; and organic carbon content. The application of the cation exchange procedure adjusts measurements of isotopically exchangeable Co to correct for the presence of non-exchangeable 57Co not in equilibrium with the solution phase. Results indicated that oxidation of added 57Co(II) to 57Co(III) or precipitation of 57Co(II) may occur on the surfaces of some soils, particularly those with a high pH or substantial quantities of Mn oxide minerals. No detectable Co(III)(aq) was found in the aqueous extracts of the soils examined.

New triple oxygen isotope data of bulk and separated fractions from SNC meteorites: Evidence for mantle homogeneity of Mars

NASA Astrophysics Data System (ADS)

Ali, Arshad; Jabeen, Iffat; Gregory, David; Verish, Robert; Banerjee, Neil R.

2016-05-01

We report precise triple oxygen isotope data of bulk materials and separated fractions of several Shergotty-Nakhla-Chassigny (SNC) meteorites using enhanced laser-assisted fluorination technique. This study shows that SNCs have remarkably identical Δ17O and a narrow range in δ18O values suggesting that these meteorites have assimilated negligibly small surface materials (<5%), which is undetectable in the oxygen isotope compositions reported here. Also, fractionation factors in coexisting silicate mineral pairs (px-ol and mask-ol) further demonstrate isotopic equilibrium at magmatic temperatures. We present a mass-dependent fractionation line for bulk materials with a slope of 0.526 ± 0.016 (1SE) comparable to the slope obtained in an earlier study (0.526 ± 0.013; Franchi et al. 1999). We also present a new Martian fractionation line for SNCs constructed from separated fractions (i.e., pyroxene, olivine, and maskelynite) with a slope of 0.532 ± 0.009 (1SE). The identical fractionation lines run above and parallel to our terrestrial fractionation line with Δ17O = 0.318 ± 0.016‰ (SD) for bulk materials and 0.316 ± 0.009‰ (SD) for separated fractions. The conformity in slopes and Δ17O between bulk materials and separated fractions confirm oxygen isotope homogeneity in the Martian mantle though recent studies suggest that the Martian lithosphere may potentially have multiple oxygen isotope reservoirs.

Electron Energy Distribution and Transfer Phenomena in Non-Equilibrium Gases

DTIC Science & Technology

2016-09-01

and quantitative determination of species difficult. In a mass spectrometry study on boron chemistry a few decade ago, a technique of isotopic...In this FTMS study on TEB, by means of the high-mass-resolution spectrum to distinguish the isobaric ions, we have identified and quantitatively ...reproduce, release, perform, display, or disclose the work. 14. ABSTRACT During this 3-year in-house experimental research task, researchers in the

Analysis of nonlocal thermodynamic equilibrium CO 4.7 μm fundamental, isotopic, and hot band emissions measured by the Michelson Interferometer for Passive Atmospheric Sounding on Envisat

NASA Astrophysics Data System (ADS)

Funke, B.; López-Puertas, M.; Bermejo-Pantaleón, D.; von Clarmann, T.; Stiller, G. P.; HöPfner, M.; Grabowski, U.; Kaufmann, M.

2007-06-01

Nonlocal thermodynamic equilibrium (non-LTE) simulations of the 12C16O(1 → 0) fundamental band, the 12C16O(2 → 1) hot band, and the isotopic 13C16O(1 → 0) band performed with the Generic Radiative Transfer and non-LTE population Algorithm (GRANADA) and the Karlsruhe Optimized and Precise Radiative Transfer Algorithm (KOPRA) have been compared to spectrally resolved 4.7 μm radiances measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). The performance of the non-LTE simulation has been assessed in terms of band radiance ratios in order to avoid a compensation of possible non-LTE model errors by retrieval errors in the CO abundances inferred from MIPAS data with the same non-LTE algorithms. The agreement with the measurements is within 5% for the fundamental band and within 10% for the hot band. Simulated 13C16O radiances agree with the measurements within the instrumental noise error. Solar reflectance at the surface or clouds has been identified as an important additional excitation mechanism for the CO(2) state. The study represents a thorough validation of the non-LTE scheme used in the retrieval of CO abundances from MIPAS data.

Iron and oxygen isotope fractionation during iron UV photo-oxidation: Implications for early Earth and Mars

NASA Astrophysics Data System (ADS)

Nie, Nicole X.; Dauphas, Nicolas; Greenwood, Richard C.

2017-01-01

Banded iron formations (BIFs) contain appreciable amounts of ferric iron (Fe3+). The mechanism by which ferrous iron (Fe2+) was oxidized into Fe3+ in an atmosphere that was globally anoxic is highly debated. Of the three scenarios that have been proposed to explain BIF formation, photo-oxidation by UV photons is the only one that does not involve life (the other two are oxidation by O2 produced by photosynthesis, and anoxygenic photosynthesis whereby Fe2+ is directly used as electron donor in place of water). We experimentally investigated iron and oxygen isotope fractionation imparted by iron photo-oxidation at a pH of 7.3. The iron isotope fractionation between precipitated Fe3+-bearing lepidocrocite and dissolved Fe2+ follows a Rayleigh distillation with an instantaneous 56Fe/54Fe fractionation factor of + 1.2 ‰. Such enrichment in the heavy isotopes of iron is consistent with the values measured in BIFs. We also investigated the nature of the mass-fractionation law that governs iron isotope fractionation in the photo-oxidation experiments (i.e., the slope of the δ56Fe-δ57Fe relationship). The experimental run products follow a mass-dependent law corresponding to the high-T equilibrium limit. The fact that a ∼3.8 Gyr old BIF sample (IF-G) from Isua (Greenland) falls on the same fractionation line confirms that iron photo-oxidation in the surface layers of the oceans was a viable pathway to BIF formation in the Archean, when the atmosphere was largely transparent to UV photons. Our experiments allow us to estimate the quantum yield of the photo-oxidation process (∼0.07 iron atom oxidized per photon absorbed). This yield is used to model iron oxidation on early Mars. As the photo-oxidation proceeds, the aqueous medium becomes more acidic, which slows down the reaction by changing the speciation of iron to species that are less efficient at absorbing UV-photons. Iron photo-oxidation in centimeter to meter-deep water ponds would take months to years to complete. Oxidation by O2 in acidic conditions would be slower. Iron photo-oxidation is thus likely responsible for the formation of jarosite-hematite deposits on Mars, provided that shallow standing water bodies could persist for extended periods of time. The oxygen isotopic composition of lepidocrocite precipitated from the photo-oxidation experiment was measured and it is related to the composition of water by mass-dependent fractionation. The precipitate-fluid 18O/16O isotope fractionation of ∼ + 6 ‰ is consistent with previous determinations of oxygen equilibrium fraction factors between iron oxyhydroxides and water.

The magnesium isotope record of cave carbonate archives

NASA Astrophysics Data System (ADS)

Riechelmann, S.; Buhl, D.; Schröder-Ritzrau, A.; Riechelmann, D. F. C.; Richter, D. K.; Vonhof, H. B.; Wassenburg, J. A.; Geske, A.; Spötl, C.; Immenhauser, A.

2012-05-01

Here we explore the potential of time-series magnesium (δ26Mg) isotope data as continental climate proxies in speleothem calcite archives. For this purpose, a total of six Pleistocene and Holocene stalagmites from caves in Germany, Morocco and Peru and two flowstones from a cave in Austria were investigated. These caves represent the semi-arid to arid (Morocco), the warm-temperate (Germany), the equatorial-humid (Peru) and the cold-humid (Austria) climate zones. Changes in the calcite magnesium isotope signature with time are placed against carbon and oxygen isotope records from these speleothems. Similar to other proxies, the non-trivial interaction of a number of environmental, equilibrium and non-equilibrium processes governs the δ26Mg fractionation in continental settings. These include the different sources of magnesium isotopes such as rain water or snow as well as soil and hostrock, soil zone biogenic activity, shifts in silicate versus carbonate weathering ratios and residence time of water in the soil and karst zone. Pleistocene stalagmites from Morocco show the lowest mean δ26Mg values (GDA: -4.26 ± 0.07 ‰ and HK3: -4.17 ± 0.15 ‰) and the data are well explained in terms of changes in aridity over time. The Pleistocene to Holocene stalagmites from Peru show the highest mean value (NC-A and NC-B δ26Mg: -3.96 ± 0.04 ‰) but only minor variations in Mg-isotope composition, which is in concert with the rather stable equatorial climate at this site. Holocene stalagmites from Germany (AH-1 mean δ26Mg: -4.01 ± 0.07 ‰; BU 4 mean δ26Mg: -4.20 ± 0.10 ‰) record changes in outside air temperature as driving factor rather than rainfall amount. The alpine Pleistocene flowstones from Austria (SPA 52: -3.00 ± 0.73 ‰; SPA 59: -3.70 ± 0.43 ‰) are affected by glacial versus interglacial climate change with outside air temperature affecting soil zone activity and weathering balance. Several data points in the Austrian and two data points in the German speleothems are shifted to higher values due to sampling in detrital layers (Mg-bearing clay minerals) of the speleothems. The data and their interpretation shown here highlight the potential but also the limitations of the magnesium isotope proxy applied in continental climate research. An obvious potential lies in its sensitivity for even subtle changes in soil-zone parameters, a hitherto rather poorly understood but extremely important component in cave archive research. Limitations are most obvious in the low resolution and high sample amount needed for analysis. Future research should focus on experimental and conceptual aspects including quantitative and well calibrated leaching and precipitation experiments.

Sulfur and oxygen isotope insights into sulfur cycling in shallow-sea hydrothermal vents, Milos, Greece

PubMed Central

2014-01-01

Shallow-sea (5 m depth) hydrothermal venting off Milos Island provides an ideal opportunity to target transitions between igneous abiogenic sulfide inputs and biogenic sulfide production during microbial sulfate reduction. Seafloor vent features include large (>1 m2) white patches containing hydrothermal minerals (elemental sulfur and orange/yellow patches of arsenic-sulfides) and cells of sulfur oxidizing and reducing microorganisms. Sulfide-sensitive film deployed in the vent and non-vent sediments captured strong geochemical spatial patterns that varied from advective to diffusive sulfide transport from the subsurface. Despite clear visual evidence for the close association of vent organisms and hydrothermalism, the sulfur and oxygen isotope composition of pore fluids did not permit delineation of a biotic signal separate from an abiotic signal. Hydrogen sulfide (H2S) in the free gas had uniform δ34S values (2.5 ± 0.28‰, n = 4) that were nearly identical to pore water H2S (2.7 ± 0.36‰, n = 21). In pore water sulfate, there were no paired increases in δ34SSO4 and δ18OSO4 as expected of microbial sulfate reduction. Instead, pore water δ34SSO4 values decreased (from approximately 21‰ to 17‰) as temperature increased (up to 97.4°C) across each hydrothermal feature. We interpret the inverse relationship between temperature and δ34SSO4 as a mixing process between oxic seawater and 34S-depleted hydrothermal inputs that are oxidized during seawater entrainment. An isotope mass balance model suggests secondary sulfate from sulfide oxidation provides at least 15% of the bulk sulfate pool. Coincident with this trend in δ34SSO4, the oxygen isotope composition of sulfate tended to be 18O-enriched in low pH (<5), high temperature (>75°C) pore waters. The shift toward high δ18OSO4 is consistent with equilibrium isotope exchange under acidic and high temperature conditions. The source of H2S contained in hydrothermal fluids could not be determined with the present dataset; however, the end-member δ34S value of H2S discharged to the seafloor is consistent with equilibrium isotope exchange with subsurface anhydrite veins at a temperature of ~300°C. Any biological sulfur cycling within these hydrothermal systems is masked by abiotic chemical reactions driven by mixing between low-sulfate, H2S-rich hydrothermal fluids and oxic, sulfate-rich seawater. PMID:25183951

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

Stable Isotope Systematics of Martian Perchlorate

NASA Astrophysics Data System (ADS)

Martin, P.; Farley, K. A.; Archer, D., Jr.; Atreya, S. K.; Conrad, P. G.; Eigenbrode, J. L.; Fairen, A.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Malespin, C.; Ming, D. W.; Navarro-Gonzalez, R.; Sutter, B.

2015-12-01

Chlorine isotopic compositions in HCl released during evolved gas analysis (EGA) runs have been detected by the Sample Analysis at Mars (SAM) instrument on the Curiosity rover ranging from approximately -9‰ to -50‰ δ37Cl, with two spatially and isotopically separated groups of samples averaging -15‰ and -45‰. These extremely low values are the first such detection of any known natural material; common terrestrial values very rarely exceed ±5‰, and the most extreme isotopic signature yet detected elsewhere in the solar system are values of around +24‰ on the Moon. The only other known location in the solar system with large negative chlorine isotopes is the Atacama Desert, where perchlorate with -14‰ δ37Cl has been detected. The Atacama perchlorate has unusual Δ17O signatures associated with it, indicating a formation mechanism involving O3, which suggests an atmospheric origin of the perchlorate and associated large isotopic anomalies. Identification of non-zero positive Δ17O signatures in the O2 released during EGA runs would allow definitive evidence for a similar process having occurred on Mars. Perchlorate is thought to be the most likely source of HCl in EGA runs due to the simultaneous onset of O2 release. If perchlorate is indeed the HCl source, atmospheric chemistry could be responsible for the observed isotopic anomalies, with variable extents of perchlorate production producing the isotopic variability. However, chloride salts have also been observed to release HCl upon heating; if the timing of O2 release is merely coincidental, observed HCl could be coming from chlorides. At thermodynamic equilibrium, the fractionation factor of perchlorate reduction is 0.93, meaning that differing amounts of post-deposition reduction of isotopically normal perchlorate to chloride could account for the highly variable Cl isotopes. Additionally, post-deposition reduction could account for the difference between the two Cl isotopic groups if perchlorate is the HCl source, as the residual perchlorate after reduction will be isotopically heavy. Therefore, conclusive determination of the origin of HCl released during EGA is vital to understanding the origin of this large δ37Cl anomaly.

Origin of primitive ocean island basalts by crustal gabbro assimilation and multiple recharge of plume-derived melts

NASA Astrophysics Data System (ADS)

Borisova, Anastassia Y.; Bohrson, Wendy A.; Grégoire, Michel

2017-07-01

Chemical Geodynamics relies on a paradigm that the isotopic composition of ocean island basalt (OIB) represents equilibrium with its primary mantle sources. However, the discovery of huge isotopic heterogeneity within olivine-hosted melt inclusions in primitive basalts from Kerguelen, Iceland, Hawaii and South Pacific Polynesia islands implies open-system behavior of OIBs, where during magma residence and transport, basaltic melts are contaminated by surrounding lithosphere. To constrain the processes of crustal assimilation by OIBs, we employed the Magma Chamber Simulator (MCS), an energy-constrained thermodynamic model of recharge, assimilation and fractional crystallization. For a case study of the 21-19 Ma basaltic series, the most primitive series ever found among the Kerguelen OIBs, we performed sixty-seven simulations in the pressure range from 0.2 to 1.0 GPa using compositions of olivine-hosted melt inclusions as parental magmas, and metagabbro xenoliths from the Kerguelen Archipelago as wallrock. MCS modeling requires that the assimilant is anatectic crustal melts (P2O5 ≤ 0.4 wt.% contents) derived from the Kerguelen oceanic metagabbro wallrock. To best fit the phenocryst assemblage observed in the investigated basaltic series, recharge of relatively large masses of hydrous primitive basaltic melts (H2O = 2-3 wt%; MgO = 7-10 wt.%) into a middle crustal chamber at 0.2 to 0.3 GPa is required. Our results thus highlight the important impact that crustal gabbro assimilation and mantle recharge can have on the geochemistry of mantle-derived olivine-phyric OIBs. The importance of crustal assimilation affecting primitive plume-derived basaltic melts underscores that isotopic and chemical equilibrium between ocean island basalts and associated deep plume mantle source(s) may be the exception rather than the rule.

Source-dependent and source-independent controls on plutonium oxidation state and colloid associations in groundwater.

PubMed

Buesseler, Ken O; Kaplan, Daniel I; Dai, Minhan; Pike, Steven

2009-03-01

Plutonium (Pu) was characterized for its isotopic composition, oxidation states, and association with colloids in groundwater samples near disposal basins in F-Area of the Savannah River Site and compared to similar samples collected six years earlier. Two sources of Pu were identified, the disposal basins, which contained a 24Pu/l39Pu isotopic signature consistent with weapons grade Pu, and 244Cm, a cocontaminant that is a progenitor radionuclide of 24Pu. 24Pu that originated primarily from 244Cm tended to be appreciably more oxidized (Pu(V/VI)), less associated with colloids (approximately 1 kDa - 0.2 microm), and more mobile than 239Pu, as suggested by our prior studies at this site. This is not evidence of isotope fractionation but rather "source-dependent" controls on 240Pu speciation which are processes that are not at equilibrium, i.e., processes that appear kinetically hindered. There were also "source-independent" controls on 239Pu speciation, which are those processes that follow thermodynamic equilibrium with their surroundings. For example, a groundwater pH increase in one well from 4.1 in 1998 to 6.1 in 2004 resulted in an order of magnitude decrease in groundwater 239Pu concentrations. Similarly, the fraction of 239Pu in the reduced Pu(III/IV) and colloidal forms increased systematically with decreases in redox condition in 2004 vs 1998. This research demonstrates the importance of source-dependent and source-independent controls on Pu speciation which would impact Pu mobility during changes in hydrological, chemical, or biological conditions on both seasonal and decadal time scales, and over short spatial scales. This implies more dynamic shifts in Pu speciation, colloids association, and transport in groundwater than commonly believed.

