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Sample records for oxygen isotope fractionation

  1. 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.

  2. 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

  3. 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)

  4. 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

  5. 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

  6. 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

  7. 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

  8. 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

  9. 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

  10. 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

  11. 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

  12. Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

    Science.gov (United States)

    Cao, Xiaobin; Liu, Yun

    2011-12-01

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

  13. 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.

  14. 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

  15. 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.

  16. 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

  17. 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)

  18. 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.

  19. 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

  20. 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.

  1. 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)

  2. 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)

  3. 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)

  4. Oxygen isotopic anomalies in Allende inclusion HAL

    International Nuclear Information System (INIS)

    Lee, T.; Mayeda, T.K.; Clayton, R.N.

    1980-01-01

    The oxygen isotopic composition has been measured on the constituent phases of Allende inclusion HAL, which has unusual mineralogical, chemical, and calcium isotopic compositions. The oxygen in HAL is heterogeneous, with the rim showing more ''normal'' composition and the hibonite core showing large deviation from both the terrestrial material and the usual inclusions. The observed pattern indicates that HAL is a bona fide and more devious member of the rare ''FUN'' family, whose isotopic composition is characterized by correlated nuclear effects and extreme mass fractionation. The data imply that HAL has suffered a large oxygen mass fractionation of 25% 0 per mass unit, followed by exchange with oxygen in a second reservoir. The present experiment supports the identification of two distinct reservoirs from which all refractory inclusions in carbonaceous meteorites derived their oxygen. The required fractionation process seems to operate according to the volatility of various elements and could have been caused by evaporation during a heating event. Nuclear anomalies can be produced in the same heating event if the progenitors of the refractory inclusions were macroscopic aggregates of tiny pre-solar interstellar dust grains and if these grains were destroyed differentially during the evaporation

  5. Isotope anomalies in oxygen isotope exchange equilibrium systems

    International Nuclear Information System (INIS)

    Kotaka, M.

    1997-01-01

    The purpose of the present work is to elucidate the isotope anomalies in oxygen isotope exchange equilibrium systems, according to the calculations of the equilibrium constants for oxygen isotopic exchange reactions, and the calculations of the oxygen isotope separation factors between two phases. The equilibrium constants (K65, K67, K68 and K69) of 16 O- 15 O, 16 O 17 O, 16 O- 18 O, and 16 O- 19 O exchange reactions between diatomic oxides were calculated in a wide temperature range on the basis of quantum statistical mechanics. Many equilibrium constants showed the anomalous mass effects, and then had the crossover temperatures and the mass independent fractionation (MIF) temperatures which held K67 = K65, K67 = K68, or K67 = K69, etc. For example, the equilibrium constants for the reactions between OH and the other diatomic oxides (MO) showed the anomalous mass effects, when M was Li, Na, Mg, K, Fe, Al, Ge, Zr, Pt, etc. The 16 O 15 O, 16 O 17 O, 16 O- 18 O, and 16 O- 19 O oxygen isotope separation factors (S65, S67, S68 and S69) between two phases were calculated, when OH and CO were in the first phase, and SiO was in the second phase. Although the oxygen isotopic exchange equilibria in the two phases had no MIF and crossover temperatures, the separation factors showed the anomalous mass effects and had the temperatures. According to what is called the normal mass effects for the equilibrium constant of isotopic exchange reaction, the value of InK68/InK67 is 1.885. Therefore, the value of InS68/InS67 should be 1.885 too. The value calculated, however, widely changed. It can be concluded from the results obtained in the present work that some oxygen isotopic exchange equilibria cause the anomalous mass effects, the anomalous oxygen isotope separation factors, and then isotope anomalies

  6. 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.

  7. 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.

  8. The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

    Science.gov (United States)

    von Sperber, Christian; Kries, Hajo; Tamburini, Federica; Bernasconi, Stefano M.; Frossard, Emmanuel

    2014-01-01

    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. During the enzymatic hydrolysis an isotopic fractionation (ε) occurs leaving an imprint on the oxygen isotope composition of the released Pi which might be used to trace phosphorus in the environment. Therefore, enzymatic assays with acid phosphatases from wheat germ and potato tuber and alkaline phosphatase from Escherichia coli were prepared in order to determine the oxygen isotope fractionation caused by these enzymes. Adenosine 5‧ monophosphate and glycerol phosphate were used as substrates. The oxygen isotope fractionation caused by acid phosphatases is 20-30‰ smaller than for alkaline phosphatases, resulting in a difference of 5-7.5‰ in δ18O of Pi depending on the enzyme. We attribute the enzyme dependence of the isotopic fractionation to distinct reaction mechanisms of the two types of phosphatases. The observed difference is large enough to distinguish between the two enzymatic processes in environmental samples. These findings show that the oxygen isotope composition of Pi can be used to trace different enzymatic processes, offering an analytical tool that might contribute to a better understanding of the P-cycle in the environment.

  9. 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...

  10. Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands)

    Science.gov (United States)

    Lazzerini, Nicolas; Lécuyer, Christophe; Amiot, Romain; Angst, Delphine; Buffetaut, Eric; Fourel, François; Daux, Valérie; Betancort, Juan Francisco; Flandrois, Jean-Pierre; Marco, Antonio Sánchez; Lomoschitz, Alejandro

    2016-10-01

    Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ18Ocalc and δ13Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ18Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in 18O relative to 16O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ18Ocalc value of eggshell calcite to the δ18Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ13Ccalc and δ18Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ13Ccalc and high δ18Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions.

  11. Biological fractionation of oxygen and carbon isotopes by recent benthic foraminifera

    International Nuclear Information System (INIS)

    Woodruff, F.; Douglas, R.G.

    1980-01-01

    Recent deep-sea benthic foraminifera from five East Pacific Rise box core tops have been analyzed for oxygen and carbon isotopic composition. The five equatorial stations, with water depths of between 3200 and 4600 m, yielded fourteen specific and generic taxonomic groups. Of the taxa analyzed, Uvigerina spp. most closely approaches oxygen isotopic equilibrium with ambient sea water. Pyrgo spp. was next closest to isotopic equilibrium, being on the average 0.59 per thousand depleted in 18 O relative to Uvigerina spp. Oridorsalis umbonatus also has relatively high delta 18 O values. Most other taxa were depleted in 18 O by large amounts. In no taxa was the carbon in the CaCO 3 secreted in carbon isotopic equilibrium with the dissolved HCO 3 - of ambient sea water. (Auth.)

  12. The oxygen isotope composition of earth's oldest rocks and evidence of a terrestrial magma ocean

    DEFF Research Database (Denmark)

    Rumble, D.; Bowring, S.; Iizuka, T.

    2013-01-01

    Analysis of Hadean and Archean rocks for O-16-O-17-O-18 isotopes demonstrates that the Terrestrial Mass Fractionation Line of oxygen isotopes has had the same slope and intercept for at least the past 4.0 and probably for as long as 4.2Ga. The homogenization of oxygen isotopes required to produce....... But other sources of heat for global melting cannot be excluded such as bolide impacts during early accretion of proto-Earth, the decay of short-lived radioactive isotopes, or the energy released during segregation of core from mantle.......Analysis of Hadean and Archean rocks for O-16-O-17-O-18 isotopes demonstrates that the Terrestrial Mass Fractionation Line of oxygen isotopes has had the same slope and intercept for at least the past 4.0 and probably for as long as 4.2Ga. The homogenization of oxygen isotopes required to produce...... such long-lived consistency was most easily established by mixing in a terrestrial magma ocean. The measured identical oxygen isotope mass fractionation lines for Earth and Moon suggest that oxygen isotope reservoirs of both bodies were homogenized at the same time during a giant moon-forming impact...

  13. Fractionation of hydrogen and oxygen isotopes between hydrated and free water molecules in aqueous urea solution

    International Nuclear Information System (INIS)

    Kakiuchi, M.; Matsuo, S.

    1985-01-01

    Ratios of D/H and 18 O/ 16 O in the vapor phase in equilibrium with aqueous urea solution with different urea molalities were measured at 15 and 25 0 C. Under the assumption that urea solutions consist of two species, i.e., the urea-water cluster and free water, the results are interpreted to give the average hydration number, i.e., the number of water molecules per urea molecule in the urea-water cluster. Good agreement was obtained for the hydration number estimated independently from hydrogen and oxygen isotopic fractions. On the basis of hydrogen isotopic data at 25 0 C, the average hydration number of urea in the cluster is 6.3 +/- 0.8 at 2.1 m and 2.75 +/- 0.08 at saturation (20.15 m). The corresponding average hydration numbers based on oxygen isotopic data were calculated to be 6.7 +/- 2.4 at 2.1 m and 2.75 +/- 0.25 at urea saturation. HD 16 O is enriched in the urea-water cluster and H 2 18 O is enriched in free water. Isotopic partitioning between the cluster and free water is markedly different from those between hydration spheres and free water in aqueous electrolyte solutions. 29 references, 6 figures, 5 tables

  14. 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...

  15. 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.

  16. Deuterium isotope fractionation between ortho-alkyl substituted phenols and t-butylthiol in oxygen bases

    International Nuclear Information System (INIS)

    Wawer, A.; Jelenska-Kazimierczuk, M.; Szydlowski, J.

    1998-01-01

    Equilibrium isotope effect in the exchange reaction of deuterium between phenol(P), 2-isopropyl phenol (IPP), 2,6-diisopropyl phenol (DIPP), 2,6-diterbutyl phenol (DTBP) and tertbutylthiol (TBT) has been studied in 296 K. The fractionation factors (α) have been measured in cyclohexane and carbon tetrachloride solutions and in a few oxygen bases: acetone, 1,4-dioxane, ethyl formate, ethyl ether, tetrahydrofurane, N,N-dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide. Using chemical shifts of phenol OH protons, the thermodynamic parameters of complex formation with the oxygen bases have been determined. The experimental data show that lnα correlates with the formation enthalpy of the phenol-oxygen base complex in DIPP-TBT-base system but there is no simple correlation in IPP-TBT-base system. Furthermore, it was found that in DTBT-TBT-base system lnα depends linearly on the basicity of the solvent (DN parameters). On the other hand, lnα correlates with acidic parameters of the solvents (AN) in IPP-TBT-base and P-TBT-base systems. All above correlations are explained by taking into account two competition processes: self association of phenol molecules and their solvation by oxygen bases. (author)

  17. Oxygen isotopic signature of CO2 from combustion processes

    Directory of Open Access Journals (Sweden)

    W. A. Brand

    2011-02-01

    Full Text Available For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires, and human induced (fossil fuel combustion, biomass burning in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects on the order of up to 26%permil; became obvious in the derived CO2 from combustion of different kinds of material, a clear differentiation of about 7‰ was also found in car exhausts which were sampled directly under ambient atmospheric conditions. We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature, sample geometries (e.g. texture and surface-volume ratios and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original total 18O signature of the material appeared to have little influence, however, a contribution of specific bio

  18. Sources and Contributions of Oxygen During Microbial Pyrite Oxidation: the Triple Oxygen Isotopes of Sulfate

    Science.gov (United States)

    Ziegler, K.; Coleman, M. L.; Mielke, R. E.; Young, E. D.

    2008-12-01

    The triple isotopes of oxygen (Δ17O' = δ17O'-0.528 × δ18O' using logarithmic deltas) can trace the oxygen sources of sulfate produced during sulfide oxidation, an important biogeochemical process on Earth's surface and possibly also on Mars [1]. δ18OSO4 compositions are determined by the isotopic selectivity of the mechanism(s) responsible for their changes, and the δ18O value of the reactants (O2 vs. H2O). The relative proportional importance and contribution of each of those sources and mechanisms, as well as their associated isotopic fractionations, are not well understood. We are investigating the use of Δ 17O as a quantitative and qualitative tracer for the different processes and oxygen sources involved in sulfate production. Δ17O signatures are distinct fingerprints of these reservoirs, independent of fractionation factors that can be ambiguous. We conducted controlled abiotic and biotic (Acidithiobacillus ferrooxidans, A.f.) laboratory experiments in which water was spiked with 18O, allowing us to quantify the sources of sulfate oxygen and therefore the processes attending sulfate formation. Results of this Δ17O tracer study show that A.f. microbes initiate pyrite S-oxidation within hours of exposure, and that sulfate is produced from ~90% atmospheric oxygen. This initial lag-phase (behavior in the initial lag-phase will aid in the understanding of the ecological conditions required for microbial populations to establish and survive. An exponential phase of growth, facilitated by microbial Fe2+-oxidation, follows. The source of sulfate rapidly switches to abiotic sulfide oxidation during exponential growth and the source of oxygen switches from atmospheric O2 to nearly ~100% water. Pending acquisition of complimentary chemistry data (in progress), we interpret our isotope data to indicate that the biotic fractionation factor ɛ18OSO4-O2 of at least ~ -25 to - 35‰ is augmented by microbially induced kinetic fractionation; it is larger than

  19. Intracellular Cadmium Isotope Fractionation

    Science.gov (United States)

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

    2011-12-01

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

  20. Sulfur cycling in contaminated aquifers: What can we learn from oxygen isotopes in sulfate? (Invited)

    Science.gov (United States)

    Knoeller, K.; Vogt, C.; Hoth, N.

    2009-12-01

    Bacterial reduction of dissolved sulfate (BSR) is a key process determining the natural attenuation in many contaminated aquifers. For example, in groundwater bodies affected by acid mine drainage (AMD) BSR reduces the contaminant load by producing alkalinity and facilitating a sustainable fixation of sulfur in the sediment. In aquifers contaminated with petroleum hydrocarbons sulfate may act as a terminal electron acceptor for the anaerobic oxidation of the organic contaminants to carbon dioxide and water. Due to the isotope selectivity of sulfate reducing bacteria, BSR shows the most pronounced isotope fractionation within the sulfur cycle. While sulfur displays a straightforward kinetic enrichment in the residual sulfate described by the enrichment factor epsilon (ɛ), the mechanism of oxygen isotope fractionation is still being discussed controversially. Nevertheless, it is agreed on that oxygen isotope exchange between ambient water and residual sulfate occurs during BSR in natural environments. With respect to this potential isotope exchange, the fractionation parameter theta (θ) is introduced instead of the kinetic enrichment factor epsilon (ɛ). The dual isotope system considering both sulfate-sulfur and sulfate-oxygen isotope fractionation and the respective fractionation parameters ɛ and θ provides an excellent tool for the recognition and quantification of BSR. Beyond that, the dual isotope approach may help identify and estimate interfering sulfur transformations such as re-oxidation and disproportionation processes which is especially vital for the understanding of the overall natural attenuation potential of the investigated aquifers. We present two examples from different field studies showing the benefits of applying the combination of sulfur and oxygen isotopes in dissolved sulfate to reveal the details of the sulfur cycle. The first case study is concerned with the evaluation of the potential for BSR in an AMD-affected aquifer close to an

  1. A Quantitative, Time-Dependent Model of Oxygen Isotopes in the Solar Nebula: Step one

    Science.gov (United States)

    Nuth, J. A.; Paquette, J. A.; Farquhar, A.; Johnson, N. M.

    2011-01-01

    The remarkable discovery that oxygen isotopes in primitive meteorites were fractionated along a line of slope I rather than along the typical slope 0,52 terrestrial fractionation line occurred almost 40 years ago, However, a satisfactory, quantitative explanation for this observation has yet to be found, though many different explanations have been proposed, The first of these explanations proposed that the observed line represented the final product produced by mixing molecular cloud dust with a nucleosynthetic component, rich in O-16, possibly resulting from a nearby supernova explosion, Donald Clayton suggested that Galactic Chemical Evolution would gradually change the oxygen isotopic composition of the interstellar grain population by steadily producing O-16 in supernovae, then producing the heavier isotopes as secondary products in lower mass stars, Thiemens and collaborators proposed a chemical mechanism that relied on the availability of additional active rotational and vibrational states in otherwise-symmetric molecules, such as CO2, O3 or SiO2, containing two different oxygen isotopes and a second, photochemical process that suggested that differential photochemical dissociation processes could fractionate oxygen , This second line of research has been pursued by several groups, though none of the current models is quantitative,

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

    Directory of Open Access Journals (Sweden)

    Tao Wang

    2010-12-01

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

  3. 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.

  4. 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

  5. The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

    Science.gov (United States)

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

    2013-12-01

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

  6. 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.

  7. Cryogenic separation of an oxygen-argon mixture in natural air samples for the determination of isotope and molecular ratios.

