Intracellular Cadmium Isotope Fractionation

Science.gov (United States)

Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

2011-12-01

Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

Iron isotope composition of particles produced by UV-femtosecond laser ablation of natural oxides, sulfides, and carbonates.

Science.gov (United States)

d'Abzac, Francois-Xavier; Beard, Brian L; Czaja, Andrew D; Konishi, Hiromi; Schauer, James J; Johnson, Clark M

2013-12-17

The need for femtosecond laser ablation (fs-LA) systems coupled to MC-ICP-MS to accurately perform in situ stable isotope analyses remains an open question, because of the lack of knowledge concerning ablation-related isotopic fractionation in this regime. We report the first iron isotope analysis of size-resolved, laser-induced particles of natural magnetite, siderite, pyrrhotite, and pyrite, collected through cascade impaction, followed by analysis by solution nebulization MC-ICP-MS, as well as imaging using electron microscopy. Iron mass distributions are independent of mineralogy, and particle morphology includes both spheres and agglomerates for all ablated phases. X-ray spectroscopy shows elemental fractionation in siderite (C-rich agglomerates) and pyrrhotite/pyrite (S-rich spheres). We find an increase in (56)Fe/(54)Fe ratios of +2‰, +1.2‰, and +0.8‰ with increasing particle size for magnetite, siderite, and pyrrhotite, respectively. Fe isotope differences in size-sorted aerosols from pyrite ablation are not analytically resolvable. Experimental data are discussed using models of particles generation by Hergenröder and elemental/isotopic fractionation by Richter. We interpret the isotopic fractionation to be related to the iron condensation time scale, dependent on its saturation in the gas phase, as a function of mineral composition. Despite the isotopic variations across aerosol size fractions, total aerosol composition, as calculated from mass balance, confirms that fs-LA produces a stoichiometric sampling in terms of isotopic composition. Specifically, both elemental and isotopic fractionation are produced by particle generation processes and not by femtosecond laser-matter interactions. These results provide critical insights into the analytical requirements for laser-ablation-based stable isotope measurements of high-precision and accuracy in geological samples, including the importance of quantitative aerosol transport to the ICP.

Equilibrium Fe isotope fractionation between inorganic aqueous Fe(III) and the siderophore complex, Fe(III)-desferrioxamine B

DEFF Research Database (Denmark)

Dideriksen, Knud; Baker, Joel A.; Stipp, Susan Louise Svane

2008-01-01

be controlled by isotope fractionation between the free and complexed iron.We have determined the equilibrium Fe isotope fractionation induced by organic ligand activity in experiments with solutions having co-existing inorganic Fe(III) species and siderophore complexes, Fedesferrioxamine B (at pH 2). The two......-type fractionation during precipitation, this experiment yielded an isotope fractionation factor of a56Fesolution-solid=1.00027. Calculations based on these results indicate that isotopic re-equilibration is unlikely to significantly affect our determined equilibrium Fe isotope fractionation between inorganically...... and organically complexed Fe. To determine the equilibrium Fe isotope fractionation between inorganically and organically bound Fe(III), experiments with variable proportions of inorganic Fe were carried out at 25 °C. Irrespective of the proportion of inorganic Fe, equilibrium fractionation factors were within...

Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

Directory of Open Access Journals (Sweden)

J. N. Crowley

2012-01-01

Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

Combined iron and magnesium isotope geochemistry of pyroxenite xenoliths from Hannuoba, North China Craton: implications for mantle metasomatism

Science.gov (United States)

Zhao, Xin Miao; Cao, Hui Hui; Mi, Xue; Evans, Noreen J.; Qi, Yu Han; Huang, Fang; Zhang, Hong Fu

2017-06-01

We present high-precision iron and magnesium isotopic data for diverse mantle pyroxenite xenoliths collected from Hannuoba, North China Craton and provide the first combined iron and magnesium isotopic study of such rocks. Compositionally, these xenoliths range from Cr-diopside pyroxenites and Al-augite pyroxenites to garnet-bearing pyroxenites and are taken as physical evidence for different episodes of melt injection. Our results show that both Cr-diopside pyroxenites and Al-augite pyroxenites of cumulate origin display narrow ranges in iron and magnesium isotopic compositions (δ57Fe = -0.01 to 0.09 with an average of 0.03 ± 0.08 (2SD, n = 6); δ26Mg = - 0.28 to -0.25 with an average of -0.26 ± 0.03 (2SD, n = 3), respectively). These values are identical to those in the normal upper mantle and show equilibrium inter-mineral iron and magnesium isotope fractionation between coexisting mantle minerals. In contrast, the garnet-bearing pyroxenites, which are products of reactions between peridotites and silicate melts from an ancient subducted oceanic slab, exhibit larger iron isotopic variations, with δ57Fe ranging from 0.12 to 0.30. The δ57Fe values of minerals in these garnet-bearing pyroxenites also vary widely (-0.25 to 0.08 in olivines, -0.04 to 0.25 in orthopyroxenes, -0.07 to 0.31 in clinopyroxenes, 0.07 to 0.48 in spinels and 0.31-0.42 in garnets). In addition, the garnet-bearing pyroxenite shows light δ26Mg (-0.43) relative to the mantle. The δ26Mg of minerals in the garnet-bearing pyroxenite range from -0.35 for olivine and orthopyroxene, to -0.34 for clinopyroxene, 0.04 for spinel and -0.68 for garnet. These measured values stand in marked contrast to calculated equilibrium iron and magnesium isotope fractionation between coexisting mantle minerals at mantle temperatures derived from theory, indicating disequilibrium isotope fractionation. Notably, one phlogopite clinopyroxenite with an apparent later metasomatic overprint has the heaviest δ57Fe

Origin of the Moon Unveiled by its Heavy Iron Isotope Composition

Science.gov (United States)

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

2002-12-01

The origin of the Moon has long been of interest and although the Giant Impact theory is currently the preferred explanation, unequivocal supporting evidence has been lacking. We have measured the iron isotope compositions of Shergotty-Nakhla-Chassigny meteorites and eucrites thought to come from Mars and Vesta, as well as samples from the Moon and the mafic Earth using high precision plasma source mass spectrometry. The mean iron isotope composition of the lunar samples, expressed in the conventional delta notation (d57Fe/54Fe) with respect to the IRMM-14 isotopic standard, is heavier (0.221 per mil (0.041: one standard deviation, 10 samples)) than those of the Earth (0.119 per mil (0.044, 7 samples)), which themselves are heavier than Martian meteorites (0.009 per mil (0.024, 6 samples)) and the eucrites measured (0.033 per mil (0.038, 7 samples)). Student's t-test calculations show that the Moon and Earth means are different from each other and from those of the other planetary bodies at >99% level of significance. The iron isotope compositions show no simple relationship with planetary heliocentric position, mantle oxygen fugacity, volatile content, or planet size. Similarly, these results do not support an origin of the Moon through co-accretion with the Earth, or as a fragment ejected from the Earth's mantle, or as another planet captured by the early Earth. In contrast, these data can be explained if the Earth, and especially the Moon, went through partial vaporisation and condensation leading to kinetic iron isotopic fractionation. Our data are also consistent with the suggested levels of enrichment of refractory elements for the bulk Earth and Moon. These new iron isotope results thus provide strong support for the origin of the Moon through a giant impact between the proto-Earth and another planet. Raleigh kinetic fractionation calculations indicate that only 1% loss of the current Fe budget of the Moon is required to explain its heavier isotopic

Iron Availability Influences Silicon Isotope Fractionation in Two Southern Ocean Diatoms (Proboscia inermis and Eucampia antarctica and a Coastal Diatom (Thalassiosira pseudonana

Directory of Open Access Journals (Sweden)

Scott Meyerink

2017-07-01

Full Text Available The fractionation of silicon (Si isotopes was measured in two Southern Ocean diatoms (Proboscia inermis and Eucampia Antarctica and a coastal diatom (Thalassiosira pseudonana that were grown under varying iron (Fe concentrations. Varying Fe concentrations had no effect on the Si isotope enrichment factor (ε in T. pseudonana, whilst E. Antarctica and P. inermis exhibited significant variations in the value of ε between Fe-replete and Fe-limited conditions. Mean ε values in P. inermis and E. Antarctica decreased from (± 1SD −1.11 ± 0.15‰ and −1.42 ± 0.41 ‰ (respectively under Fe-replete conditions, to −1.38 ± 0.27 ‰ and −1.57 ± 0.5 ‰ (respectively under Fe-limiting conditions. These variations likely arise from adaptations in diatoms arising from the nutrient status of their environment. T. pseudonana is a coastal clone typically accustomed to low Si but high Fe conditions whereas E. Antarctica and P. inermis are typically accustomed to High Si, High nitrate low Fe conditions. Growth induced variations in silicic acid (Si(OH4 uptake arising from Fe-limitation is the likely mechanism leading to Si-isotope variability in E. Antarctica and P. inermis. The multiplicative effects of species diversity and resource limitation (e.g., Fe on Si-isotope fractionation in diatoms can potentially alter the Si-isotope composition of diatom opal in diatamaceous sediments and sea surface Si(OH4. This work highlights the need for further in vitro studies into intracellular mechanisms involved in Si(OH4 uptake, and the associated pathways for Si-isotope fractionation in diatoms.

Isotope resolution of the iron peak

International Nuclear Information System (INIS)

Henke, R.P.; Benton, E.V.

1977-01-01

A stack of Lexan detectors from the Apollo 17 mission has been analyzed to obtain Z measurements of sufficient accuracy to resolve the iron peak into its isotopic components. Within this distribution several peaks are present. With the centrally located, most populated peak assumed to be 56 Fe, the measurements imply that the abundances of 54 Fe and 58 Fe are appreciable fractions of the 56 Fe abundance. This result is in agreement with those of Webber et al. and Siegman et al. but in disagreement with the predictions of Tsao et al. (Auth.)

Discovery of the iron isotopes

International Nuclear Information System (INIS)

Schuh, A.; Fritsch, A.; Heim, M.; Shore, A.; Thoennessen, M.

2010-01-01

Twenty-eight iron isotopes have been observed so far and the discovery of these isotopes is discussed here. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.

Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

Energy Technology Data Exchange (ETDEWEB)

Liu, Yunde [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Laboratory of Basin Hydrology and Wetland Eco-restoration, China University of Geosciences, Wuhan 430074 (China); Zhou, Aiguo, E-mail: aiguozhou@cug.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Gan, Yiqun; Li, Xiaoqian [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China)

2016-05-05

Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO{sub 3}{sup −}, or SO{sub 4}{sup 2−}. • Cl{sup −} significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

International Nuclear Information System (INIS)

Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Li, Xiaoqian

2016-01-01

Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO_3"−, or SO_4"2"−. • Cl"− significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

Inverse isotope effect in iron-based superconductor

International Nuclear Information System (INIS)

Shirage, Parasharam M.; Kihou, Kunihiro; Miyazawa, Kiichi; Lee, Chul-Ho; Kito, Hijiri; Yoshida, Yoshiyuki; Eisaki, Hiroshi; Tanaka, Yasumoto; Iyo, Akira

2010-01-01

We have found that (Ba, K)Fe 2 As 2 superconductor (a transition temperature, T c ∼ 38 K) shows an inverse Iron isotope effect (α Fe = -0.18 ± 0.03, where T c ∼ M -αFe and M is the iron isotope mass), i.e. the sample containing the larger iron mass depicts higher T c . Systematic studies using three types of Fe-isotopes ( 54 Fe, natural Fe and 57 Fe) reveal a clear inverse shift on T c by measurements of temperature dependent magnetization and resistivity. The inverse isotope effect that is the first case in high-T c superconductors strongly suggests that superconducting mechanism of the iron-based system is not explained by conventional BCS theory mediated by phonons.

Copper isotope fractionation by desert shrubs

International Nuclear Information System (INIS)

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

2011-01-01

Copper has two naturally occurring stable isotopes of masses 63 and 65 which can undergo mass dependent fractionation during various biotic and abiotic chemical reactions. These interactions and their resulting Cu isotope fractionations can be used to determine the mechanisms involved in the cycling of Cu in natural systems. In this study, Cu isotope changes were investigated at the organismal level in the metal-accumulating desert plant, Prosopis pubescens. Initial results suggest that the lighter Cu isotope was preferentially incorporated into the leaves of the plant, which may suggest that Cu was actively transported via intracellular proteins. The roots and stems show a smaller degree of Cu isotope fractionation and the direction and magnitude of the fractionations was dependent upon the levels of Cu exposure. Based on this and previous work with bacteria and yeast, a trend is emerging that suggests the lighter Cu isotope is preferentially incorporated into biological components, while the heavier Cu isotope tends to become enriched in aqueous solutions. In bacteria, plants and animals, intracellular Cu concentrations are strictly regulated via dozens of enzymes that can bind, transport, and store Cu. Many of these enzymes reduce Cu(II) to Cu(I). These initial results seem to fit into a broader picture of Cu isotope cycling in natural systems where oxidation/reduction reactions are fundamental in controlling the distributions of Cu isotopes.

Calcium isotope fractionation in ion-exchange chromatography

International Nuclear Information System (INIS)

Russell, W.A.; Papanastassiou, D.A.

1978-01-01

Significant fractionation of the isotopes of calcium has been observed during elution through short ion-exchange columns packed with Dowex 50W-X8 resin. A double isotopic tracer was used to provide correction for instrumental fractionation effects. The absolute 40 Ca/ 44 Ca ratio is determined by this method to 0.05% and provides a measure of the fractionation of all Ca isotopes. It is found that the lighter isotopes are preferentially retained by the resin, with variations in 40 Ca/ 44 Ca between the first and last fractions of up to 1.1%. An estimate of the separation factor between batch solute and resin gives epsilon = 2.1 x 10 -4 . Details of the chemical or physical mechanisms causing isotope fractionation of Li, Na, Ca, and other elements during ion-exchange chromatography are not yet clear

Experimental study on isotope fractionation of evaporating water of different initial isotopic composition

International Nuclear Information System (INIS)

Pooja Devi; Jain, A.K.; Rao, M.S.; Kumar, B.

2014-01-01

The studies of evaporative isotopic fractionation in controlled conditions are of particular importance for understanding the mechanism of evaporation fractionation in natural conditions. We present the measurements of the average isotopic fractionation factors during the evaporation of water having different initial isotopic compositions at constant temperature. The results show that the isotopic composition of residual water become more enriched over the time and the initial isotopic composition of evaporating water has considerable effect on the average isotopic fractionation factors. The average isotopic fractionation factors in evaporation of Water A and Water B under the present experimental conditions were found to be 0.9817 ± 0.0044 and 0.9887 ± 0.0031 for oxygen and 0.9178 ± 0.0182 and 0.9437 ± 0.0169 for hydrogen, respectively. The findings of this work should lead to a better understanding and use of stable isotope techniques in isotope hydrology by using a simple technique of evaporation pan. (author)

Boron-isotope fractionation in plants

Energy Technology Data Exchange (ETDEWEB)

Marentes, E [Univ. of Guelph, Dept. of Horticultural Science, Guelph, Ontario (Canada); Vanderpool, R A [USDA/ARS Grand Forks Human Nutrition Research Center, Grand Forks, North Dakota (United States); Shelp, B J [Univ. of Guelph, Dept. of Horticultural Science, Guelph, Ontario (Canada)

1997-10-15

Naturally-occurring variations in the abundance of stable isotopes of carbon, nitrogen, oxygen, and other elements in plants have been reported and are now used to understand various physiological processes in plants. Boron (B) isotopic variation in several plant species have been documented, but no determination as to whether plants fractionate the stable isotopes of boron, {sup 11}B and {sup 10}B, has been made. Here, we report that plants with differing B requirements (wheat, corn and broccoli) fractionated boron. The whole plant was enriched in {sup 11}B relative to the nutrient solution, and the leaves were enriched in {sup 10}B and the stem in {sup 11}B relative to the xylem sap. Although at present, a mechanistic role for boron in plants is uncertain, potential fractionating mechanisms are discussed. (author)

Boron-isotope fractionation in plants

International Nuclear Information System (INIS)

Marentes, E.; Vanderpool, R.A.; Shelp, B.J.

1997-01-01

Naturally-occurring variations in the abundance of stable isotopes of carbon, nitrogen, oxygen, and other elements in plants have been reported and are now used to understand various physiological processes in plants. Boron (B) isotopic variation in several plant species have been documented, but no determination as to whether plants fractionate the stable isotopes of boron, 11 B and 10 B, has been made. Here, we report that plants with differing B requirements (wheat, corn and broccoli) fractionated boron. The whole plant was enriched in 11 B relative to the nutrient solution, and the leaves were enriched in 10 B and the stem in 11 B relative to the xylem sap. Although at present, a mechanistic role for boron in plants is uncertain, potential fractionating mechanisms are discussed. (author)

Oxygen isotopic fractionation during bacterial sulfate reduction

Science.gov (United States)

Balci, N.; Turchyn, A. V.; Lyons, T.; Bruchert, V.; Schrag, D. P.; Wall, J.

2006-12-01

Sulfur isotope fractionation during bacterial sulfate reduction (BSR) is understood to depend on a variety of environmental parameters, such as sulfate concentration, temperature, cell specific sulfate reduction rates, and the carbon substrate. What controls oxygen isotope fractionation during BSR is less well understood. Some studies have suggested that carbon substrate is important, whereas others concluded that there is a stoichiometric relationship between the fractionations of sulfur and oxygen during BSR. Studies of oxygen fractionation are complicated by isotopic equilibration between sulfur intermediates, particularly sulfite, and water. This process can modify the isotopic composition of the extracellular sulfate pool (δ18OSO4 ). Given this, the challenge is to distinguish between this isotopic equilibration and fractionations linked to the kinetic effects of the intercellular enzymes and the incorporation of sulfate into the bacterial cell. The δ18OSO4 , in concert with the sulfur isotope composition of sulfate (δ34SSO4), could be a powerful tool for understanding the pathways and environmental controls of BSR in natural systems. We will present δ18OSO4 data measured from batch culture growth of 14 different species of sulfate reducing bacteria for which sulfur isotope data were previously published. A general observation is that δ18OSO4 shows little isotopic change (kinetic effect during BSR and/or equilibration between sulfur intermediates and the isotopically light water (~-5‰) of the growth medium. Our present batch culture data do not allow us to convincingly isolate the magnitude and the controlling parameters of the kinetic isotope effect for oxygen. However, ongoing growth of mutant bacteria missing enzymes critical in the different steps of BSR may assist in this mission.

Nickel distribution and isotopic fractionation in a Brazilian lateritic regolith: Coupling Ni isotopes and Ni K-edge XANES

Science.gov (United States)

Ratié, G.; Garnier, J.; Calmels, D.; Vantelon, D.; Guimarães, E.; Monvoisin, G.; Nouet, J.; Ponzevera, E.; Quantin, C.

2018-06-01

Ultramafic (UM) rocks are known to be nickel (Ni) rich and to weather quickly, which makes them a good candidate to look at the Ni isotope systematics during weathering processes at the Earth's surface. The present study aims at identifying the Ni solid speciation and discussing the weathering processes that produce Ni isotope fractionation in two deep laterite profiles under tropical conditions (Barro Alto, Goiás State, Brazil). While phyllosilicates and to a lower extent goethite are the main Ni-bearing phases in the saprolitic part of the profile, iron (Fe) oxides dominate the Ni budget in the lateritic unit. Nickel isotopic composition (δ60Ni values) has been measured in each unit of the regolith, i.e., rock, saprock, saprolite and laterite (n = 52). δ60Ni varies widely within the two laterite profiles, from -0.10 ± 0.05‰ to 1.43 ± 0.05‰, showing that significant Ni isotope fractionation occurs during the weathering of UM rocks. Overall, our results show that during weathering, the solid phase is depleted in heavy Ni isotopes due to the preferential sorption and incorporation of light Ni isotopes into Fe oxides; the same mechanisms likely apply to the incorporation of Ni into phyllosilicates (type 2:1). However, an isotopically heavy Ni pool is observed in the solid phase at the bottom of the saprolitic unit. This feature can be explained by two hypotheses that are not mutually exclusive: (i) a depletion in light Ni isotopes during the first stage of weathering due to the preferential dissolution of light Ni-containing minerals, and (ii) the sorption or incorporation of isotopically heavy Ni carried by percolating waters (groundwater samples have δ60Ni of 2.20 and 2.27‰), that were enriched in heavy Ni isotopes due to successive weathering processes in the overlying soil and laterite units.

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

Science.gov (United States)

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

Molybdenum isotope fractionation during adsorption to organic matter

Science.gov (United States)

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

2018-01-01

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

Geochemical importance of isotopic fractionation during respiration

International Nuclear Information System (INIS)

Schleser, G.; Foerstel, H.

1975-01-01

In 1935 it was found that atmospheric oxygen contained a relatively greater abundance of the 18 O isotope than did the oxygen bound in water (Dole effect). A major contribution to the fractionation of the stable oxygen isotopes should result from the respiration of microorganisms. In this respect our interest centers on the soil because nearly all organic material produced on land is decomposed within the soil. The oceans are less important because the primary productivity on land is twice the value for the oceans. In a first approach we measured the oxygen isotope fractionation during the respiration of E. coli K12 for different respiration rates. These results, accomplished with a chemostat, indicate that the fractionation factor α of the oxygen isotopes increases with the increasing respiratory activity, measured as Q/sub O 2 /. At low dilution rates or growth rates respectively of about 0.05 h -1 , the fractionation factor amounts to 1.006 increasing to 1.017 at dilution rates of about 1.0 h -1 . The results are interpreted as a kinetic mass fractionation due to the slightly different diffusion coefficients of 16 O 2 and 18 O 16 O. The respiration rates in conjunction with the corresponding fractionation data are compared with the respiration rates of typical soil microorganisms such as Azotobacter, in order to deduce fractionation data for these organisms. This is necessary to calculate a mean global fractionation factor. Understanding the Dole effect with these fractionation processes should finally give us the opportunity to calculate gas-exchange rates between the atmosphere and the oceans, on the basis of the behavior of the stable oxygen isotopes

Genealogy of Iron and Pallasite Meteorites as Revealed by Cr Isotopes

Science.gov (United States)

Sanborn, M.; Yin, Q. Z.; Ziegler, K. G.

2017-12-01

The parent bodies and/or chemical reservoirs from which iron and stony-iron meteorites originated are not very well understood. It is unclear if particular groups of iron or stony-iron meteorites originated from melting of already known chondritic parent bodies or are representating new chemical reservoirs. Potential connections between iron meteorites and pallasites and known parent bodies have been suggested based on oxygen isotopes. Proposed genetic relationships include the IVA irons with ordinary chondrites1 and the anomalous pallasite Eagle Station with the CV chondrites2. Here, we use the power of Cr isotopes to further resolve potential connections between IVA irons and pallasites and specific parent bodies. Our new measurements of Cr isotopic composition of silicate inclusions from two IVA irons, Steinbach and São João Nepomuceno, are shown to be indistinguishable from that of the ordinary chondrites. Coupling Cr with oxygen indicates the IVA irons likely originated from the same source as LL chondrites. In contrast with Eagle Station, the new Cr isotope measurements combined with oxygen indicates the MGP Brenham and Krasnojarsk sampled a source material similar to that of the anomalous HEDs. As with Eagle Station, the Milton pallasite exhibits a carbonaceous chondrite (CC) Cr isotope composition, indicating that Eagle Station was not the lone case of a pallasite originating from a CC reservoir. By establishing these genetic relationships using Cr isotopes, it is now evident that the differentiation activity sampled by IVA irons and pallasites represents processes occurring on a diverse set of parent bodies in the early Solar System. [1] Ruzicka and Hutson (2006) MAPS, 41, 1959. [2] Shukolyukov and Lugmair (2006) EPSL, 250, 200.

Short-term measurement of carbon isotope fractionation in plants

International Nuclear Information System (INIS)

O'Leary, M.H.; Treichel, I.; Rooney, M.

1986-01-01

Combustion-based studies of the carbon-13 content of plants give only an integrated, long-term value for the isotope fractionation associated with photosynthesis. A method is described here which permits determination of this isotope fractionation in 2 to 3 hours. To accomplish this, the plant is enclosed in a glass chamber, and the quantity and isotopic content of the CO 2 remaining in the atmosphere are monitored during photosynthesis. Isotope fractionation studies by this method give results consistent with what is expected from combustion studies of C 3 , C 4 , and Crassulacean acid metabolism plants. This method will make possible a variety of new studies of environmental and species effects in carbon isotope fractionation

Temperature dependence of carbon isotope fractionation in CAM plants

International Nuclear Information System (INIS)

Deleens, E.; Treichel, I.; O'Leary, M.H.

1985-01-01

The carbon isotope fractionation associated with nocturnal malic acid synthesis in Kalanchoë daigremontiana and Bryophyllum tubiflorum was calculated from the isotopic composition of carbon-4 of malic acid, after appropriate corrections. In the lowest temperature treatment (17 degrees C nights, 23 degrees C days), the isotope fractionation for both plants is -4 per thousand (that is, malate is enriched in (13)C relative to the atmosphere). For K. daigremontiana, the isotope fractionation decreases with increasing temperature, becoming approximately 0 per thousand at 27 degrees C/33 degrees C. Detailed analysis of temperature effects on the isotope fractionation indicates that stomatal aperture decreases with increasing temperature and carboxylation capacity increases. For B. tubiflorum, the temperature dependence of the isotope fractionation is smaller and is principally attributed to the normal temperature dependences of the rates of diffusion and carboxylation steps. The small change in the isotopic composition of remaining malic acid in both species which is observed during deacidification indicates that malate release, rather than decarboxylation, is rate limiting in the deacidification process

Temperature dependence of carbon isotope fractionation in CAM plants

Energy Technology Data Exchange (ETDEWEB)

Deleens, E.; Treichel, I.; O' Leary, M.H.

1985-09-01

The carbon isotope fractionation associated with nocturnal malic acid synthesis in Kalanchoe daigremontiana and Bryophyllum tubiflorum was calculated from the isotopic composition of carbon-4 of malic acid, after appropriate corrections. In the lowest temperature treatment (17/sup 0/C nights, 23/sup 0/C days), the isotope fractionation for both plants is -4% per thousand (that is, malate is enriched in /sup 13/C relative to the atmosphere). For K. daigremontiana, the isotope fractionation decreases with increasing temperature, becoming approximately 0% per thousand at 27/sup 0/C/33/sup 0/C. Detailed analysis of temperature effects on the isotope fractionation indicates that stomatal aperture decreases with increasing temperature and carboxylation capacity increases. For B. tubiflorum, the temperature dependence of the isotope fractionation is smaller and is principally attributed to the normal temperature dependences of the rates of diffusion and carboxylation steps. The small change in the isotopic composition of remaining malic acid in both species which is observed during deacidification indicates that malate release, rather than decarboxylation, is rate limiting in the deacidification process. 28 references, 1 figure, 4 tables.

Fractionation of boron isotopes in Icelandic hydrothermal systems

International Nuclear Information System (INIS)

Aggarwal, J.K.

1995-01-01

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 δ 1 1B 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 δ 1 1B than the high temperature systems, indicating fractionation of boron due to absorption of the lighter isotope onto secondary minerals. Fractionation of boron in carbonate deposits may indicate the level of equilibrium attained within the systems. (author). 14 refs., 2 figs

Sulfur isotope fractionation during heterogeneous oxidation of SO2 on mineral dust

Directory of Open Access Journals (Sweden)

P. Hoppe

2012-06-01

Full Text Available Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917±0.0046, which is in agreement with previous measurements of aqueous SO2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH had an overall fractionation factor of αhet = 1.0096±0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ~40%. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. All the investigated reactions showed mass-dependent fractionation of 33S relative to 34S. A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85% of sulfate production with a fractionation factor of α34 = 1.012±0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO2 by H2O2 and O3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12% of the sulfate production, and oxidation on clay minerals

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

International Nuclear Information System (INIS)

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

1986-01-01

The accuracy and precision of the doubly labeled water method for measuring energy expenditure are influenced by isotope fractionation during evaporative water loss and CO 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 0 C, and the latter was kinetically fractionated. Sweat and urine were unfractionated. By use of isotopic balance models, the fraction of water lost via fractionating routes was estimated from the isotopic abundances of body water, local drinking water, and dietary solids. Fractionated water loss averaged 23% (SD = 10%) of water turnover, which agreed with our previous estimates based on metabolic rate, but there was a systematic difference between the results based on O 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 2 production

Cl and C isotope analysis to assess the effectiveness of chlorinated ethene degradation by zero-valent iron: Evidence from dual element and product isotope values

International Nuclear Information System (INIS)

Audí-Miró, Carme; Cretnik, Stefan; Otero, Neus; Palau, Jordi; Shouakar-Stash, Orfan; Soler, Albert

2013-01-01

Highlights: ► TCE and cis-DCE Cl isotope fractionation was investigated for the first time with ZVI. ► A C–Cl bond is broken in the rate-limiting step during ethylene ZVI dechlorination. ► Dual C/Cl isotope plot is a promising tool to discriminate abiotic degradation. ► Product-related carbon isotopic fractionation gives evidence of abiotic degradation. ► Hydrogenolysis and β-dichloroelimination pathways occur simultaneously. - Abstract: This study investigated C and, for the first time, Cl isotope fractionation of trichloroethene (TCE) and cis-dichloroethene (cis-DCE) during reductive dechlorination by cast zero-valent iron (ZVI). Hydrogenolysis and β-dichloroelimination pathways occurred as parallel reactions, with ethene and ethane deriving from the β-dichloroelimination pathway. Carbon isotope fractionation of TCE and cis-DCE was consistent for different batches of Fe studied. Transformation of TCE and cis-DCE showed Cl isotopic enrichment factors (ε Cl ) of −2.6‰ ± 0.1‰ (TCE) and −6.2‰ ± 0.8‰ (cis-DCE), with Apparent Kinetic Isotope Effects (AKIE Cl ) for Cl of 1.008 ± 0.001 (TCE) and 1.013 ± 0.002 (cis-DCE). This indicates that a C–Cl bond breakage is rate-determining in TCE and cis-DCE transformation by ZVI. Two approaches were investigated to evaluate if isotope fractionation analysis can distinguish the effectiveness of transformation by ZVI as opposed to natural biodegradation. (i) Dual isotope plots. This study reports the first dual (C, Cl) element isotope plots for TCE and cis-DCE degradation by ZVI. The pattern for cis-DCE differs markedly from that reported for biodegradation of the same compound by KB-1, a commercially available Dehalococcoides-containing culture. The different trends suggest an expedient approach to distinguish abiotic and biotic transformation, but this needs to be confirmed in future studies. (ii) Product-related isotope fractionation. Carbon isotope ratios of the hydrogenolysis product cis

Relationship between microbial sulfate reduction rates and sulfur isotopic fractionation

Science.gov (United States)

Matsu'Ura, F.

2009-12-01

Sulfate reduction is one of the common processes to obtain energy for certain types of microorganisms.They use hydrogen gas or organic substrates as electron donor and sulfates as electron acceptor, and reduce sulfates to sulfides. Sulfate reducing microbes extend across domains Archea and Bacteria, and are believed to be one of the earliest forms of terrestrial life (Shen 2004). The origin of 34S-depleted (light) sulfide sulfur, especially δ34S vials, which contain 40ml of liquid culture media slightly modified from DSMZ #63 medium.Excess amount of Fe (II) is added to the DSMZ#63 medium to precipitate sulfide as iron sulfide. The vials were incubated at 25°C, 30°C, and 37°C, respectively. 21 vials were used for one temperature and sulfide and sulfate was collected from each three glass vials at every 12 hours from 72 hours to 144 hours after start of incubation. The sulfide was precipitated as iron sulfide and the sulfate was precipitated as barite. Sulfur isotope compositions of sulfate and sulfide were measured by standard method using Delta Plus mass-spectrometer. [Results and Discussion] The fractionation between sulfide and sulfate ranged from 2.7 to 11.0. The fractionation values varied among the different incubation temperature and growth phase of D. desulfuricans. The maximum fractionation values of three incubation temperatures were 9.9, 11.0, and 9.7, for 25 °C, 30°C, and 37°C, respectively. These results were different from standard model and Canfield et al. (2006). I could not find the clear correlation between ∂34S values and incubation temperatures in this experiment. The measured fractionation values during the incubation varied with incubation stage. The fractionation values clearly increased with incubation time at every temperature, and at 25°C ∂34S value was 3.6 at the 72h and it increased to 7.9 at 144 hours. This indicated the difference of sulfate reduction rate due to the growth phase of SRB. In the early logarithmic growth phase

Fraction-specific controls on the trace element distribution in iron formations : Implications for trace metal stable isotope proxies

NARCIS (Netherlands)

Oonk, Paul B.H.; Tsikos, Harilaos; Mason, Paul R.D.; Henkel, Susann; Staubwasser, Michael; Fryer, Lindi; Poulton, Simon W.; Williams, Helen M.

2017-01-01

Iron formations (IFs) are important geochemical repositories that provide constraints on atmospheric and ocean chemistry, prior to and during the onset of the Great Oxidation Event. Trace metal abundances and their Mo-Cr-U isotopic ratios have been widely used for investigating ocean redox processes

Molybdenum isotope fractionation and speciation in a euxinic lake—Testing ways to discern isotope fractionation processes in a sulfidic setting

Energy Technology Data Exchange (ETDEWEB)

Dahl, Tais W.; Wirth, Stefanie B.

2017-06-01

The molybdenum (Mo) isotope composition in euxinic shales has been used as a proxy for the global distribution of anoxic conditions in ancient oceans, and since more recently also as a proxy for sulfide concentrations in depositional environments. However, there is currently no way to distinguish isotope fractionation at low bottom water sulfide concentrations in ‘local’ basins from ‘global’ secular isotope variations associated with changing seawater composition. This uncertainty is challenging the use of Mo isotopes for paleoceanographic reconstructions. To explore this further, we present new data from sediments deposited over the past ~ 9800 years in one of the best studied euxinic localities in the world: Lake Cadagno in Switzerland. The sample set allows us to test ways to discern isotope fractionation processes at play in a highly restricted euxinic basin. Most of our drill core samples (n = 18) show high δ98Mo values similar to previously studied shallow sediments, indicative of quantitative Mo removal from the water column (Dahl et al. 2010a). However, a few samples (n = 3) deposited between about 1200 and 3400 years ago carry low δ98Mo values and have been isotopically fractionated in the lake. Sedimentological and geochemical characterizations show that these δ98Mo-fractionated sediments formed during times of frequent injection of O2- and sediment-rich river water into the deep sulfidic water column. A positive correlation between δ98Mo and sedimentary Mo contents suggests that isotope fractionation occurred during times of non-quantitative Mo removal, although Mn-oxide cycling at the chemocline might also contribute a subordinate proportion of (98Mo-depleted) molybdenum into the sulfidic zone. Sedimentary Mo/U enrichments relative to oxic lake water further supports the hypothesis that a particulate Mo shuttle was most efficient during times of quantitative Mo removal. Therefore, periods with inefficient Mo capture are ascribed to

Calcium Isotope Geochemistry: Research Horizons and Nanoscale Fractionation Processes

Science.gov (United States)

Watkins, J. M.; Depaolo, D. J.; Richter, F. M.; Fantle, M. S.; Simon, J. I.; Ryerson, F. J.; Ewing, S. A.; Turchyn, A. V.; Yang, W.; Owens, T. L.

2008-12-01

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 ‰, but gradual small improvements in analytical capability now yield 0.05 to 0.1 ‰ 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. 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

Kinetic isotopic fractionation during diffusion of ionic species in water

Science.gov (United States)

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

2006-01-01

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

Iron absorption from beans with different contents of iron, evaluated by stable isotopes.

Science.gov (United States)

Junqueira-Franco, Márcia Varella Morandi; Dutra de Oliveira, José Eduardo; Nutti, Marilia Regini; Pereira, Helton Santos; Carvalho, José Luiz Vianna de; Abrams, Steven A; Brandão, Camila Fernanda Cunha; Marchini, Júlio Sérgio

2018-06-01

The introduction of biofortified foods such as beans with higher iron content may be a useful tool in preventing iron deficiency. The biofortification aims to reach the root of the problem of malnutrition, targets the neediest population, uses embedded distribution mechanisms, is scientifically feasible and effective in terms of cost, and complements other ongoing interventions to control micronutrient deficiency. However, to ensure effectiveness, measurement of the absorption of minerals is essential. The objective of this study was to evaluate the iron bioavailability of common bean BRS Pontal (PO), targeted for biofortification, compared with common bean BRS Estilo in man through reliable techniques that have not been previously used in Brazil. The study included 29 young adult volunteers divided into 2 groups: Group CB (13 subjects) received 100 g of common beans (BRS-Estilo) cooked labeled with iron-58 ( 58 Fe) and Group TBB (16 patients) received 100 g common bean target for iron biofortification (BRS-Pontal), cooked and labeled with iron58 ( 58 Fe). The next day they received the reference dose of ferrous sulfate enriched iron-57 ( 57 Fe). Isotopic evaluation of iron for measurement of iron incorporation into erythrocytes was performed 14 days after consumption. The beans used, were produced, through conventional breeding program, by EMBRAPA/Rice and Beans. The iron absorption was evaluated by assessing the isotopic enrichment of the stable isotope. Mean iron absorption from the meal with common beans was 0.409% (±0.040%) and mean iron incorporation from the meal with target beans for biofortification 0.407% (±0.038%) and did not differ between the groups. This study tested the iron absorption from a single bean meal in healthy volunteers or non anemics, In the present study the iron absorption ratio from common bean Pontal (PO), targeted for biofortification and compared with common bean BRS Estilo was not significantly different. The iron concentration

Iron Isotope Variations in Reduced Groundwater and in Drinking Water Supplies: A Case Study of Hanoi, Vietnam

Science.gov (United States)

Teutsch, N.; Berg, M.; von Gunten, U.; Halliday, A.

2004-12-01

In reduced groundwater iron is involved in biotic and abiotic transformation processes, both of which could lead to iron isotope fractionation. The reduced groundwater aquifers in the area of the Vietnamese capital of Hanoi are the main drinking water sources for the city. These groundwaters contain arsenic, which imposes a serious health threat to millions of people. Dissolved arsenic is related to the reducing conditions prevalent in the groundwater, and iron and arsenic contents are correlated in the sediments. We are employing iron isotope composition as a tool to better understand the processes leading to the transformation of iron in the groundwater and its role in various biogeochemical processes in reduced environments. Drinking water is supplied to the city of Hanoi from several water treatment plants (WTP) which pump the raw groundwater from a lower aquifer, while the rural surroundings pump untreated groundwater from an upper aquifer by private tubewells. Surface water from the Red River delta is the main source of recharge to these two aquifers. Due to high content of particulate natural organic matter (NOM) in the sediment leading to extensive microbial activity, the groundwaters are anoxic and rich in dissolved iron(II). The iron(II) removal in the WTPs is carried by a multi-step treatment including aeration, settling, filtration, and chlorination. We have collected natural groundwater samples for isotopic analysis from two aquifers at several locations, a groundwater depth profile and its corresponding sediment phases from the upper aquifer and the underlying aquitard, raw and treated water from several WTPs, as well as the corresponding iron(III) precipitates. The iron concentrations of groundwaters analysed in this study range from 3 to 28 mg/L and δ 57Fe (57/54 deviation from IRMM 014) values vary between -1.2 and +1.5 ‰ . The sediment depth profile has a δ 57Fe around +0.3 ‰ , which implies that the high values obtained in the groundwater

Tungsten isotopic compositions of iron meteorites: Chronological constraints vs. cosmogenic effects

Science.gov (United States)

Markowski, A.; Quitté, G.; Halliday, A. N.; Kleine, T.

2006-02-01

High-precision W isotopic compositions are presented for 35 iron meteorites from 7 magmatic groups (IC, IIAB, IID, IIIAB, IIIF, IVA, and IVB) and 3 non-magmatic groups (IAB, IIICD, and IIE). Small but resolvable isotopic variations are present both within and between iron meteorite groups. Variations in the 182W/ 184W ratio reflect either time intervals of metal-silicate differentiation, or result from the burnout of W isotopes caused by a prolonged exposure to galactic cosmic rays. Calculated apparent time spans for some groups of magmatic iron meteorites correspond to 8.5 ± 2.1 My (IID), 5.1 ± 2.3 My (IIAB), and 5.3 ± 1.3 My (IVB). These time intervals are significantly longer than those predicated from models of planetesimal accretion. It is shown that cosmogenic effects can account for a large part of the W isotopic variation. No simple relationship exists with exposure ages, compromising any reliable method of correction. After allowance for maximum possible cosmogenic effects, it is found that there is no evidence that any of the magmatic iron meteorites studied here have initial W isotopic compositions that differ from those of Allende CAIs [ ɛ182W = - 3.47 ± 0.20; [T. Kleine, K. Mezger, H. Palme, E. Scherer and C. Münker, Early core formation in asteroids and late accretion of chondrite parent bodies: evidence from 182Hf- 182W in CAIs, metal-rich chondrites and iron meteorites, Geochim. Cosmochim. Acta (in press)]. Cosmogenic corrections cannot yet be made with sufficient accuracy to obtain highly precise ages for iron meteorites. Some of the corrected ages nevertheless require extremely early metal-silicate segregation no later than 1 My after formation of CAIs. Therefore, magmatic iron meteorites appear to provide the best examples yet identified of material derived from the first planetesimals that grew by runaway growth, as modelled in dynamic simulations. Non-magmatic iron meteorites have a more radiogenic W isotopic composition than magmatic

Diversity of sulfur isotope fractionations by sulfate-reducing prokaryotes

DEFF Research Database (Denmark)

Detmers, Jan; Brüchert, Volker; Habicht, K S

2001-01-01

Batch culture experiments were performed with 32 different sulfate-reducing prokaryotes to explore the diversity in sulfur isotope fractionation during dissimilatory sulfate reduction by pure cultures. The selected strains reflect the phylogenetic and physiologic diversity of presently known...... sulfate reducers and cover a broad range of natural marine and freshwater habitats. Experimental conditions were designed to achieve optimum growth conditions with respect to electron donors, salinity, temperature, and pH. Under these optimized conditions, experimental fractionation factors ranged from 2.......0 to 42.0 per thousand. Salinity, incubation temperature, pH, and phylogeny had no systematic effect on the sulfur isotope fractionation. There was no correlation between isotope fractionation and sulfate reduction rate. The type of dissimilatory bisulfite reductase also had no effect on fractionation...

Gallium isotope fractionation during Ga adsorption on calcite and goethite

Science.gov (United States)

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

Isotope pattern deconvolution as a tool to study iron metabolism in plants.

Science.gov (United States)

Rodríguez-Castrillón, José Angel; Moldovan, Mariella; García Alonso, J Ignacio; Lucena, Juan José; García-Tomé, Maria Luisa; Hernández-Apaolaza, Lourdes

2008-01-01

Isotope pattern deconvolution is a mathematical technique for isolating distinct isotope signatures from mixtures of natural abundance and enriched tracers. In iron metabolism studies measurement of all four isotopes of the element by high-resolution multicollector or collision cell ICP-MS allows the determination of the tracer/tracee ratio with simultaneous internal mass bias correction and lower uncertainties. This technique was applied here for the first time to study iron uptake by cucumber plants using 57Fe-enriched iron chelates of the o,o and o,p isomers of ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA) and ethylenediamine tetraacetic acid (EDTA). Samples of root, stem, leaves, and xylem sap, after exposure of the cucumber plants to the mentioned 57Fe chelates, were collected, dried, and digested using nitric acid. The isotopic composition of iron in the samples was measured by ICP-MS using a high-resolution multicollector instrument. Mass bias correction was computed using both a natural abundance iron standard and by internal correction using isotope pattern deconvolution. It was observed that, for plants with low 57Fe enrichment, isotope pattern deconvolution provided lower tracer/tracee ratio uncertainties than the traditional method applying external mass bias correction. The total amount of the element in the plants was determined by isotope dilution analysis, using a collision cell quadrupole ICP-MS instrument, after addition of 57Fe or natural abundance Fe in a known amount which depended on the isotopic composition of the sample.

Isotope pattern deconvolution as a tool to study iron metabolism in plants

Energy Technology Data Exchange (ETDEWEB)

Rodriguez-Castrillon, Jose A.; Moldovan, Mariella; Garcia Alonso, J.I. [University of Oviedo, Department of Physical and Analytical Chemistry, Oviedo (Spain); Lucena, Juan J.; Garcia-Tome, Maria L.; Hernandez-Apaolaza, Lourdes [Autonoma University of Madrid, Department of Agricultural Chemistry, Madrid (Spain)

2008-01-15

Isotope pattern deconvolution is a mathematical technique for isolating distinct isotope signatures from mixtures of natural abundance and enriched tracers. In iron metabolism studies measurement of all four isotopes of the element by high-resolution multicollector or collision cell ICP-MS allows the determination of the tracer/tracee ratio with simultaneous internal mass bias correction and lower uncertainties. This technique was applied here for the first time to study iron uptake by cucumber plants using {sup 57}Fe-enriched iron chelates of the o,o and o,p isomers of ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA) and ethylenediamine tetraacetic acid (EDTA). Samples of root, stem, leaves, and xylem sap, after exposure of the cucumber plants to the mentioned {sup 57}Fe chelates, were collected, dried, and digested using nitric acid. The isotopic composition of iron in the samples was measured by ICP-MS using a high-resolution multicollector instrument. Mass bias correction was computed using both a natural abundance iron standard and by internal correction using isotope pattern deconvolution. It was observed that, for plants with low {sup 57}Fe enrichment, isotope pattern deconvolution provided lower tracer/tracee ratio uncertainties than the traditional method applying external mass bias correction. The total amount of the element in the plants was determined by isotope dilution analysis, using a collision cell quadrupole ICP-MS instrument, after addition of {sup 57}Fe or natural abundance Fe in a known amount which depended on the isotopic composition of the sample. (orig.)

Reduction of hexavalent chromium by ferrous iron: A process of chromium isotope fractionation and its relevance to natural environments

DEFF Research Database (Denmark)

Døssing, Lasse Nørbye; Dideriksen, Knud; Stipp, Susan Louise Svane

2011-01-01

Stable chromium (Cr) isotopes can be used as a tracer for changing redox conditions in modern marine systems and in the geological record. We have investigated isotope fractionation during reduction of Cr(VI)aq by Fe(II)aq. Reduction of Cr(VI)aq by Fe(II)aq in batch experiments leads to significant...

Fractionation of Stable Isotopes in Atmospheric Aerosol Reactions

DEFF Research Database (Denmark)

Meusinger, Carl

-independent) fractionation processes of stable isotopes of C, N, O and S in order to investigate three different systems related to aerosols: 1. Post-depositional processes of nitrate in snow that obscure nitrate ice core records 2. Formation and aging of secondary organic aerosol generated by ozonolysis of X...... reactions and undergo complex chemical and physical changes during their lifetimes. In order to assess processes that form and alter aerosols, information provided by stable isotopes can be used to help constrain estimates on the strength of aerosol sources and sinks. This thesis studies (mass...... as required. The kndings provide important results for the studies' respective felds, including a description of the isotopic fractionation and quantum yield of nitrate photolysis in snow, equilibrium fractionation in secondary organic aerosol and fractionation constants of different oxidation pathways of SO2....

The behavior of iron and zinc stable isotopes accompanying the subduction of mafic oceanic crust: A case study from Western Alpine ophiolites

Science.gov (United States)

Inglis, Edward C.; Debret, Baptiste; Burton, Kevin W.; Millet, Marc-Alban; Pons, Marie-Laure; Dale, Christopher W.; Bouilhol, Pierre; Cooper, Matthew; Nowell, Geoff M.; McCoy-West, Alex J.; Williams, Helen M.

2017-07-01

Arc lavas display elevated Fe3+/ΣFe ratios relative to MORB. One mechanism to explain this is the mobilization and transfer of oxidized or oxidizing components from the subducting slab to the mantle wedge. Here we use iron and zinc isotopes, which are fractionated upon complexation by sulfide, chloride, and carbonate ligands, to remark on the chemistry and oxidation state of fluids released during prograde metamorphism of subducted oceanic crust. We present data for metagabbros and metabasalts from the Chenaillet massif, Queyras complex, and the Zermatt-Saas ophiolite (Western European Alps), which have been metamorphosed at typical subduction zone P-T conditions and preserve their prograde metamorphic history. There is no systematic, detectable fractionation of either Fe or Zn isotopes across metamorphic facies, rather the isotope composition of the eclogites overlaps with published data for MORB. The lack of resolvable Fe isotope fractionation with increasing prograde metamorphism likely reflects the mass balance of the system, and in this scenario Fe mobility is not traceable with Fe isotopes. Given that Zn isotopes are fractionated by S-bearing and C-bearing fluids, this suggests that relatively small amounts of Zn are mobilized from the mafic lithologies in within these types of dehydration fluids. Conversely, metagabbros from the Queyras that are in proximity to metasediments display a significant Fe isotope fractionation. The covariation of δ56Fe of these samples with selected fluid mobile elements suggests the infiltration of sediment derived fluids with an isotopically light signature during subduction.

