Tracing contamination sources in soils with Cu and Zn isotopic ratios.

Science.gov (United States)

Fekiacova, Z; Cornu, S; Pichat, S

2015-06-01

Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. Copyright © 2015 Elsevier B.V. All rights reserved.

Cu and Zn Isotopes as New Tracers of Early Solar Nebula and Asteroidal processes

Science.gov (United States)

LUCK, J.; BEN OTHMAN, D.; ALBAREDE, F.

2001-12-01

experiments have been conducted on various powder aliquots : HF-HCl cold(#1), HF-HCl hot(#2), HF-HNO3(#3) hot under pressure. Results show clearly that different Zn (and Cu) isotopic signatures (are preserved in early components. We stress that these are NOT anomalies for Zn : three isotopic ratios (66, 67 and 68 vs. 64) agree perfectly with a mass-dependent process. In particular Zn gets systematically lighter from the ``volatile" compounds (#1) to the refractory ones (#3). The rough correlation between O and Zn isotopes in these compounds could imply that Zinc, like Oxygen, experienced interaction between gaseous and solid states (e.g. spinels) at high temperatures. III- Iron Meteorites Non magmatic irons do not show much variation (less than 1 permil in range for both elements). On the other hand, meteorites from the IAB-IIICD group show not only large variations (3.5 permil in Zn), but also a negative correlation between Cu and Zn isotopes : this could be interpreted as a mixing between two endmembers, one of them being strongly fractionated in Zn isotopes. Fractionation of such extent (+3.7 permil) could reflect either volatilization during impact melting, or alteration on the parent body. Data available indicate that Cu and Zn isotopes are potentially important tracers for studying : 1- early solar nebula processes (e.g. high and low-T compounds exhibit different isotopic signatures); 2- meteorite parent body evolution (e.g. Cu and Zn isotopes correlate remarkably well with Oxygen isotopes in a well-established order : CV-CO-CM-CI). References (1)\\x90Marechal C., Telouk P. and Albarede F. (1999) Chem. Geol., 156, 251-273.

Stable isotope tracing of Ni and Cu pollution in North-East Norway: Potentials and drawbacks.

Science.gov (United States)

Šillerová, Hana; Chrastný, Vladislav; Vítková, Martina; Francová, Anna; Jehlička, Jan; Gutsch, Marissa R; Kocourková, Jana; Aspholm, Paul E; Nilsson, Lars O; Berglen, Tore F; Jensen, Henning K B; Komárek, Michael

2017-09-01

The use of Ni and Cu isotopes for tracing contamination sources in the environment remains a challenging task due to the limited information about the influence of various biogeochemical processes influencing stable isotope fractionation. This work focuses on a relatively simple system in north-east Norway with two possible endmembers (smelter-bedrock) and various environmental samples (snow, soil, lichens, PM 10 ). In general, the whole area is enriched in heavy Ni and Cu isotopes highlighting the impact of the smelting activity. However, the environmental samples exhibit a large range of δ 60 Ni (-0.01 ± 0.03‰ to 1.71 ± 0.02‰) and δ 65 Cu (-0.06 ± 0.06‰ to -3.94 ± 0.3‰) values which exceeds the range of δ 60 Ni and δ 65 Cu values determined in the smelter, i.e. in feeding material and slag (δ 60 Ni from 0.56 ± 0.06‰ to 1.00 ± 0.06‰ and δ 65 Cu from -1.67 ± 0.04‰ to -1.68 ± 0.15‰). The shift toward heavier Ni and Cu δ values was the most significant in organic rich topsoil samples in the case of Ni (δ 60 Ni up to 1.71 ± 0.02‰) and in lichens and snow in the case of Cu (δ 65 Cu up to -0.06 ± 0.06‰ and -0.24 ± 0.04‰, respectively). These data suggest an important biological and biochemical fractionation (microorganisms and/or metal uptake by higher plants, organo-complexation etc.) of Ni and Cu isotopes, which should be quantified separately for each process and taken into account when using the stable isotopes for tracing contamination in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Origin and fate of copper in a small Mediterranean vineyard catchment: New insights from combined chemical extraction and δ{sup 65}Cu isotopic composition

Energy Technology Data Exchange (ETDEWEB)

El Azzi, D. [Université de Toulouse (France); INPT, UPS (France); Laboratoire Ecologie Fonctionnelle et Environnement (ECOLAB), ENSAT, Avenue de l' Agrobiopole, 31326 Castanet Tolosan Cedex (France); CNRS (France); ECOLAB, ENSAT, Avenue de l' Agrobiopole, 31326 Castanet Tolosan Cedex (France); Viers, J. [Université de Toulouse (France); UPS, Géosciences Environnement Toulouse (GET), 14, avenue Édouard Belin, Toulouse31400 (France); CNRS, IRD, CNES (France); GET, 14, avenue Édouard Belin, Toulouse 31400 (France); Guiresse, M.; Probst, A. [Université de Toulouse (France); INPT, UPS (France); Laboratoire Ecologie Fonctionnelle et Environnement (ECOLAB), ENSAT, Avenue de l' Agrobiopole, 31326 Castanet Tolosan Cedex (France); CNRS (France); ECOLAB, ENSAT, Avenue de l' Agrobiopole, 31326 Castanet Tolosan Cedex (France); Aubert, D. [Université de Perpignan Via Domitia, CEntre de Formation et de Recherche sur les Environnements Méditérranéens (CEFREM), UMR 5110, F-66860, Perpignan (France); CNRS, CEFREM, UMR 5110, F-66860, Perpignan (France); Caparros, J.; Charles, F.; Guizien, K. [CNRS, FRE 3350, LECOB, Observatoire Océanologique, F-66651 Banyuls/mer (France); UPMC Université Paris 6, FRE 3350, LECOB, Observatoire Océanologique, F-66651 Banyuls/mer (France); Probst, J.L., E-mail: jean-luc.probst@ensat.fr [Université de Toulouse (France); INPT, UPS (France); Laboratoire Ecologie Fonctionnelle et Environnement (ECOLAB), ENSAT, Avenue de l' Agrobiopole, 31326 Castanet Tolosan Cedex (France); CNRS (France); ECOLAB, ENSAT, Avenue de l' Agrobiopole, 31326 Castanet Tolosan Cedex (France)

2013-10-01

For centuries, many Mediterranean catchments were covered with vineyards in which copper was widely applied to protect grapevines against fungus. In the Mediterranean-type flow regime, brief and intense flood events increase the stream water discharge by up to 10 times and cause soil leaching and storm runoff. Because vineyards are primarily cultivated on steep slopes, high Cu fluxes are discharged by surface water runoff into the rivers. The purpose of this work was to investigate the riverine behavior and transport of anthropogenic Cu by coupling a sequential chemical extraction (SCE) procedure, used to determine Cu partitioning between residual and non-residual fractions, with δ{sup 65}Cu isotopic measurements in each fraction. In the Baillaury catchment, France, we sampled soils (cultivated and abandoned), river bed sediments (BS), suspended particulate matter (SPM), and river water during the flash flood event of February 2009. Copper partitioning using SCE show that most of Cu in abandoned vineyard soil was in the residual phase (> 60%) whereas in cultivated soil, BS and SPM, Cu was mostly (> 25%) in non-residual fractions, mainly adsorbed onto iron oxide fractions. A small fraction of Cu was associated with organic matter (5 to 10%). Calculated enrichment factors (EF) are higher than 2 and the anthropogenic contribution was estimated between 50 to 85%. Values for δ{sup 65}Cu in bulk samples were similar to bedrock therefore; δ{sup 65}Cu on SCE fractions of superficial soils and SPM allowed for discrimination between Cu origin and distribution. Copper in residual fractions was of natural mineral origin (δ{sup 65}Cu close to local bedrock, + 0.07‰). Copper in water soluble fraction of SPM (δ{sup 65}Cu = + 0.26‰) was similar to dissolved river Cu (δ{sup 65}Cu = + 0.31‰). Copper from fungicide treatment (δ{sup 65}Cu = − 0.35‰) was bound to organic matter (δ{sup 65}Cu = − 0.20‰) without or with slight isotopic fractioning. A preferential

Mass fractionation processes of transition metal isotopes

Science.gov (United States)

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

2002-06-01

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

Electrochemically controlled iron isotope fractionation

Science.gov (United States)

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

2010-02-01

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

Cu-Zn isotope constraints on the provenance of air pollution in Central Europe: Using soluble and insoluble particles in snow and rime.

Science.gov (United States)

Novak, Martin; Sipkova, Adela; Chrastny, Vladislav; Stepanova, Marketa; Voldrichova, Petra; Veselovsky, Frantisek; Prechova, Eva; Blaha, Vladimir; Curik, Jan; Farkas, Juraj; Erbanova, Lucie; Bohdalkova, Leona; Pasava, Jan; Mikova, Jitka; Komarek, Arnost; Krachler, Michael

2016-11-01

Copper (Cu) and zinc (Zn) isotope ratios can be used to fingerprint sources and dispersion pathways of pollutants in the environment. Little is known, however, about the potential of δ 65 Cu and δ 66 Zn values in liquid and solid forms of atmospheric deposition to distinguish between geogenic, industrial, local and remote sources of these potentially toxic base metals. Here we present Cu-Zn deposition fluxes at 10 mountain-top sites in the Czech Republic, a region affected by extremely high industrial emission rates 25 years ago. Additionally, we monitored isotope composition of Cu and Zn in vertical and horizontal atmospheric deposition at two sites. We compared δ 65 Cu and δ 66 Zn values in snow and rime, extracted by diluted HNO 3 and concentrated HF. Cu and Zn isotope signatures of industrial pollution sources were also determined. Cu and Zn deposition fluxes at all study sites were minute. The mean δ 65 Cu value of atmospheric deposition (-0.07‰) was higher than the mean δ 65 Cu value of pollution sources (-1.17‰). The variability in δ 65 Cu values of atmospheric deposition was lower, compared to the pollution sources. The mean δ 66 Zn value of atmospheric deposition (-0.09‰) was slightly higher than the mean δ 66 Zn value of pollution sources (-0.23‰). The variability in δ 66 Zn values of atmospheric deposition was indistinguishable from that of pollution sources. The largest isotope differences (0.35‰) were observed between the insoluble and soluble fractions of atmospheric deposition. These differences may result from different sources of Cu/Zn for each fraction. The difference in isotope composition of soluble and insoluble particles appears to be a promising tool for pollution provenance studies in Central Europe. Copyright © 2016 Elsevier Ltd. All rights reserved.

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)

Re-partitioning of Cu and Zn isotopes by modified protein expression

Directory of Open Access Journals (Sweden)

Ragnarsdottir K Vala

2008-10-01

Full Text Available Abstract Cu and Zn have naturally occurring non radioactive isotopes, and their isotopic systematics in a biological context are poorly understood. In this study we used double focussing mass spectroscopy to determine the ratios for these isotopes for the first time in mouse brain. The Cu and Zn isotope ratios for four strains of wild-type mice showed no significant difference (δ65Cu -0.12 to -0.78 permil; δ66Zn -0.23 to -0.48 permil. We also looked at how altering the expression of a single copper binding protein, the prion protein (PrP, alters the isotope ratios. Both knockout and overexpression of PrP had no significant effect on the ratio of Cu isotopes. Mice brains expressing mutant PrP lacking the known metal binding domain have δ65Cu isotope values of on average 0.57 permil higher than wild-type mouse brains. This implies that loss of the copper binding domain of PrP increases the level of 65Cu in the brain. δ66Zn isotope values of the transgenic mouse brains are enriched for 66Zn to the wild-type mouse brains. Here we show for the first time that the expression of a single protein can alter the partitioning of metal isotopes in mouse brains. The results imply that the expression of the prion protein can alter cellular Cu isotope content.

Fingerprinting two metal contaminants in streams with Cu isotopes near the Dexing Mine, China

Energy Technology Data Exchange (ETDEWEB)

Song, Shiming [Chinese Geological Survey, Nanjing Center, Nanjing (China); Mathur, Ryan, E-mail: mathurr@juniata.edu [Department of Geology, Juniata College, Huntingdon, PA (United States); Ruiz, Joaquin [Department of Geosciences, University of Arizona, Tucson, AZ (United States); Chen, Dandan [Chinese Geological Survey, Nanjing Center, Nanjing (China); Allin, Nicholas [Department of Geology, Juniata College, Huntingdon, PA (United States); Guo, Kunyi; Kang, Wenkai [Chinese Geological Survey, Nanjing Center, Nanjing (China)

2016-02-15

Transition metal isotope signatures are becoming useful for fingerprinting sources in surface waters. This study explored the use of Cu isotope values to trace dissolved metal contaminants in stream water throughout a watershed affected by mining by-products of the Dexing Mine, the largest porphyry Cu operation in Asia. Cu isotope values of stream water were compared to potential mineral sources of Cu in the mining operation, and to proximity to the known Cu sources. The first mineral source, chalcopyrite, CuFeS{sub 2} has a ‘tight’ cluster of Cu isotope values (− 0.15‰ to + 1.65‰; + 0.37 ± 0.6‰, 1σ, n = 10), and the second mineral source, pyrite (FeS{sub 2}), has a much larger range of Cu isotope values (− 4‰ to + 11.9‰; 2.7 ± 4.3‰, 1σ, n = 16). Dissolved Cu isotope values of stream water indicated metal derived from either chalcopyrite or pyrite. Above known Cu mineralization, stream waters are approximately + 1.5‰ greater than the average chalcopyrite and are interpreted as derived from weathering of chalcopyrite. In contrast, dissolved Cu isotope values in stream water emanating from tailings piles had Cu isotope values similar to or greater than pyrite (>+6‰, a common mineral in the tailings). These values are interpreted as sourced from the tailings, even in solutions that possess significantly lower concentrations of Cu (< 0.05 ppm). Elevated Cu isotope values were also found in two soil and two tailings samples (δ{sup 65}Cu ranging between + 2 to + 5‰). These data point to the mineral pyrite in tailings as the mineral source for the elevated Cu isotope values. Therefore, Cu isotope values of waters emanating from a clearly contaminated drainage possess different Cu isotope values, permitting the discrimination of Cu derived from chalcopyrite and pyrite in solution. Data demonstrate the utility of Cu isotopic values in waters, minerals, and soils to fingerprint metallic contamination for environmental problems. - Highlights: �

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.

Influence of sulfur-bearing polyatomic species on high precision measurements of Cu isotopic composition

Science.gov (United States)

Pribil, M.J.; Wanty, R.B.; Ridley, W.I.; Borrok, D.M.

2010-01-01

An increased interest in high precision Cu isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has developed recently for various natural geologic systems and environmental applications, these typically contain high concentrations of sulfur, particularly in the form of sulfate (SO42-) and sulfide (S). For example, Cu, Fe, and Zn concentrations in acid mine drainage (AMD) can range from 100??g/L to greater than 50mg/L with sulfur species concentrations reaching greater than 1000mg/L. Routine separation of Cu, Fe and Zn from AMD, Cu-sulfide minerals and other geological matrices usually incorporates single anion exchange resin column chromatography for metal separation. During chromatographic separation, variable breakthrough of SO42- during anion exchange resin column chromatography into the Cu fractions was observed as a function of the initial sulfur to Cu ratio, column properties, and the sample matrix. SO42- present in the Cu fraction can form a polyatomic 32S-14N-16O-1H species causing a direct mass interference with 63Cu and producing artificially light ??65Cu values. Here we report the extent of the mass interference caused by SO42- breakthrough when measuring ??65Cu on natural samples and NIST SRM 976 Cu isotope spiked with SO42- after both single anion column chromatography and double anion column chromatography. A set of five 100??g/L Cu SRM 976 samples spiked with 500mg/L SO42- resulted in an average ??65Cu of -3.50?????5.42??? following single anion column separation with variable SO42- breakthrough but an average concentration of 770??g/L. Following double anion column separation, the average SO42-concentration of 13??g/L resulted in better precision and accuracy for the measured ??65Cu value of 0.01?????0.02??? relative to the expected 0??? for SRM 976. We conclude that attention to SO42- breakthrough on sulfur-rich samples is necessary for accurate and precise measurements of ??65Cu and may require

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

Iron isotopic fractionation during continental weathering

Energy Technology Data Exchange (ETDEWEB)

Fantle, Matthew S.; DePaolo, Donald J.