    Science.gov (United States)

    Keedakkadan, Habeeb Rahman; Abe, Osamu

    2015-04-30

    The separation and purification of oxygen-argon mixtures are critical in the high-precision analysis of Δ(17) O and δ(O2 /Ar) for geochemical applications. At present, chromatographic methods are used for the separation and purification of oxygen-argon mixtures or pure oxygen, but these methods require the use of high-purity helium as a carrier gas. Considerable interest has been expressed in the development of a helium-free cryogenic separation of oxygen-argon mixtures in natural air samples. The precise and simplified cryogenic separation of oxygen-argon mixtures from natural air samples presented here was made possible using a single 5A (30/60 mesh) molecular sieve column. The method involves the trapping of eluted gases using molecular sieves at liquid nitrogen temperature, which is associated with isotopic fractionation. We tested the proposed method for the determination of isotopic fractionations during the gas exchange between water and atmospheric air at equilibrium. The dependency of fractionation was studied at different water temperatures and for different methods of equilibration (bubbling and stirring). Isotopic and molecular fractionations during gas desorption from molecular sieves were studied for different amounts and types of molecular sieves. Repeated measurements of atmospheric air yielded a reproducibility (±SD) of 0.021 ‰, 0.044 ‰, 15 per meg and 1.9 ‰ for δ(17) O, δ(18) O, Δ(17) O and δ(O2 /Ar) values, respectively. We applied the method to determine equilibrium isotope fractionation during gas exchange between air and water. Consistent δ(18) O and Δ(17) O results were obtained with the latest two studies, whereas there was a significant difference in δ(18) O values between seawater and deionized water. We have revised a helium-free, cryogenic separation of oxygen-argon mixtures in natural air samples for isotopic and molecular ratio analysis. The use of a single 13X (1/8" pellet) molecular sieve yielded the smallest isotopic

  8. Preliminary results of oxygen isotope ratio measurement with a particle-gamma coincidence method

    Energy Technology Data Exchange (ETDEWEB)

    Borysiuk, Maciek, E-mail: maciek.borysiuk@pixe.lth.se; Kristiansson, Per; Ros, Linus; Abdel, Nassem S.; Elfman, Mikael; Nilsson, Charlotta; Pallon, Jan

    2015-04-01

    The possibility to study variations in the oxygen isotopic ratio with photon tagged nuclear reaction analysis (pNRA) is evaluated in the current work. The experiment described in the article was performed at Lund Ion Beam Analysis Facility (LIBAF) with a 2 MeV deuteron beam. Isotopic fractionation of light elements such as carbon, oxygen and nitrogen is the basis of many analytical tools in hydrology, geology, paleobiology and paleogeology. IBA methods provide one possible tool for measurement of isotopic content. During this experimental run we focused on measurement of the oxygen isotopic ratio. The measurement of stable isotopes of oxygen has a number of applications; the particular one driving the current investigation belongs to the field of astrogeology and specifically evaluation of fossil extraterrestrial material. There are three stable isotopes of oxygen: {sup 16}O, {sup 17}O and {sup 18}O. We procured samples highly enriched with all three isotopes. Isotopes {sup 16}O and {sup 18}O were easily detected in the enriched samples, but no significant signal from {sup 17}O was detected in the same samples. The measured yield was too low to detect {sup 18}O in a sample with natural abundances of oxygen isotopes, at least in the current experimental setup, but the spectral line from the reaction with {sup 16}O was clearly visible.

  9. 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.

  10. 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.

  11. 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...

  12. 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.

  13. Oxygen isotope fractionation between human phosphate and water revisited

    DEFF Research Database (Denmark)

    Daux, Valérie; Lécuyer, Christophe; Héran, Marie-Anne

    2008-01-01

    to investigate the impact of solid food consumption on the oxygen isotope composition of the total ingested water (drinking water+solid food water). The results, along with those from three, smaller published data sets, can be considered as random estimates of a unique delta18OW/delta18OP linear relationship...... collected at 12 sites located at latitudes ranging from 4 degrees N to 70 degrees N together with the corresponding oxygen composition of tap waters (delta18OW) from these areas. In addition, the delta18O of some raw and boiled foods were determined and simple mass balance calculations were performed......: delta18OW=1.54(+/-0.09)xdelta18OP-33.72(+/-1.51)(R2=0.87: p [H0:R2=0]=2x10(-19)). The delta18O of cooked food is higher than that of the drinking water. As a consequence, in a modern diet the delta18O of ingested water is +1.05 to 1.2 per thousand higher than that of drinking water in the area. In meat...

  14. 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.

  15. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-07-01

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

  17. Fractionation of oxygen and hydrogen isotopes at the hydrate gas forming in the sea sediments

    International Nuclear Information System (INIS)

    Pashkina, V.I.; Esikov, A.D.

    1990-01-01

    The paper gives data on isotope composition of interstitial and near-bottom waters sampled in a region of gas-hydrate formation in the Sea of Okhotsk. The studies show that heavy isotopes of oxygen and hydrogen is used in gas-hydrate formation, with the result that isotope composition of its constitution water constitutes δ 18 O=+1.99per mille, δD=+23per mille relatively to SMOW. Formation of autogenic carbonates leads to isotope exchange with interstitial water wich, in turn, changes its primary isotope composition in the direction of increasing of O-18 content. The near-bottom waters are isotope-light relatively to the SMOW standard and to the mean isotope composition of interstitial water in the studied region of gas-hydrate spreading. (orig.) [de

  18. 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)

  19. CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula.

    Science.gov (United States)

    Lyons, J R; Young, E D

    2005-05-19

    The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO.

  20. Copper isotope fractionation by desert shrubs

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  1. 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

  2. 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

  3. Triple oxygen isotope systematics of structurally bonded water in gypsum

    Science.gov (United States)

    Herwartz, Daniel; Surma, Jakub; Voigt, Claudia; Assonov, Sergey; Staubwasser, Michael

    2017-07-01

    The triple oxygen isotopic composition of gypsum mother water (gmw) is recorded in structurally bonded water in gypsum (gsbw). Respective fractionation factors have been determined experimentally for 18O/16O and 17O/16O. By taking previous experiments into account we suggest using 18αgsbw-gmw = 1.0037; 17αgsbw-gmw = 1.00195 and θgsbw-gmw = 0.5285 as fractionation factors in triple oxygen isotope space. Recent gypsum was sampled from a series of 10 ponds located in the Salar de Llamara in the Atacama Desert, Chile. Total dissolved solids (TDS) in these ponds show a gradual increase from 23 g/l to 182 g/l that is accompanied by an increase in pond water 18O/16O. Gsbw falls on a parallel curve to the ambient water from the saline ponds. The offset is mainly due to the equilibrium fractionation between gsbw and gmw. However, gsbw represents a time integrated signal biased towards times of strong evaporation, hence the estimated gmw comprises elevated 18O/16O compositions when compared to pond water samples taken on site. Gypsum precipitation is associated with algae mats in the ponds with lower salinity. No evidence for respective vital effects on the triple oxygen isotopic composition of gypsum hydration water is observed, nor are such effects expected. In principle, the array of δ18Ogsbw vs. 17Oexcess can be used to: (1) provide information on the degree of evaporation during gypsum formation; (2) estimate pristine meteoric water compositions; and (3) estimate local relative humidity which is the controlling parameter of the slope of the array for simple hydrological situations. In our case study, local mining activities may have decreased deep groundwater recharge, causing a recent change of the local hydrology.

  4. [Research advances in identifying nitrate pollution sources of water environment by using nitrogen and oxygen stable isotopes].

    Science.gov (United States)

    Mao, Wei; Liang, Zhi-wei; Li, Wei; Zhu, Yao; Yanng, Mu-yi; Jia, Chao-jie

    2013-04-01

    Water body' s nitrate pollution has become a common and severe environmental problem. In order to ensure human health and water environment benign evolution, it is of great importance to effectively identify the nitrate pollution sources of water body. Because of the discrepant composition of nitrogen and oxygen stable isotopes in different sources of nitrate in water body, nitrogen and oxygen stable isotopes can be used to identify the nitrate pollution sources of water environment. This paper introduced the fractionation factors of nitrogen and oxygen stable isotopes in the main processes of nitrogen cycling and the composition of these stable isotopes in main nitrate sources, compared the advantages and disadvantages of five pre-treatment methods for analyzing the nitrogen and oxygen isotopes in nitrate, and summarized the research advances in this aspect into three stages, i. e. , using nitrogen stable isotope alone, using nitrogen and oxygen stable isotopes simultaneously, and combining with mathematical models. The future research directions regarding the nitrate pollution sources identification of water environment were also discussed.

  5. Kinetic theory of oxygen isotopic exchange between minerals and water

    Science.gov (United States)

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

    1987-01-01

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

  6. Oxygen isotope ratios of the Icelandic crust

    International Nuclear Information System (INIS)

    Hattori, K.; Muehlenbachs, K.

    1982-01-01

    Oxygen isotope ratios of hydrothermally altered basalts from depth of up to approx.3 km are reported from three localities in Iceland: International Research Drilling Project (IRDP) core at Reydarfjordur, eastern Iceland (Tertiary age); drill cuttings from Reykjavik (Plio-Pleistocene age); and Halocene drill cuttings from the active Krafla central volcano. Whole rock samples from these three localities have delta 18 O values averaging +3.9 +- 1.3, +2.4 +- 1.1, and -7.7 +- 2.4%, respectively. The observed values in the deeper samples from Krafla are as low as the values for any rocks previously reported. There seems to be a slight negative gradient in delta 18 O with depth at the former two localities and a more pronounced one at Krafla. Oxygen isotope fractionations between epidote and quartz and those between calcite and fluid suggests that the basalts were altered at temperatures of 300 0 --400 0 C. Low deltaD and delta 18 O of epidote and low delta 34 S of anhydrite indicate that the altering fluids in all three areas originated as meteoric waters and have undergone varied 'oxygen shifts'. Differences in the 18 O shift of the fluids are attributed to differences in hydrothermal systems; low water/rock ratios ( 5) at Krafla. The convective hydrothermal activity, which is probably driven by silicic magma beneath the central volcanoes, has caused strong subsolidus depletion of 18 O in the rocks. The primary-magnetic delta 18 O value of the rocks in the Tertiary IRDP core was about +3.9%, which is lower than that obtained for fresh basalt from other places. Such exceptionally low delta 18 O magmas are common in Iceland and may occur as the result of oxygen isotope exchange with or assimilation of altered rocks that form a thick sequence beneath the island due to isostatic subsidence

  7. Oxygen Isotopes in Early Solar System Materials: A Perspective Based on Microbeam Analyses of Chondrules from CV Carbonaceous Chondrites

    Science.gov (United States)

    Jones, R. H.; Leshin, L. A.; Guan, Y.

    2004-01-01

    Some of the biggest challenges to understanding the early history of the solar system include determining the distribution of oxygen isotopes amongst materials that existed in the solar nebula, and interpreting the processes that might have resulted in the observed isotopic distributions. Oxygen isotope ratios in any individual mineral grain from a chondritic meteorite may be the cumulative product of a variety of processes, including stellar nucleosynthetic events, gas/solid interactions in the molecular cloud, mixing of independent isotopic reservoirs in the nebula, mass-independent processing in the nebula, and mass-dependent fractionation effects in various environments. It is not possible to unravel this complex isotopic record unless the distribution of oxygen isotope ratios in chondritic materials is fully understood.

  8. Oxygen isotope partitioning between rhyolitic glass/melt and CO2: An experimental study at 550-950 degrees C and 1 bar

    International Nuclear Information System (INIS)

    Palin, J.M.; Epstein, S.; Stolper, E.M.

    1996-01-01

    Oxygen isotope partitioning between gaseous CO 2 and a natural rhyolitic glass and melt (77.7 wt% SiO 2 , 0.16 wt% H 2 O total ) has been measured at 550-950 degrees C and approximately 1 bar. Equilibrium oxygen isotope fractionation factors (α CO2-rhyolite = ( 18 O/ 16 O) rhyolite ) determined in exchange experiments of 100-255 day duration. These values agree well with predictions based on experimentally determined oxygen isotope fractionation factors for CO 2 -silica glass and CO 2 -albitic glass/melt, if the rhyolitic glass is taken to be a simple mixture of normative silica and alkali feldspar components. The results indicate that oxygen isotope partitioning in felsic glasses and melts can be modeled by linear combinations of endmember silicate constituents. Rates of oxygen isotope exchange observed in the partitioning experiments are consistent with control by diffusion of molecular H 2 O dissolved in the glass/melt and are three orders of magnitude faster than predicted for rate control solely by diffusion of dissolved molecular CO 2 under the experimental conditions. Additional experiments using untreated and dehydrated (0.09 wt% H 2 O total ) rhyolitic glass quantatively support these interpretations. We conclude that diffusive oxygen isotope exchange in rhyolitic glass/melt, and probably other polymerized silicate materials, it controlled by the concentrations and diffusivities of dissolved oxygen-bearing volatile species rather than diffusion of network oxygen under all but the most volatile-poor conditions. 25 refs., 6 figs., 1 tab

  9. CAN GALACTIC CHEMICAL EVOLUTION EXPLAIN THE OXYGEN ISOTOPIC VARIATIONS IN THE SOLAR SYSTEM?

    International Nuclear Information System (INIS)

    Lugaro, Maria; Liffman, Kurt; Ireland, Trevor R.; Maddison, Sarah T.

    2012-01-01

    A number of objects in primitive meteorites have oxygen isotopic compositions that place them on a distinct, mass-independent fractionation line with a slope of one on a three-isotope plot. The most popular model for describing how this fractionation arose assumes that CO self-shielding produced 16 O-rich CO and 16 O-poor H 2 O, where the H 2 O subsequently combined with interstellar dust to form relatively 16 O-poor solids within the solar nebula. Another model for creating the different reservoirs of 16 O-rich gas and 16 O-poor solids suggests that these reservoirs were produced by Galactic chemical evolution (GCE) if the solar system dust component was somewhat younger than the gas component and both components were lying on the line of slope one in the O three-isotope plot. We argue that GCE is not the cause of mass-independent fractionation of the oxygen isotopes in the solar system. The GCE scenario is in contradiction with observations of the 18 O/ 17 O ratios in nearby molecular clouds and young stellar objects. It is very unlikely for GCE to produce a line of slope one when considering the effect of incomplete mixing of stellar ejecta in the interstellar medium. Furthermore, the assumption that the solar system dust was younger than the gas requires unusual timescales or the existence of an important stardust component that is not theoretically expected to occur nor has been identified to date.

  10. 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

  11. 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.

  12. 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

  13. Oxygen and carbon isotopic compositions of gases respired by humans

    International Nuclear Information System (INIS)

    Epstein, S.; Zeiri, L.

    1988-01-01

    Oxygen-isotope fractionation associated with respiration in human individuals at rest is linearly related to the fraction of the O 2 utilized in the respiration process. The slope of this relationship is affected by a history of smoking, by vigorous exercise, and by the N 2 /O 2 ratio of the inhaled gas. For patients who suffer anemia-related diseases, the slope of this relationship is directly proportional to their level of hemoglobin. These results introduce a new approach for studying the mechanisms of O 2 consumption in human respiration and how they are affected by related diseases

  14. A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee, Switzerland

    NARCIS (Netherlands)

    Teranes, J.L.; McKenzie, J.A.; Bernasconi, S.M.; Lotter, A.F.; Sturm, M.

    1999-01-01

    Abstract—In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in

  15. 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

  16. 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

  17. 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.

  18. 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

  19. Planetary fertility during the past 400 ka based on the triple isotope composition of atmospheric oxygen in trapped gases from the Vostok ice core

    Science.gov (United States)

    Blunier, T.; Bender, M. L.; Barnett, B.; von Fisher, J. C.

    2012-04-01

    The productivity of the biosphere leaves its imprint on the isotopic composition of atmospheric oxygen. Ultimately atmospheric oxygen, through photosynthesis, originates from seawater. Fractionations during the passage from seawater to atmospheric O2 and during respiration are mass dependent, affecting δ17O about half as much as δ18O. An "anomalous" (also termed mass independent) fractionation process changes δ17O about 1.7 times as much as δ18O during isotope exchange between O2 and CO2 in the stratosphere. The relative rates of biological O2 production and stratospheric processing determine the relationship between δ17O and δ18O of O2 in the atmosphere. Variations of this relationship thus allow us to estimate changes in the rate of mass dependent O2 production by photosynthesis versus the rate of mass independent O2-CO2 exchange in the stratosphere. However, the analysis of the 17O anomaly is complicated because each hydrological and biological process influencing δ17O and δ18O fractionates 17O and 18O in slightly different proportions. In this study we present oxygen data covering the last 400 kyr from the Vostok ice core. We reconstruct oxygen productivities from the triple isotope composition of atmospheric oxygen with a box model. Our steady state model for the oxygen cycle takes into account fractionation during photosynthesis and respiration of the land and ocean biosphere as well as fractionation when oxygen passes through the stratosphere. We consider changes of fractionation factors linked to climate variations taking into account the span of estimates of the main factors affecting our calculations. We find that ocean oxygen productivity was likely elevated relative to modern during glacials. However, this increase probably did not fully compensate for a reduction in land ocean productivity resulting in a slight reduction in total oxygen production during glacials.

  20. Theory of oxygen isotope exchange

    NARCIS (Netherlands)

    den Otter, M.W.; Boukamp, Bernard A.; Bouwmeester, Henricus J.M.