Isotopic fractionation of tritium in biological systems.

Science.gov (United States)

Le Goff, Pierre; Fromm, Michel; Vichot, Laurent; Badot, Pierre-Marie; Guétat, Philippe

2014-04-01

Isotopic fractionation of tritium is a highly relevant issue in radiation protection and requires certain radioecological considerations. Sound evaluation of this factor is indeed necessary to determine whether environmental compartments are enriched/depleted in tritium or if tritium is, on the contrary, isotopically well-distributed in a given system. The ubiquity of tritium and the standard analytical methods used to assay it may induce biases in both the measurement and the signification that is accorded to the so-called fractionation: based on an exhaustive review of the literature, we show how, sometimes large deviations may appear. It is shown that when comparing the non-exchangeable fraction of organically bound tritium (neOBT) to another fraction of tritium (e.g. tritiated water) the preparation of samples and the measurement of neOBT reported frequently led to underestimation of the ratio of tritium to hydrogen (T/H) in the non-exchangeable compartment by a factor of 5% to 50%. In the present study, corrections are proposed for most of the biological matrices studied so far. Nevertheless, the values of isotopic fractionation reported in the literature remain difficult to compare with each other, especially since the physical quantities and units often vary between authors. Some improvements are proposed to better define what should encompass the concepts of exchangeable and non-exchangeable fractions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Diffusive Fractionation of Lithium Isotopes in Olivine Grain Boundaries

Science.gov (United States)

Homolova, V.; Watson, E. B.

2012-12-01

Diffusive fractionation of isotopes has been documented in silicate melts, aqueous fluids, and single crystals. In polycrystalline rocks, the meeting place of two grains, or grain boundaries, may also be a site of diffusive fractionation of isotopes. We have undertaken an experimental and modeling approach to investigate diffusive fractionation of lithium (Li) isotopes by grain boundary diffusion. The experimental procedure consists of packing a Ni metal capsule with predominantly ground San Carlos olivine and subjecting the capsule to 1100C and 1GPa for two days in a piston cylinder apparatus to create a nominally dry, 'dunite rock'. After this synthesis step, the capsule is sectioned and polished. One of the polished faces of the 'dunite rock' is then juxtaposed to a source material of spodumene and this diffusion couple is subject to the same experimental conditions as the synthesis step. Li abundances and isotopic profiles (ratios of count rates) were analyzed using LA-ICP-MS. Li concentrations linearly decrease away from the source from 550ppm to the average concentration of the starting olivine (2.5ppm). As a function of distance from the source, the 7Li/6Li ratio decreases to a minimum before increasing to the background ratio of the 'dunite rock'. The 7Li/6Li ratio minimum coincides with the lowest Li concentrations above average 'dunite rock' abundances. The initial decrease in the 7Li/6Li ratio is similar to that seen in other studies of diffusive fractionation of isotopes and is thought to be caused by the higher diffusivity (D) of the lighter isotope relative to the heavier isotope. The relationship between D and mass (m) is given by (D1/D2) =(m2/m1)^β, where β is an empirical fractionation factor; 1 and 2 denote the lighter and heavier isotope, respectively. A fit to the Li isotopic data reveals an effective DLi of ~1.2x10^-12 m/s^2 and a β of 0.1. Numerical modelling was utilized to elucidate the relationship between diffusive fractionation

The lack of potassium-isotopic fractionation in Bishunpur chondrules

Science.gov (United States)

Alexander, C.M. O'D.; Grossman, J.N.; Wang, Jingyuan; Zanda, B.; Bourot-Denise, M.; Hewins, R.H.

2000-01-01

In a search for evidence of evaporation during chondrule formation, the mesostases of 11 Bishunpur chondrules and melt inclusions in olivine phenocrysts in 7 of them have been analyzed for their alkali element abundances and K-isotopic compositions. Except for six points, all areas of the chondrules that were analyzed had δ41K compositions that were normal within error (typically ±3%, 2s̀). The six “anomalous” points are probably all artifacts. Experiments have shown that free evaporation of K leads to large 41K enrichments in the evaporation residues, consistent with Rayleigh fractionation. Under Rayleigh conditions, a 3% enrichment in δ41K is produced by ∼12% loss of K. The range of L-chondrite-normalized K/Al ratios (a measure of the K-elemental fractionation) in the areas analyzed vary by almost three orders of magnitude. If all chondrules started out with L-chondrite-like K abundances and the K loss occurred via Rayleigh fractionation, the most K-depleted chondrules would have had compositions of up to δ41K ≅ 200%. Clearly, K fractionation did not occur by evaporation under Rayleigh conditions. Yet experiments and modeling indicate that K should have been lost during chondrule formation under currently accepted formation conditions (peak temperature, cooling rate, etc.). Invoking precursors with variable alkali abundances to produce the range of K/Al fractionation in chondrules does not explain the K-isotopic data because any K that was present should still have experienced sufficient loss during melting for there to have been a measurable isotopic fractionation. If K loss and isotopic fractionation was inevitable during chondrule formation, the absence of K-isotopic fractionation in Bishunpur chondrules requires that they exchanged K with an isotopically normal reservoir during or after formation. There is evidence for alkali exchange between chondrules and rim-matrix in all unequilibrated ordinary chondrites. However, melt inclusions can have

A 1-h time interval between a meal containing iron and consumption of tea attenuates the inhibitory effects on iron absorption: a controlled trial in a cohort of healthy UK women using a stable iron isotope.

Science.gov (United States)

Ahmad Fuzi, Salma F; Koller, Dagmar; Bruggraber, Sylvaine; Pereira, Dora Ia; Dainty, Jack R; Mushtaq, Sohail

2017-12-01

Background: Tea has been shown to be a potent inhibitor of nonheme iron absorption, but it remains unclear whether the timing of tea consumption relative to a meal influences iron bioavailability. Objective: The aim of the study was to investigate the effect of a 1-h time interval of tea consumption on nonheme iron absorption in an iron-containing meal in a cohort of iron-replete, nonanemic female subjects with the use of a stable isotope ( 57 Fe). Design: Twelve women (mean ± SD age: 24.8 ± 6.9 y) were administered a standardized porridge meal extrinsically labeled with 4 mg 57 Fe as FeSO 4 on 3 separate occasions, with a 14-d time interval between each test meal (TM). The TM was administered with water (TM-1), with tea administered simultaneously (TM-2), and with tea administered 1 h postmeal (TM-3). Fasted venous blood samples were collected for iron isotopic analysis and measurement of iron status biomarkers. Fractional iron absorption was estimated by the erythrocyte iron incorporation method. Results: Iron absorption was 5.7% ± 8.5% (TM-1), 3.6% ± 4.2% (TM-2), and 5.7% ± 5.4% (TM-3). Mean fractional iron absorption was found to be significantly higher (2.2%) when tea was administered 1 h postmeal (TM-3) than when tea was administered simultaneously with the meal (TM-2) ( P = 0.046). An ∼50% reduction in the inhibitory effect of tea (relative to water) was observed, from 37.2% (TM-2) to 18.1% (TM-3). Conclusions: This study shows that tea consumed simultaneously with an iron-containing porridge meal leads to decreased nonheme iron absorption and that a 1-h time interval between a meal and tea consumption attenuates the inhibitory effect, resulting in increased nonheme iron absorption. These findings are not only important in relation to the management of iron deficiency but should also inform dietary advice, especially that given to those at risk of deficiency. This trial was registered at clinicaltrials.gov as NCT02365103. © 2017 American Society for

Microbial production of isotopically light iron(II) in a modern chemically precipitated sediment and implications for isotopic variations in ancient rocks

Science.gov (United States)

Tangalos, G.E.; Beard, B.L.; Johnson, C.M.; Alpers, Charles N.; Shelobolina, E.S.; Xu, H.; Konishi, H.; Roden, E.E.

2012-01-01

The inventories and Fe isotope composition of aqueous Fe(II) and solid-phase Fe compounds were quantified in neutral-pH, chemically precipitated sediments downstream of the Iron Mountain acid mine drainage site in northern California, USA. The sediments contain high concentrations of amorphous Fe(III) oxyhydroxides [Fe(III)am] that allow dissimilatory iron reduction (DIR) to predominate over Fe–S interactions in Fe redox transformation, as indicated by the very low abundance of Cr(II)-extractable reduced inorganic sulfur compared with dilute HCl-extractable Fe. δ56Fe values for bulk HCl- and HF-extractable Fe were ≈ 0. These near-zero bulk δ56Fe values, together with the very low abundance of dissolved Fe in the overlying water column, suggest that the pyrite Fe source had near-zero δ56Fe values, and that complete oxidation of Fe(II) took place prior to deposition of the Fe(III) oxide-rich sediment. Sediment core analyses and incubation experiments demonstrated the production of millimolar quantities of isotopically light (δ56Fe ≈ -1.5 to -0.5‰) aqueous Fe(II) coupled to partial reduction of Fe(III)am by DIR. Trends in the Fe isotope composition of solid-associated Fe(II) and residual Fe(III)am are consistent with experiments with synthetic Fe(III) oxides, and collectively suggest an equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)am of approximately -2‰. These Fe(III) oxide-rich sediments provide a model for early diagenetic processes that are likely to have taken place in Archean and Paleoproterozoic marine sediments that served as precursors for banded iron formations. Our results suggest pathways whereby DIR could have led to the formation of large quantities of low-δ56Fe minerals during BIF genesis.

Iron Isotopic Compositions of Troilite (FeS) Inclusions from Iron Meteorites

Energy Technology Data Exchange (ETDEWEB)

Cook, David L.; Schönbächler, Maria, E-mail: david.cook@erdw.ethz.ch [Institut für Geochemie und Petrologie, ETH Zürich, Clausiusstrasse 25, 8092 Zürich (Switzerland)

2017-10-01

We report non-mass-dependent Fe isotopic data for troilite (FeS) inclusions from 10 iron meteorites, representing both non-magmatic (IAB) and magmatic groups (IIAB, IIIAB, IVA). No resolvable variations are present in the most neutron-rich isotope ({sup 58}Fe), but small deficits (≈−0.1 ε ) in {sup 56}Fe were observed in several inclusions. With the exception of several Ca–Al-rich inclusions in primitive meteorites, these are the first reported non-mass-dependent variations in Fe isotopes for material formed in the early solar system. Nucleosynthetic variations in Ni isotopes were previously reported in these same samples. The effects in Fe isotopes are not correlated with those in Ni, which suggests that the origins of the isotopic variations are decoupled from one another. The {sup 56}Fe deficits may represent incomplete mixing of the precursor dust in the protoplanetary disk. Alternatively, a parent body process (e.g., irradiation by galactic cosmic rays) may have modified the Fe isotopic compositions of some inclusions, which initially had homogeneous Fe isotopic compositions.

Soil tension mediates isotope fractionation during soil water evaporation

Science.gov (United States)

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

Chromium Stable Isotope Fractionation - An Indicator of Hexavalent Chromium Reduction.

Science.gov (United States)

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

2001-12-01

Chromium is a common anthropogenic contaminant in surface water and ground water, and is also of interest in oceanography. It is redox-active; the two common valences in natural waters are Cr(VI), which is highly soluble and toxic, and Cr(III), which is relatively insoluble. Redox reactions thus control Cr mobility in aqueous solutions, and reduction of Cr(VI) to Cr(III) is the most important reaction controlling attenuation of Cr in groundwater. Our results show that Cr(VI) reduction favors the lighter isotopes and leads to enrichment of heavier isotopes in the remaining Cr(VI). Cr isotope measurements thus show great promise as indicators of Cr(VI) reduction. We report here the first measurements of the magnitude of Cr isotope fractionation during Cr(VI) reduction and variations in δ 53Cr values obtained from three contaminated sites. Experiments were conducted to measure Cr isotope fractionation during Cr(VI) reduction by suspensions of magnetite and unamended sediments from a local pond, Urbana, IL and San Francisco Estuary near Martinez, CA. Suspensions were incubated anaerobically with constant shaking, and complete Cr(VI) reduction occurred within a few days. Cr(VI) from intermediate time points in the experiments was purified via ion exchange and 53Cr/52Cr ratios were measured via TIMS with a double isotope spike. The instantaneous per mil fractionation, ɛ , was calculated assuming a Rayleigh fractionation model. The ɛ for Cr(VI) reduction on magnetite surfaces yielded a fractionation of -3.5 ‰ . The ɛ values for the pond and estuary sediments were -3.5 ‰ and -3.3 ‰ respectively. The size of this Cr isotope fractionation is encouraging, as current precision is 0.2 \\permil. δ 53Cr values in dissolved Cr(VI) from three contaminated sites range from 1.1 ‰ to 5.8 ‰ , suggesting that Cr(VI) reduction has occurred and has induced isotopic fractionation in these settings. δ 53Cr values measured from Cr(VI) in plating baths show little or no

Rapid collection of iron hydroxide for determination of Th isotopes in seawater

Energy Technology Data Exchange (ETDEWEB)

Okubo, Ayako, E-mail: okubo.ayako@jaea.go.jp [Japan Atomic Energy Agency, Research Group for Analytical Chemistry (Japan); Obata, Hajime, E-mail: obata@aori.u-tokyo.ac.jp [Atmosphere Ocean Research Institute, The University of Tokyo (Japan); Magara, Masaaki, E-mail: magara.masaaki@jaea.go.jp [Japan Atomic Energy Agency, Research Group for Analytical Chemistry (Japan); Kimura, Takaumi, E-mail: kimura.takaumi@jaea.go.jp [Japan Atomic Energy Agency, Research Group for Analytical Chemistry (Japan); Ogawa, Hiroshi, E-mail: hogawa@aori.u-tokyo.ac.jp [Atmosphere Ocean Research Institute, The University of Tokyo (Japan)

2013-12-04

Graphical abstract: -- Highlights: •DIAION CR-20 chelating resin has successfully collected iron-hydroxide with Th isotopes. •Ferric ions in the iron hydroxide were bonded to functional groups of the chelating resin. •The time of preconcentration step was markedly reduced from a few days to 3–4 h. -- Abstract: This work introduces a novel method of recovery of iron hydroxide using a DIAION CR-20 chelating resin column to determine Th isotopes in seawater with a sector field (SF) inductively coupled plasma mass spectrometer (ICP-MS). Thorium isotopes in seawater were co-precipitated with iron hydroxide, and this precipitate was sent to chelating resin column. Ferric ions in the iron hydroxide were bonded to functional groups of the chelating resin directly, resulting in a pH increase of the effluent by release of hydroxide ion from the iron hydroxide. The co-precipitated thorium isotopes were quantitatively collected within the column, which indicated that thorium was retained on the iron hydroxide remaining on the chelating column. The chelating column quantitatively collected {sup 232}Th with iron hydroxide in seawater at flow rates of 20–25 mL min{sup −1}. Based on this flow rate, a 5 L sample was processed within 3–4 h. The >20 h aging of iron hydroxide tends to reduce the recovery of {sup 232}Th. The rapid collection method was successfully applied to the determination of {sup 230}Th and {sup 232}Th in open-ocean seawater samples.

Geochemical and iron isotopic insights into hydrothermal iron oxyhydroxide deposit formation at Loihi Seamount

Science.gov (United States)

Rouxel, Olivier; Toner, Brandy; Germain, Yoan; Glazer, Brian

2018-01-01

Low-temperature hydrothermal vents, such as those encountered at Loihi Seamount, harbor abundant microbial communities and provide ideal systems to test hypotheses on biotic versus abiotic formation of hydrous ferric oxide (FeOx) deposits at the seafloor. Hydrothermal activity at Loihi Seamount produces abundant microbial mats associated with rust-colored FeOx deposits and variably encrusted with Mn-oxyhydroxides. Here, we applied Fe isotope systematics together with major and trace element geochemistry to study the formation mechanisms and preservation of such mineralized microbial mats. Iron isotope composition of warm (oxidation of Fe(II) during mixing of the hydrothermal fluid with seawater. By comparing the results with experimentally determined Fe isotope fractionation factors, we determined that less than 20% of Fe(II) is oxidized within active microbial mats, although this number may reach 80% in aged or less active deposits. These results are consistent with Fe(II) oxidation mediated by microbial processes considering the expected slow kinetics of abiotic Fe oxidation in low oxygen bottom water at Loihi Seamount. In contrast, FeOx deposits recovered at extinct sites have distinctly negative Fe-isotope values down to -1.77‰ together with significant enrichment in Mn and occurrence of negative Ce anomalies. These results are best explained by the near-complete oxidation of an isotopically light Fe(II) source produced during the waning stage of hydrothermal activity under more oxidizing conditions. Light Fe isotope values of FeOx are therefore generated by subsurface precipitation of isotopically heavy Fe-oxides rather than by the activity of dissimilatory Fe reduction in the subsurface. Overall, Fe-isotope compositions of microbial mats at Loihi Seamount display a remarkable range between -1.2‰ and +1.6‰ which indicate that Fe isotope compositions of hydrothermal Fe-oxide precipitates are particularly sensitive to local environmental conditions where

Experimental evidence for Mo isotope fractionation between metal and silicate liquids

Science.gov (United States)

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 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.

Tellurium stable isotope fractionation in chondritic meteorites and some terrestrial samples

Science.gov (United States)

Fehr, Manuela A.; Hammond, Samantha J.; Parkinson, Ian J.

2018-02-01

New methodologies employing a 125Te-128Te double-spike were developed and applied to obtain high precision mass-dependent tellurium stable isotope data for chondritic meteorites and some terrestrial samples by multiple-collector inductively coupled plasma mass spectrometry. Analyses of standard solutions produce Te stable isotope data with a long-term reproducibility (2SD) of 0.064‰ for δ130/125Te. Carbonaceous and enstatite chondrites display a range in δ130/125Te of 0.9‰ (0.2‰ amu-1) in their Te stable isotope signature, whereas ordinary chondrites present larger Te stable isotope fractionation, in particular for unequilibrated ordinary chondrites, with an overall variation of 6.3‰ for δ130/125Te (1.3‰ amu-1). Tellurium stable isotope variations in ordinary chondrites display no correlation with Te contents or metamorphic grade. The large Te stable isotope fractionation in ordinary chondrites is likely caused by evaporation and condensation processes during metamorphism in the meteorite parent bodies, as has been suggested for other moderately and highly volatile elements displaying similar isotope fractionation. Alternatively, they might represent a nebular signature or could have been produced during chondrule formation. Enstatite chondrites display slightly more negative δ130/125Te compared to carbonaceous chondrites and equilibrated ordinary chondrites. Small differences in the Te stable isotope composition are also present within carbonaceous chondrites and increase in the order CV-CO-CM-CI. These Te isotope variations within carbonaceous chondrites may be due to mixing of components that have distinct Te isotope signatures reflecting Te stable isotope fractionation in the early solar system or on the parent bodies and potentially small so-far unresolvable nucleosynthetic isotope anomalies of up to 0.27‰. The Te stable isotope data of carbonaceous and enstatite chondrites displays a general correlation with the oxidation state and hence might

The molecular mechanism of Mo isotope fractionation during adsorption to birnessite

Science.gov (United States)

Wasylenki, L.E.; Weeks, C.L.; Bargar, J.R.; Spiro, T.G.; Hein, J.R.; Anbar, A.D.

2011-01-01

Fractionation of Mo isotopes during adsorption to manganese oxides is a primary control on the global ocean Mo isotope budget. Previous attempts to explain what drives the surprisingly large isotope effect ??97/95Modissolved-??97/95Moadsorbed=1.8??? have not successfully resolved the fractionation mechanism. New evidence from extended X-ray absorption fine structure analysis and density functional theory suggests that Mo forms a polymolybdate complex on the surfaces of experimental and natural samples. Mo in this polynuclear structure is in distorted octahedral coordination, while Mo remaining in solution is predominantly in tetrahedral coordination as MoO42- Our results indicate that the difference in coordination environment between dissolved Mo and adsorbed Mo is the cause of isotope fractionation. The molecular mechanism of metal isotope fractionation in this system should enable us to explain and possibly predict metal isotope effects in other systems where transition metals adsorb to mineral surfaces. ?? 2011 Elsevier Ltd.

Calcium isotope fractionation between aqueous compounds relevant to low-temperature geochemistry, biology and medicine

Science.gov (United States)

Moynier, Frédéric; Fujii, Toshiyuki

2017-03-01

Stable Ca isotopes are fractionated between bones, urine and blood of animals and between soils, roots and leaves of plants by >1000 ppm for the 44Ca/40Ca ratio. These isotopic variations have important implications to understand Ca transport and fluxes in living organisms; however, the mechanisms of isotopic fractionation are unclear. Here we present ab initio calculations for the isotopic fractionation between various aqueous species of Ca and show that this fractionation can be up to 3000 ppm. We show that the Ca isotopic fractionation between soil solutions and plant roots can be explained by the difference of isotopic fractionation between the different first shell hydration degree of Ca2+ and that the isotopic fractionation between roots and leaves is controlled by the precipitation of Ca-oxalates. The isotopic fractionation between blood and urine is due to the complexation of heavy Ca with citrate and oxalates in urine. Calculations are presented for additional Ca species that may be useful to interpret future Ca isotopic measurements.

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

Science.gov (United States)

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.

Hydrogen isotope fractionation in methane plasma

OpenAIRE

Robert, François; Derenne, Sylvie; Lombardi, Guillaume; Hassouni, Khaled; Michau, Armelle; Reinhardt, Peter; Duhamel, Rémi; Gonzalez, Adriana; Biron, Kasia

2017-01-01

Large variations in light element isotope ratios (H, N, C) are routinely observed in meteorite organic matter. The origin of these so-called anomalies is not accounted for by the classical theory of isotope fractionation. In the case of H, micrometer-size areas within the insoluble organic matter (IOM) isolated from meteorites by acid treatment, exhibit extreme deuterium enrichment. They are generally interpreted as components exogenous to the solar system and attributed to surviving interste...

Transient competitive complexation in biological kinetic isotope fractionation explains nonsteady isotopic effects: Theory and application to denitrification in soils

Science.gov (United States)

Maggi, Federico; Riley, William J.

2009-12-01

The theoretical formulation of biological kinetic isotope fractionation often assumes first-order or Michaelis-Menten kinetics, the latter solved under the quasi-steady state assumption. Both formulations lead to a constant isotope fractionation factor, therefore they may return incorrect estimations of isotopic effects and misleading interpretations of isotopic signatures when fractionation is not a steady process. We have analyzed the isotopic signature of denitrification in biogeochemical soil systems by Menyailo and Hungate (2006) in which high and variable 15N-N2O enrichment during N2O production and inverse isotope fractionation during N2O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with Michaelis-Menten kinetics. When Michaelis-Menten kinetics were coupled to Monod kinetics to describe biomass and enzyme dynamics, and the quasi-steady state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observed concentrations, and variable and inverse isotope fractionations. These results imply a substantial revision in modeling isotopic effects, suggesting that steady state kinetics such as first-order, Rayleigh, and classic Michaelis-Menten kinetics should be superseded by transient kinetics in conjunction with biomass and enzyme dynamics.

[Carbon isotope fractionation in plants]: Annual technical progress report

International Nuclear Information System (INIS)

O'Leary, M.H.

1988-01-01

Plants fractionate carbon isotopes during photosynthesis in ways which reflect photosynthetic pathway and environment. The fractionation is product of contributions from diffusion, carboxylation and other factors which can be understood using models which have been developed in our work. The object of our work is to use this fractionation to learn about the factors which control the efficiency of photosynthesis. Unlike previous studies, we do not rely principally on combustion methods, but instead develop more specific methods with substantially higher resolving power. We have recently developed a new short-term method for studying carbon isotope fractionation which promises to provide a level of detail about temperature, species, and light intensity effects on photosynthesis which has not been available until now. We are studying the isotopic compositions of metabolites (particularly aspartic acid) in C 3 plants in order to determine the role of phosphoenolpyruvate carboxylase in C 3 photosynthesis. We are studying the relative roles of diffusion and carboxylation in nocturnal CO 2 fixation in CAM plants. We are studying the use of isotopic content as an index of water-use efficiency in C 3 plants. We are developing new methods for studying carbon metabolism in plants. 3 refs

Experimental study of relationship between average isotopic fractionation factor and evaporation rate

Directory of Open Access Journals (Sweden)

Tao Wang

2010-12-01

Full Text Available Isotopic fractionation is the basis of tracing the water cycle using hydrogen and oxygen isotopes. Isotopic fractionation factors in water evaporating from free water bodies are mainly affected by temperature and relative humidity, and vary significantly with these atmospheric factors over the course of a day. The evaporation rate (E can reveal the effects of atmospheric factors. Therefore, there should be a certain functional relationship between isotopic fractionation factors and E. An average isotopic fractionation factor (α* was defined to describe isotopic differences between vapor and liquid phases in evaporation with time intervals of days. The relationship between α* and E based on the isotopic mass balance was investigated through an evaporation pan experiment with no inflow. The experimental results showed that the isotopic compositions of residual water were more enriched with time; α* was affected by air temperature, relative humidity, and other atmospheric factors, and had a strong functional relation with E. The values of α* can be easily calculated with the known values of E, the initial volume of water in the pan, and isotopic compositions of residual water.

Magnesium isotope fractionation in cation-exchange chromatography

International Nuclear Information System (INIS)

Oi, T.; Yanase, S.; Kakihana, H.

1987-01-01

Band displacement chromatography of magnesium has been carried out successfully for the purpose of magnesium isotope separation by using a strongly acidic cation-exchange resin and the strontium ion as the replacement ion. A small but definite accumulation of the heavier isotopes ( 25 Mg, 26 Mg) has been observed at the front parts of the magnesium chromatograms. The heavier isotopes have been fractionated preferentially into the solution phase. The single-stage separation factors have been calculated for the 25 Mg/ 24 Mg and 26 Mg/ 24 isotopic pairs at 25 0 C. The reduced partition function ratios of magnesium species involved in the present study have been estimated

Copper isotope fractionation in acid mine drainage

Science.gov (United States)

Kimball, B.E.; Mathur, R.; Dohnalkova, A.C.; Wall, A.J.; Runkel, R.L.; Brantley, S.L.

2009-01-01

We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The ??65Cu values (based on 65Cu/63Cu) of enargite (??65Cu = -0.01 ?? 0.10???; 2??) and chalcopyrite (??65Cu = 0.16 ?? 0.10???) are within the range of reported values for terrestrial primary Cu sulfides (-1??? waters (1.38??? ??? ??65Cu ??? 1.69???). The average isotopic fractionation (??aq-min = ??65Cuaq - ??65Cumin, where the latter is measured on mineral samples from the field system), equals 1.43 ?? 0.14??? and 1.60 ?? 0.14??? for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in 65Cu relative to chalcopyrite (1.37 ?? 0.14???) and enargite (0.98 ?? 0.14???) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (??aq-mino = - 0.57 ?? 0.14 ???, where mino refers to the starting mineral) and no apparent fractionation for enargite (??aq-mino = 0.14 ?? 0.14 ???). Abiotic fractionation is attributed to preferential oxidation of 65Cu+ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of 65Cuaq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of ??65Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage

Natural fractionation of uranium isotopes

Energy Technology Data Exchange (ETDEWEB)

Noordmann, Janine

2015-01-24

The topic of this thesis was the investigation of U (n({sup 238}U) / n({sup 235}U)) isotope variations in nature with a focus on samples (1) that represent the continental crust and its weathering products (i.e. granites, shales and river water) (2) that represent products of hydrothermal alteration on mid-ocean ridges (i.e. altered basalts, carbonate veins and hydrothermal water) and (3) from restricted euxinic basins (i.e. from the water column and respective sediments). The overall goal was to explore the environmental conditions and unravel the mechanisms that fractionate the two most abundant U isotopes, n({sup 238}U) and n({sup 235}U), on Earth.

Natural fractionation of uranium isotopes

International Nuclear Information System (INIS)

Noordmann, Janine

2015-01-01

The topic of this thesis was the investigation of U (n( 238 U) / n( 235 U)) isotope variations in nature with a focus on samples (1) that represent the continental crust and its weathering products (i.e. granites, shales and river water) (2) that represent products of hydrothermal alteration on mid-ocean ridges (i.e. altered basalts, carbonate veins and hydrothermal water) and (3) from restricted euxinic basins (i.e. from the water column and respective sediments). The overall goal was to explore the environmental conditions and unravel the mechanisms that fractionate the two most abundant U isotopes, n( 238 U) and n( 235 U), on Earth.

Negligible fractionation of Kr and Xe isotopes by molecular diffusion in water

Science.gov (United States)

Tyroller, Lina; Brennwald, Matthias S.; Busemann, Henner; Maden, Colin; Baur, Heinrich; Kipfer, Rolf

2018-06-01

Molecular diffusion is a key transport process for noble gases in water. Such diffusive transport is often thought to cause a mass-dependent fractionation of noble gas isotopes that is inversely proportional to the square root of the ratio of their atomic mass, referred to as the square root relation. Previous studies, challenged the commonly held assumption that the square root relation adequately describes the behaviour of noble gas isotopes diffusing through water. However, the effect of diffusion on noble gas isotopes has only been determined experimentally for He, Ne and Ar to date, whereas the extent of fractionation of Kr and Xe has not been measured. In the present study the fractionation of Kr and Xe isotopes diffusing through water immobilised by adding agar was quantified through measuring the respective isotope ratio after diffusing through the immobilised water. No fractionation of Kr and Xe isotopes was observed, even using high-precision noble gas analytics. These results complement our current understanding on isotopic fractionation of noble gases diffusing through water. Therefore this complete data set builds a robust basis to describe molecular diffusion of noble gases in water in a physical sound manner which is fundamental to assess the physical aspects of gas dynamics in aquatic systems.

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

Science.gov (United States)

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

2017-08-01

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

Weathering and vegetation controls on nickel isotope fractionation in surface ultramafic environments (Albania)

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Estrade, Nicolas; Cloquet, Christophe; Echevarria, Guillaume; Sterckeman, Thibault; Deng, Tenghaobo; Tang, YeTao; Morel, Jean-Louis

2015-08-01

The dissolved nickel (Ni) isotopic composition of rivers and oceans presents an apparent paradox. Even though rivers represent a major source of Ni in the oceans, seawater is more enriched in the heavier isotopes than river-water. Additional sources or processes must therefore be invoked to account for the isotopic budget of dissolved Ni in seawater. Weathering of continental rocks is thought to play a major role in determining the magnitude and sign of isotopic fractionation of metals between a rock and the dissolved product. We present a study of Ni isotopes in the rock-soil-plant systems of several ultramafic environments. The results reveal key insights into the magnitude and the control of isotopic fractionation during the weathering of continental ultramafic rocks. This study introduces new constraints on the influence of vegetation during the weathering process, which should be taken into account in interpretations of the variability of Ni isotopes in rivers. The study area is located in a temperate climate zone within the ophiolitic belt area of Albania. The serpentinized peridotites sampled present a narrow range of heavy Ni isotopic compositions (δ60Ni = 0.25 ± 0.16 ‰, 2SD n = 2). At two locations, horizons within two soil profiles affected by different degrees of weathering all presented light isotopic compositions compared to the parent rock (Δ60Nisoil-rock up to - 0.63 ‰). This suggests that the soil pool takes up the light isotopes, while the heavier isotopes remain in the dissolved phase. By combining elemental and mineralogical analyses with the isotope compositions determined for the soils, the extent of fractionation was found to be controlled by the secondary minerals formed in the soil. The types of vegetation growing on ultramafic-derived soils are highly adapted and include both Ni-hyperaccumulating species, which can accumulate several percent per weight of Ni, and non-accumulating species. Whole-plant isotopic compositions were found

Calcium isotope fractionation between aqueous compounds relevant to low-temperature geochemistry, biology and medicine

OpenAIRE

Frédéric Moynier; Toshiyuki Fujii

2017-01-01

Stable Ca isotopes are fractionated between bones, urine and blood of animals and between soils, roots and leaves of plants by >1000?ppm for the 44Ca/40Ca ratio. These isotopic variations have important implications to understand Ca transport and fluxes in living organisms; however, the mechanisms of isotopic fractionation are unclear. Here we present ab initio calculations for the isotopic fractionation between various aqueous species of Ca and show that this fractionation can be up to 3000?...

Mo isotope fractionation during hydrothermal evolution of porphyry Cu systems

Science.gov (United States)

Shafiei, Behnam; Shamanian, GholamHossein; Mathur, Ryan; Mirnejad, Hassan

2015-03-01

We present Mo isotope compositions of molybdenite types from three successive stages of ore deposition in several porphyry copper deposits of the Kerman region, Iran. The data provide new insights into controlling processes on Mo isotope fractionation during the hydrothermal evolution of porphyry systems. The Mo isotope compositions of 27 molybdenite samples show wide variations in δ97Mo ranging from -0.37 to +0.92 ‰. The data reveal that molybdenites in the early and transitional stages of mineralization (preferentially 2H polytypes; δ97Mo mean = 0.35 ‰) have higher δ97Mo values than late stage (mainly 3R polytypes; δ97Mo mean = 0.02 ‰) molybdenites. This trend suggests that fractionation of Mo isotopes occurred in high-temperature stages of mineralization and that hydrothermal systems generally evolve towards precipitation of molybdenite with lower δ97Mo values. Taking into account the genetic models proposed for porphyry Cu deposits along with the temperature-dependent fractionation of Mo isotope ratios, it is proposed that large variations of Mo isotopes in the early and the transitional stages of ore deposition could be controlled by the separation of the immiscible ore-forming fluid phases with different density, pH, and ƒO2 properties (i.e., brine and vapor). The fractionation of Mo isotopes during fluid boiling and Rayleigh distillation processes likely dominates the Mo isotope budget of the remaining ore-forming fluids for the late stage of mineralization. The lower δ97Mo values in the late stage of mineralization can be explained by depletion of the late ore-forming hydrothermal solutions in 97Mo, as these fluids have moved to considerable distance from the source. Finally, the relationship observed between MoS2 polytypes (2H and 3R) and their Mo isotopic compositions can be explained by the molecular vibration theory, in which heavier isotopes are preferentially partitioned into denser primary 2H MoS2 crystals.

Evaporation Induced Oxygen Isotope Fractionation in Impact Ejecta

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Macris, C. A.; Young, E. D.; Kohl, I. E.; zur Loye, T. E.

2017-12-01

Tektites are natural glasses formed as quenched impact melt ejecta. Because they experienced extreme heating while entrained in a hot impact vapor plume, tektites allow insight into the nature of these ephemeral events, which play a critical role in planetary accretion and evolution. During tektite formation, the chemical and isotopic composition of parent materials may be modified by (1) vapor/liquid fractionation at high T in the plume, (2) incorporation of meteoric water at the target site, (3) isotope exchange with atmospheric oxygen (if present), or some combination of the three. Trends from O isotope studies reveal a dichotomy: some tektite δ18O values are 4.0-4.5‰ lower than their protoliths (Luft et al. 1987; Taylor & Epstein 1962), opposite in direction to a vaporization induced fractionation; increases in δ18O with decreasing SiO2 in tektites (Taylor & Epstein 1969) is consistent with vapor fractionation. Using an aerodynamic levitation laser furnace (e.g. Macris et al. 2016), we can experimentally determine the contributions of processes (1), (2) and (3) above to tektite compositions. We conducted a series of evaporation experiments to test process (1) using powdered tektite fused into 2 mm spheres and heated to 2423-2473 K for 50-90 s while levitated in Ar in the furnace. Mass losses were from 23 to 26%, reflecting evaporation of Si and O from the melt. The starting tektite had a δ18O value of 10.06‰ (±0.01 2se) and the residues ranged from 13.136‰ (±0.006) for the least evaporated residue to 14.30‰ (±0.02) for the most evaporated (measured by laser fluorination). The increase in δ18O with increasing mass loss is consistent with Rayleigh fractionation during evaporation, supporting the idea that O isotopes are fractionated due to vaporization at high T in an impact plume. Because atmospheric O2 and water each have distinctive Δ17O values, we should be able to use departures from our measured three-isotope fractionation law to evaluate

Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

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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

Oxygen isotope fractionation in uranium oxides

International Nuclear Information System (INIS)

Zheng Yongfei

1995-01-01

Thermodynamic oxygen isotope factors for uranium oxides have been calculated by means of the modified increment method. The sequence of 18 O-enrichment in the uranium oxides with respect to the common rock-forming minerals is predicted as follows: spinel 3 < illite. Two sets of self-consistent fractionation factors between the uranium oxides and water and between the uranium oxides and the other minerals have been obtained for 0∼1200 degree C. The theoretical results are applicable to the isotopic geothermometry of uranium ores when pairing with other gangue minerals in hydrothermal uranium deposits

[Fractionation of hydrogen stable isotopes in the human body].

Science.gov (United States)

Siniak, Iu E; Grigor'ev, A I; Skuratov, V M; Ivanova, S M; Pokrovskiĭ, B G

2006-01-01

Fractionation of hydrogen stable isotopes was studied in 9 human subjects in a chamber with normal air pressure imitating a space cabin. Mass-spectrometry of isotopes in blood, urine, saliva, and potable water evidenced increases in the contents of heavy H isotope (deuterium) in the body liquids as compared with water. These results support one of the theories according to which the human organism eliminates heavy stable isotopes of biogenous chemical elements.

Isotopic Fractionation of Mercury in Great Lakes Precipitation

Science.gov (United States)

Gratz, L. E.; Keeler, G. J.; Blum, J. D.; Sherman, L. S.

2009-12-01

Mercury (Hg) is a hazardous bioaccumulative neurotoxin, and atmospheric deposition is a primary way in which mercury enters terrestrial and aquatic ecosystems. However, the chemical processes and transport regimes that mercury undergoes from emission to deposition are not well understood. Thus the use of mercury isotopes to characterize the biogeochemical cycling of mercury is a rapidly growing area of study. Precipitation samples were collected in Chicago, IL, Holland, MI, and Dexter, MI from April 2007 - October 2007 to begin examining the isotopic fractionation of atmospheric mercury in the Great Lakes region. Results show that mass-dependent fractionation relative to NIST-3133 (MDF - δ202Hg) ranged from -0.8‰ to 0.2‰ (±0.2‰) in precipitation samples, while mass-independent fractionation (MIF - Δ199Hg) varied from 0.1‰ to 0.6‰ (±0.1‰). Although clear urban-rural differences were not observed, this may be due to the weekly collection of precipitation samples rather than collection of individual events, making it difficult to truly characterize the meteorology and source influences associated with each sample and suggesting that event-based collection is necessary during future sampling campaigns. Additionally, total vapor phase mercury samples were collected in Dexter, MI in 2009 to examine isotopic fractionation of mercury in ambient air. In ambient samples δ202Hg ranged from 0.3‰ to 0.5‰ (±0.1‰), however Δ199Hg was not significant. Because mercury in precipitation is predominantly Hg2+, while ambient vapor phase mercury is primarily Hg0, these results may suggest the occurrence of MIF during the oxidation of Hg0 to Hg2+ prior to deposition. Furthermore, although it has not been previously reported or predicted, MIF of 200Hg was also detected. Δ200Hg ranged from 0.0‰ to 0.2‰ in precipitation and from -0.1‰ to 0.0‰ in ambient samples. This work resulted in methodological developments in the collection and processing of

Isotope-aided studies of the bioavailability of iron from Myanmar diets

International Nuclear Information System (INIS)

Khin Maung Naing; Myo Khin

1992-01-01

Iron deficiency is an important nutritional problem in Myanmar. The preliminary studies in this paper are to be used as a feasibility study for an iron fortification programme in Myanmar. This programme is now in the planning stages. This paper contains summaries of information gathered from a dietary survey, isotope-aided studies of the bioavailability of iron from the daily diet, and a work plan for fortifying table salt with iron. 6 refs, 6 tabs

Reliability of stable Pb isotopes to identify Pb sources and verifying biological fractionation of Pb isotopes in goats and chickens

International Nuclear Information System (INIS)

Nakata, Hokuto; Nakayama, Shouta M.M.; Yabe, John; Liazambi, Allan; Mizukawa, Hazuki; Darwish, Wageh Sobhy; Ikenaka, Yoshinori; Ishizuka, Mayumi

2016-01-01

Stable Pb isotope ratios (Pb-IRs) have been recognized as an efficient tool for identifying sources. This study carried out at Kabwe mining area, Zambia, to elucidate the presence or absence of Pb isotope fractionation in goat and chicken, to evaluate the reliability of identifying Pb pollution sources via analysis of Pb-IRs, and to assess whether a threshold for blood Pb levels (Pb-B) for biological fractionation was present. The variation of Pb-IRs in goat decreased with an increase in Pb-B and were fixed at certain values close to those of the dominant source of Pb exposure at Pb-B > 5 μg/dL. However, chickens did not show a clear relationship for Pb-IRs against Pb-B, or a fractionation threshold. Given these, the biological fractionation of Pb isotopes should not occur in chickens but in goats, and the threshold for triggering biological fractionation is at around 5 μg/dL of Pb-B in goats. - Highlights: • Presence of Pb isotope fractionation in goat and chicken was studied. • The variation of Pb-IRs in goat decreased with an increase in Pb-B. • Chickens did not show a clear relationship for Pb-IRs against Pb-B. • The biological fractionation of Pb isotopes should not occur in chickens but in goats. • Threshold for triggering biological fractionation is at 5 μg/dL of Pb-B in goats. - Biological fractionation and its threshold for stable Pb isotope ratio in goats and chickens were examined.

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

Science.gov (United States)

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.

Isotope Fractionation of Water During Evaporation Without Condensation

International Nuclear Information System (INIS)

Cappa, Christopher D.; Drisdell, Walter S.; Smith, Jared D.; Saykally, Richard J.; Cohen, Ronald C.

2005-01-01

The microscopic events engendering liquid water evaporation have received much attention over the last century, but remain incompletely understood. We present measurements of isotope fractionation occurring during free molecular evaporation from liquid microjets and show that the isotope ratios of evaporating molecules exhibit dramatic differences from equilibrium vapor values, strong variations with the solution deuterium mole fraction, and a clear temperature dependence. These results indicate the existence of an energetic barrier to evaporation and that the evaporation coefficient of water is less than unity. These new insights into water evaporation promise to advance our understanding of the processes that control the formation and lifetime of clouds in the atmosphere.

Fractionation of oxygen isotopes between mammalian bone-phosphate and environmental drinking water

International Nuclear Information System (INIS)

Luz, B.; Kolodny, V.; Horowitz, M.

1984-01-01

The delta 18 O of mammalian bone-phosphate varies linearly with delta 18 O of environmental water, but is not in isotopic equilibrium with that water. This situation is explained by a model of delta 18 O in body water in which the important fluxes of exchangeable oxygen through the body are taken into account. Fractionation of oxygen isotopes between body and environmental drinking water is dependent on the rates of drinking and respiration. Isotopic fractionation can be estimated from physiological data and the estimates correlate very well with observed fractionation. Species whose water consumption is large relative to its energy expenditure is sensitive to isotopic ratio changes in environmental water. (author)

The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

Science.gov (United States)

Summers, David P.

2003-01-01

mil to as low as -60 % (potentially comparable to that which accompanies the biosynthesis of organic matter). We need to understand what kind of fractionations are observed with reactions under the non-reducing or mildly reducing conditions now thought to be present on the early Earth. While nitrogen is receiving increased attention as a tool for these kinds of analyses, almost nothing is known about the isotope fractionation that one would expect for abiotic sources of fixed/reduced nitrogen. This project will measure the fixation from a series of abiotic reactions that may have been present on the early Earth (and other terrestrial planets) and produced organic material that could have ended up in the rock record. The work will look at a number of reactions, under a non- reducing, or mildly reducing, atmosphere, covering sources of prebiotic organic C & N from shock heating, to photochemistry, to hydrothermal reactions. Some reactions that we plan to study are; Shock heating of a non-reducing atmosphere to produce CO and NO (in collaboration with Chris McKay), formation of formaldehyde (and related compounds) from COY the formation of ammonia from nitrogen oxides (ultimately from NO) by ferrous iron reduction, and the hydrothermal synthesis of compounds including the hydrocarboxylation/hydrocarbonylation reaction (in collaboration with George Cody), reactions of oxalate to form hydrocarbons and other oxygenated compounds and the formation of lipids from oxalic/formic acid (in collaboration with Tom McCollom), and reactions of carbon monoxide & carbon dioxide with N2, ammonia or nitritehitrate to form hydrogen cyanide, nitriles, ammonia/amines and nitrous

Fractionation of lithium isotopes in cation-exchange chromatography

International Nuclear Information System (INIS)

Oi, Takao; Kawada, Kazuhiko; Kakihana, Hidetake; Hosoe, Morikazu

1991-01-01

Various methods for lithium isotope separation have been developed, and their applicability to large-scale enriched lithium isotope production has been assessed. Ion-exchange chromatography is one such method. Cation-exchange chromatography of lithium was carried out to investigate the lithium isotope effect in aqueous ion-exchange systems. The heavier isotope. 7 Li, was preferentially fractionated into the resin phase in every experiment conducted, and this result is consistent with the results of previous work. The value of the separation factor was 1.00089-1.00171 at 25C. A comparison of lithium isotope effect with those of potassium and rubidium indicated that the isotope effect originating from hydration is larger than the effect due to phase change for lithium, while the opposite is the case with potassium and rubidium

Fractionation of hydrogen isotopes by sulfate- and nitrate-reducing bacteria

Directory of Open Access Journals (Sweden)

Magdalena Rose Osburn

2016-08-01

Full Text Available Hydrogen atoms from water and food are incorporated into biomass during cellular metabolism and biosynthesis, fractionating the isotopes of hydrogen –protium and deuterium –that are recorded in biomolecules. While these fractionations are often relatively constant in plants, large variations in the magnitude of fractionation are observed for many heterotrophic microbes utilizing different central metabolic pathways. The correlation between metabolism and lipid δ2H provides a potential basis for reconstructing environmental and ecological parameters, but the calibration dataset has thus far been limited mainly to aerobes. Here we report on the hydrogen isotopic fractionations of lipids produced by nitrate-respiring and sulfate-reducing bacteria. We observe only small differences in fractionation between oxygen- and nitrate-respiring growth conditions, with a typical pattern of variation between substrates that is broadly consistent with previously described trends. In contrast, fractionation by sulfate-reducing bacteria does not vary significantly between different substrates, even when autotrophic and heterotrophic growth conditions are compared. This result is in marked contrast to previously published observations and has significant implications for the interpretation of environmental hydrogen isotope data. We evaluate these trends in light of metabolic gene content of each strain, growth rate, and potential flux and reservoir-size effects of cellular hydrogen, but find no single variable that can account for the differences between nitrate- and sulfate-respiring bacteria. The emerging picture of bacterial hydrogen isotope fractionation is therefore more complex than the simple correspondence between δ2H and metabolic pathway previously understood from aerobes. Despite the complexity, the large signals and rich variability of observed lipid δ2H suggest much potential as an environmental recorder of metabolism.

Fractionation of Hydrogen Isotopes by Sulfate- and Nitrate-Reducing Bacteria.