2003-10-01

The biological activity on continents and the oxygen content of the atmosphere determine the chemical pathways through which Fe is processed at the Earth's surface. Experiments have shown that the relevant chemical pathways fractionate Fe isotopes. Measurements of soils, streams, and deep-sea clay indicate that the {sup 56}Fe/{sup 54}Fe ratio ({delta}{sup 56}Fe relative to igneous rocks) varies from +1{per_thousand} for weathering residues like soils and clays, to -3{per_thousand} for dissolved Fe in streams. These measurements confirm that weathering processes produce substantial fractionation of Fe isotopes in the modern oxidizing Earth surface environment. The results imply that biologically-mediated processes, which preferentially mobilize light Fe isotopes, are critical to Fe chemistry in weathering environments, and that the {delta}{sup 56}Fe of marine dissolved Fe should be variable and negative. Diagenetic reduction of Fe in marine sediments may also be a significant component of the global Fe isotope cycle. Iron isotopes provide a tracer for the influence of biological activity and oxygen in weathering processes through Earth history. Iron isotopic fractionation during weathering may have been smaller or absent in an oxygen-poor environment such as that of the early Precambrian Earth.

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

A solvent extraction technique for the isotopic measurement of dissolved copper in seawater

Energy Technology Data Exchange (ETDEWEB)

Thompson, Claire M., E-mail: claire.thompson@anu.edu.au; Ellwood, Michael J., E-mail: michael.ellwood@anu.edu.au; Wille, Martin, E-mail: martin.wille@uni-tuebingen.de

2013-05-02

Graphical abstract: -- Highlights: •A new sample preparation method for seawater copper isotopic analysis (δ{sup 65}Cu). •Solvent-extraction was used to pre-concentrate metals from seawater samples. •Anion-exchange was used to purify copper from the metal-rich extract. •δ{sup 65}Cu was measured in the north Tasman Sea. •Seawater δ{sup 65}Cu may be linked to marine biological activity. -- Abstract: Stable copper (Cu) isotope geochemistry provides a new perspective for investigating and understanding Cu speciation and biogeochemical Cu cycling in seawater. In this work, sample preparation for isotopic analysis employed solvent-extraction with amino pyrollidine dithiocarbamate/diethyl dithiocarbamate (APDC/DDC), coupled with a nitric acid back-extraction, to concentrate Cu from seawater. This was followed by Cu-purification using anion-exchange. This straightforward technique is high yielding and fractionation free for Cu and allows precise measurement of the seawater Cu isotopic composition using multi-collector inductively coupled plasma mass-spectrometry. A deep-sea profile measured in the oligotrophic north Tasman Sea shows fractionation in the Cu isotopic signature in the photic zone but is relatively homogenised at depth. A minima in the Cu isotopic profile correlates with the chlorophyll a maximum at the site. These results indicate that a range of processes are likely to fractionate stable Cu isotopes in seawater.

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

Fractionation of Pb and Cu in the fine fraction (landfill.

Science.gov (United States)

Kaczala, Fabio; Orupõld, Kaja; Augustsson, Anna; Burlakovs, Juris; Hogland, Marika; Bhatnagar, Amit; Hogland, William

2017-11-01

The fractionation of metals in the fine fraction (landfill was carried out to evaluate the metal (Pb and Cu) contents and their potential towards not only mobility but also possibilities of recovery/extraction. The fractionation followed the BCR (Community Bureau of Reference) sequential extraction, and the exchangeable (F1), reducible (F2), oxidizable (F3) and residual fractions were determined. The results showed that Pb was highly associated with the reducible (F2) and oxidizable (F3) fractions, suggesting the potential mobility of this metal mainly when in contact with oxygen, despite the low association with the exchangeable fraction (F1). Cu has also shown the potential for mobility when in contact with oxygen, since high associations with the oxidizable fraction (F3) were observed. On the other hand, the mobility of metals in excavated waste can be seen as beneficial considering the circular economy and recovery of such valuables back into the economy. To conclude, not only the total concentration of metals but also a better understanding of fractionation and in which form metals are bound is very important to bring information on how to manage the fine fraction from excavated waste both in terms of environmental impacts and also recovery of such valuables in the economy.

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.

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

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....

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.

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.

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

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

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.

Determination of Cd, Pb, Zn and Cu in Sediment Compartments by Sequential Extraction and Isotope Dilution Inductively Coupled Plasma Mass Spectrometry (ID-ICP-MS

Directory of Open Access Journals (Sweden)

Gardolinski Paulo C. F. C.

2002-01-01

Full Text Available Trace concentrations of Cd, Cu, Pb and Zn in four different sediment fractions extracted in sequence were determined by isotope dilution inductively coupled mass spectrometry (IDICPMS. The metals from each fraction were extracted following the sequential extraction procedure recommended by the Bureau Commun de Référence (BCR of the Commission of the European Communities. As an alternative to external calibration, the elements were quantified by spiking the extracted solutions with 112Cd, 63Cu, 208Pb and 66Zn and application of isotope dilution. The proposed approach was applied to a sample collected from a lake and two standard reference materials, NIST2704 river sediment from the National Institute of Standards & Technology and the BCR-277 estuarine sediment. Detection limits, for each extracted solution, varied from 0.31 to 0.53 mug L¹ for Cd, 0.92 to 2.9 mug L¹ for Cu, 0.22 to 1.1 mug L¹ for Pb and 1.3 to 7.6 mug L¹ for Zn. The sum of the metals concentration in the different fractions was compatible with 95% confidence level found amounts obtained with complete digestion of the samples and with the certified values of the standard reference materials.

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

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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

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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.

Fe and Cu stable isotopes in archeological human bones and their relationship to sex.

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Jaouen, Klervia; Balter, Vincent; Herrscher, Estelle; Lamboux, Aline; Telouk, Philippe; Albarède, Francis

2012-07-01

Accurate sex assignment of ancient human remains usually relies on the availability of coxal bones or well-preserved DNA. Iron (Fe) and copper (Cu) stable isotope compositions ((56)Fe/(54)Fe and (65)Cu/(63)Cu, respectively) were recently measured in modern human blood, and an unexpected result was the discovery of a (56)Fe-depletion and a (65)Cu-enrichment in men's blood compared to women's blood. Bones, being pervasively irrigated by blood, are expected to retain the (56)Fe/(54)Fe and (65)Cu/(63)Cu signature of blood, which in turn is useful for determining the sex of ancient bones. Here, we report the (56)Fe/(54)Fe, (65)Cu/(63)Cu, and (66)Zn/(64)Zn ratios from a suite of well-preserved phalanxes (n = 43) belonging to individuals buried in the 17th and 18th centuries at the necropolis of Saint-Laurent de Grenoble, France, and for which the sex was independently estimated from pelvic bone morphology. The metals were purified from the bone matrix by liquid chromatography on ion exchange resin and the isotope compositions were measured by multiple-collector inductively coupled plasma mass spectrometry. The results show that, as expected from literature data on blood, male bone iron is depleted in (56)Fe and enriched in (65)Cu relative to female. No sex difference is found in the (66)Zn/(64)Zn ratios of bone. The concentration and isotopic data show no evidence of soil contamination. Four samples of five (77%) can be assigned their correct sex, a result comparable to sex assignment using Fe and Cu isotopes in blood (81%). Isotopic analysis of metals may therefore represent a valid method of sex assignment applicable to incomplete human remains. Copyright © 2012 Wiley Periodicals, Inc.

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

Natural fractionation of uranium isotopes

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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

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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.

New Production Routes for Medical Isotopes 64Cu and 67Cu Using Accelerator Neutrons

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Kin, Tadahiro; Nagai, Yasuki; Iwamoto, Nobuyuki; Minato, Futoshi; Iwamoto, Osamu; Hatsukawa, Yuichi; Segawa, Mariko; Harada, Hideo; Konno, Chikara; Ochiai, Kentaro; Takakura, Kosuke

2013-03-01

We have measured the activation cross sections producing 64Cu and 67Cu, promising medical radioisotopes for molecular imaging and radioimmunotherapy, by bombarding a natural zinc sample with 14 MeV neutrons. We estimated the production yields of 64Cu and 67Cu by fast neutrons from \\text{natC(d,n) with 40 MeV 5 mA deuterons. We used the present result together with the evaluated cross section of Zn isotopes. The calculated 64Cu yield is 1.8 TBq (175 g 64Zn) for 12 h of irradiation; the yields of 67Cu by 67Zn(n,p)67Cu and 68Zn(n,x)67Cu were 249 GBq (184 g 67Zn) and 287 GBq (186 g 68Zn) at the end of 2 days of irradiation, respectively. From the results, we proposed a new route to produce 67Cu with very little radionuclide impurity via the 68Zn(n,x)67Cu reaction, and showed the 64Zn(n,p)64Cu reaction to be a promising route to produce 64Cu. Both 67Cu and 64Cu are noted to be produced using fast neutrons.

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

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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?...

Effect of 67Cu and 99Mo labeled tetrathiomolybdate on the distribution of 67Cu, Cu, and 99Mo in bile fractions in sheep

International Nuclear Information System (INIS)

Gooneratne, R.; Laarveld, B.; Christensen, D.

1989-01-01

The effect of intravenous administration of 67 Cu and 99 Mo labeled tetrathiomolybdate (TTM) on the appearance of 67 Cu, stable Cu, and 99 Mo in gel chromatographic fractions of bile was examined in sheep fed either 5 or 35 mg Cu kg-1 DM. Peak excretory periods of biliary 67 Cu, stable Cu, and 99 Mo were observed at 30 min-1.25 hr, 2-3 hr, and 11-13 hr after 67 Cu and after 99 Mo labeled TTM. Sephadex G-75 gel filtration of bile samples collected at 1, 3, and 12 hr after 67 Cu administration revealed two major protein peaks of molecular weights of greater than 80,000 (peak I) and 7,000 (peak II) containing both 67 Cu and Cu. But the ratio of 67 Cu in the two peaks varied with time of bile collection. The ratio of areas of peak I:II 1 hr after 67 Cu administration was approximately 0.48; at 3 hr, 0.62, and at 12 hr 1.35. Tetrathiomolybdate administration increased both 67 Cu and stable Cu in bile by severalfold and induced a major shift of Cu into the higher molecular weight protein fraction. The experiments confirm the effectiveness of TTM as a ''decoppering'' agent. Furthermore, TTM not only promoted bile Cu excretion, but it also increased the incorporation of Cu into the macromolecular fraction. This may limit enterohepatic circulation of biliary Cu and thereby cause an overall Cu depletion and a negative Cu balance

Evaporation Induced Oxygen Isotope Fractionation in Impact Ejecta

Science.gov (United States)

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

Science.gov (United States)

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

Mathematical modeling and multicriterion optimization for photonuclear production of the 67cu isotope

International Nuclear Information System (INIS)

Dikij, N.P.; Rudychev, Y.V.; Fedorchenko, D.V.; Khazhmuradov, M.A.

2014-01-01

This paper considers a method for 67 Cu isotope production using electron bremsstrahlung by the 68 Zn(gamma, p) 67 Cu reaction. The facility for 67 Cu isotope production contains an electron accelerator, electron-gamma converter and zinc target. To optimize this facility we developed three-dimensional model of the converter and the target. Using this model, we performed the mathematical modeling of zinc target irradiation and thermal-hydraulic processes inside the target for various parameters of the electron beam and converter configurations. For mathematical modeling of radiation processes we used the MCNPX software. Thermal-hydraulic simulation utilized the commercial SolidWorks software with Flow Simulation module. Mathematical modeling revealed that efficient 67 Cu isotope production needs smaller beam diameter and higher electron energy. Under these conditions target heat power also increases, thus additional cooling is necessary. If the beam diameter and the electron energy are fixed the most effective method to satisfy the operating parameters and retain an efficient isotope yield is to optimize photonuclear spectra of the target by variation of converter thickness. We developed an algorithm for multicriterion optimization and performed the optimization of the facility with account to coupled radiation and heat transfer processes.

Diffusion of transmutation isotope in YBaCuO ceramics

International Nuclear Information System (INIS)

Malkovich, R.Sh.

2005-01-01

The diffusion of a transmutation isotope generated in YBaCuO ceramics irradiated by high-energy charged particles is mathematically analyzed. The model is based on the assumption that copper isotope atoms created in subsurface layers of ceramic grains segregate at the grain boundaries in the course of subsequent annealing and then rapidly diffuse via intergranular regions in depth of the material and penetrate into the bulk of grains [ru

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)

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.

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.

Diffusion-driven magnesium and iron isotope fractionation in Hawaiian olivine

Science.gov (United States)

Teng, F.-Z.; Dauphas, N.; Helz, R.T.; Gao, S.; Huang, S.

2011-01-01

Diffusion plays an important role in Earth sciences to estimate the timescales of geological processes such as erosion, sediment burial, and magma cooling. In igneous systems, these diffusive processes are recorded in the form of crystal zoning. However, meaningful interpretation of these signatures is often hampered by the fact that they cannot be unambiguously ascribed to a single process (e.g., magmatic fractionation, diffusion limited transport in the crystal or in the liquid). Here we show that Mg and Fe isotope fractionations in olivine crystals can be used to trace diffusive processes in magmatic systems. Over sixty olivine fragments from Hawaiian basalts show isotopically fractionated Mg and Fe relative to basalts worldwide, with up to 0.4??? variation in 26Mg/24Mg ratios and 1.6??? variation in 56Fe/54Fe ratios. The linearly and negatively correlated Mg and Fe isotopic compositions [i.e., ??56Fe=(??3.3??0.3)????26Mg], co-variations of Mg and Fe isotopic compositions with Fe/Mg ratios of olivine fragments, and modeling results based on Mg and Fe elemental profiles demonstrate the coupled Mg and Fe isotope fractionation to be a manifestation of Mg-Fe inter-diffusion in zoned olivines during magmatic differentiation. This characteristic can be used to constrain the nature of mineral zoning in igneous and metamorphic rocks, and hence determine the residence times of crystals in magmas, the composition of primary melts, and the duration of metamorphic events. With improvements in methodology, in situ isotope mapping will become an essential tool of petrology to identify diffusion in crystals. ?? 2011 Elsevier B.V.

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

Science.gov (United States)

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

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.

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

The role of soil biogeochemistry in wine taste: Soil factors influencing grape elemental composition, photosynthetic biomarkers and Cu/Zn isotopic signature of Vitis vinifera

Science.gov (United States)

Blotevogel, Simon; Oliva, Priscia; Darrozes, José; Viers, Jérôme; Audry, Stéphane; Courjault-Radé, Pierre; Orgogozo, Laurent; Le Guedard, Marina; Schreck, Eva

2015-04-01

Understanding the influence of soil composition in wine taste is of great economic and environmental interest in France and around the world. Nevertheless the impact of soil composition on wine taste is still controversially discussed. Since inorganic soil components do not have a proper taste and do not enter the plant anyway, their influence needs to be induced by nutrient absorption and its impact on plant functioning and grape composition. Indeed recent development of geological tracers of origin proof the existence of soil chemical and isotopic signatures in wine. However, type and scale of the impact of soil composition on wine taste are not well understood yet, and little experimental evidence exists due to the complexity of mechanisms involved. Thus, to provide evidence for the impact of soil composition on grape composition and potentially wine taste, we studied soil and plant material from two relevant vineyards (Soave, Italia). On those two directly adjacent vineyards, two different wines are produced with the same plant material and cultivation techniques. The vineyards only differ by their underlying bedrock - limestone versus basaltic rock - and thus present suitable conditions for investigating the impact of soil composition on grapes and wine. Pedological and mineralogical parameters were analyzed for the two vineyards whereas chemical extractions (citrate, CaCl2) were performed to determine nutrient bioavailability in both soils. Elemental compositions were determined by ICP-MS analyses in different compartments (soils, vine leaves and grapes). Isotopic fractionation of Cu and Zn was investigated in various samples as source tracers and in order to better understand fractionation mechanisms involved. Finally, plant health was studied using the Omega-3 biomarker which determines the fatty acid composition in vine leaves, directly involved in photosynthetic processes. Results show that the vineyards are characterized by two different soil types due

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...