Magnesium isotopic composition of the Earth and chondrites

NASA Astrophysics Data System (ADS)

Teng, Fang-Zhen; Li, Wang-Ye; Ke, Shan; Marty, Bernard; Dauphas, Nicolas; Huang, Shichun; Wu, Fu-Yuan; Pourmand, Ali

2010-07-01

To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ 25Mg and ±0.07‰ on δ 26Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL). Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ 25Mg = -0.13 ± 0.05 (2SD) and δ 26Mg = -0.26 ± 0.07 (2SD) for global oceanic basalts ( n = 110) and δ 25Mg = -0.13 ± 0.03 (2SD) and δ 26Mg = -0.25 ± 0.04 (2SD) for global peridotite xenoliths ( n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ 25Mg = -0.15 ± 0.04 (2SD) and δ 26Mg = -0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes. Collectively, the Mg isotopic composition of the Earth's mantle, based on oceanic basalts and peridotites, is estimated to be -0.13 ± 0.04 for δ 25Mg and -0.25 ± 0.07 for δ 26Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites. The chondritic composition of the Earth implies that Mg isotopes were well mixed during accretion of the inner solar system.

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

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

Pazhanisamy, S.; Pratt, R.F.

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

Stable isotopes in water vapor and precipitation for a coastal lagoon at mid latitudes

NASA Astrophysics Data System (ADS)

Zannoni, Daniele; Bergamasco, Andrea; Dreossi, Giuliano; Rampazzo, Giancarlo; Stenni, Barbara

2016-04-01

The stable oxygen and hydrogen isotope composition in precipitation can be used in hydrology to describe the signature of local meteoric water. The isotopic composition of water vapor is usually obtained indirectly from measurements of δD and δ18O in precipitation, assuming the isotopic equilibrium between rain and water vapor. Only few studies report isotopic data in both phases for the same area, thus providing a complete Local Meteoric Water Line (LMWL). The goal of this study is to build a complete LMWL for the lagoon of Venice (northern Italy) with observations of both water vapor and precipitation. The sampling campaign has started in March 2015 and will be carried out until the end of 2016. Water vapor is collected once a week with cold traps at low temperatures (-77°C). Precipitation is collected on event and monthly basis with a custom automatic rain sampler and a rain gauge, respectively. Liquid samples are analyzed with a Picarro L1102-i and results are reported vs VSMOW. The main meteorological parameters are continuously recorded in the same area by the campus automatic weather station. Preliminary data show an LMWL close to the Global Meteoric Water Line (GMWL) with lower slope and intercept. An evaporation line is clearly recognizable, considering samples that evaporated between the cloud base and the ground. The deviation from the GMWL parameters, especially intercept, can be attributed to evaporated rain or to the humidity conditions of the water vapor source. Water vapor collected during rainfall shows that rain and vapor are near the isotopic equilibrium, just considering air temperature measured at ground level. Temperature is one of the main factor that controls the isotopic composition of the atmospheric water vapor. Nevertheless, the circulation of air masses is a crucial parameter which has to be considered. Water vapor samples collected in different days but with the same meteorological conditions (air temperature and relative humidity) show differences in terms of δ18O up to 3‰. Isotopic ratios in rain events and water vapor are in fact dominated by a seasonal component but outliers are clearly linked to air parcel origin. The monthly measurements of δD and δ18O in precipitation of August 2015, for instance, are lower than in colder months, considering monthly average temperatures. Single rain events show a small sequence of precipitation, that leads to 40% of total precipitation of August, which lowers δ-values considerably. The sampling on event basis during occasional and discontinuous rain also allows to identify the rainout effect, which leads to lightening water during a rainfall. Statistics based on back trajectories (48 hours) show that the major part of air parcels travels across central Europe and derives from sources located in the north Atlantic, whereas, a smaller fraction of the water vapor can be attributed to Mediterranean sources.

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

PubMed

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

2018-05-15

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

Isotopic fingerprints of the Lake Żabińskie (NE Poland) hydrological system on contemporary carbonates precipitated in the lake.

PubMed

Ustrzycka, Alicja; Piotrowska, Natalia; Bonk, Alicja; Filipiak, Janusz; Tylmann, Wojciech

2018-06-01

An isotopic monitoring was undertaken in 2012-2014 at Lake Żabińskie (Mazurian Lakeland, NE Poland). The aim was to identify the factors and processes controlling an isotopic composition of the lake water and to explore the mechanism responsible for recording the climatic signal in stable isotope composition of deposited carbonates. δ 18 O and δ 2 H in the precipitation, lake water column, inflows and outflow, δ 18 O and δ 13 C in the carbonate fraction of sediments trapped in the water column were recorded with monthly resolution. A relationship between δ 18 O and δ 2 H in local precipitation was used to estimate the local meteoric water line. The dataset obtained for the water enabled to identify the modification of the water's isotopic composition due to evaporation, connected with seasonal lake water stratification and mixing patterns. Statistically significant correlation coefficients suggest that the δ 18 O of the carbonate fraction in the sediment traps depends on the δ 18 O of rainfall water and on air temperature. The fractionation coefficient α shows that in summer months the carbonate precipitation process is closest to equilibrium. As expected for an exorheic lake, no significant correlation was observed between δ 18 O and δ 13 C in precipitated carbonate.

Iron Isotope Fractionation in the Bushveld Igneous Complex Provide Insight into Fractional Crystallization

NASA Astrophysics Data System (ADS)

Rios, K. L.; Feineman, M. D.; Bybee, G. M.

2016-12-01

Dated at 2.056 Ga and encompassing an estimated 65,000 km2 in surface area and 650,000 km3 in volume the Bushveld Igneous Complex in South Africa contains the largest and most unique layered mafic intrusion in the world. It contains 80-90% of the world's minable platinum group elements. Scientists are interested in understanding the origin of this intrusion due to its massive size, unique assemblage of minerals, and strongly zoned stratigraphy. Iron isotopes may help us to understand the roles of partial mantle melting and fractional crystallization in magma genesis and differentiation. For example, it may be possible to determine what role fractional crystallization of oxides and sulfides played in the formation of the Rustenburg Layered Suite (RLS) by comparing δ56Fe in samples from the Lower, Critical, Main and Upper Zones. The use of MC-ICPMS has made it more routine to study the fractionation of stable iron isotopes in natural systems; however, this technique has only been applied in a few studies of the RLS, mostly restricted to the Upper Main and Upper Zones. In this study δ56Fe was determined in Upper Zone magnetite, Critical Zone chromitite and Critical Zone sulfides using MC-ICP-MS. Previous research has shown that early crystallizing mafic phases incorporate the lighter 54Fe isotope leaving a residual magma with a higher δ56Fe value. Therefore, if the Upper Zone magma represents a high-degree differentiate of the parental Bushveld magma, then magmas from the Upper Zone would be expected to have a higher δ56Fe than magmas contributing to the Lower, Critical and Main Zones. The results of this experiment were indeed consistent with this hypothesis. The δ56Fe values recorded for the three sample types were: magnetite 0.19 ±0.03‰; sulfides -0.45 ±0.03‰ to -0.81 ±0.03‰; and chromitite 0.03 ±0.05‰. The sulfides of the Critical Zone are isotopically lighter than would be predicted based on equilibrium sulfide-melt fractionation, if the parental melt of the Critical Zone were in equilibrium with previously published whole rock data for Upper Zone. This is consistent with interpretations of the Upper Zone as a high degree differentiate of the Bushveld Parental Magma.

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.

Method for enriching a middle isotope using vibration-vibration pumping

DOEpatents

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

1989-01-01

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

Opacity probability distribution functions for electronic systems of CN and C2 molecules including their stellar isotopic forms.

NASA Technical Reports Server (NTRS)

Querci, F.; Kunde, V. G.; Querci, M.

1971-01-01

The basis and techniques are presented for generating opacity probability distribution functions for the CN molecule (red and violet systems) and the C2 molecule (Swan, Phillips, Ballik-Ramsay systems), two of the more important diatomic molecules in the spectra of carbon stars, with a view to including these distribution functions in equilibrium model atmosphere calculations. Comparisons to the CO molecule are also shown. T he computation of the monochromatic absorption coefficient uses the most recent molecular data with revision of the oscillator strengths for some of the band systems. The total molecular stellar mass absorption coefficient is established through fifteen equations of molecular dissociation equilibrium to relate the distribution functions to each other on a per gram of stellar material basis.

Effects of Boreal Lake Wetlands on Atmospheric 13CH3D and 12CH2D2

NASA Astrophysics Data System (ADS)

Haghnegahdar, M. A.; Kohl, I. E.; Schauble, E. A.; Walter Anthony, K. M.; Young, E. D.

2017-12-01

Recently, we developed a theoretical model to investigate the potential use of 13CH3D and 12CH2D2 as tools for tracking atmospheric methane budget. We used electronic structure methods to estimate kinetic isotope fractionations associated with the major sink reactions of CH4 in air (reactions with •OH and Cl•), and literature data with reconnaissance measurements of the relative abundances of 13CH3D and 12CH2D2 to estimate the compositions of the largest atmospheric sources. Here we present new methane rare isotopologue data from boreal wetlands, comprising one of the most important sources, in order to evaluate the robustness of the model. Boreal wetlands (>55° N) account for more than half of the wetland area in the Northern hemisphere. We analyzed methane samples from high latitude lakes representing different geographical regions, geological and ecological contexts, methane fluxes, and isotopic signatures. Using clumped isotopes of CH4 we are able to determine the likely production mechanism for natural CH4 samples. So far, all of our analyzed samples except one plot in the microbial pure-culture methanogenesis field (Young et al. 2017) with ranges of -0.2‰ to +1.2‰ for Δ13CH3D, and -29.6‰ to -18.2‰ for Δ12CH2D2. These compositions are far from equilibrium. The one exception, from Lake Doughnut, Alaska, exhibits Δ13CH3D and Δ12CH2D2 values of +5.2‰ and +18.7‰, respectively, which fall near ambient thermodynamic equilibrium values. This may be an effect of methanotrophy. Mean Δ13CH3D and Δ12CH2D2 for all lake samples are +1.7‰ and -15.4‰ respectively, compared to our original estimate of +6.1‰ and +21.2‰ for the wetland methane source based on an assumption of equilibrium. If we assume that these samples are representative of the overall wetland source, Δ13CH3D decreases by 0.8‰ and Δ12CH2D2 decreases by 0.6‰ in our model of bulk atmospheric methane. Δ13CH3D and Δ12CH2D2 values of air (including •OH and Cl• sink reactions) are estimated to be +3.6‰ and +112.9‰, respectively. Even if we exclude the Lake Doughnut sample, the total effect on Δ12CH2D2 in air is no more than 2‰. Our model predicts that sink reactions generate a distinctly elevated Δ12CH2D2 (by 104‰) relative to the source composition. In contrast, differences in source compositions have a comparatively small effect, on the order of a few per mil at most.

Binding Isotope Effects for para-Aminobenzoic Acid with Dihydropteroate Synthase from Staphylococcus aureus and Plasmodium falciparum.

PubMed

Stratton, Christopher F; Namanja-Magliano, Hilda A; Cameron, Scott A; Schramm, Vern L

2015-10-16

Dihydropteroate synthase is a key enzyme in folate biosynthesis and is the target of the sulfonamide class of antimicrobials. Equilibrium binding isotope effects and density functional theory calculations indicate that the substrate binding sites for para-aminobenzoic acid on the dihydropteroate synthase enzymes from Staphylococcus aureus and Plasmodium falciparum present distinct chemical environments. Specifically, we show that para-aminobenzoic acid occupies a more sterically constrained vibrational environment when bound to dihydropteroate synthase from P. falciparum relative to that of S. aureus. Deletion of a nonhomologous, parasite-specific insert from the plasmodial dihydropteroate synthase abrogated the binding of para-aminobenzoic acid. The loop specific to P. falciparum is important for effective substrate binding and therefore plays a role in modulating the chemical environment at the substrate binding site.

O-stable Isotopes Distribution In Deep-sea Corals From Sims Measurements

NASA Astrophysics Data System (ADS)

Blamart, D.; Cuif, J.-P.; Juillet-Leclerc, A.

Urey's theoretical calculations (Urey, 1947) have predicted that the O-isotope fraction- ations between calcium carbonates and water should be large enough to be used as a paleothermometer. However, stable isotopes studies on aragonitic invertebrates includ- ing corals have also demonstrated departure of several per mil from O-equilibrium. Different tentative explanations have been proposed in the literature: (1) influence of the polymorphism form and chemical composition of the calcium carbonate (2) kinetic effects related to calcification process during rapid growth rate (3) metabolic effect due to respiration and photosynthesis. All these explanations are based on the assumption that the coral skeleton represents a structural homogeneous entity. Early microscopic studies of coral skeletons have suggested that coral skeletons are built by two different structures: (1) fibres and (2) centres of calcification confirmed by recent biominerali- sation studies. SIMS O-stable isotopes measurements have been performed on lines of centres of calcification and the surrounding aragonitic fibre on deep-sea coral (Lophe- lia Pertusa). Different transects of O-isotope distribution have been carried out in the septa and in the thick wall of Lophelia pertusa. O-isotopic values of the fibres of the septa and of the wall show a very large range of variation of around 10L' from -5 to +5L' (PDB). O-measurement performed on line of the centre of calcification from the inner part of the septa to the wall show a restricted range of variation which not exceed 1L'. O-values of the centres of calcification in the septa and in the wall are similar with a mean value of -2.9s0.3L'. Temperature derived from O values of the centre of cal- ´ cification are not consistant with the measured ones in situ indicating also a constant fractionation in this microstructure. Coupled with C-isotopes measurements O-isotope distribution should better constraint the growth mechanism, calcification process and the associated isotopic fractionation

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

PubMed

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

2012-02-01

A new PET ligand, 3-fluoro-5-(2-(2-(18)F-(fluoromethyl)-thiazol-4-yl)ethynyl)benzonitrile (18F-SP203) can quantify metabotropic glutamate subtype 5 receptors (mGluR5) in human brain by a bolus injection and kinetic modeling. As an alternative approach to a bolus injection, binding can simply be measured as a ratio of tissue to metabolite-corrected plasma at a single time point under equilibrium conditions achieved by administering the radioligand with a bolus injection followed by a constant infusion. The purpose of this study was to validate the equilibrium method as an alternative to the standard kinetic method for measuring 18F-SP203 binding in the brain. Nine healthy subjects were injected with 18F-SP203 using a bolus plus constant infusion for 300 min. A single ratio of bolus-to-constant infusion (the activity of bolus equaled to that of infusion over 219 min) was applied to all subjects to achieve equilibrium in approximately 120 min. As a measure of ligand binding, we compared total distribution volume (VT) calculated by the equilibrium and kinetic methods in each scan. The equilibrium method calculated VT by the ratio of radioactivity in the brain to the concentration of 18F-SP203 in arterial plasma at 120 min, and the kinetic method calculated VT by a two-tissue compartment model using brain and plasma dynamic data from 0 to 120 min. VT obtained via the equilibrium method was highly correlated with VT obtained via kinetic modeling. Inter-subject variability of VT obtained via the equilibrium method was slightly smaller than VT obtained via the kinetic method. VT obtained via the equilibrium method was ~10% higher than VT obtained via the kinetic method, indicating a small difference between the measurements. Taken together, the results of this study show that using the equilibrium method is an acceptable alternative to the standard kinetic method when using 18F-SP203 to measure mGluR5. Although small differences in the measurements obtained via the equilibrium and kinetic methods exist, both methods consistently measured mGluR5 as indicated by the highly correlated VT values; the equilibrium method was slightly more precise, as indirectly measured by the smaller coefficient of variability across subjects. In addition, when using 18F-SP203, the equilibrium method is more efficient because it requires much less data. Copyright © 2011. Published by Elsevier Inc.

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.

Tritium, deuterium, and oxygen-18 in water collected from unsaturated sediments near a low-level radioactive-waste burial site south of Beatty, Nevada

USGS Publications Warehouse

Prudic, David E.; Stonestrom, David A.; Striegl, Robert G.