Science.gov (United States)

Osburn, Magdalena R; Dawson, Katherine S; Fogel, Marilyn L; Sessions, Alex L

2016-01-01

Hydrogen atoms from water and food are incorporated into biomass during cellular metabolism and biosynthesis, fractionating the isotopes of hydrogen-protium and deuterium-that are recorded in biomolecules. While these fractionations are often relatively constant in plants, large variations in the magnitude of fractionation are observed for many heterotrophic microbes utilizing different central metabolic pathways. The correlation between metabolism and lipid δ(2)H provides a potential basis for reconstructing environmental and ecological parameters, but the calibration dataset has thus far been limited mainly to aerobes. Here we report on the hydrogen isotopic fractionations of lipids produced by nitrate-respiring and sulfate-reducing bacteria. We observe only small differences in fractionation between oxygen- and nitrate-respiring growth conditions, with a typical pattern of variation between substrates that is broadly consistent with previously described trends. In contrast, fractionation by sulfate-reducing bacteria does not vary significantly between different substrates, even when autotrophic and heterotrophic growth conditions are compared. This result is in marked contrast to previously published observations and has significant implications for the interpretation of environmental hydrogen isotope data. We evaluate these trends in light of metabolic gene content of each strain, growth rate, and potential flux and reservoir-size effects of cellular hydrogen, but find no single variable that can account for the differences between nitrate- and sulfate-respiring bacteria. The emerging picture of bacterial hydrogen isotope fractionation is therefore more complex than the simple correspondence between δ(2)H and metabolic pathway previously understood from aerobes. Despite the complexity, the large signals and rich variability of observed lipid δ(2)H suggest much potential as an environmental recorder of metabolism.

Preservation of Fe Isotope Proxies in the Rock Record

Science.gov (United States)

Johnson, C.; Beard, B.; Valley, J.; Valaas, E.

2005-12-01

Iron isotope variations provide powerful constraints on redox conditions and pathways involved during biogeochemical cycling of Fe in surface and near-surface environments. The relative isotopic homogeneity of igneous rocks and most bulk weathering products contrasts with the significant isotopic variations (4 per mil in 56Fe/54Fe) that accompany oxidation of Fe(II)aq, precipitation of sulfides, and reduction by bacteria. These isotopic variations often reflect intrinsic (equilibrium) Fe isotope fractionations between minerals and aqueous species whose interactions may be directly or indirectly catalyzed by bacteria. In addition, Fe isotope exchange may be limited between reactive Fe pools in low-temperature aqueous-sediment environments, fundamentally reflecting disequilibrium effects. In the absence of significant sulfide, dissimilatory Fe(III) reduction by bacteria produces relatively low 56Fe/54Fe ratios for Fe(II)aq and associated biogenic minerals such as magnetite and siderite. In contrast, Fe(II)aq that exchanges with Fe sulfides (FeS and pyrite) is relatively enriched in 56Fe/54Fe ratios. In modern and ancient environments, anoxic diagenesis tends to produce products that have low 56Fe/54Fe ratios, whereas oxidation of Fe(II)aq from hydrothermal sources tends to produce ferric Fe products that have high 56Fe/54Fe ratios. Redox cycling by bacteria tends to produce reactive ferric Fe reservoirs that have low 56Fe/54Fe ratios. Application of Fe isotopes as a proxy for redox conditions in the ancient rock record depends upon the preservation potential during metamorphism, given the fact that most Archean sedimentary sequences have been subjected to regional greenschist- to granulite-facies metamorphism. The 1.9 Ga banded iron formations (BIFs) of the Lake Superior region that are intruded by large ~1 Ga intrusions (e.g., Duluth gabbro) provide a test of the preservation potential for primary, low-temperature Fe isotope variations in sedimentary rocks. 56Fe/54

Calculation of Site-specific Carbon-isotope Fractionation in Pedogenic Oxide Minerals

Energy Technology Data Exchange (ETDEWEB)

Rustad, James R.; Zarzycki, Piotr

2008-07-29

Ab initio molecular dynamics and quantum chemistry techniques are used to calculate the structure, vibrational frequencies, and carbon-isotope fractionation factors of the carbon dioxide component [CO2(m)] of soil (oxy)hydroxide minerals goethite, diaspore, and gibbsite. We have identified two possible pathways of incorporation of CO2(m) into (oxy)hydroxide crystal structures: one in which the C4+ substitutes for four H+ [CO2(m)A] and another in which C4+ substitutes for (Al3+,Fe3+) + H+ [CO2(m)B]. Calculations of isotope fractionation factors give large differences between the two structures, with the CO2(m)A being isotopically lighter than CO2(m)B by ≈10 per mil in the case of gibbsite and nearly 20 per mil in the case of goethite. The reduced partition function ratio of CO2(m)B structure in goethite differs from CO2(g) by <1 per mil. The predicted fractionation for gibbsite is >10 per mil higher, close to those measured for calcite and aragonite. The surprisingly large difference in the carbon-isotope fractionation factor between the CO2(m)A and CO2(m)B structures within a given mineral suggests that the isotopic signatures of soil (oxy)hydroxide could be heterogeneous.

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

Science.gov (United States)

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

Boron isotope fractionation in column chromatography with glucamine type fibers

International Nuclear Information System (INIS)

Sonoda, Akinari; Makita, Yoji; Hirotsu, Takahiro

2008-01-01

Glucamine type polymers have specific affinity toward boric acid and borate ion. Among them, Chelest Fiber GRY-L showed larger fractionation for boron isotopes than other polymers in our previous study. For this study, we used Chelest Fibers with different fiber lengths (1.0 mm, 0.5 mm, and 0.3 mm) as column packing materials to perform chromatographic separation of boron isotopes. The shorter fiber has larger packing density when packed into the column using a dry method. The 0.3-mm-long fiber has a larger backpressure than fibers of other lengths. Boron adsorption capacities were measured using the breakthrough operation. At this time, the 0.5-mm-long fiber showed the highest capacity. When we measured the isotope ratio profile for fibers of different length using column chromatography, 0.5-mm-long fibers displayed the highest boron isotope fractionation. The 0.5-mm-long fiber is promising as a packing material of column chromatography for boron isotope separation. We also changed operation methods. The lower eluent concentration and the slower flow rate are suitable for boron isotope separation. (author)

Ca isotopic fractionation patterns in forest ecosystems

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Kurtz, A. C.; Takagi, K.

2012-12-01

Calcium stable isotope ratios are an emerging tracer of the biogeochemical cycle of Ca that are just beginning to see significant application to forest ecosystems. The primary source of isotopic fractionation in these systems is discrimination against light Ca during uptake by plant roots. Cycling of vegetation-fractionated Ca establishes isotopically distinct Ca pools within a forest ecosystem. In some systems, the shallow soil exchangeable Ca pool is isotopically heavy relative to Ca inputs. This has been explained by preferential removal of light Ca from the soil. In other systems, the soil exchange pool is isotopically light relative to inputs, which is explained by recycling of plant-fractionated light Ca back into soil. Thus vegetation uptake of light Ca has been called on to account for both isotopically heavy and light Ca in the shallow soil exchange pools. We interpret patterns in ecosystem δ44Ca with the aid of a simple box model of the forest Ca cycle. We suggest that the δ44Ca of exchangeable Ca in the shallow soil pool primarily reflects the relative magnitude of three key fluxes in a forest Ca cycle, 1) the flux of external Ca into the system via weathering or atmospheric deposition, 2) the uptake flux of Ca from soils into the vegetation pool, and 3) the return flux of Ca to shallow soils via remineralization of leaf litter. Two observations that emerge from our model may aid in the application of Ca isotopes to provide insight into the forest Ca cycle. First, regardless of the magnitude of both vegetation Ca uptake and isotopic fractionation, the δ44Ca of the soil exchange pool will equal the input δ44Ca unless the plant uptake and remineralization fluxes are out of balance. A second observation is that the degree to which the shallow soil exchange pool δ44Ca can differ from the input ratio is controlled by the relative rates of biological uptake and external Ca input. Significant differences between soil exchange and input δ44Ca are seen only

Uranium isotope fractionation resulting from UF6 vapor distillation from containers

International Nuclear Information System (INIS)

Hedge, W.D.; Turner, C.M.

1985-01-01

This empirical study for possible isotopic fractionation due to UF 6 vapor distillation from valved containers was performed to determine the effects of repeated vapor sampling. Four different experiments were performed, each of which varied by the method of measuring the isotopic contents and/or by the difference in temperature gradients as follows: The ratio of the parent UF 6 to the desublimed UF 6 collected at liquid nitrogen temperature and homogenized was measured by sampling the containers. The ratio of the parent UF 6 to the desublimed UF 6 collected at liquid nitrogen temperature and homogenized was measured by direct comparison to each other without subsampling. The ratio of the parent UF 6 to the desublimed UF 6 collected at liquid nitrogen and ice-water temperatures and homogenized was measured by indirect comparison to a common UF 6 reference material without subsampling. The ratio of the parent UF 6 to the desublimed UF 6 collected at liquid nitrogen temperature without homogenizing was measured by indirect comparison to a common UF 6 reference. Gas-phase, relative mass spectrometry was used for all isotopic measurements. Results of the study indicate that fractionation does occur. The U-235 isotope becomes more enriched in the parent container as the UF 6 is vaporized from it and desublimed into the receiving cylinder; i.e., the vaporized fraction is enriched in the U-238 isotope. The degree of fractionation indicates that the separation is due to the U-238 isotope of UF 6 having a higher vapor pressure than the U-235 isotope of UF 6 . 3 refs., 4 figs., 4 tabs

Determination of the interchangeable heavy-metal fraction in soils by isotope dilution mass spectrometry

International Nuclear Information System (INIS)

Gaebler, H.E.; Bahr, A.; Mieke, B.

1999-01-01

An isotope dilution technique using enriched stable isotopes is applied to determine the interchangeable heavy-metal fraction in soils. Metals in two soil samples are extracted at constant pH, with water, NH 4 NO 3 , and EDTA. A spike of enriched stable isotopes is added to the suspension of sample and eluant at the beginning of the extraction. The heavy-metal fraction which exchanges with the added spike during the extraction is called the interchangeable fraction. The extractable heavy-metal fractions are obtained from the heavy-metal concentrations in the eluates. Isotope ratios and concentrations are determined by HR-ICP-MS. The isotope dilution technique described enables both the extractable and the interchangeable heavy-metal fractions to be determined in the same experiment. The combination of both results gives additional information on elemental availability under different conditions that cannot be obtained by analyzing the extractable heavy-metal fractions alone. It is demonstrated that in some cases different eluants just shift the distribution of the interchangeable fraction of an element between the solid and liquid phases (e.g., Pb and Cd in a topsoil sample) while the amount of the interchangeable fraction itself remains constant. For other elements, as Ni, Zn, and Cr, the use of different eluants (different pH, complexing agents) sometimes enlarges the interchangeable fraction. (orig.)

Isotopes produced by galactic cosmic rays in iron meteorites

International Nuclear Information System (INIS)

Birck, J.L.; Allegre, C.J.

1985-01-01

The elements Li, Mg, K, Ca, Ti, V, Cr have been investigated in the iron meteorites Grant and Carbo. Their isotopic ratios show clearly the effects of spallation by galactic cosmic rays. Our experimental technique allows us to determine the concentration of spallation products with a precision close to 1 per mil for a number of isotopes. The effects of shielding are clearly evidenced in the calcium data and the exposure ages are calculated by using the 40 K measurements

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis

Science.gov (United States)

VanStone, Nancy; Przepiora, Andrzej; Vogan, John; Lacrampe-Couloume, Georges; Powers, Brian; Perez, Ernesto; Mabury, Scott; Sherwood Lollar, Barbara

2005-08-01

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. > 9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and δ13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched δ13C values compared to the upgradient mean. In addition, δ13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis.

Science.gov (United States)

VanStone, Nancy; Przepiora, Andrzej; Vogan, John; Lacrampe-Couloume, Georges; Powers, Brian; Perez, Ernesto; Mabury, Scott; Sherwood Lollar, Barbara

2005-08-01

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. >9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and delta13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched delta13C values compared to the upgradient mean. In addition, delta13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.

Consumption of galacto-oligosaccharides increases iron absorption from a micronutrient powder containing ferrous fumarate and sodium iron EDTA: a stable-isotope study in Kenyan infants.

Science.gov (United States)

Paganini, Daniela; Uyoga, Mary A; Cercamondi, Colin I; Moretti, Diego; Mwasi, Edith; Schwab, Clarissa; Bechtler, Salome; Mutuku, Francis M; Galetti, Valeria; Lacroix, Christophe; Karanja, Simon; Zimmermann, Michael B

2017-10-01

Background: Whether consumption of prebiotics increases iron absorption in infants is unclear. Objective: We set out to determine whether prebiotic consumption affects iron absorption from a micronutrient powder (MNP) containing a mixture of ferrous fumarate and sodium iron EDTA (FeFum+NaFeEDTA) in Kenyan infants. Design: Infants ( n = 50; aged 6-14 mo) consumed maize porridge that was fortified with an MNP containing FeFum+NaFeEDTA and 7.5 g galacto-oligosaccharides (GOSs) (Fe+GOS group, n = 22) or the same MNP without GOSs (Fe group, n = 28) each day for 3 wk. Then, on 2 consecutive days, we fed all infants isotopically labeled maize porridge and MNP test meals containing 5 mg Fe as 57 FeFum+Na 58 FeEDTA or ferrous sulfate ( 54 FeSO 4 ). Iron absorption was measured as the erythrocyte incorporation of stable isotopes. Iron markers, fecal pH, and bacterial groups were assessed at baseline and 3 wk. Comparisons within and between groups were done with the use of mixed-effects models. Results: There was a significant group-by-compound interaction on iron absorption ( P = 0.011). The median percentages of fractional iron absorption from FeFum+NaFeEDTA and from FeSO 4 in the Fe group were 11.6% (IQR: 6.9-19.9%) and 20.3% (IQR: 14.2-25.7%), respectively, ( P iron absorption was greater from the FeFum+NaFeEDTA ( P = 0.047) in the Fe+GOS group but not from the FeSO 4 ( P = 0.653). The relative iron bioavailability from FeFum+NaFeEDTA compared with FeSO 4 was higher in the Fe+GOS group than in the Fe group (88% compared with 63%; P = 0.006). There was a significant time-by-group interaction on Bifidobacterium spp. ( P = 0.008) and Lactobacillus / Pediococcus / Leuconostoc spp. ( P = 0.018); Lactobacillus / Pediococcus / Leuconostoc spp. decreased in the Fe group ( P = 0.013), and there was a nonsignificant trend toward higher Bifidobacterium spp. in the Fe+GOS group ( P = 0.099). At 3 wk, iron absorption was negatively correlated with fecal pH ( P iron absorption by 62

Transient competitive complexation in biological kinetic isotope fractionation explains non-steady isotopic effects: Theory and application to denitrification in soils

Energy Technology Data Exchange (ETDEWEB)

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

2009-06-01

The theoretical formulation of biological kinetic reactions in isotopic applications often assume first-order or Michaelis-Menten-Monod kinetics under the quasi-steady-state assumption to simplify the system kinetics. However, isotopic e ects have the same order of magnitude as the potential error introduced by these simpli cations. Both formulations lead to a constant fractionation factor which may yield incorrect estimations of the isotopic effect and a misleading interpretation of the isotopic signature of a reaction. We have analyzed the isotopic signature of denitri cation in biogeochemical soil systems by Menyailo and Hungate [2006], where high {sup 15}N{sub 2}O enrichment during N{sub 2}O production and inverse isotope fractionation during N{sub 2}O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with the quasi-steady-state Michaelis-Menten-Monod kinetics. When the quasi-steady-state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observations and aided in interpretation of experimental isotopic signatures. These results may imply a substantial revision in using the Rayleigh equation for interpretation of isotopic signatures and in modeling biological kinetic isotope fractionation with first-order kinetics or quasi-steady-state Michaelis-Menten-Monod kinetics.

Liquid--vapor isotope fractionation factors in argon--krypton binary mixtures

International Nuclear Information System (INIS)

Lee, M.W.; Neufeld, P.; Bigeleisen, J.

1977-01-01

An equilibrium isotope effect has been studied as a continuous function of the potential field acting on the atom undergoing isotopic exchange. This has been accomplished through a study of the liquid vapor isotope fractionation factors for both, 36 Ar/ 40 Ar and 80 Kr/ 84 Kr in a series of binary mixtures which span the range between the pure components at 117.5 0 K. The 36 Ar/ 40 Ar fractionation factor increases (linearly) from (lnα)2.49 x 10 -3 in pure liquid argon to 2.91 x 10 -3 in an infinitely dilute solution in liquid krypton. Conversely, the 80 Kr/ 84 Kr fractionation factor decreases (linearly) from (lnα)0.98 x 10 -3 in pure liquid krypton to 0.64 x 10 -3 in an infinetely dilute solution in pure liquid argon. The mean force constants 2 U>/sub c/ on both argon and krypton atoms in the mixtures are derived from the respective isotope fractionation factors.The mean force constants for argon and krypton as a function of composition have been calculated by a modified corresponding states theory which uses the pure liquids as input parameters. The discrepancy is 8 percent at X/sub Ar/ + O. A systematic set of calculations has been made of 2 U> (Ar) and 2 U> (Kr) as a function of composition using radial distribution functions generated by the Weeks--Chandler--Anderson perturbation theory

On the noble gas isotopic fractionation in naturally occurring gases

International Nuclear Information System (INIS)

Marty, B.

1984-01-01

The isotopic composition of neon in the mantle is an important geochemical constraint on the formation of the earth and subsequent degassing. Some deviation of neon isotopic composition in natural gas and rock samples from the atmospheric value which can not be accounted for by the known nuclear process has been reported, and Nagao et al. interpreted the deviation as the result of mass fractionation in natural gas in Japan. The possible cause of such fractionation was investigated. Gaseous diffusion, such as (a) free-molecule diffusion, (b) mutual diffusion and (c) thermal diffusion, is able to cause isotopic fractionation. After the detailed consideration on these three diffusion processes, conclusion that free-molecule diffusion occurs only in very particular condition, and it is questionable that thermal diffusion occurs in nature, were obtained. (b) which means the interaction of two or more gases, is supposed to occur in nature, and is able to confirm experimentally. In mutual diffusion only, gas transfer is concerned, but other form of fractionation should not be neglected. In solid diffusion, gas is trapped by fine grained sedimentary rocks, and may be fractionated by adsorption and communication to exterior through minute channels. Underground water also works as noble gas reservoir. For example, when gas stream is in contact with water, continuous exchange is possible to take place at the interface of gas and liquid, which contributes to the fractionation. (Ishimitsu, A.)

Stable isotope fractionation during bacterial sulfate reduction is controlled by reoxidation of intermediates

Science.gov (United States)

Mangalo, Muna; Meckenstock, Rainer U.; Stichler, Willibald; Einsiedl, Florian

2007-09-01

Bacterial sulfate reduction is one of the most important respiration processes in anoxic habitats and is often assessed by analyzing the results of stable isotope fractionation. However, stable isotope fractionation is supposed to be influenced by the reduction rate and other parameters, such as temperature. We studied here the mechanistic basics of observed differences in stable isotope fractionation during bacterial sulfate reduction. Batch experiments with four sulfate-reducing strains ( Desulfovibrio desulfuricans, Desulfobacca acetoxidans, Desulfonatronovibrio hydrogenovorans, and strain TRM1) were performed. These microorganisms metabolize different carbon sources (lactate, acetate, formate, and toluene) and showed broad variations in their sulfur isotope enrichment factors. We performed a series of experiments on isotope exchange of 18O between residual sulfate and ambient water. Batch experiments were conducted with 18O-enriched (δ 18O water = +700‰) and depleted water (δ 18O water = -40‰), respectively, and the stable 18O isotope shift in the residual sulfate was followed. For Desulfovibrio desulfuricans and Desulfonatronovibrio hydrogenovorans, which are both characterized by low sulfur isotope fractionation ( ɛS > -13.2‰), δ 18O values in the remaining sulfate increased by only 50‰ during growth when 18O-enriched water was used for the growth medium. In contrast, with Desulfobacca acetoxidans and strain TRM1 ( ɛS factor ( ɛS exchange with water during sulfate reduction. However, this neither takes place in the sulfate itself nor during formation of APS (adenosine-5'-phosphosulfate), but rather in intermediates of the sulfate reduction pathway. These may in turn be partially reoxidized to form sulfate. This reoxidation leads to an incorporation of oxygen from water into the "recycled" sulfate changing the overall 18O isotopic composition of the remaining sulfate fraction. Our study shows that such incorporation of 18O is correlated with the

Silicon isotope fractionation during silica precipitation from hot-spring waters

Science.gov (United States)

Geilert, Sonja; Vroon, Pieter; Keller, Nicole; Gudbrnadsson, Snorri; Stefánsson, Andri; van Bergen, Manfred

2014-05-01

Hot-spring systems in the Geysir geothermal area, Iceland, have been studied to explore silicon isotope fractionation in a natural setting where sinter deposits are actively formed over a temperature interval between 20° and 100° C. The SiO2(aq)concentrations in spring and stream waters range between 290 and 560ppm and stay relatively constant along downstream trajectories, irrespective of significant cooling gradients. The waters are predominantly oversaturated in amorphous silica at the temperatures measured in the field. Correlations between the saturation indices, temperature and amounts of evaporative water loss suggest that cooling and evaporation are the main causes of subaqueous silica precipitation. The δ30Si values of dissolved silica in spring water and outflowing streams average around +1o probably due to the small quantities of instantaneously precipitating silica relative to the dissolved amount. Siliceous sinters, in contrast, range between -0.1o to -4.0o consistent with a preferred incorporation of the light silicon isotope and with values for precipitated silica becoming more negative with downstream decreasing temperatures. Larger fractionation magnitudes are inversely correlated with the precipitation rate, which itself is dependent on temperature, saturation state and the extent of a system. The resulting magnitudes of solid-fluid isotopic fractionation generally decline from -3.5o at 10° C to -2.0o at 90° C. These values confirm a similar relationship between fractionation magnitude and temperature that we found in laboratory-controlled silica-precipitation experiments. However, a relatively constant offset of ca. -2.9o between field and experimental fractionation values indicates that temperature alone cannot be responsible for the observed shifts. We infer that precipitation kinetics are a prominent control of silicon isotope fractionation in aqueous environments, whereby the influence of the extent of the system on the precipitation

Interplay of crystal fractionation, sulfide saturation and oxygen fugacity on the iron isotope composition of arc lavas: An example from the Marianas

Science.gov (United States)

Williams, H. M.; Prytulak, J.; Woodhead, J. D.; Kelley, K. A.; Brounce, M.; Plank, T.

2018-04-01

Subduction zone systems are central to a multitude of processes from the evolution of the continental crust to the concentration of metals into economically viable deposits. The interplay between oxygen fugacity, sulfur saturation, fluid exsolution and fractionating mineral assemblages that gives rise to typical arc magma chemical signatures is, however, still poorly understood and novel geochemical approaches are required to make further progress. Here we examine a well-characterized suite of arc lavas from the Marianas (W. Pacific) for their stable Fe isotope composition. In agreement with previous work and mass balance considerations, contributions from sediments and/or fluids are shown to have negligible effect on Fe isotopes. Instead, we focus on disentangling processes occurring during basalt through dacite differentiation using a sample suite from the island of Anatahan. Anatahan whole rock Fe isotope compositions (δ57Fe) range from -0.05 ± 0.05 to 0.17 ± 0.03 (2 S.D.)‰. A fractionation model is constructed, where three distinct stages of differentiation are required to satisfy the combined major and trace element and isotopic observations. In particular, the sequestration of isotopically heavy Fe into magnetite and isotopically light Fe into sulfide melts yields important constraints. The data require that lavas are first undersaturated with respect to crystalline or molten sulfide, followed by the crystallisation of magnetite, which then triggers late sulfide saturation. The model demonstrates that the final stage of removal of liquid or crystalline sulfide can effectively sequester Cu (and presumably other chalcophiles) and that late stage exsolution of magmatic fluids or brines may not be required to do this, although these processes are not mutually exclusive. Finally, the new Fe isotope data are combined with previous Tl-Mo-V stable isotope determinations on the same samples. Importantly, the multi-valent transition metal stable isotope systems of

The study of the deuterium isotopic fractionation through the cell membrane of the plant

International Nuclear Information System (INIS)

Berdea, P.; Cuna, Stela; Deliu, C.

2002-01-01

The purpose of this study is to prove that there is a water deuterium isotope fractionation when the water passes through the cell membrane. The carrots (Daucus carota) were grown in vitro in a Murashige and Skoog mineral-salt medium and have been exposed to a water solution with a uniform isotopic content. After seven days the cell culture was filtered and the cell water was vacuum extracted. The water from aqueous solution and the cell water were analyzed for hydrogen by isotope ratio mass spectrometry. The procedure was repeated for 14 and 21 day old cell cultures. The measurements have revealed a water deuterium isotopic fractionation between extra-cellular water and cellular water. The deuterium content was found to be higher within the cells by 10 o / oo for non-embryonic cells and 13 o / oo for the embryonic cells. This fractionation is a non-evaporative fractionation between intracellular and extra-cellular water and it represents a new step in the overall fractionation of deuterium water in the plants. The existence of such isotopic fractionation through the cell membrane implies that the relationship between the deuterium content of cellulose nitrate in plant and meteoric water should be revised. Also, this finding is of interest for understanding the balance and dynamics of the hydrogen isotopes in the environment. (authors)

Silicon isotope fractionation by marine sponges and the reconstruction of the silicon isotope composition of ancient deep water

Science.gov (United States)

de La Rocha, Christina L.

2003-05-01

The silicon isotope composition (δ30Si) of biogenic opal provides a view of the silica cycle at times in the past. Reconstructions require the knowledge of silicon isotope fractionation during opal biomineralization. The δ30Si of specimens of hexactinellid sponges and demosponges growing in the modern ocean ranged from -1.2‰ to -3.7‰ (n = 6), corresponding to the production of opal that has a δ30Si value 3.8‰ ± 0.8‰ more negative than seawater silicic acid and a fractionation factor (α) of 0.9964. This is three times the fractionation observed during opal formation by marine diatoms and terrestrial plants and is the largest fractionation of silicon isotopes observed for any natural process on Earth. The δ30Si values of sponge spicules across the Eocene-Oligocene boundary at Ocean Drilling Program Site 689 on Maud Rise range from -1.1‰ to -3.0‰, overlapping the range observed for sponges growing in modern seawater.

Monitoring biodegradation of hydrocarbons by stable isotope fractionation

Science.gov (United States)

Dorer, Conrad; Fischer, Anko; Herrmann, Steffi; Richnow, Hans-Hermann; Vogt, Carsten

2010-05-01

nitrate, sulfate or ferric iron as electron acceptor or using light as energy source [3,4,5]. Significantly different lambda values were also observed for the anaerobic degradation of xylenes initiated by the BSS [5]. The different lambda values obtained for the anaerobic degradation of toluene and xylenes might be caused by slightly different reaction mechanisms of BSS isoenzymes. In comparison, lambda and/or ɛbulk values for the methyl monohydroxylation of toluene with oxygen as co-substrate were significantly different for two tested strains each containing a different toluene attacking enzyme, indicating that specific enzymes for aerobic methyl group oxidation reactions can be detected by CSIA and 2D-CSIA. Our results show that the combined carbon and hydrogen isotope fractionation approach has great potential to elucidate biodegradation pathways of monoaromatic hydrocarbons in microcosm and field studies. Current work focus on (i) 2D-CSIA of aromatic and aliphatic hydrocarbons in degradation experiments using whole cells, and (ii) 2D-CSIA of aromatic hydrocarbons in in vitro experiments using cell extracts. [1] Fischer et al. (2008) Environ. Sci. Technol. 42, 4356-4363 [2] Mancini et al. (2008) Environ. Sci. Technol. 42, 8290-8296 [3] Vogt et al. (2008) Environ. Sci. Technol. 42, 7793-7800 [4] Tobler et al. (2008) Environ. Sci. Technol. 42, 7786-7792 [5] Herrmann et al. (2009) Environ. Microbiol. Reports 1, 535-544

Tritium isotope fractionation in biological systems and in analytical procedures

International Nuclear Information System (INIS)

Kim, M.A.; Baumgaertner, Franz

1989-01-01

The organically bound tritium (OBT) is evaluated in biological systems by determining the tritium distribution ratio (R-value), i.e. tritium concentrations in organic substance to cell water. The determination of the R-value always involves isotope fractionation is applied analytical procedures and hence the evaluation of the true OBT -value in a given biological system appears more complicated than hitherto known in the literature. The present work concentrates on the tritium isotope fractionation in the cell water separation and on the resulting effects on the R-value. The analytical procedures examined are vacuum freeze drying under equilibrium and non-equilibrium conditions and azeotropic distillation. The vaporization isotope effects are determined separately in the phase transition of solid or liquid to gas in pure tritium water systems as well as in real biological systems, e.g. corn plant. The results are systematically analyzed and the influence of isotope effects on the R-value is rigorously quantified

Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin

Energy Technology Data Exchange (ETDEWEB)

Shen, Xiaoli [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Department of Environmental Engineering, Quzhou University, Quzhou 324000 (China); Xu, Zemin [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhang, Xichang [Laboratory for Teaching in Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Yang, Fangxing, E-mail: fxyang@zju.edu.cn [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Department of Effect-Directed Analysis, Helmholtz Centre for Environmental Research — UFZ, Leipzig 04318 (Germany)

2015-11-01

In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2 mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10 mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from − 29.0‰ to − 26.5‰ in soil spiked with 2 mg/kg lambda-cyhalothrin, and to − 27.5‰ with 10 mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as − 2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. - Highlights: • Abiotic and biotic degradation of lambda-cyhalothrin were observed in soil. • Biodegradation of lambda-cyhalothrin was evaluated by CSIA. • Biodegradation of lambda-cyhalothrin leads to carbon isotope fractionation. • An enrichment factor ε of lambda-cyhalothrin was determined as − 2.53‰.

Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin

International Nuclear Information System (INIS)

Shen, Xiaoli; Xu, Zemin; Zhang, Xichang; Yang, Fangxing

2015-01-01

In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2 mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10 mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from − 29.0‰ to − 26.5‰ in soil spiked with 2 mg/kg lambda-cyhalothrin, and to − 27.5‰ with 10 mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as − 2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. - Highlights: • Abiotic and biotic degradation of lambda-cyhalothrin were observed in soil. • Biodegradation of lambda-cyhalothrin was evaluated by CSIA. • Biodegradation of lambda-cyhalothrin leads to carbon isotope fractionation. • An enrichment factor ε of lambda-cyhalothrin was determined as − 2.53‰

Diet-consumer nitrogen isotope fractionation for prolonged fasting arthropods.

Science.gov (United States)

Mizota, Chitoshi; Yamanaka, Toshiro

2011-12-01

Nitrogen acquisition for cellular metabolism during diapause is a primary concern for herbivorous arthropods. Analyses of naturally occurring stable isotopes of nitrogen help elucidate the mechanism. Relevant articles have cited (58 times up to mid-June 2011) anomalously elevated δ(15)N (per mil deviation of (15)N/(14)N, relative to atmospheric nitrogen=0 ‰) values (diet-consumer nitrogen isotope fractionation; up to 12 ‰) for a prolonged fasting raspberry beetle (Byturus tomentosus Degeer (Coleoptera: Byturidae)), which feeds on red raspberries (Rubus idaeus: δ(15)N= ~ +2 ‰). Biologists have hypothesised that extensive recycling of amino acid nitrogen is responsible for the prolonged fasting. Since this hypothesis was proposed in 1995, scientists have integrated biochemical and molecular knowledge to support the mechanism of prolonged diapausing of animals. To test the validity of the recycling hypothesis, we analysed tissue nitrogen isotope ratios for four Japanese arthropods: the shield bug Parastrachia japonensis Scott (Hemiptera: Cydnidae), the burrower bug Canthophorus niveimarginatus Scott (Hemiptera: Cydnidae), leaf beetle Gastrophysa atrocyanea Motschulsky (Coleoptera: Chrysomelidae) and the Japanese oak silkworm Antheraea yamamai (Lepidoptera: Saturniidae), all of which fast for more than 6 months as part of their life-history strategy. Resulting diet-consumer nitrogen isotope discrimination during fasting ranged from 0 to 7‰, as in many commonly known terrestrial arthropods. We conclude that prolonged fasting of arthropods does not always result in anomalous diet-consumer nitrogen isotope fractionation, since the recycling process is closed or nearly closed with respect to nitrogen isotopes.

CARBON ISOTOPE FRACTIONATION IN PROTOPLANETARY DISKS

International Nuclear Information System (INIS)

Woods, Paul M.; Willacy, Karen

2009-01-01

We investigate the gas-phase and grain-surface chemistry in the inner 30 AU of a typical protoplanetary disk (PPD) using a new model which calculates the gas temperature by solving the gas heating and cooling balance and which has an improved treatment of the UV radiation field. We discuss inner-disk chemistry in general, obtaining excellent agreement with recent observations which have probed the material in the inner regions of PPDs. We also apply our model to study the isotopic fractionation of carbon. Results show that the fractionation ratio, 12 C/ 13 C, of the system varies with radius and height in the disk. Different behavior is seen in the fractionation of different species. We compare our results with 12 C/ 13 C ratios in the solar system comets, and find a stark contrast, indicative of reprocessing.

CO2-dependent carbon isotope fractionation in the dinoflagellate Alexandrium tamarense

Science.gov (United States)

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

2017-09-01

The carbon isotopic composition of marine sedimentary organic matter is used to resolve long-term histories of pCO2 based on studies indicating a CO2-dependence of photosynthetic carbon isotope fractionation (εP). It recently was proposed that the δ13C values of dinoflagellates, as recorded in fossil dinocysts, might be used as a proxy for pCO2. However, significant questions remain regarding carbon isotope fractionation in dinoflagellates and how such fractionation may impact sedimentary records throughout the Phanerozoic. Here we investigate εP as a function of CO2 concentration and growth rate in the dinoflagellate Alexandrium tamarense. Experiments were conducted in nitrate-limited chemostat cultures. Values of εP were measured on cells having growth rates (μ) of 0.14-0.35 d-1 and aqueous carbon dioxide concentrations of 10.2-63 μmol kg-1 and were found to correlate linearly with μ/[CO2(aq)] (r2 = 0.94) in accord with prior, analogous chemostat investigations with eukaryotic phytoplankton. A maximum fractionation (εf) value of 27‰ was characterized from the intercept of the experiments, representing the first value of εf determined for an algal species employing Form II RubisCO-a structurally and catalytically distinct form of the carbon-fixing enzyme. This value is larger than theoretical predictions for Form II RubisCO and not significantly different from the ∼25‰ εf values observed for taxa employing Form ID RubisCO. We also measured the carbon isotope contents of dinosterol, hexadecanoic acid, and phytol from each experiment, finding that each class of biomarker exhibits different isotopic behavior. The apparent CO2-dependence of εP values in our experiments strengthens the proposal to use dinocyst δ13C values as a pCO2 proxy. Moreover, the similarity between the εf value for A. tamarense and the consensus value of ∼25‰ indicates that the CO2-sensitivity of carbon isotope fractionation saturates at similar CO2 levels across all three

Chromium isotope fractionation during oxidative weathering of a modern basaltic weathering profile

DEFF Research Database (Denmark)

D'Arcy, Joan Mary; Døssing, Lasse Nørbye; Frei, Robert

Chromium can be used as a tracer of redox sensitive environmental processes. In soils Cr (III) is inert, immobile and resides predominantly in minerals, clays and oxides. Cr (VI) is toxic, soluble and mobile and is usually lost from the soil to local run off. Chromium isotopes have been shown...... to fractionate under both reducing and oxidizing conditions [1, 2]. Recent studies on d53Cr isotopes in laterite soils show that oxidative weathering of Cr-bearing rocks is accompanied by an isotopic fractionation, where by the lighter isotopes are retained in the residual soil and the heavier isotope...... is enriched in local runoff [1]. This study aims to quantify the stable Cr isotope composition of two modern basaltic weathering profiles, to help better understand the processes that oxidize inert Cr (III) to toxic Cr (VI). We sampled basaltic weathering profiles and associated river waters from areas of two...

Chromium isotope fractionation during coprecipitation with calcium carbonate

DEFF Research Database (Denmark)

Rodler, Alexandra; Sánchez-Pastor, Nuria; Fernández-Díaz, Lurdes

The chromium (Cr) isotopic composition of carbonates can potentially be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenvironmental changes, for example related to the rise of oxygen during the Ar...... et al., 2007, Water Air Soil Poll. 179, 381-390. [2] Sánchez-Pastor et al., 2011, Cryst. Growth Des. 11, 3081-3089.......The chromium (Cr) isotopic composition of carbonates can potentially be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenvironmental changes, for example related to the rise of oxygen during...... the Archaean and Protoerozoic, needs careful assessment of the signal robustness and necessitates a thorough understanding of the Cr cycle in Earth system processes. We conducted experiments testing the incorporation and isotopic fractionation of chromate into the calcite lattice. Our experiments indicate...

Fe-isotope fractionation in magmatic-hydrothermal mineral deposits: A case study from the Renison Sn-W deposit, Tasmania

Science.gov (United States)

Wawryk, Christine M.; Foden, John D.

2015-02-01

We present 50 new iron isotopic analyses of source granite and mineral separates from the Renison tin deposit in western Tasmania. The aim of the study is to characterise the composition of minerals within a tin deposit associated with a reduced, S-type magma. We have analysed bulk samples of granite, and separates of pyrrhotite, pyrite, arsenopyrite, magnetite, chalcopyrite and siderite by multi-collector inductively coupled mass spectrometry. The isotopic compositions of mineral separates are consistent with theoretical predictions of equilibrium fractionation based on Mössbauer spectroscopy and other parametric calculations. Mineral-mineral pairs yield temperatures of formation that are in agreement with prior detailed fluid inclusion studies, but are spatially inconsistent with declining fluid temperatures with distance from the causative intrusion, limiting the use of Fe isotopes as a potential geothermometer, at least in this case. Comparison of our data with published data from other deposits clearly demonstrates that pyrite, magnetite and chalcopyrite from the hottest ore fluids (>300-400 °C) at Renison are isotopically heavier than minerals sampled from a deposit formed at similar temperatures, but associated with a more oxidised and less differentiated intrusion.

Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils

International Nuclear Information System (INIS)

Mahieu, Koenraad; De Visscher, Alex; Vanrolleghem, Peter A.; Van Cleemput, Oswald

2008-01-01

A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between 12 CH 4 , 13 CH 4 , and 12 CH 3 D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7 vol% in the concentration and a RMSD of 0.8 per mille in the δ 13 C value, with δ 13 C the relative 13 C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods

Fractionation in position-specific isotope composition during vaporization of environmental pollutants measured with isotope ratio monitoring by 13C nuclear magnetic resonance spectrometry

International Nuclear Information System (INIS)

Julien, Maxime; Parinet, Julien; Nun, Pierrick; Bayle, Kevin; Höhener, Patrick; Robins, Richard J.; Remaud, Gérald S.

2015-01-01

Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by 13 C NMR (irm- 13 C NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources. - Highlights: • Position-Specific Isotope Analysis (PSIA) by 13 C NMR spectrometry. • PSIA on isotope fractionation during several vaporization processes. • PSIA for isotope profiling in environment pollutants. • Intramolecular 13 C reveal normal and inverse effects, bulk values being unchanged. - PSIA in pollutants during evaporation processes shows more detailed information for discerning the nature of the process involved than does bulk isotope measurements

Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

Science.gov (United States)

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

1986-01-01

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

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

Science.gov (United States)

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

Fractionation of silver isotopes in native silver explained by redox reactions

Science.gov (United States)

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

2018-03-01

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

Scalable fractionation of iron oxide nanoparticles using a CO2 gas-expanded liquid system

International Nuclear Information System (INIS)

Vengsarkar, Pranav S.; Xu, Rui; Roberts, Christopher B.

2015-01-01

Iron oxide nanoparticles exhibit highly size-dependent physicochemical properties that are important in applications such as catalysis and environmental remediation. In order for these size-dependent properties to be effectively harnessed for industrial applications scalable and cost-effective techniques for size-controlled synthesis or size separation must be developed. The synthesis of monodisperse iron oxide nanoparticles can be a prohibitively expensive process on a large scale. An alternative involves the use of inexpensive synthesis procedures followed by a size-selective processing technique. While there are many techniques available to fractionate nanoparticles, many of the techniques are unable to efficiently fractionate iron oxide nanoparticles in a scalable and inexpensive manner. A scalable apparatus capable of fractionating large quantities of iron oxide nanoparticles into distinct fractions of different sizes and size distributions has been developed. Polydisperse iron oxide nanoparticles (2–20 nm) coated with oleic acid used in this study were synthesized using a simple and inexpensive version of the popular coprecipitation technique. This apparatus uses hexane as a CO 2 gas-expanded liquid to controllably precipitate nanoparticles inside a 1L high-pressure reactor. This paper demonstrates the operation of this new apparatus and for the first time shows the successful fractionation results on a system of metal oxide nanoparticles, with initial nanoparticle concentrations in the gram-scale. The analysis of the obtained fractions was performed using transmission electron microscopy and dynamic light scattering. The use of this simple apparatus provides a pathway to separate large quantities of iron oxide nanoparticles based upon their size for use in various industrial applications.

Chlorine isotope fractionation during supergene enrichment of copper

Science.gov (United States)

Reich, M.; Barnes, J.; Barra, F.; Milojevic, C.; Drew, D.

2017-12-01

Supergene enrichment of Cu deposits in the Atacama Desert has played a critical role in making this the prime Cu-producing province of the world. The Cu-hydroxychloride atacamite is a major component of supergene zones in this region whereas in similar deposits elsewhere it is rare. Atacamite requires saline water to form and dissolves rapidly when exposed to fresh, meteoric water. Previous chlorine stable isotope data [1] for atacamite mineralization at the Radomiro Tomic, Chuquicamata and Mina Sur Cu deposits show δ37Cl values that range from -0.1 to +0.2‰, indicating a similar nonmagmatic source for the introduction of chloride. However, distal atacamite mineralization on the periphery of these orebodies show more fractionated and lighter δ37Cl values (-3.2 to -0.1‰). Although little disagreement currently exists about the involvement of saline groundwater during the formation of atacamite [2], no δ37Cl data are currently available for atacamite within a single deposit and/or supergene enrichment profile that allow explaining the aforementioned differences in the observed δ37Cl values. Furthermore, no experimental data for chlorine isotope fractionation between Cu-hydroxychloride minerals and water exist that help evaluate possible mechanisms of fractionation along the groundwater flow path. Here we present a new database that combines detailed mineralogical observations with δ37Cl data of atacamite along a thick ( 100 m) supergene enrichment profile at the Barreal Seco IOCG deposit in the Atacama Desert of northern Chile. Chlorine stable isotope data of atacamite vary between -0.62 and +2.1 ‰ and show a well-defined trend where δ37Cl values progressively decrease (become lighter) with depth. These data, when combined with new experimental determinations of chlorine isotope fractionation between atacamite and water, point to changes triggered by the progressive deepening of groundwater tables during Andean uplift and the extreme desiccation of

Chromium stable isotope fractionation in modern biogeochemical cycling

DEFF Research Database (Denmark)

Paulukat, Cora Stefanie

oxygen in the Earth’s atmosphere. Oxidative rock weathering on land induces oxidation of immobile Cr(III) to mobile Cr(VI). Isotopically relatively heavy Cr(VI) is released to runoff, and transported by rivers to the oceans, where it is incorporated into chemical sediments and carbonate shells...... laterite soils from India, formed on ultramafic rocks, indicates extensive leaching of isotopically heavy Cr(VI). Transferring this knowledge to ancient weathering profiles, negatively fractionated Cr is clear evidence for the presence of free oxygen in the atmosphere. The second part demonstrates...

Bioavailability of iron to rats from processed soybean fractions determined by intrinsic and extrinsic labeling techniques

International Nuclear Information System (INIS)

Weaver, C.M.; Nelson, N.; Elliott, J.G.

1984-01-01

Intrinsic and extrinsic labeling techniques were used to measure iron bioavailability from soybean fractions (isolated soy protein, defatted flour, soy hulls, insoluble material and whey) by iron-depleted and non-iron-depleted rats. As expected, absorption of iron was higher in the iron-depleted than in the non-iron-depleted rats. In the iron-depleted group, significantly more iron was absorbed from soy whey than from other fractions. No other significant difference in iron absorption associated with iron source was observed. The higher absorption rate of iron from whey by the iron-depleted rats probably was related to a lower quantity of food consumed during the test meal by this group. Intrinsic and extrinsic labeling techniques produced similar assessments of bioavailability of iron

Fractionation of hydrogen isotopes by sulfate- and nitrate-reducing bacteria

OpenAIRE

Magdalena Rose Osburn; Katherine S Dawson; Marilyn L Fogel; Alex Sessions

2016-01-01

Hydrogen atoms from water and food are incorporated into biomass during cellular metabolism and biosynthesis, fractionating the isotopes of hydrogen –protium and deuterium –that are recorded in biomolecules. While these fractionations are often relatively constant in plants, large variations in the magnitude of fractionation are observed for many heterotrophic microbes utilizing different central metabolic pathways. The correlation between metabolism and lipid δ2H provides a potential basis f...

Oxygen isotopic fractionation of O₂ during adsorption and desorption processes using molecular sieve at low temperatures.

Science.gov (United States)

Ahn, Insu; Kusakabe, Minoru; Lee, Jong Ik

2014-06-15

Cryogenic trapping using molecular sieves is commonly used to collect O2 extracted from silicates for (17)O/(16)O and (18)O/(16)O analyses. However, gases which interfere with (17)O/(16)O analysis, notably NF3, are also trapped and their removal is essential for accurate direct measurement of the (17)O/(16)O ratio. It is also necessary to identify and quantify any isotopic fractionation associated with the use of cryogenic trapping using molecular sieves. The oxygen isotopic compositions of O2 before and after desorption from, and adsorption onto, 13X and 5A molecular sieves (MS13X and MS5A) at 0°C, -78°C, -114°C, and -130°C were measured in order to determine the oxygen isotopic fractionation at these temperatures. We also investigated whether isotopic fractionation occurred when O2 gas was transferred sequentially into a second cold finger, also containing molecular sieve. It was confirmed that significant oxygen isotopic fractionation occurs between the gaseous O2 and that adsorbed onto molecular sieve, if desorption and adsorption are incomplete. As the fraction of released or untrapped O2 becomes smaller with decreasing trapping temperature (from 0 to -130°C), the isotopic fractionation becomes larger. Approximately half of the total adsorbed O2 is released from the molecular sieve during desorption at -114°C, which is the temperature recommended for separation from NF3 (retained on the molecular sieve), and this will interfere with (17)O/(16)O measurements. The use of a single cold finger should be avoided, because partial desorption is accompanied by oxygen isotopic fractionation, thereby resulting in inaccurate isotopic data. The use of a dual cold finger arrangement is recommended because, as we have confirmed, the transfer of O2 from the first trap to the second is almost 100%. However, even under these conditions, a small isotopic fractionation (0.18 ± 0.05‰ in δ(17)O values and 0.26 ± 0.06‰ in δ(18)O values) occurred, with O2 in

Carbon isotope fractionation by thermophilic phototrophic sulfur bacteria: evidence for autotrophic growth in natural populations

Science.gov (United States)

Madigan, M. T.; Takigiku, R.; Lee, R. G.; Gest, H.; Hayes, J. M.

1989-01-01

Purple phototrophic bacteria of the genus Chromatium can grow as either photoautotrophs or photoheterotrophs. To determine the growth mode of the thermophilic Chromatium species, Chromatium tepidum, under in situ conditions, we have examined the carbon isotope fractionation patterns in laboratory cultures of this organism and in mats of C. tepidum which develop in sulfide thermal springs in Yellowstone National Park. Isotopic analysis (13C/12C) of total carbon, carotenoid pigments, and bacteriochlorophyll from photoautotrophically grown cultures of C. tepidum yielded 13C fractionation factors near -20%. Cells of C. tepidum grown on excess acetate, wherein synthesis of the Calvin cycle enzyme ribulose-1,5-bisphosphate carboxylase/oxygenase ribulose bisphosphate carboxylase) was greatly repressed, were isotopically heavier, fractionation factors of ca. -7% being observed. Fractionation factors determined by isotopic analyses of cells and pigment fractions of natural populations of C. tepidum growing in three different sulfide thermal springs in Yellowstone National Park were approximately -20%, indicating that this purple sulfur bacterium grows as a photoautotroph in nature.

Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

Science.gov (United States)

Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

2013-05-01

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

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

Directory of Open Access Journals (Sweden)

F. Keppler

2018-05-01

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

Isotopic fractionation and profile evolution of a melting snowcover

Institute of Scientific and Technical Information of China (English)

周石硚; 中尾正义; 桥本重将; 坂井亚规子; 成田英器; 石川信敬

2001-01-01

Successive snow pits were dug intensively in a melting snowcover. Water was successfully separated from snow grains in the field for the first time. By measuring δ18O values of water and snow grain samples as well as comparing isotopic profiles, it is found that meltwater percolating down in snow develops quick and clear isotopic fractionation with snow grains, but exerts no clear impact on the δ18O profile of the snowcover through which the meltwater percolates.