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.)

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

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)

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

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.

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.

Solid/solution Cu fractionations/speciation of a Cu contaminated soil after pilot-scale electrokinetic remediation and their relationships with soil microbial and enzyme activities

International Nuclear Information System (INIS)

Wang Quanying; Zhou Dongmei; Cang Long; Li Lianzhen; Wang Peng

2009-01-01

The aim of this study was to investigate the detailed metal speciation/fractionations of a Cu contaminated soil before and after electrokinetic remediation as well as their relationships with the soil microbial and enzyme activities. Significant changes in the exchangeable and adsorbed-Cu fractionations occurred after electrokinetic treatment, while labile soil Cu in the solution had a tendency to decrease from the anode to the cathode, and the soil free Cu 2+ ions were mainly accumulated in the sections close to the cathode. The results of regression analyses revealed that both the soil Cu speciation in solution phase and the Cu fractionations in solid phase could play important roles in the changes of the soil microbial and enzyme activities. Our findings suggest that the bioavailability of soil heavy metals and their ecotoxicological effects on the soil biota before and after electroremediation can be better understood in terms of their chemical speciation and fractionations. - The assessment of the roles of soil solution speciation and solid-phase fractionations in metal bioavailability after electrokinetic remediation deserves close attention.

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...

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

Steroid isotopic standards for gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS).

Science.gov (United States)

Zhang, Ying; Tobias, Herbert J; Brenna, J Thomas

2009-03-01

Carbon isotope ratio (CIR) analysis of urinary steroids using gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS) is a recognized test to detect illicit doping with synthetic testosterone. There are currently no universally used steroid isotopic standards (SIS). We adapted a protocol to prepare isotopically uniform steroids for use as a calibrant in GCC-IRMS that can be analyzed under the same conditions as used for steroids extracted from urine. Two separate SIS containing a mixture of steroids were created and coded CU/USADA 33-1 and CU/USADA 34-1, containing acetates and native steroids, respectively. CU/USADA 33-1 contains 5alpha-androstan-3beta-ol acetate (5alpha-A-AC), 5alpha-androstan-3alpha-ol-17-one acetate (androsterone acetate, A-AC), 5beta-androstan-3alpha-ol-11, 17-dione acetate (11-ketoetiocholanolone acetate, 11k-AC) and 5alpha-cholestane (Cne). CU/USADA 34-1 contains 5beta-androstan-3alpha-ol-17-one (etiocholanolone, E), 5alpha-androstan-3alpha-ol-17-one (androsterone, A), and 5beta-pregnane-3alpha, 20alpha-diol (5betaP). Each mixture was prepared and dispensed into a set of about 100 ampoules using a protocol carefully designed to minimize isotopic fractionation and contamination. A natural gas reference material, NIST RM 8559, traceable to the international standard Vienna PeeDee Belemnite (VPDB) was used to calibrate the SIS. Absolute delta(13)C(VPDB) and Deltadelta(13)C(VPDB) values from randomly selected ampoules from both SIS indicate uniformity of steroid isotopic composition within measurement reproducibility, SD(delta(13)C)<0.2 per thousand. This procedure for creation of isotopic steroid mixtures results in consistent standards with isotope ratios traceable to the relevant international reference material.

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

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...

Nuclear structure far from stability: the neutron-rich 69-79Cu isotopes

International Nuclear Information System (INIS)

Franchoo, Serge

2015-01-01

Far from stability, the nuclear structure that is predicted by the shell model is evolving. Old magic numbers disappear, while new ones appear. Our understanding of the underlying nuclear force that drives these changes is still incomplete. After a short overview across the nuclear chart, we discuss the strength functions of the shell-model orbitals in the neutron-rich copper isotopes towards the 78 Ni doubly-magic nucleus. These were measured in a 72 Zn(d, 3 He) 71 Cu proton pick-up reaction in inverse kinematics with a radioactive beam at the Ganil laboratory in France. We also present the latest results from a 80 Zn(p,2p) 79 Cu knockout experiment at Riken in Japan, leading to selective population of hole states in 79 Cu. Our findings show that the Z=28 shell gap in the neutron-rich copper isotopes is surprisingly steady against the addition of neutrons beyond N=40. (author)

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.

Iron Isotope Fractionation in Microbial and Non-Biological Precipitates, and the Human Body

Science.gov (United States)

von Blanckenburg, F.; Boettcher, M. E.; Hofmann, B.; Walczyk, T.

2001-12-01

We have investigated biotic and abiotic stable iron isotope fractionation pathways in experiments, the low-T natural environment, and the human body. Fe samples were analysed using a Nu Plasma Multicollector ICP-MS. All measured samples plot on the theoretically predicted exponential fractionation line in the Delta57Fe versus Delta56Fe space, demonstrating absence of ArN or ArO interferences. An experimental calibration of Fe isotope fractionation during abiotic formation of iron (III) oxyhydroxide and iron(II) minerals from aqueous solution resulted in significant differences: (a) During fast precipitation of FeOOH during alkalization of a Fe(III)Cl3 solution at room temperature the solid is only slightly enriched by about 0.1permil in 57Fe compared to the solution. (b) Slow precipitation of akaganeite (beta-FeOOH) from aqueous Fe(III)Cl3 solution leads to a depletion of 57Fe by about -2.2permil in the solid phase without a significant influence of temperature. (c) Precipitation of FeOOH during oxidation of aqueous Fe(II) solutions by oxygen yields an enrichment of up to 4.8permil in 57Fe in the solid phase. (d) Iron(II) carbonate precipitation between 20 and 60C leads to an almost negligible depletion in 57Fe compared to aqueous ferrous ions. Interpretation: Large enrichment of the heavy isotope is observed where Fe is oxidised, whereas small to interme-diate depletions of heavy Fe isotopes occur upon forma-tion of Fe-minerals without change in redox state. Addi-tionally, kinetic effects, the speciation of the aqueous solution, or the effect of crystal structures may have to be considered. Biotic isotope fractionation by microorganisms was investigated at two field sites. In a Fe mine (Gonzen, Switzerland), Fe-precipitating microbes (Gallionella ferrugina and Leptohrix ochtraceae) have formed Fe(III)-oxyhydroxides that are ca. 0.6permil heavier in Delta57Fe than the Fe-rich parent solutions. At Cady Mts, California, filamentous fabrics of goethite, thought to

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

Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology.

Science.gov (United States)

Balliana, Eleonora; Aramendía, Maite; Resano, Martin; Barbante, Carlo; Vanhaecke, Frank

2013-03-01

Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic

Cu-Zn-Pb multi isotopic characterization of a small watershed (Loire river basin, France)

Science.gov (United States)

Desaulty, A. M.; Millot, R.; Perret, S.; Bourrain, X.

2015-12-01

Combating metal pollution in surface water is a major environmental, public health and economic issue. Knowledge of the behavior of metals, such as copper (Cu), zinc (Zn) and lead (Pb) in sediments and dissolved load, is a key factor to improve the management of rivers. Recent advances in mass spectrometry related to the development of MC-ICPMS allow to analyze the isotopic composition of these elements, and previous studies show the effectiveness of isotopic analyses to determine the anthropogenic sources of pollution in environment. The goal of this study is to use the Cu-Zn-Pb multi-isotopic signature to track the pollutions in surface water, and to understand the complex processes causing the metals mobilization and transport in environment. More particularly we investigate the mechanisms of distribution between the dissolved load and particulate load, known to play an important role in the transport of metals through river systems. As case study, we chose a small watershed, poorly urbanized in the Loire river basin. Its spring is in a pristine area, while it is only impacted some kilometers further by the releases rich in metals coming from a hospital water treatment plant. First a sampling of these liquid effluents as well as dissolved load and sediment from upstream to downstream was realized and their concentrations and isotopic data were determined. Then to simulate a lot of potential natural and anthropogenic modifications of environmental conditions, we made sequential extraction protocol using various reagents on the sediments. Isotopic analyzes were performed also on the various extracting solutions. Isotopic ratios were measured using a Neptune MC-ICPMS at the BRGM, after a protocol of purification for Zn and Cu. The results showed that, these isotopic systematics reveal important informations about the mechanists of mobilization and transport of metals through river systems. However experiments performed under laboratory conditions will be necessary

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

Science.gov (United States)

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

2006-05-01

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

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

Predicting trace metal solubility and fractionation in Urban soils from isotopic exchangeability

International Nuclear Information System (INIS)

Mao, L.C.; Young, S.D.; Tye, A.M.; Bailey, E.H.

2017-01-01

Metal-salt amended soils (MA, n = 23), and historically-contaminated urban soils from two English cities (Urban, n = 50), were investigated to assess the effects of soil properties and contaminant source on metal lability and solubility. A stable isotope dilution method, with and without a resin purification step, was used to measure the lability of Cd, Cu, Ni, Pb and Zn. For all five metals in MA soils, lability (%E-values) could be reasonably well predicted from soil pH value with a simple logistic equation. However, there was evidence of continuing time-dependent fixation of Cd and Zn in the MA soils, following more than a decade of storage under air-dried conditions, mainly in high pH soils. All five metals in MA soils remained much more labile than in Urban soils, strongly indicating an effect of contaminant source on metal lability in the latter. Metal solubility was predicted for both sets of soil by the geochemical speciation model WHAM-VII, using E-value as an input variable. For soils with low metal solution concentrations, over-estimation of Cd, Ni and Zn solubility was associated with binding to the Fe oxide fraction while accurate prediction of Cu solubility was dependent on humic acid content. Lead solubility was most poorly described, especially in the Urban soils. Generally, slightly poorer estimation of metal solubility was observed in Urban soils, possibly due to a greater incidence of high pH values. The use of isotopically exchangeable metal to predict solubility is appropriate both for historically contaminated soils and where amendment with soluble forms of metal is used, as in toxicological trials. However, the major limitation to predicting solubility may lie with the accuracy of model input variables such as humic acid and Fe oxide contents where there is often a reliance on relatively crude analytical estimations of these variables. Trace metal reactivity in urban soils depends on both soil properties and the original source material

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...

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.

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...

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.

Stable Fe isotope fractionation during anaerobic microbial dissimilatory iron reduction at low pH

Science.gov (United States)

Chanda, P.; Amenabar, M. J.; Boyd, E. S.; Beard, B. L.; Johnson, C.

2017-12-01

In low-temperature anaerobic environments microbial dissimilatory iron reduction (DIR) plays an important role in Fe cycling. At neutral pH, sorption of aqueous Fe(II) (Fe(II)aq, produced by DIR) catalyzes isotopic exchange between Fe(II) and solid Fe(III), producing 56Fe/54Fe fractionations on the order of 3‰ during DIR[1,2,3]. At low pH, however, the absence of sorbed Fe(II) produces only limited abiologic isotopic exchange[4]. Here we investigated the scope of isotopic exchange between Fe(II)aq and ferric (hydr)oxides (ferrihydrite and goethite) and the associated stable Fe isotope fractionation during DIR by Acidianus strain DS80 at pH 3.0 and 80°C[5]. Over 19 days, 13% reduction of both minerals via microbial DIR was observed. The δ56Fe values of the fluid varied from -2.31 to -1.63‰ (ferrihydrite) and -0.45 to 0.02‰ (goethite). Partial leaching of bulk solid from each reactor with dilute HCl showed no sorption of Fe(II), and the surface layers of the solids were composed of Fe(III) with high δ56Fe values (ferrihydrite: 0.20 to 0.48‰ and goethite: 1.20 to 1.30‰). These results contrast with the lack of Fe isotope exchange in abiologic low-pH systems and indicate a key role for biology in catalyzing Fe isotope exchange between Fe(II)aq and Fe(III) solids, despite the absence of sorbed Fe(II). The estimated fractionation factor (ΔFeFe(III) -Fe(II)aq 2.6‰) from leaching of ferrihydrite is similar to the abiologic equilibrium fractionation factor ( 3.0‰)[3]. The fractionation factor (ΔFeFe(III) -Fe(II)aq 2.0‰) for goethite is higher than the abiologic fractionation factor ( 1.05‰)[2], but is consistent with the previously proposed "distorted surface layer" of goethite produced during the exchange with Fe(II)aq at neutral pH[1]. This study indicates that significant variations in Fe isotope compositions may be produced in low-pH environments where biological cycling of Fe occurs, in contrast to the expected lack of isotopic fractionation in

Soluble/insoluble (dilute-HCl-extractable fractionation of Cd, Pb and Cu in Antarctic snow and its relationship with metal fractionations in the aerosol

Directory of Open Access Journals (Sweden)

Annibaldi A.

2013-04-01

Full Text Available A chemical fractionation methodology for determination of the (water soluble and the insoluble (dilute-HCl-extractable fractions of Cd, Pb and Cu in Antarctic snow was set-up and verified for the additivity of the two fractions detected. Molten samples were filtrated and the water-insoluble fraction was extracted by dilute ultrapure HCl (pH ~1.5. Metal determinations were carried out in the two fractions by square wave anodic stripping voltammetry. The total metal concentrations in samples collected in the 2000–2001 austral summer in a clean area (Faraglione Camp in the neighbourhood of the Mario Zucchelli Italian Station were of the order of Cd 10-20 pg g−1, Pb 20–40 pg g−1, Cu 60–120 pg g−1 with an approximate equidistribution between soluble and insoluble fractions. These fractionations compare well (and show a quite consistent temporal trend with those observed in the aerosol samples collected in the same area/period and confirm the close relationship between metal distributions in snow/ice and in the aerosol. At the station metal concentrations increase due to anthropic contribution and the distribution changes with Cd predominantly present in the soluble fraction (~80%, while Pb and Cu are more concentrated in the insoluble fraction, 70–80% and ~70%, respectively.

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.)

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.

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

Isotope effect study of κ-(BEDT-TTF)2Cu(NCS)2: Labeling in the anion

International Nuclear Information System (INIS)

Kini, A.M.; Wang, H.H.; Schlueter, J.A.

1995-01-01

Since the initial discovery of organic superconductivity in 1979, a large number of organic superconductors have now been synthesized. However, the mechanism of electron-pairing in these novel superconductors has remained largely unresolved. Isotope effect studies constitute an important experimental tool for the investigation of whether or not the electron-pairing mechanism in organic superconductors is phonon-mediated, as in conventional superconductors. Recent isotope effect studies in the authors' laboratory, involving seven different isotopically labeled BEDT-TTF (or ET) derivatives, have demonstrated the following: (1) intramolecular phonon modes involving C double-bond C and Csingle bondS stretching vibrations in the ET donor molecule are not the dominant mediators of electron-pairing, and (2) in κ-(ET) 2 Cu(NCS) 2 , there exist two competing isotope effects--a normal mass effect, i.e., lowering of T c upon isotopic labeling, when the ET molecular mass is increased by concurrent 13 C and 34 S labeling, in addition to an inverse isotope effect upon deuterium labeling in ET. It is of great interest to investigate if there is an isotope effect when the charge-compensating anions, which are also located within the non-conducting layer in the superconducting cation-radical salts, are isotopically labeled. The existence of an isotope effect when the anions are labeled would be indicative of electron-pairing with the mediation of vibrational frequencies associated with the anions. In this paper, the authors present the results of the first isotope effect study in which isotopic labeling in the anion portion of κ-(ET) 2 Cu(NCS) 2 is carried out. The authors find no isotope effect when the carbon and nitrogen atoms of the thiocyanate groups in the anion are replaced with 13 C and 15 N isotopes

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

Oxygen isotope effect in YBa2Cu3O7 prepared by burning YBa2Cu3 in 16O and 18O

Science.gov (United States)

Yvon, Pascal J.; Schwarz, R. B.; Pierce, C. B.; Bernardez, L.; Conners, A.; Meisenheimer, R.