    2001-01-01

    Transients for oxygen molecular mass numbers 32, 34 and 36 are derived which can be used for the interpretation of oxygen isotope exchange data based on measurement of concentrations of 16O2, 16O18O and 18O2 in the gas phase. Key parameters in the theory are the rate at which oxygen molecules are

  1. The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

    Science.gov (United States)

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

    2015-07-01

    Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (myo-inositol hexakisphosphate, IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields available Pi and less phosphorylated inositol derivates as products. The hydrolysis of organic P compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'-monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as a substrate were prepared. During the hydrolysis of IP6 by phytase, four of the six Pi were released, and one oxygen atom from water was incorporated into each Pi. This incorporation of oxygen from water into Pi was subject to an apparent inverse isotopic fractionation (ϵ ~ 6 to 10 ‰), which was similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ~ 7 ‰), where less than three Pi were released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ~ -12 ‰), similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ϵ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking

  2. Oxygen Isotopes in Chondritic Interplanetary Dust: Parent-Bodies and Nebular Oxygen Reservoirs

    International Nuclear Information System (INIS)

    Aleon, J; McKeegan, K D; Leshin, L

    2006-01-01

    Planetary objects have preserved various amounts of oxygen issued from isotopically different oxygen reservoirs reflecting their origin and physico-chemical history. An 16 O-rich component is preserved in refractory inclusions (CAIs) whereas meteorites matrices are enriched in an 16 O-poor component. The origin of these components is still unclear. The most recent models are based on isotope selective photodissociation of CO in a 16 O-rich nebula/presolr cloud resulting in a 16 O-poor gas in the outer part of the nebula. However because most meteorite components are thought to be formed in the inner 3AU of the solar nebula, the precise isotopic composition of outer solar system components is yet unknown. In that respect, the oxygen isotopic composition of cometary dust is a key to understand the origin of the solar system. The Stardust mission will bring back to the Earth dust samples from comet Wild2, a short period comet from the Jupiter family. A precise determination of the oxygen isotope composition of Wild2 dust grains is essential to decipher the oxygen reservoirs of the outer solar system. However, Stardust samples may be extremely fragmented upon impact in the collector. In addition, interplanetary dust particles (IDPs) collected in the stratosphere are likely to contain comet samples. Therefore, they started to investigate the oxygen isotopic composition of a suite of chondritic interplanetary dust particles that includes IDPs of potential cometary origin using a refined procedure to increase the lateral resolution for the analysis of Stardust grains or IDP subcomponents down to ∼ 3 (micro)m. High precision data for 4 IDPs were previously reported, here they have measured 6 additional IDPs

  3. Oxygen Isotope Records in Modern Oyster Shells from Chi Ku, Tainan and Their Implication of Seasonality

    Science.gov (United States)

    Chen, Y. C.; Mii, H. S.; Li, K. T.

    2015-12-01

    To exam whether oxygen isotope records of Crassostrea gigasoysters can be used as proxies of environment, 133 cultivated oysters and 21 water samples were collected from Chi Ku area, Tainan City, southern Taiwan in December of 2012, and from March, 2013 to July, 2014. Instrumental air and water temperatures and precipitation records were obtained from a nearest Central Weather Bureau (CWB) station roughly 16 km north of Chi Ku. The oxygen and carbon isotope values of the ligamental area of the modern oyster shells are from -6.92‰ to -0.08‰ (-3.05 ± 1.17‰, N = 2280; 1σ; VPDB) and from -5.57‰ to 0.63‰ (-1.88 ± 0.81‰), respectively. Oxygen isotope values of the water samples are mainly between -0.28‰ and 0.74‰ (0.18 ± 0.29‰, N = 20; 1σ; VSMOW). However, water oxygen isotope value of -2.75‰ was observed for the water sample collected immediately after a typhoon heavy rainfall. Seasonal temperature fluctuation pattern of estimated oxygen isotope temperatures from modern shells is similar to that of CWB instrumental records. However, the oxygen isotope temperatures are respectively about 3 °C and 10°C higher than those of instrumental records for winter and summer. Higher estimated oxygen isotope temperatures are most likely caused by underestimated fraction of freshwater. We analyzed 5 archaeological oyster shells of Siraya culture (500~250B.P.) collected from Wu Chien Tuso North (WCTN) archaeological site of Tainan branch of Southern Taiwan Science Park to infer the harvest season of mollusks. Oxygen isotope values of the ligamental area of the archaeological oyster shells are between -5.98‰ and -1.26‰ (-3.34 ± 1.37‰, N = 60; 1σ), and carbon isotope values are between -3.21‰ and 0.60‰ (-2.04‰ ± 0.55‰). The oxygen isotope records of archaeological oyster shells also showed clear seasonality. Most of the oysters were collected in autumn and winter. Oxygen isotope values of archaeological oyster shells was 1‰ greater than that

  4. A latitudinal study of oxygen isotopes within horsehair

    Science.gov (United States)

    Thompson, E.; Bronk Ramsey, C.; McConnell, J. R.

    2016-12-01

    This study aims to explore the hypothesis that 'if oxygen isotope ratios deplete with decreasing temperature then a study of oxygen isotope ratios within horsehair from Oxfordshire to Iceland will show a latitudinal depletion gradient'. By looking at oxygen isotope values at different geographical positions, we can track the relationship with latitude and with different regional climate features. This will provide a firmer understanding of how to compare climate records from different locations. Additionally, a comparison of the horse breeds from this study to those analysed within previous studies will create an even better understanding of the intra-species variation within the δ18O values of horsehair. A total of 24 horses were sampled on the 7th March from Thordale Stud in Shetland, the Icelandic Food And Veterinary Authority in Iceland, the Exmoor Pony Centre in Exmoor and the Pigeon House Equestrian Centre in Oxfordshire. By starting the sampling process from the most recent growth at the follicle, the sampling date becomes a chronological marker, temporally fixing the first sample within a sequential set of data points extending for one year or longer, depending on the length of each individual hair. The samples were analysed for oxygen isotope values using an IRMS coupled within a Sercon HTEA. Preliminary results show a latitudinal gradient is evident on comparison between the locations, consistent with the findings of Darling and Talbot's study of fresh water isotopes in the British Isles (2003). These results support the hypothesis, showing that a study of oxygen isotope ratios within horse hair from Oxfordshire to Iceland showing a latitudinal depletion gradient, consistent with a depletion of oxygen isotope ratios due to decreasing temperatures. Darling, W. and Talbot, J. (2003). The O and H stable isotope composition of freshwaters in the British Isles. 1. Rainfall. Hydrol. Earth System Science, 7(2), pp.163-181.

  5. The transport of oxygen isotopes in hydrothermal systems

    International Nuclear Information System (INIS)

    McKibbin, R.; Absar, A.; Blattner, P.

    1986-01-01

    As groundwater passes through porous rocks, exchange of oxygen between the fluid and the solid matrix causes a change in the oxygen isotope concentrations in both water and rock. If the rate at which the exchange takes place can be estimated (as a function of the isotope concentrations and temperature) then the time taken for a rock/water system to come to equilibrium with respect to isotope concentration might be calculated. In this paper, the equation for isotope transport is derived using conservation laws, and a simple equation to describe the rate of isotope exchange is proposed. These are combined with the equations for fluid flow in a porous medium, to produce a general set of equations describing isotope transport in a hydrothermal system. These equations are solved numerically, using typical parameters, for the one-dimensional case. Oxygen isotope data from the basement rocks underlying Kawerau geothermal field are modelled. The results indicate that the time taken for exchange of 18 O to present-day values is less than the postulated age of hydrothermal alteration in that field. This suggests that, although controlled by similar parameters, oxygen isotope exchange, in felsic rocks at least, is much faster than hydrothermal alteration. This conclusion is consistent with the petrographic observations from the Kawerau system as well as other geothermal fields

  6. 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

  7. 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

  8. 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.

  9. Accurate and precise measurement of oxygen isotopic fractions and diffusion profiles by selective attenuation of secondary ions (SASI).

    Science.gov (United States)

    Téllez, Helena; Druce, John; Hong, Jong-Eun; Ishihara, Tatsumi; Kilner, John A

    2015-03-03

    The accuracy and precision of isotopic analysis in Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) relies on the appropriate reduction of the dead-time and detector saturation effects, especially when analyzing species with high ion yields or present in high concentrations. Conventional approaches to avoid these problems are based on Poisson dead-time correction and/or an overall decrease of the total secondary ion intensity by reducing the target current. This ultimately leads to poor detection limits for the minor isotopes and high uncertainties of the measured isotopic ratios. An alternative strategy consists of the attenuation of those specific secondary ions that saturate the detector, providing an effective extension of the linear dynamic range. In this work, the selective attenuation of secondary ion signals (SASI) approach is applied to the study of oxygen transport properties in electroceramic materials by isotopic labeling with stable (18)O tracer and ToF-SIMS depth profiling. The better analytical performance in terms of accuracy and precision allowed a more reliable determination of the oxygen surface exchange and diffusion coefficients while maintaining good mass resolution and limits of detection for other minor secondary ion species. This improvement is especially relevant to understand the ionic transport mechanisms and properties of solid materials, such as the parallel diffusion pathways (e.g., oxygen diffusion through bulk, grain boundary, or dislocations) in electroceramic materials with relevant applications in energy storage and conversion devices.

  10. 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

  11. Oxygen isotopes in mammal bone phosphate: A new tool for paleohydrological and paleoclimatological research?

    Science.gov (United States)

    Longinelli, Antonio

    1984-02-01

    Oxygen isotope analyses of water in blood of humans and domestic pigs indicate that the oxygen isotope fractionation effects between ingested water and body water are the same in all specimens of the same species. The δ18O of body water has been shown to vary linearly with the mean δ18O of local meteoric water. This conclusion also holds for the bone phosphate. Thus, δ18O( PO3-4) values of unaltered fossil bones from humans and domestic pigs can be used to reconstruct the δ18O values of local meteoric waters during the life-times of the mammals. Such data can be used for paleohydrological and paleoclimatological studies both on land and at sea.

  12. Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

    Science.gov (United States)

    Yurimoto; Ito; Nagasawa

    1998-12-04

    A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

  13. Fractionation behavior of chromium isotopes during coprecipitation with calcium carbonate

    DEFF Research Database (Denmark)

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

    2015-01-01

    Interest in chromium (Cr) isotope incorporation into carbonates arises from the observation that Cr isotopic composition of carbonates could be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenviro......Interest in chromium (Cr) isotope incorporation into carbonates arises from the observation that Cr isotopic composition of carbonates could be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track...

  14. 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

  15. Analysis of Atmospheric Nitrate Deposition in Lake Tahoe Using Multiple Oxygen Isotopes

    Science.gov (United States)

    McCabe, J. R.; Michalski, G. M.; Hernandez, L. P.; Thiemens, M. H.; Taylor, K.; Kendall, C.; Wankel, S. D.

    2002-12-01

    oxygen isotopes of atmospheric nitrate are mass-independently fractionated and contain Δ17O values of 20 to 30 \\permil, while all other sources are mass dependent (Δ17O = 0 \\permil). Any subsequent fractionation of the atmospheric nitrate will leave the mass-independent signature unchanged making Δ17O of nitrate a conservative tracer of atmospheric nitrate. Results from measurements of the oxygen isotope composition of nitrate in Lake Tahoe are used to resolve the atmospheric contribution.

  16. 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...

  17. 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

  18. Iron Isotope Fractionation during Fe(II) Oxidation Mediated by the Oxygen-Producing Marine Cyanobacterium Synechococcus PCC 7002

    Energy Technology Data Exchange (ETDEWEB)

    Swanner, E. D.; Bayer, T.; Wu, W.; Hao, L.; Obst, M.; Sundman, A.; Byrne, J. M.; Michel, F. M.; Kleinhanns, I. C.; Kappler, A.; Schoenberg, R.

    2017-04-11

    In this study, we couple iron isotope analysis to microscopic and mineralogical investigation of iron speciation during circumneutral Fe(II) oxidation and Fe(III) precipitation with photosynthetically produced oxygen. In the presence of the cyanobacterium Synechococcus PCC 7002, aqueous Fe(II) (Fe(II)aq) is oxidized and precipitated as amorphous Fe(III) oxyhydroxide minerals (iron precipitates, Feppt), with distinct isotopic fractionation56Fe) values determined from fitting the δ56Fe(II)aq (1.79‰ and 2.15‰) and the δ56Feppt (2.44‰ and 2.98‰) data trends from two replicate experiments. Additional Fe(II) and Fe(III) phases were detected using microscopy and chemical extractions and likely represent Fe(II) and Fe(III) sorbed to minerals and cells. The iron desorbed with sodium acetate (FeNaAc) yielded heavier δ56Fe compositions than Fe(II)aq. Modeling of the fractionation during Fe(III) sorption to cells and Fe(II) sorption to Feppt, combined with equilibration of sorbed iron and with Fe(II)aq using published fractionation factors, is consistent with our resulting δ56FeNaAc. The δ56Feppt data trend is inconsistent with complete equilibrium exchange with Fe(II)aq. Because of this and our detection of microbially excreted organics (e.g., exopolysaccharides) coating Feppt in our microscopic analysis, we suggest that electron and atom exchange is partially suppressed in this system by biologically produced organics. These results indicate that cyanobacteria influence the fate and composition of iron in sunlit environments via their role in Fe(II) oxidation through O2 production, the capacity of their cell surfaces to sorb iron, and the interaction of secreted organics with Fe(III) minerals.

  19. 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.

  20. 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

  1. 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....

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

    Science.gov (United States)

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

    2017-10-01

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

  3. 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.

  4. 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.

  5. 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.

  6. Carbon, nitrogen and oxygen isotope fractionation during food cooking: Implications for the interpretation of the fossil human record.

    Science.gov (United States)

    Royer, Aurélien; Daux, Valérie; Fourel, François; Lécuyer, Christophe

    2017-08-01

    Stable isotope data provide insight into the reconstruction of ancient human diet. However, cooking may alter the original stable isotope compositions of food due to losses and modifications of biochemical and water components. To address this issue, carbon, nitrogen and oxygen isotope ratios were measured on meat aliquots sampled from various animals such as pork, beef, duck and chicken, and also from the flesh of fishes such as salmon, European seabass, European pilchard, sole, gilt-head bream, and tuna. For each specimen, three pieces were cooked according to the three most commonly-known cooking practices: boiling, frying and roasting on a barbecue. Our data show that cooking produced isotopic shifts up to 1.8‰, 3.5‰, and 5.2‰ for δ 13 C, δ 15 N, and δ 18 O values, respectively. Such variations between raw and cooked food are much greater than previously estimated in the literature; they are more sensitive to the type of food rather than to the cooking process itself, except in the case of boiling. Reconstructions of paleodietary may thus suffer slight bias in cases of populations with undiversified diets that are restrained toward a specific raw or cooked product, or using a specific cooking mode. In cases of oxygen isotope compositions from skeletal remains (bones, teeth), they not only constitute a valuable proxy for reconstructing past climatic conditions, but they could also be used to improve our knowledge of past human diet. © 2017 Wiley Periodicals, Inc.

  7. 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

  8. 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

  9. Carbon and Oxygen isotopic composition in paleoenvironmental determination

    International Nuclear Information System (INIS)

    Silva, J.R.M. da.

    1978-01-01

    This work reports that the carbon and oxygen isotopic composition separate the mollusks from marine environment of the mollusks from continental environment in two groups isotopically different, making the biological control outdone by environment control, in the isotopic fragmentation mechanisms. The patterns from the continental environment are more rich in O 16 than the patterns from marine environments. The C 12 is also more frequent in the mollusks from continental environments. The carbon isotopic composition in paterns from continental environments is situated betwen - 10.31 and - 4,05% and the oxygen isotopic composition is situated between - 6,95 and - 2,41%. To the marine environment patterns the carbon isotopic composition is between - 2,08 and + 2,65% and the oxigen isotopic composition is between - 2,08 and + 0,45%. Was also analysed fossil marine mollusks shells and their isotopic composition permit the formulation of hypothesis about the environment which they lived. (C.D.G.) [pt

  10. Stable hydrogen, oxygen and sulfur isotopes composition in different tissues of cattle

    International Nuclear Information System (INIS)

    Sun Fengmei; Shi Guangyu; Wang Huiwen; Yang Shuming

    2012-01-01

    In order to research on stable hydrogen, oxygen, sulfur isotopes composition in different tissues of cattle, as well as the breed, δ 2 H and δ 34 S values of different defatted muscle, cattle tail hair, blood, liver, also δ 2h and δ 18 O values of water from muscle were determined by isotope ratio mass spectrometry. The stable sulfur isotope composition was not affected by cattle variety, meanwhile the hydrogen was uncertain; the δ 2 H and δ 34 S values between different defatted muscle, blood, liver, cattle hair were significantly different, at the same time the δ 34 S and δ 2 H values between each tissue were not significantly correlated; the δ 2 H values were strongly correlated with the δ 18 O values of muscle water. The above results indicated that stable sulfur and hydrogen isotopes fractionation in the various tissues were discrepant, thus the proper tissue should be selected according to the purpose and object in the beef traceability. (authors)

  11. Carbon, hydrogen oxygen isotope studies on imbedded old tree ring and paleoclimate reconstruction

    International Nuclear Information System (INIS)

    Sun Yanrong; Mu Zhiguo; Cui Haiting

    2002-01-01

    Tree ring is a kind of natural archives, on which the isotopic analysis is important to study global climate and environmental change. The authors mainly provide a comprehensive introduction to the fractionation models of carbon, hydrogen and oxygen isotope in plants, their research technique and the extract methods from cellulose. That results show isotopic tracer can record the message of climatic variation and has become a powerful tool for paleoclimate reconstruction and for the modern environment changing research. Especially studying on PAGES. the cellulose isotopic analyses of imbedded old tree ring have become the mainly quantitative means of environmental evolvement. In addition, China is a typical monsoon country, research in tree ring stable isotope seasonal variation can give a lot of important information on that. Up to now, the research techniques and works on tree ring in China are still in its earlier stage, and remain many limitations. It needs further accumulate basic research materials, intensity regional contrast and intercross studies on relative subjects

  12. Major events in Neogene oxygen isotopic records

    International Nuclear Information System (INIS)

    Kennett, J.P.; Hodell, D.A.