Magnesium isotope fractionation in bacterial mediated carbonate precipitation experiments

Science.gov (United States)

Parkinson, I. J.; Pearce, C. R.; Polacskek, T.; Cockell, C.; Hammond, S. J.

2012-12-01

Magnesium is an essential component of life, with pivotal roles in the generation of cellular energy as well as in plant chlorophyll [1]. The bio-geochemical cycling of Mg is associated with mass dependant fractionation (MDF) of the three stable Mg isotopes [1]. The largest MDF of Mg isotopes has been recorded in carbonates, with foraminiferal tests having δ26Mg compositions up to 5 ‰ lighter than modern seawater [2]. Magnesium isotopes may also be fractionated during bacterially mediated carbonate precipitation and such carbonates are known to have formed in both modern and ancient Earth surface environments [3, 4], with cyanobacteria having a dominant role in carbonate formation during the Archean. In this study, we aim to better constrain the extent to which Mg isotope fractionation occurs during cellular processes, and to identify when, and how, this signal is transferred to carbonates. To this end we have undertaken biologically-mediated carbonate precipitation experiments that were performed in artificial seawater, but with the molar Mg/Ca ratio set to 0.6 and with the solution spiked with 0.4% yeast extract. The bacterial strain used was marine isolate Halomonas sp. (gram-negative). Experiments were run in the dark at 21 degree C for two to three months and produced carbonate spheres of various sizes up to 300 μm in diameter, but with the majority have diameters of ~100 μm. Control experiments run in sterile controls (`empty` medium without bacteria) yielded no precipitates, indicating a bacterial control on the precipitation. The carbonate spheres are produced are amenable to SEM, EMP and Mg isotopic analysis by MC-ICP-MS. Our new data will shed light on tracing bacterial signals in carbonates from the geological record. [1] Young & Galy (2004). Rev. Min. Geochem. 55, p197-230. [2] Pogge von Strandmann (2008). Geochem. Geophys. Geosys. 9 DOI:10.1029/2008GC002209. [3] Castanier, et al. (1999). Sed. Geol. 126, 9-23. [4] Cacchio, et al. (2003

Stable chromium isotopic composition of meteorites and metal-silicate experiments: Implications for fractionation during core formation

Science.gov (United States)

Bonnand, P.; Williams, H. M.; Parkinson, I. J.; Wood, B. J.; Halliday, A. N.

2016-02-01

We present new mass independent and mass dependent Cr isotope compositions for meteorites measured by double spike thermal ionisation mass spectrometry. Small differences in both mass independent 53Cr and 54Cr relative to the Bulk Silicate Earth are reported and are very similar to previously published values. Carbonaceous chondrites are characterised by an excess in 54Cr compared to ordinary and enstatite chondrites which make mass independent Cr isotopes a useful tool for distinguishing between meteoritic groups. Mass dependent stable Cr isotope compositions for the same samples are also reported. Carbonaceous and ordinary chondrites are identical within uncertainty with average δ53 Cr values of - 0.118 ± 0.040 ‰ and - 0.143 ± 0.074 ‰ respectively. The heaviest isotope compositions are recorded by an enstatite chondrite and a CO carbonaceous chondrite, both of which have relatively reduced chemical compositions implying some stable Cr isotope fractionation related to redox processes in the circumstellar disk. The average δ53 Cr values for chondrites are within error of the estimate for the Bulk Silicate Earth (BSE) also determined by double spiking. The lack of isotopic difference between chondritic material and the BSE provides evidence that Cr isotopes were not fractionated during core formation on Earth. A series of high-pressure experiments was also carried out to investigate stable Cr isotope fractionation between metal and silicate and no demonstrable fractionation was observed, consistent with our meteorites data. Mass dependent Cr isotope data for achondrites suggest that Cr isotopes are fractionated during magmatic differentiation and therefore further work is required to constrain the Cr isotopic compositions of the mantles of Vesta and Mars.

Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin.

Science.gov (United States)

Shen, Xiaoli; Xu, Zemin; Zhang, Xichang; Yang, Fangxing

2015-11-01

In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from -29.0‰ to -26.5‰ in soil spiked with 2mg/kg lambda-cyhalothrin, and to -27.5‰ with 10mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as -2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. Copyright © 2015 Elsevier B.V. All rights reserved.

Pressure dependent isotopic fractionation in the photolysis of formaldehyde-d2

DEFF Research Database (Denmark)

Nilsson, E.J.K.; Schmidt, Johan Albrecht; Johnson, Matthew Stanley

2014-01-01

role in the observed pressure dependent photolytic fractionation of deuterium. The model shows that part of the fractionation is a result of competition between the isotopologue dependent rates of unimolecular dissociation and collisional relaxation. We suggest that the remaining fractionation is due......The isotope effects in formaldehyde photolysis are the key link between the δD of methane emissions and the δD of atmospheric in situ hydrogen production. A few recent studies have suggested that a pressure dependence in the isotopic fractionation can partly explain enrichment of deuterium...... with altitude in the atmosphere. The mechanism and the extent of this pressure dependency is, however, not adequately described. In the present work D2CO and H2CO were photolyzed in a static reaction chamber at bath gas pressures of 50, 200, 400, 600 and 1000 mbar; these experiments compliment and extend our...

Calcium isotope fractionation in liquid chromatography with benzo-18-crown-6 resin in aqueous hydrobromic acid medium

International Nuclear Information System (INIS)

Sato, Takuya; Oi, Takao

2015-01-01

Liquid chromatography operated in a breakthrough mode was employed to study calcium isotope fractionation in the aqueous hydrobromic acid medium. Highly porous silica beads, the inner pores of which were embedded with a benzo-18-crown-6 ether resin, were used as column packing material. Enrichment of heavier isotopes of calcium was observed in the frontal part of respective calcium chromatograms. The values of the isotope fractionation coefficient were on the order of 10 -3 . The observed isotope fractionation coefficient was dependent on the concentration of hydrobromic acid in the calcium feed solution; a higher HBr concentration resulted in a smaller fractionation coefficient value. The present calcium isotope effects were most probably mass-dependent, indicating that they mostly came from isotope effects based on molecular vibration. Molecular orbital calculations supported the present experimental results in a qualitative fashion. Chromatography operated in aqueous HBr media is a better system of Ca isotope separation than that operated in aqueous HCl media. (author)

Can a sponge fractionate isotopes?

Science.gov (United States)

Patel, B; Patel, S; Balani, M C

1985-03-22

activities can be modified is by fractionation on the basis of mass of isotope. In view of the remarkable concentration factors observed for stable and radioactive isotopes of the same element and the specific activities reached, it is desirable that species of sponges, especially from the coastal and estuarine environments, be monitored to detect levels of pollution due to anthropogenic substances.

Isotopic fractionation associated with [NiFe]- and [FeFe]-hydrogenases

Energy Technology Data Exchange (ETDEWEB)

Yang, Hui; Gandhi, Hasand; Cornish, Adam J.; Moran, James J.; Kreuzer, Helen W.; Ostrom, Nathaniel; Hegg, Eric L.

2016-01-30

Hydrogenases catalyze the reversible formation of H2 from electrons and protons with high efficiency. Understanding the relationships between H2 production, H2 uptake, and H2-H2O exchange can provide insight into the metabolism of microbial communities in which H2 is an essential component in energy cycling. In this manuscript, we used stable H isotopes (1H and 2H) to probe the isotope effects associated with three [FeFe]-hydrogenases and three [NiFe]-hydrogenases. All six hydrogenases displayed fractionation factors for H2 formation that were significantly less than 1, producing H2 that was severely depleted in 2H relative to the substrate, water. Consistent with differences in their active site structure, the fractionation factors for each class appear to cluster, with the three [NiFe]-hydrogenases (α = 0.27-0.40) generally having smaller values than the three [FeFe]-hydrogenases (α = 0.41-0.55). We also obtained isotopic fractionation factors associated with H2 uptake and H2-H2O exchange under conditions similar to those utilized for H2 production, providing us with a more complete picture of the three reactions catalyzed by hydrogenases. The fractionation factors determined in our studies can be used as signatures for different hydrogenases to probe their activity under different growth conditions and to ascertain which hydrogenases are most responsible for H2 production and/or uptake in complex microbial communities.

Isotopic fractionation during the uptake and elimination of inorganic mercury by a marine fish

International Nuclear Information System (INIS)

Xu, Xiaoyu; Wang, Wen-Xiong

2015-01-01

This study investigated the mass dependent (MDF) and independent fractionation (MIF) of stable mercury isotopes in fish during the uptake and elimination of inorganic species. Mercury accumulation during the exposure led to re-equilibration of organ isotopic compositions with the external sources, and elimination terminated the equilibrating with isotope ratios moving back to the original values. Generally, the isotopic behaviors corresponded to the changes of Hg accumulation in the muscle and liver, causing by the internal transportation, organ redistribution, and mixing of different sources. A small degree of MDF caused by biotransformation of Hg in the liver was documented during the elimination, whereas MIF was not observed. The absence of MIF during geochemical and metabolic processes suggested that mercury isotopes can be used as source tracers. Additionally, fish liver is a more responsive organ than muscle to track Hg source when it is mainly composed of inorganic species. - Highlights: • Isotopic behavior of Hg(II) during the uptake and elimination by a marine fish was studied. • Hg isotopic fractionation in the organ corresponded to the changes of Hg bioaccumulation. • Internal transportation, redistribution and mixing of different sources explained the isotopic changes. • Mass dependent fractionation in the liver was found during Hg elimination. • Liver is more responsive than muscle to track Hg sources using Hg stable isotopes. - Fish liver is a more responsive organ than muscle when mercury stable isotopes are applied to track sources that are mainly composed of inorganic species.

Isotopic fractionation of gases during its migration: experiments and 2D numerical simulation

Science.gov (United States)

Kara, S.; Prinzhofer, A.

2003-04-01

Several works have been developed in the last decade on the experimental isotope fractionation of gases during migration (Prinzhofer et al., 1997 and Zhang &Krooss, 2001 among others). We add to these results new experiments on diffusion of CO_2, which becomes currently a crucial subject for environmental purpose. Our experiments showed that transport by diffusion of CO_2 through a water saturated shale induces a significant and systematic carbon isotopic fractionation with heavier (13C enriched) CO_2 migrating first. In all experiments, significant isotope fractionation was found but still remains without quantitative interpretation. To interpret these data, we developed a 2D numerical model at the pore scale. The general principle of this model is the study of transport by water solubilization/diffusion of gas in a capillary saturated with water with two different media : a mobile zone representing free water and a immobile zone representing bounded water. The model takes also into account solubilization coefficients of gas in water, as well as the migration distance and the volume of upstream and downstream reservoirs. Using our numerical model, we could reproduce the evolution of isotopic fractionations and the velocity of CO_2 migration versus the production factor F (proportion of diffused gas). We determined some physical parameters of the porous medium (bentonite) which are not directly measurable at the present time. Furthermore, we used these parameters to reproduce the curves of isotopic fractionation obtained by Pernaton (1998) on methane migration with the same porous rock. We used also a modified version of this model with infinite reservoirs to reproduce the curves of isotopic fractionation of Zhang &Krooss (2001). Application of this model to geological scale is under progress, in order to implement it into sedimentary basins modelling. REFERENCES: Zhang T. and Krooss M. (2001). Geochim. Cosmochim. Acta, Vol. 65, No.16, pp. 2723-2742. Pernaton E

Observations of Carbon Isotopic Fractionation in Interstellar Formaldehyde

Science.gov (United States)

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

2012-01-01

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

Micro-scale novel stable isotope fractionation during weathering disclosed by femtosecond laser ablation

Science.gov (United States)

Schuessler, J. A.; von Blanckenburg, F.

2012-12-01

The stable isotope fractionation of metals and metalloids during chemical weathering and alteration of rocks at low temperature is a topic receiving increasing scientific attention. For these systems, weathering of primary minerals leads to selective partitioning of isotopes between the secondary minerals formed from them, and the dissolved phase of soil or river water. While the isotopic signatures of these processes have been mapped-out at the catchment or the soil scale, the actual isotopic fractionation is occurring at the mineral scale. To identify the processes underlying such micro-scale fractionation, the development of micro-analytical tools allows to investigate mechanisms of isotope fractionation in-situ, in combination with textural information of weathering reactions. We have developed a second-generation UV femtosecond (fs) laser system at GFZ Potsdam. The advantage of UV-fs laser ablation is the reduction of laser-induced isotopic and elemental fractionation by avoiding 'thermal effects' during ablation, such that accurate isotope ratios can be measured by standard-sample-standard bracketing using laser ablation multicollector ICP-MS; where the matrix of the bracketing standard does not need to match that of the sample [1]. Our system consists of the latest generation femtosecond solid-state laser (Newport Spectra Physics Solstice), producing an ultra short pulse width of about 100 femtoseconds at a wavelength of 196 nm. The system is combined with a custom-build computer-controlled sample stage and allows fully automated isotope analyses through synchronised operation of the laser with the Neptune MC-ICP-MS. To assess precision and accuracy of our laser ablation method, we analysed various geological reference materials. We obtained δ30Si values of -0.31 ± 0.23 (2SD, n = 13) for basalt glass BHVO-2G, and -1.25 ± 0.21 (2SD, n = 27) for pure Si IRMM17 when bracketed against NBS-28 quartz. δ56Fe and δ26Mg values obtained from non-matrix matched

Cadmium isotope fractionation of materials derived from various industrial processes

Energy Technology Data Exchange (ETDEWEB)

Martinková, Eva, E-mail: eva.cadkova@geology.cz [Czech Geological Survey, Geologická 6, 152 00 Prague 5 (Czech Republic); Chrastný, Vladislav, E-mail: chrastny@fzp.czu.cz [Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcká 129, 165 21 Prague 6 (Czech Republic); Francová, Michaela, E-mail: michaela.francova@fzp.czu.cz [Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcká 129, 165 21 Prague 6 (Czech Republic); Šípková, Adéla, E-mail: adela.sipkova@geology.cz [Czech Geological Survey, Geologická 6, 152 00 Prague 5 (Czech Republic); Čuřík, Jan, E-mail: jan.curik@geology.cz [Czech Geological Survey, Geologická 6, 152 00 Prague 5 (Czech Republic); Myška, Oldřich, E-mail: oldrich.myska@geology.cz [Czech Geological Survey, Geologická 6, 152 00 Prague 5 (Czech Republic); Mižič, Lukáš, E-mail: lukas.mizic@geology.cz [Czech Geological Survey, Geologická 6, 152 00 Prague 5 (Czech Republic)

2016-01-25

Highlights: • All studied industrial processes were accompanied by Cd isotope fractionation. • ϵ{sup 114/110} Cd values of the waste materials were discernible from primary sources. • Technology in use plays an important role in Cd isotope fractionation. - Abstract: Our study represents ϵ{sup 114/110} Cd {sub NIST3108} values of materials resulting from anthropogenic activities such as coal burning, smelting, refining, metal coating, and the glass industry. Additionally, primary sources (ore samples, pigment, coal) processed in the industrial premises were studied. Two sphalerites, galena, coal and pigment samples exhibited ϵ{sup 114/110} Cd{sub NIST3108} values of 1.0 ± 0.2, 0.2 ± 0.2, 1.3 ± 0.1, −2.3 ± 0.2 and −0.1 ± 0.3, respectively. In general, all studied industrial processes were accompanied by Cd isotope fractionation. Most of the industrial materials studied were clearly distinguishable from the samples used as a primary source based on ϵ{sup 114/110} Cd {sub NIST3108} values. The heaviest ϵ{sup 114/110} Cd{sub NIST3108} value of 58.6 ± 0.9 was found for slag resulting from coal combustion, and the lightest ϵ{sup 114/110} Cd{sub NIST3108} value of −23 ± 2.5 was observed for waste material after Pb refinement. It is evident that ϵ{sup 114/110} Cd {sub NIST3108} values depend on technological processes, and in case of incomplete Cd transfer from source to final waste material, every industrial activity creates differences in Cd isotope composition. Our results show that Cd isotope analysis is a promising tool to track the origins of industrial waste products.

Mass-Dependent and -Independent Fractionation of Mercury Isotopes in Aquatic Systems

Science.gov (United States)

Bergquist, B. A.; Joel, B. D.; Jude, D. J.

2008-12-01

Mercury is a globally distributed and highly toxic pollutant. Although Hg is a proven health risk, much of the natural cycle of Hg is not well understood and new approaches are needed to track Hg and the chemical transformations it undergoes in the environment. Recently, we demonstrated that Hg isotopes exhibit two types of isotope fractionation: (1) mass dependent fractionation (MDF) and (2) mass independent fractionation (MIF) of only the odd isotopes (Bergquist and Blum, 2007). The observation of large MIF of Hg isotopes (up to 5 permil) is exciting because only a few other isotopic systems have been documented to display large MIF, the most notable of which are oxygen and sulfur. In both cases, the application of MIF has proven very useful in a variety of fields including cosmochemistry, paleoclimatology, physical chemistry, atmospheric chemistry, and biogeochemistry. Both MDF and MIF isotopic signatures are observed in natural samples, and together they open the door to a new method for tracing Hg pollution and for investigating Hg behavior in the environment. For example, fish record MDF that appears to be related to size and age. Additionally, fish display MIF signatures that are consistent with the photo-reduction of methylmercury (Bergquist and Blum, 2007). If the MDF and MIF in ecosystems can be understood, the signatures in fish could inform us about the sources and processes transforming Hg and why there are differences in the bioaccumulation of Hg in differing ecosystems and populations of fish. This requires sampling of a variety of ecosystems, the sampling of many components of the ecosystems, and the use of other tracers such as carbon and nitrogen isotopes. We have expanded our studies of aquatic ecosystems to include several lakes in North America. Similar to other isotopic systems used to study food web dynamics and structure (i.e., C and N), the MDF of Hg in fish appears to be related to size and age. The MDF recorded in fish likely reflects

Determination of Trace Iron in Red Wine by Isotope Dilution Mass Spectrometry Using Multiple-Collector Inductively Coupled Plasma Mass Spectrometry

International Nuclear Information System (INIS)

Zhou Tao; Wang Jun; Lu Hai; Zhou Yuanjing; Li Haifeng

2009-01-01

This paper introduces determination of trace iron in red wine certified reference material by isotope dilution mass spectrometry (IDMS) method using a multiplecollector inductively coupled plasma mass spectrometry, equipped with a hexapole collision cell. The measurement procedure of iron isotopic abundance ratios was deeply researched. Reduced polyatomic ion interferences to iron isotopes ion by collision reaction using Ar and H 2 gas, high precise isotopic abundance ratios were achieved. Two relative measurement methods (ICP-MS and ICP-OES) were used to analyze trace iron in red wine. The results are compared with IDMS results, which indicate that they are accordant. The uncertainty analyses include each uncertainty factor in whole experiment and the uncertainty of used certified reference material and it shows that the procedure blank is not neglectable to detect limit and precision of the method. The establishment of IDMS method for analysis of trace iron in red wine supports the certification of certified reference materials. (authors)

Scalable fractionation of iron oxide nanoparticles using a CO{sub 2} gas-expanded liquid system

Energy Technology Data Exchange (ETDEWEB)

Vengsarkar, Pranav S.; Xu, Rui; Roberts, Christopher B., E-mail: croberts@eng.auburn.edu [Auburn University, Department of Chemical Engineering (United States)

2015-10-15

Iron oxide nanoparticles exhibit highly size-dependent physicochemical properties that are important in applications such as catalysis and environmental remediation. In order for these size-dependent properties to be effectively harnessed for industrial applications scalable and cost-effective techniques for size-controlled synthesis or size separation must be developed. The synthesis of monodisperse iron oxide nanoparticles can be a prohibitively expensive process on a large scale. An alternative involves the use of inexpensive synthesis procedures followed by a size-selective processing technique. While there are many techniques available to fractionate nanoparticles, many of the techniques are unable to efficiently fractionate iron oxide nanoparticles in a scalable and inexpensive manner. A scalable apparatus capable of fractionating large quantities of iron oxide nanoparticles into distinct fractions of different sizes and size distributions has been developed. Polydisperse iron oxide nanoparticles (2–20 nm) coated with oleic acid used in this study were synthesized using a simple and inexpensive version of the popular coprecipitation technique. This apparatus uses hexane as a CO{sub 2} gas-expanded liquid to controllably precipitate nanoparticles inside a 1L high-pressure reactor. This paper demonstrates the operation of this new apparatus and for the first time shows the successful fractionation results on a system of metal oxide nanoparticles, with initial nanoparticle concentrations in the gram-scale. The analysis of the obtained fractions was performed using transmission electron microscopy and dynamic light scattering. The use of this simple apparatus provides a pathway to separate large quantities of iron oxide nanoparticles based upon their size for use in various industrial applications.

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

Science.gov (United States)

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

2013-01-01

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

Carbon and Hydrogen Stable Isotope Fractionation during Aerobic Bacterial Degradation of Aromatic Hydrocarbons†

Science.gov (United States)

Morasch, Barbara; Richnow, Hans H.; Schink, Bernhard; Vieth, Andrea; Meckenstock, Rainer U.

2002-01-01

13C/12C and D/H stable isotope fractionation during aerobic degradation was determined for Pseudomonas putida strain mt-2, Pseudomonas putida strain F1, Ralstonia pickettii strain PKO1, and Pseudomonas putida strain NCIB 9816 grown with toluene, xylenes, and naphthalene. Different types of initial reactions used by the respective bacterial strains could be linked with certain extents of stable isotope fractionation during substrate degradation. PMID:12324375

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

Science.gov (United States)

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.

Biological fractionation of lead isotopes in Sprague-Dawley rats lead poisoned via the respiratory tract.

Directory of Open Access Journals (Sweden)

Jing Wu

Full Text Available It was considered that lead isotope ratios did not change during physical, chemical, or biological processes. Thus, lead isotope ratios have been used as fingerprints to identify possible lead sources. However, recent evidence has shown that the lead isotope ratios among different biological samples in human are not always identical from its lead origins in vitro. An animal experiment was conducted to explore the biological fractionation of lead isotopes in biological systems.24 male Sprague-Dawley (SD rats were divided into groups that received acute lead exposure (0, 0.02, 0.2, or 2 mg/kg body weight of lead acetate via the respiratory route every day for 5 days. Biological samples (i.e., blood, urine, and feces were collected for comparison with the lead acetate (test substance and the low-lead animal feed (diet administered to the rats. The lead isotope ratios were determined by inductively coupled plasma mass spectrometry (ICP-MS.There are significant differences (p<0.05 in lead isotope ratios between blood, urine, and feces. Moreover, a nonlinear relationship between the blood lead concentration and the blood lead isotope ratios was observed. There is also a threshold effect to the fractionation function. Only the blood isotope ratio of (204Pb/(206Pb matches the test substance well. As for feces, when (204Pb/(206Pb ratio is considered, there is no significant difference between feces-test substance pairs in medium and high dose group.The biological fractionation of lead isotopes in SD rats was observed. Moreover, there might be a threshold for the biological fractionation of lead isotopes which is depending on whole blood lead level. It is considered to be more reliable that we compared the isotope ratios of potential lead hazards with both blood and feces lead fingerprints especially for (204Pb/(206Pb ratio under high-dose exposure.

Effect Of Substrates On The Fractionation Of Hydrogen Isotopes During Lipid-Biosynthesis By Haloarcula marismortui

Science.gov (United States)

Dirghangi, S. S.; Pagani, M.

2010-12-01

Lipids form an important class of proxies for paleoclimatological research, and hydrogen isotope ratios of lipids are being increasingly used for understanding changes in the hydrological system. Proper understanding of hydrogen isotope fractionation during lipid biosynthesis is therefore important and attention has been directed toward understanding the magnitude of hydrogen isotope fractionation that occurs during lipid biosynthesis in various organisms. Hydrogen isotope ratios of lipids depend on the hydrogen isotopic composition of the ambient water, hydrogen isotopic composition of NADPH used during biosynthesis, growth conditions, pathways of lipid biosynthesis, and substrates in the case of heterotrophic organisms. Recently it has been observed that NADPH contributes a significant part of the hydrogen in fatty acids synthesized by bacteria during heterotrophic growth (Zhang et al, 2009). As NADPH is formed by reduction of NADP+ during metabolism of substrates, different metabolic pathways form NADPH with different D/H ratios, which in turn results in variation in D/H ratios of lipids (Zhang et al, 2009). Therefore, substrates play a significant role in hydrogen isotopic compositions of lipids. For this study, we are investigating the effects of substrates on hydrogen isotope fractionation during biosynthesis of isoprenoidal lipids by heterotrophically growing halophilic archaea. Haloarcula marismortui is a halophilic archaea which synthesizes Archaeol (a diether lipid) and other isoprenoidal lipids. We have grown Haloarcula marismortui in pure cultures on three different substrates and are in the process of evaluating isotopic variability of Archaeol and other lipids associated with substrate and the D/H composition of ambient water. Our results will be helpful for a better understanding of hydrogen isotope fractionations during lipid synthesis by archaea. Also, halophilic archaea are the only source of archaeol in hypersaline environments. Therefore, our

Assessment of Bacterial Degradation of Aromatic Hydrocarbons in the Environment by Analysis of Stable Carbon Isotope Fractionation

International Nuclear Information System (INIS)

Meckenstock, Rainer U.; Morasch, Barbara; Kaestner, Matthias; Vieth, Andrea; Richnow, Hans Hermann

2002-01-01

13 C/ 12 C stable carbon isotope fractionation was used to assess biodegradation in contaminated aquifers with toluene as a model compound. Different strains of anaerobic bacteria (Thauera aromatica, Geobacter metallireducens, and the sulfate-reducing strain TRM1) showed consistent 13 C/ 12 C carbon isotope fractionation with fractionation factors between αC = 1.0017 and 1.0018. In contrast, three cultures of aerobic organisms, using different mono- and dioxygenase enzyme systems to initiate toluene degradation, showed variable isotope fractionation factors of αC = 1.0027 (Pseudomonasputida strain mt-2), αC = 1.0011 (Ralstonia picketii), andαC = 1.0004 (Pseudomonas putida strain F1). The great variability of isotope fractionation between different aerobic bacterial strains suggests that interpretation of isotope data in oxic habitats can only be qualitative. A soil column was run as a model system for contaminated aquifers with toluene as the carbon source and sulfate as the electron acceptor and samples were taken at different ports along the column. Microbial toluene degradation was calculated based on the 13 C/ 12 C isotope fractionation factors of the batch culture experiments together with the observed 13 C/ 12 C isotope shifts of the residual toluene fractions. The calculated percentage of biodegradation, B, correlated well with the decreasing toluene concentrations at the sampling ports and indicated the increasing extent of biodegradation along the column. The theoretical toluene concentrations as calculated based on the isotope values matched the measured concentrations at the different sampling ports indicating that the Rayleigh equation can be used to calculate biodegradation in quasi closed systems based on measured isotope shifts. A similar attempt was performed to assess toluene degradation in a contaminated, anoxic aquifer. A transect of groundwater wells was monitored along the main direction of the groundwater flow and revealed decreasing

EQUILIBRIUM AND KINETIC NITROGEN AND OXYGEN-ISOTOPE FRACTIONATIONS BETWEEN DISSOLVED AND GASEOUS N2O

NARCIS (Netherlands)

INOUE, HY; MOOK, WG

1994-01-01

Experiments were performed to determine the equilibrium as well as kinetic stable nitrogen and oxygen isotope fractionations between aqueous dissolved and gaseous N2O. The equilibrium fractionations, defined as the ratio of the isotopic abundance ratios (15R and 18R, respectively) of gaseous and

Site-specific and multielement approach to the determination of liquid-vapor isotope fractionation parameters. The case of alcohols

International Nuclear Information System (INIS)

Moussa, I.; Naulet, N.; Martin, M.L.; Martin, G.J.

1990-01-01

Isotope fractionation phenomena occurring at the natural abundance level in the course of liquid-vapor transformation have been investigated by using the SNIF-NMR method (site-specific natural isotope fractionation studied by NMR) which has a unique capability of providing simultaneous access to fractionation parameters associated with different molecular isotopomers. This new approach has been combined with the determination of overall carbon and hydrogen fractionation effects by isotope ratio mass spectrometry (IRMS). The results of distillation and evaporation experiments of alcohols performed in technical conditions of practical interest have been analyzed according to the Rayleigh-type model. In order to check the performance of the column, unit fractionation factors were measured beforehand for water and for the hydroxylic sites of methanol and ethanol for which liquid-vapor equilibrium constants were already known. Inverse isotope effects are determined in distillation experiments for the overall carbon isotope ratio and for the site-specific hydrogen isotope ratios associated with the methyl and methylene sites of methanol and ethanol. In contrast, normal isotope effects are produced by distillation for the hydroxylic sites and by evaporation for all the isotopic ratios

Cr-isotope fractionation during oxidative weathering of ultramafic rocks and its impact on river waters

DEFF Research Database (Denmark)

Paulukat, Cora Stefanie; Døssing, Lasse Nørbye; Mondal, Sisir K.

We investigated Cr isotope fractionation during soil formation from Precambrian ultramafic rocks. A soil profile was logged in an active open-cast chromite mine (Sukinda Valley, India). In addition, mine and river waters, as well as seawater were collected to trace the Cr-isotope signal...... values as heavy as +1.33±0.05‰. Where the drainage water merges with the river water, a slightly positively fractionated δ53Cr value (0.03±0.019‰) reflects a mixed isotope signal. With increasing distance from the mine, river water δ53Cr again becomes increasingly positively fractionated, indicating...... into the sea. The aim of the study is to recognize Cr isotope fractionation processes within the mining-area and the impact of the mine runoff on the δ53Cr of the nearby river. The weathering profile shows a distinct upward trend to more negative δ53Cr values. While the well preserved rocks at the base closely...

The iron-isotope fractionation dictated by the carboxylic functional: An ab-initio investigation

Science.gov (United States)

Ottonello, G.; Vetuschi Zuccolini, M.

2008-12-01

The ground-state geometries, electronic energies and vibrational properties of carboxylic complexes of iron were investigated both in vacuo and under the effect of a reaction field, to determine thermodynamic properties of iron-acetates and the role of the carboxylic functional on the isotopic imprinting of this metal in metalorganic complexation. The electronic energy, zero point corrections and thermal corrections of these substances at variational state were investigated at the DFT/B3LYP level of theory with different basis set expansions and the effect of the reaction field on the variational structures was investigated through the Polarized Continuun Model. Thermochemical cycle calculations, combined with solvation energy calculations and appropriate scaling from absolute to conventional properties allowed to compute the Gibbs free energy of formation from the elements of the investigated aqueous species and to select the best procedure to be applied in the successive vibrational analysis. The best compliance with the few existing thermodynamic data for these substances was obtained by coupling the gas phase calculations at DFT/B3LYP level with the [6-31G(d,p)]-[6-31G+(d,p)] (for cations and neutral molecules - anions; respectively) with solvation calculations adopting atomic radii optimized for the HF/6-31G(d) level of theory (UAHF). A vibrational analysis conducted on 54Fe, 56Fe, 57Fe and 58Fe gaseous isotopomers yielded reduced partition function ratios which increased not only with the nominal valence of the central cation, as expected, but, more importantly, with the extent of the complexation operated by the organic functional. Coupling thermodynamic data with separative effects it was shown that this last is controlled, as expected, by the relative bond strength of the complex in both aggregation states. Through the Integral Equation Formalism of the Polarized Continuum Model (IEFPCM) the effect of the ionic strength of the solution and of a T

Influence of the enzyme dissimilatory sulfite reductase on stable isotope fractionation during sulfate reduction

Science.gov (United States)

Mangalo, Muna; Einsiedl, Florian; Meckenstock, Rainer U.; Stichler, Willibald

2008-03-01

The stable isotopes of sulfate are often used as a tool to assess bacterial sulfate reduction on the macro scale. However, the mechanisms of stable isotope fractionation of sulfur and oxygen at the enzymatic level are not yet fully understood. In batch experiments with water enriched in 18O we investigated the effect of different nitrite concentrations on sulfur isotope fractionation by Desulfovibrio desulfuricans. With increasing nitrite concentrations, we found sulfur isotope enrichment factors ranging from -11.2 ± 1.8‰ to -22.5 ± 3.2‰. Furthermore, the δ18O values in the remaining sulfate increased from approximately 50-120‰ when 18O-enriched water was supplied. Since 18O-exchange with ambient water does not take place in sulfate, but rather in intermediates of the sulfate reduction pathway (e.g. SO32-), we suggest that nitrite affects the steady-state concentration and the extent of reoxidation of the metabolic intermediate sulfite to sulfate during sulfate reduction. Given that nitrite is known to inhibit the production of the enzyme dissimilatory sulfite reductase, our results suggest that the activity of the dissimilatory sulfite reductase regulates the kinetic isotope fractionation of sulfur and oxygen during bacterial sulfate reduction. Our novel results also imply that isotope fractionation during bacterial sulfate reduction strongly depends on the cell internal enzymatic regulation rather than on the physico-chemical features of the individual enzymes.

Mercury isotope fractionation during transfer from post-desulfurized seawater to air.

Science.gov (United States)

Huang, Shuyuan; Lin, Kunning; Yuan, Dongxing; Gao, Yaqin; Sun, Lumin

2016-12-15

Samples of dissolved gaseous mercury (DGM) in the post-desulfurized seawater discharged from a coal-fired power plant together with samples of gaseous elemental mercury (GEM) over the post-desulfurized seawater surface were collected and analyzed to study the mercury isotope fractionation during transfer from post-desulfurized seawater to air. Experimental results showed that when DGM in the seawater was converted to GEM in the air, the δ 202 Hg and Δ 199 Hg values were changed, ranging from -2.98 to -0.04‰ and from -0.31 to 0.64‰, respectively. Aeration played a key role in accelerating the transformation of DGM to GEM, and resulted in light mercury isotopes being more likely to be enriched in the GEM. The ratio Δ 199 Hg/Δ 201 Hg was 1.626 in all samples, suggesting that mercury mass independent fractionation occurred owing to the nuclear volume effect during the transformation. In addition, mass independent fractionation of mercury even isotopes was found in the GEM above the post-desulfurized seawater surface in the aeration pool. Copyright © 2016 Elsevier Ltd. All rights reserved.

High-precision determination of the isotopic composition of dissolved iron in iron depleted seawater by double spike multicollector-ICPMS.

Science.gov (United States)

Lacan, Francois; Radic, Amandine; Labatut, Marie; Jeandel, Catherine; Poitrasson, Franck; Sarthou, Geraldine; Pradoux, Catherine; Chmeleff, Jerome; Freydier, Remi

2010-09-01

This work demonstrates the feasibility of the measurement of the isotopic composition of dissolved iron in seawater for an iron concentration range, 0.05-1 nmol L(-1), allowing measurements in most oceanic waters, including Fe depleted waters of high nutrient low chlorophyll areas. It presents a detailed description of our previously published protocol, with significant improvements on detection limit and blank contribution. Iron is preconcentrated using a nitriloacetic acid superflow resin and purified using an AG 1-x4 anion exchange resin. The isotopic ratios are measured with a multicollector-inductively coupled plasma mass spectrometer (MC-ICPMS) Neptune, coupled with a desolvator (Aridus II or Apex-Q), using a (57)Fe-(58)Fe double spike mass bias correction. A Monte Carlo test shows that optimum precision is obtained for a double spike composed of approximately 50% (57)Fe and 50% (58)Fe and a sample to double spike quantity ratio of approximately 1. Total procedural yield is 91 +/- 25% (2SD, n = 55) for sample sizes from 20 to 2 L. The procedural blank ranges from 1.4 to 1.1 ng, for sample sizes ranging from 20 to 2 L, respectively, which, converted into Fe concentrations, corresponds to blank contributions of 0.001 and 0.010 nmol L(-1), respectively. Measurement precision determined from replicate measurements of seawater samples and standard solutions is 0.08 per thousand (delta(56)Fe, 2SD). The precision is sufficient to clearly detect and quantify isotopic variations in the oceans, which so far have been observed to span 2.5 per thousand and thus opens new perspectives to elucidate the oceanic iron cycle.

The Behaviour of Chromium Isotopes during the Oxidative Weathering of Ultramafic Rocks

DEFF Research Database (Denmark)

Paulukat, Cora Stefanie; Døssing, Lasse Nørbye; Mondal, Sisir K.

The chromium isotope system has been proven to be a redox-sensitve proxy in ancient and modern environmental studies (e.g. [1], [2]). In this study we investigated Cr isotope fractionation during soil formation from Archean (3.1-3.3 Ga) ultramafic rocks, intruded into metamorphic rocks of the Iron...

Tracing low-temperature aqueous metal migration in mineralized watersheds with Cu isotope fractionation

International Nuclear Information System (INIS)

Mathur, R.; Munk, L.A.; Townley, B.; Gou, K.Y.; Gómez Miguélez, N.; Titley, S.; Chen, G.G.; Song, S.; Reich, M.; Tornos, F.; Ruiz, J.

2014-01-01

Highlights: • Cu isotope fractionation of ores and waters identifies copper sulfide weathering. • Redox reactions cause isotopic shift measured in areas of sulfide weathering. • Consistent isotope signature in different deposit, climate, or concentration. - Abstract: Copper isotope signatures in waters emanating from mineralized watersheds provide evidence for the source aqueous copper in solution. Low-temperature aqueous oxidation of Cu sulfide minerals produces significant copper isotopic fractionation between solutions and residues. Abiotic experimental data of fractionation (defined as Δ liquid–solid ‰ = δ 65 Cu liquid − δ 65 Cu solid ) are on the order of 1–3‰ and are unique for copper rich-sulfide minerals. Data presented here from ores and waters within defined boundaries of porphyry copper, massive sulfide, skarn, and epithermal ore deposits mimic abiotic experiments. Thus, the oxidation of sulfide minerals appears to cause the signatures in the waters although significant biological, temperature, and pH variations exist in the fluids. Regardless of the deposit type, water type, concentration of Cu in solution, or location, the data provide a means to trace sources of metals in solutions. This relationship allows for tracking sources and degree of metal migration in low temperature aqueous systems and has direct application to exploration geology and environmental geochemistry

Biological fractionation of lead isotopes in Sprague-Dawley rats lead poisoned via the respiratory tract.

Science.gov (United States)

Wu, Jing; Liu, Duojian; Xie, Qing; Wang, Jingyu

2012-01-01

It was considered that lead isotope ratios did not change during physical, chemical, or biological processes. Thus, lead isotope ratios have been used as fingerprints to identify possible lead sources. However, recent evidence has shown that the lead isotope ratios among different biological samples in human are not always identical from its lead origins in vitro. An animal experiment was conducted to explore the biological fractionation of lead isotopes in biological systems. 24 male Sprague-Dawley (SD) rats were divided into groups that received acute lead exposure (0, 0.02, 0.2, or 2 mg/kg body weight of lead acetate) via the respiratory route every day for 5 days. Biological samples (i.e., blood, urine, and feces) were collected for comparison with the lead acetate (test substance) and the low-lead animal feed (diet) administered to the rats. The lead isotope ratios were determined by inductively coupled plasma mass spectrometry (ICP-MS). There are significant differences (pblood, urine, and feces. Moreover, a nonlinear relationship between the blood lead concentration and the blood lead isotope ratios was observed. There is also a threshold effect to the fractionation function. Only the blood isotope ratio of (204)Pb/(206)Pb matches the test substance well. As for feces, when (204)Pb/(206)Pb ratio is considered, there is no significant difference between feces-test substance pairs in medium and high dose group. The biological fractionation of lead isotopes in SD rats was observed. Moreover, there might be a threshold for the biological fractionation of lead isotopes which is depending on whole blood lead level. It is considered to be more reliable that we compared the isotope ratios of potential lead hazards with both blood and feces lead fingerprints especially for (204)Pb/(206)Pb ratio under high-dose exposure.

An Investigation into the Relationship Between Distillate Yield and Stable Isotope Fractionation

Science.gov (United States)

Sowers, T.; Wagner, A. J.

2016-12-01

Recent breakthroughs in laser spectrometry have allowed for faster, more efficient analyses of stable isotopic ratios in water samples. Commercially available instruments from Los Gatos Research and Picarro allow users to quickly analyze a wide range of samples, from seawater to groundwater, with accurate isotope ratios of D/H to within ± 0.2 ‰ and 18O/16O to within ± 0.03 ‰. While these instruments have increased the efficiency of stable isotope laboratories, they come with some major limitations, such as not being able to analyze hypersaline waters. The Los Gatos Research Liquid Water Isotope Analyzer (LWIA) can accurately and consistently measure the stable isotope ratios in waters with salinities ranging from 0 to 4 grams per liter (0 to 40 parts per thousand). In order to analyze water samples with salinities greater than 4 grams per liter, however, it was necessary to develop a consistent method through which to reduce salinity while causing as little fractionation as possible. Using a consistent distillation method, predictable fractionation of δ 18O and δ 2 H values was found to occur. This fractionation occurs according to a linear relationship with respect to the percent yield of the water in the sample. Using this method, samples with high salinity can be analyzed using laser spectrometry instruments, thereby enabling laboratories with Los Gatos or Picarro instruments to analyze those samples in house without having to dilute them using labor-intensive in-house standards or expensive premade standards.

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

Science.gov (United States)

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

2013-12-01

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

Carbon isotope fractionation by sulfate-reducing bacteria using different pathways for the oxidation of acetate.

Science.gov (United States)

Goevert, Dennis; Conrad, Ralf

2008-11-01

Acetate is a key intermediate in the anaerobic degradation of organic matter. In anoxic environments, available acetate is a competitive substrate for sulfate-reducing bacteria (SRB) and methane-producing archaea. Little is known about the fractionation of carbon isotopes by sulfate reducers. Therefore, we determined carbon isotope compositions in cultures of three acetate-utilizing SRB, Desulfobacter postgatei, Desulfobacter hydrogenophilus, and Desulfobacca acetoxidans. We found that these species showed strong differences in their isotope enrichment factors (epsilon) of acetate. During the consumption of acetate and sulfate, acetate was enriched in 13C by 19.3% per hundred in Desulfobacca acetoxidans. By contrast, both D. postgatei and D. hydrogenophilus showed a slight depletion of 13C resulting in epsilon(ac)-values of 1.8 and 1.5% per hundred, respectively. We suggest that the different isotope fractionation is due to the different metabolic pathways for acetate oxidation. The strongly fractionating Desulfobacca acetoxidans uses the acetyl-CoA/carbon monoxide dehydrogenase pathway, which is also used by acetoclastic methanogens that show a similar fractionation of acetate (epsilon(ac) = -21 to -27% per hundred). In contrast, Desulfobacter spp. oxidize acetate to CO2 via the tricarboxylic acid (TCA) cycle and apparently did not discriminate against 13C. Our results suggestthat carbon isotope fractionation in environments with sulfate reduction will strongly depend on the composition of the sulfate-reducing bacterial community oxidizing acetate.

Boron geochemistry from some typical Tibetan hydrothermal systems: Origin and isotopic fractionation

International Nuclear Information System (INIS)

Zhang, Wenjie; Tan, Hongbing; Zhang, Yanfei; Wei, Haizhen; Dong, Tao

2015-01-01

The Tibetan plateau is characterized by intense hydrothermal activity and abnormal enrichment of trace elements in geothermal waters. Hydrochemistry and B isotope samples from geothermal waters in Tibet were systematically measured to describe the fractionation mechanisms and provide constraints on potential B reservoirs. B concentrations range from 0.35 to 171.90 mg/L, and isotopic values vary between −16.57 ‰ and +0.52 ‰. Geothermal fields along the Indus-Yarlung Zangbo suture zone and N–S rifts are observed with high B concentrations and temperatures. The similar hydrochemical compositions of high-B geothermal waters with magmatic fluid and consistent modeling of B isotopic compositions with present δ"1"1B values imply that the B in high-B geothermal waters is mainly contributed by magmatic sources, probably through magma degassing. In contrast, geothermal fields in other regions of the Lhasa block have relatively low B concentrations and temperatures. After considering the small fractionation factor and representative indicators of Na/Ca, Cl/HCO_3, Na + K and Si, the conformity between modeling results and the isotopic compositions of host rocks suggests that the B in low-temperature geothermal fields is mainly sourced from host rocks. According to simulated results, the B in some shallow geothermal waters not only originated from mixing of cold groundwater with deep thermal waters, but it was also contributed by equilibration with marine sedimentary rocks with an estimated proportion of 10%. It was anticipated that this study would provide useful insight into the sources and fractionation of B as well as further understanding of the relationships between B-rich salt lakes and geothermal activities in the Tibetan plateau. - Highlights: • Chemical and boron isotopic data of geothermal waters in Tibetan plateau were introduced. • Unusual enrichment of boron in Tibetan geothermal waters is related to magmatic and host rocks. • Boron

Thorium isotopes in colloidal fraction of water from San Marcos Dam, Chihuahua, Mexico

Science.gov (United States)

Cabral-Lares, M.; Melgoza, A.; Montero-Cabrera, M. E.; Renteria-Villalobos, M.

2013-07-01

The main interest of this stiidy is to assess the contents and distribution of Th-series isotopes in colloidal fraction of surface water from San Marcos dam, because the suspended particulate matter serves as transport medium for several pollutants. The aim of this work was to assess the distribution of thorium isotopes (232Th and 230Th) contained in suspended matter. Samples were taken from three surface points along the San Marcos dam: water input, midpoint, and near to dam wall. In this last point, a depth sampling was also carried out. Here, three depth points were taken at 0.4, 8 and 15 meters. To evaluate the thorium behavior in surface water, from every water sample the colloidal fraction was separated, between 1 and 0.1 μm. Thorium isotopes concentraron in samples were obtained by alpha spectrometry. Activity concentrations obtained of 232Th and 230Th in surface points ranged from 0.3 to 0.5 Bq ṡ L-1, whereas in depth points ranged from 0.4 to 3.2 Bq ṡ L-1, respectively. The results show that 230Th is in higher concentration than 232Th in colloidal fraction. This can be attributed to a preference of these colloids to adsorb uranium. Thus, the activity ratio 230Th/232Th in colloidal fraction showed values from 2.3 to 10.2. In surface points along the dam, 230Th activity concentration decreases while 232Th concentration remains constant. On the other hand, activity concentrations of both isotopes showed a pointed out enhancement with depth. The results have shown a possible lixiviation of uranium from geological substrate into the surface water and an important fractionation of thorium isotopes, which suggest that thorium is non-homogeneously distributed along San Marcos dam.

Large effect of irradiance on hydrogen isotope fractionation of alkenones in Emiliania huxleyi

Science.gov (United States)

van der Meer, Marcel T. J.; Benthien, Albert; French, Katherine L.; Epping, Eric; Zondervan, Ingrid; Reichart, Gert-Jan; Bijma, Jelle; Sinninghe Damsté, Jaap S.; Schouten, Stefan

2015-07-01

The hydrogen isotopic (δD) composition of long-chain alkenones produced by certain haptophyte algae has been suggested as a potential proxy for reconstructing paleo sea surface salinity. However, environmental parameters other than salinity may also affect the δD of alkenones. We investigated the impact of the level of irradiance on hydrogen isotopic fractionation of alkenones versus growth water by cultivating two strains of the cosmopolitan haptophyte Emiliania huxleyi at different light intensities. The hydrogen isotope fractionation decreased by approximately 40‰ when irradiance was increased from 15 to 200 μmol photons m-2 s-1 above which it was relatively constant. The response is likely a direct effect of photosystem I and II activity as the relationship of the fractionation factor α versus light intensity can be described by an Eilers-Peeters photosynthesis model. This irradiance effect is in agreement with published δD data of alkenones derived from suspended particulate matter collected from different depths in the photic zone of the Gulf of California and the eastern tropical North Pacific. However, haptophyte algae tend to bloom at relatively high light intensities (>500 μmol photons m-2 s-1) occurring at the sea surface, at which hydrogen isotope fractionation is relatively constant and not affected by changes in light intensity. Alkenones accumulating in the sediment are likely mostly derived from these surface water haptophyte blooms, when the largest amount of biomass is produced. Therefore, the observed irradiance effect is unlikely to affect the applicability of the hydrogen isotopic composition of sedimentary long chain alkenones as a proxy for paleosalinity.