1989-04-01

We prepared YBa2Cu3 powder by ball milling a 2:1 molar mixture of the intermetallics BaCu and CuY. We synthesized YBa2Cu3(16O)7-x and YBa2Cu3(18O)7-x by oxidizing the YBa2Cu3 powder in 16O and 18O. The 16O/18O ratios were determined by laser-ionization and sputtering-ionization mass spectroscopy. The YBa2Cu3(160)7-x sample had 99.8 at. %16O, and the YBa2Cu3(18O)7-x sample had 96.5 at. %18O. Susceptibility measurements of the superconducting transition temperature (Tc=91.7 K for 16O; half-point transition at 84 K show an isotope effect of 0.4+/-0.1 K.

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

Contrasting Cu-Au and Sn-W Granite Metallogeny through the Zircon Geochemical and Isotopic Record

Science.gov (United States)

Gardiner, Nicholas; Hawkesworth, Chris; Robb, Laurence; Whitehouse, Martin; Roberts, Nick; Kirkland, Chris

2017-04-01

Magmatic genesis and evolution - mediated by geodynamic setting - exert a primary control on the propensity of granites to be metal fertile. A revolution in our understanding of these petrogenetic processes has been made through a range of mineral-based tools, most notably the common accessory mineral zircon. There is consequently considerable interest in whether the geochemical and isotopic compositions of zircon can be applied to metallogenic problems. The paired magmatic belts of Myanmar have broadly contrasting metallogenic affinities (Sn-W versus Cu-Au), and are interpreted to have formed on the accretionary margin of the subducting Neo-Tethys Ocean. They therefore present the opportunity to geochemically compare and contrast the zircon compositions in two end-member types of granite-hosted mineral deposits generated in collisional settings. We present an integrated zircon isotope (U-Pb, Lu-Hf, O) and trace element dataset that fingerprint: (a) source; (b) redox conditions; and (c) degree of fractionation. These variables all impact on magma fertility, and our key question to address is whether they can be reliably traced and calibrated within the Myanmar zircon record. Granitoid-hosted zircons from the I-type copper arc have juvenile ɛHf (+7 to +12) and mantle-like δ18O (5.3 ‰), whereas zircons from the S-type tin belt have low ɛHf (-7 to -13) and heavier δ18O (6.2-7.7 ‰). Plotting Hf versus U/Yb reaffirms that the tin belt magmas contain greater crustal contributions than the copper arc rocks. Links between whole rock Rb/Sr and zircon Eu/Eu* highlights that the latter can be used to monitor magma fractionation in systems that crystallize plagioclase (low Sr/Y). Ce/Ce* and Eu/Eu* in zircon are thus sensitive to redox and fractionation respectively, and can be used to evaluate the sensitivity of zircons to the metallogenic affinity of their host rocks. Tin contents that exceed the solubility limit are required in order to make a magmatic

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

Interplay between Single-Particle and Collective Effects in the Odd-A Cu Isotopes beyond N=40

CERN Document Server

Stefanescu, I; Balabanski, D L; Blasi, N; Blazhev, A; Bree, N; Cederkäll, J; Cocolios, T E; Davinson, T; Diriken, J; Eberth, J; Ekström, A; Fedorov, D; Fedosseev, V; Fraile-Prieto, L M; Franchoo, S; Gladnishki, K; Huyse, M; Ivanov, O; Ivanov, I; Iwanicki, J; Jolie, J; Konstantinopoulos, T; Kröll, Th; Krücken, R; Köster, U; Lagoyannis, A; Lo Bianco, G; Maierbeck, P; Marsh, B A; Napiorkowski, P; Patronis, N; Pauwels, D; Rainovski, G; Reiter, P; Riisager, K; Seliverstov, M; Sletten, G; Van de Walle, J; Van Duppen, P; Voulot, D; Warr, N; Wenander, F; Wrzosek, K

2008-01-01

Collective properties of the low-lying levels in the odd-A 67–73Cu were investigated by Coulomb excitation with radioactive beams. The beams were produced at ISOLDE and postaccelerated by REX-ISOLDE up to 2.99  MeV/u. In 67,69Cu, low-lying 1/2-, 5/2-, and 7/2- states were populated. In 71,73Cu, besides the known transitions deexciting the single-particle-like 5/2- and core-coupled 7/2- levels, γ rays of 454 and 135 keV, respectively, were observed for the first time. Based on a reanalysis of β-decay work and comparison with the systematics, a spin 1/2- is suggested for these excited states. Three B(E2) values were determined in each of the four isotopes. The results indicate a significant change in the structure of the odd-A Cu isotopes beyond N=40 where single-particle-like and collective levels are suggested to coexist at very low excitation energies.

Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

Science.gov (United States)

Rolison, John M.; Stirling, Claudine H.; Middag, Rob; Gault-Ringold, Melanie; George, Ejin; Rijkenberg, Micha J. A.

2018-04-01

The chemical response of the Precambrian oceans to rising atmospheric O2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shift in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the 'Great Oxidation Event' around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise

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

The preliminary result of the δ65Cu and δ34S values of major ore minerals in the Erdenetiin-Ovoo Cu-Mo porphyry deposit, Northern Mongolia

Science.gov (United States)

KIM, Y.; Lee, I.; Oyungerel, S.; Jargal, L.; Tsedenbal, T.; Ryu, J. S.

2016-12-01

The copper isotope (δ65Cu) and sulfur isotope (δ34S) compositions of major ore minerals from the Erdenetiin-Ovoo Cu-Mo porphyry deposit were measured to trace sources of copper and sulfur, and to evaluate the precipitation environment of ore minerals. The major ore minerals are pyrite, chalcopyrite, molybdenite and chalcocite developed in the QSP (Quartz-Sericite-Pyrite) alteration zone. The sulfide minerals such as sphalerite and covellite, and carbonate ore minerals like malachite, azurite are also identified. The copper isotope ratios (65Cu/63Cu) of copper ore minerals (chalcopyrite, chalcocite, malachite, azurite, covellite and chrysocolla) were analyzed by the MC-ICPMS in KBSI located in Ochang, South Korea. The measured δ65Cu values relative to NIST 976 range from -1.01 ‰ to 5.76 ‰. The average δ65Cu values of sulfide minerals such as chalcopyrite (1.03 ‰), chalcocite (0.62 ‰) and covellite (0.51 ‰) seem to be relatively lower than those of carbonate and silicate Cu minerals such as malachite (0.24 ‰), azurite (2.17 ‰) and chrysocolla (5.76 ‰). The sulfur isotope ratios (34S/32S) of major sulfide minerals were measured by EA-CF-IRMS (Elemental Analyzer - Continuous Flow - Isotope Ratio Mass Spectrometer) in NCIRF, Seoul National University. The average δ34SV-CDT value is -1.1 ‰ indicating the magmatic signature of sulfur. There is the difference of δ34S values between sulfide minerals. While the δ34S values of pyrite, chalcopyrite and molybdenite range from -0.9 to 0.8 ‰, the δ34S values of chalcocite range from -2.6 ‰ to -1.4 ‰. These lower values might be attributed to the sulfur isotope fractionation during its precipitation.

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.

Multi isotopic characterization (Li-Cu-Zn-Pb) of waste waters pollution in a small watershed (Loire River basin, France)

Science.gov (United States)

Millot, R.; Desaulty, A. M.; Perret, S.; Bourrain, X.

2016-12-01

The goal of this study is to use multi-isotopic signature to track the pollution in surface waters, and to understand the complex processes causing the metals mobilization and transport in the environment. In the present study, we investigate waste water releases from a hospital water treatment plant and its potential impact in a small river basin near Orléans in France (Egoutier watershed: 15 km²and 5 km long). We decided to monitor this small watershed which is poorly urbanized in the Loire river basin. Its spring is located in a pristine area (forested area), while it is only impacted some kilometers further by the releases rich in metals coming from a hospital water treatment plant. A sampling of these liquid effluents as well as dissolved load and sediment from upstream to downstream was realized and their concentrations and isotopic data were determined. Isotopic ratios were measured using a MC-ICP-MS at BRGM, after a specific protocol of purification for each isotopic systematics. Lithium isotopic compositions are rather homogeneous in river waters along the main course of the stream. The waste water signal is very different from the natural background with significant heavy lithium contribution (high δ7Li). Lead isotopic compositions are rather homogenous in river waters and sediments with values close to geologic background. For Zn, the sediments with high concentrations and depleted isotopic compositions (low δ66Zn), typical of an anthropic pollution, are strongly impacted. The analyses of Cu isotopes in sediments show the impact of waster waters, but also isotopic fractionations due to redox processes in the watershed. To better understand these processes controlling the release of metals in water, sequential extractions on sediments are in progress under laboratory conditions and will provide important constraints for metal distribution in this river basin.

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

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)

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.

Heavy element stable isotope ratios. Analytical approaches and applications

International Nuclear Information System (INIS)

Tanimizu, Masaharu; Sohrin, Yoshiki; Hirata, Takafumi

2013-01-01

Continuous developments in inorganic mass spectrometry techniques, including a combination of an inductively coupled plasma ion source and a magnetic sector-based mass spectrometer equipped with a multiple-collector array, have revolutionized the precision of isotope ratio measurements, and applications of inorganic mass spectrometry for biochemistry, geochemistry, and marine chemistry are beginning to appear on the horizon. Series of pioneering studies have revealed that natural stable isotope fractionations of many elements heavier than S (e.g., Fe, Cu, Zn, Sr, Ce, Nd, Mo, Cd, W, Tl, and U) are common on Earth, and it had been widely recognized that most physicochemical reactions or biochemical processes induce mass-dependent isotope fractionation. The variations in isotope ratios of the heavy elements can provide new insights into past and present biochemical and geochemical processes. To achieve this, the analytical community is actively solving problems such as spectral interference, mass discrimination drift, chemical separation and purification, and reduction of the contamination of analytes. This article describes data calibration and standardization protocols to allow interlaboratory comparisons or to maintain traceability of data, and basic principles of isotope fractionation in nature, together with high-selectivity and high-yield chemical separation and purification techniques for stable isotope studies.

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.

Variability in carbon isotope fractionation of trichloroethene during degradation by persulfate activated with zero-valent iron: Effects of inorganic anions

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); 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)

2016-04-01

Stable carbon isotope analysis has the potential to be used for assessing the performance of in situ remediation of organic contaminants. Successful application of this isotope technique requires understanding the magnitude and variability in carbon isotope fractionation associated with the reactions under consideration. This study investigated the influence of inorganic anions (sulfate, bicarbonate, and chloride) on carbon isotope fractionation of trichloroethene (TCE) during its degradation by persulfate activated with zero-valent iron. The results demonstrated that the significant carbon isotope fractionation (enrichment factors ε ranging from − 3.4 ± 0.3 to − 4.3 ± 0.3 ‰) was independent on the zero-iron dosage, sulfate concentration, and bicarbonate concentration. However, the ε values (ranging from − 7.0 ± 0.4 to − 13.6 ± 1.2 ‰) were dependent on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during TCE degradation by persulfate activated with zero-valent iron. The dependence of ε values on chloride concentration, indicated that TCE degradation mechanisms may be different from the degradation mechanism caused by sulfate radical (SO{sub 4}·{sup −}). Ignoring the effect of chloride on ε value may cause numerous uncertainties in quantitative assessment of the performance of the in situ chemical oxidation (ISCO). - Highlights: • Significant C isotope fractionation for TCE degradation by Fe{sup 0} activated persulfate. • The enrichment factors was independent of Fe{sup 0}, SO{sub 4}{sup 2−}, or HCO{sub 3}{sup −} concentration. • Cl{sup −} significantly influenced the carbon isotope fractionation.

Variability in carbon isotope fractionation of trichloroethene during degradation by persulfate activated with zero-valent iron: Effects of inorganic anions

International Nuclear Information System (INIS)

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

2016-01-01

Stable carbon isotope analysis has the potential to be used for assessing the performance of in situ remediation of organic contaminants. Successful application of this isotope technique requires understanding the magnitude and variability in carbon isotope fractionation associated with the reactions under consideration. This study investigated the influence of inorganic anions (sulfate, bicarbonate, and chloride) on carbon isotope fractionation of trichloroethene (TCE) during its degradation by persulfate activated with zero-valent iron. The results demonstrated that the significant carbon isotope fractionation (enrichment factors ε ranging from − 3.4 ± 0.3 to − 4.3 ± 0.3 ‰) was independent on the zero-iron dosage, sulfate concentration, and bicarbonate concentration. However, the ε values (ranging from − 7.0 ± 0.4 to − 13.6 ± 1.2 ‰) were dependent on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during TCE degradation by persulfate activated with zero-valent iron. The dependence of ε values on chloride concentration, indicated that TCE degradation mechanisms may be different from the degradation mechanism caused by sulfate radical (SO_4·"−). Ignoring the effect of chloride on ε value may cause numerous uncertainties in quantitative assessment of the performance of the in situ chemical oxidation (ISCO). - Highlights: • Significant C isotope fractionation for TCE degradation by Fe"0 activated persulfate. • The enrichment factors was independent of Fe"0, SO_4"2"−, or HCO_3"− concentration. • Cl"− significantly influenced the carbon isotope fractionation.

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

Copper absorption from foods labelled intrinsically and extrinsically with Cu-65 stable isotope.

Science.gov (United States)

Harvey, L J; Dainty, J R; Beattie, J H; Majsak-Newman, G; Wharf, S G; Reid, M D; Fairweather-Tait, S J

2005-03-01

To determine copper absorption from copper containing foods labelled either intrinsically or extrinsically with a highly enriched Cu-65 stable isotope label. A longitudinal cross-over study. The study was conducted at the Institute of Food Research, Human Nutrition Unit, Norwich, UK. Subjects were recruited locally via advertisements placed around the Norwich Research Park. A total of 10 volunteers (nine female, one male) took part in the study, but not all volunteers completed each of the test meals. A highly enriched Cu-65 stable isotope label was administered to volunteers in the form of a reference dose or in breakfast test meals consisting of red wine, soya beans, mushrooms or sunflower seeds. Faecal monitoring and mass spectrometry techniques were used to estimate the relative quantities of copper absorbed from the different test meals. True copper absorption from the reference dose (54%) was similar to extrinsically labelled red wine (49%) and intrinsically labelled sunflower seeds (52%), but significantly higher than extrinsically labelled mushrooms (35%), intrinsically (29%) and extrinsically (15%) labelled soya beans and extrinsically labelled sunflower seed (32%) test meals. The use of Cu-65 extrinsic labels in copper absorption studies requires validation according to the food being examined; intrinsic and extrinsic labelling produced significantly different results for sunflower seeds.

Nd isotopes and crustal growth rate

International Nuclear Information System (INIS)

Albarede, F.

1988-01-01

Sm/Nd isotopic constraints on crustal growth is discussed. In order to constrain Sm/Nd fractionation between continental crust and depleted mantle, an extensive data base of isotopic measurements (assumed to be adequately representative of continental crust) was compiled. The results imply that the evolution of depleted mantles was roughly linear, with no major discontinuities over the course of geologic time. This is different from other determinations of depleting mantle evolution, which show nonlinear behavior. The Sm/Nd evolution lines for continental crust and depleted mantle intersect between 3.8 to 4.0 Ga, which may indicate that the onset of continental growth was later than 4.5 Ga. A mathematical model is described, the results of which imply that time integrated crustal additions from the mantle are about 1.8 to 2.5 cu km/a, whereas crustal subtractions by sediment recycling are about 0.6 to 1.5 cu km/a. This results in a net time integrated crustal growth rate of about 1 cu km/a, which is similar to present day rates determined, for example, by Reymer and Schubert

Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

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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

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

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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

Non-traditional Stable Isotope Systematics of Seafloor Hydrothermal Systems

Science.gov (United States)

Rouxel, O. J.