    1986-01-01

    Changes in oxygen isotopic ratios of foraminiferal calcite during the cainozoic have been one of the primary tools for investigating the history of Arctic and Antarctic glaciation, although interpretations of the oxygen isotopic record differ markedly. The ambiguity in interpretation results mainly from the partitioning of temperature from ice volume effects in delta 18 O changes. Oxygen isotopic records for the Cainozoic show an increase in delta 18 O values towards the present, reflecting gradual cooling and increased glaciation of the Earth's climate since the late Cretaceous. A variety of core material from the South Atlantic and South-west Pacific oceans are investigated. This composite data represents one of the most complete available with which to evaluate the evolution of glaciation during the Neogene. Expansion of ice shelves in Antarctica undoubtedly accompanied the increased glaciation of the northern hemisphere, since eustatic sea-level lowering would positively reinforce ice growth on Antarctica

  13. 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

  14. 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

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. Oxygen isotopic ratio of the diatom siliceous valves: development of a new method in quantitative paleoclimatology

    International Nuclear Information System (INIS)

    Labeyrie, Laurent.

    1979-07-01

    This paper describes a new method allowing the measurement of the 18 O/ 16 O ratio of the biogenic silica oxygen, which takes into account the effects due to the organic matter and hydration water associated with this type of silica. By isotopic exchange with enriched water, we have been able to fix a treatment which eliminate all contamination and memory effects. This has permitted us to study the temperature dependance of the hydrated silica-water oxygen isotopic fractionation. As application, we present a study of the variations of the delta 18 O of fossil diatoms valves along an Equatorial Pacific sediment core covering the last 20.000 years. The results demonstrate the usefulness of the delta 18 O of the diatom silica for paleoclimatic investigations [fr

  20. 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

  1. 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.

  2. 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.

  3. 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

  4. The Oxygen Isotopic Composition of Phosphate: A Tracer for Phosphate Sources and Cycling

    Energy Technology Data Exchange (ETDEWEB)

    Mclaughlin, K. [Southern California Coastal Water Research Project, Costa Mesa, University of California, CA (United States); Young, M. B.; Paytan, A.; Kendall, C. [U.S. Geological Survey, University of California, CA (United States)

    2013-05-15

    Phosphorus (P) is a limiting macro-nutrient for primary productivity and anthropogenic P-loading to aquatic ecosystems is one of the leading causes of eutrophication in many ecosystems throughout the world. Because P has only one stable isotope, traditional isotope techniques are not possible for tracing sources and cycling of P in aquatic systems. However, much of the P in nature is bonded to four oxygen (O) atoms as orthophosphate (PO{sub 4}{sup 3-}). The P-O bonds in orthophosphate are strongly resistant to inorganic hydrolysis and do not exchange oxygen with water without biological mediation (enzyme-mediated recycling). Thus, the oxygen isotopic composition of dissolved inorganic phosphate ({delta}{sup 18}O{sub p}) may be used as a tracer for phosphate sources and cycling in aquatic ecosystems. Recently, several studies have been conducted utilizing {delta}{sup 18}O{sub p} as a tracer for phosphate sources and cycling in various aquatic environments. Specifically, work to date indicates that {delta}{sup 18}O{sub p} is useful for determining sources of phosphate to aquatic systems if these sources have unique isotopic signatures and phosphate cycling within the system is limited compared to input fluxes. In addition, because various processes imprint specific fractionation effects, the {delta}{sup 18}O{sub p} tracer can be utilized to determine the degree of phosphorous cycling and processing through the biomass. This chapter reviews several of these studies and discusses the potential to utilize the {delta}{sup 18}O{sub p} of phosphate in rivers and streams. (author)

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

    Science.gov (United States)

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

    2013-06-01

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

  6. Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

    Science.gov (United States)

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

    2016-12-01

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

  7. 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...

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

    Science.gov (United States)

    Maggi, Federico; Riley, William J.

    2009-12-01

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

  9. [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

  10. Do oxygen stable isotopes track precipitation moisture source in vascular plant dominated peatlands?

    Science.gov (United States)

    Charman, D.; Amesbury, M. J.; Newnham, R.; Loader, N.; Goodrich, J. P.; Gallego-Sala, A. V.; Royles, J.; Keller, E. D.; Baisden, W. T.

    2014-12-01

    Variations in the isotopic composition of precipitation are determined by fractionation processes which occur during temperature and humidity dependent phase changes associated with evaporation and condensation. Oxygen stable isotope ratios have therefore been frequently used as a source of palaeoclimate data from a variety of proxy archives. Exploitation of this record from ombrotrophic peatlands, where the source water used in cellulose synthesis is derived solely from precipitation, has been mostly limited to Northern Hemisphere Sphagnum-dominated bogs, with limited application in the Southern Hemisphere (SH) or in peatlands dominated by vascular plants. Throughout New Zealand (NZ), the preserved root matrix of the restionaceous wire rush (Empodisma spp.) forms deep peat deposits. NZ provides an ideal location to undertake empirical research into oxygen isotope fractionation in vascular peatlands because sites are ideally suited to single taxon analysis, preserve potentially high resolution full Holocene palaeoclimate records and are situated in the climatically sensitive SH mid-latitudes. Crucially, large gradients exist in the mean isotopic composition of precipitation across NZ, caused primarily by the relative influence of different climate modes. We test the capacity for δ18O analysis of Empodisma alpha cellulose from ombrotrophic restiad peatlands in NZ to provide a methodology for developing palaeoclimate records. We took surface plant, water and precipitation samples over spatial (six sites spanning >10° latitude) and temporal (monthly measurements over one year) gradients. We found a strong link between the isotopic compositions of surface root water, the most likely source water for plant growth, and precipitation in both datasets. Back-trajectory modelling of precipitation moisture source for rain days prior to sampling showed clear seasonality in the temporal data that was reflected in surface root water. The link between source water and plant

  11. Rate of oxygen isotope exchange between selenate and water.

    Science.gov (United States)

    Kaneko, Masanori; Poulson, Simon R

    2012-04-17

    The rate of oxygen isotope exchange between selenate and water was investigated at conditions of 10 to 80 °C and pH -0.6 to 4.4. Oxygen isotope exchange proceeds as a first-order reaction, and the exchange rate is strongly affected by reaction temperature and pH, with increased rates of isotope exchange at higher temperature and lower pH. Selenate speciation (HSeO(4)(-) vs SeO(4)(2-)) also has a significant effect on the rate of isotope exchange. The half-life for isotope exchange at example natural conditions (25 °C and pH 7) is estimated to be significantly in excess of 10(6) years. The very slow rate of oxygen isotope exchange between selenate and water under most environmental conditions demonstrates that selenate-δ(18)O signatures produced by biogeochemical processes will be preserved and hence that it will be possible to use the value of selenate-δ(18)O to investigate the biogeochemical behavior of selenate, in an analogous fashion to the use of sulfate-δ(18)O to study the biogeochemical behavior of sulfate.

  12. Normalization of oxygen and hydrogen isotope data

    Science.gov (United States)

    Coplen, T.B.

    1988-01-01

    To resolve confusion due to expression of isotopic data from different laboratories on non-corresponding scales, oxygen isotope analyses of all substances can be expressed relative to VSMOW or VPDB (Vienna Peedee belemnite) on scales normalized such that the ??18O of SLAP is -55.5% relative to VSMOW. H3+ contribution in hydrogen isotope ratio analysis can be easily determined using two gaseous reference samples that differ greatly in deuterium content. ?? 1988.

  13. Stable Oxygen-18 and Deuterium Isotopes

    DEFF Research Database (Denmark)

    Müller, Sascha

    The application of stable Oxygen-18 (18O) and Deuterium (2H) isotopes, as a tracer for fluxes between different compartments of the water cycle was subject of the present PhD-thesis. During a three year period, temporal data from a wide range of water cycle constituents was collected from...... the Skjern River catchment, Denmark. The presented applications focused on studying the isotopic 'input signal' to the hydrosphere in the form of precipitation, the isotopic 'output signal' with its related dynamic processes at a coastal saltwater-freshwater interface (groundwater isotopes) and the temporal...... development within a given lowland headwater catchment (stream water isotopes). Based on our investigations on the precipitation isotopic composition a local meteoric water line (LMWL) was constructed and expressed as: δ2H=7.4 δ18O + 5.36‰. Moreover, we showed that under maritime temperature climate influence...

  14. 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

  15. Copper isotope fractionation in acid mine drainage

    Science.gov (United States)

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

    2009-01-01

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

  16. Dolomite clumped isotope constraints on the oxygen isotope composition of the Phanerozoic Sea

    Science.gov (United States)

    Ryb, U.; Eiler, J. M.

    2017-12-01

    The δ18O value of the Phanerozoic Sea has been debated several decades, largely motivated by an 8‰ increase in δ18O of sedimentary carbonates between the Cambrian and the present. Some previous studies have interpreted this increase to be a primary depositional signal, resulting from an increase in the 18O content of ocean water over time, or from a decrease in ocean temperature increasing the oxygen isotope fractionation between seawater and carbonates. In contrast, other studies have interpreted lower δ18O compositions as the products of diagenetic alteration at elevated burial temperatures. Here, we show that the Phanerozoic dolomite δ18O record overlaps with that of well-preserved calcite fossils, and use carbonate clumped isotope measurements of Cambrian to Pleistocene dolomites to calculate their formation temperatures and the isotopic compositions of their parent-waters. The observed variation in dolomite δ18O is largely explained by dolomite formation at burial temperatures of up to 158°C. The δ18O values of dolomite parent-waters range -2 to +12‰ and are correlated with formation temperatures. Such correlation is consistent with the modification of seawater (0±2‰, VSMOW) toward isotopically heavier compositions through water-rock reactions at elevated burial temperatures. The similarity between the dolomite and calcite δ18O records, and published clumped isotope-based calculations of water compositions, suggests that like dolomite, temporal variations of the calcite δ18O record may also be largely driven by diagenetic alteration. Finally, the relationship we observe between temperature of dolomitization and d18O of dolomite suggests platform carbonates generally undergo dolomitization through reaction with modified marine waters, and that there is no evidence those waters were ever significantly lower in d18O than the modern ocean.

  17. No oxygen isotope exchange between water and APS-sulfate at surface temperature: Evidence from quantum chemical modeling and triple-oxygen isotope experiments

    Science.gov (United States)

    Kohl, Issaku E.; Asatryan, Rubik; Bao, Huiming

    2012-10-01

    In both laboratory experiments and natural environments where microbial dissimilatory sulfate reduction (MDSR) occurs in a closed system, the δ34S ((34S/32S)sample/(34S/32S)standard - 1) for dissolved SO42- has been found to follow a typical Rayleigh-Distillation path. In contrast, the corresponding δ18O ((18O/16O)sample/(18O/16O)standard) - 1) is seen to plateau with an apparent enrichment of between 23‰ and 29‰ relative to that of ambient water under surface conditions. This apparent steady-state in the observed difference between δ18O and δ18OO can be attributed to any of these three steps: (1) the formation of adenosine-5'-phosphosulfate (APS) from ATP and SO42-, (2) oxygen exchange between sulfite (or other downstream sulfoxy-anions) and water later in the MDSR reaction chain and its back reaction to APS and sulfate, and (3) the re-oxidation of produced H2S or precursor sulfoxy-anions to sulfate in environments containing Fe(III) or O2. This study examines the first step as a potential pathway for water oxygen incorporation into sulfate. We examined the structures and process of APS formation using B3LYP/6-31G(d,p) hybrid density functional theory, implemented in the Gaussian-03 program suite, to predict the potential for oxygen exchange. We conducted a set of in vitro, enzyme-catalyzed, APS formation experiments (with no further reduction to sulfite) to determine the degree of oxygen isotope exchange between the APS-sulfate and water. Triple-oxygen-isotope labeled water was used in the reactor solutions to monitor oxygen isotope exchange between water and APS sulfate. The formation and hydrolysis of APS were identified as potential steps for oxygen exchange with water to occur. Quantum chemical modeling indicates that the combination of sulfate with ATP has effects on bond strength and symmetry of the sulfate. However, these small effects impart little influence on the integrity of the SO42- tetrahedron due to the high activation energy required for

  18. Natural fractionation of uranium isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Noordmann, Janine

    2015-01-24

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

  19. 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.

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

    Science.gov (United States)

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

    2018-06-01

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

  1. Technical note: Consistent calculation of aquatic gross production from oxygen triple isotope measurements

    Directory of Open Access Journals (Sweden)

    J. Kaiser

    2011-07-01

    Full Text Available Oxygen triple isotope measurements can be used to calculate aquatic gross oxygen production rates. Past studies have emphasised the appropriate definition of the 17O excess and often used an approximation to derive production rates from the 17O excess. Here, I show that the calculation can be phrased more consistently and without any approximations using the relative 17O/16O and 18O/16O isotope ratio differences (delta values directly. I call this the "dual delta method". The 17O excess is merely a mathematical construct and the derived production rate is independent of its definition, provided all calculations are performed with a consistent definition. I focus on the mixed layer, but also show how time series of triple isotope measurements below the mixed layer can be used to derive gross production.

    In the calculation of mixed layer productivity, I explicitly include isotopic fractionation during gas invasion and evasion, which requires the oxygen supersaturation s to be measured as well. I also suggest how bubble injection could be considered in the same mathematical framework. I distinguish between concentration steady state and isotopic steady state and show that only the latter needs to be assumed in the calculation. It is even possible to derive an estimate of the net production rate in the mixed layer that is independent of the assumption of concentration steady state.

    I review measurements of the parameters required for the calculation of gross production rates and show how their systematic uncertainties as well as the use of different published calculation methods can cause large variations in the production rates for the same underlying isotope ratios. In particular, the 17O excess of dissolved O2 in equilibrium with atmospheric O2 and the 17O excess of photosynthetic O2 need to

  2. Nitrogen and oxygen isotopic constraints on the origin of atmospheric nitrate in coastal Antarctica

    Directory of Open Access Journals (Sweden)

    J. Savarino

    2007-01-01

    isotopic composition, known atmospheric transport patterns and the current understanding of kinetics and isotope effects of relevant atmospheric chemical processes, we suggest that elevated tropospheric nitrate levels during Period 3 are most likely the result of nitrate sedimentation from polar stratospheric clouds (PSCs, whereas elevated nitrate levels during Period 4 are likely to result from snow re-emission of nitrogen oxide species. We are unable to attribute the source of the nitrate during periods 1 and 2 to local production or long-range transport, but note that the oxygen isotopic composition is in agreement with day and night time nitrate chemistry driven by the diurnal solar cycle. A precise quantification is difficult, due to our insufficient knowledge of isotope fractionation during the reactions leading to nitrate formation, among other reasons.

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

    Science.gov (United States)

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

    2017-08-01

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

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

    Science.gov (United States)

    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

  5. Growth history of cultured pearl oysters based on stable oxygen isotope analysis

    Science.gov (United States)

    Nakashima, R.; Furuta, N.; Suzuki, A.; Kawahata, H.; Shikazono, N.