1997-01-01

Pore water was extracted in March 1996 from cores collected from test holes UZB-1 and UZB-2 drilled November 1992 and September 1993, respectively, in the Amargosa Desert south of Beatty, Nevada. The test holes are part of a study to determine factors affecting water and gas movement through unsaturated sediments. The holes are about 100 meters south of the southwest corner of the fence enclosing a commercial burial area for low-level radioactive waste. Water vapor collected from test hole UZB-2 in April 1994 and July 1995 had tritium concentrations greater than would be expected from atmospheric deposition. An apparatus was built in which pore water was extracted by cryodistillation from the previously obtained core samples. The extracted core water was analyzed for the radioactive isotope tritium and for the stable isotopes deuterium (D) and oxygen-18 (18O). The isotopic composition of core water was compared with that of water vapor previously collected from air ports in test hole UZB-2 and to additional samples collected during May 1996. Core water becomes increasingly depleted in D and 18O from the land surface to a depth of 30 meters, indicating that net evaporation of water is occurring near the land surface. Below a depth of 30 meters the stable-isotopic composition of core water becomes nearly constant and roughly equal to that of ground water. The stable isotopes plot on an evaporation trend. The source of the partly evaporated water could be either ground water or past precipitation having the same average isotopic composition as ground water but not modern precipitation, based on 18 months of record. Profiles of D and 18O in water vapor roughly parallel those in core water. The stable isotopes of core water appear to be in isotopic equilibrium with water vapor from UZB-2 when temperature-dependent fractionation is considered. The data are consistent with the hypothesis of evaporative discharge of ground water at the land surface. The concentration of tritium in core water from depths less than 50 meters was higher than that of present-day atmospheric air, indicating that elevated tritium concentrations preceded the drilling. The concentrations of tritium in core water from the deepest sample (85 meters) and in UZB-2 groundwater (110 meters) were below detection. Thus, tritium in the unsaturated zone is not being introduced through ground water. The shape of the tritium profile for core water was similar to the shape of the tritium profile for water vapor collected April 1994, except that concentrations were consistently lower in core water than in water vapor. Tritium concentrations in water vapor increased from April 1994 to May 1996. Similar to the stable isotopes, the highest tritium concentrations were measured at shallow depths. Concentrations of tritium in water vapor during core collection were estimated assuming isotopic equilibrium with core water. The computed concentrations for November 1992 and September 1993 form consistent temporal trends with subsequent tritium concentrations in water vapor collected April 1994, July 1995, and May 1996. Observations of a bimodal distribution of tritium, in which the highest concentrations are in a gravel layer at a depth of 1-2 meters, indicate lateral migration of tritium through the vicinity of UZB-2.

Stable isotope fractionation of tungsten during adsorption on Fe and Mn (oxyhydr)oxides

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Kubo, Sayuri; Tanaka, Masato; Senda, Ryoko; Iizuka, Tsuyoshi; Tanimizu, Masaharu; Takahashi, Yoshio

2017-05-01

The similar, but not identical chemical properties of W compared with Mo suggest that the stable isotope system of W could be a novel proxy to explore the modern and ancient ocean as is the case in the well-established utility of Mo isotopes. We experimentally investigated the isotopic fractionation of W during adsorption on Fe and Mn (oxyhydr)oxides (ferrihydrite and δ-MnO2), a key process in the global ocean budget of this element. Our adsorption experiments confirmed that W isotopes fractionate substantially on both ferrihydrite and δ-MnO2: lighter W isotopes are preferentially adsorbed on both oxides as a result of equilibrium isotopic exchange between dissolved and adsorbed species, and the obtained values of Δ186/183Wliquid-solid (= δ186Wdissolved - δ186Wadsorbed) are 0.76 ± 0.09‰ for ferrihydrite and 0.88 ± 0.21‰ for δ-MnO2 (2σ, n = 6). Compared with the case of Mo isotopes, fractionation of W isotopes is (i) of comparable magnitude between ferrihydrite and δ-MnO2, and (ii) much smaller than that of Mo on δ-MnO2. Our previous XAFS observations and newly-performed DFT calculations both indicate that the observed W isotopic fractionations are caused by the symmetry change from Td (tetrahedral) WO42- to distorted Oh (octahedral) monomeric W species via formation of inner-sphere complexes on both ferrihydrite and δ-MnO2. The similar isotopic fractionations between the two oxides relate to the strong tendency for W to form inner-sphere complexes, which causes the symmetry change, in contrast to the outer-sphere complex of Mo on ferrihydrite. The smaller isotopic fractionation of W compared with Mo on δ-MnO2 despite their similar molecular symmetry seems to be due to their different degrees of distortion of Oh species. Our findings imply that the isotopic composition of W in modern oxic seawater is likely to become heavier relative to the input by removal of lighter W isotopes via adsorption on ferromanganese oxides in analogy with the Mo isotope budget. In contrast, the isotopic composition of W in ancient seawater should have evolved in response to the extent of deposition of both Fe and Mn oxides; this is likely to be different compared with that of the Mo isotopes, which is strongly associated with the occurrence of Mn oxides relative to Fe oxides.

Continuous and simultaneous measurements of precipitation and vapor isotopes over two monsoon seasons during 2016-2017 in Singapore

NASA Astrophysics Data System (ADS)

Jackisch, D.; He, S.; Ong, M. R.; Goodkin, N.

2017-12-01

Water isotopes are important tracers of climate dynamics and their measurement can provide valuable insights into the relationship between isotopes and atmospheric parameters and overall convective activities. While most studies provide data on daily or even monthly time scales, high-temporal in-situ stable isotope measurements are scarce, especially in the tropics. In this study, we presented δ18O and δ2H values in precipitation and vapor continuously and simultaneously measured using laser spectroscopy in Singapore during the 2016/2017 Northeast (NE) Asian monsoon and 2017 Southwest (SW) Asian monsoon. We found that δ-values of precipitation and vapor exhibit quite different patterns during individual events, although there is a significant correlation between the δ-values of precipitation and of vapor. δ-values in precipitation during individual precipitation events show a distinct V-shape pattern, with the lowest isotope values observed in the middle of the event. However, isotopes in water vapor mostly show an L-shape and are characterized by a gradual decrease with the onset of rainfall. The difference in δ-values of precipitation and vapor is generally constant during the early stage of the events but gradually increases near the end. It is likely that vapor and precipitation are closer to equilibrium at the early stage of a rain event, but diverge at the later stages. This divergence can be largely attributed to the evaporation of raindrops. We notice a frequent drop in d-excess of precipitation, whereas d-excess in vapor increases. In addition, a significant correlation exists between outgoing longwave radiation (OLR) and isotopes in both precipitation and vapor, suggesting an influence of regional convective activity.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

Conventional oxygen isotope (δ18O) has widely been used for paleoclimate studies. However, multiple influencing factors such as temperature, precipitation and kinetic effects during carbonate precipitation complicate the interpretation of δ18O data sometimes. Triple oxygen isotope (Δ17O) in carbonates could be sensitive to kinetic effect occur during its precipitation in water. Carbonates may also record the Δ17O signature of the parent waters, providing a basis in the natural carbonates for identifying kinetic processes such as rapid degassing at lower relative humidity inside a cave during speleothem deposition. Clumped isotopes (Δ47) in carbonates give the formation temperatures of the carbonates if precipitated under isotopic equilibrium. The first goal of the study is to explore the applicability of Δ17O for paleohydrolocial studies. The second is to reconstruct paleotemperature with suitable natural carbonates using Δ47values. This is a rare paleoclimate study utilizing two sophisticated new tools. CO2 produced from carbonates by acid digestion was used for both Δ47 and Δ17O analysis. Purified CO2 samples were directly introduced into the Mass spectrometer (MAT 253) for clumped isotope analysis [1] and CO2-O2 exchange method in presence of platinum for Δ17O analysis [2,3]. We measured Δ47 and Δ17O values in synthetic carbonates precipitated at different temperatures (10-90 oC) and Δ17O values in the water from which the carbonate precipitated. We observed consistent Δ47 values in the carbonates while Δ17O were found to vary. Probably a proper slope (between δ18O and δ17O) selection for carbonates would give consistent results. We also measured Δ47 and Δ17O in modern and well dated speleothems from Chinese and Indian caves to study the paleohydrology and paleotemperature. Δ47 and Δ17O were also measured in modern natural carbonate depositions such as corals, foraminifer and marbles to explore their potentials for paleoclimate studies. Implications of the results will be presented and discussed. [1] Laskar, A. H., et al. Terra Nova, 28, 265-270, 2016. [2] Mahata, S., et al. Analytical Chemistry, 85, 6894-6901, 2013. [3] Mahata, S. et al. Rapid. Comm. Mass Spect., 30, 119-131, 2016.

Oxygen Isotope Variability within Nautilus Shell Growth Bands

PubMed Central

2016-01-01

Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis of oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. To create the observed range of δ18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands. PMID:27100183

Oxygen isotope variability within Nautilus shell growth bands

DOE PAGES

Linzmeier, Benjamin J.; Kozdon, Reinhard; Peters, Shanan E.; ...

2016-04-21

Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis ofmore » oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ 18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ 18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. In addition, to create the observed range of δ 18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands.« less

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

USGS Publications Warehouse

Revesz, Kinga; Coplen, Tyler

2008-01-01

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

Occurrences of ikaite and pseudomorphs after ikaite in Patagonian lakes - crystal morphologies and stable isotope composition

NASA Astrophysics Data System (ADS)

Oehlerich, Markus; Mayr, Christoph; Griesshaber, Erika; Ohlendorf, Christian; Zolitschka, Bernd; Sánchez-Pastor, Nuria; Kremer, Barbara; Lücke, Andreas; Oeckler, Oliver; Schmahl, Wolfgang

2010-05-01

Ikaite (CaCO3•6H2O), a hydrated calcium carbonate mineral occasionally found in marine sediments, has so far rarely been reported from non-marine sites. Modern ikaite and calcitic pseudomorphs after ikaite were recently discovered in Patagonian Argentina at the polymictic lakes of Laguna Potrok Aike (51°57´S, 70°23´W) and Laguna Cháltel (49°57´S, 71°07´W), respectively. Both lakes are of volcanic origin and have phosphorous-rich, alkaline waters, but differ in altitude (790 m asl and 110 m asl for Laguna Cháltel and Laguna Potrok Aike, respectively) and water temperature. The aim of this study is (1) to investigate conditions for the formation of ikaite and its transformation to more stable, water-free carbonate pseudomorphs after ikaite and (2) to assess the potential of ikaite and calcite pseudomorphs after ikaite as a paleoenvironmental tool in freshwater lakes. Crystallographic, morphological and isotopic characteristics of the pseudomorphs were investigated. Ikaite crystals were found (in September 2008) primarily on aquatic macrophytes and cyanobacteria colonies at Laguna Potrok Aike. Ikaite crystals transformed quickly to calcite pseudomorphs after ikaite after recovery from the cool lake water (4°C). The crystal structure of ikaite was investigated with single crystal X-ray diffraction on samples that were permanently kept cold (in the lake water). At Laguna Cháltel calcite pseudomorphs after ikaite were discovered in littoral sediment cores from 25 m water depth. The mm-sized, porous, polycrystalline calcium carbonate aggregates from the 104 cm long sediment core of Laguna Cháltel are morphologically pseudomorphs after ikaite. SEM and XRD analyses highlight that these pseudomorphs consist of several µm-small calcite crystals in a calcitic matrix. The shape of these micro-crystals changes from rounded to fibrous with increasing sediment depth. Some specimens show casts of cyanobacteria trichomes. The oxygen isotopic composition of calcite pseudomorphs after ikaite from both lakes was analyzed. Calculating water temperatures during the ikaite precipitation assuming isotopic equilibrium for calcite and including modern water isotope ranges do not result in realistic estimates. Thus, either the calcite isotope fractionation factors are not applicable to these pseudomorphs, because e.g. the transformation to calcite pseudomorphs after ikaite caused isotope exchange or the carbonate precipitation occurred in disequilibrium. Nevertheless, the offset between oxygen isotope values of the sedimentary calcitic pseudomorphs from Laguna Cháltel and the modern ones from Laguna Potrok Aike corresponds to the differences present in lake water isotopic composition. Thus, calcite pseudomorphs after ikaite may serve as a proxy for paleo-lake water isotope variations. The crystallisation of ikaite in these lacustrine environments is presently simulated by different methods: (1) Evaporation from the lake water and (2) with modified diffusion silica gel experiments using the lake water and synthetic solutions.

Isotope separation by photochromatography

DOEpatents

Suslick, Kenneth S.

1977-01-01

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

Strontium isotope geochemistry of groundwater in the central part of the Dakota (Great Plains) aquifer, USA

USGS Publications Warehouse

Gosselin, D.C.; Harvey, F.E.; Frost, C.; Stotler, R.; Macfarlane, P.A.

2004-01-01

The Dakota aquifer of the central and eastern Great Plains of the United States is an important source of water for municipal supplies, irrigation and industrial use. Although the regional flow system can be characterized generally as east to northeasterly from the Rocky Mountains towards the Missouri River, locally the flow systems are hydrologically complex. This study uses Sr isotopic data from groundwater and leached aquifer samples to document the complex subsystems within the Dakota aquifer in Nebraska and Kansas. The interaction of groundwater with the geologic material through which it flows has created spatial patterns in the isotopic measurements that are related to: long-term water-rock interaction, during which varying degrees of isotopic equilibrium between water and rock has been achieved; and the alteration of NaCl fluids by water-rock interaction. Specifically, Sr isotopic data distinguish brines from Kansas and western Nebraska from those in eastern Nebraska: the former are interpreted to reflect interaction with Permian rocks, whereas the latter record interaction with Pennsylvanian rocks. The Sr isotopic composition of groundwater from other parts of Nebraska and Kansas are a function of the dynamic interaction between groundwater and unlithified sediments (e.g., glacial till and loess), followed by interaction with oxidized and unoxidized sediments within the Dakota Formation. This study illustrates the power of combining Sr chemistry with more conventional geochemical data to obtain a more complete understanding of groundwater flow systems within regional aquifer systems where extensive monitoring networks do not exist. ?? 2003 Elsevier Ltd. All rights reserved.

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

PubMed

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

2016-11-01

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

The relative abundances of resolved l2CH2D2 and 13CH3D and mechanisms controlling isotopic bond ordering in abiotic and biotic methane gases

NASA Astrophysics Data System (ADS)

Young, E. D.; Kohl, I. E.; Lollar, B. Sherwood; Etiope, G.; Rumble, D.; Li, S.; Haghnegahdar, M. A.; Schauble, E. A.; McCain, K. A.; Foustoukos, D. I.; Sutclife, C.; Warr, O.; Ballentine, C. J.; Onstott, T. C.; Hosgormez, H.; Neubeck, A.; Marques, J. M.; Pérez-Rodríguez, I.; Rowe, A. R.; LaRowe, D. E.; Magnabosco, C.; Yeung, L. Y.; Ash, J. L.; Bryndzia, L. T.

2017-04-01

We report measurements of resolved 12CH2D2 and 13CH3D at natural abundances in a variety of methane gases produced naturally and in the laboratory. The ability to resolve 12CH2D2 from 13CH3D provides unprecedented insights into the origin and evolution of CH4. The results identify conditions under which either isotopic bond order disequilibrium or equilibrium are expected. Where equilibrium obtains, concordant Δ12CH2D2 and Δ13CH3D temperatures can be used reliably for thermometry. We find that concordant temperatures do not always match previous hypotheses based on indirect estimates of temperature of formation nor temperatures derived from CH4/H2 D/H exchange, underscoring the importance of reliable thermometry based on the CH4 molecules themselves. Where Δ12CH2D2 and Δ13CH3D values are inconsistent with thermodynamic equilibrium, temperatures of formation derived from these species are spurious. In such situations, while formation temperatures are unavailable, disequilibrium isotopologue ratios nonetheless provide novel information about the formation mechanism of the gas and the presence or absence of multiple sources or sinks. In particular, disequilibrium isotopologue ratios may provide the means for differentiating between methane produced by abiotic synthesis vs. biological processes. Deficits in 12CH2D2 compared with equilibrium values in CH4 gas made by surface-catalyzed abiotic reactions are so large as to point towards a quantum tunneling origin. Tunneling also accounts for the more moderate depletions in 13CH3D that accompany the low 12CH2D2 abundances produced by abiotic reactions. The tunneling signature may prove to be an important tracer of abiotic methane formation, especially where it is preserved by dissolution of gas in cool hydrothermal systems (e.g., Mars). Isotopologue signatures of abiotic methane production can be erased by infiltration of microbial communities, and Δ12CH2D2 values are a key tracer of microbial recycling.

The Relative Abundances of Resolved 12CH2D2 and 13CH3D and Mechanisms Controlling Isotopic Bond Ordering in Abiotic and Biotic Methane Gases

NASA Astrophysics Data System (ADS)

Young, E. D.; Kohl, I. E.; Sherwood Lollar, B.; Etiope, G.; Rumble, D.; Li, S.; Haghnegahdar, M. A.; Schauble, E. A.; McCain, K.; Foustoukos, D.; Sutcliffe, C. N.; Warr, O.; Ballentine, C. J.; Onstott, T. C.; Hosgormez, H.; Neubeck, A.; Marques, J. M.; Perez-Rodriguez, I. M.; Rowe, A. R.; LaRowe, D.; Magnabosco, C.; Bryndzia, T.