2009-05-01

Seafloor hydrothermal activity at mid-ocean ridges is one of the fundamental processes controlling the chemistry of the oceans and the altered oceanic crust. Past studies have demonstrated the complexity and diversity of seafloor hydrothermal systems and have highlighted the importance of subsurface environments in controlling the composition of hydrothermal fluids and mineralization types. Traditionally, the behavior of metals in seafloor hydrothermal systems have been investigated by integrating results from laboratory studies, theoretical models, mineralogy and fluid and mineral chemistry. Isotope ratios of various metals and metalloids, such as Fe, Cu, Zn, Se, Cd and Sb have recently provided new approaches for the study of seafloor hydrothermal systems. Despite these initial investigations, the cause of the isotopic variability of these elements remains poorly constrained. We have little understanding of the isotope variations between vent types (black or white smokers) as well as the influence of source rock composition (basalt, felsic or ultrabasic rocks) and alteration types. Here, I will review and present new results of metal isotope systematics of seafloor hydrothermal systems, in particular: (1) determination of empirical isotope fractionation factors for Zn, Fe and Cu-isotopes through isotopic analysis of mono-mineralic sulfide grains lining the internal chimney wall in contact with hydrothermal fluid; (2) comparison of Fe- and Cu-isotope signatures of vent fluids from mid- oceanic and back-arc hydrothermal fields, spanning wide ranges of pH, temperature, metal concentrations and contributions of magmatic fluids enriched in SO2. Ultimately, the use of complementary non-traditional stable isotope systems may help identify and constrain the complex interactions between fluids,minerals, and organisms in seafloor hydrothermal systems.

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.

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

Directory of Open Access Journals (Sweden)

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.

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

Natural variations of copper and sulfur stable isotopes in blood of hepatocellular carcinoma patients

Science.gov (United States)

Balter, Vincent; Nogueira da Costa, Andre; Paky Bondanese, Victor; Jaouen, Klervia; Lamboux, Aline; Sangrajrang, Suleeporn; Vincent, Nicolas; Fourel, François; Télouk, Philippe; Gigou, Michelle; Lécuyer, Christophe; Srivatanakul, Petcharin; Bréchot, Christian; Albarède, Francis; Hainaut, Pierre

2015-01-01

The widespread hypoxic conditions of the tumor microenvironment can impair the metabolism of bioessential elements such as copper and sulfur, notably by changing their redox state and, as a consequence, their ability to bind specific molecules. Because competing redox state is known to drive isotopic fractionation, we have used here the stable isotope compositions of copper (65Cu/63Cu) and sulfur (34S/32S) in the blood of patients with hepatocellular carcinoma (HCC) as a tool to explore the cancer-driven copper and sulfur imbalances. We report that copper is 63Cu-enriched by ∼0.4‰ and sulfur is 32S-enriched by ∼1.5‰ in the blood of patients compared with that of control subjects. As expected, HCC patients have more copper in red blood cells and serum compared with control subjects. However, the isotopic signature of this blood extra copper burden is not in favor of a dietary origin but rather suggests a reallocation in the body of copper bound to cysteine-rich proteins such as metallothioneins. The magnitude of the sulfur isotope effect is similar in red blood cells and serum of HCC patients, implying that sulfur fractionation is systemic. The 32S-enrichment of sulfur in the blood of HCC patients is compatible with the notion that sulfur partly originates from tumor-derived sulfides. The measurement of natural variations of stable isotope compositions, using techniques developed in the field of Earth sciences, can provide new means to detect and quantify cancer metabolic changes and provide insights into underlying mechanisms.

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.

Neutron-rich isotopes around the r-process 'waiting-point' nuclei 2979Cu50 and 3080Zn50

International Nuclear Information System (INIS)

Kratz, K.L.; Gabelmann, H.; Pfeiffer, B.; Woehr, A.

1991-01-01

Beta-decay half-lives (T 1/2 ) and delayed-neutron emission probabilities (P n ) of very neutron-rich Cu to As nuclei have been measured, among them the new isotopes 77 Cu 48 , 79 Cu 50 , 81 Zn 51 and 84 Ga 53 . With the T 1/2 and P n -values of now four N≅50 'waiting-point' nuclei known, our hypothesis that the r-process has attained a local β-flow equilibrium around A≅80 is further strengthened. (orig.)

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

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

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

Science.gov (United States)

Summers, David P.

2003-01-01

One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per

Normal variations in the isotopic composition of metabolically relevant transition metals in human blood

Science.gov (United States)

Van Heghe, L.; Cloquet, C.; Vanhaecke, F.

2012-04-01

Cu, Fe and Zn are transition metals with great catalytic, structural and regulating importance in the human body. Hence, an aberrant metabolism of these elements can have serious implications on the health of a person. It is assumed that, due to differences in isotope fractionation, the isotopic composition of these elements in whole blood of patients can be different from that in blood of healthy subjects. Therefore, isotopic analysis of the element affected by the disease can be a promising approach for early diagnosis. A method for isotopic analysis of Cu, Fe and Zn in human whole blood was developed. The simultaneous chromatographic isolation of these elements and the conditions for isotope ratio measurement via multi-collector ICP - mass spectrometry (MC-ICP-MS) were optimized. So far, only whole blood of supposedly healthy volunteers (reference population) was analyzed. Results for Fe confirmed the known differences in isotopic composition between male and female blood. It is also shown that other parameters can have influence as well, e.g., the isotopic composition of Zn seems to be governed by the diet.

Effects of trace element concentration on enzyme controlled stable isotope fractionation during aerobic biodegradation of toluene.

Science.gov (United States)

Mancini, Silvia A; Hirschorn, Sarah K; Elsner, Martin; Lacrampe-Couloume, Georges; Sleep, Brent E; Edwards, Elizabeth A; Lollar, Barbara Sherwood

2006-12-15

The effects of iron concentration on carbon and hydrogen isotopic fractionation during aerobic biodegradation of toluene by Pseudomonas putida mt-2 were investigated using a low iron medium and two different high iron media. Mean carbon enrichment factors (epsilonc) determined using a Rayleigh isotopic model were smaller in culture grown under high iron conditions (epsilonc = -1.7+/-0.1%) compared to low iron conditions (epsilonc = -2.5+/-0.3%). Mean hydrogen enrichment factors (epsilonH) were also significantly smaller for culture grown under high iron conditions (epsilonH = -77 +/-4%) versus low iron conditions (EpsilonH = -159+/-11%). A mechanistic model for enzyme kinetics was used to relate differences in the magnitude of isotopic fractionation for low iron versus high iron cultures to the efficiency of the enzymatic transformation. The increase of carbon and hydrogen enrichment factors at low iron concentrations suggests a slower enzyme-catalyzed substrate conversion step (k2) relative to the enzyme-substrate binding step (k-l) at low iron concentration. While the observed differences were subtle and, hence, do not significantly impact the ability to use stable isotope analysis in the field, these results demonstrated that resolvable differences in carbon and hydrogen isotopic fractionation were related to low and high iron conditions. This novel result highlights the need to further investigate the effects of other trace elements known to be key components of biodegradative enzymes.

Iron isotope fractionation during hydrothermal ore deposition and alteration

Science.gov (United States)

Markl, Gregor; von Blanckenburg, Friedhelm; Wagner, Thomas

2006-06-01

Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.

Application of the stable-isotope system to the study of sources and fate of Hg in the environment: A review

International Nuclear Information System (INIS)

Yin Runsheng; Feng Xinbin; Shi Wenfang

2010-01-01

With the improvement of analytical methods and the development of multiple-collector inductively coupled plasma-mass spectrometry (MC-ICP/MS), research on non-traditional stable isotope (Cu, Zn, Fe, Se, Mo, Cr, Hg) in geochemistry has made tremendous progress in the past decade. Recent studies have demonstrated that both organic and inorganic reactions may cause Hg isotope fractionation, and variations of Hg isotopic composition in the environment have been successfully employed to explain Hg pollution history, Hg sources and tracking Hg pathways in nature. Furthermore, Hg isotopic fractionation studies can be a powerful tool in the calibration of global Hg cycling models. Stable isotope geochemistry of Hg is therefore becoming a new frontier subject in earth sciences. Based on summarizing previous research, this paper outlines the main advances in the study of Hg stable isotopes with particular emphasis placed on a brief explanation of Hg isotope analytical techniques, possible Hg isotope fractionation mechanisms observed in both natural and experimental processes, Hg isotope composition variations in different environmental matrices, and the application prospects of the Hg stable isotopes in environmental geosciences.

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

Zn and Cu isotopes as tracers of anthropogenic contamination in a sediment core from an urban lake

Science.gov (United States)

Thapalia, Anita; Borrok, David M.; Van Metre, Peter C.; Musgrove, MaryLynn; Landa, Edward R.

2010-01-01

In this work, we use stable Zn and Cu isotopes to identify the sources and timing of the deposition of these metals in a sediment core from Lake Ballinger near Seattle, Washington, USA. The base of the Lake Ballinger core predates settlement in the region, while the upper sections record the effects of atmospheric emissions from a nearby smelter and rapid urbanization of the watershed. δ66Zn and δ65Cu varied by 0.50‰ and 0.29‰, respectively, over the 500 year core record. Isotopic changes were correlated with the presmelter period (∼1450 to 1900 with δ66Zn = +0.39‰ ± 0.09‰ and δ65Cu = +0.77‰ ± 0.06‰), period of smelter operation (1900 to 1985 with δ66Zn = +0.14 ± 0.06‰ and δ65Cu = +0.94 ± 0.10‰), and postsmelting/stable urban land use period (post 1985 with δ66Zn = 0.00 ± 0.10‰ and δ65Cu = +0.82‰ ± 0.12‰). Rapid early urbanization during the post World War II era increased metal loading to the lake but did not significantly alter the δ66Zn and δ65Cu, suggesting that increased metal loads during this time were derived mainly from mobilization of historically contaminated soils. Urban sources of Cu and Zn were dominant since the smelter closed in the 1980s, and the δ66Zn measured in tire samples suggests tire wear is a likely source of Zn.

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

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.

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.

Magnetic Moment of $^{59}$Cu

CERN Multimedia

2002-01-01

Experiment IS358 uses the intense and pure beams of copper isotopes provided by the ISOLDE RILIS (resonance ionization laser ion source). The isotopes are implanted and oriented in the low temperature nuclear orientation set-up NICOLE. Magnetic moments are measured by $\\beta$-NMR. Copper (Z=29), with a single proton above the proton-magic nickel isotopes provides an ideal testground for precise shell model calculations of magnetic moments and their experimental verification. In the course of our experiments we already determined the magnetic moments of $^{67}$Ni, $^{67}$Cu, $^{68g}$Cu, $^{69}$Cu and $^{71}$Cu which provide important information on the magicity of the N=40 subshell closure. In 2001 we plan to conclude our systematic investigations by measuring the magnetic moment of the neutron-deficient isotope $^{59}$Cu. This will pave the way for a subsequent study of the magnetic moment of $^{57}$Cu with a complementary method.

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...

Fractional Josephson vortices at YBa$_2$Cu$_3$O$_{7-x}$ grain boundaries

OpenAIRE

Mints, R. G.; Papiashvili, Ilya

2001-01-01

We report numerical simulations of magnetic flux patterns in asymmetric 45$^{\\circ}$ [001]-tilt grain boundaries in YBa$_2$Cu$_3$O$_{7-x}$ superconducting films. The grain boundaries are treated as Josephson junctions with the critical current density $j_c(x)$ alternating along the junctions. We demonstrate the existence of Josephson vortices with fractional flux quanta for both periodic and random $j_c(x)$. A method is proposed to extract fractional vortices from experimental flux patterns.

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.

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

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)

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

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...

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

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

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.

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

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.

High-precision gamma-ray spectroscopy of 61Cu, an emerging medical isotope used in positron emission tomography

Science.gov (United States)

Nelson, N.; Ellison, P.; Nickles, R.; McCutchan, E.; Sonzogni, A.; Smith, S.; Greene, J.; Carpenter, M.; Zhu, S.; Lister, C.; Moran, K.

2017-09-01

61Cu (t1 / 2 = 3.339h) is an important medical isotope used in positron emission tomography (PET) tumor hypoxia imaging scans; however, its beta-plus decay and the subsequent gamma decay of 61Ni has not been studied in over 30 years. Therefore, high quality decay data of 61Cu is desired to determine the overall dose delivered to a patient. In this study, 61Cu was produced at the University of Wisconsin - Madison cyclotron and then assayed using the Gammasphere array at Argonne National Laboratory. Consisting of 70 Compton-suppressed high-purity germanium (HPGe) detectors, Gammasphere provides precise decay data that exceeds that of previous 61Cu studies. γ-ray singles and coincident data were recorded and then analyzed using Radware gf3m software. Through γ- γ coincidence techniques, new γ-ray transitions were identified and high precision determination of γ-ray intensities were made. These modifications and additions to the current decay scheme will be presented, and their impact on the resulting does estimates will be discussed. DOE Isotope Program is acknowledged for funding ST5001030. Work supported by the U.S. DOE under Grant No. DE-FG02-94ER40848 and Contract Nos. DE-AC02-98CH10946 and DE-AC02-06CH11357 and by the Science Undergraduate Laboratory Internship Program (SULI).

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.

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

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

In the last decade, several studies have demonstrated that stable isotope tools are highly applicable for monitoring anaerobic biodegradation processes. An important methodological approach is to characterize distinct degradation pathways with respect to the specific mechanism of C-H-bond cleavage and to quantify the extent of biodegradation by compound specific isotope analysis (CSIA). Here, enrichment factors (ɛbulk) needed for a CSIA field site approach must be determined in laboratory reference experiments. Recent research results from different laboratories have shown that single ɛbulk values for similar degradation pathways can be highly variable; thus, the use of two-dimensional compound specific isotope analysis (2D-CSIA) has been encouraged for characterizing biodegradation pathways more precisely. 2D-CSIA for hydrocarbons can be expressed by the slope of the linear regression for hydrogen versus carbon discrimination known as lambda ≈ ɛHbulk/ɛCbulk. We determined the carbon and hydrogen isotope fractionation for the biodegradation of benzene, toluene and xylenes by various reference cultures. Specific enzymatic reactions initiating different biodegradation pathways could be distinguished by 2D-CSIA. For the aerobic di- and monohydroxylation of the benzene ring, lambda values always lower than 9 were observed. Enrichment cultures degrading benzene anaerobically produced significant different values: lambda values between 8-19 were oberved for nitrate-reducing consortia, whereas sulfate-reducing and methanogenic consortia showed always lambda values greater than 20 [1,2]. The observed variations suggest that (i) aerobic benzene biodegradation can be distinguished from anaerobic biodegradation, and (ii) that more than a single mechanism seems to exist for the activation of benzene under anoxic conditions. lambda values for anaerobic toluene degradation initiated by the enzyme benzylsuccinate synthase (BSS) ranged from 4 to 41, tested with strains using

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

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

Intracrystalline oxygen isotope effects in CuSO4.5H2O and their dependence on crystallization temperature

International Nuclear Information System (INIS)

Heinzinger, K.

1976-01-01

In copper sulphate pentahydrate the water molecules occupy three different sites, connected with different oxygen isotope ratios. Results of measurements of the change of these isotope ratios with crystallization temperature are reported. The temperature dependence found here provides the basis for the determination of crystallization temperatures of hydrated crystals from such intracrystalline oxygen isotope fractionation. Suppositions necessary for the application of this method are discussed. (author)

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.