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

Science.gov (United States)

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

2010-01-01

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

Assessment of Bacterial Degradation of Aromatic Hydrocarbons in the Environment by Analysis of Stable Carbon Isotope Fractionation

Energy Technology Data Exchange (ETDEWEB)

Meckenstock, Rainer U. [Eberhard-Karls University of Tuebingen, Center for Applied Geoscience (Germany)], E-mail: rainer.meckenstock@uni-tuebingen.de; Morasch, Barbara [University of Konstanz, Faculty of Biology (Germany); Kaestner, Matthias; Vieth, Andrea; Richnow, Hans Hermann [Center for Environmental Research, Department of Remediation Research (Germany)

2002-05-15

{sup 13}C/{sup 12}C stable carbon isotope fractionation was used to assess biodegradation in contaminated aquifers with toluene as a model compound. Different strains of anaerobic bacteria (Thauera aromatica, Geobacter metallireducens, and the sulfate-reducing strain TRM1) showed consistent {sup 13}C/{sup 12}C carbon isotope fractionation with fractionation factors between {alpha}C = 1.0017 and 1.0018. In contrast, three cultures of aerobic organisms, using different mono- and dioxygenase enzyme systems to initiate toluene degradation, showed variable isotope fractionation factors of {alpha}C = 1.0027 (Pseudomonasputida strain mt-2), {alpha}C = 1.0011 (Ralstonia picketii), and{alpha}C = 1.0004 (Pseudomonas putida strain F1). The great variability of isotope fractionation between different aerobic bacterial strains suggests that interpretation of isotope data in oxic habitats can only be qualitative. A soil column was run as a model system for contaminated aquifers with toluene as the carbon source and sulfate as the electron acceptor and samples were taken at different ports along the column. Microbial toluene degradation was calculated based on the {sup 13}C/{sup 12}C isotope fractionation factors of the batch culture experiments together with the observed {sup 13}C/{sup 12}C isotope shifts of the residual toluene fractions. The calculated percentage of biodegradation, B, correlated well with the decreasing toluene concentrations at the sampling ports and indicated the increasing extent of biodegradation along the column. The theoretical toluene concentrations as calculated based on the isotope values matched the measured concentrations at the different sampling ports indicating that the Rayleigh equation can be used to calculate biodegradation in quasi closed systems based on measured isotope shifts. A similar attempt was performed to assess toluene degradation in a contaminated, anoxic aquifer. A transect of groundwater wells was monitored along the main

Joint interpretation of enantiomer and stable isotope fractionation for chiral pesticides degradation

DEFF Research Database (Denmark)

Jin, Biao; Rolle, Massimo

2016-01-01

introduce a modeling approach with the aim of unifying and integrating the interpretation of isotopic and enantiomeric fractionation. The model is based on the definition of enantiomer-specific isotopologues and jointly predicts the evolution of concentration, enantiomer fractionation, as well as changes...

Effect of Different Carbon Substrates on Nitrate Stable Isotope Fractionation During Microbial Denitrification

DEFF Research Database (Denmark)

Wunderlich, Anja; Meckenstock, Rainer; Einsiedl, Florian

2012-01-01

-labeled water and 18O-labeled nitrite were added to the microcosm experiments to study the effect of putative backward reactions of nitrite to nitrate on the stable isotope fractionation. We found no evidence for a reverse reaction. Significant variations of the stable isotope enrichment factor ε were observed......In batch experiments, we studied the isotope fractionation in N and O of dissolved nitrate during dentrification. Denitrifying strains Thauera aromatica and “Aromatoleum aromaticum strain EbN1” were grown under strictly anaerobic conditions with acetate, benzoate, and toluene as carbon sources. 18O...... of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification....

Fractionation of mercury stable isotopes during coal combustion and seawater flue gas desulfurization

International Nuclear Information System (INIS)

Huang, Shuyuan; Yuan, Dongxing; Lin, Haiying; Sun, Lumin; Lin, Shanshan

2017-01-01

In the current study, fractionation of mercury isotopes during coal combustion and seawater flue gas desulfurization (SFGD) in a coal-fired power plant using a SFGD system was investigated. Fourteen samples were collected from the power plant. The samples were pretreated with a combustion-trapping method and were analyzed with a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). Compared with the raw coal, the bottom ash was enriched with lighter mercury isotopes with δ 202 Hg values ranging from −0.45 to −0.03‰. The fly ash was enriched with lighter mercury isotopes with δ 202 Hg values ranging from −1.49 to −0.73‰ for Chinese coal and from −1.47 to −0.62‰ for Indonesian coal. The δ 202 Hg of fresh seawater and desulfurized seawater was found to be −1.32 and −0.32‰ respectively. These δ 202 Hg values indicated that the desulfurized seawater was enriched with heavier mercury isotopes. Based upon the calculated results obtained from the mass balance equation, it was suggested that the stack emissions were enriched with lighter mercury isotopes. Mass independent fractionation was observed in most of the samples with a Δ 199 Hg/Δ 201 Hg ratio of approximately 0.96. The results help in improving the understanding of mercury isotope fractionation during coal combustion and SFGD, and are also useful in tracing the mercury emissions from coal fired power plants. - Highlights: • Spread of 1.5‰ was observed in δ 202 Hg values of raw coals and coal related samples. • The δ 202 Hg values were more negative in fly ash than those in the raw coal. • The flue gas had a significant Hg fractionation after desulfurization. • The stack emissions were enriched with lighter isotopes compared with the raw coal.

Controllable isotope fractionation with thermal ionisation mass-spectrometers

International Nuclear Information System (INIS)

Hebeda, E.H.

1980-01-01

Isotopic ratios measured with thermal ionisation mass-spectrometers are biased by fractionation effects. A sample must therefore be analyzed according to the same procedures as applied for the analysis of the standard reference material. A comparison of the behaviour of the sample with that of the standard can then be used as a criterion whether the analytical results are acceptable or not. In this way it is possible to obtain reproducibilities similar to those for elements acceptable or not. In this way it is possible to obtain reproducibilities similar to those for elements where the fractionation can be determined by an internal standard. This procedure of controlled fractionation is demonstrated by means of the 88 Sr/ 86 Sr ratios measured on geological samples and the SRM 987 standard. (orig.)

Modern rather than Mesoarchaean oxidative weathering responsible for the heavy stable Cr isotopic signatures of the 2.95 Ga old Ijzermijn iron formation (South Africa)

Science.gov (United States)

Albut, Gülüm; Babechuk, Michael G.; Kleinhanns, Ilka C.; Benger, Manuela; Beukes, Nicolas J.; Steinhilber, Bernd; Smith, Albertus J. B.; Kruger, Stephanus J.; Schoenberg, Ronny

2018-05-01

Previously reported stable Cr isotopic fractionation in Archaean paleosols and iron formations (IFs) have been interpreted as a signature of oxidative weathering of Cr(III) to Cr(VI) in soils, and delivery of isotopically heavy Cr(VI) into the oceans. One of the oldest reported fingerprints of this process is isotopically heavy Cr preserved in the 2.95 Ga old Ijzermijn IF, Sinqeni Formation of the Mozaan Group (Pongola Supergroup), South Africa and could suggest that atmospheric free oxygen was present ca. 600 million years earlier than the Great Oxidation Event (GOE). However, fractionated stable Cr isotopic signatures have only been found to date in surface outcrop samples of the White Mfolozi Inlier exposed along the White Mfolozi River Gorge. In this study, the latter outcrop was resampled along with two drill cores of the Ijzermijn IF and a drill core of the Scotts Hill IF to represent multiple exposures of Mozaan Group IFs with different states of preservation. A detailed geochemical comparison on bulk samples of different units was undertaken using stable Cr isotopes coupled with trace and major elements. Outcrop iron-rich mudstones (Fe - lutites) show very low LOI [wt] %, and very low Fe(II)/Fetot ratios, and lower Ca and Mg relative to equivalent facies in drill cores, indicating the effects that oxidative recent surface weathering had on Fe/Mn-rich carbonate minerals of the IF. Overall rare earth element and yttrium (REE + Y) mixing models agree well with previous studies, confirming that they were minimally disturbed by weathering and are consistent with a high magnitude of continental solutes delivered in a near-shore depositional environment, with a minor contribution of hydrothermally derived fluids that upwelled into shallower depositional setting. Importantly, all drill core samples of this study revealed δ53/52Cr values within the igneous inventory, despite variable amounts of detrital Cr input that includes nearly detritus-free, chert

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

Science.gov (United States)

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

2015-04-07

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

Neutrino energy loss rates due to key iron isotopes for core-collapse physics

International Nuclear Information System (INIS)

Nabi, J.-U.

2008-07-01

Accurate estimates of neutrino energy loss rates are needed for the study of the late stages of the stellar evolution, in particular for the cooling of neutron stars and white dwarfs. The energy spectra of neutrinos and antineutrinos arriving at the Earth can also provide useful information on the primary neutrino fluxes as well as neutrino mixing scenario. Proton-neutron quasi-particle random phase approximation (pn-QRPA) theory has recently being used for a microscopic calculation of stellar weak interaction rates of fp-shell nuclide, particularly iron isotopes, with success. Here I present the calculation of neutrino and antineutrino energy loss rates due to key iron isotopes in stellar matter using the pn-QRPA theory. The rates are calculated on a fine grid of temperature-density scale suitable for core-collapse simulators. The calculated rates are compared against earlier calculations. The neutrino cooling rates due to even-even isotopes of iron, 54,56 Fe, are in good agreement with the rates calculated using the large-scale shell model. The pn-QRPA calculated neutrino energy loss rates due to 55 Fe are enhanced roughly around an order of magnitude compared to the large-scale shell model calculation during the oxygen and silicon shell burning stages of massive stars and favor a lower entropy for the cores of massive stars. (author)

Isotope aided studies on the bioavailability of iron and zinc from human diets

International Nuclear Information System (INIS)

Raghuramulu, N.

1992-01-01

Iron deficiency anaemia is a major public health problem in many developing countries including India. Recent multicentric studies indicated that in rural population of India, 60% of preschool children and 40-60 % of women of child bearing age may suffer from anaemia. Studies by Sood et al indicated that iron stores are generally lower in the population as compared to populations in other countries. It is therefore possible that prelatent iron deficiency may be even higher who look otherwise healthy and adequately nourished. Iron absorption from habitual diets of Indians has been determined in the past by the chemical balance methods. Iron absorption determined by this method may be a gross over estimate. A more reliable estimate of iron absorption from composite meals can be obtained by the radio isotopic methods in which foods are extrinsically or intrinsically tagged with radio iron ( 55 Fe or 59 Fe). Using these methods iron absorption from a few habitual diets was studied. 15 refs

Mg isotope systematics during magmatic processes: Inter-mineral fractionation in mafic to ultramafic Hawaiian xenoliths

Science.gov (United States)

Stracke, A.; Tipper, E. T.; Klemme, S.; Bizimis, M.

2018-04-01

Observed differences in Mg isotope ratios between bulk magmatic rocks are small, often on a sub per mill level. Inter-mineral differences in the 26Mg/24Mg ratio (expressed as δ26Mg) in plutonic rocks are on a similar scale, and have mostly been attributed to equilibrium isotope fractionation at magmatic temperatures. Here we report Mg isotope data on minerals in spinel peridotite and garnet pyroxenite xenoliths from the rejuvenated stage of volcanism on Oahu and Kauai, Hawaii. The new data are compared to literature data and to theoretical predictions to investigate the processes responsible for inter-mineral Mg isotope fractionation at magmatic temperatures. Theory predicts up to per mill level differences in δ26Mg between olivine and spinel at magmatic temperatures and a general decrease in Δ26Mgolivine-spinel (=δ26Mgolivine - δ26Mgspinel) with increasing temperature, but also with increasing Cr# in spinel. For peridotites with a simple petrogenetic history by melt depletion, where increasing depletion relates to increasing melting temperatures, Δ26Mgolivine-spinel should thus systematically decrease with increasing Cr# in spinel. However, most natural peridotites, including the Hawaiian spinel peridotites investigated in this study, are overprinted by variable extents of melt-rock reaction, which disturb the systematic primary temperature and compositionally related olivine-spinel Mg isotope systematics. Diffusion, subsolidus re-equilibration, or surface alteration may further affect the observed olivine-spinel Mg isotope fractionation in peridotites, making Δ26Mgolivine-spinel in peridotites a difficult-to-apply geothermometer. The available Mg isotope data on clinopyroxene and garnet suggest that this mineral pair is a more promising geothermometer, but its application is restricted to garnet-bearing igneous (garnet pyroxenites) and metamorphic rocks (eclogites). Although the observed δ26Mg variation is on a sub per mill range in bulk magmatic rocks

Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment

International Nuclear Information System (INIS)

Marchesi, Massimo; Thomson, Neil R.; Aravena, Ramon; Sra, Kanwartej S.; Otero, Neus; Soler, Albert

2013-01-01

Highlights: • Treatability and C fractionation of 1,1,1-TCA by base-catalyzed S 2 O 8 2− was studied. • The rate of degradation of 1,1,1-TCA increased with a higher OH − :S 2 O 8 2− ratio. •Base-catalyzed S 2 O 8 2− can potentially treat recalcitrant compound like 1,1,1-TCA. • An enrichment factor of −7.0‰ independent of the OH − :S 2 O 8 2− ratio was obtained. • Carbon isotope can potentially be used to estimate the ISCO treatment efficacy. -- Abstract: The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S 2 O 8 2− ) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S 2 O 8 2− molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ∼5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S 2 O 8 2− molar ratio of −7.0 ± 0.2‰ was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S 2 O 8 2− molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system

Diagenetic fractionation of carbon isotopes in particulate and dissolved organic matter in sediments from Skan Bay, Alaska

International Nuclear Information System (INIS)

Alperin, M.J.; Reeburgh, W.S.

1991-01-01

Isotope fractionation during organic matter diagenesis was investigated by measuring detailed depth distributions of stable carbon isotope ratios in sediment particulate organic carbon (POC) and dissolved organic carbon (DOC) reservoirs. The δ 13 C value of the POC shifted systematically from -19 per-thousand at the surface to -21 per-thousand at 10 cm. Significant trends were also apparent in the δ 13 C-DOC profile. Proceeding down-core, DOC became isotopically heavier between 0 and 5 cm and isotopically lighter at greater depths. Two mechanisms could account for the observed down-core shift in δ 13 C-POC: (a) temporal changes in the isotope ratios of deposited organic matter and (b) isotope fractionation associated with diagenesis. The δ 15 C-DOC depth distribution is sensitive to which mechanism controls the isotopic composition of the POC reservoir. A diagenetic model that couples POC and DOC reservoirs was used to discriminate between temporal changes and diagenetic alteration of the POC isotopic composition. The model indicated that observed trends in δ 13 C-POC and δ 13 C-DOC depth distributions are consistent with isotopic fractionation of POC during diagenesis

Stable carbon isotope fractionation in the search for life on early Mars

Science.gov (United States)

Rothschild, L. J.; Desmarais, D.

1989-01-01

The utility of measurements of C-13/C-12 ratios in organic vs inorganic deposits for searching for signs of life on early Mars is considered. It is suggested that three assumptions are necessary. First, if there was life on Mars, it caused the fractionation of carbon isotopes in analogy with past biological activity on earth. Second, the fractionation would be detectable. Third, if a fractionation would be observed, there exist no abiotic explanations for the observed fractionation pattern.

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

NARCIS (Netherlands)

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

2010-01-01

Stable Hg isotope ratios provide a new tool to trace environmental Hg cycling. Thiols (-SH) are the dominant Hg-binding groups in natural organic matter. Here, we report experimental and computational results on equilibrium Hg isotope fractionation between dissolved Hg(II) species and thiol-bound

Stable Isotope Fractionation Caused by Glycyl Radical Enzymes during Bacterial Degradation of Aromatic Compounds

Science.gov (United States)

Morasch, Barbara; Richnow, Hans H.; Vieth, Andrea; Schink, Bernhard; Meckenstock, Rainer U.

2004-01-01

Stable isotope fractionation was studied during the degradation of m-xylene, o-xylene, m-cresol, and p-cresol with two pure cultures of sulfate-reducing bacteria. Degradation of all four compounds is initiated by a fumarate addition reaction by a glycyl radical enzyme, analogous to the well-studied benzylsuccinate synthase reaction in toluene degradation. The extent of stable carbon isotope fractionation caused by these radical-type reactions was between enrichment factors (ɛ) of −1.5 and −3.9‰, which is in the same order of magnitude as data provided before for anaerobic toluene degradation. Based on our results, an analysis of isotope fractionation should be applicable for the evaluation of in situ bioremediation of all contaminants degraded by glycyl radical enzyme mechanisms that are smaller than 14 carbon atoms. In order to compare carbon isotope fractionations upon the degradation of various substrates whose numbers of carbon atoms differ, intrinsic ɛ (ɛintrinsic) were calculated. A comparison of ɛintrinsic at the single carbon atoms of the molecule where the benzylsuccinate synthase reaction took place with compound-specific ɛ elucidated that both varied on average to the same extent. Despite variations during the degradation of different substrates, the range of ɛ found for glycyl radical reactions was reasonably narrow to propose that rough estimates of biodegradation in situ might be given by using an average ɛ if no fractionation factor is available for single compounds. PMID:15128554

Study on bioavailability of dietary iron of women by using activable isotopic tracer and neutron activation analysis techniques

International Nuclear Information System (INIS)

Zhang Yangmei; Ni Bangfa; Tian Weizhi; Wang Pingsheng; Cao Lei

2002-01-01

The bioavailability of diet iron of 10 healthy young women in Beijing area is studied by using two enriched isotopes 54 Fe and 58 Fe, and neutron activation analysis techniques. The abundance of 54 Fe and 58 Fe is 61.4% and 23.4%, respectively. In additional, the atomic absorption spectrometry is employed to measure total iron in fecal samples. Dysprosium, rarely absorbed by human body, is used to monitor the residence time of tracer isotopes in order to collect the fecal samples completely. The results show that the bioavailability of dietary iron in young women is (14.9 +- 3.9)%

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

Science.gov (United States)

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] = 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.

Molybdenum isotope fractionation in the mantle

Science.gov (United States)

Liang, Yu-Hsuan; Halliday, Alex N.; Siebert, Chris; Fitton, J. Godfrey; Burton, Kevin W.; Wang, Kuo-Lung; Harvey, Jason

2017-02-01

We report double-spike molybdenum (Mo) isotope data for forty-two mafic and fifteen ultramafic rocks from diverse locations and compare these with results for five chondrites. The δ98/95Mo values (normalized to NIST SRM 3134) range from -0.59 ± 0.04 to +0.10 ± 0.08‰. The compositions of one carbonaceous (CI) and four ordinary chondrites are relatively uniform (-0.14 ± 0.01‰, 95% ci (confidence interval)) in excellent agreement with previous data. These values are just resolvable from the mean of 10 mid-ocean ridge basalts (MORBs) (0.00 ± 0.02‰, 95% ci). The compositions of 13 mantle-derived ultramafic xenoliths from Kilbourne Hole, Tariat and Vitim are more diverse (-0.39 to -0.07‰) with a mean of -0.22 ± 0.06‰ (95% ci). On this basis, the isotopic composition of the bulk silicate Earth (BSE or Primitive Mantle) is within error identical to chondrites. The mean Mo concentration of the ultramafic xenoliths (0.19 ± 0.07 ppm, 95% ci) is similar in magnitude to that of MORB (0.48 ± 0.13 ppm, 95% ci), providing evidence, either for a more compatible behaviour than previously thought or for selective Mo enrichment of the subcontinental lithospheric mantle. Intraplate and ocean island basalts (OIBs) display significant isotopic variability within a single locality from MORB-like to strongly negative (-0.59 ± 0.04‰). The most extreme values measured are for nephelinites from the Cameroon Line and Trinidade, which also have anomalously high Ce/Pb and low Mo/Ce relative to normal oceanic basalts. δ98/95Mo correlates negatively with Ce/Pb and U/Pb, and positively with Mo/Ce, explicable if a phase such as an oxide or a sulphide liquid selectively retains isotopically heavy Mo in the mantle and fractionates its isotopic composition in low degree partial melts. If residual phases retain Mo during partial melting, it is possible that the [Mo] for the BSE may be misrepresented by values estimated from basalts. This would be consistent with the high Mo

Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment

Energy Technology Data Exchange (ETDEWEB)

Marchesi, Massimo, E-mail: m2marche@uwaterloo.ca [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Thomson, Neil R. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Aravena, Ramon [Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Sra, Kanwartej S. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada); Otero, Neus; Soler, Albert [Departament de Cristal.lographia, Mineralogia i Diposits Minerals, Facultat de Geologia, Universitat de Barcelona, Barcelona, Spain 08028 (Spain)

2013-09-15

Highlights: • Treatability and C fractionation of 1,1,1-TCA by base-catalyzed S{sub 2}O{sub 8}{sup 2−} was studied. • The rate of degradation of 1,1,1-TCA increased with a higher OH{sup −}:S{sub 2}O{sub 8}{sup 2−} ratio. •Base-catalyzed S{sub 2}O{sub 8}{sup 2−} can potentially treat recalcitrant compound like 1,1,1-TCA. • An enrichment factor of −7.0‰ independent of the OH{sup −}:S{sub 2}O{sub 8}{sup 2−} ratio was obtained. • Carbon isotope can potentially be used to estimate the ISCO treatment efficacy. -- Abstract: The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S{sub 2}O{sub 8}{sup 2−}) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S{sub 2}O{sub 8}{sup 2−} molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ∼5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S{sub 2}O{sub 8}{sup 2−} molar ratio of −7.0 ± 0.2‰ was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S{sub 2}O{sub 8}{sup 2−} molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system.

Sulfur and Oxygen Isotope Fractionation During Bacterial Sulfur Disproportionation Under Anaerobic Haloalkaline Conditions

NARCIS (Netherlands)

Poser, Alexander; Vogt, Carsten; Knöller, Kay; Sorokin, Dimitry Y.; Finster, Kai W.; Richnow, Hans H.

2016-01-01

Sulfur and oxygen isotope fractionation of elemental sulfur disproportionation at anaerobic haloalkaline conditions was evaluated for the first time. Isotope enrichment factors of the strains Desulfurivibrio alkaliphilus and Dethiobacter alkaliphilus growing at pH 9 or 10 were −0.9‰ to −1‰ for

Isotope-aided studies of the bioavailability of iron from diets and fortified foods to be used in iron fortifications programmes in Chile and Ecuador: Validation of in vitro techniques

International Nuclear Information System (INIS)

Hertrampf, E.; Pizarro, F.; Olivares, M.; Walter, T.; Fuenmayor, G.; Estevez, E.; Yepez, R.

1992-01-01

In selected typical Ecuatorian foods to be used in nutritional intervention programmes, we measured iron bioavailability in humans, with a double isotopic method. The interaction with some accompanied foods or beverages was also studied. Iron bioavailability from wheat flour foods was good (9%). When vermicelli soup was eaten together with lemonade sweetened with raw sugar cane, mean iron absorption was the highest (15%). Camomile infusion do not affect iron absorption from bread. At the same time, we will validate an in vitro iron availability technique comparing it with the results obtained in other laboratories involved in the present CRP and with the results obtained in the same foods with in vivo double isotopic. We will also start studies of in vitro zinc availability. (author). 26 refs, 2 figs, 7 tabs

Isotope effects of sulfur in chemical reactions

International Nuclear Information System (INIS)

Mikolajczuk, A.

1999-01-01

Sulfur is an important component of organic matter because it forms compounds with many elements. Due to high chemical activity of sulfur, it takes part in biological and geological processes in which isotope effects are occurring. It has been shown during last years research of isotope effects that we have take into account not only mass difference but also many other physical properties of nuclides e.g. even or odd number of neutrons in nuclei, shape and distribution of charge, turn of nuclear spin etc. The factor remains that new theoretical ideas have been formed on the base of data, being obtained in fractionation processes of heavy element isotope, particularly uranium. Now it is being well known that effects unconnected with vibration energy have also caused an effect on fractionation of considerably lighter elements like iron and magnesium. The important question is, if these effects would come to light during the separation of sulfur isotopes. Sulfur have three even isotopes M = (32, 34, 36) and one odd M 33). This problem is still open. (author)

Applications of Isotope Ratio Mass Spectrometry in Sports Drug Testing Accounting for Isotope Fractionation in Analysis of Biological Samples.

Science.gov (United States)

Piper, Thomas; Thevis, Mario

2017-01-01

The misuse of anabolic-androgenic steroids (AAS) in sports aiming at enhancing athletic performance has been a challenging matter for doping control laboratories for decades. While the presence of a xenobiotic AAS or its metabolite(s) in human urine immediately represents an antidoping rule violation, the detection of the misuse of endogenous steroids such as testosterone necessitates comparably complex procedures. Concentration thresholds and diagnostic analyte ratios computed from urinary steroid concentrations of, e.g., testosterone and epitestosterone have aided identifying suspicious doping control samples in the past. These ratios can however also be affected by confounding factors and are therefore not sufficient to prove illicit steroid administrations. Here, carbon and, in rare cases, hydrogen isotope ratio mass spectrometry (IRMS) has become an indispensable tool. Importantly, the isotopic signatures of pharmaceutical steroid preparations commonly differ slightly but significantly from those found with endogenously produced steroids. By comparing the isotope ratios of endogenous reference compounds like pregnanediol to that of testosterone and its metabolites, the unambiguous identification of the urinary steroids' origin is accomplished. Due to the complex urinary matrix, several steps in sample preparation are inevitable as pure analyte peaks are a prerequisite for valid IRMS determinations. The sample cleanup encompasses steps such as solid phase or liquid-liquid extraction that are presumably not accompanied by isotopic fractionation processes, as well as more critical steps like enzymatic hydrolysis, high-performance liquid chromatography fractionation, and derivatization of analytes. In order to exclude any bias of the analytical results, each step of the analytical procedure is optimized and validated to exclude, or at least result in constant, isotopic fractionation. These efforts are explained in detail. © 2017 Elsevier Inc. All rights reserved.

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

Science.gov (United States)

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.

The temperature dependent strontium isotope fractionation (δ88/86Sr) during calcium carbonate precipitation

International Nuclear Information System (INIS)

Fietzke, J.; Eisenhauer, A.

2006-01-01

Full text: In order to study the influence of stable isotope fractionation during inorganic and biologically controlled CaCO 3 precipitation we have developed the analytical principles for the measurement of strontium (Sr) isotope fractionation. We have established a measurement protocol for the application on a MC-ICP-MS (AXIOM) using the common bracketing standard technique. The Sr-standard CRM NBS987 was used as reference material for all measurements and to calculate the Sr fractionation. Latter value is expressed by the δ-notation defined as: δ 88/86 Sr = [( 88 Sr/ 86 Sr)sample / ( 88 Sr/ 86 Sr)standard ] * 1000 -1. A first set of experiments focused on the temperature dependency of Sr-isotope fractionation. For this purpose inorganically precipitated aragonite and calcite was prepared under controlled conditions in a temperature range from 10 to 50 o C. In addition, cultured and naturally grown corals were analyzed for their δ 88/86 Sr values. Repeated measurements of IAPSO seawater standard showed a mean δ 88/86 Sr value of 0.383 ± 0.008 (2 SEM) being the isotopically heaviest material measured so far. The first results of the inorganically precipitated aragonite and the natural corals revealed a clear temperature dependency of the δ 88/86 Sr values. For inorganic aragonite the slope of this correlation is about 0.0055 permil/ o C. However, for naturally grown corals (Pavona clavus) a 6 fold steeper slope of 0.033 permil/ o C was determined. This strong temperature dependency implies the potential to use stable Sr isotopes as a new marine (paleo)temperature proxy. (author)

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

Energy Technology Data Exchange (ETDEWEB)

Frierdich, Andrew J. [Univ. of Wisconsin, Madison, WI (United States); Univ. of Iowa, Iowa City, IA (United States); Beard, Brian L. [Univ. of Wisconsin, Madison, WI (United States); Rosso, Kevin M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Scherer, Michelle M. [Univ. of Iowa, Iowa City, IA (United States); Spicuzza, Michael J. [Univ. of Wisconsin, Madison, WI (United States); Valley, John W. [Univ. of Wisconsin, Madison, WI (United States); Johnson, Clark M. [Univ. of Wisconsin, Madison, WI (United States)

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 Fe 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

Pathways of coupled arsenic and iron cycling in high arsenic groundwater of the Hetao basin, Inner Mongolia, China: an iron isotope approach

Science.gov (United States)

Guo, Huaming; Liu, Chen; Lu, Hai; Wanty, Richard B.; Wang, Jun; Zhou, Yinzhu

2013-01-01

High As groundwater is widely distributed all over the world, which has posed a significant health impact on millions of people. Iron isotopes have recently been used to characterize Fe cycling in aqueous environments, but there is no information on Fe isotope characteristics in the groundwater. Since groundwater As behavior is closely associated with Fe cycling in the aquifers, Fe isotope signatures may help to characterize geochemical processes controlling As concentrations of shallow groundwaters. This study provides the first observation of Fe isotope fractionation in high As groundwater and evaluation of Fe cycling and As behaviors in shallow aquifers in terms of Fe isotope signatures. Thirty groundwater samples were taken for chemical and isotopic analysis in the Hetao basin, Inner Mongolia. Thirty-two sediments were sampled as well from shallow aquifers for Fe isotope analysis. Results showed that groundwater was normally enriched in isotopically light Fe with δ56Fe values between −3.40‰ and 0.58‰ and median of −1.14‰, while heavier δ56Fe values were observed in the sediments (between −1.10‰ and 0.75‰, median +0.36‰). In reducing conditions, groundwaters generally had higher δ56Fe values, in comparison with oxic conditions. High As groundwaters, generally occurring in reducing conditions, had high δ56Fe values, while low As groundwaters normally had low δ56Fe values. Although sediment δ56Fe values were generally independent of lithological conditions, a large variation in sediment δ56Fe values was observed in the oxidation–reduction transition zone. Three pathways were identified for Fe cycling in shallow groundwater, including dissimilatory reduction of Fe(III) oxides, re-adsorption of Fe(II), and precipitation of pyrite and siderite. Dissimilatory reduction of Fe(III) oxides resulted in light δ56Fe values (around −1.0‰) and high As concentration (>50 μg/L) in groundwater in anoxic conditions. Re-adsorption of isotopically

Carbon isotope fractionation of chlorinated ethenes during oxidation by Fe{sup 2+} activated persulfate

Energy Technology Data Exchange (ETDEWEB)

Marchesi, Massimo, E-mail: m2marche@uwaterloo.ca [Departament de Cristallografia, Mineralogia i Diposits Minerals, Universitat de Barcelona, Barcelona, Catalunya 08028 (Spain); Earth and Environmental Department, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Aravena, Ramon [Earth and Environmental Department, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Sra, Kanwartej S. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada); Thomson, Neil R. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Otero, Neus; Soler, Albert [Departament de Cristallografia, Mineralogia i Diposits Minerals, Universitat de Barcelona, Barcelona, Catalunya 08028 (Spain); Mancini, Silvia [Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada)

2012-09-01

The increased use of persulfate (S{sub 2}O{sub 8}{sup 2-}) for in situ chemical oxidation to treat groundwater and soils contaminated by chlorinated hydrocarbon compounds (CHCs) requires unbiased methods to assess treatment performance. Stable carbon isotope analysis offers a potential tool for assessing the in situ treatment performance of persulfate at sites contaminated with CHCs. This study investigated the extent of C isotope fractionation during oxidation of tetrachloroethene (PCE), trichloroethene (TCE) and cis-dichloroethene (cis-DCE) by persulfate activated by ferrous ion (Fe{sup 2+}). An average carbon isotope enrichment factor {epsilon}{sub bulk} of - 4.9 Per-Mille-Sign for PCE, - 3.6 Per-Mille-Sign for TCE and - 7.6 Per-Mille-Sign for cis-DCE were obtained in batch experiments. Variations in the initial S{sub 2}O{sub 8}{sup 2-}/Fe{sup 2+}/CHC molar ratios did not result in any significant differences in carbon isotope fractionation. The occurrence of carbon isotope fractionation during oxidation and the lack of dependence of enrichment factors upon the S{sub 2}O{sub 8}{sup 2-}/Fe{sup 2+}/CHC molar ratio demonstrate that carbon isotope analysis can potentially be used at contaminated sites as an additional technique to estimate treatment efficacy during oxidation of CHCs by Fe{sup 2+} activated persulfate. Highlights: Black-Right-Pointing-Pointer The performance of in situ chemical oxidation (ISCO) is still difficult to assess. Black-Right-Pointing-Pointer We investigated the potential of carbon isotope analysis as a new assessing tool. Black-Right-Pointing-Pointer C isotope of PCE, TCE and DCE oxidized by persulfate activated by Fe{sup 2+} was measured. Black-Right-Pointing-Pointer Enrichment factors of - 4.9 Per-Mille-Sign for PCE, - 3.6 Per-Mille-Sign for TCE and - 7.6 Per-Mille-Sign for cisDCE were obtained. Black-Right-Pointing-Pointer Carbon isotope can potentially be used to estimate the ISCO treatment efficacy.

ISOTOPIC MASS FRACTIONATION OF SOLAR WIND: EVIDENCE FROM FAST AND SLOW SOLAR WIND COLLECTED BY THE GENESIS MISSION

International Nuclear Information System (INIS)

Heber, Veronika S.; Baur, Heinrich; Wieler, Rainer; Bochsler, Peter; McKeegan, Kevin D.; Neugebauer, Marcia; Reisenfeld, Daniel B.; Wiens, Roger C.

2012-01-01

NASA's Genesis space mission returned samples of solar wind collected over ∼2.3 years. We present elemental and isotopic compositions of He, Ne, and Ar analyzed in diamond-like carbon targets from the slow and fast solar wind collectors to investigate isotopic fractionation processes during solar wind formation. The solar wind provides information on the isotopic composition for most volatile elements for the solar atmosphere, the bulk Sun and hence, on the solar nebula from which it formed 4.6 Ga ago. Our data reveal a heavy isotope depletion in the slow solar wind compared to the fast wind composition by 63.1 ± 2.1 per mille for He, 4.2 ± 0.5 per mille amu –1 for Ne and 2.6 ± 0.5 per mille amu –1 for Ar. The three Ne isotopes suggest that isotopic fractionation processes between fast and slow solar wind are mass dependent. The He/H ratios of the collected slow and fast solar wind samples are 0.0344 and 0.0406, respectively. The inefficient Coulomb drag model reproduces the measured isotopic fractionation between fast and slow wind. Therefore, we apply this model to infer the photospheric isotopic composition of He, Ne, and Ar from our solar wind data. We also compare the isotopic composition of oxygen and nitrogen measured in the solar wind with values of early solar system condensates, probably representing solar nebula composition. We interpret the differences between these samples as being due to isotopic fractionation during solar wind formation. For both elements, the magnitude and sign of the observed differences are in good agreement with the values predicted by the inefficient Coulomb drag model.

ISOTOPIC MASS FRACTIONATION OF SOLAR WIND: EVIDENCE FROM FAST AND SLOW SOLAR WIND COLLECTED BY THE GENESIS MISSION

Energy Technology Data Exchange (ETDEWEB)

Heber, Veronika S.; Baur, Heinrich; Wieler, Rainer [Institute for Geochemistry and Petrology, ETH Zurich, Clausiusstrasse 25, CH-8092 Zurich (Switzerland); Bochsler, Peter [Physikalisches Institut, Universitaet Bern, Sidlerstasse 5, CH-3012 Bern (Switzerland); McKeegan, Kevin D. [Department of Earth and Space Sciences, University of California Los Angeles, 595 Charles Young Drive East, Box 951567, Los Angeles, CA 90095-1567 (United States); Neugebauer, Marcia [Lunar and Planetary Laboratory, University of Arizona, Tucson, AZ 85721-0092 (United States); Reisenfeld, Daniel B. [Department of Physics and Astronomy, University of Montana, Missoula, MT 59812 (United States); Wiens, Roger C., E-mail: heber@ess.ucla.edu [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

2012-11-10

NASA's Genesis space mission returned samples of solar wind collected over {approx}2.3 years. We present elemental and isotopic compositions of He, Ne, and Ar analyzed in diamond-like carbon targets from the slow and fast solar wind collectors to investigate isotopic fractionation processes during solar wind formation. The solar wind provides information on the isotopic composition for most volatile elements for the solar atmosphere, the bulk Sun and hence, on the solar nebula from which it formed 4.6 Ga ago. Our data reveal a heavy isotope depletion in the slow solar wind compared to the fast wind composition by 63.1 {+-} 2.1 per mille for He, 4.2 {+-} 0.5 per mille amu{sup -1} for Ne and 2.6 {+-} 0.5 per mille amu{sup -1} for Ar. The three Ne isotopes suggest that isotopic fractionation processes between fast and slow solar wind are mass dependent. The He/H ratios of the collected slow and fast solar wind samples are 0.0344 and 0.0406, respectively. The inefficient Coulomb drag model reproduces the measured isotopic fractionation between fast and slow wind. Therefore, we apply this model to infer the photospheric isotopic composition of He, Ne, and Ar from our solar wind data. We also compare the isotopic composition of oxygen and nitrogen measured in the solar wind with values of early solar system condensates, probably representing solar nebula composition. We interpret the differences between these samples as being due to isotopic fractionation during solar wind formation. For both elements, the magnitude and sign of the observed differences are in good agreement with the values predicted by the inefficient Coulomb drag model.

Strontium isotope fractionation in soils and pedogenic processes

Energy Technology Data Exchange (ETDEWEB)

Shalev, Netta [Institute of Earth Sciences, The Hebrew University of Jerusalem, 91904 Jerusalem (Israel); Geological Survey of Israel, 30 Malkhe Israel Street, 95501 Jerusalem (Israel); Lazar, Boaz [Institute of Earth Sciences, The Hebrew University of Jerusalem, 91904 Jerusalem (Israel); Halicz, Ludwik; Stein, Mordechai; Gavrieli, Ittai; Sandler, Amir; Segal, Irena [Geological Survey of Israel, 30 Malkhe Israel Street, 95501 Jerusalem (Israel)

2013-07-01

The stable isotope composition of strontium (the ratio {sup 88}Sr/{sup 86}Sr expressed as δ{sup 88/86}Sr) showed significant fractionation in mountain soils of the Judea Highland. In order to understand this phenomenon, we studied the elemental composition and the stable and radiogenic Sr isotopic composition in soil transects conducted from semi-arid (desert fringe) to wetter (Mediterranean) climate zones. These transects were selected because the degree of soil leaching depends on the amount of precipitation and the permeability of the underlying bedrock. These soils are the pedogenic products of leaching of the accumulated desert dust and the underlying carbonate bed-rocks resulting in, among others, enrichment of the residual soils in Al-clays. A clear negative correlation was found between the δ{sup 88/86}Sr and Al{sub 2}O{sub 3} (Al-clay content) values of the soils, the high δ{sup 88/86}Sr-low Al{sub 2}O{sub 3} being the dust end-member. This preliminary study demonstrates the feasibility of using stable {sup 88}Sr-{sup 86}Sr isotopes as tracers of terrestrial weathering processes. (authors)

Temperature and Pressure Depences on the Isotopic Fractionation Effect in the Thermal Decomposition of Ozone

Directory of Open Access Journals (Sweden)

Su-Ju Kim

1997-12-01

Full Text Available To understand the mass-independent isotopic fractionation effects, thermal decomposition of ozone was performed. Initial oxygen gas was converted to ozone completely. Then, the ozone was decomposed to oxygen at various temperatures(30~150C. Isotopic compositions of product oxygen and residual ozone were measured using a stable isotope mass spectrometer. The experimental results were compared with the studies which were peformed at the similar conditions. From the raw experimental data, the functions of the instantaneous fractionation factors were calculated by the least square fit. The results clearly showed the temperature dependence. They also showed the pressure dependence and the surface effect. This study may play an important role in the study of ozone decomposition mechanism. It can be applied to explain the mass-independent isotopic pattern found in stratospheric ozone and in meteorites.

Carbon-13 isotopic composition of distillation fractions of some Egyptian crude oils

International Nuclear Information System (INIS)

Aly, A.I.M.; Hamza, M.S.; Abd Elsamie, S.G.

1991-01-01

13 C/ 13 C ratios were determined for some crude oil fields in the Gulf of Suez and Western Desert provinces. The crude oil was subjected to distillation at atmospheric pressure and subsequently under vacuum. Distillation fractions were collected at 25 degree C intervals. Carbon-13 content of these distillation fractions showed some differences in the degree of isotopic fractionation. The results were interpreted in view of the age of the source rocks and the degree of maturation process. The carbon-13 content of distillation fractions may be helpful in revealing petroleum mechanisms which can be exploited in exploration.4 fig

Diatom-induced silicon isotopic fractionation in Antarctic sea ice

Science.gov (United States)

Francois, F.; Damien, C.; Jean-Louis, T.; Anthony, W.; Luc, A.

2006-12-01

We measured silicon-isotopic composition of dissolved silicon and biogenic silica collected by sequential melting from spring 2003 Antarctic pack ice (Australian sector). Sea ice is a key ecosystem in the Southern Ocean and its melting in spring has been often thought to have a seeding effect for the surface waters, triggering blooms in the mixed layer. This work is the first investigation of the silicon isotopes' proxy in sea ice and allows to estimate the activity of sea-ice diatoms in the different brine structures and the influence of sea- ice diatoms on the spring ice edge blooms. The relative use of the dissolved silicon pool by sea-ice diatoms is usually assessed by calculating nutrient:salinity ratios in the brines. However such an approach is biased by difficulties in evaluating the initial nutrient concentrations in the different brines structures, and by the impossibility to account for late sporadic nutrient replenishments. The silicon-isotopic composition of biogenic silica is a convenient alternative since it integrates an average Si utilization on all generations of diatoms. Measurements were performed on a MC-ICP-MS, in dry plasma mode using external Mg doping. Results are expressed as delta29Si relative to the NBS28 standard. From three sea ice cores with contrasted physico-chemical characteristics, we report significant isotopic fractionations linked to the diatoms activity, with distinct silicon biogeochemical dynamics between different brine structure. The diatoms in snow ice and in brine pockets of frazil or congelation ice have the most positive silicon-isotopic composition (+0.53 to +0.86 p.mil), indicating that they grow in a closed system and use a significant part of the small dissolved silicon pool. In the brine channels and skeletal layer, diatoms display a relatively less positive Si-isotopic composition (+0.41 to +0.70 p.mil), although it is still heavier compared to equilibrium fractionation (+0.38 p.mil). This suggests that they have

Assessing the impact of iron ore mining to the groundwater in Goa, using stable isotopes

International Nuclear Information System (INIS)

Arzoo Ansari, Md.; Sinha, U.K.; Mohokar, H.V.; Deodhar, Archana; Mendhekar, G.N.; Jaryal, Ajay

2017-01-01

Goa contributes about 50% of the total iron ore exported from the country. Iron ore share is 95% of total mining and quarrying sector in Goa. It represents the second most important industry next to tourism. The iron ore is predominantly mined by opencast mining throughout Goa. The reduction of the forest cover, huge dumps, dust mineral particles, water contamination and health problems are some of the principal harmful effects of extensive mining which is of great concern to the environment. The objective of this study is to assess the impact of iron ore mining to groundwater in downstream side of the mine pits using isotope hydrological techniques

Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

Science.gov (United States)

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

The fractioning factor and the number of theorical plates in isotopic enrichment columns determined simultaneously

International Nuclear Information System (INIS)

Ducatti, Carlos

1997-01-01

Using an analytical approach and an analytical graphical method, it was determined simultaneously the fractioning factor and the number of theoretical plates in isotopic enrichment columns during the conditions of dinamical isotopic equilibrium. (author). 5 refs., 2 figs., 2 tabs

Calcium isotope fractionation in a silicate dominated Cenozoic aquifer system

Science.gov (United States)

Li, Junxia; DePaolo, Donald J.; Wang, Yanxin; Xie, Xianjun

2018-04-01

To understand the characteristics of Ca isotope composition and fractionation in silicate-dominated Quaternary aquifer system, hydrochemical and isotope studies (87Sr/86Sr, 13CDIC and 44/40Ca) were conducted on groundwater, sediment and rock samples from the Datong basin, China. Along the groundwater flow path from the basin margin to the center, groundwater hydrochemical type evolves from Ca-HCO3 to Na-HCO3/Na-Cl type, which results from aluminosilicate hydrolysis, vertical mixing, cation exchange between CaX2 and NaX, and calcite/dolomite precipitation. These processes cause the decrease in groundwater Ca concentration and the associated modest fractionation of groundwater Ca isotopes along the flowpath. The groundwater δ44/40Ca value varies from -0.11 to 0.49‰. The elevated δ44/40Ca ratios in shallow groundwater are attributed to vertical mixing involving addition of irrigation water, which had the average δ44/40Ca ratio of 0.595‰. Chemical weathering of silicate minerals and carbonate generates depleted δ44/40Ca signatures in groundwater from Heng Mountain (east area) and Huanghua Uplift (west area), respectively. Along the groundwater flow path from Heng Mountain to central area of east area, cation exchange between CaX2 and NaX on clay mineral results in the enrichment of heavier Ca isotope in groundwater. All groundwater samples are oversaturated with respect to calcite and dolomite. The groundwater environment rich in organic matter promotes the precipitation of carbonate minerals via the biodegradation of organic carbon, thereby further promoting the elevation of groundwater δ44/40Ca ratios.

Non-mass-dependent fractionation of sulfur and oxygen isotopes during UV photolysis of sulfur dioxide

Science.gov (United States)

Pen, Aranh

Since the discovery of anomalous sulfur isotope abundance in the geological record in sulfate and sulfide minerals (Farquhar et al., 2000), much effort has been put into understanding their origin to provide new insights into the environmental conditions on the early Earth (Farquhar et al., 2001; Pavlov and Kasting, 2002; Ono et al., 2003; Zahnle et al., 2006; Farquhar et al., 2007; Lyons, 2007; Lyons, 2008). This discovery gained immense interest because of its implications for both the lack of oxygen in the atmosphere during the Archean era 2.5-3.8 Gya (billion years ago), and for rise of oxygen, or the "Great Oxidation Event", that occurred 2.2-2.4 Gya (Holland, 2002). These signatures are believed to be produced in an anticorrelation to oxygen abundance in the early atmosphere, which will aid in quantifying the rate of oxygenation during the "Great Oxidation Event". According to Farquhar et al. (2000), the non-mass-dependent (NMD), or anomalous, fractionation signatures were produced by photochemical reactions of volcanic sulfur species in Earth's early atmosphere (> 2.3 Gya) due to the lack of an oxygen and ozone shield, resulting in an atmosphere transparent to solar ultraviolet (UV) radiation (Farquhar et al., 2001). Interpretation of the anomalous rock records, though, depends on the identification of (1) chemical reactions that can produce the NMD signature (Farquhar and Wing, 2003); and (2) conditions necessary for conversion of the gas-phase products into solid minerals (Pavlov and Kasting, 2002). The focus of my research addresses the first step, which is to determine whether the chemical reactions that occurred in Earth's early atmosphere, resulting in NMD fractionation of sulfur isotopes, were due to broadband UV photochemistry, and to test isotopic self-shielding as the possible underlying mechanism. In this project, our goals were to test isotopic self-shielding during UV photolysis as a possible underlying mechanism for anomalous sulfur isotopic

Impact of Redox Condition on Fractionation and Bioaccessibility of Arsenic in Arsenic-Contaminated Soils Remediated by Iron Amendments: A Long-Term Experiment

Directory of Open Access Journals (Sweden)

Quan Zhang

2018-01-01

Full Text Available Iron-bearing amendments, such as iron grit, are proved to be effective amendments for the remediation of arsenic- (As- contaminated soils. In present study, the effect of redox condition on As fractions in As-contaminated soils remediated by iron grit was investigated, and the bioaccessibility of As in soils under anoxic condition was evaluated. Results showed that the labile fractions of As in soils decreased significantly after the addition of iron grit, while the unlabile fractions of As increased rapidly, and the bioaccessibility of As was negligible after 180 d incubation. More labile fractions of As in iron-amended soils were transformed into less mobilizable or unlabile fractions with the contact time. Correspondingly, the bioaccessibility of As in iron-amended soils under the aerobic condition was lower than that under the anoxic condition after 180 d incubation. The redistribution of loosely adsorbed fraction of As in soils occurred under the anoxic condition, which is likely ascribed to the reduction of As(V to As(III and the reductive dissolution of Fe-(hydroxides. The stabilization processes of As in iron-amended soils under the anoxic and aerobic conditions were characterized by two stages. The increase of crystallization of Fe oxides, decomposition of organic matter, molecular diffusion, and the occlusion within Fe-(hydroxides cocontrolled the transformation of As fractions and the stabilization process of As in iron-amended soils under different redox conditions. In terms of As bioaccessibility, the stabilization process of As in iron-amended soils was shortened under the aerobic condition in comparison with the anoxic condition.