2016-12-01

We report measurements of resolved 12CH2D2 and 13CH3D at natural abundances in a variety of methane gases produced naturally and in the laboratory. The ability to resolve 12CH2D2 from 13CH3D provides unprecedented insights into the origin and evolution of CH4. The results identify conditions under which either isotopic bond order disequilibrium or equilibrium are expected. Where equilibrium obtains, concordant Δ12CH2D2 and Δ13CH3D temperatures can be used reliably for thermometry. We find that concordant temperatures do not always match previous hypotheses based on indirect estimates of temperature of formation nor temperatures derived from CH4/H2 D/H exchange, underscoring the importance of reliable thermometry based on the CH4 molecules themselves. Where Δ12CH2D2 and Δ13CH3D values are inconsistent with thermodynamic equilibrium, temperatures of formation derived from these species are spurious. In such situations, while formation temperatures are unavailable, disequilibrium isotopologue ratios nonetheless provide important information about the formation mechanism of the gas and the presence or absence of multiple sources or sinks. In particular, disequilibrium isotopologue ratios may provide the means for differentiating between methane produced by abiotic synthesis versus biological processes. Deficits in 12CH2D2 compared with equilibrium values in CH4 gas made by surface-catalyzed abiotic reactions are so large as to point towards a quantum tunneling origin. Tunneling also accounts for the more moderate depletions in 13CH3D that accompany the low 12CH2D2 abundances produced by abiotic reactions. The tunneling signature of abiotic CH4 formation may prove to be an important tracer of abiotic methane formation, especially where it is preserved by dissolution of gas in cool hydrothermal systems (e.g., Mars). Isotopologue signatures of abiotic methane production can be erased by infiltration of microbial communities, and Δ12CH2D2 values are a key tracer of microbial recycling.

Reference measurements for total mercury and methyl mercury content in marine biota samples using direct or species-specific isotope dilution inductively coupled plasma mass spectrometry.

PubMed

Krata, Agnieszka; Vassileva, Emilia; Bulska, Ewa

2016-11-01

The analytical procedures for reference measurements of the total Hg and methyl mercury (MeHg) mass fractions at various concentration levels in marine biota samples, candidates for certified reference materials (oyster and clam Gafrarium tumidum), were evaluated. Two modes of application of isotope dilution inductively coupled plasma mass spectrometry method (ID ICP-MS), namely direct isotope dilution and species-specific isotope dilution analysis with the use of two different quantification mass spectrometry techniques were compared. The entire ID ICP-MS measurement procedure was described by mathematical modelling and the combined uncertainty of measurement results was estimated. All factors influencing the final results as well as isotopic equilibrium were systematically investigated. This included the procedural blank, the moisture content in the biota samples and all factors affecting the blend ratio measurements (instrumental background, spectral interferences, dead time and mass discrimination effects as well as the repeatability of measured isotopic ratios). Modelling of the entire measurement procedures and the use of appropriate certified reference materials enable to assure the traceability of obtained values to the International System of Units (SI): the mole or the kilogram. The total mass fraction of mercury in oyster and clam biota samples, after correction for moisture contents, was found to be: 21.1 (1.1) 10(-9) kg kg(-1) (U =5.1% relative, k=2) and 390.0 (9.4) 10(-9) kg kg(-1) (U=2.4% relative, k=2), respectively. For the determination of mercury being present as methyl mercury, the non-chromatographic separation on anion-exchange resin AG1-X8 of the blended samples was applied. The content of MeHg (as Hg) in oyster sample was found: 4.81 (24) 10(-9)kgkg(-1) (U=5.0%, k=2) and 4.84 (21) 10(-9)kgkg(-1) (U=4.3%, k=2) with the use of quadrupole (ICP QMS) or sector field (ICP SFMS) inductively coupled plasma mass spectrometers, respectively. In the case of clam sample, the concentration of MeHg (as Hg) was found to be: 61.0 (2.3) 10(-)(9)kgkg(-1) (U=3.8%, k=2) and 61.3 (2.2) 10(-)(9)kgkg(-1) (U=3.6%, k=2), respectively. The mass fractions for total Hg and MeHg determined in this study were used as a contribution of the International Atomic Energy Agency (IAEA) Environment Laboratories in the characterisation of the IAEA 461 and IAEA 470 certified reference materials. The obtained good agreement with the reference values further validated the methods developed in this study. Copyright © 2016 Elsevier B.V. All rights reserved.

Modeling stable isotope transport in metamorphic and hydrothermal systems

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Foraminiferal Stable Isotope Record at Millville, NJ: Implications for the onset of the PETM

NASA Astrophysics Data System (ADS)

Wright, J. D.; Miller, K. G.

2016-12-01

Traditional paleoceanographic tools (magneto-biostratigraphy, orbital cycles) are insufficient to assign rates to the initial release of carbon during the rapid onset of the PETM (<10 kyr). The ODP Leg 174AX Millville, NJ PETM section (70 m paleodepth) is >10 times more expanded relative to the thickest open ocean sites (e.g., Site 690). The onset interval at Millville is defined by a bulk carbonate δ13C of 3.5‰ across 25 cm interval. Two groups used the geochemical changes to constrain the timing for the initial pulse of carbon. Wright and Schaller (2013) focused on the differential responses in δ13C and %CaCO3 arguing that the release was fast (<1 year). Conversely, Zeebe et al. (2016) assumed the initial covariance in δ18O and δ13C represented equilibrium conditions, modeling a 4 kyr duration for the release. We generated planktonic and benthic foraminiferal stable isotope records across the onset of the PETM CIE at Millville. Most of the δ13C change recorded by foraminifera occurred over the 25 cm onset interval. However, foraminiferal δ18O values continue to decrease for another 1.5 m above the initial δ13C decrease contradicting Zeebe et al.'s assumption of equilibrium conditions. The foraminiferal stable isotope pattern is similar to the modeled response following a large, instantaneous release of light carbon to the atmosphere, that produces a rapid (decadal) scale warming in the surface air masses followed by continued warming but at a slower rate. Differential responses in δ13C, δ18O, and %CaCO3 at the onset of the PETM are consistent with an instantaneous initial release of carbon with centennial-scale warming that continued well after the initial carbon pulse similar to that predicted by climate models. Fitting the Millville isotope records to these models suggests that peak warmth followed the initial release by 100 to 200 years. The mid-shelf location of Millville a made it responsive to atmospheric changes unlike open ocean sites where thermal inertia dampens the larger atmosphere changes.

Some investigations of the deposition of travertine from Hot Springs-I. The isotopic chemistry of a travertine-depositing spring

USGS Publications Warehouse

Friedman, I.

1970-01-01

The isotopic compositions of the travertine and of the hot spring solutions were studied at Main Springs and New Highland Terrace in the Mammoth Hot Springs area of Yellowstone Park. The springs issue at 74??C and a pH of 6.65 and the carbon isotopic composition of the travertine depositing at the orifice is +2%.??C13 (PDB). As the water travels out from the orifice, it cools and loses CO2. The travertine depositing at lower temperature is enriched in C13, reaching values of +4.8%. and the solution has a pH of 8.2 at 27??C. The ??C13 of the carbon species in solution is about -2.3%. at 74?? and about +4.3 at 27??C. Therefore, the difference in ??C13 between the solid and solution is approximately 4%. at 74?? and decreases to zero at about 20??C. These differences are shown to be due to kinetic (non-equilibrium) factors. The ??O18 contents of the travertine and water show that in most samples the carbonate oxygen is in equilibrium with the water O18 at the temperatures of deposition. This is especially true for travertine depositing slowly and at temperatures above about 50??C. Calculations based on pH and alkalinity titrations of the hot spring waters in situ show that at the spring orifice the water is very high in free CO2, which is quickly lost in transit. The springs are supersaturated with respect to both aragonite and calcite during most of their travel in the open air. The carbon isotopic composition of the travertine is similar to that in the marine carbonates that are adjacent to the springs and that are the probable source of the calcium carbonate. The travertine from inactive prehistoric springs near Mammoth has similar ??C13 and O18 to that from the active springs. Soda Butte, an inactive center 25 miles east of Mammoth, contains heavier carbon and oxygen than the springs near Mammoth. ?? 1970.

Equilibrium carbon and hydrogen isotope fractionation in iron

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2009-12-01

Recent theoretical and experimental studies (e.g., [1-3]) have suggested that Si- and Fe-isotopic signatures can be used to characterize the compositions and conditions of segregation of metallic cores in planetary interiors. This study expands the theoretical framework to include carbon and hydrogen, which may also be alloying elements. Hydrogen (D/H) and carbon (13C/12C) fractionations in iron-rich metallic melts are estimated by modeling analogous iron-rich crystals, i.e., dhcp-FeH and η-Fe2C. C- and H-atoms in these crystals are completely coordinated by iron. The driving energy for equilibrium fractionation is assumed to come from the reduction of vibrational frequencies when heavy isotopes are substituted for light ones; vibrations are assumed to be harmonic. This treatment is crude at high temperature, and for the relatively anharmonic vibrations typical of hydrogen-bearing substances, but may provide a reasonably accurate, semi-quantitative approximation of real fractionation behavior. Vibrational frequencies of all crystals are modeled with density functional theory, using gradient-corrected functionals and ultrasoft pseudopotentials. For both carbon and hydrogen, the models suggest that the metal phase will be strongly depleted in heavy isotopes. At 2000 K, 1 atm, η-Fe2C will have 3‰ lower 13C/12C than coexisting diamond. Combining this result with previous high-temperature theoretical and experimental studies (e.g., [4]), metal-graphite fractionation is expected to be very similar, while metal-CO2 fractionation will be almost twice as large, ca. -5‰. Deuterium/hydrogen fractionations are expected to be an order of magnitude larger, with 50-70‰ lower D/H in dhcp-FeH than in coexisting H2 gas at 2000 K, and approximately 100‰ lower D/H than water vapor. These fractionations are much larger than those inferred for silicon and iron, as expected given the differences in atomic mass. References: 1. Georg et al. (2007) Nature 447:1102; 2. Rustad & Yin (2009) Nature Geoscience doi:10.1038/ngeo546; 3. Polyakov (2009) Science 323:912; 4. Polyakov & Kharlashina (1995) GCA 59:2561.

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Isotope separation by photochromatography

DOEpatents

Suslick, K.S.

1975-10-03

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

Isotope fractionation of sandy-soil water during evaporation - an experimental study.

PubMed

Rao, Wen-Bo; Han, Liang-Feng; Tan, Hong-Bing; Wang, Shuai

2017-06-01

Soil samples containing water with known stable isotopic compositions were prepared. The soil water was recovered by using vacuum/heat distillation. The experiments were held under different conditions to control rates of water evaporation and water recovery. Recoveries, δ 18 O and δ 2 H values of the soil water were determined. Analyses of the data using a Rayleigh distillation model indicate that under the experimental conditions only loosely bound water is extractable in cases where the recovery is smaller than 100 %. Due to isotopic exchange between vapour and remaining water in the micro channels or capillaries of the soil matrix, isotopic fractionation may take place under near-equilibrium conditions. This causes the observed relationship between δ 2 H and δ 18 O of the extracted water samples to have a slope close to 8. The results of this study may indicate that, in arid zones when soil that initially contains water dries out, the slope of the relationship between δ 2 H and δ 18 O values should be close to 8. Thus, a smaller slope, as observed by some groundwater and soil water samples in arid zones, may be caused by evaporation of water before the water has entered the unsaturated zone.

Isotopic Probe Illuminates the Role of the Electrode Surface in Proton Coupled Hydride Transfer Electrochemical Reduction of Pyridinium on Pt(111)

DOE PAGES

Zeitler, Elizabeth L.; Ertem, Mehmed Z.; Pander, III, James E.; ...

2015-10-21

A recently proposed mechanism for electrochemical CO 2 reduction on Pt (111) catalyzed by aqueous acidic pyridine solutions suggests that the observed redox potential of ca. -600 mV vs. SCE is due to the one-electron reduction of pyridinium through proton coupled electron transfer (PCET) to form H atoms adsorbed on the Pt surface (H ads). The initial pyridinium reduction was probed isotopically via deuterium substitution. A combined experimental and theoretical analysis found equilibrium isotope effects (EIE) due to deuterium substitution at the acidic pyridinium site. A shift in the cathodic cyclic voltammetric half wave potential of -25 mV was observed,more » consistent with the theoretical prediction of -40 mV based on the recently proposed reaction mechanism where pyridinium is essential to establish a high concentration of Bronsted acid in contact with the substrate CO 2 and with the Pt surface. A prefeature in the cyclic voltammogram was examined under isotopic substitution and indicated an H-ads intermediate in pyridinium reduction. In conclusion, the theoretical prediction and observation of an BM supported the assignment of the cathodic wave to the proposed reduction of pyridinium through PCET forming H ads and eventually H 2 on the Pt surface.« less

Evaluation of Crayfish Growth and Assimilation on Animal and Detrital Food Sources: Are Stable Isotopes Telling the Whole Story?

NASA Astrophysics Data System (ADS)

Warren, L. L.; Wotton, R. S.; Wharton, G.; Fortino, K.; Ulseth, A. J.; Hershey, A. E.

2005-05-01

Crayfish are the dominant omnivores of many ecosystems and have strong direct and indirect effects through predation and organic matter processing. Despite this, the importance of detritus for crayfish production is poorly understood. We conducted a laboratory experiment where we fed crayfish an ad. lib. diet of only detritus, only fish tissue, or a mixture the above. The crayfish grew more on a diet which contained meat but growth was highly correlated with the amount of food consumed. The least amount of food was consumed in the detritus treatment, an intermediate amount of food in the meat treatment, and the most food in the mix treatment, suggesting that consumption of detritus by crayfish is related to more than simply the abundance of detritus. Nonetheless, isotopic evidence indicated that the crayfish were not assimilating leaf C and N. Additionally, crayfish in the meat containing treatments never exceeded the del 15N signature of their source by the approximately 3 units expected following fractionation, despite coming to isotopic equilibrium with their source. These findings suggest that crayfish may fractionate C and N uniquely. This difference may have to do with gut microbial activity and may have implications for the interpretation crayfish isotopic signatures.

Interpretation of Ferroan Anorthosite Ages and Implications for the Lunar Magma Ocean

NASA Technical Reports Server (NTRS)

Neal, C. R.; Draper, D. S.

2017-01-01

Ferroan Anorthosites (FANs) are considered to have purportedly crystallized directly from the lunar magma ocean (LMO) as a flotation crust. LMO modeling suggests that such anorthosites started to form only after greater than 70 percent of the LMO had crystallized. Recent age dates for FANs have questioned this hypothesis as they span too large of an age range. This means a younger age for the Moon-forming giant impact or the LMO hypothesis is flawed. However, FANs are notoriously difficult to age-date using the isochron method. We have proposed a mechanism for testing the LMO hypothesis through using plagioclase trace element abundances to calculate equilibrium liquids and compare them with LMO crystallization models. We now examine the petrography of the samples that have Sm-Nd (Samarium-Neodymium) age dates (Rb-Sr (Rubidium-Strontium) isotopic systematics may have been disturbed) and propose a relative way to age date FANs.

Carbonate-Promoted Hydrogenation of Carbon Dioxide to Multicarbon Carboxylates

PubMed Central

2018-01-01

CO2 hydrogenation is a potential alternative to conventional petrochemical methods for making commodity chemicals and fuels. Research in this area has focused mostly on transition-metal-based catalysts. Here we show that hydrated alkali carbonates promote CO2 hydrogenation to formate, oxalate, and other C2+ carboxylates at elevated temperature and pressure in the absence of transition-metal catalysts or solvent. The reactions proceed rapidly, reaching up to 56% yield (with respect to CO32–) within minutes. Isotope labeling experiments indicate facile H2 and C–H deprotonations in the alkali cation-rich reaction media and identify probable intermediates for the C–C bond formations leading to the various C2+ products. The carboxylate salts are in equilibrium with volatile carboxylic acids under CO2 hydrogenation conditions, which may enable catalytic carboxylic acid syntheses. Our results provide a foundation for base-promoted and base-catalyzed CO2 hydrogenation processes that could complement existing approaches. PMID:29806007

Isomeric ratios in photonuclear reactions of molybdenum isotopes induced by bremsstrahlung in the giant dipole resonance region

NASA Astrophysics Data System (ADS)

Thiep, Tran Duc; An, Truong Thi; Cuong, Phan Viet; Vinh, Nguyen The; Hue, Bui Minh; Belov, A. G.; Maslov, O. D.; Mishinsky, G. V.; Zhemenik, V. I.

2017-01-01

We have determined the isomeric ratios of isomeric pairs 97m,gNb, 95m,gNb and 91m,gMo produced in 98Mo(γ, p)97m,gNb, 96Mo(γ, p)95m,gNb and 92Mo(γ, n)91m,gMo photonuclear reactions in the giant dipole resonance (GDR) region by the activation method. The results were analyzed, discussed and compared with the similar data from literature to examine the role of excitation energy, neutron configuration, channel effect and direct and pre-equilibrium processes in (γ, p) photonuclear reactions. In this work the isomeric ratios for 97m,gNb from 14 to 19 MeV, for 195m,gNb from14 to 24 MeV except 20 and 23.5 MeV and for 91m,gMo at 14 and 15 MeV are the first time measurements.

Conjugate Acid-Base Pairs, Free Energy, and the Equilibrium Constant

ERIC Educational Resources Information Center

Beach, Darrell H.