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

The Effect of Preceding Crops on the Chemical Fractions of Copper (Cu in the Rhizosphere and the Bulk Soil and its Relationship with Copper Uptake by Wheat

Directory of Open Access Journals (Sweden)

shahrzad kabirinejad

2017-02-01

Full Text Available Introduction: Preceding crops as a source of organic matter are an important source of micronutrient and can play an important role in the soil fertility and the micronutrients cycle of soil. In addition to the role of the organic matter in increasing the concentration of micronutrients in soil solution, attention also should be paid to the role of the kind and the quantity of the root’s exudates that are released in response to the incorporation of different plant residues in the rhizosphere. Present research was conducted with the objective of studying the effect of the kind of preceding crops: Trifolium (Trifolium pretense L, Sofflower (Carthamus tinectirus L, Sorghum (Sorghum bicolor L, Sunflower (Heliantus annus L and control (fallow on the chemical forms of copper in the wheat rhizosphere and the bulk soil and Cu uptake by wheat and also investigating the correlation between the fractions of Cu in soil and Cu uptake in wheat. Materials and Methods: The present research was conducted as split plot in a Randomized Complete Block design (RCBD with 3 replications and 5 treatments, in field conditions. In the beginning, the preceding crops were cultivated in the experimental plots and after ending growth, preceding crops were harvested. Then the wheat was cultivated in the experimental plots. Finally, after harvesting the wheat, soil samples were collected from the two parts of the root zone (the wheat rhizosphere and the bulk soil. The soil samples were air dried ground and passed through a 2-mm sieve and stored for chemical analysis. Soil pH (in the soil saturation extract and organic matter (Walkley–Black wet digestion were measured in standard methods (1. The Total Organic Carbon (TOC was measured by Analyzer (Primacs SLC TOC Analyzer (CS22, Netherlands. The available Cu in soil was extracted by DTPA and determined using atomic absorption spectroscopy (2. The fractionation of soil Cu was carried out using the MSEP method (3. Results and

Coulomb Excitation of Odd-Mass and Odd-Odd Cu Isotopes using REX-ISOLDE and Miniball

CERN Multimedia

Lauer, M; Iwanicki, J S

2002-01-01

We propose to study the properties of the odd-mass and the odd-odd neutron-rich Cu nuclei applying the Coulomb excitation technique and using the REX-ISOLDE facility coupled to the Miniball array. The results from the Coulex experiments accomplished at REX-ISOLDE after its upgrade to 3 MeV/u during the last year have shown the power of this method and its importance in order to obtain information on the collective properties of even-even nuclei. Performing an experiment on the odd-mass and on the odd-odd neutron-rich Cu isotopes in the vicinity of N=40 should allow us to determine and interpret the effective proton and neutron charges in the region and to unravel the lowest proton-neutron multiplets in $^{68,70}$Cu. This experiment can take the advantage of the unique opportunity to accelerate isomerically separated beams using the RILIS ion source at ISOLDE.

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.

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.

Magnetic dipole moments of 58Cu and 59Cu by in-source laser spectroscopy

International Nuclear Information System (INIS)

Stone, N. J.; Koester, U.; Stone, J. Rikovska; Fedorov, D. V.; Fedoseyev, V. N.; Flanagan, K. T.; Hass, M.; Lakshmi, S.

2008-01-01

Online measurements of the magnetic dipole moments and isotope shifts of 58 Cu and 59 Cu by the in-source laser spectroscopy method are reported. The results for the magnetic moments are μ ( 58 Cu) =+0.52(8) μ N ,μ( 59 Cu) =+1.84(3) μ N and for the isotope shifts δν 59,65 =1.72(22) GHz and δν 58,65 =1.99(30) GHz in the transition from the 3d 10 4s 2 S 1/2 ground state to the 3d 10 4p 2 P 1/2 state in Cu I. The magnetic moment of 58 Cu is discussed in the context of the strength of the subshell closure at 56 Ni, additivity rules and large-scale shell model calculations

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.

Temperature dependence of the fraction of re-emitted positrons, the positron work function, and the positronium fraction for Cu(III)+S

International Nuclear Information System (INIS)

Schultz, P.J.; Lynn, K.G.

1982-01-01

A beam of 1 keV positrons incident on a Cu(111)+S surface has been used to study the dependence on temperature of the positron work function (phi/sub +/), the yield of re-emitted positrons (Y) and of the positronium (Ps) fraction. A positive dependence of the slow-positron yield on temperature is found which is attributed in part to a reduction in the magnitude of phi/sub +/ (approx. 25%) at 50 K relative to its value at 300 K. A similar, though weaker, positive dependence on temperature was seen for the Ps fraction down to 40 K. We present a suggestion for the apparent lack of reflection

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.

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...

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...

Intracrystalline site preference of hydrogen isotopes in the water of crystallization of copper sulfate pentahydrate

International Nuclear Information System (INIS)

Kita, I.; Matsuo, S.

1981-01-01

Difference in the isotopic partition at different sites of the water of crystallization of CuSO 4 .5H 2 O (the site preference) was estimated for the hydrogen isotopes. Fractional dehydration of CuSO 4 .5H 2 O under vacuum at 0 and 25 0 C was used to determine the isotopic ratio, the amount of dehydrated water, and the rate process of dehydration. The following results were obtained. (1) Two maxima occur in the isotopic ratio in the dehydration range, F < 0.8. (2) The dehydration occurs by the three sequential zeroth-order rate processes which have different rate constants for dehydration. The three different rate constants may be explained by the combination of the rate constants of dehydration of the water molecules dehydrated. The estimation of the difference in hydrogen isotope distribution for different sites, i.e., four of the five water molecules in the coordination sphere of copper ion (site A) and one bonded to the sulfate ion through hydrogen bonding (site B) was made. The site preference of hydrogen isotopes (delta D,%) was concluded to be -3.20 +- 0.52 for site A and +2.26 +- 2.09 for site B, where the delta D value was referred to the isotopic ratio of the mother liquor from which the crystal was formed

Intracrystalline site preference of hydrogen isotopes in the water of crystallization of copper sulfate pentahydrate

Energy Technology Data Exchange (ETDEWEB)

Kita, I.; Matsuo, S.

1981-04-02

Difference in the isotopic partition at different sites of the water of crystallization of CuSO/sub 4/.5H/sub 2/O (the site preference) was estimated for the hydrogen isotopes. Fractional dehydration of CuSO/sub 4/.5H/sub 2/O under vacuum at 0 and 25/sup 0/C was used to determine the isotopic ratio, the amount of dehydrated water, and the rate process of dehydration. The following results were obtained. (1) Two maxima occur in the isotopic ratio in the dehydration range, F < 0.8. (2) The dehydration occurs by the three sequential zeroth-order rate processes which have different rate constants for dehydration. The three different rate constants may be explained by the combination of the rate constants of dehydration of the water molecules dehydrated. The estimation of the difference in hydrogen isotope distribution for different sites, i.e., four of the five water molecules in the coordination sphere of copper ion (site A) and one bonded to the sulfate ion through hydrogen bonding (site B) was made. The site preference of hydrogen isotopes (delta D,%) was concluded to be -3.20 +- 0.52 for site A and +2.26 +- 2.09 for site B, where the delta D value was referred to the isotopic ratio of the mother liquor from which the crystal was formed.

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.

Cu induced reactions on 110Cd-108Cd-106Cd, 109Ag-107Ag and 110Pd. New rhenium, osmium and iridium isotopes

International Nuclear Information System (INIS)

Cabot, C.; Della Negra, S.; Deprun, C.; Gauvin, H.; Le Beyec, Y.

1978-01-01

By 63 Cu induced reactions on 110 Cd, 108 Cd, 106 Cd, 109 Ag, 107 Ag and 110 Pd targets, new isotopes were searched in the Ir, Os, Re region. Cross bombardments and excitation function measurements were used to identify new α emitting isotopes. The α-decay measurements are compared to the Qα values obtained from different mass predictions

Isotope effects in the diffusion of hydrogen and deuterium in ferromagnetic binary alloys of the Cu3Au type

International Nuclear Information System (INIS)

Hirscher, M.; Maier, C.U.; Schwendemann, B.; Kronmueller, H.

1989-01-01

The diffusion behaviour of hydrogen and deuterium at low temperatures was investigated in ordered and disordered alloys of Ni 3 Fe, Ni 3 Mn, and Fe 3 Pt by means of magnetic after-effect (MAE) measurements. After hydrogen charging all specimens show characteristic MAE relaxation spectra, which can be described taking into account the different octahedral positions of the hydrogen atoms in the Cu 3 Au structure. The observed isotope effect can qualitatively be explained by a thermally activated tunnelling process of the hydrogen isotopes. (orig.)

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

Quantum and thermal ionic motion, oxygen isotope effect, and superexchange distribution in La₂CuO₄

DEFF Research Database (Denmark)

Haefliger, P. S.; Gerber, S.; Pramod, R.

2014-01-01

We study the zero-point and thermal ionic motion in La2CuO4 by means of high-resolution neutron-diffraction experiments. Our results demonstrate anisotropic motion of O and, to a lesser extent, Cu ions, both consistent with the structure of coupled CuO6 octahedra, and quantify the relative effect...... in J values that are subject to significant (8-12%) isotope effects. We demonstrate that this motional broadening of J can have substantial effects on certain electronic and magnetic properties in cuprates.......We study the zero-point and thermal ionic motion in La2CuO4 by means of high-resolution neutron-diffraction experiments. Our results demonstrate anisotropic motion of O and, to a lesser extent, Cu ions, both consistent with the structure of coupled CuO6 octahedra, and quantify the relative effects...

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

In-source laser spectroscopy of $^{75, 77, 78}$Cu Direct evidence for a change in the quasiparticle energy sequence in $^{75, 77}$Cu and an absence of longer-lived isomers in $^{78}$Cu

CERN Document Server

Koster, U; Serot, O; Fedosseev, V N; Kratz, K L; Stone, N J; Sjodin, A M; Materna, T; Flanagan, K T; Molkanov, P L; Stone, J R; Seliverstov, M D; Mathieu, L; Marsh, B A

2011-01-01

This paper describes measurements on the isotopes (75,77,78)Cu by the technique of in-source laser spectroscopy, at the ISOLDE facility, CERN. The role of this technique is briefly discussed in the context of this and other, higher resolution, methods applied to copper isotopes in the range (57-78)Cu. The data, analyzed in comparison with previous results on the lighter isotopes (59,63)Cu, establish the ground-state nuclear spin of (75,77)Cu as 5/2 and yield their magnetic dipole moments as +1.01(5)mu(N) and +1.61(5)mu(N), respectively. The results on (78)Cu show no evidence for long-lived isomerism at this mass number and are consistent with a spin in the range 3-6 and moment of 0.0(4) mu(N)

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

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.

What Drives Carbon Isotope Fractionation by the Terrestrial Biosphere?

Science.gov (United States)

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

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)

Smith, C. N.; Kesler, S. E.; Blum, J. D.; Rytuba, J. J.

2007-12-01

We present here the first study of the isotopic composition of Hg in rocks, ore deposits, and active hydrothermal systems from the California Coast Ranges, one of Earth's largest Hg-depositing systems. The Franciscan Complex and Great Valley Sequence, which form the bedrock in the California Coast Ranges, are intruded and overlain by Tertiary volcanic rocks including the Clear Lake Volcanic Sequence. These rocks contain two types of Hg deposits, hot-spring deposits that form at shallow depths (<300 m) and silica-carbonate deposits that extend to greater depths (200 to 1000 m), as well as active springs and geothermal systems that release Hg to the present surface. The Franciscan Complex and Great Valley Sequence contain clastic sedimentary rocks with higher concentrations of Hg than volcanic rocks of the Clear Lake Volcanic Field. Mean Hg isotope compositions for all three rock units are similar, although the range of values in Franciscan Complex rocks is greater than in either Great Valley or Clear Lake rocks. Hot spring and silica-carbonate Hg deposits have similar average isotopic compositions that are indistinguishable from averages for the three rock units, although δ202Hg values for the Hg deposits have a greater variance than the country rocks. Precipitates from dilute spring and saline thermal waters in the area have similarly large variance and a mean δ202Hg value that is significantly lower than the ore deposits and rocks. These observations indicate there is little or no isotopic fractionation during release of Hg from its source rocks into hydrothermal solutions. Isotopic fractionation does appear to take place during transport and concentration of Hg in deposits, especially in their uppermost parts. Boiling of hydrothermal fluids is likely the most important process causing of the observed Hg isotope fractionation. This should result in the release of Hg with low δ202Hg values into the atmosphere from the top of these hydrothermal systems and a

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

International Nuclear Information System (INIS)

Grossmann, E.L.

1984-01-01

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 13 C of bicarbonate ion and thus aragonite-HCO 3 - and calcite-HCO 3 - isotopic enrichment factors (epsilonsub(ar-b) and epsilonsub(cl-b), respectively). Only species which precipitate in 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 similar delta 13 C values and yield an average epsilonsub(cl-b) value of -0.2 +- 0.1 per mille between 8 deg and 10 deg C. Calcitic Uvigerina curticosta, Uvigerina peregrina, and megalospheric B, argentea, Slope and Basin dwellers, are -0.7 +- 0.1 per mille enriched relative to ambient bicarbonate for 3 to 9 deg C. (author)

There is no temperature dependence of net biochemical fractionation of hydrogen and oxygen isotopes in tree-ring cellulose.

Science.gov (United States)

Roden, J S; Ehleringer, J R

2000-01-01

The isotopic composition of tree-ring cellulose was obtained over a two-year period from small diameter, riparian zone trees along an elevational transect in Big Cottonwood Canyon, Utah, USA to test for a possible temperature dependence of net biological fractionation during cellulose synthesis. The isotope ratios of stream water varied by only 3.6% and 0.2% in deltaD and delta18O, respectively, over an elevation change of 810m. The similarity in stream water and macroenvironment over the short (13km) transect produced nearly constant stem and leaf water deltaD and delta18O values. In addition, what few seasonal variations observed in the isotopic composition of source water and atmospheric water vapor or in leaf water evaporative enrichment were experienced equally by all sites along the elevational transect. The temperature at each site along the transect spanned a range of > or = 5 degrees C as calculated using the adiabatic lapse rate. Since the deltaD and delta18O values of stem and leaf water varied little for these trees over this elevation/temperature transect, any differences in tree-ring cellulose deltaD and delta18O values should have been associated with temperature effects on net biological fractionation. However, the slopes of the regressions of elevation versus the deltaD and delta18O values of tree-ring cellulose were not significantly different from zero indicating little or no temperature dependence of net biological fractionation. Therefore, cross-site climatic reconstruction studies using the isotope ratios of cellulose need not be concerned that temperatures during the growing season have influenced results.

Transpiration flow controls Zn transport in Brassica napus and Lolium multiflorum under toxic levels as evidenced from isotopic fractionation

Science.gov (United States)

Couder, Eléonore; Mattielli, Nadine; Drouet, Thomas; Smolders, Erik; Delvaux, Bruno; Iserentant, Anne; Meeus, Coralie; Maerschalk, Claude; Opfergelt, Sophie; Houben, David

2015-11-01

Stable zinc (Zn) isotope fractionation between soil and plant has been used to suggest the mechanisms affecting Zn uptake under toxic conditions. Here, changes in Zn isotope composition in soil, soil solution, root and shoot were studied for ryegrass (Lolium multiflorum L.) and rape (Brassica napus L.) grown on three distinct metal-contaminated soils collected near Zn smelters (total Zn 0.7-7.5%, pH 4.8-7.3). The Zn concentrations in plants reflected a toxic Zn supply. The Zn isotopic fingerprint of total soil Zn varied from -0.05‰ to +0.26 ± 0.02‰ (δ66Zn values relative to the JMC 3-0749L standard) among soils, but the soil solution Zn was depleted in 66Zn, with a constant Zn isotope fractionation of about -0.1‰ δ66Zn unit compared to the bulk soil. Roots were enriched with 66Zn relative to soil solution (δ66Znroot - δ66Znsoil solution = Δ66Znroot-soil solution = +0.05 to +0.2 ‰) and shoots were strongly depleted in 66Zn relative to roots (Δ66Znshoot-root = -0.40 to -0.04 ‰). The overall δ66Zn values in shoots reflected that of the bulk soil, but were lowered by 0.1-0.3 ‰ units as compared to the latter. The isotope fractionation between root and shoot exhibited a markedly strong negative correlation (R2 = 0.83) with transpiration per unit of plant weight. Thus, the enrichment with light Zn isotopes in shoot progressed with increasing water flux per unit plant biomass dry weight, showing a passive mode of Zn transport by transpiration. Besides, the light isotope enrichment in shoots compared to roots was larger for rape than for rye grass, which may be related to the higher Zn retention in rape roots. This in turn may be related to the higher cation exchange capacity of rape roots. Our finding can be of use to trace the biogeochemical cycles of Zn and evidence the tolerance strategies developed by plants in Zn-excess conditions.