Ferric reductase activity of low molecular weight human milk fraction is associated with enhanced iron solubility and uptake in Caco-2 cells.

Science.gov (United States)

Pullakhandam, Raghu; Nair, Madhavan Krishnapillai; Kasula, Sunanda; Kilari, Sreenivasulu; Thippande, Tippeswamy Gowda

2008-09-19

It is known that the fractional absorption of extrinsic iron from human milk is higher in infants and adults. A low molecular weight milk fraction has been proposed to increase the bioavailability of iron from human milk. Nevertheless, the mechanisms remained elusive. Here in we demonstrate ferric reductase activity (Km7.73x10(-6)M) in low molecular weight human milk fraction (10kF, filtrate derived from ultra filtration of milk whey through 10kDa cutoff membrane), which increased ferric iron solubility and iron uptake in Caco-2 cells. The 10kF fraction was as effective as ascorbic acid (1:20 iron to ascorbic acid) in increasing the ferric iron solubility and uptake in Caco-2 cells. Further, gel filtration chromatography on peptide column led to co-elution of ferric reductase and iron solubilization activities at an apparent molecular mass of iron in Caco-2 cells. Thus, it is concluded that human milk possesses ferric reductase activity and is associated with ferric iron solubilization and enhanced absorption.

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

Science.gov (United States)

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

2011-01-01

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

Extending the Rayleigh equation to allow competing isotope fractionating pathways to improve quantification of biodegradation

NARCIS (Netherlands)

van Breukelen, B.M.

2007-01-01

The Rayleigh equation relates the change in isotope ratio of an element in a substrate to the extent of substrate consumption via a single kinetic isotopic fractionation factor (α). Substrate consumption is, however, commonly distributed over several metabolic pathways each potentially having a

Oxygen and hydrogen isotope fractionation during cellulose metabolism in Lemna gibba L

International Nuclear Information System (INIS)

Yakir, D.; DeNiro, M.J.

1990-01-01

Lemna gibba L. B3 was grown under heterotrophic, photoheterotrophic, and autotrophic conditions in water having a variety of hydrogen and oxygen isotopic compositions. The slopes of the linear regression lines between the isotopic composition of water and leaf cellulose indicated that under the three growth conditions about 40, 70, and 100% of oxygens and carbon-bound hydrogens of cellulose exchanged with those of water prior to cellulose formation. Using the equations of the linear relationships, we estimated the overall fractionation factors between water and the exchanged oxygen and carbon bound-hydrogen of cellulose. At least two very different isotope effects must determine the hydrogen isotopic composition of Lemna cellulose. One reflects the photosynthetic reduction of NADP, while the second reflects exchange reactions that occur subsequent to NADP reduction. Oxygen isotopic composition of cellulose apparently is determined by a single type of exchange reaction with water. Under different growth conditions, variations in metabolic fluxes affect the hydrogen isotopic composition of cellulose by influencing the extent to which the two isotope effects mentioned above are recorded. The oxygen isotopic composition of cellulose is not affected by such changes in growth conditions

Nitrogen isotope fractionations in the Fischer-Tropsch synthesis and in the Miller-Urey reaction

International Nuclear Information System (INIS)

Chun-Chan Kung; Hayatsu, R.; Studier, M.H.; Clayton, R.N.; Chicago Univ., IL; Chicago Univ., IL

1979-01-01

Nitrogen isotope fractionations have been measured in Fischer-Tropsch and Miller-Urey reactions in order to determine whether these processes can account for the large 15 N/ 14 N ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in 15 N by only 3 promille relative to the starting material (NH 3 ). The 15 N enrichment in polymers from the Miller-Urey reaction was 10-12 promille. Both of these fractionations are small compared to the 80-90 promille differences observed between enstatite chondrites and carbonaceous chondrites. These large differences are apparently due to temporal or spatial variations in the isotopic composition of nitrogen in the solar nebula, rather than to fractionation during the production of organic compounds. (orig.)

Isotope Fractionation Studies in Prestellar Cores: The Case of Nitrogen

Science.gov (United States)

Milam, Stefanie N.; Charnley, Steven B.

2011-01-01

Isotopically fractionated material is found in many solar system objects, including meteorites and comets. It is considered, in some cases, to trace interstellar material that was incorporated into the solar system without undergoing significant processing, thus preserving the fractionation. In interstellar molecular clouds, ion-molecule chemistry continually cycles nitrogen between the two main reservoirs - N and N2 - leading to only minor N-15 enrichments. Charnley and Rodgers showed that depletion of CO removes oxygen from the gas and weakens this cycle such that significant N-15 fractionation can occur for N2 and other N-bearing species in such cores. Observations are being conducted at millimeter and submillimeter wavelengths employing various facilities in order to both spatially and spectrally, resolve emission from these cores. A preliminary study to obtain the N-14/N-15 ratio in nitriles (HCN and HNC) was conducted at the Arizona Radio Observatory's 12m telescope on Kitt Peak, AZ. Spectra were obtained at high resolution (0.08 km/s) in order to resolve dynamic properties of each source as well as to resolve hyperfine structure present in certain isotopologues. This study included four dark cloud cores, observed to have varying levels of molecular depletion: L1521E, L1498, L1544, and L1521F. Previous studies of the N-14/N-15 ratio towards LI544 were obtained with N2H+ and NIH3, yielding ratios of 446 and >700, respectively. The discrepancy observed in these two measurements suggests a strong chemical dependence on the fractionation of nitrogen. Ratios (C,N, and D) obtained from isotopologues for a particular molecule are likely tracing the same chemical heritage and are directly comparable within a given source. Results and comparisons between the protostellar evolutionary state and isomer isotope fractionation as well as between other N-bearing species will be presented.

Binary stars as sources of iron and of s-process isotopes

International Nuclear Information System (INIS)

Iben, Icko Jr.; Bologna Univ.; Sussex Univ., Brighton

1986-01-01

Sources of elements and isotopes in stars, during the development of stars, is examined. The paper was presented to the conference on ''The early universe and its evolution'', Erice, Italy, 1986. Intermediate mass stars in their asymptotic giant branch phase of evolution as sources of carbon, merging white dwarfs as sources of iron, and helium star cataclysmics as sources of s-process elements, are all discussed. (U.K.)

Ice-liquid isotope fractionation factors for O-18 and H-2 deduced from the isotopic correction constants for the triple point of water

NARCIS (Netherlands)

Wang, Xing; Meijer, Harro A. J.

2018-01-01

The stable isotopes of water are extensively used as tracers in many fields of research. For this use, it is essential to know the isotope fractionation factors connected to various processes, the most important of which being phase changes. Many experimental studies have been performed on phase

Effects of alkalinity and salinity at low and high light intensity on hydrogen isotope fractionation of long-chain alkenones produced by Emiliania huxleyi

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G. M. Weiss

2017-12-01

Full Text Available Over the last decade, hydrogen isotopes of long-chain alkenones have been shown to be a promising proxy for reconstructing paleo sea surface salinity due to a strong hydrogen isotope fractionation response to salinity across different environmental conditions. However, to date, the decoupling of the effects of alkalinity and salinity, parameters that co-vary in the surface ocean, on hydrogen isotope fractionation of alkenones has not been assessed. Furthermore, as the alkenone-producing haptophyte, Emiliania huxleyi, is known to grow in large blooms under high light intensities, the effect of salinity on hydrogen isotope fractionation under these high irradiances is important to constrain before using δDC37 to reconstruct paleosalinity. Batch cultures of the marine haptophyte E. huxleyi strain CCMP 1516 were grown to investigate the hydrogen isotope fractionation response to salinity at high light intensity and independently assess the effects of salinity and alkalinity under low-light conditions. Our results suggest that alkalinity does not significantly influence hydrogen isotope fractionation of alkenones, but salinity does have a strong effect. Additionally, no significant difference was observed between the fractionation responses to salinity recorded in alkenones grown under both high- and low-light conditions. Comparison with previous studies suggests that the fractionation response to salinity in culture is similar under different environmental conditions, strengthening the use of hydrogen isotope fractionation as a paleosalinity proxy.

Effects of alkalinity and salinity at low and high light intensity on hydrogen isotope fractionation of long-chain alkenones produced by Emiliania huxleyi

Science.gov (United States)

Weiss, Gabriella M.; Pfannerstill, Eva Y.; Schouten, Stefan; Sinninghe Damsté, Jaap S.; van der Meer, Marcel T. J.

2017-12-01

Over the last decade, hydrogen isotopes of long-chain alkenones have been shown to be a promising proxy for reconstructing paleo sea surface salinity due to a strong hydrogen isotope fractionation response to salinity across different environmental conditions. However, to date, the decoupling of the effects of alkalinity and salinity, parameters that co-vary in the surface ocean, on hydrogen isotope fractionation of alkenones has not been assessed. Furthermore, as the alkenone-producing haptophyte, Emiliania huxleyi, is known to grow in large blooms under high light intensities, the effect of salinity on hydrogen isotope fractionation under these high irradiances is important to constrain before using δDC37 to reconstruct paleosalinity. Batch cultures of the marine haptophyte E. huxleyi strain CCMP 1516 were grown to investigate the hydrogen isotope fractionation response to salinity at high light intensity and independently assess the effects of salinity and alkalinity under low-light conditions. Our results suggest that alkalinity does not significantly influence hydrogen isotope fractionation of alkenones, but salinity does have a strong effect. Additionally, no significant difference was observed between the fractionation responses to salinity recorded in alkenones grown under both high- and low-light conditions. Comparison with previous studies suggests that the fractionation response to salinity in culture is similar under different environmental conditions, strengthening the use of hydrogen isotope fractionation as a paleosalinity proxy.

Iron Mineralogy and Speciation in Clay-Sized Fractions of Chinese Desert Sediments

Science.gov (United States)

Lu, Wanyi; Zhao, Wancang; Balsam, William; Lu, Huayu; Liu, Pan; Lu, Zunli; Ji, Junfeng

2017-12-01

Iron released from Asian desert dust may be an important source of bioavailable iron for the North Pacific Ocean and thereby may stimulate primary productivity. However, the Fe species of the fine dusts from this source region are poorly characterized. Here we investigate iron species and mineralogy in the clay-sized fractions (iron phases (ferrihydrite and lepidocrocite) and reducible iron oxides (dominated by goethite) are 0.81 wt % and 2.39 wt %, respectively, and Fe dissolved from phyllosilicates extracted by boiling HCl (dominated by chlorite) is 3.15 wt %. Dusts originating from deserts in northwestern China, particularly the Taklimakan desert, are relatively enriched in easily reducible Fe phases, probably due to abundant Fe contained in fresh weathering products resulting from the rapid erosion associated with active uplift of mountains to the west. Data about Fe speciation and mineralogy in Asian dust sources will be useful for improving the quantification of soluble Fe supplied to the oceans, especially in dust models.

Revised models of interstellar nitrogen isotopic fractionation

Science.gov (United States)

Wirström, E. S.; Charnley, S. B.

2018-03-01

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of 15N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised 15N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirström et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included 15N fractionation of CN in neutral-neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing 15N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching 14N/15N ratios of >2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the 14N/15N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk 15N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

Fractionation of hydrogen, oxygen and carbon isotopes in n-alkanes and cellulose of three Sphagnum species

NARCIS (Netherlands)

Brader, A.V.; Winden, J.F.; Bohncke, S.J.P.; Beets, C.J.; Reichart, G.-J.; De Leeuw, J.W.

2010-01-01

Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were

Carbon isotope fractionation between amorphous calcium carbonate and calcite in earthworm-produced calcium carbonate

International Nuclear Information System (INIS)

Versteegh, E.A.A.; Black, S.; Hodson, M.E.

2017-01-01

In this study we investigate carbon isotope fractionation during the crystallization of biogenic calcium carbonate. Several species of earthworm including Lumbricus terrestris secrete CaCO_3. Initially a milky fluid comprising micro-spherules of amorphous CaCO_3 (ACC) is secreted into pouches of the earthworm calciferous gland. The micro-spherules coalesce and crystalize to form millimetre scale granules, largely comprising calcite. These are secreted into the earthworm intestine and from there into the soil. L. terrestris were cultured for 28 days in two different soils, moistened with three different mineral waters at 10, 16 and 20 °C. The milky fluid in the calciferous glands, granules in the pouches of the calciferous glands and granules excreted into the soil were collected and analysed by FTIR spectroscopy to determine the form of CaCO_3 present and by IRMS to determine δ"1"3C values. The milky fluid was ACC. Granules removed from the pouches and soil were largely calcite; the granules removed from the pouches contained more residual ACC than those recovered from the soil. The δ"1"3C values of milky fluid and pouch granules became significantly more negative with increasing temperature (p ≤ 0.001). For samples from each temperature treatment, δ"1"3C values became significantly (p ≤ 0.001) more negative from the milky fluid to the pouch granules to the soil granules (−13.77, −14.69 and −15.00 respectively at 10 °C; −14.37, −15.07 and −15.18 respectively at 16 °C and −14.89, −15.41 and −15.65 respectively at 20 °C). Fractionation of C isotopes occurred as the ACC recrystallized to form calcite with the fractionation factor ε_c_a_l_c_i_t_e_-_A_C_C = −1.20 ± 0.52‰. This is consistent with the crystallization involving dissolution and reprecipitation rather than a solid state rearrangement. Although C isotopic fractionation has previously been described between different species of dissolved inorganic carbon

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

Science.gov (United States)

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 (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.

Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes

Energy Technology Data Exchange (ETDEWEB)

Babcsányi, Izabella; Chabaux, François; Granet, Mathieu; Meite, Fatima; Payraudeau, Sylvain; Duplay, Joëlle; Imfeld, Gwenaël, E-mail: imfeld@unistra.fr

2016-07-01

Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ{sup 65}Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (− 0.12 to 0.24‰ ± 0.08‰). The values were in the range of those of the fungicides (− 0.21 to 0.11‰) and included the geogenic δ{sup 65}Cu value of the untreated soil (0.08‰). However, δ{sup 65}Cu values significantly differed between particle-size soil fractions (− 0.37 ± 0.10‰ in fine clays and 0.23 ± 0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20{sup th} July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ{sup 65}Cu values from 0.52 to 1.35‰ in the dissolved phase (< 0.45 μm) compared to − 0.34 to − 0.02‰ in the SPM phase, indicating that clay and fine clay fractions were the main vectors of SPM-bound Cu in runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments. - Highlights: • We investigated Cu sorption processes in vineyard soils and runoff transport. • Cu export by runoff from the catchment accounted for 1% of the applied Cu mass. • δ{sup 65}Cu values differed between the particle-size soil

Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes

International Nuclear Information System (INIS)

Babcsányi, Izabella; Chabaux, François; Granet, Mathieu; Meite, Fatima; Payraudeau, Sylvain; Duplay, Joëlle; Imfeld, Gwenaël

2016-01-01

Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ"6"5Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (− 0.12 to 0.24‰ ± 0.08‰). The values were in the range of those of the fungicides (− 0.21 to 0.11‰) and included the geogenic δ"6"5Cu value of the untreated soil (0.08‰). However, δ"6"5Cu values significantly differed between particle-size soil fractions (− 0.37 ± 0.10‰ in fine clays and 0.23 ± 0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20"t"h July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ"6"5Cu values from 0.52 to 1.35‰ in the dissolved phase (< 0.45 μm) compared to − 0.34 to − 0.02‰ in the SPM phase, indicating that clay and fine clay fractions were the main vectors of SPM-bound Cu in runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments. - Highlights: • We investigated Cu sorption processes in vineyard soils and runoff transport. • Cu export by runoff from the catchment accounted for 1% of the applied Cu mass. • δ"6"5Cu values differed between the particle-size soil fractions. • The clay soil

Textural and Isotopic Evidence for Silica Cementation in 1.88 GA Granular Iron Formation

Science.gov (United States)

Brengman, L. A.; Fedo, C.; Martin, W.

2016-12-01

Controls on quartz precipitation mechanisms and silicon isotope fractionation during diagenesis of Precambrian iron formation (IF) are not well constrained. The goal of this study is to identify textural evidence for the relative timing of silica cementation of granular units from the near un-metamorphosed 1.88 Ga Biwabik IF and determine the silicon isotope composition for such a silicification event. The lowermost IF (lower cherty, LC) consists of granular units associated with high-energy sedimentary structures interpreted to represent shallow-marine shelf deposition. Up-section is marked by an abrupt shift to banded units interpreted as a transition to quiescent (deeper) water, followed by a return to granular textures and shallower conditions (upper cherty, UC). We first surveyed granular samples of the lower stromatolitic (LC) and upper oncolitic facies (UC) to identify sedimentary textures and cement. LC units consist of microquartz (chert), megaquartz, hematite, carbonate, and detrital quartz, chert, and quartz/Fe-oxide intraclastic material. In UC samples, space between granular material (hematite, magnetite, quartz ooids/intraclasts) is filled by mega-quartz cement, and cross-cutting mega-quartz veins. We targeted mega-quartz cement, and veins for δ30Si analysis via secondary ion mass spectrometry. The average measured δ30Si value of cement (δ30Siavg. cement UC6b = -3.11 ± 0.21 ‰) is significantly different than associated veins (δ30Siavg. vein UC6b = 0.21 ± 0.21 ‰; δ30Siavg. vein LC4 = 0.39 ± 0.21 ‰), both within and between samples. We interpret the relative difference between cement and veins to represent quartz precipitation under different geochemical conditions, and therefore at different times. Combining isotopic and textural evidence, we interpret silica cementation to pre-date veins, and represent quartz precipitation that either varied in rate, or occurred under closed-system conditions affected by Rayleigh distillation. Both

Trapped Melt in IIIAB Irons: Solid/Liquid Elemental Partitioning During the Fractionation of the IIIAB Magma

Science.gov (United States)

Wasson, John T.

1999-01-01

Group IIIAB, the largest iron-meteorite group, shows compositional trends (including a three-order-of-magnitude It concentration range) indicating that it formed by fractional crystallization of a metallic magma. Because about 200 irons are available, and all degrees of crystallization are well represented, IIIAB offers an excellent set of samples for the study of crystallization at all depths of the asteroidal core. On log-log Ir-Au, and Ir-As diagrams IIIAB forms a broad band; the breadth represents real meteorite-to-meteorite variations, far outside experimental or sampling uncertainties. A successful model must explain the width of this band; I suggest that it mainly resulted from the trapping of parental magma within the crystallizing solid. Because S is essentially insoluble in metal, the abundance of FeS is a measure of the fraction of trapped liquid. The trapped-melt model is supported by the observation that irons having higher S contents plot closer to the inferred composition of the magmatic parental liquid. The lowest S values are found in the irons occupying the left envelope of the IIIAB Ir-Au or Ir-As compositional fields, thus it is this set of irons that should be interpreted as the solid products of a fractionating magma. This simplifies the modeling of the crystallization process and allows inferences regarding the distribution ratios for other elements in the evolved IIIAB system. The large (multiton) Cape York irons show wide variations in their trapped-melt fractions; their compositions seem best understood in terms of a low initial S content of the IIIAB magma, about 20 mg/g. The inferred initial IIIAB distribution coefficient for Ir, 4.6, is much higher than published values based on laboratory studies of low-S systems; I suggest that low-S (and low-P) partition-ratio measurements tend to err in the direction of unity. In IIIAB distribution coefficients for Au, As, and Ni were still < 1 when the most evolved IIIAB irons formed, another

Oxygen isotope fractionation in the CaCO3-DIC-H2O system

Science.gov (United States)

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

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

Science.gov (United States)

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

2017-12-01

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

Uranium isotope ratios of Muonionalusta troilite and complications for the absolute age of the IVA iron meteorite core

Science.gov (United States)

Brennecka, Gregory A.; Amelin, Yuri; Kleine, Thorsten

2018-05-01

The crystallization ages of planetary crustal material (given by basaltic meteorites) and planetary cores (given by iron meteorites) provide fiducial marks for the progress of planetary formation, and thus, the absolute ages of these objects fundamentally direct our knowledge and understanding of planet formation and evolution. The lone precise absolute age of planetary core material was previously obtained on troilite inclusions from the IVA iron meteorite Muonionalusta. This previously reported Pb-Pb age of 4565.3 ± 0.1 Ma-assuming a 238U/235U =137.88-only post-dated the start of the Solar System by approximately 2-3 million years, and mandated fast cooling of planetary core material. Since an accurate Pb-Pb age requires a known 238U/235U of the sample, we have measured both 238U/235U and Pb isotopic compositions of troilite inclusions from Muonionalusta. The measured 238U/235U of the samples range from ∼137.84 to as low as ∼137.22, however based on Pb and U systematics, terrestrial contamination appears pervasive and has affected samples to various extents for Pb and U. The cause of the relative 235U excess in one sample does not appear to be from terrestrial contamination or the decay of short-lived 247Cm, but is more likely from fractionation of U isotopes during metal-silicate separation during core formation, exacerbated by the extreme U depletion in the planetary core. Due to limited Pb isotopic variation and terrestrial disturbance, no samples of this study produced useful age information; however the clear divergence from the previously assumed 238U/235U of any troilite in Muonionalusta introduces substantial uncertainty to the previously reported absolute age of the sample without knowledge of the 238U/235U of the sample. Uncertainties associated with U isotope heterogeneity do not allow for definition of a robust age of solidification and cooling for the IVA core. However, one sample of this work-paired with previous work using short

Lattice Boltzmann Simulation of Water Isotope Fractionation During Growth of Ice Crystals in Clouds

Science.gov (United States)

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

2006-12-01

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 existing quantitative models that directly relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be a direct relationship 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. 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 sticking coefficient (or accommodation coefficient) for ice is uncertain. The ratio D/k is a length that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions using a dimensionless Damkohler number

Study of ferrallitisation process in soil by application of isotopic dilution kinetic technique to iron

International Nuclear Information System (INIS)

Thomann, Christiane

1978-01-01

Isotopic dilution kinetic technique applied to iron may contribute to make clear the conditions of ''potential'' mobility of iron in soils, under the action of three factors: moisture, incubation period and organic matter imputs. Comparison between surface horizons of three tropical soils: leached ferruginous tropical soil, weakly ferrallitic red soil and ferrallitic soil shows that in the ferrallitisation process, weakly ferrallitic soil would take place between the two other types of soils with a maximum mobility of iron. This mobility decreases when organic matter rate decreases leading then to ''beige'' soil (ferruginous leached tropical soil), and when hydroxide rate increases, which leads to ferrallitic soil. In podzol (A 1 horizon), for the same rate of organic matter, potential mobility of iron is higher than in ferallitic soil, because it contains ten times more free iron than the podzol [fr

The effects of atmospheric [CO2] on carbon isotope fractionation and magnesium incorporation into biogenic marine calcite

Science.gov (United States)

Vieira, Veronica

1997-01-01

The influences of atmospheric carbon dioxide on the fractionation of carbon isotopes and the magnesium incorporation into biogenic marine calcite were investigated using samples of the calcareous alga Amphiroa and benthic foraminifer Sorites grown in the Biosphere 2 Ocean system under variable atmospheric CO2 concentrations (approximately 500 to 1200 ppm). Carbon isotope fractionation was studied in both the organic matter and the skeletal carbonate. Magnesium analysis was to be performed on the carbonate removed during decalcification. These data have not been collected due to technical problems. Carbon isotope data from Amphiroa yields a linear relation between [CO2] and Delta(sup 13)C(sub Corg)values suggesting that the fractionation of carbon isotopes during photosynthesis is positively correlated with atmospheric [CO2]. [CO2] and Delta(sup 13)C(sub Corg) values for Sorites produce a relation that is best described by a hyperbolic function where Delta(sup 13)C(sub Corg) values increase between 300 and 700 ppm and decrease from 700 to 1200 ppm. Further investigation of this relation and Sorites physiology is needed.

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

Science.gov (United States)

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

2014-01-01

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

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

Science.gov (United States)

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

2017-12-01

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

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

Science.gov (United States)

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

Characterization of iron speciation in urban and rural single particles using XANES spectroscopy and micro X-ray fluorescence measurements: investigating the relationship between speciation and fractional iron solubility

OpenAIRE

Oakes, M.; Weber, R. J.; Lai, B.; Russell, A.; Ingall, E. D.

2012-01-01

Soluble iron in fine atmospheric particles has been identified as a public health concern by participating in reactions that generate reactive oxygen species (ROS). The mineralogy and oxidation state (speciation) of iron have been shown to influence fractional iron solubility (soluble iron/total iron). In this study, iron speciation was determined in single particles at urban and rural sites in Georgia USA using synchrotron-based techniques, such as X-ray Absorption Near-Edge Structure (XANES...

Stable chlorine isotopes in arid non-marine basins: Instances and possible fractionation mechanisms

International Nuclear Information System (INIS)

Eastoe, C.J.

2016-01-01

Stable chlorine isotopes are useful geochemical tracers in processes involving the formation and evolution of evaporitic halite. Halite and dissolved chloride in groundwater that has interacted with halite in arid non-marine basins has a δ 37 Cl range of 0 ± 3‰, far greater than the range for marine evaporites. Basins characterized by high positive (+1 to +3‰), near-0‰, and negative (−0.3 to −2.6‰) are documented. Halite in weathered crusts of sedimentary rocks has δ 37 Cl values as high as +5.6‰. Salt-excluding halophyte plants excrete salt with a δ 37 Cl range of −2.1 to −0.8‰. Differentiated rock chloride sources exist, e.g. in granitoid micas, but cannot provide sufficient chloride to account for the observed data. Single-pass application of known fractionating mechanisms, equilibrium salt-crystal interaction and disequilibrium diffusive transport, cannot account for the large ranges of δ 37 Cl. Cumulative fractionation as a result of multiple wetting-drying cycles in vadose playas that produce halite crusts can produce observed positive δ 37 Cl values in hundreds to thousands of cycles. Diffusive isotope fractionation as a result of multiple wetting-drying cycles operating at a spatial scale of 1–10 cm can produce high δ 37 Cl values in residual halite. Chloride in rainwater is subject to complex fractionation, but develops negative δ 37 Cl values in certain situations; such may explain halite deposits with bulk negative δ 37 Cl values. Future field studies will benefit from a better understanding of hydrology and rainwater chemistry, and systematic collection of data for both Cl and Br. - Highlights: • δ 37 Cl in halite from arid, non-marine sedimentary basins ranges from −3 to +5.5‰. • Cl − in vadose playas may develop large isotope fractionation through cyclic wetting and drying. • Cl − in phreatic playas undergoes no fractionation as a result of cyclic wetting and drying. • Cl − in weathered

Iron Bioavailability from Ferric Pyrophosphate in Extruded Rice Cofortified with Zinc Sulfate Is Greater than When Cofortified with Zinc Oxide in a Human Stable Isotope Study.

Science.gov (United States)

Hackl, Laura; Zimmermann, Michael B; Zeder, Christophe; Parker, Megan; Johns, Paul W; Hurrell, Richard F; Moretti, Diego

2017-03-01

Background: Extruded rice grains are often cofortified with iron and zinc. However, it is uncertain if the addition of zinc to iron-fortified rice affects iron absorption and whether this is zinc-compound specific. Objective: We investigated whether zinc, added as zinc oxide (ZnO) or zinc sulfate (ZnSO 4 ), affects human iron absorption from extruded rice fortified with ferric pyrophosphate (FePP). Methods: In 19 iron-depleted Swiss women (plasma ferritin ≤16.5 μ/L) aged between 20 and 39 y with a normal body mass index (in kg/m 2 ; 18.7-24.8), we compared iron absorption from 4 meals containing fortified extruded rice with 4 mg Fe and 3 mg Zn. Three of the meals contained extruded rice labeled with FePP ( 57 FePP): 1 ) 1 meal without added zinc ( 57 FePP-Zn), 2 ) 1 cofortified with ZnO ( 57 FePP+ZnO), and 3 ) 1 cofortified with ZnSO 4 ( 57 FePP+ZnSO 4 ). The fourth meal contained extruded rice without iron or zinc, extrinsically labeled with ferrous sulfate ( 58 FeSO 4 ) added as a solution after cooking. All 4 meals contained citric acid. Iron bioavailability was measured by isotopic iron ratios in red blood cells. We also measured relative in vitro iron solubility from 57 FePP-Zn, 57 FePP+ZnO, and 57 FePP+ZnSO 4 expressed as a fraction of FeSO 4 solubility. Results: Geometric mean fractional iron absorption (95% CI) from 57 FePP+ZnSO 4 was 4.5% (3.4%, 5.8%) and differed from 57 FePP+ZnO (2.7%; 1.8%, 4.1%) ( P iron bioavailabilities compared with 58 FeSO 4 were 62%, 57%, and 38% from 57 FePP+ZnSO 4 , 57 FePP-Zn, and 57 FePP+ZnO, respectively. In vitro solubility from 57 FePP+ZnSO 4 differed from that of 57 FePP-Zn (14.3%; P iron-depleted women, iron absorption from FePP-fortified extruded rice cofortified with ZnSO 4 was 1.6-fold (95% CI: 1.4-, 1.9-fold) that of rice cofortified with ZnO. These findings suggest that ZnSO 4 may be the preferable zinc cofortificant for optimal iron bioavailability of iron-fortified extruded rice. This trial was registered at

Isotope Fractionation by Diffusion in Liquids (Final Technical Report)

Energy Technology Data Exchange (ETDEWEB)

Richter, Frank [Univ. of Chicago, IL (United States)

2016-11-09

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

Oxygen, hydrogen, sulfur, and carbon isotopes in the Pea Ridge magnetite-apatite deposit, southeast Missouri, and sulfur isotope comparisons to other iron deposits in the region

Science.gov (United States)

Johnson, Craig A.; Day, Warren C.; Rye, Robert O.

2016-01-01

Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ18O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ18O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes.Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ34S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition

Large sulfur isotope fractionations in Martian sediments at Gale crater

Science.gov (United States)

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.

Interpreting isotopic analyses of microbial sulfate reduction in oil reservoirs

Science.gov (United States)

Hubbard, C. G.; Engelbrektson, A. L.; Druhan, J. L.; Cheng, Y.; Li, L.; Ajo Franklin, J. B.; Coates, J. D.; Conrad, M. E.

2013-12-01

Microbial sulfate reduction in oil reservoirs is often associated with secondary production of oil where seawater (28 mM sulfate) is commonly injected to maintain reservoir pressure and displace oil. The hydrogen sulfide produced can cause a suite of operating problems including corrosion of infrastructure, health exposure risks and additional processing costs. We propose that monitoring of the sulfur and oxygen isotopes of sulfate can be used as early indicators that microbial sulfate reduction is occurring, as this process is well known to cause substantial isotopic fractionation. This approach relies on the idea that reactions with reservoir (iron) minerals can remove dissolved sulfide, thereby delaying the transport of the sulfide through the reservoir relative to the sulfate in the injected water. Changes in the sulfate isotopes due to microbial sulfate reduction may therefore be measurable in the produced water before sulfide is detected. However, turning this approach into a predictive tool requires (i) an understanding of appropriate fractionation factors for oil reservoirs, (ii) incorporation of isotopic data into reservoir flow and reactive transport models. We present here the results of preliminary batch experiments aimed at determining fractionation factors using relevant electron donors (e.g. crude oil and volatile fatty acids), reservoir microbial communities and reservoir environmental conditions (pressure, temperature). We further explore modeling options for integrating isotope data and discuss whether single fractionation factors are appropriate to model complex environments with dynamic hydrology, geochemistry, temperature and microbiology gradients.

Ice-vapor equilibrium fractionation factor of hydrogen and oxygen isotopes

DEFF Research Database (Denmark)

Ellehøj, Mads Dam; Steen-Larsen, Hans Christian; Johnsen, Sigfus Johann

2013-01-01

RATIONALE: The equilibrium fractionation factors govern the relative change in the isotopic composition during phase transitions of water. The commonly used results, which were published more than 40 years ago, are limited to a minimum temperature of -33 degrees C. This limits the reliability...... values, with a temperature dependency in accordance with theory for equilibrium fractionation. We obtain the following expressions for the temperature dependency of the fractionation coefficients: ln(alpha(delta 2H)) = 0.2133 - 203.10/T + 48888/T-2 ln(alpha(delta 18O)) = 0.0831 - 49.192/T + 8312.5/T2...... Compared with previous experimental work, a significantly larger for H-2 is obtained while, for O-18, is larger for temperatures below -20 degrees C and slightly lower for temperatures above this. CONCLUSIONS: Using the new values for alpha, a Rayleigh distillation model shows significant changes in both...

Oxygen isotope fractionations across individual leaf carbohydrates in grass and tree species.

Science.gov (United States)

Lehmann, Marco M; Gamarra, Bruno; Kahmen, Ansgar; Siegwolf, Rolf T W; Saurer, Matthias

2017-08-01

Almost no δ 18 O data are available for leaf carbohydrates, leaving a gap in the understanding of the δ 18 O relationship between leaf water and cellulose. We measured δ 18 O values of bulk leaf water (δ 18 O LW ) and individual leaf carbohydrates (e.g. fructose, glucose and sucrose) in grass and tree species and δ 18 O of leaf cellulose in grasses. The grasses were grown under two relative humidity (rH) conditions. Sucrose was generally 18 O-enriched compared with hexoses across all species with an apparent biosynthetic fractionation factor (ε bio ) of more than 27‰ relative to δ 18 O LW , which might be explained by isotopic leaf water and sucrose synthesis gradients. δ 18 O LW and δ 18 O values of carbohydrates and cellulose in grasses were strongly related, indicating that the leaf water signal in carbohydrates was transferred to cellulose (ε bio  = 25.1‰). Interestingly, damping factor p ex p x , which reflects oxygen isotope exchange with less enriched water during cellulose synthesis, responded to rH conditions if modelled from δ 18 O LW but not if modelled directly from δ 18 O of individual carbohydrates. We conclude that δ 18 O LW is not always a good substitute for δ 18 O of synthesis water due to isotopic leaf water gradients. Thus, compound-specific δ 18 O analyses of individual carbohydrates are helpful to better constrain (post-)photosynthetic isotope fractionation processes in plants. © 2017 John Wiley & Sons Ltd.

Fractionated exposure of high energy iron ions has a sparing effect in vivo

Science.gov (United States)

Chang, P. Y.; Bakke, J.; Puey, A.

The radiation environment in deep space is complex and includes a broad spectrum of charged and highly energetic particle radiations. Exposure to these types of radiations may pose potential health risks in manned space missions. The detection of particle radiation-induced genomic alterations in vivo, particularly in slow or non-dividing tissues, is therefore important to provide relevant information in estimating risks. We are using a plasmid-based lacZ transgenic mouse model system to rapidly measure, in a statistically reliable way, the mutagenic potential of charged particle radiations relevant in the space environment. The lacZ transgenic mouse has been constructed so that every cell of the animal contains multiple copies of an integrated target reporter gene, allowing us to measure tissue-specific radiation-induced changes as a function of dosing regime. The nature of these mutations can also be characterized by restriction fragment length polymorphisms (RFLP). To examine the impact of dose protraction, animals were exposed to a single dose or daily fractions of 1 GeV/n iron ions. Cytotoxicity in the peripheral blood was measured by enumerating the frequency of circulating micronucleated reticulocytes (fMN-RET) in a time course from 24 h up to 1 week after completion of the radiation protocol. Brain and spleen tissues were harvested at 8 weeks after exposure and mutant frequencies (MF) in the transgene in these tissues were measured. Results from the fractionated protocol were compared to the responses obtained after the animals were exposed to the single dose treatment. We noted significantly lower levels of micronucleated reticulocytes in peripheral blood at 48 h after fractionated doses of iron ions when compared to the same total dose delivered in a single exposure demonstrating that protracted exposures of particle radiation resulted in an overall sparing effect in cytogenetic toxicity in the hematopoietic system in animals. Transgene mutation analysis

Calcium isotope fractionation between soft and mineralized tissues as a monitor of calcium use in vertebrates

Science.gov (United States)

Skulan, Joseph; DePaolo, Donald J.

1999-01-01

Calcium from bone and shell is isotopically lighter than calcium of soft tissue from the same organism and isotopically lighter than source (dietary) calcium. When measured as the 44Ca/40Ca isotopic ratio, the total range of variation observed is 5.5‰, and as much as 4‰ variation is found in a single organism. The observed intraorganismal calcium isotopic variations and the isotopic differences between tissues and diet indicate that isotopic fractionation occurs mainly as a result of mineralization. Soft tissue calcium becomes heavier or lighter than source calcium during periods when there is net gain or loss of mineral mass, respectively. These results suggest that variations of natural calcium isotope ratios in tissues may be useful for assessing the calcium and mineral balance of organisms without introducing isotopic tracers. PMID:10570137

Iron and silicon isotope behaviour accompanying weathering in Icelandic soils, and the implications for iron export from peatlands

Science.gov (United States)

Opfergelt, S.; Williams, H. M.; Cornelis, J. T.; Guicharnaud, R. A.; Georg, R. B.; Siebert, C.; Gislason, S. R.; Halliday, A. N.; Burton, K. W.

2017-11-01

Incipient warming of peatlands at high latitudes is expected to modify soil drainage and hence the redox conditions, which has implications for Fe export from soils. This study uses Fe isotopes to assess the processes controlling Fe export in a range of Icelandic soils including peat soils derived from the same parent basalt, where Fe isotope variations principally reflect differences in weathering and drainage. In poorly weathered, well-drained soils (non-peat soils), the limited Fe isotope fractionation in soil solutions relative to the bulk soil (Δ57Fesolution-soil = -0.11 ± 0.12‰) is attributed to proton-promoted mineral dissolution. In the more weathered poorly drained soils (peat soils), the soil solutions are usually lighter than the bulk soil (Δ57Fesolution-soil = -0.41 ± 0.32‰), which indicates that Fe has been mobilised by reductive mineral dissolution and/or ligand-controlled dissolution. The results highlight the presence of Fe-organic complexes in solution in anoxic conditions. An additional constraint on soil weathering is provided by Si isotopes. The Si isotope composition of the soil solutions relative to the soil (Δ30Sisolution-soil = 0.92 ± 0.26‰) generally reflects the incorporation of light Si isotopes in secondary aluminosilicates. Under anoxic conditions in peat soils, the largest Si isotope fractionation in soil solutions relative to the bulk soil is observed (Δ30Sisolution-soil = 1.63 ± 0.40‰) and attributed to the cumulative contribution of secondary clay minerals and amorphous silica precipitation. Si supersaturation in solution with respect to amorphous silica is reached upon freezing when Al availability to form aluminosilicates is limited by the affinity of Al for metal-organic complexes. Therefore, the precipitation of amorphous silica in peat soils indirectly supports the formation of metal-organic complexes in poorly drained soils. These observations highlight that in a scenario of decreasing soil drainage with

Diffusion related isotopic fractionation effects with one-dimensional advective–dispersive transport

Energy Technology Data Exchange (ETDEWEB)

Xu, Bruce S. [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada); Lollar, Barbara Sherwood [Earth Sciences Department, University of Toronto, 22 Russell Street, Toronto, ON M5S 3B1 (Canada); Passeport, Elodie [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada); Chemical Engineering and Applied Chemistry Department, University of Toronto, 200 College Street, Toronto, ON M5S 3E5 (Canada); Sleep, Brent E., E-mail: sleep@ecf.utoronto.ca [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada)

2016-04-15

Aqueous phase diffusion-related isotope fractionation (DRIF) for carbon isotopes was investigated for common groundwater contaminants in systems in which transport could be considered to be one-dimensional. This paper focuses not only on theoretically observable DRIF effects in these systems but introduces the important concept of constraining “observable” DRIF based on constraints imposed by the scale of measurements in the field, and on standard limits of detection and analytical uncertainty. Specifically, constraints for the detection of DRIF were determined in terms of the diffusive fractionation factor, the initial concentration of contaminants (C{sub 0}), the method detection limit (MDL) for isotopic analysis, the transport time, and the ratio of the longitudinal mechanical dispersion coefficient to effective molecular diffusion coefficient (D{sub mech}/D{sub eff}). The results allow a determination of field conditions under which DRIF may be an important factor in the use of stable carbon isotope measurements for evaluation of contaminant transport and transformation for one-dimensional advective–dispersive transport. This study demonstrates that for diffusion-dominated transport of BTEX, MTBE, and chlorinated ethenes, DRIF effects are only detectable for the smaller molar mass compounds such as vinyl chloride for C{sub 0}/MDL ratios of 50 or higher. Much larger C{sub 0}/MDL ratios, corresponding to higher source concentrations or lower detection limits, are necessary for DRIF to be detectable for the higher molar mass compounds. The distance over which DRIF is observable for VC is small (less than 1 m) for a relatively young diffusive plume (< 100 years), and DRIF will not easily be detected by using the conventional sampling approach with “typical” well spacing (at least several meters). With contaminant transport by advection, mechanical dispersion, and molecular diffusion this study suggests that in field sites where D{sub mech}/D{sub eff} is

Diffusion related isotopic fractionation effects with one-dimensional advective–dispersive transport

International Nuclear Information System (INIS)

Xu, Bruce S.; Lollar, Barbara Sherwood; Passeport, Elodie; Sleep, Brent E.

2016-01-01

Aqueous phase diffusion-related isotope fractionation (DRIF) for carbon isotopes was investigated for common groundwater contaminants in systems in which transport could be considered to be one-dimensional. This paper focuses not only on theoretically observable DRIF effects in these systems but introduces the important concept of constraining “observable” DRIF based on constraints imposed by the scale of measurements in the field, and on standard limits of detection and analytical uncertainty. Specifically, constraints for the detection of DRIF were determined in terms of the diffusive fractionation factor, the initial concentration of contaminants (C_0), the method detection limit (MDL) for isotopic analysis, the transport time, and the ratio of the longitudinal mechanical dispersion coefficient to effective molecular diffusion coefficient (D_m_e_c_h/D_e_f_f). The results allow a determination of field conditions under which DRIF may be an important factor in the use of stable carbon isotope measurements for evaluation of contaminant transport and transformation for one-dimensional advective–dispersive transport. This study demonstrates that for diffusion-dominated transport of BTEX, MTBE, and chlorinated ethenes, DRIF effects are only detectable for the smaller molar mass compounds such as vinyl chloride for C_0/MDL ratios of 50 or higher. Much larger C_0/MDL ratios, corresponding to higher source concentrations or lower detection limits, are necessary for DRIF to be detectable for the higher molar mass compounds. The distance over which DRIF is observable for VC is small (less than 1 m) for a relatively young diffusive plume (< 100 years), and DRIF will not easily be detected by using the conventional sampling approach with “typical” well spacing (at least several meters). With contaminant transport by advection, mechanical dispersion, and molecular diffusion this study suggests that in field sites where D_m_e_c_h/D_e_f_f is larger than 10, DRIF

Fractionation of sulfur isotopes in the chemical and biochemical oxidation of sulfide to sulfate

International Nuclear Information System (INIS)

Maass, I.; Wetzel, K.; Weise, G.; Heyer, J.

1983-01-01

The behaviour of sulfur isotopes in the chemical and biochemical oxidation of marcasite (FeS 2 ) to sulfate has been investigated in rest and shaker cultures at 30 0 C. The microbiological oxidation was carried out using a mixed culture of Thiobacillus. The results show a considerably faster formation of sulfate in the biochemical oxidation in comparison with the chemical oxidation. Isotope analyses of the formed sulfates indicate no or only very small isotope fractionations depending on experimental conditions. The highest enrichment of 32 S in the sulfate is 1.7 per mille. In accordance with the results of other authors it is concluded that in both chemical and biochemical weathering of sedimentary sulfides resulting in the formation of sulfates isotope effects are not of importance. (author)

Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes.

Science.gov (United States)

Babcsányi, Izabella; Chabaux, François; Granet, Mathieu; Meite, Fatima; Payraudeau, Sylvain; Duplay, Joëlle; Imfeld, Gwenaël

2016-07-01

Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ(65)Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (-0.12 to 0.24‰±0.08‰). The values were in the range of those of the fungicides (-0.21 to 0.11‰) and included the geogenic δ(65)Cu value of the untreated soil (0.08‰). However, δ(65)Cu values significantly differed between particle-size soil fractions (-0.37±0.10‰ in fine clays and 0.23±0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20(th) July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ(65)Cu values from 0.52 to 1.35‰ in the dissolved phase (runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments. Copyright © 2016 Elsevier B.V. All rights reserved.

Graphite content and isotopic fractionation between calcite-graphite pairs in metasediments from the Mgama Hills, Southern Kenya

International Nuclear Information System (INIS)

Arneth, J.D.; Schidlowski, M.; Sarbas, B.; Goerg, U.; Amstutz, G.C.

1985-01-01

Amphibolite-grade metasediments from the Mgama Hills region, Kenya, contain conspicuous quantities of graphite, most probably derived from organic progenitor materials,. The highest graphite contents are found in schists whereas calcite marbles intercalated in the sequence contain relatively low amounts. The graphitic constituents are consistently enriched in 13 C relative to common sedimentary organic material, with the highest isotopic ratios in graphite from the marbles. Carbon isotope fractionations between calcite and graphite mostly vary between 3.3 and 7.1 per mille, which comes close to both empirically recorded and thermodynamically calculated fractionations in the temperature range of the upper amphibolite facies. However, larger values occasionally encountered in the marbles suggest that complete isotopic equilibrium is not always attained in amphibolite-facies metamorphism. (author)

Variation of carbon isotope fractionation in hydrogenotrophic methanogenic microbial cultures and environmental samples at different energy status

NARCIS (Netherlands)

Penning, H.; Plugge, C.M.; Galand, P.E.; Conrad, R.

2005-01-01

Methane is a major product of anaerobic degradation of organic matter and an important greenhouse gas. Its stable carbon isotope composition can be used to reveal active methanogenic pathways, if associated isotope fractionation factors are known. To clarify the causes that lead to the wide

The variability in iron speciation in size fractionated residual oil fly ash particulate matter (ROFA PM).

Science.gov (United States)

Pattanaik, Sidhartha; Huggins, Frank E; Huffman, Gerald P

2016-08-15

Ambient particulate matter (PM) containing iron can catalyze Fenton reaction leading to the production of reactive oxygen species in cells. It can also catalyze atmospheric redox reaction. These reactions are governed by the physicochemical characteristics of iron in ambient PM. As a surrogate for ambient PM, we prepared residual oil fly ash PM (ROFA PM) in a practical fire tube boiler firing residual oils with varying sulfur and ash contents. The ROFA particles were resolved into fine PM or PM2.5 (aerodynamic diameter (AD)iron speciation in PM2.5+ was ascertained using X-ray absorption spectroscopy and leaching method while that in PM2.5 was reported earlier. The results of both studies are compared to get an insight into the variability in the iron speciation in different size fractions. The results show the predominance of ferric sulfate, with a minor spinal ferrite in both PM (i.e. ZnxNi1-xFe2O4 in PM2.5, ZnFe2O4 in PM2.5+). The iron solubility in ROFA PM depends on its speciation, mode of incorporation of iron into particle's carbonaceous matrix, the grade and composition of oils, and pH of the medium. The soluble fraction of iron in PM is critical in assessing its interaction with the biological systems and its toxic potential. Copyright © 2016 Elsevier B.V. All rights reserved.

Normal and Inverse Diffusive Isotope Fractionation of Deuterated Toluene and Benzene in Aqueous Systems

DEFF Research Database (Denmark)

Rolle, Massimo; Jin, Biao

2017-01-01

Diffusive isotope fractionation of organic contaminants in aqueous solution is difficult to quantify, and only a few experimental data sets are available for compounds of environmental interest. In this study, we investigate diffusive fractionation of perdeuterated and nondeuterated benzene...... and toluene. Multitracer experiments were carried out in 1-D gel dissection tubes and in a quasi-2-D flow-through porous medium. The experiments allowed us to simultaneously and directly compare the diffusive and dispersive behavior of benzene and toluene. We observed an unexpected, opposite behavior...... of the two monoaromatic hydrocarbons. Toluene showed a normal diffusive isotope effect (DC7D8/DC7H8 = 0.96) with enrichment of the nondeuterated isotopologue in the direction of the diffusive and transverse dispersive fluxes. Conversely, the measured trends for benzene indicate inverse diffusive...