    2007-12-01

    We investigated the oxygen isotopic ratio in shells of the pearl oyster Pinctada martensii cultivated in embayments in Mie Prefecture, central Japan, to evaluate the biomineralization of shell structures of the species and its pearls in response to environmental change. Microsamples for oxygen isotope analysis were collected from the surfaces of shells (outer, middle, and inner shell layers) and pearls. Water temperature variations were estimated from the oxygen isotope values of the carbonate. Oxygen isotope profiles of the prismatic calcite of the outer shell layer reflected seasonal variations of water temperature, whereas those of nacreous aragonites of the middle and inner shell layers and pearls recorded temperatures from April to November, June to September, and July to September, respectively. Lower temperatures in autumn and winter might slow the growth of nacreous aragonites. The oxygen isotope values are controlled by both variations of water temperature and shell structures; the prismatic calcite of this species is useful for reconstructing seasonal changes of calcification temperature.

  6. 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?...

  7. OXYGEN ISOTOPIC COMPOSITIONS OF SOLAR CORUNDUM GRAINS

    International Nuclear Information System (INIS)

    Makide, Kentaro; Nagashima, Kazuhide; Huss, Gary R.; Krot, Alexander N.

    2009-01-01

    Oxygen is one of the major rock-forming elements in the solar system and the third most abundant element of the Sun. Oxygen isotopic composition of the Sun, however, is not known due to a poor resolution of astronomical spectroscopic measurements. Several Δ 17 O values have been proposed for the composition of the Sun based on (1) the oxygen isotopic measurements of the solar wind implanted into metallic particles in lunar soil ( 2 O 3 ) is thermodynamically the first condensate from a cooling gas of solar composition. Corundum-bearing CAIs, however, are exceptionally rare, suggesting either continuous reaction of the corundum condensates with a cooling nebular gas and their replacement by hibonite (CaAl 12 O 19 ) or their destruction by melting together with less refractory condensates during formation of igneous CAIs. In contrast to the corundum-bearing CAIs, isolated micrometer-sized corundum grains are common in the acid-resistant residues from unmetamorphosed chondrites. These grains could have avoided multistage reprocessing during CAI formation and, therefore, can potentially provide constraints on the initial oxygen isotopic composition of the solar nebula, and, hence, of the Sun. Here we report oxygen isotopic compositions of ∼60 micrometer-sized corundum grains in the acid-resistant residues from unequilibrated ordinary chondrites (Semarkona (LL3.0), Bishunpur (LL3.1), Roosevelt County 075 (H3.2)) and unmetamorphosed carbonaceous chondrites (Orgueil (CI1), Murray (CM2), and Alan Hills A77307 (CO3.0)) measured with a Cameca ims-1280 ion microprobe. All corundum grains, except two, are 16 O-rich (Δ 17 O = -22.7 per mille ± 8.5 per mille, 2σ), and compositionally similar to the mineralogically pristine CAIs from the CR carbonaceous chondrites (-23.3 per mille ± 1.9 per mille, 2σ), and solar wind returned by the Genesis spacecraft (-27 per mille ± 6 per mille, 2σ). One corundum grain is highly 17 O-enriched (δ 17 O ∼ +60 per mille, δ 18 O

  8. Triple oxygen isotopes in biogenic and sedimentary carbonates

    Science.gov (United States)

    Passey, Benjamin H.; Hu, Huanting; Ji, Haoyuan; Montanari, Shaena; Li, Shuning; Henkes, Gregory A.; Levin, Naomi E.

    2014-09-01

    The 17O anomaly (Δ17O) of natural waters has been shown to be sensitive to evaporation in a way analogous to deuterium excess, with evaporated bodies of water (e.g., leaf waters, lake waters, animal body waters) tending to have lower Δ17O than primary meteoric waters. In animal body water, Δ17O relates to the intake of evaporated waters, evaporative effluxes of water, and the Δ17O value of atmospheric O2, which itself carries signatures of global carbon cycling and photochemical reactions in the stratosphere. Carbonates have the potential to record the triple oxygen isotope compositions of parent waters, allowing reconstruction of past water compositions, but such investigations have awaited development of methods for high-precision measurement of Δ17O of carbonate. We describe optimized methods based on a sequential acid digestion/reduction/fluorination approach that yield Δ17O data with the high precision (∼0.010‰, 1σ) needed to resolve subtle environmental signals. We report the first high-precision Δ17O dataset for terrestrial carbonates, focusing on vertebrate biogenic carbonates and soil carbonates, but also including marine invertebrates and high-temperature carbonates. We determine apparent three-isotope fractionation factors between the O2 analyte derived from carbonate and the parent waters of the carbonate. These in combination with appropriate temperature estimates (from clumped isotope thermometry, or known or estimated body temperatures) are used to calculate the δ18O and Δ17O of parent waters. The clearest pattern to emerge is the strong 17O-depletion in avian, dinosaurian, and mammalian body water (from analyses of eggshell and tooth enamel) relative to meteoric waters, following expected influences of evaporated water (e.g., leaf water) and atmospheric O2 on vertebrate body water. Parent waters of the soil carbonates studied here have Δ17O values that are similar to or slightly lower than global precipitation. Our results suggest

  9. Mo isotope fractionation during hydrothermal evolution of porphyry Cu systems

    Science.gov (United States)

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

    2015-03-01

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

  10. 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

  11. Oxygen isotope thermometry of quartz-Al2SiO5veins in high-grade metamorphic rocks on Naxos island (Greece)

    Science.gov (United States)

    Putlitz, Benita; Valley, John; Matthews, Alan; Katzir, Yaron

    2002-04-01

    Diffusion models predict that peak metamorphic temperatures are best recorded by the oxygen isotope fractionation between minerals in a bi-mineralic rock in which a refractory accessory mineral with slow oxygen diffusion rate is modally minor to a mineral with a faster diffusion rate. This premise is demonstrated for high-grade metamorphism on the island of Naxos, Greece, where quartz-kyanite oxygen isotope thermometry from veins in high-grade metamorphic pelites gives temperatures of 635-690 °C. These temperatures are in excellent agreement with independent thermometry for the regional M2 peak metamorphic conditions and show that the vein minerals isotopically equilibrated at the peak of metamorphism. Quartz-sillimanite fractionations in the same veins give similar temperatures (680+/-35 °C) and suggest that the veins grew near to the kyanite-sillimanite boundary, corresponding to pressures of 6.5 to 7.5 kbar for temperatures of 635-685 °C. By contrast, quartz-kyanite and quartz-biotite pairs in the host rocks yield lower temperature estimates than the veins (590-600 and 350-550 °C, respectively). These lower apparent temperatures are also predicted from calculations of diffusional resetting in the polyphase host-rock system. The data demonstrate that bimineralic vein assemblages can be used as accurate thermometers in high-temperature rocks whereas retrograde exchange remains a major problem in many polymineralic rocks.

  12. How the oxygen isotope ratio of rain water influences the isotope ratio of chicken eggshell carbonate

    Science.gov (United States)

    Price, Gregory; Grimes, Stephen

    2015-04-01

    The stable oxygen isotope ratio of chicken eggshell carbonate was analysed from chicken eggs laid under free range, and organic farming regimes from across the UK. The eggshell carbonate oxygen isotope data shows a clear depletion in delta18O distribution from the southwest to the northeast. Although consistently offset by around 1 permil, the same isotopic distribution as that seen in eggshell carbonate is observed in the delta18O ratio of rainfall and groundwater from across the UK. This distribution is related to the Rayleigh distillation of rainfall driven by westerly winds across the UK landmass. The clear relationship observed between eggshell delta18O values and that of rainwater presumably reflects the nature of free range chickens which must be drinking locally derived rainwater and supplementing their diet and water intake with locally derived food. These results suggest that the oxygen isotope value of chicken eggshells can be used as a forensic tool to identify the locality that free range and organic eggs were laid within the UK. Furthermore, if suitable material is preserved in the archaeological and geological record then such a relationship can potentially be used to establish the oxygen isotope value of rainwater from which ancient and / or ancestral birds lived.

  13. [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.

  14. 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

  15. 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

  16. Anatomy of the thriple oxygen isotope Terrestrial Fractionatoin Line

    Science.gov (United States)

    Sharp, Z. D.; Pack, A.

    2017-12-01

    In the triple oxygen isotope system, it is well established that the δ17O value of nearly all terrestrial materials is approximately ½ that of the corresponding δ18O value. In triple isotope space then, all samples plot on a slope 1/2 line, termed the Terrestrial Fractionation Line (TFL). It has recently been recognized that subtle, but significant departures from the TFL exist, given by Δ'17O = δ'17O -λ× δ'18O + γ, where λ is the slope of the TFL (γ is the y-intercept and assumed to be zero in most studies). There have been many published λ values, ranging from 0.52 to 0.5305. λ values determined from a best-fit to rock and mineral samples range from 0.5244 to 0.5266. λ values from meteoric waters are 0.527 to 0.528 (γ = 0.007 to 0.034), explained by equilibrium and kinetic processes. Extreme polar glacial samples define a λ >0.53. As pointed out by Matsuhisia et al. (GCA, 1978), there is no single factor that controls the δ17O-δ18O slope, and clearly there is no `correct' TFL line. However, some generalities can be noted. 1) Meteoric waters generally plot with a λ = 0.528 with a Δ'17O = 0.033. At both high and low δ18O values, the Δ'17O values of meteoritic waters decrease. Mantle derived samples plot in a limited δ space, with δ18O values of 5-9‰ and a Δ'17O of -0.05‰. Rock and mineral samples falling outside this narrow range have undergone interaction with meteoric or ocean water at some point in their history, either by alteration or neoform mineral growth. The quartz-water triple isotope fractionation factor varies with temperatures, ranging from 0.5237 to 0.5266 at 0°C and 200°C, respective. A fit to published rock data gives an overall λ = 0.5237-0.5240. These results are most likely explained by the sum of hydrothermal and low-temperature mineral-water fractionations. Attempting to place any significance on a TFL from a set of data in unwarranted without understanding the processes controlling the isotopic compositions of

  17. 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.

  18. 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.

  19. 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.

  20. Do oxygen isotope values in collagen reflect the ecology and physiology of neotropical mammals?

    Directory of Open Access Journals (Sweden)

    Brooke eCrowley

    2015-11-01

    Full Text Available Stable isotope data provide insight into the foraging ecology of animals. Traditionally, carbon and nitrogen isotope values have been used to infer dietary and habitat preferences. Oxygen isotopes are used less frequently but may complement the ecological information provided by carbon and nitrogen, particularly in densely forested or arid environments. Additionally, because oxygen is preserved in both bioapatite and collagen, it is useful for paleoecological studies. To investigate the suitability of oxygen isotopes for complementing and building on ecological applications of carbon and nitrogen isotopes, we analyze all three isotopes in bone collagen for nearly identical assemblages of Costa Rican mammals in two ecologically distinct habitats - a evergreen rainforest and a seasonal dry forest. We assess the degree to which differences in habitat, activity pattern, diet, arboreality, and thermoregulation are revealed by each of the isotope systems. Our results highlight the potential of oxygen isotopes in modern and paleoecological contexts. In addition to reflecting habitat type, oxygen isotope values in collagen distinguish species on the basis of vertical habitat stratification and drinking behavior. Within a locality, individuals with low oxygen isotope values likely track meteoric water, whereas those with elevated values most likely consume evaporatively-enriched plant tissues, such as canopy leaves. These patterns will be useful in reconstructing paleoenvironments and interpreting ecological differences among taxa both extant and extinct.

  1. 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.

  2. Calcium-aluminum-rich inclusions with fractionation and unknown nuclear effects (FUN CAIs)

    DEFF Research Database (Denmark)

    Krot, Alexander N.; Nagashima, Kazuhide; Wasserburg, Gerald J.

    2014-01-01

    We present a detailed characterization of the mineralogy, petrology, and oxygen isotopic compositions of twelve FUN CAIs, including C1 and EK1-4-1 from Allende (CV), that were previously shown to have large isotopic fractionation patterns for magnesium and oxygen, and large isotopic anomalies...

  3. 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

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

    Science.gov (United States)

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

    2010-01-01

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

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

    Science.gov (United States)

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

    2015-04-01

    The current view on the phosphorus (P) cycle in forest ecosystems relies mostly on measurements and correlations of pools, and to a lower extent on measurement of fluxes. We have no direct insight into the processes phosphate goes through at the ecosystem level, and into the relative importance of organic and mineral pools in sustaining P nutrition of trees. The analysis of oxygen isotopes associated to P (18Op) is expected to bring this type of information. The German Priority Program SPP 1685 aims to test the overall hypothesis that the P-depletion of soils drives forest ecosystems from P acquiring systems (efficient mobilization of P from the mineral phase) to P recycling systems (highly efficient cycling of P). Our contribution to this project will consist in studying the relative importance of biological and geochemical processes in controlling the P cycle in temperate beech forest ecosystems in Germany along a gradient of decreasing soil P availability. We will follow the fate of phosphate from litter fall to the uptake of P by plants via P release by decomposition of organic matter or after release from P-containing minerals, by using a multi-isotope approach (O in water and phosphate plus 33P). To address our research question we will rely on measurements in experimental forest sites and on laboratory incubations of the organic layer or the mineral soil. We present here the first results issued from the 2014 sampling on three study sites, where we characterized the P pools in surface soil horizons by a sequential extraction (modified after Tiessen and Moir, 2007) and we analysed the 18Op of the resin extractable- and microbial-P fractions. Contrary to what was previously found (e.g. Tamburini et al. 2012) the isotopic composition of these fractions in most of the samples does not reflect the equilibrium value (as the result of the dominance of the pyrophosphatase activity on the other enzymatic processes, Blake et al. 2005). Depending on the P availability

  6. Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

    International Nuclear Information System (INIS)

    Sato, S.

    1987-01-01

    Hydrogen isotope exchange between H 2 , gaseous H 2 O, and the surface hydroxyls of TiO 2 , and oxygen isotope exchange between O 2 , CO 2 , CO, H 2 O vapor, and the hydroxyls over TiO 3 were studied at room temperature in the dark and under illumination. Hydrogen isotope exchange between H 2 O and the hydroxyls occurred rapidly in the dark, but the exchange involving H 2 did not occur at all even under illumination. Oxygen isotope exchange among H 2 O vapor, CO 2 , and the hydroxyls easily took place in the dark, but the exchange involving O 2 required band-gap illumination. Dioxygen isotope equilibration was much faster than the other photoexchange reactions. Although the oxygen exchange between O 2 and illuminated TiO 2 has been considered to involve lattice-oxygen exchange, the present experiments revealed that the hydroxyls of TiO 2 mainly participate in the exchange reaction. The oxygen exchange between O 2 and H 2 O vapor was strongly inhibited by H 2 O vapor itself probably because oxygen adsorption was retarded by adsorbed water. Oxygen in CO was not exchanged with the other substrates under any conditions tested

  7. 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.

  8. 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.

  9. 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

  10. Bulk Oxygen Isotopic Composition of Ultracarbonaceous Antarctic Micrometeorites with the NanoSIMS

    Science.gov (United States)

    Kakazu, Y.; Engrand, C.; Duprat, J.; Briani, G.; Bardin, N.; Mostefaoui, S.; Duhamel, R.; Remusat, L.

    2014-09-01

    We analyzed the carbon and oxygen isotope ratios of two UCAMMs with the NanoSIMS in order to understand the origin and formation of UCAMMs. One UCAMM has 16O-rich composition and a highly heterogeneous oxygen isotopic distribution.

  11. 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)

  12. 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

  13. 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.

  14. 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.

  15. Oxygen isotope exchange on palladium catalysts

    International Nuclear Information System (INIS)

    Kravchuk, L.S.; Beschetvertnaya, T.I.; Novorodskij, V.G.; Novikova, M.G.; Zaretskij, M.V.; Valieva, S.V.

    1983-01-01

    Oxygen heteromolecular isotope exchange on unreduced palladium catalysts, distingushing by metal content is studied. Content of 18 O in gaseous phase is eoual to 46%. Calculations of heteroexchange rates are conducted with decrease of the 18 O in the gaseous phase over solid sample. Method of oxygen thermodesorption has been used to establish that palladium, deposited on γ-Al 2 O 3 during exchange process is in oxidized state; in this case strength of Pd-O bond is determined by content dispersity) of the metal. It is shown that significant increase of exchange rate on the samples with Pd >> 0.5 mass.% content can be induced as by side decomposition reaction of its oxide and corresponding dilution of gaseous mixture by ''light'' oxygen so by possibility of exchange with oxygen of PdO phase

  16. 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

  17. Hydrogen and oxygen isotope ratios of geothermal waters in the southern hachimantai area

    International Nuclear Information System (INIS)

    Matsubaya, Osamu; Etchu, Hiroshi; Takenaka, Teruo; Yoshida, Yutaka.