Pb isotope investigations on Cu-Au deposits from Carajas Province, Amazonian craton, Brazil

International Nuclear Information System (INIS)

Macambira, M.J.B.; Galarza, M.A.T.; Souza, S.R.B.; Silva, C.M.G

2001-01-01

The Carajas Province is the most important mineral province of Brazil hosting deposits of iron, copper, gold, manganese, nickel and others. In the last years, discoveries of large Cu-Au deposits in Carajas Province have demonstrated the vocation of this region for such deposits, which are, in general, associated with volcanosedimentary sequences and, in some cases, with Archean and/or Paleoproterozoic granitic instrusions. The age and nature of the deposits, as well as the metal source, are still not well understood. Someone believe that these deposits are volcano-exhalant in nature (e.g. Ferreira Filho, 1985; Vieira et al., 1988; Almada and Villas, 1999), while others propose a hydrothermal source for the ore associated with granitic intrusions (e.g. Winter, 1994; Lindenmayer et al., 1998; Tallarico et al., 2000). This work presents a brief discussion about three Cu-Au deposits from Carajas Basin (Bahia, Aguas Claras, and Pojuca deposits) based on new Pb isotope data on zircon and sulfides carried out in the Para-Iso Laboratory of the University of Para, Brazil (au)

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

Science.gov (United States)

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

2018-06-01

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

Carbon-13 isotope fractionation in the decarboxylation of phenylpropiolic (PPA) below and above its melting point and in the decarboxylation of PPA in phenylacetylene medium

International Nuclear Information System (INIS)

Zielinski, M.; Zielinska, A.; Papiernik-Zielinska, H.

2000-01-01

C-13 isotope fractionation in the decarboxylation of pure phenylpropiolic acid (PPA) below and above its melting point and the decarboxylation of PPA in phenylacetylene solutions has been investigated in sealed under vacuum reaction vessels. The reactive PPA undergoing decarboxylation polymerizes with the liquid product, phenylacetylene in reaction cage producing a condensation compound, which does not decarboxylate measurably in the 120-190 o C. Especially low final carbon dioxide yields (about 11%) have been obtained in the decarboxylation of PPA in phenylacetylene solution at 132 o C and below this temperature. The carbon dioxide is depleted in carbon-13. The ratio of the carbon isotope ratios of carboxylic carbon of PPA before decarboxylation, R( 13 C/ 12 C so ), and of the first portions of carbon dioxide obtained at partial decarboxylation R( 13 C/ 12 C) pf , located in the range 1.007-1.010, indicates that the pure kinetic fractionation of 13 C in the elementary decarboxylation step is negligible and the C-13 fractionation in the condensed phase dimer/monomer equilibria contributes mainly to the resultant experimental carbon isotope fractionation. A preliminary discussion of the experimental isotope findings is presented. (author)

High permeation rates in liposome systems explain rapid glyphosate biodegradation associated with strong isotope fractionation.

Science.gov (United States)

Ehrl, Benno; Mogusu, Emmanuel O; Kim, Kyoungtea; Hofstetter, Heike; Pedersen, Joel A; Elsner, Martin

2018-05-23

Bacterial uptake of charged organic pollutants such as the widely used herbicide glyphosate is typically attributed to active transporters, whereas passive membrane permeation as an uptake pathway is usually neglected. For 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) liposomes, pH-dependent membrane permeation coefficients (Papp) of glyphosate, determined by nuclear magnetic resonance (NMR) spectroscopy, varied from Papp(pH 7.0) = 3.7 (+/-0.3) × 10-7 m∙s-1 to Papp(pH 4.1) = 4.2 (+/-0.1) × 10-6 m∙s-1. This surprisingly rapid membrane permeation depended on glyphosate speciation and was, at physiological pH, in the range of polar, non-charged molecules suggesting that passive membrane permeation is a potential uptake pathway during glyphosate biodegradation. To test this hypothesis, a Gram-negative glyphosate degrader, Ochrobactrum sp. FrEM, was isolated from glyphosate-treated soil and glyphosate permeation rates inferred from the liposome model were compared to bacterial degradation rates. Estimated maximum permeation rates were, indeed, two orders of magnitudes higher than glyphosate degradation rates. Moreover, biodegradation of millimolar glyphosate concentrations gave rise to pronounced carbon isotope fractionation with an apparent kinetic isotope effect of AKIEcarbon= 1.014 ± 0.003. This value is consistent with unmasked enzymatic isotope fractionation demonstrating that glyphosate biodegradation was little mass transfer-limited and glyphosate exchange across the cell membrane was rapid relative to enzymatic turnover.

Generation of covariance files for the isotopes of Cr, Fe, Ni, Cu, and Pb in ENDF/B-VI

International Nuclear Information System (INIS)

Hetrick, D.M.; Larson, D.C.; Fu, C.Y.

1991-02-01

The considerations that governed the development of the uncertainty files for the isotopes of Cr, Fe, Ni, Cu, and Pb in ENDF/B-VI are summarized. Four different approaches were used in providing the covariance information. Some examples are given which show the standard deviations as a function of incident energy and the corresponding correlation matrices. 11 refs., 5 tabs

Pyrolysis compound specific isotopic analysis (δ13C and δD Py-CSIA) of soil organic matter size fractions under four vegetation covers.

Science.gov (United States)

Jiménez-Morillo, Nicasio T.; González-Vila, Francisco J.; Almendros, Gonzalo; De la Rosa, José M.; González-Pérez, José A.

2015-04-01

A chemical characterization of soil organic matter (SOM) under different ground cover from a Mediterranean climate (Doñana National Park, Andalusia, Spain) is approached using bulk δ15N, δ13C, δ18O and δD isotopic analysis (C/TC-IRMS) and δ13C and δD pyrolysis compound specific isotopic analysis (Py-CSIA: Py-GC-C/TC-IRMS). Soil samples were collected in sandy soils, Arenosols (WRB 2006) from the Doñana National Park (SW Spain) under different vegetation cover: cork oak (Quercus suber, QS), eagle fern (Pteridium aquilinum, PA), pine (Pinus pinea, PP) and rockrose (Halimium halimifolium, HH). Two size fractions; coarse (C: 1-2 mm) and fine (F: studied from each soil. A complete conventional analytical pyrolysis (Py-GC/MS) of these samples have been studied in detail (Jiménez-Morillo et al., 2015). Bulk isotopic analysis of stable light elements (δ15N, δ13C, δ18O and δD) revealed particular isotopic signatures showing differences related with the main vegetation cover and the different soil size fraction. All samples had a carbon isotopic signature between -26 and -29 ‰, which indicated that the organic matter in the two fractions of each soil sample derived from C3-type plants. The bulk δD isotopic signature in whole soil sample indicate a lower deuterium fractionation occurs in SOM under arboreal than under no-arboreal vegetation, this can be caused by the occurrence of a higher water evaporation rate under bush vegetation and/or to differences due to leaf morphology as previously described (Leaney et al., 1985). A δ15N vs. δ18O chart may provide some clues about N origin in the soil and particularly about the original source of nitrates (Kendall et al., 1996). In in all sample and size fractions our values are in the chart area corresponding to NO3 in precipitation, with lighter δ18O (c. 20 ‰) values compatible with fertilizers may be from adjacent crops. In addition we were able to assign δ13C and δD values for a number of specific SOM

Chapter 2. Peculiarities of radioactive particle formation and isotope fractionation resulted from underground nuclear explosions

International Nuclear Information System (INIS)

1996-01-01

Radioactive particles, forming terrain fallouts from underground nuclear explosion differ sufficiently from radioactive particles, produced by atmospheric nuclear explosions. Patterns of underground nuclear explosion development, release of radioactivity to the atmosphere, formation of a cloud and base surge, peculiarities of formed radioactive particles, data on isotope fractionation in radioactive particles are presented. Scheme of particle activation, resulted from underground explosions is given

Gas-phase isotope fractionation factor for the proton-bound dimer of the ethoxide

International Nuclear Information System (INIS)

Ellenberger, M.R.; Farneth, W.E.; Dixon, D.A.

1981-01-01

The gas-phase isotope fractionation factor, phi/sub gp/, for A 2 L - where A = EtO and L = H or D has been measured by using ion cyclotron resonance spectroscopy. Two approaches to the formation of the A 2 L - dimers are presented. The value for phi/sub gp/ is 0.46 +- 0.1. This low value for phi/sub gp/ is consistent with motion of a proton in a potential with a small central maximum or no maximum

Noble Gas Isotope Evidence for Mantle Volatiles in the Cu-Mo Porphyry and Main Stage Polymetallic Veins at Butte, Montana

Science.gov (United States)

Hofstra, A. H.; Rusk, B. G.; Manning, A. H.; Hunt, A. G.; Landis, G. P.

2017-12-01

Recent studies suggest that volatiles released from mafic intrusions may be important sources of heat, sulfur, and metals in porphyry Cu-Mo-Au and epithermal Au-Ag deposits associated with intermediate to silicic stocks. The huge Cu-Mo porphyry and Main Stage polymetallic vein deposits at Butte are well suited to test this hypothesis because there is no geologic or isotopic evidence of basaltic intrusions in the mine or drill holes. The Butte porphyry-vein system is associated with quartz monzonite stocks and dikes within the southwest part of the Late Cretaceous Boulder batholith. The Boulder batholith was emplaced into Mesoproterozoic to Mesozoic sedimentary rocks and Late Cretaceous volcanic rocks. The Boulder batholith and Butte intrusions have Sri and eNd values indicative of crustal contamination. Eu and Ce anomalies in zircon from Butte intrusions provide evidence of oxidation due to magma degassing. To ascertain the source of volatiles in this system, 11 samples from the Cu-Mo porphyry and 16 from Main Stage veins were selected. The isotopic composition of Ar, Ne, and He extracted from fluid inclusions in quartz, magnetite, pyrite, chalcopyrite, sphalerite, galena, enargite, and covellite were determined. Helium isotopes exceed blank levels in all samples and Ne and Ar in some samples. On a 38Ar/36Ar vs. 40Ar/36Ar diagram, data plot near air. On a 20Ne/22Ne vs. 21Ne/22Ne diagram, data extend from air along the trajectories of OIB and MORB. On a 36Ar/4He vs. 3He/4He RA diagram, data extend from crust toward the air-mantle mixing line. The maximum 3He/4He RA values in the Cu-Mo porphyry (2.86) and Main Stage veins (3.46) are from pyrite and these values correspond to 36 and 43 % mantle helium. The Ne and He results show that fluid inclusions contain volatiles discharged from mantle magmas and that these volatiles were diluted by groundwater containing He derived from country rocks. Despite the lack of mafic intrusions in the Butte magmatic center, noble gas

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.

The measurement of the chemically mobile fraction of lead in soil using isotopic dilution analysis

International Nuclear Information System (INIS)

Kirchhoff, J.; Brand, J.; Schuettelkopf, H.

1992-12-01

The chemically available fraction of lead in eight soils measured by isotopic dilution analysis using 212 Pb ranged from 7 to 16% of the total content of lead in soil. The soluble fractions achieved values up to 63% of the total content in 1 M NH 4 NO 3 , 1 M MgCl 2 and 0.05 M DTPA solutions. Increasing the contact time between water and soil, the water-soil ratio from 1:1 to 5:1 and increasing the temperature of the soil-water suspension raised the chemically available fraction in soil. Comparing various soil parameters and the mobile fraction of lead, only pH shows a significant correlation. The amphoteric character of lead causes a minimum of mobility about pH 6; pH-values below are responsible for the higher mobility of lead as Pb 2+ , at pH-values above 6 soluble hydroxy and humic acid complexes are formed. (orig.) [de

A novel methodology to investigate isotopic biosignatures

Science.gov (United States)

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

2012-04-01

An enduring goal of trace metal isotopic studies of Earth History is to find isotopic 'fingerprints' of life or of life's individual physiochemical processes. Generally, such signatures are sought by relating an isotopic effect observed in controlled laboratory conditions or a well-characterized environment to a more complex system or the geological record. However, such an approach is ultimately limited because life exerts numerous isotopic fractionations on any one element so it is hard to dissect the resultant net fractionation into its individual components. Further, different organisms, often with the same apparent cellular function, can express different isotopic fractionation factors. We have used a novel method to investigate the isotopic fractionation associated with a single physiological process-enzyme specific isotopic fractionation. We selected Cd isotopes since only one biological use of Cd is known, CdCA (a Cd/Zn carbonic anhydrase from the coastal diatom T. Weissflogii). Thus, our investigation can also inform the long standing mystery as to why this generally toxic element appears to have a nutrient-like dissolved isotopic and concentration profile in the oceans. We used the pET-15b plasmid to insert the CdCA gene into the E. coli genome. There is no known biochemical function for Cd in E. coli, making it an ideal vector for studying distinct physiological processes within a single organism. The uptake of Cd and associated isotopic fractionation was determined for both normal cells and those expressing CdCA. It was found that whole cells always exhibited a preference for the light isotopes of Cd, regardless of the expression of CdCA; adsorption of Cd to cell surfaces was not seen to cause isotopic fractionation. However, the cleaning procedure employed exerted a strong control on the observed isotopic composition of cells. Using existing protein purification techniques, we measured the Cd isotopic composition of different subcellular fractions of E

Mass spectrometric determination of magnesium isotopic ratios and its corrections for electron multiplier discrimination and mass fractionation

International Nuclear Information System (INIS)

Deng Zhongguo

1989-01-01

The mass spectrometric determination of magnesium isotopic ratios by the use of uranyl nitrate added to magnesium samples to act as a binding agent is reported. Prebaking empty filaments and preheating filaments with deposited magnesium samples on its surface in a vacuum are employed to reduce the Na signal from the thenium-ribbon. Methods for correcting magnesium isotopic ratios for electron multiplier discrimination and mass fractionation are described in detail. The results of the determination of natural magnesium isotopic ratios are 25 Mg/ 24 Mg = 0.12660 (1±0.01%) and 26 Mg/ 24 Mg = 0.13938 (1±0.10%). The magnesium isotopic ratios of rich - 26 Mg-2 sample and rich- 25 Mg-1 sample are 24 Mg/ 26 Mg = 0.003463 (1±0.2%), 25 Mg/ 26 Mg = 0.001656 (±0.2%) and 24 Mg/ 25 Mg = 0.006716 (1±0.2%), 26 Mg/ 25 Mg = 0.007264 (1±0.2%) respectively

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

Science.gov (United States)

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

2016-03-15

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

Silicon Isotope Fractionation During Acid Water-Igneous Rock Interaction

Science.gov (United States)

van den Boorn, S. H.; van Bergen, M. J.; Vroon, P. Z.

2007-12-01

Silica enrichment by metasomatic/hydrothermal alteration is a widespread phenomenon in crustal environments where acid fluids interact with silicate rocks. High-sulfidation epithermal ore deposits and acid-leached residues at hot-spring settings are among the best known examples. Acid alteration acting on basalts has also been invoked to explain the relatively high silica contents of the surface of Mars. We have analyzed basaltic-andesitic lavas from the Kawah Ijen volcanic complex (East Java, Indonesia) that were altered by interaction with highly acid (pH~1) sulfate-chloride water of its crater lake and seepage stream. Quantitative removal of major elements during this interaction has led to relative increase in SiO2 contents. Our silicon isotope data, obtained by HR-MC-ICPMS and reported relative to the NIST RM8546 (=NBS28) standard, show a systematic increase in &δ&&30Si from -0.2‰ (±0.3, 2sd) for unaltered andesites and basalts to +1.5‰ (±0.3, 2sd) for the most altered/silicified rocks. These results demonstrate that silicification induced by pervasive acid alteration is accompanied by significant Si isotope fractionation, so that alterered products become isotopically heavier than the precursor rocks. Despite the observed enrichment in SiO2, the rocks have experienced an overall net loss of silicon upon alteration, if Nb is considered as perfectly immobile. The observed &δ&&30Si values of the alteration products appeared to correlate well with the inferred amounts of silicon loss. These findings would suggest that &28Si is preferentially leached during water-rock interaction, implying that dissolved silica in the ambient lake and stream water is isotopically light. However, layered opaline lake sediments, that are believed to represent precipitates from the silica-saturated water show a conspicuous &30Si-enrichment (+1.2 ± 0.2‰). Because anorganic precipitation is known to discriminate against the heavy isotope (e.g. Basile- Doelsch et al., 2006

Magma differentiation fractionates Mo isotope ratios: Evidence from the Kos Plateau Tuff (Aegean Arc)

Science.gov (United States)

Voegelin, Andrea R.; Pettke, Thomas; Greber, Nicolas D.; von Niederhäusern, Brigitte; Nägler, Thomas F.