1969-01-01

Describes a method of calculating the equilibrium constant from free energy data. Values of the equilibrium constants of six Bronsted-Lowry reactions calculated by the author's method and by a conventional textbook method are compared. (LC)

Method for laser induced isotope enrichment

DOEpatents

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

2004-09-07

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

Method of enhancing selective isotope desorption from metals

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1984-01-01

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

[Influence of deuterium depleted water on freeze-dried tissue isotopic composition and morphofunctional body performance in rats of different generations].

PubMed

Dzhimak, S S; Baryshev, M G; Basov, A A; Timakov, A A

2014-01-01

The influence of deuterium depleted water on the body of different rats generations was investigated in physiological conditions. As a result of this study it was established that the most significant and rapid reduction in D/H equilibrium was observed in plasma (by 36.2%), and lyophilized kidney tissues (by 15.8%). Less pronounced deuterium decrease was characteristic of liver tissue (9.3%) and heart (8.5%). Stabilization of the isotopic exchange reaction rate was fixed in the blood and tissues of rats, starting from the second generation. At the same time when deuterium depleted water (40 ppm) was used in dietary intake, the change in morphological and functional parameters in laboratory animals associated with the processes of adaptation to the effects of substress isotopic D/H gradient was also noted. The study shows that modification of:only drinking water intake regime can't significantly change the deuterium content in tissues of metabolically active organs, because of the concurrent deuterium receipt in food substances of plant and animal origin.

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

The Gibbs Variational Method in Thermodynamics of Equilibrium Plasma: 1. General Conditions of Equilibrium and Stability for One-Component Charged Gas

DTIC Science & Technology

2018-04-01

systems containing ionized gases. 2. Gibbs Method in the Integral Form As per the Gibbs general methodology , based on the concept of heterogeneous...ARL-TR-8348 ● APR 2018 US Army Research Laboratory The Gibbs Variational Method in Thermodynamics of Equilibrium Plasma: 1...ARL-TR-8348 ● APR 2018 US Army Research Laboratory The Gibbs Variational Method in Thermodynamics of Equilibrium Plasma: 1. General

Dating thermal events at Cerro Prieto using fission track annealing

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

Sanford, S.J.; Elders, W..

1981-01-01

Data from laboratory experiments and geologic fading studies were compiled from published sources to produce lines of iso-annealing for apatite in time-temperature space. Fission track ages were calculated for samples from two wells at Cerro Prieto, one with an apparently simple and one with an apparently complex thermal history. Temperatures were estimated by empirical vitrinite reflectance geothermometry, fluid inclusion homogenization and oxygen isotope equilibrium. These estimates were compared with logs of measured borehole temperatures.

Problem-based test: replication of mitochondrial DNA during the cell cycle.

PubMed

Sétáló, György

2013-01-01

Terms to be familiar with before you start to solve the test: cell cycle, generation time, S-phase, cell culture synchronization, isotopic pulse-chase labeling, density labeling, equilibrium density-gradient centrifugation, buoyant density, rate-zonal centrifugation, nucleoside, nucleotide, kinase enzymes, polymerization of nucleic acids, re-replication block, cell fractionation, Svedberg (sedimentation constant = [ S]), nuclear DNA, mitochondrial DNA, heavy and light mitochondrial DNA chains, heteroplasmy, mitochondrial diseases Copyright © 2013 Wiley Periodicals, Inc.

2H and 18O depletion of water close to organic surfaces

NASA Astrophysics Data System (ADS)

Chen, Guo; Auerswald, Karl; Schnyder, Hans

2016-06-01

Hydrophilic surfaces influence the structure of water close to them and may thus affect the isotope composition of water. Such an effect should be relevant and detectable for materials with large surface areas and low water contents. The relationship between the volumetric solid : water ratio and the isotopic fractionation between adsorbed water and unconfined water was investigated for the materials silage, hay, organic soil (litter), filter paper, cotton, casein and flour. Each of these materials was equilibrated via the gas phase with unconfined water of known isotopic composition to quantify the isotopic difference between adsorbed water and unconfined water. Across all materials, isotopic fractionation was significant (p<0.05) and negative (on average -0.91 ± 0.22 ‰ for 18/16O and -20.6 ± 2.4 ‰ for 2/1H at an average solid : water ratio of 0.9). The observed isotopic fractionation was not caused by solutes, volatiles or old water because the fractionation did not disappear for washed or oven-dried silage, the isotopic fractionation was also found in filter paper and cotton, and the fractionation was independent of the isotopic composition of the unconfined water. Isotopic fractionation became linearly more negative with increasing volumetric solid : water ratio and even exceeded -4 ‰ for 18/16O and -44 ‰ for 2/1H. This fractionation behaviour could be modelled by assuming two water layers: a thin layer that is in direct contact and influenced by the surface of the solid and a second layer of varying thickness depending on the total moisture content that is in equilibrium with the surrounding vapour. When we applied the model to soil water under grassland, the soil water extracted from 7 and 20 cm depth was significantly closer to local meteoric water than without correction for the surface effect. This study has major implications for the interpretation of the isotopic composition of water extracted from organic matter, especially when the volumetric solid : water ratio is larger than 0.5 or for processes occurring at the solid-water interface.

Mg-Fe Isotope Systems of Mantle Xenoliths: Constrains on the Evolution of Siberian Craton

NASA Astrophysics Data System (ADS)

An, Y.; Kiseeva, E. S.; Sobolev, N. V.; Zhang, Z.

2017-12-01

Mantle xenoliths bring to the surface a variety of lithologies (dunites, lherzolites, harzburgites, wehrlites, eclogites, pyroxenites, and websterites) and represent snapshots of the geochemical processes that occur deep within the Earth. Recent improvements in the precision of the MC-ICP-MS measurements have allowed us to expand the amount of data on Mg and Fe isotopes for mantle-derived samples. For instance, to constrain the isotopic composition of the Earth based on the study of spinel and garnet peridotites (An et al., 2017; Teng et al., 2010), to trace the origin and to investigate the isotopic fractionation mechanism during metamorphic process using cratonic or orogenic eclogites (Li et al., 2011; Wang et al., 2012) and to reveal the metasomatism-induced mantle heterogeneity by pyroxenites (Hu et al., 2016). Numerous multi-stage modification events and mantle layering are detected in the subcontinental lithospheric mantle under the Siberian craton (Ashchepkov et al., 2008a; Sobolev et al., 1975, etc). Combined analyses of Mg and Fe isotopic systems could provide new constraints on the formation and evolution of the ancient cratonic mantle. In order to better constrain the magnitude and mechanism of inter-mineral Mg and Fe isotopic fractionations at high temperatures, systematic studies of mantle xenoliths are needed. For example, theoretical calculations and natural samples measurements have shown that large equilibrium Mg isotope fractionations controlled by the difference in coordination number of Mg among minerals could exist (Huang et al., 2013; Li et al., 2011). Thus, the Mg isotope geothermometer could help us trace the evolution history of ancient cratons. In this study we present Mg and Fe isotopic data for whole rocks and separated minerals (clinopyroxene (cpx) and garnet (grt)) from different types of mantle xenoliths (garnet pyroxenites, eclogites, grospydites and garnet peridotites) from a number of kimberlite pipes in Siberian craton (Udachnaya, Obnazhennaya, Mir, and Zagadochnaya). The large Mg and Fe isotope fractionations between clinopyroxene and garnet for various mantle rocks (Δ26Mg cpx-gnt= 0.360‰ 0.888‰, Δ56Fe cpx-gnt= 0.018‰ 0.348‰) indicate that the Siberian cratonic lithosphetic mantle has undergone multiple complex metasomatic and re-equilibration events.

Magnesium Isotopic Composition of Kamchatka Sub-Arc Mantle Peridotites

NASA Astrophysics Data System (ADS)

Hu, Y.; Teng, F. Z.; Ionov, D. A.

2016-12-01

Subduction of the oceanic slab may add a crustal isotopic signal to the mantle wedge. The highly variable Mg isotopic compositions (δ26Mg) of the subducted oceanic crust input[1] and arc lava output[2] imply a distinctive Mg isotopic signature of the mantle wedge. Magnesium isotopic data on samples from the sub-arc mantle are still limited, however. To characterize the Mg isotopic composition of typical sub-arc mantle, 17 large and fresh spinel harzburgite xenoliths from Avacha volcano were analyzed. The harzburgites were formed by 30% melt extraction at ≤ 1 2 GPa and fluid fluxing condition, and underwent possible fluid metasomatism as suggested by distinctively high orthopyroxene mode in some samples, the presence of accessory amphibole and highly variable Ba/La ratios[3]. However, their δ26Mg values display limited variation from -0.32 to -0.21, which are comparable to the mantle average at -0.25 ± 0.07[4]. The overall mantle-like and homogenous δ26Mg of Avacha sub-arc peridotites are consistent with their similar chemical compositions and high MgO contents (> 44 wt%) relative to likely crustal fluids. Furthermore, clinopyroxene (-0.24 ± 0.10, 2SD, n = 5), a late-stage mineral exsolved from high-temperature, Ca-rich residual orthopyroxene, is in broad Mg isotopic equilibrium with olivine (-0.27 ± 0.04, 2SD, n = 17) and orthopyroxene (-0.22 ± 0.06, 2SD, n = 17). Collectively, this study finds that the Kamchatka mantle wedge, as represented by the Avacha peridotites, has a mantle-like δ26Mg, and low-degree fluid-mantle interaction does not cause significant Mg isotope fractionation in sub-arc mantle peridotites. [1] Wang et al., EPSL, 2012 [2] Teng et al., PNAS, 2016 [3] Ionov, J. Petrol., 2010, [4] Teng et al., GCA, 2010.

Tracing alteration of mantle peridotite in the Samail ophiolite using Mg isotopes

NASA Astrophysics Data System (ADS)

de Obeso, J. C.; Kelemen, P. B.; Higgins, J. A.

2017-12-01

Magnesium is one of the main constituents of mantle peridotite ( 22.8 wt%), which has a homogeneous Mg isotopic composition (d26Mg = -0.25 ± 0.04 ‰ (2 sd) DSM3, Teng et al 2010 GCA). Mg isotopes are used as tracers of continental and oceanic weathering as they exhibit variable degrees of fractionation during alteration depending on the lithology. Here we report some of the first Mg isotopic compositions of the mantle section of the Samail ophiolite in Oman and its alteration products. The mantle section of the ophiolite is composed mainly of depleted harzburgites and dunites with mantle-like d26Mg (-0.25, -0.21 ‰). Mantle peridotite is far from equilibrium in near surface conditions leading to rapid, extensive serpentinization, carbonation and oxidation, as well as other geochemical changes. Our analyzed samples encompass most of the alteration of peridotite products observed in Oman including listvenites (completely carbonated peridotite) near the basal thrust of the ophiolite, massive magnesite veins within peridotite outcrops, and heavily altered harzburgites. Magnesite listvenites have d26Mg slightly below mantle values (-0.33, -0.33‰) while dolomite listvenites are significantly lighter (-1.46, -0.89‰). This suggests that heavy Mg isotopes were removed from the listvenites during ophiolite emplacement. Heavily altered peridotite from Wadi Fins exhibit alteration halos with drastic changes in composition. The most oxidized areas are enriched in Fe and depleted in Mg compared to the cores of the samples. These variations in Mg concentrations are complemented by a shift to heavy Mg isotopic compositions (0.74, 0.86‰), among the heaviest d26Mg values that have been reported in altered peridotite. Potential sinks for light isotopes removed from such alteration zones are massive magnesite veins with very light compositions (-3.39, -3.14‰). The fractionation of Mg isotopes observed in the mantle section of the ophiolite spans more than 50% of the known terrestrial fractionation.

Radiation protection and radioactive scales in oil and gas production.

PubMed

Testa, C; Desideri, D; Meli, M A; Roselli, C; Bassignani, A; Colombo, G; Fantoni, R F

1994-07-01

Low specific-activity scales consisting of alkaline earth metal carbonates and sulfates are often present in some gaseous and liquid hydrocarbon plants. These scales contain a certain concentration of radium, uranium, and thorium which can cause a risk of gamma irradiation and internal radiocontamination when they must be mechanically removed. The gamma dose rates and the 238U, 232Th, 226Ra concentrations were determined in sludges, scales, and waters of some gas and oil hydrocarbon plants located in Italy, Congo, and Tunisia. 238U and 232Th concentrations were were low. The isotopes 238U and 234U resulted in radioactive equilibrium, while 232Th and 228Th were not always equilibrium. A rough correlation was found between the gamma dose rate and the 226Ra concentration. Some considerations and conclusions about radiation protection problems are pointed out.

Fusion reactions initiated by laser-accelerated particle beams in a laser-produced plasma.

PubMed

Labaune, C; Baccou, C; Depierreux, S; Goyon, C; Loisel, G; Yahia, V; Rafelski, J

2013-01-01

The advent of high-intensity-pulsed laser technology enables the generation of extreme states of matter under conditions that are far from thermal equilibrium. This in turn could enable different approaches to generating energy from nuclear fusion. Relaxing the equilibrium requirement could widen the range of isotopes used in fusion fuels permitting cleaner and less hazardous reactions that do not produce high-energy neutrons. Here we propose and implement a means to drive fusion reactions between protons and boron-11 nuclei by colliding a laser-accelerated proton beam with a laser-generated boron plasma. We report proton-boron reaction rates that are orders of magnitude higher than those reported previously. Beyond fusion, our approach demonstrates a new means for exploring low-energy nuclear reactions such as those that occur in astrophysical plasmas and related environments.

Experimental paleotemperature equation for planktonic foraminifera

NASA Astrophysics Data System (ADS)

Erez, Jonathan; Luz, Boaz

1983-06-01

Small live individuals of Globigerinoides sacculifer which were cultured in the laboratory reached maturity and produced garnets. Fifty to ninety percent of their skeleton weight was deposited under controlled water temperature (14° to 30°C) and water isotopic composition, and a correction was made to account for the isotopic composition of the original skeleton using control groups. Comparison of. the actual growth temperatures with the calculated temperature based on paleotemperature equations for inorganic CaCO 3 indicate that the foraminifera precipitate their CaCO 3 in isotopic equilibrium. Comparison with equations developed for biogenic calcite give a similarly good fit. Linear regression with CRAIG'S (1965) equation yields: t = -0.07 + 1.01 t̂ (r= 0.95) where t is the actual growth temperature and t̂ Is the calculated paleotemperature. The intercept and the slope of this linear equation show that the familiar paleotemperature equation developed originally for mollusca carbonate, is equally applicable for the planktonic foraminifer G. sacculifer. Second order regression of the culture temperature and the delta difference ( δ18Oc - δ18Ow) yield a correlation coefficient of r = 0.95: t̂ = 17.0 - 4.52(δ 18Oc - δ 18Ow) + 0.03(δ 18Oc - δ 18Ow) 2t̂, δ 18Oc and δ18Ow are the estimated temperature, the isotopic composition of the shell carbonate and the sea water respectively. A possible cause for nonequilibnum isotopic compositions reported earlier for living planktonic foraminifera is the improper combustion of the organic matter.

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.

Light element geochemistry of the Apollo 16 site

NASA Technical Reports Server (NTRS)

Kerridge, J. F.; Kaplan, I. R.; Petrowski, C.; Chang, S.

1975-01-01

The abundance and isotopic composition of carbon, sulfur, and nitrogen, the abundance of helium and hydrogen, and the content of metallic iron are reported for lunar surface samples from the Apollo 16 landing site at Cayley-Descartes. The light elements show marked interstation variability at the site. The abundances in soils of C, N, He, and H are apparently controlled mainly by exposure to the solar wind, through implantation or stripping processes. Carbon abundances (but not observed isotopic distributions) are compatible with a model in which equilibrium is established after 10,000-100,000 yr between solar wind input and loss by proton stripping. Sulfur abundances in soils are apparently controlled by abundances in local country rocks, but the lunar S cycle is quite complex. A metallic iron component may have originated by solar wind reduction of lunar Fe(2+).

Temperature effects on the fractionation of multiple sulfur isotopes by Thermodesulfobacterium and Desulfovibrio strains

NASA Astrophysics Data System (ADS)

Wang, P.; Sun, C.; Ono, S.; Lin, L.