Determination of sulfur isotopic composition for the study of iron sulfides origin, biotic or abiotic, in anoxic corrosion

International Nuclear Information System (INIS)

Grousset, Sophie

2016-01-01

The first goal of this project was to develop a methodology based on the study of the sulfur isotopic composition enabling the determination of iron sulfides origin, biotic or abiotic, within the corrosion products layers (CPL). Then, the aim was to apply this methodology to real corrosion systems in order to determine the mechanisms of iron sulfides formation. Sulfur isotopic analyses methodologies, adapted to micrometric iron sulfides layers observed in real corrosion systems, were developed in nanoSIMS and ToF-SIMS. The study of iron sulfides formed in anoxic carbonated medium with or without sulphate-reducing bacteria validated the use of these methods for the determination of iron sulfides origin. The application of these methods coupled with the precise characterization of irons sulfides formed in the real corrosion systems show two kind of corrosion pattern. In pattern 1, the iron sulfides are localized in the external part of the CPL. They result from the Fe 2+ migration from the metal surface to areas rich in biotic S 2- . In this pattern, corrosion rates are lower than 20 μm/year for laboratory systems, and lower than 5 μm/year for archaeological objects. In pattern 2, the large presence of conductive phases in the CPL results in the delocalization of electrons, and so a disequilibrium of the charges at the metal's surface. That leads to the migration of biotic S 2- in the CPL till the metal where they precipitate in iron sulphides. This pattern shows high corrosion rates (∼100 μm/an) that might be resulting from the accumulation of bio-corrosion and chloride corrosion mechanisms. (author) [fr

Sulfur isotopic fractionation of carbonyl sulfide during degradation by soil bacteria and enzyme

Science.gov (United States)

Kamezaki, Kazuki; Hattori, Shohei; Ogawa, Takahiro; Toyoda, Sakae; Kato, Hiromi; Katayama, Yoko; Yoshida, Naohiro

2017-04-01

Carbonyl sulfide (COS) is an atmospheric trace gas that possess great potential for tracer of carbon cycle (Campbell et al., 2008). COS is taken up by vegetation during photosynthesis like absorption of carbon dioxide but COS can not emit by respiration of vegetation, suggesting possible tracer for gross primary production. However, some studies show the COS-derived GPP is larger than the estimates by using carbon dioxide flux because COS flux by photolysis and soil flux are not distinguished (e.g. Asaf et al., 2013). Isotope analysis is a useful tool to trace sources and transformations of trace gases. Recently our group developed a promising new analytical method for measuring the stable sulfur isotopic compositions of COS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ enabling us to easily analyze sulfur isotopes in COS (Hattori et al., 2015). Soil is thought to be important as both a source and a sink of COS in the troposphere. In particular, soil has been reported as a large environmental sink for atmospheric COS. Bacteria isolated from various soils actively degrade COS, with various enzymes such as carbonic anhydrase and COSase (Ogawa et al., 2013) involved in COS degradation. However, the mechanism and the magnitude of bacterial contribution in terms of a sink for atmospheric COS is still uncertain. Therefore, it is important to quantitatively evaluate this contribution using COS sulfur isotope analysis. We present isotopic fractionation constants for COS by laboratory incubation experiments during degradation by soil bacteria and COSase. Incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia, Cupriavidus, and Thiobacillus, isolated from natural soil or activated sludge and enzyme purified from a bacteria. As a result, the isotopic compositions of OCS were increased during degradation of

The use of radioisotopes and low abundance stable isotopes for the study of bioavailability and the metabolism of iron, zinc and copper

International Nuclear Information System (INIS)

Aggett, P.J.; Fairweather Tait, S.

1994-01-01

The use of whole body counting and imaging with ''area of interest'' counting to monitor the metabolism of zinc in healthy volunteers and patients with coeliac diseases and cirrhosis is described as are studies of interaction between iron and copper. Stable isotopes of iron, copper and zinc have been used to investigate the metabolism of these elements in young infants and have proved useful in assessing the validity of current estimated requirements particularly of iron. Stable isotopes have also been used to improve the classic metabolic balance approach to the study of the homeostasis of zinc in zinc deprived volunteers, and have progressed to studies using plasma kinetic curves of the systemic compartmentation of zinc

Insights into iron sources and pathways in the Amazon River provided by isotopic and spectroscopic studies

Science.gov (United States)

Mulholland, Daniel Santos; Poitrasson, Franck; Boaventura, Geraldo Resende; Allard, Thierry; Vieira, Lucieth Cruz; Santos, Roberto Ventura; Mancini, Luiz; Seyler, Patrick

2015-02-01

The present study investigated the weathering and transport mechanisms of Fe in the Amazon River. A particular emphasis was placed on Fe partitioning, speciation, and isotopic fractionation in the contrasting waters of the Solimões and Negro rivers and their mixing zone at the beginning of the Amazon River. Samples collected in the end-member rivers and thirteen sites distributed throughout the mixing zone were processed through frontal vacuum filtration and tangential-flow ultrafiltration to separate the different suspended solid fractions, i.e., particulate (P > 0.45 μm and P > 0.22 μm), colloidal (0.22 μm > C > 5 kDa) and truly dissolved elements (TD particulate fractions yielded light isotopic compositions of -0.344‰ for P > 0.22 μm and -0.104‰ for P > 0.45 μm fractions). The mineral particulate-rich waters of the Solimões River had dissolved and colloidal fractions with light isotopic composition (-0.532‰ and -0.176‰, respectively), whereas the particulate fractions yielded δ57Fe values close to those of the continental crust (i.e., -0.029‰ for P > 0.22 μm and 0.028‰ for P > 0.45 μm). Ten kilometers downstream from the Negro and Solimões junction, the concentrations of colloidal and dissolved Fe species deviate markedly from conservative mixing. A maximum Fe loss of 43 μg/L (i.e., 50% of the dissolved and colloidal Fe) is observed 110 km downstream from the rivers junction. The contrasting Negro and Solimões Rivers isotopic compositions along the pore-sized water fractions is attributable to the biogeochemical processes involving different types of upland soils and parental materials. For instance, the isotopic composition of colloidal and dissolved Fe from the Negro River are consistent with Fe oxidation and complexation mechanisms at the interface between waterlogged podzols and river networks, as supported by strong organo-Fe complexes signals observed by EPR. Conversely, the particulate and colloidal fractions from the Solim

Tracking transformation processes of organic micropollutants in aquatic environments using multi-element isotope fractionation analysis

International Nuclear Information System (INIS)

Hofstetter, Thomas B.; Bolotin, Jakov; Skarpeli-Liati, Marita; Wijker, Reto; Kurt, Zohre; Nishino, Shirley F.; Spain, Jim C.

2011-01-01

The quantitative description of enzymatic or abiotic transformations of man-made organic micropollutants in rivers, lakes, and groundwaters is one of the major challenges associated with the risk assessment of water resource contamination. Compound-specific isotope analysis enables one to identify (bio)degradation pathways based on changes in the contaminants' stable isotope ratios even if multiple reactive and non-reactive processes cause concentrations to decrease. Here, we investigated how the magnitude and variability of isotope fractionation in some priority pollutants is determined by the kinetics and mechanisms of important enzymatic and abiotic redox reactions. For nitroaromatic compounds and substituted anilines, we illustrate that competing transformation pathways can be assessed via trends of N and C isotope signatures.

Liquid-Vapor Argon Isotope Fractionation from the Triple Point to the Critical Point

DEFF Research Database (Denmark)

Phillips, J. T.; Linderstrøm-Lang, C. U.; Bigeleisen, J.

1972-01-01

are compared at the same molar volume. The isotope fractionation factor α for 36Ar∕40Ar between liquid and vapor has been measured from the triple point to the critical temperature. The results are compared with previous vapor pressure data, which cover the range 84–102°K. Although the agreement is within....... The fractionation factor approaches zero at the critical temperature with a nonclassical critical index equal to 0.42±0.02.〈∇2Uc〉/ρc in liquid argon is derived from the experimental fractionation data and calculations of 〈∇2Ug〉/ρg for a number of potential functions for gaseous argon....

Experimental calibration of vanadium partitioning and stable isotope fractionation between hydrous granitic melt and magnetite at 800 °C and 0.5 GPa

Science.gov (United States)

Sossi, Paolo A.; Prytulak, Julie; O'Neill, Hugh St. C.

2018-04-01

Vanadium has multiple oxidation states in silicate melts and minerals, a property that also promotes fractionation of its isotopes. As a result, vanadium isotopes vary during magmatic differentiation, and can be powerful indicators of redox processes at high temperatures if their partitioning behaviour can be determined. To quantify the partitioning and isotope fractionation factor of V between magnetite and melt, piston cylinder experiments were performed in which magnetite and a hydrous, haplogranitic melt were equilibrated at 800 °C and 0.5 GPa over a range of oxygen fugacities ({f_{{{O}2}}}), bracketing those of terrestrial magmas. Magnetite is isotopically light with respect to the coexisting melt, a tendency ascribed to the VI-fold V3+ and V4+ in magnetite, and a mixture of IV- and VI-fold V5+ and V4+ in the melt. The magnitude of the fractionation factor systematically increases with increasing log{f_{{{O}2}}} relative to the Fayalite-Magnetite-Quartz buffer (FMQ), from Δ51Vmag-gl = - 0.63 ± 0.09‰ at FMQ - 1 to - 0.92 ± 0.11‰ (SD) at ≈ FMQ + 5, reflecting constant V3+/V4+ in magnetite but increasing V5+/V4+ in the melt with increasing log{f_{{{O}2}}}. These first mineral-melt measurements of V isotope fractionation factors underline the importance of both oxidation state and co-ordination environment in controlling isotopic fractionation. The fractionation factors determined experimentally are in excellent agreement with those needed to explain natural isotope variations in magmatic suites. Furthermore, these experiments provide a useful framework in which to interpret vanadium isotope variations in natural rocks and magnetites, and may be used as a potential fingerprint the redox state of the magma from which they crystallise.

In vivo iron metabolism by IRMS

Science.gov (United States)

Iron isotopes are used in both biological and geological investigations. Three low-abundance stable isotopes are available for human studies. They have been widely used to study iron metabolism. They have provided valuable insights into iron deficiency, one of the most common micronutrient deficienc...

Simulation of dual carbon-bromine stable isotope fractionation during 1,2-dibromoethane degradation.

Science.gov (United States)

Jin, Biao; Nijenhuis, Ivonne; Rolle, Massimo

2018-06-01

We performed a model-based investigation to simultaneously predict the evolution of concentration, as well as stable carbon and bromine isotope fractionation during 1,2-dibromoethane (EDB, ethylene dibromide) transformation in a closed system. The modelling approach considers bond-cleavage mechanisms during different reactions and allows evaluating dual carbon-bromine isotopic signals for chemical and biotic reactions, including aerobic and anaerobic biological transformation, dibromoelimination by Zn(0) and alkaline hydrolysis. The proposed model allowed us to accurately simulate the evolution of concentrations and isotope data observed in a previous laboratory study and to successfully identify different reaction pathways. Furthermore, we illustrated the model capabilities in degradation scenarios involving complex reaction systems. Specifically, we examined (i) the case of sequential multistep transformation of EDB and the isotopic evolution of the parent compound, the intermediate and the reaction product and (ii) the case of parallel competing abiotic pathways of EDB transformation in alkaline solution.

Experimental observation and combined investigation of high-performance fusion of iron-region isotopes in optimal growing microbiological associations

International Nuclear Information System (INIS)

Vysotskii, Vladimir I.; Kornilova, Alla A.; Tashirev, Alexandr B.; Kornilova, Julia

2006-01-01

The report represents the results of combined (Moessbauer and mass-spectroscopy) examinations of isotopes transmutation process in growing microbiological associations in the iron-region of atomic mass (50 < A < 60). It was shown that the effectiveness of isotopes transmutation during the process of growth of microbiological associations at optimal conditions is by 10-20 times more than the effectiveness of the same transmutation in one-line' (clean) microbiological cultures. (author)

Variation in stable carbon isotopes in organic matter from the Gunflint Iron Formation

International Nuclear Information System (INIS)

Barghoorn, E.S.; Knoll, A.H.; Dembicki, H. Jr.; Meinschein, W.G.

1977-01-01

In order to examine possible variations in organic carbon isotopic ratios within a single Precambrian formation, the kerogen separated from 15 samples of the approximately 2000 m.y. old Gunflint Iron Formation and the conformably overlying Rove Formation, representing a wide range of lithologies and geographic localities, was isotopically analyzed. From the resulting data, four conclusions can be drawn: (1) delta 13 C values of the shallow water algal chert facies are significantly more negative (-25 to -30 parts per thousand) than those of the deeper water chert-carbonate and taconite facies (-15 to -20 parts per thousand). Comparative data for modern marine algal mats shows a range of delta 13 C values from -8.4 to -19 parts per thousand PDB. Values obtained for fresh water mats were slightly more negative. (2) These differences in isotopic ratios can be correlated with similar differences in preserved microbiotas. (3) Anthraxolite lenses are depleted in 13 C relative to the reduced carbon in surrounding sediments. (4) The effect of Keweenawan diabase intrusions upon the carbon isotopic composition is pronounced, but limited to the immediate vicinity of the contact. (author)

Isotopic exchangeability as a measure of the available fraction of the human pharmaceutical carbamazepine in river sediment

Energy Technology Data Exchange (ETDEWEB)

Williams, Mike, E-mail: mike.williams@csiro.au [CSIRO Land and Water, PMB No 2, Glen Osmond, SA, 5064 (Australia); Kookana, Rai [CSIRO Land and Water, PMB No 2, Glen Osmond, SA, 5064 (Australia)

2010-08-01

Cabamazepine (CBZ), an antiepileptic pharmaceutical compound, is a pollutant of aquatic ecosystems entering via wastewater treatment plants that is considered to be persistent to degradation. An isotope exchange technique was employed using radiolabelled CBZ as a model compound, to determine the amount of isotopic exchangeability of CBZ in river sediment. The amount of isotopically exchangeable CBZ was used as an estimate of the extent of desorption hysteresis in solution from river sediment, including a treatment where the sediment was amended with black carbon. The isotopically exchangeable CBZ was measured by equilibrating {sup 12}C-CBZ with sediment for 0 to 28 days followed by a 24 hour equilibration with {sup 14}C-CBZ at the end of the incubation period. The isotopically exchangeable fraction of CBZ decreased over time in the sediment, particularly following amendment with black carbon. This has important implications for the fate of CBZ, which, apart from being resistant to degradation, is constantly released into aquatic ecosystems from wastewater treatment plants. This study demonstrates the availability of a relatively quick and simple alternative to batch desorption techniques for the assessment of the available fraction of organic compounds in sediments following their release into aquatic ecosystems.

Isotopic exchangeability as a measure of the available fraction of the human pharmaceutical carbamazepine in river sediment

International Nuclear Information System (INIS)

Williams, Mike; Kookana, Rai

2010-01-01

Cabamazepine (CBZ), an antiepileptic pharmaceutical compound, is a pollutant of aquatic ecosystems entering via wastewater treatment plants that is considered to be persistent to degradation. An isotope exchange technique was employed using radiolabelled CBZ as a model compound, to determine the amount of isotopic exchangeability of CBZ in river sediment. The amount of isotopically exchangeable CBZ was used as an estimate of the extent of desorption hysteresis in solution from river sediment, including a treatment where the sediment was amended with black carbon. The isotopically exchangeable CBZ was measured by equilibrating 12 C-CBZ with sediment for 0 to 28 days followed by a 24 hour equilibration with 14 C-CBZ at the end of the incubation period. The isotopically exchangeable fraction of CBZ decreased over time in the sediment, particularly following amendment with black carbon. This has important implications for the fate of CBZ, which, apart from being resistant to degradation, is constantly released into aquatic ecosystems from wastewater treatment plants. This study demonstrates the availability of a relatively quick and simple alternative to batch desorption techniques for the assessment of the available fraction of organic compounds in sediments following their release into aquatic ecosystems.

Mercury stable isotope fractionation in a tropical ecosystem including human hair: New insights for an isotope balance

Science.gov (United States)

Laffont, Laure; Sonke, Jeroen; Maurice, Laurence; Behra, Philippe

2010-05-01

Mercury contamination is an environmental problem in the Amazon basin still relevant today as impacts on human health are poorly studied. In Bolivia, indigenous people have elevated methylmercury concentrations (between 2719 and 23701 ng.g-1) in their hair. This highly toxic molecule is formed after methylation of inorganic Hg released by chemical and physical weathering and from human activities. The aim of our study is to propose a first isotope balance in a Bolivian Amazon ecosystem, through variations in Hg isotopic compositions. The discovery of mass-independent fracionation (MIF) of odd-isotopes in our organic samples (fish and human hair) opened a new way of research in tracing the sources and the processes involved in the cycle of Hg. Four types of samples are studied: liquid Hg0 from gold mining, sediment samples, fish coming from the Beni River basin (from the main channel and an associated floodplain lake) and hair from gold miners and fish-eating native populations. Hg isotopic compositions were analyzed on a Thermo-Finnigan Neptune MC-ICP-MS at the LMTG after sample digestion by HCl/HNO3 or by H2O2/HNO3 for fish samples, at 120°C. The δ202Hg values (relative to NIST 3133) are signicantly different with respect to the external precision on UM-Almaden#2 of 0.18 ‰ (2σ, n = 42): -0.34 ± 0.02 ‰ for liquid mercury, between -1.33 and -0.81 ‰ for bottom and floodplain sediments (n=18), between -0.87 and 2.22 ‰ for miners hair (n=26), +1.29 ± 0.41 ‰ for native hair (n=13) and between -0.91 and -0.21 ‰ for fish samples (n=53). A large mass-independent isotope fractionation (MIF) was observed for odd isotope ratios in all hair samples and fish samples whereas weak anomalies were measured for sediment samples: - ∆199Hg anomaly: -0.12 to -0.04 ‰ for sediment, -0.22 to +0.63 ‰ for fish samples and +0.13 to +1.63 ‰ for hair - ∆201Hg anomaly: -0.12 to -0.02 ‰ for sediment, -0.21 to +0.43 ‰ for fish samples and +0.06 to +1.25 ‰ for hair

Intracrystalline fractionation of oxygen isotopes between hydroxyl and non-hydroxyl sites in kaolinite measured by thermal dehydroxylation and partial fluorination

Science.gov (United States)

Girard, Jean-Pierre; Savin, Samuel M.

1996-02-01

Thermal dehydroxylation and partial fluorination techniques were used to measure intracrystalline fractionation of oxygen isotopes between hydroxyl and non-hydroxyl sites in kaolinite. Several aliquots of a well characterized, fine-grained (rates, and target temperatures. Measured δ18O values of both the liberated water and the dehydroxylated residue are consistent over a wide range of temperatures (550 850°C) when dehydroxylation is performed in a single-step fashion at a rapid heating rate (>50°C/min.). Similar dehydroxylation experiments indicate that brucite dehydroxylation occurs without any significant isotopic fractionation of the oxygen isotopes. By extrapolation we postulate that no significant fractionation occurs during single-step thermal dehydroxylation of fine-grained kaolinite, provided that dehydroxylation is performed under well controlled conditions. In contrast, gibbsite dehydroxylation is accompanied by substantial isotopic fractionation. This is probably the result of the complex, multi-pathway dehydroxylation reaction of this mineral. Similarly, thermal dehydroxylation of coarsegrained (>1 μm) kaolinites and dickites of weathering and hydrothermal origin yield results that are dependent on the temperature of dehydroxylation. We suggest that this effect may be caused by isotopic exchange during diffusion of water molecules through coarse particles. Partial fluorination of fine-grained kaolinite in the presence of excess F2 at low temperatures (rate of reaction of hydroxyl oxygen than of non-hydroxyl oxygen, but examination of the isotopic data as well as XRD and IR analyses of the residues after partial fluorination indicates that the separation between the two types of oxygen is not complete. The results, therefore, do not yield a reliable δ18O value of the hydroxyl oxygen. The results of this study suggest that the thermal dehydroxylation technique may be appropriate for analysis of OH groups in fine-grained kaolinite. The partial

Enhanced sensitivity of DNA- and rRNA-based stable isotope probing by fractionation and quantitative analysis of isopycnic centrifugation gradients.

Science.gov (United States)

Lueders, Tillmann; Manefield, Mike; Friedrich, Michael W

2004-01-01

Stable isotope probing (SIP) of nucleic acids allows the detection and identification of active members of natural microbial populations that are involved in the assimilation of an isotopically labelled compound into nucleic acids. SIP is based on the separation of isotopically labelled DNA or rRNA by isopycnic density gradient centrifugation. We have developed a highly sensitive protocol for the detection of 'light' and 'heavy' nucleic acids in fractions of centrifugation gradients. It involves the fluorometric quantification of total DNA or rRNA, and the quantification of either 16S rRNA genes or 16S rRNA in gradient fractions by real-time PCR with domain-specific primers. Using this approach, we found that fully 13C-labelled DNA or rRNA of Methylobacterium extorquens was quantitatively resolved from unlabelled DNA or rRNA of Methanosarcina barkeri by cesium chloride or cesium trifluoroacetate density gradient centrifugation respectively. However, a constant low background of unspecific nucleic acids was detected in all DNA or rRNA gradient fractions, which is important for the interpretation of environmental SIP results. Consequently, quantitative analysis of gradient fractions provides a higher precision and finer resolution for retrieval of isotopically enriched nucleic acids than possible using ethidium bromide or gradient fractionation combined with fingerprinting analyses. This is a prerequisite for the fine-scale tracing of microbial populations metabolizing 13C-labelled compounds in natural ecosystems.

Modeling of isotope fractionation at the catchment scale: How promising is compound specific isotope analysis (CSIA) as a tool for analyzing diffuse pollution by agrochemicals?

Science.gov (United States)

Lutz, S. R.; van Meerveld, H. J.; Waterloo, M. J.; Broers, H. P.; van Breukelen, B. M.

2012-04-01

Concentration measurements are indispensable for the assessment of subsurface and surface water pollution by agrochemicals such as pesticides. However, monitoring data is often ambiguous and easily misinterpreted as a decrease in concentration could be caused by transformation, dilution or changes in the application of the pesticide. In this context, compound specific isotope analysis (CSIA) has recently emerged as a complementary monitoring technique. It is based on the measurement of the isotopic composition (e.g. δ13C and δ2H) of the contaminant. Since transformation processes are likely accompanied by isotope fractionation, thus a change in this composition, CSIA offers the opportunity to gain additional knowledge about transport and degradation processes as well as to track pollutants back to their sources. Isotopic techniques have not yet been applied in a comprehensive way in the analysis of catchment-wide organic pollution. We therefore incorporated fractionation processes associated with the fate of pesticides into the numerical flow and solute transport model HydroGeoSphere in order to assess the feasibility of CSIA within the context of catchment monitoring. The model was set up for a hypothetical hillslope transect which drains into a river. Reactive solute transport was driven by two pesticides applications within one year and actual data for rainfall and potential evapotranspiration from a meteorological station in the Netherlands. Degradation of the pesticide was assumed to take place at a higher rate under the prevailing oxic conditions in the topsoil than in deeper, anoxic subsurface layers. In terms of CSIA, these two degradation pathways were associated with different strengths of isotope fractionation for both hydrogen and carbon atoms. By simulating changes in δ13C and δ2H, the share of the oxic and the anoxic reaction on the overall degradation could be assessed. Model results suggest that CSIA is suitable for assessing degradation of

Recycled iron fuels new production in the eastern equatorial Pacific Ocean.

Science.gov (United States)

Rafter, Patrick A; Sigman, Daniel M; Mackey, Katherine R M

2017-10-24

Nitrate persists in eastern equatorial Pacific surface waters because phytoplankton growth fueled by nitrate (new production) is limited by iron. Nitrate isotope measurements provide a new constraint on the controls of surface nitrate concentration in this region and allow us to quantify the degree and temporal variability of nitrate consumption. Here we show that nitrate consumption in these waters cannot be fueled solely by the external supply of iron to these waters, which occurs by upwelling and dust deposition. Rather, a substantial fraction of nitrate consumption must be supported by the recycling of iron within surface waters. Given plausible iron recycling rates, seasonal variability in nitrate concentration on and off the equator can be explained by upwelling rate, with slower upwelling allowing for more cycles of iron regeneration and uptake. The efficiency of iron recycling in the equatorial Pacific implies the evolution of ecosystem-level mechanisms for retaining iron in surface ocean settings where it limits productivity.

Assessing the stability of soil organic matter by fractionation and 13C isotope techniques

Science.gov (United States)

Larionova, A. A.; Zolotareva, B. N.; Kvitkina, A. K.; Evdokimov, I. V.; Bykhovets, S. S.; Stulin, A. F.; Kuzyakov, Ya. V.; Kudeyarov, V. N.

2015-02-01

Carbon pools of different stabilities have been separated from the soil organic matter of agrochernozem and agrogray soil samples. The work has been based on the studies of the natural abundance of the carbon isotope composition by C3-C4 transition using the biokinetic, size-density, and chemical fractionation (6 M HCl hydrolysis) methods. The most stable pools with the minimum content of new carbon have been identified by particle-size and chemical fractionation. The content of carbon in the fine fractions has been found to be close to that in the nonhydrolyzable residue. This pool makes up 65 and 48% of Corg in the agrochernozems and agrogray soils, respectively. The combination of the biokinetic approach with particle-size fractionation or 6 M HCl hydrolysis has allowed assessing the size of the medium-stable organic carbon pool with a turnover time of several years to several decades. The organic matter pool with this turnover rate is usually identified from the variation in the 13C abundance by C3-C4 transition. In the agrochernozems and agrogray soils, the medium-stable carbon pool makes up 35 and 46% of Corg, respectively. The isotope indication may be replaced by a nonisotope method to significantly expand the study of the inert and mediumstable organic matter pools in the geographical aspect, but this requires a comparative analysis of particle-size and chemical fractionation data for all Russian soils.

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

Science.gov (United States)

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

2018-02-01

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

Isotopic fractionation of soil water during evaporation

Energy Technology Data Exchange (ETDEWEB)

Leopoldo, P R [Faculdade de Ciencias Medicas e Biologicas de Botucatu (Brazil); Salati, E; Matsui, E [Centro de Energia Nuclear na Agricultura, Piracicaba (Brazil)

1974-07-01

The study of the variation of D/H relation in soil water during evaporation is studied. The isotopic fractionation of soil water has been observed in two soils of light and heavy texture. Soil columns were utilized. Soil water was extracted in a system operated under low pressure and the gaseous hydrogen was obtained by decomposition of the water and was analyzed in a GD-150 mass spectrometer for deuterium content. The variation of the delta sub(eta) /sup 0///sub 00/ value during evaporation showed that for water held at potentials below 15 atm, the deuterium content of soil water stays practically constant. For water held at potentials higher than 15 atm, corresponding to the third stage of evaporation, there is a strong tendency of a constant increase of delta sub(eta) /sup 0///sub 00/ of the remaining water.

Mercury (Hg) in meteorites: Variations in abundance, thermal release profile, mass-dependent and mass-independent isotopic fractionation

Science.gov (United States)

Meier, Matthias M. M.; Cloquet, Christophe; Marty, Bernard

2016-06-01

We have measured the concentration, isotopic composition and thermal release profiles of Mercury (Hg) in a suite of meteorites, including both chondrites and achondrites. We find large variations in Hg concentration between different meteorites (ca. 10 ppb to 14,000 ppb), with the highest concentration orders of magnitude above the expected bulk solar system silicates value. From the presence of several different Hg carrier phases in thermal release profiles (150-650 °C), we argue that these variations are unlikely to be mainly due to terrestrial contamination. The Hg abundance of meteorites shows no correlation with petrographic type, or mass-dependent fractionation of Hg isotopes. Most carbonaceous chondrites show mass-independent enrichments in the odd-numbered isotopes 199Hg and 201Hg. We show that the enrichments are not nucleosynthetic, as we do not find corresponding nucleosynthetic deficits of 196Hg. Instead, they can partially be explained by Hg evaporation and redeposition during heating of asteroids from primordial radionuclides and late-stage impact heating. Non-carbonaceous chondrites, most achondrites and the Earth do not show these enrichments in vapor-phase Hg. All meteorites studied here have however isotopically light Hg (δ202Hg = ∼-7 to -1) relative to the Earth's average crustal values, which could suggest that the Earth has lost a significant fraction of its primordial Hg. However, the late accretion of carbonaceous chondritic material on the order of ∼2%, which has been suggested to account for the water, carbon, nitrogen and noble gas inventories of the Earth, can also contribute most or all of the Earth's current Hg budget. In this case, the isotopically heavy Hg of the Earth's crust would have to be the result of isotopic fractionation between surface and deep-Earth reservoirs.

Carbon isotopic fractionation in live benthic foraminifera -comparison with inorganic precipitate studies

Energy Technology Data Exchange (ETDEWEB)

Grossmann, E L [University of Southern California, Los Angeles (USA). Dept. of Geological Sciences

1984-07-01

Carbon and oxygen isotopic analyses have been performed on live-stained aragonitic and calcitic benthic foraminifera and dissolved inorganic carbon from the Southern California Borderland to examine carbon isotopic fractionation in foraminifera. Temperature, salinity and pH data have also been collected to permit accurate determination of the delta/sup 13/C of bicarbonate ion and thus aragonite-HCO/sub 3//sup -/ and calcite-HCO/sub 3//sup -/ isotopic enrichment factors (epsilonsub(ar-b) and epsilonsub(cl-b), respectively). Only species which precipitate in /sup 18/O equilibrium have been considered. epsilonsub (ar-b) values based on Hoeglundina elegans range from 1.9 per mille at 2.7 deg C to 1.1 per mille at 9.5 deg C. The temperature dependence of epsilonsub(ar-b) is considerably greater than the equilibrium equation would predict and may be due to a vital effect. The calcitic foraminifera Cassidulina tortuosa, Cassidulina braziliensis, and Cassidulina limbata, Bank and Terrace dwellers, have s

Model for the isotopic fractionation of water in the Amazon basin

International Nuclear Information System (INIS)

Dall'Olio, A.; Azevedo, C.T. de

1979-01-01

Two models on the isotopic fractionation of water are presented. In the first model. It is assumed that the only source of water vapour for the Amazon region is the Atlantic Ocean, introduced by the predominant easterly winds. The second model contains the assumption that the forest also serves as a source of water vapour contributing an equal volume of water to the regional rains as the vapour of oceanic origin. (Author) [pt

Carbon and hydrogen isotope fractionation under continuous light: implications for paleoenvironmental interpretations of the High Arctic during Paleogene warming.

Science.gov (United States)

Yang, Hong; Pagani, Mark; Briggs, Derek E G; Equiza, M A; Jagels, Richard; Leng, Qin; Lepage, Ben A

2009-06-01

The effect of low intensity continuous light, e.g., in the High Arctic summer, on plant carbon and hydrogen isotope fractionations is unknown. We conducted greenhouse experiments to test the impact of light quantity and duration on both carbon and hydrogen isotope compositions of three deciduous conifers whose fossil counterparts were components of Paleogene Arctic floras: Metasequoia glyptostroboides, Taxodium distichum, and Larix laricina. We found that plant leaf bulk carbon isotopic values of the examined species were 1.75-4.63 per thousand more negative under continuous light (CL) than under diurnal light (DL). Hydrogen isotope values of leaf n-alkanes under continuous light conditions revealed a D-enriched hydrogen isotope composition of up to 40 per thousand higher than in diurnal light conditions. The isotope offsets between the two light regimes is explained by a higher ratio of intercellular to atmospheric CO(2) concentration (C (i)/C (a)) and more water loss for plants under continuous light conditions during a 24-h transpiration cycle. Apparent hydrogen isotope fractionations between source water and individual lipids (epsilon(lipid-water)) range from -62 per thousand (Metasequoia C(27) and C(29)) to -87 per thousand (Larix C(29)) in leaves under continuous light. We applied these hydrogen fractionation factors to hydrogen isotope compositions of in situ n-alkanes from well-preserved Paleogene deciduous conifer fossils from the Arctic region to estimate the deltaD value in ancient precipitation. Precipitation in the summer growing season yielded a deltaD of -186 per thousand for late Paleocene, -157 per thousand for early middle Eocene, and -182 per thousand for late middle Eocene. We propose that high-latitude summer precipitation in this region was supplemented by moisture derived from regionally recycled transpiration of the polar forests that grew during the Paleogene warming.

Study on the cause of iron-deficiency anemia in adolescent athletes by INAA with enriched stable isotopes

International Nuclear Information System (INIS)

Qian, Q.F.; Wu, S.Q.; Tian, J.B.; Huo, Z.P.; Chen, J.D.; Li, K.J.

1991-01-01

Iron deficiency anemia is still one of the most common nutritional deficiency diseases throughout the world. The incidence of iron deficiency is high especially in children, adolescent, and endurance athletes. The authors studied the iron absorption rate and iron balance in six child football players during training and non-training periods. The neutron activation method with enriched stable isotope 58Fe has been adopted. The results show that the rate of iron absorption in athletes during the training period (9.1 + 2.9%) was significantly lower than that during the non-training period (11.9 + 4.7%); the iron balance was negative and the sweat iron loss increased during training. Hair is one of the metabolism excretory organs. The physiological changes of body would influence the trace element contents in hair. The hairs collected from four athletes were measured by Synchrotron-induced X-ray Fluorescence analysis, so as to get the trace element contents. Preliminary results show that the changes of iron content in the hairs are in accordance with the athlete's physical activity. There are no perceptible changes for Zn and Ca. It is verified that exercise is one of the causes of iron deficiency in athletes. It is necessary to increase iron supply in an athletes' nutritional intake to ensure optimal performance ability

Evidence for mass-independent and mass-dependent fractionation of the stable isotopes of mercury by natural processes in aquatic ecosystems

International Nuclear Information System (INIS)

Jackson, Togwell A.; Whittle, D. Michael; Evans, Marlene S.; Muir, Derek C.G.

2008-01-01

Isotopic and chemical analyses were performed on crustaceans, forage fish, top predator fish, and sediment cores from Lake Ontario and two boreal forest lakes to investigate fractionation of the stable isotopes of Hg in aquatic ecosystems. Multicollector inductively coupled mass spectrometry was used to determine Hg isotope abundances. The Hg isotope data for all three lakes showed mass-independent variation in the organisms but only mass-dependent variation in the sediments. The mass-independent isotope effect was characterised by (1) selective enrichment in isotopes of odd mass number ( 199 Hg and 201 Hg), (2) enrichment in 201 Hg relative to 199 Hg, (3) an inverse relationship between isotopes of odd and even mass number in fish, and (4) a positive correlation with methylHg (CH 3 Hg + ) concentration, and hence with trophic level (although lake whitefish were consistently anomalous, possibly owing to biochemical demethylation). Isotope signatures of species at the same trophic level varied with habitat and diet, differentiating between planktonic and benthic crustaceans and their predators, and between fish that frequent deep, cold water and fish of similar diet that prefer warmer, shallower water, because of corresponding differences in CH 3 Hg + and inorganic Hg content. Isotopic analysis of CH 3 Hg + and inorganic Hg extracted from lake trout proved that the mass-independent isotope effect was due to anomalously high abundances of 199 Hg and 201 Hg in CH 3 Hg + , as implied by the data for whole organisms, suggesting mass-independent fractionation during microbial methylation of Hg. The purely mass-dependent variation in the sediments is attributable to the fact that Hg in sediments is mostly inorganic. The mass-independent fractionation of Hg isotopes can be explained by effects of nuclear spin or nuclear field shift, or both, and penetration of the inner electron shells of Hg by valence electrons of Hg-binding ligands. The results of the research

Microbial Oxidation of Hg(0) - Its Effect on Hg Stable Isotope Fractionation and Methylmercury Production

Energy Technology Data Exchange (ETDEWEB)

Yee, Nathan [Rutgers Univ., New Brunswick, NJ (United States); Barkay, Tamar [Rutgers Univ., New Brunswick, NJ (United States); Reinfelder, John [Rutgers Univ., New Brunswick, NJ (United States)

2016-06-28

relationship between Hg concentrations and rates of denitrification in enrichment cultures. In part III of our project, we examined in more detail the effects of microbial interactions on Hg transformations. We discovered that both sulfate reducing and iron reducing bacteria coexist in freshwater sediments and both microbial groups contribute to mercury methylation. We showed that mercury methylation by sulfate reducing and iron reducing bacteria are temporally and spatially separated processes. We also discovered that methanogens can methylate mercury. We showed that Methanospirillum hungatei JF-1 methylated Hg at comparable rates, but with higher yields, than those observed for sulfate-reducing bacteria and iron-reducing bacteria. Finally, we demonstrated that syntrophic interactions between different microbial groups increase mercury methylation rates. We showed that Hg methylation rates are stimulated via inter-species hydrogen and acetate transfer (i) from sulfate-reducing bacteria to methanogens and (ii) from fermenters to the sulfate-reducing bacteria. In part IV of the project, we studied Hg bioavailability and Hg isotope fractionation. We demonstrated that thiol-bound Hg is bioavailable to mercury resistant bacteria. We found that uptake of Hg from Hg-glutathione and Hg-cysteine complexes does not require functioning glutathione and cystine/cysteine transport systems. We demonstrated that a wide range of methylmercury complexes (e.g. MeHgOH, MeHg-cysteine, and MeHg-glutathione) are bioavailable to mercury resistant bacteria. The rate of MeHg demethylation varies more between different species of mercury resistant bacteria than among MeHg complexes. We showed that microbial demethylation of MeHg depends more on the species of microorganism than on the types and relative concentrations of thiols or other MeHg ligands present. Finally, we demonstrated that Hg methylation by Geobacter sulfurreducens PCA and Desulfovibrio desulfuricans ND132 imparts mass

Iron isotope analysis of red and black pigments on pottery in Nasca, Peru

OpenAIRE

Eerkens, JW; Barfod, GH; Vaughn, KJ; Williams, PR; Lesher, CE

2014-01-01

The Nasca culture of the south coast of Peru developed during the first millennium ad and is known internationally for its elaborately decorated polychrome pots. Despite decades of iconographic analysis, little is known about the more technological aspects of Nasca pigment production and application. We present results from a pilot study on iron isotopes as a potential line of inquiry into the differences between red and black pigments in Nasca pigments. As well, we conduct a small firing exp...

Co-ordinated research programme on isotope-aided studies of the bioavailability of iron and zinc from human diets

International Nuclear Information System (INIS)

1992-01-01

Nutritional deficiencies of essential micronutrients (particularly of iron, but also of zinc and selenium) are known to affect hundreds of millions of people throughout the world, mainly in developing countries. Such deficiencies can lead to significant deficits in mental development, growth, work performance, immune competence and other biological parameters. In many of the population groups that are affected, the deficiencies are thought to be due not to an absolute lack of the element in the diet but rather to is poor bioavailability. Much work has already been done on this subject, particularly in some developed countries and particularly with respect to iron. However, there is still appears to be a need for more research on factors affecting bioavailability and the means to improve it by simple dietary modification and fortification using food products of the kind that may be locally available in developing countries. Isotope techniques potentially have a large role to play in studies of the bioavailability of iron and other trace elements. To support work in this area, the IAEA initiated a Co-ordinated Research Programme (CRP) at the end of 1990 on ''Isotope-Aided Studies of the Bioavailability of Iron and Zinc from Human Diets''. The first Research Co-ordination Meeting (RCM) of participants in this CRP is the subject of the present report. Refs, figs and tabs

The palaeoenvironmental implications of carbonate petrography, kerogen distribution and carbon and oxygen isotope variations in the early Proterozoic transition from Campbellrand limestone to Kuruman iron-formation deposition in Griqualand West

International Nuclear Information System (INIS)

Beukes, N.J.; Klein, C.; Kaufman, A.J.; Hayes, J.M.

1990-01-01

The Griqualand West area of the Transvaal basin in South Africa offers a unique opportunity to study the relationships between the deposition of limestone and iron-formation. The stratigraphic sequence includes the transition from microbialaminated Campbellrand carbonates to the conformably Kuruman iron formation composed mainly of microbanded iron-formation. The relationships between carbonate mineral paragenesis, kerogen abundance, and isotopic compositions of carbon and oxygen for the same drill core samples are reported. The significance of whole rock carbon-isotopic compositions of iron-formations relative to those of limestones and dolomites are explored. 6 refs

Isotopic fractionation of NBS oxalic acid and its influence in the calculated age of materials

International Nuclear Information System (INIS)

Nehmi, V.A.

1979-10-01

The intensity of the isotopic fractionation during the oxidation of NBS oxalic acid to carbon dioxide was checked. 30 reactions of oxidation of NBS oxalic acid with potassium permanganate were made. The resultant isotopic composition of CO 2 has been determined with a mass-spectrometer. A conclusion has been reached that the average of Δ 13 C is - 18.9% o with variation between - 17.7 and - 21.2%o. For values of Δ 13 C equal to - 22.0%o, the calculated age with isotopic correction shows the following deviations in relation to non-corrected age: 4% for materials of 1,000 years and 0.3% for 20,000 years.(Author) [pt

Boron isotope fractionation in magma via crustal carbonate dissolution.

Science.gov (United States)

Deegan, Frances M; Troll, Valentin R; Whitehouse, Martin J; Jolis, Ester M; Freda, Carmela

2016-08-04

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

Boron isotope fractionation in magma via crustal carbonate dissolution

Science.gov (United States)

Deegan, Frances M.; Troll, Valentin R.; Whitehouse, Martin J.; Jolis, Ester M.; Freda, Carmela

2016-08-01

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to -41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

Salinity dependent hydrogen isotope fractionation in alkenones produced by coastal and open ocean haptophyte algae

NARCIS (Netherlands)

M'boule, D.; Chivall, D.; Sinke-Schoen, D.; Sinninghe Damsté, J.S.; Schouten, S.; van der Meer, M.T.J.

2014-01-01

The hydrogen isotope fractionation in alkenones produced by haptophyte algae is a promising new proxy for paleosalinity reconstructions. To constrain and further develop this proxy the coastal haptophyte Isochrysis galbana and the open ocean haptophyte alga Emiliania huxleyi were cultured at

Using Gas Chromatography/Isotope Ratio Mass Spectrometry to Determine the Fractionation Factor for H2 Production by Hydrogenases

International Nuclear Information System (INIS)

Yang, Hui; Ghandi, H.; Shi, Liang; Kreuzer, Helen W.; Ostrom, Nathaniel; Hegg, Eric L.

2012-01-01

Hydrogenases catalyze the reversible formation of H2, and they are key enzymes in the biological cycling of H2. H isotopes should be a very useful tool in quantifying proton trafficking in biological H2 production processes, but there are several obstacles that have thus far limited the use of this tool. In this manuscript, we describe a new method that overcomes some of these barriers and is specifically designed to measure isotopic fractionation during enzyme-catalyzed H2 evolution. A key feature of this technique is that purified hydrogenases are employed, allowing precise control over the reaction conditions and therefore a high level of precision. A custom-designed high-throughput gas chromatography-isotope ratio mass spectrometer is employed to measure the isotope ratio of the H2. Using this method, we determined that the fractionation factor of H2 production by the (NiFe)-hydrogenase from Desulfivibrio fructosovran is 0.27. This result indicates that, as expected, protons are highly favored over deuterons during H2 evolution. Potential applications of this new method are discussed.

Isotope aided studies on the bioavailability of iron and zinc from human diets consumed in India

International Nuclear Information System (INIS)

Raghuramulu, N.; Das, P.; Prasad, P.

1994-01-01

Total iron, and zinc, in-vitro ionizable iron and soluble zinc were estimated by the chemical and extrinsic isotope tag methods for comparison in various foodstuffs as such, and after processing, and also in diets. It has been observed that the values got were more or less similar by both the procedures. The in-vitro ionizable iron in groundnut was low with low total iron as well. Total iron and ionizable iron were also estimated in commonly consumed breakfast preparations. The effect of tea on ionizable iron when taken along with breakfast was also investigated. It was found that different breakfast preparations varied narrowly with regards to total iron (4.6-7.2 mg) and percent ionizable iron (25%-33%). However, tea had a pronounced effect on ionizable iron resulting in inhibition to various extents. Total and soluble zinc were analyzed in green leafy vegetables and groundnut. Though the total zinc was low and similar in both foodstuffs, the percent soluble Zn was found to be high in green leafy vegetables as compared to groundnut. Tannin and ascorbic acid contents were estimated in a few foodstuffs. Tannin content in green leafy vegetables was found to be about 150 mg. Ascorbic acid concentration was high in cereals (except in rice) and whole pulses. The split pulses (dals) were found to be poor sources of ascorbic acid. Ionizable iron and soluble zinc were found to increase to various extents on processing. Germination was found to increase ascorbic acid, whereas it had no effect on tannin. (author). 4 figs, 8 tabs

Relative contribution of phytates, fibers, and tannins to low iron and zinc in vitro solubility in pearl millet (Pennisetum glaucum) flour and grain fractions.

Science.gov (United States)

Lestienne, Isabelle; Caporiccio, Bertrand; Besançon, Pierre; Rochette, Isabelle; Trèche, Serge

2005-10-19

In vitro digestions were performed on pearl millet flours with decreased phytate contents and on two dephytinized or nondephytinized pearl millet grain fractions, a decorticated fraction, and a bran fraction with low and high fiber and tannin contents, respectively. Insoluble residues of these digestions were then incubated with buffer or enzymatic solutions (xylanases and/or phytases), and the quantities of indigestible iron and zinc released by these different treatments were determined. In decorticated pearl millet grain, iron was chelated by phytates and by insoluble fibers, whereas zinc was almost exclusively chelated by phytates. In the bran of pearl millet grain, a high proportion of iron was chelated by iron-binding phenolic compounds, while the rest of iron as well as the majority of zinc were chelated in complexes between phytates and fibers. The low effect of phytase action on iron and zinc solubility of bran of pearl millet grain shows that, in the case of high fiber and tannin contents, the chelating effect of these compounds was higher than that of phytates.

Reconciling PM10 analyses by different sampling methods for Iron King Mine tailings dust.

Science.gov (United States)

Li, Xu; Félix, Omar I; Gonzales, Patricia; Sáez, Avelino Eduardo; Ela, Wendell P

2016-03-01

The overall project objective at the Iron King Mine Superfund site is to determine the level and potential risk associated with heavy metal exposure of the proximate population emanating from the site's tailings pile. To provide sufficient size-fractioned dust for multi-discipline research studies, a dust generator was built and is now being used to generate size-fractioned dust samples for toxicity investigations using in vitro cell culture and animal exposure experiments as well as studies on geochemical characterization and bioassay solubilization with simulated lung and gastric fluid extractants. The objective of this study is to provide a robust method for source identification by comparing the tailing sample produced by dust generator and that collected by MOUDI sampler. As and Pb concentrations of the PM10 fraction in the MOUDI sample were much lower than in tailing samples produced by the dust generator, indicating a dilution of Iron King tailing dust by dust from other sources. For source apportionment purposes, single element concentration method was used based on the assumption that the PM10 fraction comes from a background source plus the Iron King tailing source. The method's conclusion that nearly all arsenic and lead in the PM10 dust fraction originated from the tailings substantiates our previous Pb and Sr isotope study conclusion. As and Pb showed a similar mass fraction from Iron King for all sites suggesting that As and Pb have the same major emission source. Further validation of this simple source apportionment method is needed based on other elements and sites.