    1985-01-01

    Geothermal waters from the Matsukawa and Kakkonda Geothermal Plants, wells at Amihari-Motoyu, and Nyuto and Tazawako areas were isotopically studied. The geothermal waters from Mutsukawa, Kakkonda and Amihari-Motoyu have hydrogen isotope ratios similar to the local meteoric waters, while have higher oxygen isotope ratios than the local meteoric waters. This relationship of hydrogen and oxygen isotope ratios, that is called ''oxygen shift'', means that these geothermal waters are meteoric waters undergone the oxygen isotope exchange with rocks at high temperature of underground. The exygen shifts are 2 -- 3 per mil in Matsukawa and Kakkonda, and 7 per mil in Amihari-Motoyu. This difference may be important to understand the processe of water-rock interaction in this area. The geothermal waters at Nyuto and Tazawako areas also show 2 -- 3 per mil oxygen shift. The steam from the Tazawako-cho well and the hot spring water form the Tsurunoyu are estimated to be vapor and liquid phases separated form a single geothermal water of NaCl type, though the hot water from the Tsurunoyu is diluted with shallow meteoric water. (author)

  18. Analytical techniques for determination of framework oxygen isotope ratio of wairakite

    International Nuclear Information System (INIS)

    Noto, Masami; Kusakabe, Minoru; Uchida, Tetsuo.

    1990-01-01

    Dehydration techniques were developed for the analysis of isotopic ratios of framework oxygen of wairakite, one of calcium zeolites often encountered in geothermal systems. Channel water in wairakite were separated from aluminosilicate framework by dehydration in vacuum at 300 deg, 400 deg, 450 deg, 500 deg, 550 deg, 650 deg, 750 deg, 850 deg, and 950 degC, and by stepwise heating at temperatures from 300 deg to 700 degC. The oxygen isotopic analyses of the separated channel water and the residual aluminosilicate framework of wairakite indicated that dehydration at temperatures higher than 400 degC is accompanied by isotopic exchang between the framework oxygen and dehydrating water vapor. The isotopic exchange during the high temperature dehydration makes the δ 18 O of framework oxygen lower and that of channel water higher than those obtained by dehydration at 300 degC. These results are consistent with dehydration behavior of wairakite under vacuum that the maximum rate of dehydration of channel water is attained at about 400 degC. Consequently it is recommended to dehydrate wairakite at a temperature as low as possible in order to avoid the effect of the isotopic exchange. Time required to attain complete dehydration becomes longer with lowering the temperature of dehydration. To compromise these conflicting effects, the optimum conditions of dehydration have been found that most of the channel water is dehydrated at 300 degC for 24 hours, followed by stepwise heating for additional 17 hours up to 700 degC. We obtained a better than ± 0.1 reproducibility for the framework oxygen isotopic determinations with this technique. (author)

  19. 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...

  20. 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.)

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

    Science.gov (United States)

    Summers, David P.

    2003-01-01

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

  2. Can oxygen stable isotopes be used to track precipitation moisture source in vascular plant-dominated peatlands?

    Science.gov (United States)

    Amesbury, Matthew J.; Charman, Dan J.; Newnham, Rewi M.; Loader, Neil J.; Goodrich, Jordan; Royles, Jessica; Campbell, David I.; Keller, Elizabeth D.; Baisden, W. Troy; Roland, Thomas P.; Gallego-Sala, Angela V.

    2015-11-01

    Variations in the isotopic composition of precipitation are determined by fractionation processes which occur during temperature- and humidity-dependent phase changes associated with evaporation and condensation. Oxygen stable isotope ratios have therefore been frequently used as a source of palaeoclimate data from a variety of proxy archives, which integrate this signal over time. Applications from ombrotrophic peatlands, where the source water used in cellulose synthesis is derived solely from precipitation, have been mostly limited to Northern Hemisphere Sphagnum-dominated bogs, with few in the Southern Hemisphere or in peatlands dominated by vascular plants. New Zealand (NZ) provides an ideal location to undertake empirical research into oxygen isotope fractionation in vascular peatlands because single taxon analysis can be easily carried out, in particular using the preserved root matrix of the restionaceous wire rush (Empodisma spp.) that forms deep Holocene peat deposits throughout the country. Furthermore, large gradients are observed in the mean isotopic composition of precipitation across NZ, caused primarily by the relative influence of different climate modes. Here, we test whether δ18O of Empodisma α-cellulose from ombrotrophic restiad peatlands in NZ can provide a methodology for developing palaeoclimate records of past precipitation δ18O. Surface plant, water and precipitation samples were taken over spatial (six sites spanning >10° latitude) and temporal (monthly measurements over one year) gradients. A link between the isotopic composition of root-associated water, the most likely source water for plant growth, and precipitation in both datasets was found. Back-trajectory modelling of precipitation moisture source for rain days prior to sampling showed clear seasonality in the temporal data that was reflected in root-associated water. The link between source water and plant cellulose was less clear, although mechanistic modelling predicted mean

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

    Science.gov (United States)

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

    2013-12-01

    Pyromorphite (Pb5[PO4]3Cl) is an abundant mineral in oxidized zones of lead-bearing ore deposits and due to its very low solubility product effectively binds Pb during supergene alteration of galena (PbS). The capacity of a soil or near-surface fluid to immobilize dissolved Pb depends critically on the availability of phosphate in this soil or fluid. Potential phosphorus sources in soil include (i) release during biological processes, i.e. leaching from litter/lysis of microbial cells (after intracellular enzyme activity) in soil and hydrolysis from soil organic matter by extracellular enzymes and (ii) inorganic phosphate from the dissolution of apatite in the adjacent basement rocks. Intracellular enzyme activity in plants/microorganisms associated with kinetic fractionation produces an oxygen isotope composition distinctly different from inorganic processes in soil. This study presents the first oxygen isotope data for phosphate (δ18OP) in pyromorphite and a comprehensive data set for apatite from crystalline rocks. We investigated 38 pyromorphites from 26 localities in the Schwarzwald (Southwest Germany) and five samples from localities outside the Schwarzwald in addition to 12 apatite separates from gneissic and granitic host rocks. Pyromorphites had δ18OP values between +10‰ and +19‰, comparable to literature data on δ18OP in the readily available P fraction in soil (resin-extractable P) from which minerals potentially precipitate in soils. δ18OP values below the range of equilibrium isotope fractionation can be attributed either to apatites that formed geochemically (δ18OP of apatites:+6‰ to +9‰) or less likely to biological processes (extracellular enzyme activity). However, for most of our samples isotopic equilibrium with ambient water was indicated, which suggests biological activity. Therefore, we conclude that the majority of pyromorphites in oxidized zones of ore bodies formed from biologically cycled phosphate. This study highlights that

  4. New estimates of oxygen isotope fractionation by plants and soils - Implications for the isotopic composition of the atmosphere

    International Nuclear Information System (INIS)

    Angert, A.; Luz, B.

    2002-01-01

    Oxygen concentration and δ 18 O of O 2 have been monitored in light and heavy soils. Steep oxygen gradients were present at the heavy soil site (minimal O 2 concentration was 1% at 150cm depth) and δ 18 O values typically ranged from 0 per mille to -1.6 per mille relative to air O 2 . In the light-soil site, the O 2 concentration was 20.38% to 20.53% and δ 18 O values ranged from -0.06±0.015 per mille to 0.06±0.015 per mille relative to atmospheric O 2 . The fractionation in soil respiration was estimated from the observed [O 2 ] and δ 18 O profiles and their change with time by a five-box numerical model. Diffusion due to concentration and temperature gradients was taken into account. Good agreement was found between the model results and the measured values. The average discrimination against 18 O in the two study sites was 12±1 per mille. The current understanding of the composition of air O 2 attributes the magnitude of the fractionation in soil respiration to biochemical mechanisms alone. Thus the discrimination against 18 O is assumed to be 18 per mille in cyanide-sensitive dark respiration and 25 per mille to 30 per mille in cyanide-resistant respiration. The discrimination we report is significantly less than in dark respiration. This overall low discrimination is explained by slow diffusion in soil aggregates, and in root tissues that results in low O 2 concentration in the consumption site. Since about half of the terrestrial respiration occurs in soils, our new discrimination estimate lowers significantly the discrimination value for terrestrial uptake. Higher then currently assumed discrimination was found in experiments with illuminated plants. This high discrimination might compensate for the low discrimination found in soils. (author)

  5. 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)

  6. Oxygen isotope exchange rate between dissolved sulfate and water at hydrothermal temperatures

    International Nuclear Information System (INIS)

    Chiba, H.; Sakai, H.

    1985-01-01

    Oxygen isotope exchange rate between dissolved sulfate and water was experimentally determined at 100, 200 and 300 deg C. The isotope exchange rate is strongly dependent on temperature and pH of the solution. Combining the temperature and pH dependence of the reaction rate, the exchange reaction was estimated to be first-order with respect to sulfate. The logarithm of apparent rate constant of exchange reaction at a given temperature is a function of the pH calculated at the experimental temperatures. From the pH dependence of the apparent rate constant, it was deduced that the isotope exchange reaction between dissolved sulfate and water proceeds through collision between H 2 SO 4 0 and H 2 O at low pH, and between HSO 4 - and H 2 O at intermediate pH. The isotope exchange rate obtained indicates that oxygen isotope geothermometry utilizing the studied isotope exchange is suitable for temperature estimation of geothermal reservoirs. The extrapolated half-life of this reaction to oceanic temperature is about 10 9 years, implying that exchange between oceanic sulfate and water cannot control the oxygen isotope ratio of oceanic sulfates. (author)

  7. Could a secular increase in organic burial explain the rise of oxygen? Insights from a geological carbon cycle model constrained by the carbon isotope record

    Science.gov (United States)

    Krissansen-Totton, J.; Kipp, M.; Catling, D. C.

    2017-12-01

    The stable isotopes of carbon in marine sedimentary rock provide a window into the evolution of the Earth system. Conventionally, a relatively constant carbon isotope ratio in marine sedimentary rocks has been interpreted as implying constant organic carbon burial relative to total carbon burial. Because organic carbon burial corresponds to net oxygen production from photosynthesis, it follows that secular changes in the oxygen source flux cannot explain the dramatic rise of oxygen over Earth history. Instead, secular declines in oxygen sink fluxes are often invoked as causes for the rise of oxygen. However, constant fractional organic burial is difficult to reconcile with tentative evidence for low phosphate concentrations in the Archean ocean, which would imply lower marine productivity and—all else being equal—less organic carbon burial than today. The conventional interpretation of the carbon isotope record rests on the untested assumption that the isotopic ratio of carbon inputs into the ocean reflect mantle isotopic values throughout Earth history. In practice, differing rates of carbonate and organic weathering will allow for changes in isotopic inputs, as suggested by [1] and [2]. However, these inputs can not vary freely because large changes in isotopic inputs would induce secular trends in carbon reservoirs, which are not observed in the isotope record. We apply a geological carbon cycle model to all Earth history, tracking carbon isotopes in crustal, mantle, and ocean reservoirs. Our model is constrained by the carbon isotope record such that we can determine the extent to which large changes in organic burial are permitted. We find both constant organic burial and 3-5 fold increases in organic burial since 4.0 Ga can be reconciled with the carbon isotope record. Changes in the oxygen source flux thus need to be reconsidered as a possible contributor to Earth's oxygenation. [1] L. A. Derry, Organic carbon cycling and the lithosphere, in Treatise on

  8. 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.

  9. 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

  10. 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.)

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

    Science.gov (United States)

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

    2014-11-01

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

  12. 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

  13. 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)

  14. Stable isotope ratio measurements in hydrogen, nitrogen, and oxygen using Raman scattering

    International Nuclear Information System (INIS)

    Harney, R.C.; Bloom, S.D.; Milanovich, F.P.

    1975-01-01

    A method for measuring stable isotope ratios using laser Raman scattering was developed which may prove of significant utility and benefit in stable isotope tracer studies. Crude isotope ratio measurements obtained with a low-power laser indicate that with current technology it should be possible to construct an isotope ratio measurement system using laser Raman scattering that is capable of performing 0.1 percent accuracy isotope ratio measurements of 16 O/ 18 O in natural abundance oxygen gas or 14 N/ 15 N in natural abundance nitrogen gas in times less than two minutes per sample. Theory pertinent to the technique, designs of specific isotope ratio spectrometer systems, and data relating to isotope ratio measurements in hydrogen, nitrogen, and oxygen are presented. In addition, the current status of several studies utilizing this technique is discussed. (auth)

  15. 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

  16. 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.

  17. 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

  18. 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‰.

  19. 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‰

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

    Science.gov (United States)

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

    2016-02-01

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

  1. A Plant-Based Proxy for the Oxygen Isotope Ratio of Atmospheric Water Vapor

    Science.gov (United States)

    Helliker, B.

    2007-12-01

    Atmospheric water vapor is a major component of the global hydrological cycle, but the isotopic balance of vapor is largely unknown. It is shown here that the oxygen isotope ratio of leaf water in the epiphytic Crassulacean acid metabolism (CAM) plant Tillandsia usneoides (Spanish Moss) is controlled by the oxygen isotope ratio of atmospheric water vapor in both field and lab studies. Assuming that the leaf-water isotopic signature (and hence the atmospheric water vapor signature) is recorded in plant organic material, the atmospheric water vapor oxygen isotope ratios for Miami, Florida (USA) were reconstructed for several years from 1878 to 2005 using contemporary and herbarium specimens. T. usneoides ranges from Virginia, USA southwards through the tropics to Argentina, and the CAM epiphytic lifeform is widespread in other species. Therefore, epiphytes may be used to reconstruct the isotope ratio of atmospheric water for spatial scales that span over 60° of latitude and temporal scales that cover the last century of global temperature increase.

  2. 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.

  3. 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.

  4. 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

  5. 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...

  6. Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition

    International Nuclear Information System (INIS)

    Zielinski, M.; Zielinska, A.; Papiernik-Zielinska, H.; McKenzie, J.A.; Bernasconi, S.; Paul, H.

    1998-01-01

    Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition above and below its melting temperature have been studied and compared with the primary (PKIE) and secondary kinetic isotope effects (SKIE) of 13 C and 18 O, respectively, in the decarboxylation of other heterocyclic acids. The temperature dependence of the secondary oxygen-18 isotope effects is negative in the total 221-255 deg C temperature interval investigated initially. The 13 C KIE measured above melting point of N.A. (temperature interval 235-270 deg C) are located in the range 1.007-1.009. Below melting point of nicotinic acid the 13 C KIE are larger and reveal the negative temperature dependence ( 13 C KIE decreases with decreasing the reaction temperature from 1.013/at 230 deg C to 1.0114/at 221 deg C). A discussion of the above isotopic results is presented. (author)

  7. The effects of high perioperative inspiratory oxygen fraction for adult surgical patients

    DEFF Research Database (Denmark)

    Wetterslev, Jørn; Meyhoff, Christian S; Jørgensen, Lars N

    2015-01-01

    BACKGROUND: Available evidence on the effects of a high fraction of inspired oxygen (FIO2) of 60% to 90% compared with a routine fraction of inspired oxygen of 30% to 40%, during anaesthesia and surgery, on mortality and surgical site infection has been inconclusive. Previous trials and meta......-analyses have led to different conclusions on whether a high fraction of supplemental inspired oxygen during anaesthesia may decrease or increase mortality and surgical site infections in surgical patients. OBJECTIVES: To assess the benefits and harms of an FIO2 equal to or greater than 60% compared...... and reran the searches in March 2015. We will consider two studies of interest when we update the review. SELECTION CRITERIA: We included randomized clinical trials that compared a high fraction of inspired oxygen with a routine fraction of inspired oxygen during anaesthesia, surgery and recovery...

  8. 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

  9. 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

  10. 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.

  11. 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

  12. Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

    Science.gov (United States)

    Schauer, Andrew J; Kunasek, Shelley A; Sofen, Eric D; Erbland, Joseph; Savarino, Joel; Johnson, Ben W; Amos, Helen M; Shaheen, Robina; Abaunza, Mariana; Jackson, Terri L; Thiemens, Mark H; Alexander, Becky

    2012-09-30

    Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data. Copyright © 2012 John Wiley & Sons, Ltd.

  13. Oxygen stable isotopes variation in water precipitation in Poland – anthropological applications

    Directory of Open Access Journals (Sweden)

    Lisowska-Gaczorek Aleksandra

    2017-03-01

    Full Text Available The main objective of oxygen isotope analysis is to determine the probable place of origin of an individual or the reconstruction of migration paths. The research are methodologically based on referencing oxygen isotope ratios of apatite phosphates (δ18Op to the range of environmental background δ18O, most frequently determined on the basis of precipitation.

  14. 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.

  15. 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

  16. Chlorine isotope fractionation during supergene enrichment of copper

    Science.gov (United States)

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

    2017-12-01

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

  17. Oxygenation of spontaneous canine tumors during fractionated radiation therapy

    International Nuclear Information System (INIS)

    Achermann, R.E.; Ohlerth, S.M.; Bley, C.R.; Inteeworn, N.; Schaerz, M.; Wergin, M.C.; Kaser-Hotz, B.; Gassmann, M.; Roos, M.