2012-12-01

Microbial dissimilatory sulfate reduction is one of the major mechanisms driving anaerobic mineralization of organic matter in global ocean. While sulfate-reducing prokaryotes are well known to fractionate sulfur isotopes during dissimilatory sulfate reduction, unraveling the isotopic compositions of sulfur-bearing minerals preserved in sedimentary records could provide invaluable constraints on the evolution of seawater chemistry and metabolic pathways. Variations in the sulfur isotope fractionations are partly due to inherent differences among species and also affected by environmental conditions. The isotope fractionations caused by microbial sulfate reduction have been interpreted to be a sequence of enzyme-catalyzed isotope fractionation steps. Therefore, the fractionation factor depends on (1) the sulfate flux into and out of the cell, and (2) the flux of sulfur transformation between the internal pools. Whether the multiple sulfur isotope effect could be quantitatively predicted using such a metabolic flux model would provide insights into the cellular machinery catalyzing with sulfate reduction. This study examined the multiple sulfur isotope fractionation patterns associated with a thermophilic Thermodesulfobacterium-related strain and a mesophilic Desulfovibrio gigas over a wide temperature range. The Thermodesulfobacterium-related strain grew between 34 and 79°C with an optimal temperature at 72°C and the highest cell-specific sulfate reduction rate at 77°C. The 34ɛ values ranged between 8.2 and 31.6‰ with a maximum at 68°C. The D. gigas grew between 10 and 45 °C with an optimal temperature at 30°C and the highest cell-specific sulfate reduction rate at 41°C. The 34ɛ values ranged between 10.3 and 29.7‰ with higher magnitude at both lower and higher temperatures. The results of multiple sulfur isotope measurements expand the previously reported range and cannot be described by a solution field of the metabolic flux model, which calculates the Δ33S and 34ɛ values assuming equilibrium fractionation among internal steps. Either larger isotope effects or kinetic fractionation has to be considered in the metabolic flux model to explain the multiple sulfur isotope effect produced by these two strains. Overall, the metabolic flux model warrants further revision and further studies regarding physiological responses to growth conditions may probably offer a linkage between multiple sulfur isotope effects and environmental factors for microbial dissimilatory sulfate reduction.

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

PubMed

Pazhanisamy, S; Pratt, R F

1989-08-22

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

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

NASA Astrophysics Data System (ADS)

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

2004-12-01

Recent developments in mass spectrometry techniques have created opportunities to examine the partitioning behavior of stable isotopes of transition metals with a focus on application to iron isotopes. Iron oxidizing and reducing bacteria have been shown to cause isotope fractionations similar in magnitude to those observed in sedimentary environments and it is believed that biological activity is responsible for the most significant Fe isotope fractionation in natural settings. Debate over the use of Fe isotopes as a biological marker resulted from subsequent measurements of fractionations in a variety of abiotic systems. The accumulated evidence, in both biotic and abiotic systems, points to a connection between redox processes and Fe isotope fractionation, however the exact mechanism for isotope fractionation is not yet well understood. Here, we present both a newly-developed theory based on chemical kinetics and preliminary experimental results that quantitatively delineate the relationship between driving force in a charge transfer reaction and resulting Fe isotope fractionation. The theory, based on R. Marcus's chemical kinetics theory for electron transfer (Ann. Rev. Phys. Chem. 15 (1964), 155), predicts that fractionation increases linearly with driving force with a proportionality related to two factors: the difference between isotopic equilibrium exchange of products and reactants, and the reorganization energy along the reaction coordinate. The theoretical predictions were confirmed by measurements of isotopic fractionation associated with electroplating iron metal from a ferrous chloride solution. Isotope fractionation of Fe electroplated under potentiostatic conditions was measured as a function of applied electrochemical potential. As plating voltage was varied from -50 mV to -2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ 56Fe values ranging from -0.106(±0.01) to -2.290(±±0.006)‰ , and corresponding δ 57Fe values of -0.145(±.011) and -3.354(±.019)‰ . The slope of the line created by plotting δ 56Fe vs δ 57Fe is equal to 0.6723(±.0032), consistent with fractionation due to a kinetic process involving unsolvated iron atoms. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. The magnitude of fractionation is similar to observations of Fe reduction by certain bacteria, suggesting that electrochemical processes may be responsible for observed biogeochemical signatures. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.

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

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

Makarov, G N; Petin, A N

2016-03-31

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

Method of isotope separation by chemi-ionization

DOEpatents

Wexler, Sol; Young, Charles E.

1977-05-17

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

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

NASA Astrophysics Data System (ADS)

Yan, Jiawei; Ke, Youqi

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

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

USGS Publications Warehouse

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

2001-01-01

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

Variations of geothermometry and chemical-isotopic compositions of hot spring fluids in the Rehai geothermal field, southwestern China

NASA Astrophysics Data System (ADS)

Du, Jianguo; Liu, Congqiang; Fu, Bihong; Ninomiya, Yoshiki; Zhang, Youlian; Wang, Chuanyuan; Wang, Hualiu; Sun, Zigang

2005-04-01

Geothermal variations, origins of carbon-bearing components and reservoir temperatures in the Rehai geothermal field (RGF) of Tengchong volcanic area, Yunnan Province, southwestern China, are discussed on the basis of carbon isotope compositions, combined with helium isotope ratios and geothermal data from 1973 to 2000. δ 13C values of CO 2, CH 4, HCO 3-, CO 3= and travertine in the hot springs range from -7.6‰ to -1.18‰, -56.9‰ to -19.48‰, -6.7‰ to -4.2‰, -6.4‰ to -4.2‰ and -27.1‰ to +0.6‰, respectively. The carbon dioxide probably has a mantle/magma origin, but CH 4 and He have multiple origins. HCO 3- and CO 3= in RGF thermal fluids are predominantly derived from igneous carbon dioxide, but other ions originate from rocks through which the fluids circulate. The 13C values of CO 2, HCO 3- (aq) and CO 3= (aq) illustrate that isotopic equilibriums between CO 2 and HCO 3- (aq), and CO 3= (aq) and between DIC and travertine were not achieved, and no carbon isotope fractionation between HCO 3- (aq) and CO 3= (aq) of the hot springs in RGF was found. Using various geothermometers, temperatures of the geothermal reservoirs are estimated in a wide range from 69 °C to 450 °C that fluctuated from time to time. The best estimate of subsurface reservoir temperature may be 250-300 °C. Contributions of mantle fluids and shallow crust fluids in Rehai geothermal field varied with time, which resulted in variations of chemical and isotopic compositions and reservoir temperatures.

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

USGS Publications Warehouse

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

2001-01-01

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

Isotopic composition of atmospheric moisture from pan water evaporation measurements.

PubMed

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

2015-01-01

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

Carbon isotope ratios and isotopic correlations between components in fruit juices

NASA Astrophysics Data System (ADS)

Wierzchnicki, Ryszard

2013-04-01

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

Systematics of first and second shape transition temperatures in heavy nuclei

NASA Astrophysics Data System (ADS)

Goodman, Alan L.; Jin, Taihao

1996-09-01

Thirty-one even-even isotopes (Z=72-80 and N=110-126) have two shape transition temperatures, where Tc2>~Tc1. For temperatures above Tc1, the equilibrium shape is spherical if the rotational frequency is zero. For these 31 nuclei, a slow rotation of the spherical shape creates a prolate shape rotating about its symmetry axis if the temperature is between Tc1 and Tc2, and an oblate shape rotating about its symmetry axis if the temperature is above Tc2.

Measurements of concentrations of chlorofluoromethanes (CFMs) carbon dioxide and carbon isotope ratio in stratospheric and tropospheric air by grab-sampling systems

NASA Technical Reports Server (NTRS)

Itoh, T.; Kubo, H.; Honda, H.; Tominaga, T.; Makide, Y.; Yakohata, A.; Sakai, H.

1985-01-01

Measurements of concentrations of chlorofluoromethanes (CFMs), carbon dioxide and carbon isotope ratio in stratospheric and tropospheric air by grab-sampling systems are reported. The balloon-borne grab-sampling system has been launched from Sanriku Balloon Center three times since 1981. It consists of: (1) six sampling cylinders, (2) eight motor driven values, (3) control and monitor circuits, and (4) pressurized housing. Particular consideration is paid to the problem of contamination. Strict requirements are placed on the choice of materials and components, construction methods, cleaning techniques, vacuum integrity, and sampling procedures. An aluminum pressurized housing and a 4-m long inlet line are employed to prevent the sampling air from contamination by outgassing of sampling and control devices. The sampling is performed during the descent of the system. Vertical profiles of mixing ratios of CF2Cl2, CFCl3 and CH4 are given. Mixing ratios of CF2Cl2 and CFCl3 in the stratosphere do not show the discernible effect of the increase of those in the ground level background, and decrease with altitude. Decreasing rate of CFCl3 is larger than that of CF2Cl2. CH4 mixing ratio, on the other hand, shows diffusive equilibrium, as the photodissociation cross section of CH4 is small and concentrations of OH radical and 0(sup I D) are low.

Quantitative Determination of Isotope Ratios from Experimental Isotopic Distributions

PubMed Central

Kaur, Parminder; O’Connor, Peter B.

2008-01-01

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

Reassessment of the 13C/12C and 14C/12C isotopic fractionation ratio and its impact on high-precision radiocarbon dating

NASA Astrophysics Data System (ADS)

Fahrni, Simon M.; Southon, John R.; Santos, Guaciara M.; Palstra, Sanne W. L.; Meijer, Harro A. J.; Xu, Xiaomei

2017-09-01

The vast majority of radiocarbon measurement results (14C/12C isotopic ratios or sample activities) are corrected for isotopic fractionation processes (measured as 13C/12C isotopic ratios) that occur in nature, in sample preparation and measurement. In 1954 Harmon Craig suggested a value of 2.0 for the fractionation ratio b that is used to correct 14C/12C ratios for shifts in the 13C/12C ratios and this value has been applied by the radiocarbon community ever since. While theoretical considerations suggest moderate deviations of b from 2.0, some measurements have suggested larger differences (e.g. b = 2.3, measured by Saliège and Fontes in 1984). With the high precision attained in radiocarbon measurements today (±2‰), even a relatively small deviation of b from 2.0 can impact the accuracy of radiocarbon data, and it is, therefore, of interest to re-evaluate the fractionation corrections. In the present study, the fractionation ratio b was determined by independent experiments on the chemical reduction of carbon dioxide (CO2) to elemental carbon (graphitization reaction) and on the photosynthetic uptake of CO2 by C3 and C4 plants. The results yielded b = 1.882 ± 0.019 for the reduction of CO2 to solid graphite and b = 1.953 ± 0.025 for the weighted mean of measurements involving C3 and C4 photosynthesis pathways. In addition, the analysis of over 9600 full-sized OX-I and OX-II normalizing standards measured between 2002 and 2012 confirms b values lower than 2.0. The obtained values are in good agreement with quantum mechanical estimates of the equilibrium fractionation and classic kinetic fractionation as well as with results from other light three-isotope systems (oxygen, magnesium, silicon and sulfur). While the value of the fractionation ratio varies with the relative importance of kinetic and equilibrium fractionation, the values obtained in the present study cluster around b = 1.9. Our findings suggest that a significant fraction of all samples ("unknowns") would be shifted by 2‰ (16 radiocarbon years) or more due to this effect: for example, for b = 1.882, between 16.8% and 25.9% of almost 60,000 radiocarbon values measured at the Keck Carbon Cycle AMS facility between 2002 and 2012 would be affected. The implications for radiocarbon dating and its accuracy are discussed.

Time constraints on the origin of large volume basalts derived from O-isotope and trace element mineral zoning and U-series disequilibria in the Laki and Grímsvötn volcanic system

NASA Astrophysics Data System (ADS)

Bindeman, Ilya N.; Sigmarsson, Olgeir; Eiler, John

2006-05-01

The 1783-1784 AD fissure eruption of Laki (Iceland) produced 15 km 3 of homogeneous basaltic lavas and tephra that are characterized by extreme (3‰) 18O-depletion relative to normal mantle. Basaltic tephra erupted over the last 8 centuries and as late as in November 2004 from the Grímsvötn central volcano, which together with Laki are a part of a single volcanic system, is indistinguishable in δ18O from Laki glass. This suggests that all tap a homogeneous and long-lived low- δ18O magma reservoir. In contrast, we observe extreme oxygen isotope heterogeneity (2.2-5.2‰) in olivine and plagioclase contained within these lavas and tephra, and disequilibrium mineral-glass oxygen-isotope fractionations. Such low- δ18O glass values, and extreme 3‰ range in δ18O olivine have not been described in any other unaltered basalt. The energy constrained mass balance calculation involving oxygen isotopes and major element composition calls for an origin of the Laki-Grímsvötn quartz tholeiitic basaltic melts with δ18O = 3.1‰ by bulk digestion of low- δ18O hydrated basaltic crust with δ18O = - 4‰ to + 1‰, rather than magma mixing with ultra-low- δ18O silicic melt. The abundant Pleistocene hyaloclastites, which were altered by synglacial meltwaters, can serve as a likely assimilant material for the Grímsvötn magmas. The ( 226Ra / 230Th) activity ratio in Laki lavas and 20th century Grímsvötn tephras is 13% in-excess of secular equilibrium, but products of the 20th century Grímsvötn eruptions have equilibrium ( 210Pb / 226Ra). Modeling of oxygen isotope exchange between disequilibrium phenocrysts and magmas, and these short-lived U-series nuclides yields a coherent age for the Laki-Grímsvötn magma reservoir between 100 and 1000 yrs. We propose the existence of uniquely fingerprinted, low- δ18O, homogeneous, large volume, and long-lived basaltic reservoir beneath the Laki-Grímsvötn volcanic system that has been kept alive in its position above the center of the Icelandic mantle plume. Melt generation, crustal assimilation, magma storage and homogenization all took place in only a few thousands of years at most.

The influence of diet on the δ 13C of shell carbon in the pulmonate snail Helix aspersa

NASA Astrophysics Data System (ADS)

Stott, Lowell D.

2002-02-01

The influence of diet and atmospheric CO 2 on the carbon isotope composition of shell aragonite and shell-bound organic carbon in the pulmonate snail Helix aspersa raised in the laboratory was investigated. Three separate groups of snails were raised on romaine lettuce (C3 plant, δ 13C=-25.8‰), corn (C4 plant, δ 13C=-10.5‰), and sour orange ( 12C-enriched C3 plant, δ 13C=-39.1‰). The isotopic composition of body tissues closely tracked the isotopic composition of the snail diet as demonstrated previously. However, the isotopic composition of the acid insoluble organic matrix extracted from the aragonite shells does not track diet in all groups. In snails that were fed corn the isotopic composition of the organic matrix was more negative than the body by as much as 5‰ whereas the matrix was approximately 1‰ heavier than the body tissues in snails fed a diet of C3 plant material. These results indicate that isotopic composition of the organic matrix carbon cannot be used as an isotopic substrate for paleodietary reconstructions without first determining the source of the carbon and any associated fractionations. The isotopic composition of the shell aragonite is offset from the body tissues by 12.3‰ in each of the culture groups. This offset was not influenced by the consumption of carbonate and is not attributable to the diffusion of atmospheric CO 2 into the hemolymph. The carbon isotopic composition of shell aragonite is best explained in terms of equilibrium fractionations associated with exchange between metabolic CO 2 and HCO 3 in the hemolymph and the fractionation associated with carbonate precipitation. These results differ from previous studies, based primarily on samples collected in the field, that have suggested atmospheric carbon dioxide contributes significantly to the shell δ 13C. The culture results indicate that the δ 13C of aragonite is a good recorder of the isotopic composition of the snail body tissue, and therefore a better recorder of diet than is the insoluble shell organic carbon. Because the systematic fractionation of carbon isotopes within the snail is temperature dependent, the δ 13C of the shell could provide an independent technique for estimating paleotemperature changes.

Thallium isotope variations in seawater and hydrogenetic, diagenetic, and hydrothermal ferromanganese deposits

USGS Publications Warehouse

Rehkamper, M.; Frank, M.; Hein, J.R.; Porcelli, D.; Halliday, A.; Ingri, J.; Liebetrau, V.

2002-01-01

Results are presented for the first in-depth investigation of TI isotope variations in marine materials. The TI isotopic measurements were conducted by multiple collector-inductively coupled plasma mass spectrometry for a comprehensive suite of hydrogenetic ferromanganese crusts, diagenetic Fe-Mn nodules, hydrothermal manganese deposits and seawater samples. The natural variability of TI isotope compositions in these samples exceeds the analytical reproducibility (?? 0.05???) by more than a factor of 40. Hydrogenetic Fe-Mn crusts have ??205TI of + 10 to + 14, whereas seawater is characterized by values as low as -8 (??205TI represents the deviation of the 205TI/203TI ratio of a sample from the NIST SRM 997 TI isotope standard in parts per 104). This ~ 2??? difference in isotope composition is thought to result from the isotope fractionation that accompanies the adsorption of TI onto ferromanganese particles. An equilibrium fractionation factor of ?? ~ 1.0021 is calculated for this process. Ferromanganese nodules and hydrothermal manganese deposits have variable TI isotope compositions that range between the values obtained for seawater and hydrogenetic Fe-Mn crusts. The variability in ??205TI in diagenetic nodules appears to be caused by the adsorption of TI from pore fluids, which act as a closed-system reservoir with a TI isotope composition that is inferred to be similar to seawater. Nodules with ??205TI values similar to seawater are found if the scavenging of TI is nearly quantitative. Hydrothermal manganese deposits display a positive correlation between ??205TI and Mn/Fe. This trend is thought to be due to the derivation of TI from distinct hydrothermal sources. Deposits with low Mn/Fe ratios and low ??205TI are produced by the adsorption of TI from fluids that are sampled close to hydrothermal sources. Such fluids have low Mn/Fe ratios and relatively high temperatures, such that only minor isotope fractionation occurs during adsorption. Hydrothermal manganese deposits with high Mn/Fe and high ??205Ti are generated by scavenging of TI from colder, more distal hydrothermal fluids. Under such conditions, adsorption is associated with significant isotope fractionation, and this produces deposits with higher ??205TI values coupled with high Mn/Fe. ?? 2002 Elsevier Science B.V. All rights reserved.