2014-03-01

We investigated high temperature Mo isotope fractionation in a hydrous supra-subduction volcano-plutonic system (Kos, Aegean Arc, Greece) in order to address the debate on the δ98/95Mo variability of the continental crust. In this igneous system, where differentiation is interpreted to be dominated by fractional crystallization, bulk rock data from olivine basalt to dacite show δ98/95Mo ratios increasing from + 0.3 to + 0.6‰ along with Mo concentrations increasing from 0.8 to 4.1 μg g- 1. Data for hornblende and biotite mineral separates reveal the extraction of light Mo into crystallizing silicates, with minimum partition coefficients between hornblende-silicate melt and biotite-silicate melt of 0.6 and 0.4 δ98/95Mo, respectively.

Oxygen isotope fractionation between bird bone phosphate and drinking water

Science.gov (United States)

Amiot, Romain; Angst, Delphine; Legendre, Serge; Buffetaut, Eric; Fourel, François; Adolfssen, Jan; André, Aurore; Bojar, Ana Voica; Canoville, Aurore; Barral, Abel; Goedert, Jean; Halas, Stanislaw; Kusuhashi, Nao; Pestchevitskaya, Ekaterina; Rey, Kevin; Royer, Aurélien; Saraiva, Antônio Álamo Feitosa; Savary-Sismondini, Bérengère; Siméon, Jean-Luc; Touzeau, Alexandra; Zhou, Zhonghe; Lécuyer, Christophe

2017-06-01

Oxygen isotope compositions of bone phosphate (δ18Op) were measured in broiler chickens reared in 21 farms worldwide characterized by contrasted latitudes and local climates. These sedentary birds were raised during an approximately 3 to 4-month period, and local precipitation was the ultimate source of their drinking water. This sampling strategy allowed the relationship to be determined between the bone phosphate δ18Op values (from 9.8 to 22.5‰ V-SMOW) and the local rainfall δ18Ow values estimated from nearby IAEA/WMO stations (from -16.0 to -1.0‰ V-SMOW). Linear least square fitting of data provided the following isotopic fractionation equation: δ18Ow = 1.119 (±0.040) δ18Op - 24.222 (±0.644); R 2 = 0.98. The δ18Op-δ18Ow couples of five extant mallard ducks, a common buzzard, a European herring gull, a common ostrich, and a greater rhea fall within the predicted range of the equation, indicating that the relationship established for extant chickens can also be applied to birds of various ecologies and body masses. Applied to published oxygen isotope compositions of Miocene and Pliocene penguins from Peru, this new equation computes estimates of local seawater similar to those previously calculated. Applied to the basal bird Confuciusornis from the Early Cretaceous of Northeastern China, our equation gives a slightly higher δ18Ow value compared to the previously estimated one, possibly as a result of lower body temperature. These data indicate that caution should be exercised when the relationship estimated for modern birds is applied to their basal counterparts that likely had a metabolism intermediate between that of their theropod dinosaur ancestors and that of advanced ornithurines.

Assessment of nitrogen and oxygen isotopic fractionation during nitrification and its expression in the marine environment.

Science.gov (United States)

Casciotti, Karen L; Buchwald, Carolyn; Santoro, Alyson E; Frame, Caitlin

2011-01-01

Nitrification is a microbially-catalyzed process whereby ammonia (NH(3)) is oxidized to nitrite (NO(2)(-)) and subsequently to nitrate (NO(3)(-)). It is also responsible for production of nitrous oxide (N(2)O), a climatically important greenhouse gas. Because the microbes responsible for nitrification are primarily autotrophic, nitrification provides a unique link between the carbon and nitrogen cycles. Nitrogen and oxygen stable isotope ratios have provided insights into where nitrification contributes to the availability of NO(2)(-) and NO(3)(-), and where it constitutes a significant source of N(2)O. This chapter describes methods for determining kinetic isotope effects involved with ammonia oxidation and nitrite oxidation, the two independent steps in the nitrification process, and their expression in the marine environment. It also outlines some remaining questions and issues related to isotopic fractionation during nitrification. Copyright © 2011 Elsevier Inc. All rights reserved.

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.

Processes controlling silicon isotopic fractionation in a forested tropical watershed: Mule Hole Critical Zone Observatory (Southern India)

Science.gov (United States)

Riotte, Jean; Meunier, Jean-Dominique; Zambardi, Thomas; Audry, Stéphane; Barboni, Doris; Anupama, Krishnamurthy; Prasad, Srinivasan; Chmeleff, Jérôme; Poitrasson, Franck; Sekhar, Muddu; Braun, Jean-Jacques

2018-05-01

Assessing the dynamics of the silica cycle in the critical zone remains challenging, particularly within the soil, where multiple processes are involved. To improve our understanding of this cycle in the Tropics, and more specifically the role played by vegetation, we combined elemental Si mass balance with the δ30Si signatures of the compartments involved in the water-plant-rock interactions of a tropical forested watershed, Mule Hole (Southern India). To accomplish this, we analysed (1) the δ30Si values of present-day litter phytoliths from tree leaves and grass, as well as soil amorphous silica (ASi); (2) the Si isotope fractionation induced by phytolith dissolution; (3) the silicon mass balance inferred from isotopes at the soil-plant scale; and (4) the consistency between water sources and the δ30Si signatures in the ephemeral stream. The δ30Si values of present-day litter phytoliths and soil ASi vary within a narrow range of 1.10-1.40‰ for all samples, but two deep vertisol samples which likely trapped phytoliths from different vegetation growing under more humid conditions, as indicated by pollen analysis. A homogeneous signature of litter is a minimum condition for using δ30Si as a proxy for the litter/phytolith source of Si. However, litter-ash dissolution experiments demonstrate that the incipient dissolution of phytoliths fractionates Si isotopes, with the preferential dissolution of 28Si over 30Si yielding δ30Si values as low as -1.41‰. Values close to the whole-sample signatures, i.e., above 1‰, were recovered in the solution after a few hours of water-ash interaction. At the soil-plant scale, the average δ30Si value of soil-infiltrating solutions is slightly lighter than the average phytolith signature, which suggests phytoliths as the source of soil dissolved Si. The isotopic budget of dissolved Si within the soil layer, which was obtained based on previous elemental fluxes, is imbalanced. Equilibrating the isotopic budget would imply

Fractionation of carbon isotopes by thermophilic methanogenic bacteria

International Nuclear Information System (INIS)

Ivanov, M.V.; Belyaev, S.S.; Zyakun, A.M.; Bondar, V.A.; Shipin, O.P.; Laurinavichus, K.S.

1985-01-01

The authors investigated the pattern of fractionation of stable carbon isotopes by the thermophilic methane-forming bacteria under different growth conditions and at various rates of formation of methane. A pure culture of Methanobacterium thermoautotrophicum was used in the experiments under the following growth conditions: temperature 65-70 0 C; pH 7.2-7.6; NaCl content 0-0.9 g/liter. The methanogenic bacteria were cultivated in 0.15 liter flasks in mineral medium. A mixture of CO 2 and H 2 in a 1:4 ratio by volume served as the sole carbon and energy source. In all experiments, not more than 5% of the initial CO 2 level was utilized. The rate of methane generation was altered by adjusting the physicochemical growth parameters (temperature from 45-70 0 C, salinity from 0.9 to 40 g/liter NaCl, pH from 6.3 to 7.2). Methane in the samples was quantitatively determined in a chromatograph which had a flame-ionization detector and a column containing Porapak Q sorbent at T = 120 0 C. The carrier gas was CO 2 . The average specific rate of methane formation was calculated as ml CH 4 per mg dry biomass of bacteria per h. Soluble mineral carbon was isolated form the acidified culture liquid in the form of CO 2 and was quantitatively determined in a Chrom-4 chromatography provided with a katharometer and a column containing activated charcoal at T = 150 0 . The gas carrier was helium. The isotopic composition of carbon was determined in a CH-7 mass-spectrometer and was expressed in 13 C values (per thousand) with respect to the international PDB standard

Implications for behavior of volatile elements during impacts—Zinc and copper systematics in sediments from the Ries impact structure and central European tektites

Science.gov (United States)

Rodovská, Zuzana; Magna, TomáÅ.¡; Žák, Karel; Kato, Chizu; Savage, Paul S.; Moynier, Frédéric; Skála, Roman; Ježek, Josef

2017-10-01

Moldavites are tektites genetically related to the Ries impact structure, located in Central Europe, but the source materials and the processes related to the chemical fractionation of moldavites are not fully constrained. To further understand moldavite genesis, the Cu and Zn abundances and isotope compositions were measured in a suite of tektites from four different substrewn fields (South Bohemia, Moravia, Cheb Basin, Lusatia) and chemically diverse sediments from the surroundings of the Ries impact structure. Moldavites are slightly depleted in Zn ( 10-20%) and distinctly depleted in Cu (>90%) relative to supposed sedimentary precursors. Moreover, the moldavites show a wide range in δ66Zn values between 1.7 and 3.7‰ (relative to JMC 3-0749 Lyon) and δ65Cu values between 1.6 and 12.5‰ (relative to NIST SRM 976) and are thus enriched in heavy isotopes relative to their possible parent sedimentary sources (δ66Zn = -0.07 to +0.64‰; δ65Cu = -0.4 to +0.7‰). In particular, the Cheb Basin moldavites show some of the highest δ65Cu values (up to 12.5‰) ever observed in natural samples. The relative magnitude of isotope fractionation for Cu and Zn seen here is opposite to oxygen-poor environments such as the Moon where Zn is significantly more isotopically fractionated than Cu. One possibility is that monovalent Cu diffuses faster than divalent Zn in the reduced melt and diffusion will not affect the extent of Zn isotope fractionation. These observations imply that the capability of forming a redox environment may aid in volatilizing some elements, accompanied by isotope fractionation, during the impact process. The greater extent of elemental depletion, coupled with isotope fractionation of more refractory Cu relative to Zn, may also hinge on the presence of carbonyl species of transition metals and electromagnetic charge, which could exist in the impact-induced high-velocity jet of vapor and melts.

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

Science.gov (United States)

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

2014-01-01

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, continuous-flow technique using capillary GC/combustion IRMS. Quadriceps muscles were removed from four Sprague–Dawley rats after each was infused at a different rate with (1-13C)leucine for 6–8 h. Muscle leucine enrichment (at.% excess) measured by both methods differed by less than 4%, except at low (13C)leucine enrichments (IRMS was used to assess muscle (13C)leucine enrichment and fractional muscle protein synthesis rate in ten normal young men and women infused with (1,2-13C2)leucine for 12–14 h. This approach reduced the variability of the isotope abundance measure and gave estimates of muscle protein synthesis rate (0.050 ± 0.011% h−1 (mean ± SEM); range = 0.023–0.147% h−1) that agree with published values determined using the standard analytical approach. The measurement of (13C)leucine enrichment from skeletal muscle protein by capillary GC/combustion IRMS provides a simple, acceptable and practical alternative to preparative GC/ninhydrin IRMS. PMID:1420371

Subcellular differences in handling Cu excess in three freshwater fish species contributes greatly to their differences in sensitivity to Cu

International Nuclear Information System (INIS)

Eyckmans, Marleen; Blust, Ronny; De Boeck, Gudrun

2012-01-01

Since changes in metal distribution among tissues and subcellular fractions can provide insights in metal toxicity and tolerance, we investigated this partitioning of Cu in gill and liver tissue of rainbow trout (Oncorhynchus mykiss), common carp (Cyprinus carpio) and gibel carp (Carassius auratus gibelio). These fish species are known to differ in their sensitivity to Cu exposure with gibel carp being the most tolerant and rainbow trout the most sensitive. After an exposure to 50 μg/l (0.79 μM) Cu for 24 h, 3 days, 1 week and 1 month, gills and liver of control and exposed fish were submitted to a differential centrifugation procedure. Interestingly, there was a difference in accumulated Cu in the three fish species, even in control fishes. Where the liver of rainbow trout showed extremely high Cu concentrations under control conditions, the amount of Cu accumulated in their gills was much less than in common and gibel carp. At the subcellular level, the gills of rainbow trout appeared to distribute the additional Cu exclusively in the biologically active metal pool (BAM; contains heat-denaturable fraction and organelle fraction). A similar response could be seen in gill tissue of common carp, although the percentage of Cu in the BAM of common carp was lower compared to rainbow trout. Gill tissue of gibel carp accumulated more Cu in the biologically inactive metal pool (BIM compared to BAM; contains heat-stable fraction and metal-rich granule fraction). The liver of rainbow trout seemed much more adequate in handling the excess Cu (compared to its gills), since the storage of Cu in the BIM increased. Furthermore, the high % of Cu in the metal-rich granule fraction and heat-stable fraction in the liver of common carp and especially gibel carp together with the better Cu handling in gill tissue, pointed out the ability of the carp species to minimize the disadvantages related to Cu stress. The differences in Cu distribution at the subcellular level of gills and

Subcellular differences in handling Cu excess in three freshwater fish species contributes greatly to their differences in sensitivity to Cu

Energy Technology Data Exchange (ETDEWEB)

Eyckmans, Marleen, E-mail: marleen.eyckmans@ua.ac.be [Laboratory for Ecophysiology, Biochemistry and Toxicology, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp (Belgium); Blust, Ronny; De Boeck, Gudrun [Laboratory for Ecophysiology, Biochemistry and Toxicology, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp (Belgium)

2012-08-15

Since changes in metal distribution among tissues and subcellular fractions can provide insights in metal toxicity and tolerance, we investigated this partitioning of Cu in gill and liver tissue of rainbow trout (Oncorhynchus mykiss), common carp (Cyprinus carpio) and gibel carp (Carassius auratus gibelio). These fish species are known to differ in their sensitivity to Cu exposure with gibel carp being the most tolerant and rainbow trout the most sensitive. After an exposure to 50 {mu}g/l (0.79 {mu}M) Cu for 24 h, 3 days, 1 week and 1 month, gills and liver of control and exposed fish were submitted to a differential centrifugation procedure. Interestingly, there was a difference in accumulated Cu in the three fish species, even in control fishes. Where the liver of rainbow trout showed extremely high Cu concentrations under control conditions, the amount of Cu accumulated in their gills was much less than in common and gibel carp. At the subcellular level, the gills of rainbow trout appeared to distribute the additional Cu exclusively in the biologically active metal pool (BAM; contains heat-denaturable fraction and organelle fraction). A similar response could be seen in gill tissue of common carp, although the percentage of Cu in the BAM of common carp was lower compared to rainbow trout. Gill tissue of gibel carp accumulated more Cu in the biologically inactive metal pool (BIM compared to BAM; contains heat-stable fraction and metal-rich granule fraction). The liver of rainbow trout seemed much more adequate in handling the excess Cu (compared to its gills), since the storage of Cu in the BIM increased. Furthermore, the high % of Cu in the metal-rich granule fraction and heat-stable fraction in the liver of common carp and especially gibel carp together with the better Cu handling in gill tissue, pointed out the ability of the carp species to minimize the disadvantages related to Cu stress. The differences in Cu distribution at the subcellular level of gills