    2004-01-01

    Background and purpose: tumor oxygenation predicts treatment outcome, and reoxygenation is considered important in the efficacy of fractionated radiation therapy. Therefore, the purpose of this study was to document the changes of the oxygenation status in spontaneous canine tumors during fractionated radiation therapy using polarographic needle electrodes. Material and methods: tumor oxygen partial pressure (pO 2 ) measurements were performed with the eppendorf-pO 2 -Histograph. The measurements were done under general anesthesia, and probe tracks were guided with ultrasound. pO 2 was measured before radiation therapy in all dogs. In patients treated with curative intent, measurements were done sequentially up to eight times (total dose: 45-59.5 Gy). Oxygenation status of the palliative patient group was examined before each fraction of radiation therapy up to five times (total dose: 24-30 Gy). Results: 15/26 tumors had a pretreatment median pO 2 ≤ 10 mmHg. The pO 2 values appeared to be quite variable in individual tumors during fractionated radiation therapy. The pO 2 of initially hypoxic tumors (pretreatment median pO 2 ≤ 10 mmHg) remained unchanged during fractionated radiotherapy, whereas in initially normoxic tumors the pO 2 decreased. Conclusion: hypoxia is common in spontaneous canine tumors, as 57.7% of the recorded values were ≥ 10 mmHg. The data of this study showed that initially hypoxic tumors remained hypoxic, whereas normoxic tumors became more hypoxic. (orig.)

  18. Expanding the isotopic toolbox: Applications of hydrogen and oxygen stable isotope ratios to food web studies

    OpenAIRE

    Hannah B Vander Zanden; David X Soto; Gabriel J Bowen; Keith A Hobson; Keith A Hobson

    2016-01-01

    The measurement of stable carbon (δ13C) and nitrogen (δ15N) isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H) and oxygen (δ18O) isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applicat...

  19. Expanding the Isotopic Toolbox: Applications of Hydrogen and Oxygen Stable Isotope Ratios to Food Web Studies

    OpenAIRE

    Vander Zanden, Hannah B.; Soto, David X.; Bowen, Gabriel J.; Hobson, Keith A.

    2016-01-01

    The measurement of stable carbon (δ13C) and nitrogen (δ15N) isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H) and oxygen (δ18O) isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applicatio...

  20. Study of the carbon and oxygen isotopic compositions in marine shells of Salvador-Bahia, Brazil

    International Nuclear Information System (INIS)

    Freitas, J.C.B. de.

    1977-01-01

    The carbon and oxygen isotopic composition of 68 samples of marine shells from the region of Salvador was determined. These samples are from points on the open coast and in the interior of the Todos os Santos Bay and they are composed in part by recent specimens and in part by old specimens taken from Quaternary sediments. The results for δ 18 O are in the range of -2,83per mille to + 1,21per mille (PDB) and for δ 13 C in the range of -3,10per mille to +2,63per mille (PDB). The reults for the recent shells from the interior of the Todos os Santos Bay show variations in the δ 13 C values associated to the dominance of organic matter in some regions. For the old samoles, gathered in te variations in the δ 13 C values was associated to the existence in points of that region of deposits of fluvio-lagunar sediments, originated during the last marine transgression. It was identified, for a few species with the same age and location, the effect of biological fractionations. Nevertheless, the observed dominant factor on the isotopic differentiation was the environmental fractionation. (Author) [pt

  1. Oxygen Isotopes in Intra-Back Arc Basalts from the Andean Southern Volcanic Zone

    Science.gov (United States)

    Parks, B. H.; Wang, Z.; Saal, A. E.; Frey, F. A.; Blusztajn, J.

    2013-12-01

    The chemical compositions of volcanic rocks from the Andean Southern Volcanic Zone (SVZ) reflect complex and dynamic interactions among the subducting oceanic lithosphere, the mantle wedge, and the overlying continental crust. Oxygen isotope ratios of olivine phenocrysts can be a useful means to identifying their relative contributions to the arc magmatism. In this study, we report high-precision oxygen-isotope ratios of olivine phenocrysts in a set of intra-back arc basalts from the SVZ. The samples were collected from monogenetic cinder cones east of the volcanic front (35-39 degrees S), and have been geochemically well-characterized with major and trace element contents, and Sr-Nd-Pb isotope compositions. Compared to lavas from the volcanic front, these intra-back arc lavas have similar radiogenic isotope, and a more alkalic and primitive (higher MgO content) chemical composition. We determined the oxygen-isotope ratios using the CO2-laser-fluorination method set up at the Department of Geology and Geophysics, Yale University following the techniques reported in Wang et al (2011). The samples were analyzed with standards of Gore Mountain Garnet (5.77×0.12‰ 1σ; Valley et al., 1995) and Kilbourne Hole Olivine (5.23×0.07‰ 1σ; Sharp, 1990) in order to account for minor changes in the vacuum line during analyses. The obtained δ18OSMOW values of olivine phenocrysts from the intra-back arc basalts vary from 4.98×0.01 to 5.34×0.01‰. This range, surprisingly, is similar to the δ18O values of olivines from mantle peridotites (5.2×0.2‰). Preliminary results indicate significant correlations of 87Sr/86Sr, 143Nd/144Nd and trace element ratios of the basaltic matrix with the δ18O values of olivine phenocrysts, indicating at least three components involved in the formation of the arc volcanism. By comparing the δ18O with the variations of major and trace element contents (e.g., MgO, TiO2 and Ni), and trace element ratios (e.g. Ba/Nb), we evaluate the effects

  2. Monitoring biodegradation of hydrocarbons by stable isotope fractionation

    Science.gov (United States)

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

    2010-05-01

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

  3. Workshop on Oxygen in the Terrestrial Planets

    Science.gov (United States)

    2004-01-01

    This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in

  4. 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...

  5. Oxygen isotope analysis of phosphate: improved precision using TC/EA CF-IRMS.

    Science.gov (United States)

    LaPorte, D F; Holmden, C; Patterson, W P; Prokopiuk, T; Eglington, B M

    2009-06-01

    Oxygen isotope values of biogenic apatite have long demonstrated considerable promise for paleothermometry potential because of the abundance of material in the fossil record and greater resistance of apatite to diagenesis compared to carbonate. Unfortunately, this promise has not been fully realized because of relatively poor precision of isotopic measurements, and exceedingly small size of some substrates for analysis. Building on previous work, we demonstrate that it is possible to improve precision of delta18O(PO4) measurements using a 'reverse-plumbed' thermal conversion elemental analyzer (TC/EA) coupled to a continuous flow isotope ratio mass spectrometer (CF-IRMS) via a helium stream [Correction made here after initial online publication]. This modification to the flow of helium through the TC/EA, and careful location of the packing of glassy carbon fragments relative to the hot spot in the reactor, leads to narrower, more symmetrically distributed CO elution peaks with diminished tailing. In addition, we describe our apatite purification chemistry that uses nitric acid and cation exchange resin. Purification chemistry is optimized for processing small samples, minimizing isotopic fractionation of PO4(-3) and permitting Ca, Sr and Nd to be eluted and purified further for the measurement of delta44Ca and 87Sr/86Sr in modern biogenic apatite and 143Nd/144Nd in fossil apatite. Our methodology yields an external precision of +/- 0.15 per thousand (1sigma) for delta18O(PO4). The uncertainty is related to the preparation of the Ag3PO4 salt, conversion to CO gas in a reversed-plumbed TC/EA, analysis of oxygen isotopes using a CF-IRMS, and uncertainty in constructing calibration lines that convert raw delta18O data to the VSMOW scale. Matrix matching of samples and standards for the purpose of calibration to the VSMOW scale was determined to be unnecessary. Our method requires only slightly modified equipment that is widely available. This fact, and the

  6. 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.

  7. 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.

  8. Absolute isotopic abundances of Ti in meteorites

    International Nuclear Information System (INIS)

    Niederer, F.R.; Papanastassiou, D.A.; Wasserburg, G.J.

    1985-01-01

    The absolute isotope abundance of Ti has been determined in Ca-Al-rich inclusions from the Allende and Leoville meteorites and in samples of whole meteorites. The absolute Ti isotope abundances differ by a significant mass dependent isotope fractionation transformation from the previously reported abundances, which were normalized for fractionation using 46 Ti/ 48 Ti. Therefore, the absolute compositions define distinct nucleosynthetic components from those previously identified or reflect the existence of significant mass dependent isotope fractionation in nature. We provide a general formalism for determining the possible isotope compositions of the exotic Ti from the measured composition, for different values of isotope fractionation in nature and for different mixing ratios of the exotic and normal components. The absolute Ti and Ca isotopic compositions still support the correlation of 50 Ti and 48 Ca effects in the FUN inclusions and imply contributions from neutron-rich equilibrium or quasi-equilibrium nucleosynthesis. The present identification of endemic effects at 46 Ti, for the absolute composition, implies a shortfall of an explosive-oxygen component or reflects significant isotope fractionation. Additional nucleosynthetic components are required by 47 Ti and 49 Ti effects. Components are also defined in which 48 Ti is enhanced. Results are given and discussed. (author)

  9. 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.

  10. 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

  11. 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.

  12. Stable Isotope (delta OXYGEN-18, Delta Deuterium, Delta CARBON-13) Dendroclimatological Studies in the Waterloo Region of Southern Ontario, Canada, Between AD 1610 and 1990.

    Science.gov (United States)

    Buhay, William Mark

    Oxygen (delta^{18} O), hydrogen (delta^2H) and carbon (delta^{13}C) isotopes were measured in wood cellulose from elm, white pine and maple trees that grew in southwestern Ontario, Canada. The measured oxygen and hydrogen isotopic data were used for model-based reconstructions of delta^{18}{O}_{meteoric water}, mean annual temperature (MAT) and relative humidity for a period, AD 1610 to 1880, that precedes instrumental records of climate. The carbon isotope measurements were compared with the Cellulose Model inferred climate data to reveal additional environmental information. Modifications made to the Cellulose Model focused on the dynamics of oxygen and hydrogen isotopic fractionation in plants during evapotranspiration and photosynthetic assimilation. For instance, kinetic fractionation of ^{18}O was found to be predictable from theoretical considerations of leaf energy balance and boundary layer dynamics. Kinetic fractionation during evapotranspiration is sensitive to the nature of the boundary layer, which is controlled by leaf size and morphology. Generally, plants with small segmented leaves have a lower component of turbidity in the leaf boundary layer, which results in higher kinetic fractionation values, than do plants having large simple leaves and more turbulent boundary layers. Kinetic ^2H enrichment in plant leaf water can also be rationalized in terms of leaf size and morphology when an apparent temperature-dependent isotope effect, acting in opposition to evaporative enrichment, is taken into account. Accounting for this temperature -dependent isotope effect helps to: (1) reconcile hydrogen kinetic fractionation inconsistencies for different leaves; (2) explain a temperature effect previously attributed to variable biochemical fractionation during cellulose synthesis, and; (3) verify hydrogen biochemical effects in plants. This improved characterization of the oxygen and hydrogen isotopic effects in plants, using the modified Cellulose Model, helped

  13. 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.

  14. 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...

  15. 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)

  16. 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.

  17. An experimental study on the effect of carbonic anhydrase on the oxygen isotope exchange kinetics and equilibrium in the carbonic acid system

    Science.gov (United States)

    Uchikawa, J.; Zeebe, R. E.

    2011-12-01

    Stable oxygen isotopes of marine biogenic carbonates are often depleted in 18O relative to the values expected for thermodynamic equilibrium with ambient seawater. One possibility is that 18O-depletion in carbonates is kinetically controlled. The kinetic isotope effect associated with the hydration of CO2 results in 18O-depleted HCO3-. If the HCO3- is utilized before re-establishing equilibrium with ambient water under rapid calcification, the 18O-depletion will be recorded in carbonates. But one caveat in this kinetic model is the fact that many marine calcifiers posses carbonic anhydrase, a zinc-bearing enzyme that catalyzes the CO2 hydration reaction. It is expected that this enzyme accelerates 18O-equilibration in the carbonic acid system by facilitating direct oxygen isotope exchange between HCO3- and H2O via CO2 hydration. Clearly this argues against the conceptual framework of the kinetic model. Yet the critical variable here is the effectiveness of the carbonic anhydrase, which is likely to depend on its concentration and the carbonate chemistry of the aqueous medium. It is also hitherto unknown whether the presence of carbonic anhydrase alters the equilibrium oxygen isotope fractionations between dissolved carbonate species and water. We performed a series of quantitative inorganic carbonate precipitation experiments to examine the changes in the oxygen isotope equilibration time as a function of carbonic anhydrase concentrations. We conducted experiments at pH 8.3 and 8.9. These pH values are similar to the average surface ocean pH and the elevated pH levels observed within calcification microenvironments of certain corals and planktonic foraminifera. A summary of our new experimental results will be presented.

  18. 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.

  19. 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.

  20. 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

  1. 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

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

    Science.gov (United States)

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

    2018-01-01

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

  3. 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

  4. 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

  5. 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.

  6. Nitrogen and Oxygen Isotopic Studies of the Marine Nitrogen Cycle.

    Science.gov (United States)

    Casciotti, Karen L

    2016-01-01

    The marine nitrogen cycle is a complex web of microbially mediated reactions that control the inventory, distribution, and speciation of nitrogen in the marine environment. Because nitrogen is a major nutrient that is required by all life, its availability can control biological productivity and ecosystem structure in both surface and deep-ocean communities. Stable isotopes of nitrogen and oxygen in nitrate and nitrite have provided new insights into the rates and distributions of marine nitrogen cycle processes, especially when analyzed in combination with numerical simulations of ocean circulation and biogeochemistry. This review highlights the insights gained from dual-isotope studies applied at regional to global scales and their incorporation into oceanic biogeochemical models. These studies represent significant new advances in the use of isotopic measurements to understand the modern nitrogen cycle, with implications for the study of past ocean productivity, oxygenation, and nutrient status.

  7. Application of carbon and oxygen stable isotopes to the study of Brazilian precambrian

    International Nuclear Information System (INIS)

    Torquato, J.R.F.

    1980-01-01

    Samples of carbonated rocks of precambrian age are studied. The stable carbon and oxygen isotopes are applied to the study of terrestrial materials considering the variations of some element isotopic composition in function of the environment of sedimentation. The isotopic analysis was done using mass spectrometers. The analytical results and the description of region geology of the site of each sample are presented. The isotopic data are interpreted aiming to the environment of sedimentation. New techniques for better improvement of carbon and oxygen ratios, are proposed, such as: to use the analysis of surface trend and the isotopic logging in mapping of surface and subsurface. A new method for approximated determination of the ages of precambrian carbonated rocks, considering the limitations of their new technique, is also presented. (M.C.K.) [pt

  8. 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.

  9. 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

  10. 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.

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

    Science.gov (United States)

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

    2011-06-01

    , besides the detailed geochemical analyses along downstream sections, we present new evidences of non-equilibrium calcite-water fractionation in lower temperature range (13.3 to 51.3 °C). Our measurements and calculations on natural hot water travertine precipitations at Pamukkale and Egerszalók revealed that the δ 18O travertine is equal with the δ 18O HCO3 at the orifice of the thermal springs, which means that practically there is no oxygen isotope fractionation between these two phases. High rate of CO 2 degassing with rapid precipitation of carbonate could be responsible for this as it was theoretically supposed by O'Neil et al. (1969). Thus, for the determination of the deposition temperature of a fossil travertine deposit we propose to use the water-bicarbonate oxygen isotope equilibrium fractionation instead of the water-travertine fractionation, which can result 8-9 °C difference in the calculated values. Our study is the first detailed empirical proof of O'Neil's hypothesis on a natural carbonate depositing system. The presented observations can be used to identify more precisely the deposition temperature of fossil travertines during paleoclimate studies.

  12. Characterization of phenols biodegradation by compound specific stable isotope analysis

    Science.gov (United States)

    Wei, Xi; Gilevska, Tetyana; Wenzig, Felix; Hans, Richnow; Vogt, Carsten

    2015-04-01

    Biodegradation of phenol and alkylphenols has been described under both oxic and anoxic conditions. In the absence of molecular oxygen, the degradation of phenolic compounds is initiated by microorganisms through carboxylation, fumarate addition to the methyl moiety or anoxic hydroxylation of the methyl moiety. Comparatively, under aerobic condition, the initiation mechanisms are revealed to be monoxygenation or dihydroxylation for phenol and ring hydroxylation or methyl group oxidation for cresols. While several studies biochemically characterized the enzymes and reaction mechanisms in the relevant degradation pathways, isotope fractionation patterns were rarely reported possibly due to constraints in current analytical methods. In this study, the carbon isotope fractionation patterns upon the degradation of phenol and cresols by several strains were analyzed by using isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). The corresponding enrichment factors for carbon (ƐC) have been obtained. Cresols degradation by various strains showed generally moderate carbon isotope fractionation patterns with notable differences. For p-cresol degradation, five strains were examined. The aerobic strain Acinetobacter calcoaceticus NCIMB8250 exploits ring hydroxylation by molecular oxygen as initial reaction, and a ƐC value of -1.4±0.2‰ was obtained. Pseudomonas pseudoalcaligenes NCIMB 9867, an aerobic strain initiating cresols degradation via oxygen-dependent side chain hydroxylation, yielded a ƐC value of -2.3±0.2‰. Under nitrate-reducing conditions, Geobacter metallireducens DSM 7210 and Azoarcus buckelii DSM 14744 attacks p-cresol at the side chain by monohydroxylation using water as oxygen source; the two strains produced ƐC values of -3.6±0.4‰ and -2±0.1‰, accordingly. The sulfate-reducing Desulfosarcina cetonica DSM 7267 activating cresols by fumarate addition to the methyl moiety yielded ƐC values of -1.9±0.2‰ for p

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

    Science.gov (United States)

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

    2013-04-01

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

  14. 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.