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

PubMed

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

2012-07-30

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

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).

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

Studying regions on Earth that are analogous to Mars serve as case studies for studying astrobiology and planetary surface rock formation processes. Rio Tinto, Spain is very rich in iron sulfates, and has an environment that is possibly very similar to the former environment on Mars. Certain bacteria play significant roles in accelerating pyrite oxidation rates, the products of which contribute to the formation of ferrous sulfates, such as melanterite. During mineral crystallization in an aqueous solution, there are systematic isotopic differences between dissolved species and solid phases. Quantifying this fractionation enables isotopic analysis to be used to trace the original isotopic signature of the dissolved species. Isotope fractionation has been determined for minerals such as gypsum and epsomite, and from these results and theoretical predictions, it is expected that melanterite, a mineral potentially found on Mars, would be more enriched in oxygen-18 relative to the aqueous solution from which it crystallized.Thus, determining the oxygen-18 isotopic fractionation between melanterite and dissolved sulfate has many potential benefits for understanding surface processes on Mars and its past environment. To investigate the oxygen isotope fractionation for melanterite, acidic aqueous solutions saturated with dissolved hydrated ferrous sulfate were evaporated at 25 deg C and 40 deg C and under different conditions to induce different evaporation rates. During evaporation, the aqueous solution and crystallized melanterite were sampled at different stages. Oxygen-18 isotopic compositions were then measured. However, the fractionations observed in the experiments were opposite from predictions. At 25 deg C without enhanced evaporation, the dissolved sulfate was +5.5 per mil relative to the solid, while at 40 deg C it was +4.3 per mil. With enhanced evaporation, fractionation was +2.1 per mil, while at 40 deg C it was +3.6 per mil. In addition, at 40 deg C, evaporation rates and fractionation were larger than at 25 deg C. Because no Rayleigh fractionation was observed, this system was not in equilibrium, and was most likely dominated by kinetics. Because of the unexpected results, further research will be conducted on the oxygen isotope fractionation of melanterite.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

The isotope record of short- and long-term dietary changes in sheep tooth enamel: Implications for quantitative reconstruction of paleodiets

NASA Astrophysics Data System (ADS)

Zazzo, A.; Balasse, M.; Passey, B. H.; Moloney, A. P.; Monahan, F. J.; Schmidt, O.

2010-06-01

Quantitative reconstruction of paleodiet by means of sequential sampling and carbon isotope analysis in hypsodont tooth enamel requires a precise knowledge of the isotopic enrichment between dietary carbon and carbon from enamel apatite ( ɛD-E), as well as of the timing and duration of the enamel mineralization process (amelogenesis). To better constrain these parameters, we performed a series of controlled feeding experiments on sheep ranging in age from 6 to 24 months-old. Twenty-eight lambs and 14 ewes were fed isotopically distinct diets for different periods of time, and then slaughtered, allowing the timing and rate of molar growth to be determined. High resolution sampling and stable carbon isotope analysis of breath CO 2 performed on six individuals following a diet-switch showed that 70-90% of dietary carbon had turned over in less than 24 h. Sequential sampling and carbon isotopic analysis was performed on the first (M 1) and second (M 2) lower molars of four lambs as well as on the third lower molar (M 3) of 11 ewes. The changes in diet were recorded in all molars. We found that the length of enamel matrix apposition is approximately one-quarter of the final tooth length during crown extension, and that enamel maturation spans slightly less than 3 months in M 1, and 4 months in M 2 and M 3. Portions of enamel in equilibrium with dietary carbon were used to calculate ɛD-E values. Animals on grass silage diets had values similar to previous observations, whereas animal switched to pelleted corn diets had values ca. 4‰ lower, a pattern consistent with lower methane production observed for animals fed concentrate diets. The tooth enamel forward model of Passey and Cerling (2002) closely predicted the amplitude of isotope changes recorded in tooth enamel, but slightly underestimated the rate of isotope change, suggesting that the rate of accumulation of carbonate during maturation may not be constant over time. Although stable isotope profiles in tooth enamel represent underdetermined systems, our results demonstrate that they can provide useful information about dietary variability if the mineralization process is taken into account.

Oxygen isotope constraints on the alteration temperatures of CM chondrites

NASA Astrophysics Data System (ADS)

Verdier-Paoletti, Maximilien J.; Marrocchi, Yves; Avice, Guillaume; Roskosz, Mathieu; Gurenko, Andrey; Gounelle, Matthieu

2017-01-01

We report a systematic oxygen isotopic survey of Ca-carbonates in nine different CM chondrites characterized by different degrees of alteration, from the least altered known to date (Paris, 2.7-2.8) to the most altered (ALH 88045, CM1). Our data define a continuous trend that crosses the Terrestrial Fractionation Line (TFL), with a general relationship that is indistinguishable within errors from the trend defined by both matrix phyllosilicates and bulk O-isotopic compositions of CM chondrites. This bulk-matrix-carbonate (BMC) trend does not correspond to a mass-dependent fractionation (i.e., slope 0.52) as it would be expected during fluid circulation along a temperature gradient. It is instead a direct proxy of the degree of O-isotopic equilibration between 17,18O-rich fluids and 16O-rich anhydrous minerals. Our O-isotopic survey revealed that, for a given CM, no carbonate is in O-isotopic equilibrium with its respective surrounding matrix. This precludes direct calculation of the temperature of carbonate precipitation. However, the O-isotopic compositions of alteration water in different CMs (inferred from isotopic mass-balance calculation and direct measurements) define another trend (CMW for CM Water), parallel to BMC but with a different intercept. The distance between the BMC and CMW trends is directly related to the temperature of CM alteration and corresponds to average carbonates and serpentine formation temperatures of 110 °C and 75 °C, respectively. However, carbonate O-isotopic variations around the BMC trend indicate that they formed at various temperatures ranging between 50 and 300 °C, with 50% of the carbonates studied here showing precipitation temperature higher than 100 °C. The average Δ17O and the average carbonate precipitation temperature per chondrite are correlated, revealing that all CMs underwent similar maximum temperature peaks, but that altered CMs experienced protracted carbonate precipitation event(s) at lower temperatures than the least altered CMs. Our data suggest that the Δ17O value of Ca-carbonates could be a reliable proxy of the degree of alteration experienced by CM chondrites.

Iron Isotopes in Meteorites

NASA Astrophysics Data System (ADS)

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

2001-12-01

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

Southern Greenland water vapour isotopic composition at the crossroads of Atlantic and Arctic moisture

NASA Astrophysics Data System (ADS)

Bonne, J. L.; Steen-Larsen, H. C.; Risi, C. M.; Werner, M.; Sodemann, H.; Lacour, J. L.; Fettweis, X.; Cesana, G.; Delmotte, M.; Cattani, O.; Clerbaux, C.; Sveinbjörnsdottir, A. E.; Masson-Delmotte, V.

2014-12-01

Since September 2011, a continuous water vapour isotopic composition monitoring instrument has been remotely operated in Ivittuut (61.21°N, 48.17°W), southern Greenland. Meteorological parameters are monitored and precipitation has been sampled and analysed for isotopic composition, suggesting equilibrium between surface vapour and precipitation. The data depict small summer diurnal variations. δ18O and deuterium excess (d-excess) are generally anti-correlated and show important seasonal variations (with respective amplitudes of 10 and 20 ‰), and large synoptic variations associated to low-pressure systems (typically +5‰ on δ18O and -15‰ on d-excess). The moisture sources, estimated based on Lagrangian back-trajectories, are primarily influenced by the western North Atlantic, and north-eastern American continent. Notable are important seasonal and synoptic shifts of the moisture sources, and sporadic influences of the Arctic or the eastern North Atlantic. Moisture sources variations can be related to changes in water vapour isotopic composition, and the isotopic fingerprints can be attributed to the areas of moisture origins. Isotopic enabled AGCMs nudged to meteorology (LMDZiso, ECHAM5-wiso), despite biases, correctly capture the δ18O changes, but underestimate the d-excess changes. They allow to identify a high correlation between the southern Greenland d-excess and the simulated relative humidity and d-excess in the moisture source region south of Greenland. An extreme high temperature event in July 2012 affecting all Greenland, similar to ice sheet melt events during the medieval periods and one event in 1889 documented by Greenland ice core records, has been analysed regarding water vapour isotopic composition, using remote sensing (IASI) and in situ observations from Bermuda to northern Greenland (NEEM station). Our southern Greenland observations allow to track the water vapour evolution during this event along the moisture transport path, depicting the northward propagation of an isotopic signal inherited from the meteorological conditions during evaporation. Overall, our observations provide valuable information for interpreting Greenland ice core records as well as for evaluating water vapour isotopic simulations in atmospheric models.

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

PubMed

Bonin, Alice; Tsilanizara, Aimé

2017-06-01

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

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

PubMed

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

2015-09-30

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

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

USDA-ARS?s Scientific Manuscript database

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

Lattice Boltzmann Simulation of Kinetic Isotope Effect During Snow Crystal Formation

NASA Astrophysics Data System (ADS)

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

2007-12-01

The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically-symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over- saturation, determines crystal morphology, there are no quantitative models that relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be direct relationships between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D lattice Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. Crystal growth patterns can be varied between random growth and deterministic growth (along the maximum concentration gradient for example). The input parameters needed are the isotope- dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the condensation coefficient for ice is uncertain. The ratio D/k is a length (order 1 micron) that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). However, few natural crystals form under such conditions. At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, and kinetic effects control isotopic fractionation. Fractionation factors for dendritic crystals are similar to those predicted by the spherical diffusion model, but the model also gives estimates of crystal heterogeneity. Dendritic crystals are constrained to be relatively large, with dimension much greater than about 20D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. An approach using a larger scale simulation and the domain decomposition method can provide a vapor flux for a nested smaller scale calculation. The results clarify the controls on crystal growth, and the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation.

Equilibrium sampling by reweighting nonequilibrium simulation trajectories

NASA Astrophysics Data System (ADS)

Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

2016-03-01

Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems.

Equilibrium sampling by reweighting nonequilibrium simulation trajectories.

PubMed

Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

2016-03-01

Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems.

Results from the (U-Th)/He dating systems in Japan Atomic Energy Agency

NASA Astrophysics Data System (ADS)

Yamada, K.; Hanamuro, T.; Tagami, T.; Yamada, R.; Umeda, K.

2007-12-01

Japan Atomic Energy Agency (JAEA) has jointly set up the lab of the (U-Th)/He dating in cooperation with Kyoto University and National Research Institute for Earth Science and Disaster Prevention. We use the MM5400 rare gas mass spectrometer and the SPQ9000 ICP quadrupole mass spectrometer, belonging to JAEA, and built a new vacuum heater using infrared laser to extract helium. HF decomposes zircon after the alkali-fusion method using XRF bead sampler and LiBO3 in the preparation of ICP solution. Helium is quantified using sensitivity method. Uranium and thorium are using standard addition method. Quantifications of uranium-238 and thorium-232 are only need for parent isotopes to date samples because they are expected that the state of secular equilibrium becomes established and samarium does not compose the samples. At the present stage, we calibrate our systems by dating some standards, such as zircon from the Fish Canyon Tuff and apatite from the Durango, those are the international age standard, and apatite and zircon from the Tanzawa Tonalite Complex, that was dated in Yamada's PhD thesis, as a working standard. We report the results and detailed views of the dating systems.

Detecting isotopic ratio outliers

NASA Astrophysics Data System (ADS)

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

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

Evaporation in equilibrium, in vacuum, and in hydrogen gas

NASA Technical Reports Server (NTRS)

Nagahara, Hiroko

1993-01-01

Evaporation experiments were conducted for SiO2 in three different conditions: in equilibrium, in vacuum, and in hydrogen gas. Evaporation rate in vacuum is about two orders of magnitude smaller than that in equilibrium, which is consistent with previous works. The rate in hydrogen gas changes depending on hydrogen pressure. The rate at 10 exp -7 bar of hydrogen pressure is as small as that of free evaporation, but at 10 exp -5 bar of hydrogen pressure it is larger than that in equilibrium. In equilibrium and in vacuum, the evaporation rate is limited by decomposition of SiO2 on the crystal surface, but it is limited by a diffusion process for evaporation in hydrogen gas. Therefore, evaporation rate of minerals in the solar nebula can be shown neither by that in equilibrium nor by that in vacuum. The maximum temperature of the solar nebula at the midplane at 2-3 AU where chondrites are believed to have originated is calculated to be as low as 150 K, 1500 K, or in between them. The temperature is, in any case, not high enough for total evaporation of the interstellar materials. Therefore, evaporation of interstellar materials is one of the most important processes for the origin and fractionation of solid materials. The fundamental process of evaporation of minerals has been intensively studied for these several years. Those experiments were carried out either in equilibrium or in vacuum; however, evaporation in the solar nebula is in hydrogen (and much smaller amount of helium) gas. In order to investigate evaporation rate and compositional (including isotopic) fractionation during evaporation, vaporization experiments for various minerals in various conditions are conducted. At first, SiO2 was adopted for a starting material, because thermochemical data and its nature of congruent vaporization are well known. Experiments were carried out in a vacuum furnace system.

A Tale of Two Limpets (Patella vulgata and Patella stellaeformis): Evaluating a New Proxy for Late Holocene Climate Change in Coastal Areas

NASA Astrophysics Data System (ADS)

Fenger, T. L.; Surge, D. M.; Schoene, B. R.; Carter, J. G.; Milner, N.

2006-12-01

Shells of the European limpet, Patella vulgata, from Late Holocene archaeological deposits potentially contain critical information about climate change in coastal areas. Before deciphering climate information preserved in these zooarchaeological records, we studied the controls on oxygen isotope ratios (δ18O) in modern specimens. We tested the hypothesis that P. vulgata precipitates its shell in isotopic equilibrium with ambient water by comparing δ18OSHELL with expected values. Expected δ18OSHELL was constructed using the calcite-water fractionation equation, observed sea surface temperature (SST), and assuming δ18OWATER is +0.10‰ (VSMOW). Comparison between expected and measured δ18OSHELL revealed a +1.51±0.21‰ (VPDB) offset from expected values. Consequently, estimated SST calculated from δ18OSHELL was 6.50±2.45°C lower than observed SST. However, because the offset was relatively uniform, an adjustment can be made to account for this predictable vital effect and past SST can be reliably reconstructed. To further investigate the source of offset in this genus, we analyzed a fully marine tropical species (Patella stellaeformis) to minimize seasonal variation in environmental factors that influence δ18OSHELL. P. stellaeformis was evaluated to determine whether it has a similar offset from equilibrium as P. vulgata. We tested the hypotheses that: (1) δ18OSHELL in tropical species also displays vital effects; and (2) the offset from equilibrium (if any) would be constant and predictable. Our results indicated: (1) aragonite comprises most of P. stellaeformis' shell; and (2) δ18OSHELL is statistically indistinguishable from expected values calculated using the aragonite-water fractionation equation (Kolmogorov-Smirnov test statistic=0.61, D0.05[56, 57]=1.36) in contrast with our observations in P. vulgata. Differences in mineralogy or growth rates at different latitudes may play a role in mechanisms that influence vital effects.

Bottom-sediment chemistry in Devil's Lake, northeast North Dakota

USGS Publications Warehouse

Komor, S.C.

1994-01-01

High magnesium calcite 8 mole percent MgCO3 is the most abundant carbonate at the sediment surface. With increasing depth abundances of high magnesium carbonate decrease and abundances of low magnesium calcite aragonite and dolomite increase. Carbon isotope compositions of bulk carbonates range from δ13C = -0.7 to +0.5%. These values are close to equilibrium with dissolved inorganic carbon in lake water (δ13C = -2%) but far from equilibrium with dissolved inorganic carbon in pore water (δ13C = -16.3- -10/0%). Disequilibrium between pore water and carbonates suggests that the carbonates did not recrystallize substantially in the presence of pore water. Therefore the change of carbonate mineral proportions with depth in the sediments is due mainly to temporal changes in the proportions of endogenic, detrital, and biologic carbonates that were deposited on the lake bottom rather than postdepositional carbonate diagenesis.

Sclerochronology and geochemical variation in limpet shells (Patella vulgata): A new archive to reconstruct coastal sea surface temperature

NASA Astrophysics Data System (ADS)

Fenger, Tracy; Surge, Donna; SchöNe, Bernd; Milner, Nicky

2007-07-01

Climate archives contained in shells of the European limpet, Patella vulgata, accumulated in archaeological deposits can potentially provide much needed information about Holocene environmental change in midlatitude coastal areas. Before reconstructing climate information preserved in these zooarchaeological records, we studied the controls on oxygen and carbon isotope ratios (δ18O and δ13C, respectively) in modern specimens. We tested the hypothesis that P. vulgata precipitates its shell in isotopic equilibrium with the ambient water by comparing δ18OSHELL with predicted values. Predicted δ18OSHELL was constructed using observed sea surface temperature (SST) records and the equilibrium fractionation equation for calcite and water. We assumed a constant δ18OWATER value of +0.10‰ (VSMOW) based on published regional measurements. Comparison of δ18OSHELL with predicted values revealed that δ18OSHELL values were higher than expected by +1.01 ± 0.21‰. Consequently, estimated SST calculated from δ18OSHELL was 4.2 ± 2.3°C lower than observed SST. However, because of the relatively uniform offset between observed and expected δ18O, an adjustment can be made to account for this predictable vital effect. Thus past climate can be reliably reconstructed using this temperature proxy once the offset is taken into account. δ13C values have a similar cyclicity to the δ18O variation and therefore vary seasonally. However, δ13C is slightly out of phase relative to δ18O. An overall negative shift in δ13CSHELL over the lifetime of the individual indicates a vital effect associated with ontogeny. Further study of environmental and ecological factors that influence shell δ13C is required to evaluate fully the potential of carbon isotope ratios as a useful environmental proxy.