Stable carbon isotope fractionation of organic cyst-forming dinoflagellates: Evaluating the potential for a CO2 proxy

Science.gov (United States)

Hoins, Mirja; Van de Waal, Dedmer B.; Eberlein, Tim; Reichart, Gert-Jan; Rost, Björn; Sluijs, Appy

2015-07-01

Over the past decades, significant progress has been made regarding the quantification and mechanistic understanding of stable carbon isotope fractionation (13C fractionation) in photosynthetic unicellular organisms in response to changes in the partial pressure of atmospheric CO2 (pCO2). However, hardly any data is available for organic cyst-forming dinoflagellates while this is an ecologically important group with a unique fossil record. We performed dilute batch experiments with four harmful dinoflagellate species known for their ability to form organic cysts: Alexandrium tamarense, Scrippsiella trochoidea, Gonyaulax spinifera and Protoceratium reticulatum. Cells were grown at a range of dissolved CO2 concentrations characterizing past, modern and projected future values (∼5-50 μmol L-1), representing atmospheric pCO2 of 180, 380, 800 and 1200 μatm. In all tested species, 13C fractionation depends on CO2 with a slope of up to 0.17‰ (μmol L)-1. Even more consistent correlations were found between 13C fractionation and the combined effects of particulate organic carbon quota (POC quota; pg C cell-1) and CO2. Carbon isotope fractionation as well as its response to CO2 is species-specific. These results may be interpreted as a first step towards a proxy for past pCO2 based on carbon isotope ratios of fossil organic dinoflagellate cysts. However, additional culture experiments focusing on environmental variables other than pCO2, physiological underpinning of the recorded response, testing for possible offsets in 13C values between cells and cysts, as well as field calibration studies are required to establish a reliable proxy.

Single isotope fractionation of (16)O(-) implications for early history of solar system

Science.gov (United States)

Arrhenius, G.

1980-01-01

Chemical fractionation processes are investigated with emphasis on selective single isotope fractionation in polyisotopic systems, particularly in oxygen. The related temperature parameters of meteoritic condensates and of their source medium are investigated by a thermometric method that is independent of assumptions regarding temperatures and pressures in the solar nebula. The crucial nonlinear chemical fractionation of O-16 was demonstrated experimentally. The effect was achieved in condensed CO2 formed from CO with C-12 O-16 selectively excited by H Ly alpha. The effect was verified by mass spectrometric measurements. The meteorite paleotemperature estimates were advanced from defining only thermal exposure to evaluating time and temperature independently. Grain temperatures at condensation of refractory inclusion materials are indicated to be less than 900 K in agreement with radiation temperature considerations and observations in circumstellar dust shells.

The mechanism of oxygen isotopic fractionation during fungal denitrification - A pure culture study

Science.gov (United States)

Wrage-Moennig, Nicole; Rohe, Lena; Anderson, Traute-Heidi; Braker, Gesche; Flessa, Heinz; Giesemann, Annette; Lewicka-Szczebak, Dominika; Well, Reinhard

2014-05-01

Nitrous oxide (N2O) from soil denitrification originates from bacteria and - to an unknown extent - also from fungi. During fungal denitrification, oxygen (O) exchange takes place between H2O and intermediates of the denitrification process as in bacterial exchange[1,2]. However, information about enzymes involved in fungal O exchanges and the associated fractionation effects is lacking. The objectives of this study were to estimate the O fractionation and O exchange during the fungal denitrifying steps using a conceptual model[2] adapted from concepts for bacterial denitrification[3], implementing controls of O exchange proposed by Aerssens, et al.[4] and using fractionation models by Snider et al.[5] Six different pure fungal cultures (five Hypocreales, one Sordariales) known to be capable of denitrification were incubated under anaerobic conditions, either with nitrite or nitrate. Gas samples were analyzed for N2O concentration and its isotopic signatures (SP, average δ15N, δ18O). To investigate O exchange, both treatments were also established with 18O-labelled water as a tracer in the medium. The Hypocreales strains showed O exchange mainly at NO2- reductase (Nir) with NO2- as electron acceptor and no additional O exchange at NO3- reductase (Nar) with NO3- as electron acceptor. The only Hypocreales species having higher O exchange with NO3- than with NO2- also showed O exchange at Nar. The Sordariales species tested seems capable of O exchange at NO reductase (Nor) additionally to O exchange at Nir with NO2-. The data will help to better interpret stable isotope values of N2O from soils. .[1] D. M. Kool, N. Wrage, O. Oenema, J. Dolfing, J. W. Van Groenigen. Oxygen exchange between (de)nitrification intermediates and H2O and its implications for source determination of NO?3- and N2O: a review. Rapid Commun. Mass Spec. 2007, 21, 3569. [2] L. Rohe, T.-H. Anderson, B. Braker, H. Flessa, A. Giesemann, N. Wrage-Mönnig, R. Well. Fungal Oxygen Exchange between

Measurement of Muscle Protein Fractional Synthetic Rate by Capillary Gas Chromatography/Combustion Isotope Ratio Mass Spectrometry

OpenAIRE

Yarasheski, Kevin E.; Smith, Kenneth; Rennie, Michael J.; Bier, Dennis M.

1992-01-01

The measurement of skeletal muscle protein fractional synthetic rate using an infusion of (1-13C)leucine and measuring the isotopic abundance of the tracer in skeletal muscle protein by preparative gas chromatography (GC)/ninhydrin isotope ratio mass spectrometry (IRMS) is laborious and subject to errors owing to contamination by 12C. The purpose of this study was to compare muscle (13C)leucine enrichment measured with the conventional preparative GC/ninhydrin IRMS approach to a new, continuo...

Barium isotope fractionation during experimental formation of the double carbonate BaMn[CO3](2) at ambient temperature.

Science.gov (United States)

Böttcher, Michael E; Geprägs, Patrizia; Neubert, Nadja; von Allmen, Katja; Pretet, Chloé; Samankassou, Elias; Nägler, Thomas F

2012-09-01

In this study, we present the first experimental results for stable barium (Ba) isotope ((137)Ba/(134)Ba) fractionation during low-temperature formation of the anhydrous double carbonate BaMn[CO(3)](2). This investigation is part of an ongoing work on Ba fractionation in the natural barium cycle. Precipitation at a temperature of 21±1°C leads to an enrichment of the lighter Ba isotope described by an enrichment factor of-0.11±0.06‰ in the double carbonate than in an aqueous barium-manganese(II) chloride/sodium bicarbonate solution, which is within the range of previous reports for synthetic pure BaCO (3) (witherite) formation.

Fractionation between inorganic and organic carbon during the Lomagundi (2.22 2.1 Ga) carbon isotope excursion

Science.gov (United States)

Bekker, A.; Holmden, C.; Beukes, N. J.; Kenig, F.; Eglinton, B.; Patterson, W. P.

2008-07-01

The Lomagundi (2.22-2.1 Ga) positive carbon isotope excursion in shallow-marine sedimentary carbonates has been associated with the rise in atmospheric oxygen, but subsequent studies have demonstrated that the carbon isotope excursion was preceded by the rise in atmospheric oxygen. The amount of oxygen released to the exosphere during the Lomagundi excursion is constrained by the average global fractionation between inorganic and organic carbon, which is poorly characterized. Because dissolved inorganic and organic carbon reservoirs were arguably larger in the Paleoproterozoic ocean, at a time of lower solar luminosity and lower ocean redox state, decoupling between these two variables might be expected. We determined carbon isotope values of carbonate and organic matter in carbonates and shales of the Silverton Formation, South Africa and in the correlative Sengoma Argillite Formation, near the border in Botswana. These units were deposited between 2.22 and 2.06 Ga along the margin of the Kaapvaal Craton in an open-marine deltaic setting and experienced lower greenschist facies metamorphism. The prodelta to offshore marine shales are overlain by a subtidal carbonate sequence. Carbonates exhibit elevated 13C values ranging from 8.3 to 11.2‰ vs. VPDB consistent with deposition during the Lomagundi positive excursion. The total organic carbon (TOC) contents range from 0.01 to 0.6% and δ13C values range from - 24.8 to - 13.9‰. Thus, the isotopic fractionation between organic and carbonate carbon was on average 30.3 ± 2.8‰ ( n = 32) in the shallow-marine environment. The underlying Sengoma shales have highly variable TOC contents (0.14 to 21.94%) and δ13C values (- 33.7 to - 20.8‰) with an average of - 27.0 ± 3.0‰ ( n = 50). Considering that the shales were also deposited during the Lomagundi excursion, and taking δ13C values of the overlying carbonates as representative of the δ13C value of dissolved inorganic carbon during shale deposition, a carbon

EXPERIMENTAL INVESTIGATION OF IRRADIATION-DRIVEN HYDROGEN ISOTOPE FRACTIONATION IN ANALOGS OF PROTOPLANETARY HYDROUS SILICATE DUST

Energy Technology Data Exchange (ETDEWEB)

Roskosz, Mathieu; Remusat, Laurent [IMPMC, CNRS UMR 7590, Sorbonne Universités, Université Pierre et Marie Curie, IRD, Muséum National d’Histoire Naturelle, CP 52, 57 rue Cuvier, Paris F-75231 (France); Laurent, Boris; Leroux, Hugues, E-mail: mathieu.roskosz@mnhn.fr [Unité Matériaux et Transformations, Université Lille 1, CNRS UMR 8207, Bâtiment C6, F-59655 Villeneuve d’Ascq (France)

2016-11-20

The origin of hydrogen in chondritic components is poorly understood. Their isotopic composition is heavier than the solar nebula gas. In addition, in most meteorites, hydrous silicates are found to be lighter than the coexisting organic matter. Ionizing irradiation recently emerged as an efficient hydrogen fractionating process in organics, but its effect on H-bearing silicates remains essentially unknown. We report the evolution of the D/H of hydrous silicates experimentally irradiated by electrons. Thin films of amorphous silica, amorphous “serpentine,” and pellets of crystalline muscovite were irradiated at 4 and 30 keV. For all samples, irradiation leads to a large hydrogen loss correlated with a moderate deuterium enrichment of the solid residue. The entire data set can be described by a Rayleigh distillation. The calculated fractionation factor is consistent with a kinetically controlled fractionation during the loss of hydrogen. Furthermore, for a given ionizing condition, the deuteration of the silicate residues is much lower than the deuteration measured on irradiated organic macromolecules. These results provide firm evidence of the limitations of ionizing irradiation as a driving mechanism for D-enrichment of silicate materials. The isotopic composition of the silicate dust cannot rise from a protosolar to a chondritic signature during solar irradiations. More importantly, these results imply that irradiation of the disk naturally induces a strong decoupling of the isotopic signatures of coexisting organics and silicates. This decoupling is consistent with the systematic difference observed between the heavy organic matter and the lighter water typically associated with minerals in the matrix of most carbonaceous chondrites.

Isotopic Evidence of Unaccounted for Fe and Cu Erythropoietic Pathways

Science.gov (United States)

Albarede, F.; Telouk, P.; Lamboux, A.; Jaouen, K.; Balter, V.

2011-12-01

Despite its potential importance for understanding perturbations in the Fe-Cu homeostatic pathways, the natural isotopic variability of these metals in the human body remains unexplored. We measured the Fe, Cu, and Zn isotope compositions of total blood, serum, and red blood cells of ~50 young blood donors by multiple-collector ICP-MS after separation and purification by anion exchange chromatography. Zn is on average 0.2 permil heavier in erythrocytes (δ 66Zn=0.44±0.33 permil) with respect to serum but shows much less overall isotopic variability than Fe and Cu, which indicates that isotope fractionation depends more on redox conditions than on ligand coordination. On average, Fe in erythrocytes (δ 56Fe=-2.59±0.47 permil) is isotopically light by 1-2 permil with respect to serum, whereas Cu in erythrocytes (δ 65Cu=0.56±0.50 permil) is 0.8 percent heavier. Fe and Cu isotope compositions clearly separate erythrocytes of men and women. Fe and Cu from B-type men erythrocytes are visibly more fractionated than all the other blood types. Isotope compositions provide an original method for evaluating metal mass balance and homeostasis. Natural isotope variability shows that the current models of Fe and Cu erythropoiesis, which assume that erythropoiesis is restricted to bone marrow, violate mass balance requirements. It unveils unsuspected major pathways for Fe, with erythropoietic production of isotopically heavy ferritin and hemosiderin, and for Cu, with isotopically light Cu being largely channeled into blood and lymphatic circulation rather than into superoxide dismutase-laden erythrocytes. Iron isotopes provide an intrinsic measuring rod of the erythropoietic yield, while Cu isotopes seem to gauge the relative activity of erythropoiesis and lymphatics.

Carbon isotope fractionation by anoxygenic phototrophic bacteria in euxinic Lake Cadagno

DEFF Research Database (Denmark)

Posth, Nicole Rita Elisabeth; Bristow, L. A.; Cox, R. P.

2017-01-01

carbon (POC) in the Lake Cadagno chemocline. This large fractionation between the DIC and POC was also found in culture experiments carried out with anoxygenic phototrophic bacteria isolated from the lake. In the Lake Cadagno chemocline, anoxygenic phototrophic bacteria controlled the bulk C......Anoxygenic phototrophic bacteria utilize ancient metabolic pathways to link sulfur and iron metabolism to the reduction of CO2. In meromictic Lake Cadagno, Switzerland, both purple sulfur (PSB) and green sulfur anoxygenic phototrophic bacteria (GSB) dominate the chemocline community and drive...

Iron Isotopes in Spherical Hematite and Goethite Concretions from the Navajo Sandstone (Utah, USA): A Prospective Study for "Martian Blueberries"

Science.gov (United States)

Busigny, V.; Dauphas, N.

2006-03-01

Iron isotopes of terrestrial hematite and goethite concretions provide clues on fluid transport, reservoir sizes, redox variations and biotic versus abiotic processes. This opens several avenues of research for future work on Martian blueberries.

Isotope fractionation of sandy-soil water during evaporation - an experimental study.

Science.gov (United States)

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.

Assessment of diffusive isotopic fractionation in polar firn, and application to ice core trace gas records

DEFF Research Database (Denmark)

Buizert, C.; Sowers, T.; Blunier, T.

2013-01-01

During rapid variations of the atmospheric mixing ratio of a trace gas, diffusive transport in the porous firn layer atop ice sheets and glaciers alters the isotopic composition of that gas relative to the overlying atmosphere. Records of past atmospheric trace gas isotopic composition from ice...... cores and firn need to be corrected for this diffusive fractionation artifact. We present a novel, semi-empirical method to accurately estimate the magnitude of the diffusive fractionation in the ice core record. Our method (1) consists of a relatively simple analytical calculation; (2) requires only...... commonly available ice core data; (3) is not subject to the uncertainties inherent to estimating the accumulation rate, temperature, close-off depth and depth-diffusivity relationship back in time; (4) does not require knowledge of the true atmospheric variations, but uses the smoothed records obtained...

Deuterium isotope effects and fractionation factors of hydrogen-bonded A:T base pairs of DNA

International Nuclear Information System (INIS)

Vakonakis, Ioannis; Salazar, Miguel; Kang, Mijeong; Dunbar, Kim R.; Li Wang, Andy C.

2003-01-01

Deuterium isotope effects and fractionation factors of N1...H3-N3 hydrogen bonded Watson-Crick A:T base pairs of two DNA dodecamers are presented here. Specifically, two-bond deuterium isotope effects on the chemical shifts of 13 C2 and 13 C4, 2 Δ 13 C2 and 2 Δ 13 C4, and equilibrium deuterium/protium fractionation factors of H3, Φ, were measured and seen to correlate with the chemical shift of the corresponding imino proton, δ H3 . Downfield-shifted imino protons associated with larger values of 2 Δ 13 C2 and 2 Δ 13 C4 and smaller Φ values, which together suggested that the effective H3-N3 vibrational potentials were more anharmonic in the stronger hydrogen bonds of these DNA molecules. We anticipate that 2 Δ 13 C2, 2 Δ 13 C4 and Φ values can be useful gauges of hydrogen bond strength of A:T base pairs

Oxygen isotope fractionation and algal symbiosis in benthic foraminifera from the Gulf of Elat, Israel

International Nuclear Information System (INIS)

Buchardt, B.; Hansen, H.J.

1977-01-01

In order to investigate possible isotopic fractionations due to algal symbiosis the oxygen and carbon isotope compositions of shell carbonate from symbiont-free and symbiont-bearing benthic foraminifera have been compared to that of molluscs living at the same locality. The material was collected over a depth profile in the Gulf of Elat (Aqaba), Israel, covering the interval from 4 to 125 metres. After corrections variations for temperature with depth, characteristic 18 O-depletions were observed in the foraminiferal shell carbonate when compared to the molluscs. These depletions are interpreted as 1) a constant vital effect seen in all the foraminifera studied and 2) an additional, light-dependent vital effect observed in the symbiont-bearing forms only, caused by incorporation of photosynthetic oxygen formed by the symbiotic algae. This additional vital effect emphasizes the difficulties in applying foraminifera to oxygen isotope palaeotemperature analyses. No well-defined differences in carbon isotope compositions are observed between symbiont-bearing and symbiont-free foraminifera. (author)

Oxygen isotope fractionation and algal symbiosis in benthic foraminifera from the Gulf of Elat, Israel

Energy Technology Data Exchange (ETDEWEB)

Buchardt, B; Hansen, H J [Copenhagen Univ. (Denmark)

1977-01-01

In order to investigate possible isotopic fractionations due to algal symbiosis the oxygen and carbon isotope compositions of shell carbonate from symbiont-free and symbiont-bearing benthic foraminifera have been compared to that of molluscs living at the same locality. The material was collected over a depth profile in the Gulf of Elat (Aqaba), Israel, covering the interval from 4 to 125 metres. After correcting for variations of temperature with depth, characteristic /sup 18/O-depletions were observed in the foraminiferal shell carbonate when compared to the molluscs. These depletions are interpreted as 1) a constant vital effect seen in all the foraminifera studied and 2) an additional, light-dependent vital effect observed in the symbiont-bearing forms only, caused by incorporation of photosynthetic oxygen formed by the symbiotic algae. This additional vital effect emphasizes the difficulties in applying foraminifera to oxygen isotope palaeotemperature analyses. No well-defined differences in carbon isotope compositions are observed between symbiont-bearing and symbiont-free foraminifera.

Iron and zinc absorption from weaning foods prepared from germinated cereals and legumes using isotope tracers

Energy Technology Data Exchange (ETDEWEB)

Valdez, D H; Kuizon, M D; Marero, L M; Mallillin, A C; Cruz, E M; Madriaga, J R [Department of Science and Technology, Manila (Philippines). Food and Nutrition Research Inst.

1994-12-31

Iron bioavailability from weaning foods prepared from 70:30 combination of germinated rice:mungbean (GRM); germinated rice: cowpea (GRC) and germinated corn:mungbean (GCM) was determined by radioisotopic measurements of iron absorption in human subjects. The gruels were prepared as plain with sugar and flavoring labeled by the extrinsic tag method, and served as hot porridge. It was estimated that iron-deficient infants would absorb 3.5% from GRM, 4.9% from GRC and 5.6% from GCM. Differences between absorption among the weaning foods were not statistically significant. Planning of diets for these age group should include other sources of iron especially heme. Zinc absorption from the weaning food formulations will be studied by the in vitro and in vivo methods. For the in vivo method on human subjects, the absorption of zinc will be determined from the measurement of the whole body retention of the isotope 14 days after intake of the labeled mean. Serum zinc level will be determined to assess the zinc status of the subjects. (author). 23 refs, 1 fig., 4 tabs.

Iron and zinc absorption from weaning foods prepared from germinated cereals and legumes using isotope tracers

International Nuclear Information System (INIS)

Valdez, D.H.; Kuizon, M.D.; Marero, L.M.; Mallillin, A.C.; Cruz, E.M.; Madriaga, J.R.

1994-01-01

Iron bioavailability from weaning foods prepared from 70:30 combination of germinated rice:mungbean (GRM); germinated rice: cowpea (GRC) and germinated corn:mungbean (GCM) was determined by radioisotopic measurements of iron absorption in human subjects. The gruels were prepared as plain with sugar and flavoring labeled by the extrinsic tag method, and served as hot porridge. It was estimated that iron-deficient infants would absorb 3.5% from GRM, 4.9% from GRC and 5.6% from GCM. Differences between absorption among the weaning foods were not statistically significant. Planning of diets for these age group should include other sources of iron especially heme. Zinc absorption from the weaning food formulations will be studied by the in vitro and in vivo methods. For the in vivo method on human subjects, the absorption of zinc will be determined from the measurement of the whole body retention of the isotope 14 days after intake of the labeled mean. Serum zinc level will be determined to assess the zinc status of the subjects. (author). 23 refs, 1 fig., 4 tabs

Phytic acid concentration influences iron bioavailability from biofortified beans in Rwandese women with low iron status.

Science.gov (United States)

Petry, Nicolai; Egli, Ines; Gahutu, Jean B; Tugirimana, Pierrot L; Boy, Erick; Hurrell, Richard

2014-11-01

The common bean is a staple crop in many African and Latin American countries and is the focus of biofortification initiatives. Bean iron concentration has been doubled by selective plant breeding, but the additional iron is reported to be of low bioavailability, most likely due to high phytic acid (PA) concentrations. The present study evaluated the impact of PA on iron bioavailability from iron-biofortified beans. Iron absorption, based on erythrocyte incorporation of stable iron isotopes, was measured in 22 Rwandese women who consumed multiple, composite bean meals with potatoes or rice in a crossover design. Iron absorption from meals containing biofortified beans (8.8 mg Fe, 1320 mg PA/100 g) and control beans (5.4 mg Fe, 980 mg PA/100 g) was measured with beans containing either their native PA concentration or with beans that were ∼50% dephytinized or >95% dephytinized. The iron concentration of the cooked composite meals with biofortified beans was 54% higher than in the same meals with control beans. With native PA concentrations, fractional iron absorption from the control bean meals was 9.2%, 30% higher than that from the biofortified bean meals (P bean meals (406 μg) was 19% higher (P bean meals. With ∼50% and >95% dephytinization, the quantity of iron absorbed from the biofortified bean meals increased to 599 and 746 μg, respectively, which was 37% (P bean meals. PA strongly decreases iron bioavailability from iron-biofortified beans, and a high PA concentration is an important impediment to the optimal effectiveness of bean iron biofortification. Plant breeders should focus on lowering the PA concentration of high-iron beans. This trial was registered at clinicaltrials.gov as NCT01521273. © 2014 American Society for Nutrition.

Iron isotope constraints on arsenic release from Mekong Delta sediments, Cambodia

Science.gov (United States)

Matsumoto, T.; Yamaguchi, K. E.; Hirata, T.; Yamagata, Y.; Yamaguchi, A.; Abe, G.

2017-12-01

Arsenic-contaminated groundwater is a world-wide environmental problem and threatens more than 100 million people living in delta areas of South, SE and East Asia. It is typically associated with reducing aquifers with organic-rich alluvial sediments, little thermal gradients, low sulfate concentrations, and slow flushing rates. Such conditions are typical for low-lying countries in Asian deltas; however, compared to Bangladesh, Cambodia has received far less attention. Upon reductive dissolution of Fe-(oxyhydr)oxides that adsorbed As, Fe and As are released into solution as dissolved Fe2+ and arsenate, respectively. Following the oxidation of dissolved Fe2+, newly-formed Fe-(oxyhydr)oxides adsorb As again. Thus, in anoxic waters, concentrations of As correlate with those of dissolved Fe2+. Fluctuating redox conditions in the aquifer are control As release, although inhibition of adsorption of arsenate and arsenite onto the Fe-(oxyhydr)oxides occurs when the concentrations of phosphate, bicarbonate, silicate, and/or organic matter become sufficiently high. Biogeochemical redox reactions of Fe result in significant isotope fractionation (e.g., Johnson et al., 2008). We hypothesized that magnitude of isotope fractionation of Fe in the aquifer sediments, reflecting repeated (incomplete) redox reactions of Fe, may be proportional to the amount of total As release. We aim to calibrate the As release from aquifer sediment by Fe isotope analysis. As a preliminary study, series of sediment samples were collected from the Mekong Delta, Cambodia, in September 2016. Based on measurements by XRF, ICP-AES and ICP-MS, concentrations of As varied significantly covering the range from 4.5 to 15.5 µg/g with a median value of 11 µg/g (higher than the average crustal value of 5 µg/g), and those of Fe is from 2.6 to 9.7 wt.% with a median value of 7.1 wt.%. Concentrations of As and Fe show positive correlation (R2 = 0.72), indicating an effective redox cycling of Fe and As as

Experimental evaporation of hyperacid brines: Effects on chemical composition and chlorine isotope fractionation

Science.gov (United States)

Rodríguez, Alejandro; van Bergen, Manfred J.; Eggenkamp, H. G. M.

2018-02-01

Hyperacid brines from active volcanic lakes are some of the chemically most complex aqueous solutions on Earth. Their compositions provide valuable insights into processes of elemental transfer from a magma body to the surface and interactions with solid rocks and the atmosphere. This paper describes changes in chemical and δ37Cl signatures observed in a 1750 h isothermal evaporation experiment on hyperacid (pH 0.1) sulphate-chloride brine water from the active lake of Kawah Ijen volcano (Indonesia). Although gypsum was the only evaporite mineral identified in the evolving brine, decreasing Si concentrations may ultimately result in amorphous silica precipitation. Geochemical simulations predict the additional formation of elemental sulphur at lower water activities (aH2O ≤ 0.65) that were not reached in the experiment. Absence of other sulphates and halides despite the high load of dissolved elements (initial TDS ca. 100 g/kg) can be attributed to increased solubility of metals, promoted by extensive formation of complexes between the variety of cations and the major anions (HSO4-, Cl-, F-) present. Chlorine deviations from a conservative behaviour point to losses of gaseous hydrogen chloride (HCl(g)) and consequently an increase in Br/Cl ratios. Chlorine isotope fractionation that accompanied the escape of HCl(g) showed a marked change in sign and magnitude in the course of progressive evaporation of the brine. The calculated factor of fractionation between HCl(g) and dissolved Cl for the initial interval (before 500 h) is positive (1000lnαHCl(g)-Cldiss. = + 1.55 ± 0.49‰to + 3.37 ± 1.11‰), indicating that, at first, the escaping HCl(g) was isotopically heavier than the dissolved Cl remaining in the brine. Conversely, fractionation shifted to the opposite direction in the subsequent interval (1000lnαHCl(g)-Cldiss. = 5.67 ± 0.17‰to - 5.64 ± 0.08‰), in agreement with values reported in literature. It is proposed that Cl isotopic fractionation in

Hypoxia induces copper stable isotope fractionation in hepatocellular carcinoma, in a HIF-independent manner.

Science.gov (United States)

Bondanese, Victor P; Lamboux, Aline; Simon, Melanie; Lafont, Jérôme E; Albalat, Emmanuelle; Pichat, Sylvain; Vanacker, Jean-Marc; Telouk, Philippe; Balter, Vincent; Oger, Philippe; Albarède, Francis

2016-11-09

Hepatocellular carcinoma (HCC) is the most frequent type of primary liver cancer, with increasing incidence worldwide. The unrestrained proliferation of tumour cells leads to tumour hypoxia which in turn promotes cancer aggressiveness. While changes in the concentration of copper (Cu) have long been observed upon cancerization, we have recently reported that the isotopic composition of copper is also altered in several types of cancer. In particular, we showed that in hepatocellular carcinoma, tumour tissue contains heavier copper compared to the surrounding parenchyma. However, the reasons behind such isotopic signature remained elusive. Here we show that hypoxia causes heavy copper enrichment in several human cell lines. We also demonstrate that this effect of hypoxia is pH, HIF-1 and -2 independent. Our data identify a previously unrecognized cellular process associated with hypoxia, and suggests that in vivo tumour hypoxia determines copper isotope fractionation in HCC and other solid cancers.

Galactic cosmic ray iron composition

International Nuclear Information System (INIS)

Scherzer, R.; Enge, W.; Beaujean, R.

1980-11-01

We have studied the isotopic compostition of galactic cosmic ray iron in the energy interval 500-750 MeV/nucleon with a visual track detector system consisting of nuclear emulsion and cellulose-nitrate platic. Stopping iron nuclei were identified from ionization - range measurements in the two detector parts. Cone lengths were measured in the plastic sheets and the residual ranges of the particles were measured in plastic and in emulsion. We have determined the mass of 17 iron nuclei with an uncertainty of about 0.3 amu. The isotopic composition at the detector level was found to be 52 Fe: 53 Fe: 54 Fe: 55 Fe: 56 Fe: 57 Fe: 58 Fe = 0:1: 4:3:8:1:0. These numbers are not in conflict with the assumption that the isotopic composition of cosmic ray iron at the source is similar to the solar system composition. (author)

Isotope dilution analysis for urinary fentanyl and its main metabolite, norfentanyl, in patients by isotopic fractionation using capillary gas chromatography

Energy Technology Data Exchange (ETDEWEB)

Sera, Shoji; Goromaru, Tsuyoshi [Fukuyama Univ., Hiroshima (Japan). Faculty of Pharmacy and Pharmaceutical Sciences; Sameshima, Teruko; Kawasaki, Koichi; Oda, Toshiyuki

1998-07-01

Isotope dilution analysis was applied to determine urinary excretion of fentanyl (FT) and its main metabolite, norfentanyl (Nor-FT), by isotopic fractionation using a capillary gas chromatograph equipped with a surface ionization detector (SID). Urinary FT was determined quantitatively in the range of 0.4-40 ng/ml using deuterium labeled FT (FT-{sup 2}H{sub 19}), as an internal standard. We also performed isotope dilution analysis of Nor-FT in urine. N-Alkylation was necessary to sensitively detect Nor-FT with SID. Methyl derivative was selected from 3 kinds of N-alkyl derivatives to increase sensitivity and peak resolution, and to prevent interference with urinary compound. Nor-FT concentration was quantitatively determined in the range of 10-400 ng/ml using deuterium labeled Nor-FT (Nor-FT-{sup 2}H{sub 10}). No endogenous compounds or concomitant drugs interfered with the detection of FT and Nor-FT in the urine of patients. The present method will be useful for pharmacokinetic studies and the evaluation of drug interactions in FT metabolism. (author)

Isotope dilution analysis for urinary fentanyl and its main metabolite, norfentanyl, in patients by isotopic fractionation using capillary gas chromatography

International Nuclear Information System (INIS)

Sera, Shoji; Goromaru, Tsuyoshi; Sameshima, Teruko; Kawasaki, Koichi; Oda, Toshiyuki

1998-01-01

Isotope dilution analysis was applied to determine urinary excretion of fentanyl (FT) and its main metabolite, norfentanyl (Nor-FT), by isotopic fractionation using a capillary gas chromatograph equipped with a surface ionization detector (SID). Urinary FT was determined quantitatively in the range of 0.4-40 ng/ml using deuterium labeled FT (FT- 2 H 19 ), as an internal standard. We also performed isotope dilution analysis of Nor-FT in urine. N-Alkylation was necessary to sensitively detect Nor-FT with SID. Methyl derivative was selected from 3 kinds of N-alkyl derivatives to increase sensitivity and peak resolution, and to prevent interference with urinary compound. Nor-FT concentration was quantitatively determined in the range of 10-400 ng/ml using deuterium labeled Nor-FT (Nor-FT- 2 H 10 ). No endogenous compounds or concomitant drugs interfered with the detection of FT and Nor-FT in the urine of patients. The present method will be useful for pharmacokinetic studies and the evaluation of drug interactions in FT metabolism. (author)

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

Science.gov (United States)

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

Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm

Science.gov (United States)

Coutaud, Margot; Méheut, Merlin; Glatzel, Pieter; Pokrovski, Gleb S.; Viers, Jérôme; Rols, Jean-Luc; Pokrovsky, Oleg S.

2018-01-01

Despite the importance of phototrophic biofilms in metal cycling in freshwater systems, metal isotope fractionation linked to metal adsorption and uptake by biofilm remains very poorly constrained. Here, copper isotope fractionation by a mature phototrophic biofilm during Cu surface adsorption and incorporation was studied in batch reactor (BR) and open drip flow reactor (DFR) systems at ambient conditions. X-ray Absorption Spectroscopy (both Near Edge Structure, XANES, and Extended Fine Structure, EXAFS) at Cu K-edge of the biofilm after its interaction with Cu in BR experiments allowed characterizing the molecular structure of assimilated Cu and quantifying the degree of CuII to CuI reduction linked to Cu assimilation. For both BR and DFR experiments, Cu adsorption caused enrichment in heavy isotope at the surface of the biofilm relative to the aqueous solution, with an apparent enrichment factor for the adsorption process, ε65Cuads, of +1.1 ± 0.3‰. In contrast, the isotope enrichment factor during copper incorporation into the biofilm (ε65Cuinc) was highly variable, ranging from -0.6 to +0.8‰. This variability of the ε65Cuinc value was likely controlled by Cu cellular uptake via different transport pathways resulting in contrasting fractionation. Specifically, the CuII storage induced enrichment in heavy isotope, whereas the toxicity response of the biofilm to Cu exposure resulted in reduction of CuII to CuI, thus yielding the biofilm enrichment in light isotope. EXAFS analyses suggested that a major part of the Cu assimilated by the biofilm is bound to 5.1 ± 0.3 oxygen or nitrogen atoms, with a small proportion of Cu linked to sulfur atoms (NS biofilm exhibited a similar trend over time of exposure. Our study demonstrates the complexity of biological processes associated with live phototrophic biofilms, which produce large and contrasting isotope fractionations following rather small Cu redox and speciation changes during uptake, storage or release of

Short-term carbon isotopic fractionation in plants

International Nuclear Information System (INIS)

Rooney, M.A.

1988-01-01

A system was developed for measuring carbon isotopic fractionation in plants over a time interval of 1-3 hours, in contrast to leaf combustion studies which give long-term, integrated discrimination measurements. The system was used to study environmental effects on soybean (Glycine max) and corn (Zea mays) discrimination. Changes in leaf temperature, photon flux density (PFD), O 2 concentration, and CO 2 concentration produced little or no change in measured discrimination (Δ). For soybean, Δ increased with decreasing PFD. For corn, Δ decreased with decreasing O 2 concentration. For both soybean and corn, Δ increased with increasing CO 2 concentration. These changes in Δ were interpreted as environmental effects on stomatal conductance and photosynthetic capacity, which indirectly affect Δ by altering C i /C a . Respiratory discrimination in the dark and light was also investigated. Respired CO 2 was 5 per-thousand and 0-1 per-thousand more positive than leaf carbon for soybean and corn, respectively. Photorespiratory discrimination was 6-7 per-thousand for soybean, supporting the contention that glycine decarboxylase may be the source of discrimination in the photorespiratory pathway

Reassessment of the C-13/C-12 and C-14/C-12 isotopic fractionation ratio and its impact on high-precision radiocarbon dating

NARCIS (Netherlands)

Fahrni, Simon M.; Southon, John R.; Santos, Guaciara M.; Palstra, Sanne W. L.; Meijer, Harro A. J.; Xu, Xiaomei

2017-01-01

The vast majority of radiocarbon measurement results (C-14/C-12 isotopic ratios or sample activities) are corrected for isotopic fractionation processes (measured as C-13/C-12 isotopic ratios) that occur in nature, in sample preparation and measurement. In 1954 Harmon Craig suggested a value of 2.0

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

Science.gov (United States)

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

2014-01-01

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

Isotopic distributions, element ratios, and element mass fractions from enrichment-meter-type gamma-ray measurements of MOX

International Nuclear Information System (INIS)

Close, D.A.; Parker, J.L.; Haycock, D.L.; Dragnev, T.

1991-01-01

The gamma-ray spectra from ''infinitely'' thick mixed oxide samples have been measured. The plutonium isotopics, the U/Pu ratio, the high-Z mass fractions (assuming only plutonium, uranium, and americium), and the low-Z mass fraction (assuming the matrix is only oxygen) can be determined by carefully analyzing the data. The results agree well with the chemical determination of these parameters. 8 refs., 3 figs., 3 tabs

Spatial evolution of Zn-Fe-Pb isotopes of sphalerite within a single ore body: A case study from the Dongshengmiao ore deposit, Inner Mongolia, China

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Gao, Zhaofu; Zhu, Xiangkun; Sun, Jian; Luo, Zhaohua; Bao, Chuang; Tang, Chao; Ma, Jianxiong

2018-01-01

Analyses of sphalerite minerals from the characteristic brecciated Zn-Pb ores of the main ore body in the giant Dongshengmiao deposit have revealed variations in δ66Zn from 0.17 to 0.40‰ and in δ56Fe from -1.78 to -0.35‰. Further, the investigated pyrrhotite samples have iron that is isotopically similar to that of associated sphalerite minerals. The most distinctive pattern revealed by the zinc and iron isotope data is the lateral trend of increasing δ66Zn and δ56Fe values from southwest to northeast within the main ore body. The lead isotopic homogeneity of ore sulfides from the main ore body suggests that there is only one significant source for metal, thus precluding the mixing of multiple metal sources as the key factor controlling spatial variations of zinc and iron isotopes. The most likely control on spatial variations is Rayleigh fractionation during hydrothermal fluid flow, with lighter Zn and Fe isotopes preferentially incorporated into the earliest sulfides to precipitate from fluids. Precipitations of sphalerite and pyrrhotite have played vital roles in the Zn and Fe isotopic variations, respectively, of the ore-forming system. Accordingly, the larger isotopic variability for Fe than Zn within the same hydrothermal system perhaps resulted from a larger proportion of precipitation for pyrrhotite than for sphalerite. The lateral trend pattern revealed by the zinc and iron isotope data is consistent with the occurrence of a cystic-shaped breccia zone, which is characterized by marked elevation in Cu. The results further confirm that Zn and Fe isotopes can be used as a vectoring tool for mineral prospecting.

Valence-associated uranium isotope fractionation of uranium enriched phosphate in a shallow aquifer, Lee County, Florida

International Nuclear Information System (INIS)

Weinberg, J.M.; Levine, B.R.; Cowart, J.B.

1993-01-01

The source of anomalously high concentrations of uranium, characterized by U-234/U-238 activity ratios significantly less than unity, in shallow groundwaters of Lee County, Florida, was investigated. Uranium in cores samples was separated into U(IV) and U(VI) oxidation state fractions, and uranium analyses were conducted by alpha spectrometry. Uranium mobility was also studied in selected leaching experiments. Results indicate that mobilization of unusually soluble uranium, present in uranium enriched phosphate of the Pliocene age Tamiami Formation at determined concentrations of up to 729 ppm, is the source for high uranium concentrations in groundwater. In leaching experiments, approximately one-third of the uranium present in the uranium enriched phosphate was mobilized into the aqueous phase. Results of previous investigations suggest that U-234, produced in rock by U-238 decay, is selectively oxidized to U(VI). The uranium enriched phosphate studied in this investigation is characterized by selective reduction of U-234, with a pattern of increasing isotopic fractionation with core depth. As a consequence, U-234/U-238 activity ratios greater than 1.0 in the U(IV) fraction, and less than 1.0 in the U(VI) fraction have developed in the rock phase. In leaching experiments, the U(VI) fraction from the rock was preferentially mobilized into the aqueous phase, suggesting that U-234/U-238 activity ratios of leaching groundwaters are strongly influenced by the isotopic characteristics of the U(VI) fraction of rock. It is suggested that preferential leaching of U(VI), present in selectivity reduced uranium enriched phosphate, is the source for low activity ratio groundwaters in Lee County

Growth phase dependent hydrogen isotopic fractionation in alkenone-producing haptophytes

Directory of Open Access Journals (Sweden)

M. D. Wolhowe

2009-08-01

Full Text Available Recent works have investigated use of the hydrogen isotopic composition of C₃₇ alkenones (δD_K37s, lipid biomarkers of certain haptophyte microalgae, as an independent paleosalinity proxy. We discuss herein the factors impeding the success of such an application and identify the potential alternative use of δD_K37s measurements as a proxy for non-thermal, physiological stress impacts on the U₃₇^K' paleotemperature index. Batch-culture experiments with the haptophyte Emiliania huxleyi (CCMP 1742 were conducted to determine the magnitude and variability of the isotopic contrasts between individual C₃₇ alkenones. Further experiments were conducted with Emiliania huxleyi (CCMP 1742 andGephyrocapsa oceanica (PZ3-1 to determine whether, and to what extent, δD_K37s varies between the physiological extremes of nutrient-replete exponential growth and nutrient-depleted senescence. Emiliania huxleyi was observed to exhibit an isotopic contrast between di- and tri-unsaturated C₃₇ alkenones (α_K37:3-K37:2≈0.97 that is nearly identical to that reported recently by others for environmental samples. Furthermore, this contrast appears to be constant with growth stage. The consistency of the offset across different growth stages suggests that a single, well-defined value for α_K37:3-K37:2 may exist and that its use in an isotope mass-balance will allow accurate determination of δD values for individual alkenones without having to rely on time- and labor-intensive chemical separations. The isotopic fractionation between growth medium and C₃₇ alkenones was observed to increase dramatically upon the onset of nutrient-depletion-induced senescence, suggesting that δD_K37s may serve as an objective tool for recognizing and potentially correcting, at least semi-quantitatively, for the effects

Decoding mass-independent fractionation of sulfur isotopes in modern atmosphere using cosmogenic 35S: A five-isotope approach and possible implications for Archean sulfur isotope records

Science.gov (United States)

Lin, M.; Thiemens, M. H.; Shen, Y.; Zhang, X.; Huang, X.; Chen, K.; Zhang, Z.; Tao, J.

2017-12-01

The signature of sulfur isotopic mass-independent fractionation (S-MIF) observed in Archean sediments have been interpreted as a proxy of the origins and evolution of atmospheric oxygen and early life on Earth [1]. Photochemistry of SOx in the short (negative Δ36S. After eliminating combustion impacts, the obtained Δ36S/Δ33S slope of -4.0 in the modern atmosphere is close to the Δ36S/Δ33S slope (-3.6) in some records from Paleoarchean [4], an era probably with active volcanism [5]. The significant role of volcanic OCS in the Archean atmosphere has been called for in terms of its ability to provide a continual SO2 high altitude source for photolysis [2]. The strong but previously underappreciated stratospheric signature of S-MIF in tropospheric sulfates suggests that a more careful investigation of wavelength-dependent sulfur isotopic fractionation at different altitudes are required. The combustion-induced negative Δ36S may be linked to recombination reactions of elemental sulfur [6], and relevant experiments are being conducted to test the isotope effect. Although combustion is unlikely in Archean, recombination reactions may occur in other previously unappreciated processes such as volcanism and may contribute in part to the heavily depleted 36S in some Paleoarchean records [5,7]. The roles of both photochemical and non-photochemical reactions in the variability of Archean S-MIF records require further analysis in the future. Refs: [1] Farquhar et al., Science 2000; [2] Shaheen et al., PNAS 2014; [3] Lin et al., PNAS 2016; [4] Wacey et al., Precambrian Res 2015; [5] Muller et al., PNAS 2016; [6] Babikov, PNAS 2017; [7] Shen et al., EPSL, 2009.

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

Science.gov (United States)

Bullen, Tomas 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.

What Drives Carbon Isotope Fractionation by the Terrestrial Biosphere?

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Still, Christopher; Rastogi, Bharat

2017-11-01

During photosynthesis, terrestrial plants preferentially assimilate the lighter and much more abundant form of carbon, 12C, which accounts for roughly 99% of naturally occurring forms of this element. This photosynthetic preference for lighter carbon is driven principally by differences in molecular diffusion of carbon dioxide with differing 13C/12C across stomatal pores on leaves, followed by differences in carboxylation rates by the Rubisco enzyme that is central to the process of photosynthesis. As a result of these slight preferences, which work out to about a 2% difference in the fixation rates of 12CO2 versus 13CO2 by C3 vegetation, plant tissues are depleted in the heavier form of carbon (13C) relative to atmospheric CO2. This difference has been exploited in a wide range of scientific applications, as the photosynthetic isotope signature is passed to ecosystem carbon pools and through ecological food webs. What is less appreciated is the signature that terrestrial carbon exchanges leave on atmospheric CO2, as the net uptake of carbon by land plants during their growing season not only draws down the local CO2 concentration, it also leaves behind relatively more CO2 molecules containing 13C. The converse happens outside the growing season, when autotrophic and heterotrophic respiration predominate. During these periods, atmospheric CO2 concentration increases and its corresponding carbon isotope composition becomes relatively depleted in 13C as the products of photosynthesis are respired, along with some small isotope fractionation that happen downstream of the initial photosynthetic assimilation. Similar phenomena were first observed at shorter time scales by the eminent carbon cycle scientist, Charles (Dave) Keeling. Keeling collected samples of air in glass flasks from sites along the Big Sur coast that he later measured for CO2 concentration and carbon isotope composition (δ13C) in his lab (Keeling, 1998). From these samples, Keeling observed increasing

Underestimation of phosphorus fraction change in the supernatant after phosphorus adsorption onto iron oxides and iron oxide-natural organic matter complexes.

Science.gov (United States)

Yan, Jinlong; Jiang, Tao; Yao, Ying; Wang, Jun; Cai, Yuanli; Green, Nelson W; Wei, Shiqiang

2017-05-01

The phosphorus (P) fraction distribution and formation mechanism in the supernatant after P adsorption onto iron oxides and iron oxide-humic acid (HA) complexes were analyzed using the ultrafiltration method in this study. With an initial P concentration of 20mg/L (I=0.01mol/L and pH=7), it was shown that the colloid (1kDa-0.45μm) component of P accounted for 10.6%, 11.6%, 6.5%, and 4.0% of remaining total P concentration in the supernatant after P adsorption onto ferrihydrite (FH), goethite (GE), ferrihydrite-humic acid complex (FH-HA), goethite-humic acid complex (GE-HA), respectively. The oxide aggregates was the main mechanism for the formation of the colloid P in the supernatant. And colloidal adsorbent particles co-existing in the supernatant were another important reason for it. Additionally, dissolve organic matter dissolved from iron oxide-HA complexes could occupy large adsorption sites of colloidal iron causing less colloid P in the supernatant. Ultimately, we believe that the findings can provide a new way to deeply interpret the geochemical cycling of P, even when considering other contaminants such as organic pollutants, heavy metal ions, and arsenate at the sediment/soil-water interface in the real environment. Copyright © 2016. Published by Elsevier B.V.

Level densities of iron isotopes and lower-energy enhancement of y-strength function

International Nuclear Information System (INIS)

Voinov, A V; Grimes, S M; Agvaanluvsan, U; Algin, E; Belgya, T; Brune, C R; Guttormsen, M; Hornish, M J; Massey, T N; Mitchell, G; Rekstad, J; Schiller, A; Siem, S

2005-01-01

The neutron spectrum from the 55 Mn(d,n) 56 Fe reaction has been measured at E d = 7 MeV. The level density of 56 Fe obtained from neutron evaporation spectrum has been compared to the level density from Oslo-type 57 Fe( 3 He, aγ) 56 Fe experiment [1]. The good agreement supports the recent results [1, 8] including an availability of a low-energy enhancement in the γ-strength function for iron isotopes. The new level density function allowed us to investigate an excitation energy dependence of this enhancement, which is shown to increase with increasing excitation energy

Iron and stony-iron meteorites

DEFF Research Database (Denmark)

Ruzicka, Alex M.; Haack, Henning; Chabot, Nancy L.

2017-01-01

By far most of the melted and differentiated planetesimals that have been sampled as meteorites are metal-rich iron meteorites or stony iron meteorites. The parent asteroids of these meteorites accreted early and differentiated shortly after the solar system formed, producing some of the oldest...... and interpretations for iron and stony iron meteorites (Plate 13.1). Such meteorites provide important constraints on the nature of metal-silicate separation and mixing in planetesimals undergoing partial to complete differentiation. They include iron meteorites that formed by the solidification of cores...... (fractionally crystallized irons), irons in which partly molten metal and silicates of diverse types were mixed together (silicate-bearing irons), stony irons in which partly molten metal and olivine from cores and mantles were mixed together (pallasites), and stony irons in which partly molten metal...

Isotopic fractionation between organic carbon and carbonate carbon in Precambrian banded ironstone series from Brazil

International Nuclear Information System (INIS)

Schidlowski, M.; Eichmann, R.; Fiebiger, W.

1976-01-01

37 delta 13 Csub(org) and 9 delta 13 Csub(carb) values furnished by argillaceous and carbonate sediments from the Rio das Velhas and Minas Series (Minas Gerais, Brazil) have yielded means of -24.3 +- 3.9 promille [PDB] and -0.9 +- 1.4 promille [PDB], respectively. These results, obtained from a major sedimentary banded ironstone province with an age between 2 and 3 x 10 9 yr, support previous assumptions that isotopic fractionation between inorganic and organic carbon in Precambrian sediments is about the same as in Phanerozoic rocks. This is consistent with a theoretically expected constancy of the kinetic fractionation factor governing biological carbon fixation and, likewise, with a photosynthetic pedigree of the reduced carbon fraction of Precambrian rocks. (orig.) [de

Mass Dependent Fractionation of Hg Isotopes in Source Rocks, Mineral Deposits and Spring Waters of the California Coast Ranges, USA

Science.gov (United States)