Majorite-Garnet Partitioning of the Highly Siderophile Elements: New Results and Application to Mars

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Waeselmann, N.; Humayun, M.

2015-01-01

HSE and Os isotopes are used to constrain processes such as accretion, mantle evolution, crustal recycling, and core-mantle mixing, and to constrain the timing and depth of differentiation of Mars. Although showed that the HSE contents of the martian mantle could have been established by metal-silicate equilibrium in early Mars, the role of a cooling magma ocean and associated crystallization in further fractionating the HSEs is unclear. Garnet is thought to have played an important role in controlling trace element concentrations in the martian mantle reservoirs. However, testing these models, including Os isotopes, has been hindered by a dearth of partitioning data for the HSE in deep mantle phases - majorite, wadsleyite, ringwoodite, akimotoite - that may be present in the martian mantle. We examine the partitioning behavior of HSEs between majorite garnet (gt), olivine (oliv), and silicate liquid (melt).

Models for coupled fluid flow, mineral reaction, and isotopic alteration during contact metamorphism: The Notch Peak aureole, Utah

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

Ferry, J.M.; Dipple, G.M.

Three different models were developed to simulate the effect of contact metamorphism and fluid-rock interaction on the prograde mineralogical and O isotopic evolution of calcareous argillites from the Notch Peak aureole, Utah. All models assume local mineral-fluid equilibrium, a steady-state temperature profile corresponding to peak metamorphic values, and the thermodynamic data for minerals and fluid of Berman (1988). The preferred model, metamorphism with flow of a time-integrated fluid flux of 2 {plus minus} 0.5 {center dot} 10{sup 4} mol/cm{sup 2} in the direction of increasing temperature, successfully reproduces the principal petrologic and isotopic features of the aureole: (1) occurrence andmore » positions (in map view) of diopside-in, tremolite-out, grossular-in, wollastonite-in, and quartz-out isograds; (2) stable coexistence of tremolite + calcite + quartz + diopside over an {approx}1 km distance between the diopside-in and tremolite-out isograds; (3) variable whole-rock {sup 18}O depletions of {approx}6-9{per thousand} adjacent to the contact; and (4) a gradual and irregular increase in {delta}{sup 18}O with increasing distance from the pluton. Results demonstrate how isotopic and petrologic data for contact aureoles can be integrated to provide quantitative constraints on the magnitude and geometry of metamorphic fluid flow.« less

Isotopic composition of atmospheric nitrate in a tropical marine boundary layer.

PubMed

Savarino, Joel; Morin, Samuel; Erbland, Joseph; Grannec, Francis; Patey, Matthew D; Vicars, William; Alexander, Becky; Achterberg, Eric P

2013-10-29

Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone budget. Uncertainties in the ozone budget are amplified by our poor understanding of the fate of NOx (= NO + NO2), particularly the importance of nighttime chemical NOx sinks. Here, we present year-round observations of the multiisotopic composition of atmospheric nitrate in the tropical MBL at the Cape Verde Atmospheric Observatory. We show that the observed oxygen isotope ratios of nitrate are compatible with nitrate formation chemistry, which includes the BrNO3 sink at a level of ca. 20 ± 10% of nitrate formation pathways. The results also suggest that the N2O5 pathway is a negligible NOx sink in this environment. Observations further indicate a possible link between the NO2/NOx ratio and the nitrogen isotopic content of nitrate in this low NOx environment, possibly reflecting the seasonal change in the photochemical equilibrium among NOx species. This study demonstrates the relevance of using the stable isotopes of oxygen and nitrogen of atmospheric nitrate in association with concentration measurements to identify and constrain chemical processes occurring in the MBL.

Isotopic disequilibrium in Globigerina bulloides and carbon isotope response to productivity increase in Southern Ocean.

PubMed

Prasanna, K; Ghosh, Prosenjit; Bhattacharya, S K; Mohan, K; Anilkumar, N

2016-02-23

Oxygen and carbon isotope ratios in planktonic foraminifera Globigerina bulloides collected from tow samples along a transect from the equatorial Indian ocean to the Southern Ocean (45°E and 80°E and 10°N to 53°S) were analysed and compared with the equilibrium δ(18)O and δ(13)C values of calcite calculated using the temperature and isotopic composition of the water column. The results agree within ~0.25‰ for the region between 10°N and 40°S and 75-200 m water depth which is considered to be the habitat of Globigerina bulloides. Further south (from 40°S to 55°S), however, the measured δ(18)O and δ(13)C values are higher than the expected values by ~2‰ and ~1‰ respectively. These enrichments can be attributed to either a 'vital effect' or a higher calcification rate. An interesting pattern of increase in the δ(13)C(DIC) value of the surface water with latitude is observed between 35°S and~ 60°S, with a peak at~ 42°S. This can be caused by increased organic matter production and associated removal. A simple model accounting for the increase in the δ(13)C(DIC) values is proposed which fits well with the observed chlorophyll abundance as a function of latitude.

Theoretical modeling of rhenium isotope fractionation, natural variations across a black shale weathering profile, and potential as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Miller, Christian A.; Peucker-Ehrenbrink, Bernhard; Schauble, Edwin A.

2015-11-01

We present the first data documenting environmental variations in the isotope composition of Re, and the first theoretical models of equilibrium Re isotope fractionation factors. Variations of δ187Re at modern surface temperatures are predicted to be ‰ level for redox (ReVII ⇌ ReIV) and perrhenate thiolation reactions (ReVIIO4- ⇌ReVIIOXS4-X- ⇌ReVII S4-). Nuclear volume fractionations are calculated to be smaller than mass dependent effects. Values of δ187Re from New Albany Shale samples presented in this work and in a previous study show a range of 0.8‰ over a stratigraphic interval of ∼20 m. The magnitude of variation is consistent with theoretical predictions and may provide evidence for changing δ187Re of seawater in the geologic past. A -0.3‰ change in δ187Re across a 14 m horizontal black shale weathering profile is accompanied by a hundred-fold decrease in Re concentration and a 75% decrease in organic carbon associated with the transition from reducing to oxic weathering environment. We attribute decreasing δ187Re to the loss of organically bound Re component (δ187Re = -0.28‰). The Re isotope composition of the complementary detrital silicate fraction varies from -0.59 to -1.5‰, depending on the choice of silicate Re concentration.

Isotopic composition of atmospheric nitrate in a tropical marine boundary layer

PubMed Central

Savarino, Joel; Morin, Samuel; Erbland, Joseph; Grannec, Francis; Patey, Matthew D.; Vicars, William; Alexander, Becky; Achterberg, Eric P.

2013-01-01

Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone budget. Uncertainties in the ozone budget are amplified by our poor understanding of the fate of NOx (= NO + NO2), particularly the importance of nighttime chemical NOx sinks. Here, we present year-round observations of the multiisotopic composition of atmospheric nitrate in the tropical MBL at the Cape Verde Atmospheric Observatory. We show that the observed oxygen isotope ratios of nitrate are compatible with nitrate formation chemistry, which includes the BrNO3 sink at a level of ca. 20 ± 10% of nitrate formation pathways. The results also suggest that the N2O5 pathway is a negligible NOx sink in this environment. Observations further indicate a possible link between the NO2/NOx ratio and the nitrogen isotopic content of nitrate in this low NOx environment, possibly reflecting the seasonal change in the photochemical equilibrium among NOx species. This study demonstrates the relevance of using the stable isotopes of oxygen and nitrogen of atmospheric nitrate in association with concentration measurements to identify and constrain chemical processes occurring in the MBL. PMID:23431201

Void reactivity feedback analysis for U-based and Th-based LWR incineration cycles

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

Lindley, B.A.; Parks, G.T.; Franceschini, F.

2013-07-01

In reduced-moderation LWRs, an external supply of transuranic (TRU) can be incinerated by mixing it with a fertile isotope ({sup 238}U or {sup 232}Th) and recycling all the actinides after each cycle. Performance is limited by coolant reactivity feedback - the moderator density coefficient (MDC) must be kept negative. The MDC is worse when more TRU is loaded, but TRU feed is also needed to maintain criticality. To assess the performance of this fuel cycle in different neutron spectra, three LWRs are considered: 'reference' PWRs and reduced-moderation PWRs and BWRs. The MDC of the equilibrium cycle is analysed by reactivitymore » decomposition with perturbed coolant density by isotope and neutron energy. The results show that using {sup 232}Th as a fertile isotope yields superior performance to {sup 238}U. This is due essentially to the high resonance η of U bred from Th (U3), which increases the fissility of the U3-TRU isotope vector in the Th-fueled system relative to the U-fueled system, and also improves the MDC in a sufficiently hard spectrum. Spatial separation of TRU and U3 in the Th-fueled system renders further improvement by hardening the neutron spectrum in the TRU and softening it in the U3. This improves the TRU η and increases the negative MDC contribution from reduced thermal fission in U3. (authors)« less

Critical temperature for shape transition in hot nuclei within covariant density functional theory

NASA Astrophysics Data System (ADS)

Zhang, W.; Niu, Y. F.

2018-05-01

Prompted by the simple proportional relation between critical temperature for pairing transition and pairing gap at zero temperature, we investigate the relation between critical temperature for shape transition and ground-state deformation by taking even-even Cm-304286 isotopes as examples. The finite-temperature axially deformed covariant density functional theory with BCS pairing correlation is used. Since the Cm isotopes are the newly proposed nuclei with octupole correlations, we studied in detail the free energy surface, the Nilsson single-particle (s.p.) levels, and the components of s.p. levels near the Fermi level in 292Cm. Through this study, the formation of octupole equilibrium is understood by the contribution coming from the octupole driving pairs with Ω [N ,nz,ml] and Ω [N +1 ,nz±3 ,ml] for single-particle levels near the Fermi surfaces as it provides a good manifestation of the octupole correlation. Furthermore, the systematics of deformations, pairing gaps, and the specific heat as functions of temperature for even-even Cm-304286 isotopes are discussed. Similar to the relation between the critical pairing transition temperature and the pairing gap at zero temperature Tc=0.6 Δ (0 ) , a proportional relation between the critical shape transition temperature and the deformation at zero temperature Tc=6.6 β (0 ) is found for both octupole shape transition and quadrupole shape transition for the isotopes considered.

Moisture rainout fraction over the Indian Ocean during austral summer based on (18) {O}/{}(16) {O}18O/16O ratios of surface seawater, rainwater at latitude range of 10({°) } {N}textendash 60({°) } {S}10∘N–60∘S

NASA Astrophysics Data System (ADS)

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

2018-06-01

Oxygen isotope ratios (^{18}O/^{16}O) of surface seawater and rainwater samples from the Indian Ocean region (10°Nendash 60°S) during austral summer collected onboard ORV Sagar Nidhi during 2011-2013 have been measured along with salinity, sea surface temperature and relative humidity. The rainwater is isotopically lighter (by 4.6± 2.7\\permille ) compared to the equilibrium condensation of the vapour arising from the seawater at the ambient condition. The isotopic composition of the vapour at high altitude responsible for the rain formation at the sampling location is estimated from a global atmospheric water isotope model (IsoGSM2). The apparent deficit of ˜ 5\\permille can be explained by invoking a high degree of rainout (on average, about 70% of the overhead atmospheric moisture) during transport of the source vapour to the sampling location undergoing a Rayleigh fractionation. The required rainout fraction is higher (˜ 80%) in the latitude belt 40°endash 60°S compared to the equatorial belt (˜ 60%). The pattern of variation in the rainout fraction with latitude is consistent with the well-known evaporation/precipitation processes in the Indian Ocean.

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.

Isotope fractionation by multicomponent diffusion (Invited)

NASA Astrophysics Data System (ADS)

Watkins, J. M.; Liang, Y.; Richter, F. M.; Ryerson, F. J.; DePaolo, D. J.

2013-12-01

Isotope fractionation by multicomponent diffusion The isotopic composition of mineral phases can be used to probe the temperatures and rates of mineral formation as well as the degree of post-mineralization alteration. The ability to interpret stable isotope variations is limited by our knowledge of three key parameters and their relative importance in determining the composition of a mineral grain and its surroundings: (1) thermodynamic (equilibrium) partitioning, (2) mass-dependent diffusivities, and (3) mass-dependent reaction rate coefficients. Understanding the mechanisms of diffusion and reaction in geological liquids, and how these mass transport processes discriminate between isotopes, represents an important problem that is receiving considerable attention in the geosciences. Our focus in this presentation will be isotope fractionation by chemical diffusion. Previous studies have documented that diffusive isotope effects vary depending on the cation as well as the liquid composition, but the ability to predict diffusive isotope effects from theory is limited; for example, it is unclear whether the magnitude of diffusive isotopic fractionations might also vary with the direction of diffusion in composition space. To test this hypothesis and to further guide the theoretical treatment of isotope diffusion, two chemical diffusion experiments and one self diffusion experiment were conducted at 1250°C and 0.7 GPa. In one experiment (A-B), CaO and Na2O counter-diffuse rapidly in the presence of a small SiO2 gradient. In the other experiment (D-E), CaO and SiO2 counter-diffuse more slowly in a small Na2O gradient. In both chemical diffusion experiments, Ca isotopes become fractionated by chemical diffusion but by different amounts, documenting for the first time that the magnitude of isotope fractionation by diffusion depends on the direction of diffusion in composition space. The magnitude of Ca isotope fractionation that develops is positively correlated with the rate of CaO diffusion; in A-B, the total variation is 2.5‰ whereas in D-E it is only 1.3‰. The diffusion of isotopes in a multicomponent system is modeled using a new expression for the isotope-specific diffusive flux that includes self diffusion terms in addition to the multicomponent chemical diffusion matrix. Kinetic theory predicts a mass dependence on isotopic mobility, i.e., self diffusivity, but it is unknown whether or how the mass dependence on self diffusivity translates into a mass dependence on chemical diffusion coefficients. The new experimental results allow us to assess several empirical expressions relating the self diffusivity and its mass dependence to the elements of the diffusion matrix and their mass dependence. Several plausible theoretical treatments can fit the data equally well. We are currently at the stage where experiments are guiding the theoretical treatment of the isotope fractionation by diffusion problem, underscoring the importance of experiments for aiding interpretations of isotopic variations in nature.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Method for separating boron isotopes

DOEpatents

Rockwood, Stephen D.

1978-01-01

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

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

USGS Publications Warehouse

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

1989-01-01

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

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

USGS Publications Warehouse

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

2017-01-01

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

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.

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.

Origins of GEMS Grains

NASA Technical Reports Server (NTRS)

Messenger, S.; Walker, R. M.

2012-01-01

Interplanetary dust particles (IDPs) collected in the Earth s stratosphere contain high abundances of submicrometer amorphous silicates known as GEMS grains. From their birth as condensates in the outflows of oxygen-rich evolved stars, processing in interstellar space, and incorporation into disks around new stars, amorphous silicates predominate in most astrophysical environments. Amorphous silicates were a major building block of our Solar System and are prominent in infrared spectra of comets. Anhydrous interplanetary dust particles (IDPs) thought to derive from comets contain abundant amorphous silicates known as GEMS (glass with embedded metal and sulfides) grains. GEMS grains have been proposed to be isotopically and chemically homogenized interstellar amorphous silicate dust. We evaluated this hypothesis through coordinated chemical and isotopic analyses of GEMS grains in a suite of IDPs to constrain their origins. GEMS grains show order of magnitude variations in Mg, Fe, Ca, and S abundances. GEMS grains do not match the average element abundances inferred for ISM dust containing on average, too little Mg, Fe, and Ca, and too much S. GEMS grains have complementary compositions to the crystalline components in IDPs suggesting that they formed from the same reservoir. We did not observe any unequivocal microstructural or chemical evidence that GEMS grains experienced prolonged exposure to radiation. We identified four GEMS grains having O isotopic compositions that point to origins in red giant branch or asymptotic giant branch stars and supernovae. Based on their O isotopic compositions, we estimate that 1-6% of GEMS grains are surviving circumstellar grains. The remaining 94-99% of GEMS grains have O isotopic compositions that are indistinguishable from terrestrial materials and carbonaceous chondrites. These isotopically solar GEMS grains either formed in the Solar System or were completely homogenized in the interstellar medium (ISM). However, the chemical compositions of GEMS grains are extremely heterogeneous and seem to rule out this possibility. Based on their solar isotopic compositions and their non-solar elemental compositions we propose that most GEMS grains formed in the nebula as late-stage non-equilibrium condensates.