  15. 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

  16. 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

  17. 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

  18. 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...

  19. Planetary fertility during the past 400 ka based on the triple isotope composition of O2 in trapped gases from the Vostok ice core

    Directory of Open Access Journals (Sweden)

    J. C. von Fischer

    2012-10-01

    Full Text Available The productivity of the biosphere leaves its imprint on the isotopic composition of atmospheric oxygen. Ultimately, atmospheric oxygen, through photosynthesis, originates from seawater. Fractionations during the passage from seawater to atmospheric O2 and during respiration affect δ17O approximately half as much as δ18O. An "anomalous" (also termed mass independent fractionation process changes δ17O about 1.7 times as much as δ18O during isotope exchange between O2 and CO2 in the stratosphere. The relative rates of biological O2 production and stratospheric processing determine the relationship between δ17O and δ18O of O2 in the atmosphere. Variations of this relationship thus allow us to estimate changes in the rate of O2 production by photosynthesis versus the rate of O2–CO2 isotope exchange in the stratosphere. However, the analysis of the 17O anomaly is complicated because each hydrological and biological process fractionates δ17O and δ18O in slightly different proportions. In this study we present O2 isotope data covering the last 400 ka (thousand years from the Vostok ice core. We reconstruct oxygen productivities from the triple isotope composition of atmospheric oxygen with a box model. Our steady state model for the oxygen cycle takes into account fractionation during photosynthesis and respiration by the land and ocean biosphere, fractionation during the hydrologic cycle, and fractionation when oxygen passes through the stratosphere. We consider changes of fractionation factors linked to climate variations, taking into account the span of estimates of the main factors affecting our calculations. We find that ocean oxygen productivity was within 20% of the modern value throughout the last 400 ka. Given the presumed reduction in terrestrial oxygen productivity, the total oxygen production during glacials was likely reduced.

  20. 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.

  1. Simultaneous determination of stable carbon, oxygen, and hydrogen isotopes in cellulose.

    Science.gov (United States)

    Loader, N J; Street-Perrott, F A; Daley, T J; Hughes, P D M; Kimak, A; Levanič, T; Mallon, G; Mauquoy, D; Robertson, I; Roland, T P; van Bellen, S; Ziehmer, M M; Leuenberger, M

    2015-01-06

    A technological development is described through which the stable carbon-, oxygen-, and nonexchangeable hydrogen-isotopic ratios (δ(13)C, δ(18)O, δ(2)H) are determined on a single carbohydrate (cellulose) sample with precision equivalent to conventional techniques (δ(13)C 0.15‰, δ(18)O 0.30‰, δ(2)H 3.0‰). This triple-isotope approach offers significant new research opportunities, most notably in physiology and medicine, isotope biogeochemistry, forensic science, and palaeoclimatology, when isotopic analysis of a common sample is desirable or when sample material is limited.

  2. Growth of the European abalone ( Haliotis tuberculata L.) in situ: Seasonality and ageing using stable oxygen isotopes

    Science.gov (United States)

    Roussel, Sabine; Huchette, Sylvain; Clavier, Jacques; Chauvaud, Laurent

    2011-02-01

    The ormer, Haliotis tuberculata is the only European abalone species commercially exploited. The determination of growth and age in the wild is an important tool for fisheries and aquaculture management. However, the ageing technique used in the past in the field is unreliable. The stable oxygen isotope composition ( 18O/ 16O) of the shell depends on the temperature and oxygen isotope composition of the ambient sea water. The stable oxygen isotope technique, developed to study paleoclimatological changes in shellfish, was applied to three H. tuberculata specimens collected in north-west Brittany. For the specimens collected, the oxygen isotope ratios of the shell reflected the seasonal cycle in the temperature. From winter-to-winter cycles, estimates of the age and the annual growth increment, ranging from 13 to 55 mm per year were obtained. This study shows that stable oxygen isotopes can be a reliable tool for ageing and growth studies of this abalone species in the wild, and for validating other estimates.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  4. Oxygen isotope exchange in La2NiO(4±δ).

    Science.gov (United States)

    Ananyev, M V; Tropin, E S; Eremin, V A; Farlenkov, A S; Smirnov, A S; Kolchugin, A A; Porotnikova, N M; Khodimchuk, A V; Berenov, A V; Kurumchin, E Kh

    2016-04-07

    Oxygen surface exchange kinetics and diffusion have been studied by the isotope exchange method with gas phase equilibration using a static circulation experimental rig in the temperature range of 600-800 °C and oxygen pressure range of 0.13-2.5 kPa. A novel model which takes into account distributions of the dissociative adsorption and incorporation rates has been developed. The rates of the elementary stages have been calculated. The rate-determining stages for a La2NiO(4±δ) polycrystalline specimen have been discussed. The diffusion activation energies calculated using the gas phase equilibration method (1.4 eV) differ significantly from those calculated using isotope exchange depth profiling (0.5-0.8 eV), which was attributed to the influence of different oxygen diffusion pathways.

  5. 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.

  6. 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.

  7. 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.

  8. 99 Tc NMR determination of the oxygen isotope content in 18 O-enriched water.

    Science.gov (United States)

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

    2018-03-01

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

  9. 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

  10. [Correlation between the inspired fraction of oxygen, maternal partial oxygen pressure, and fetal partial oxygen pressure during cesarean section of normal pregnancies].

    Science.gov (United States)

    Castro, Carlos Henrique Viana de; Cruvinel, Marcos Guilherme Cunha; Carneiro, Fabiano Soares; Silva, Yerkes Pereira; Cabral, Antônio Carlos Vieira; Bessa, Roberto Cardoso

    2009-01-01

    Despite changes in pulmonary function, maternal oxygenation is maintained during obstetric regional blocks. But in those situations, the administration of supplementary oxygen to parturients is a common practice. Good fetal oxygenation is the main justification; however, this has not been proven. The objective of this randomized, prospective study was to test the hypothesis of whether maternal hyperoxia is correlated with an increase in fetal gasometric parameters in elective cesarean sections. Arterial blood gases of 20 parturients undergoing spinal block with different inspired fractions of oxygen were evaluated and correlated with fetal arterial blood gases. An increase in maternal inspired fraction of oxygen did not show any correlation with an increase of fetal partial oxygen pressure. Induction of maternal hyperoxia by the administration of supplementary oxygen did not increase fetal partial oxygen pressure. Fetal gasometric parameters did not change even when maternal parameters changed, induced by hyperoxia, during cesarean section under spinal block.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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...

  16. 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.

  17. Stable isotope (C, O) and monovalent cation fractionation upon synthesis of carbonate-bearing hydroxyl apatite (CHAP) via calcite transformation

    Science.gov (United States)

    Böttcher, Michael E.; Schmiedinger, Iris; Wacker, Ulrike; Conrad, Anika C.; Grathoff, Georg; Schmidt, Burkhard; Bahlo, Rainer; Gehlken, Peer-L.; Fiebig, Jens

    2016-04-01

    Carbonate-bearing hydroxyl-apatite (CHAP) is of fundamental and applied interest to the (bio)geochemical, paleontological, medical and material science communities, since it forms the basic mineral phase in human and animal teeth and bones. In addition, it is found in non-biogenic phosphate deposits. The stable isotope and foreign element composition of biogenic CHAP is widely used to estimate the formation conditions. This requires careful experimental calibration under well-defined boundary conditions. Within the DFG project EXCALIBOR, synthesis of carbonate-bearing hydroxyapatite was conducted via the transformation of synthetic calcite powder in aqueous solution as a function of time, pH, and temperature using batch-type experiments. The aqueous solution was analyzed for the carbon isotope composition of dissolved inorganic carbonate (gas irmMS), the oxygen isotope composition of water (LCRDS), and the cationic composition. The solid was characterized by powder X-ray diffraction, micro Raman and FTIR spectroscopy, SEM-EDX, elemental analysis (EA, ICP-OES) and gas irmMS. Temperature was found to significantly impact the transformation rate of calcite to CHAP. Upon complete transformation, CHAP was found to contain up to 5% dwt carbonate, depending on the solution composition (e.g., pH), both incorporated on the A and B type position of the crystal lattice. The oxygen isotope fractionation between water and CHAP decreased with increasing temperature with a tentative slope shallower than those reported in the literature for apatite, calcite or aragonite. In addition, the presence of dissolved NH4+, K+ or Na+ in aqueous solution led to partial incorporation into the CHAP lattice. How these distortions of the crystal lattice may impact stable isotope discrimination is subject of future investigations.

  18. 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

  19. Tracing the oxygen triple isotopic composition of tropospheric molecular oxygen in biogenic apatite - a new tool for palaeoclimatology

    Science.gov (United States)

    Pack, A.; Süssenberger, A.; Gehler, A.; Wotzlaw, J.

    2009-04-01

    It has been demonstrated that tropospheric molecular oxygen posses a significant isotope anomaly [1, 2 and refs. therein]. Relative to the rocks- and minerals-defined terrestrial fractionation line (TFL), tropospheric O2 has an anomaly of -0.35‰ [2]. Because almost all oxygen on Earth is contained in rocks, we suggest that the rocks- and minerals-defined TFL [3] should be used as reference when reporting isotope anomalies with ∆17O = δ'17OSMOW - βTFL δ'18OSMOW. We have developed a new technique for the determination of δ17O and δ18O of silicates by means of laser fluorination GC-CF-irmMS. We have determined βTFL to 0.5247 (N > 100), which is identical to the value reported by other laboratories and techniques [2, 3]. The uncertainty in ∆17O is ±0.03 (1σ) for a single analysis. It was suggested that ∆17O of tropospheric O2 can be used as proxy for the global bioactivity rate [GBR, 1] as well as for past atmospheric CO2 concentrations [4]. Past ∆17O of tropospheric O2 can be determined by analyzing O2 trapped in ice [1, 5] or by analyzing sulfates from terrestrial sulphide oxidation [4]. Disadvantage of ice core data is the limitation in time back mammals of different body mass (Mb) from Northern Germany (except Indian Elephant). The ∆17O of apatite varies between -0.16‰ for a wood mouse (Apodemus sylvaticus) and +0.04‰ for a wild boar (Sus scrofa). Samples were analyzed between 5 and 7 times in order to reduce the analytical uncertainty to ±0.012-0.025‰. Our data confirm the prediction from mass balance that animals inherit a ∆17O signature from anomalous air O2. We have developed a detailed mass balance for mammals with respect to ∆17O. The mass balance considers the oxygen fluxes (drinking and food water, respired O2, metabolic water, excrements, evaporated water and exhaled CO2). The fractionation in δ18O and ∆17O (from associated β-value) was considered for each of the fluxes. The result is an allometric scaling model for ∆17

  20. 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....

  1. Non-linear Isotope Effects

    DEFF Research Database (Denmark)

    Schmidt, Johan Albrecht

    ’s stratosphere is nearly mass dependent, and only a small fraction of the observed anomalous oxygen-17 excess can be attributed to N2O photolysis. In contrast, stratospheric photolysis produces a significant inverse clumped isotope effect.(ii) Stratospheric OCS photolysis significantly enrich the remaining OCS...

  2. 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.

  3. Should direct measurements of tumor oxygenation relate to the radiobiological hypoxic fraction of a tumor?

    International Nuclear Information System (INIS)

    Fenton, Bruce M.; Kiani, Mohammad F.; Siemann, Dietmar W.

    1995-01-01

    Purpose: Numerous previous studies have attempted to relate the radiobiological hypoxic fraction (HF) to direct measures of tumor oxygenation such as HbO 2 saturations, tumor pO 2 levels, or hypoxic cell labeling. Although correlations have been found within tumor lines, no overall relationships were seen across tumor lines. The current objective was to examine the effect on HF of changes in the fractions of the oxygenated and anoxic tumor cells that remain clonogenic. Methods and Materials: A mathematical model was developed that relates the HF to direct measures of tumor oxygenation. The primary assumptions were that: (a) the tumor is divided into distinct compartments of either fully oxygenated or fully anoxic cells, and (b) the survival of the oxygenated cells is negligible compared to that of the anoxic cells. Based on these assumptions, the HF is plotted as a function of the fractions of clonogenic or nonclonogenic, and oxygenated or anoxic cells. Results: If all cells are clonogenic, then the HF equals the fraction of anoxic cells. If a higher fraction of anoxic than oxygenated cells are nonclonogenic, then the HF will be overestimated by the fraction of the tumor measured to be anoxic using direct measuring techniques. If a higher fraction of the oxygenated than anoxic cells are nonclonogenic, the HF will be underestimated by the fraction of anoxic cells. Conclusion: Correlations between the HF and direct measures of tumor oxygenation have been described within tumor lines evaluated under different physiological condition. However, such relationships can be totally unpredictable between different tumors if the fraction of the anoxic cells that is clonogenic varies substantially. Clearly, if tumor anoxia cannot be detected using direct measures, this is an accurate indication that the tumor is well oxygenated. When tumor anoxia is present, however, the conclusions are ambiguous. Even when a small fraction of the tumor is measured as anoxic, direct measures

  4. 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.)

  5. Chromatographic determination of the relative retention of isotopic species of oxygen in methanol and methan-d3-ol

    International Nuclear Information System (INIS)

    Pauls, R.E.; Mahle, N.H.; Shepard, A.T.; Gaw, J.C.; Rogers, L.B.

    1976-08-01

    A high-precision gas chromatograph was used in conjunction with a quadrupole mass filter and an on-line computer to study the fractionation of oxygen isotopes by Porapak T and glycerol in CH 3 OH and CD 3 OH as a function of temperature. Values of relative retention on the order of 1.002 compared favorably with results for the vapor pressure ratio obtained by classical means. Differences from unity were much smaller for the activity-coefficient ratio than for the vapor-pressure ratio. Differential thermodynamic data were also reported

  6. 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.

  7. Stepwise fluorination - a useful approach for the isotopic analysis of hydrous minerals

    Energy Technology Data Exchange (ETDEWEB)

    Haimson, M; Knauth, L P [Arizona State Univ., Tempe (USA). Dept. of Geology

    1983-09-01

    Analytical uncertainties in oxygen isotopic studies of hydrous silica have been investigated using a partial fluorination procedure in which fractional oxygen yields are achieved by reducing the amount of fluorine. Stepwise reaction of opaline silica results in a set of sequential oxygen fractions which show a wide range of delta/sup 18/O values due to variable amounts of water, organic matter, and other impurities. Delta-values for successive fractions in non-biogenic opal systematically increase as water is reacted away and then remain constant to within +- 0.2 per thousand as the remaining silica reacts. Delta-values in biogenic silica increase similarly but then decrease when low /sup 18/O oxide impurities begin to react. The troublesome water component in opal is readily removed by stepwise fluorination. This technique allows more precise oxygen isotope analysis of non-biogenic opal-A, and may improve the analytical precision for biogenic silica and any silicate mineral containing a significant water component.

  8. Oxygen isotopic composition of mammal bones as a new tool for studying ratios of paleoenvironmental water and paleoclimates

    International Nuclear Information System (INIS)

    Longinelli, A.

    1984-04-01

    The purpose of this study is to try to establish quantitative relationships between the average oxygen isotopic composition of local meteoric water, the oxygen isotopic composition of mammal body water and the oxygen isotopic composition of phosphate in mammal bones. These relationships, after calibration of the method on living specimens, would allow quantitative paleoclimatological research based on the measurement of delta 18 O(PO 4 3- ) of fossil mammal bones

  9. 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

  10. 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

  11. 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

  12. Exploring Neutron-Rich Oxygen Isotopes with MoNA

    International Nuclear Information System (INIS)

    Frank, N.; Gade, A.; Peters, W. A.; Thoennessen, M.; Baumann, T.; Bazin, D.; Lecouey, J.-L.; Scheit, H.; Schiller, A.; Brown, J.; DeYoung, P. A.; Finck, J. E.; Hinnefeld, J.; Howes, R.; Luther, B.

    2007-01-01

    The Modular Neutron Array (MoNA) was used in conjunction with a large-gap dipole magnet (Sweeper) to measure neutron-unbound states in oxygen isotopes close to the neutron dripline. While no excited states were observed in 24 O, a resonance at 45(2) keV above the neutron separation energy was observed in 23 O

  13. Tumor oxygenation in a transplanted rat rhabdomyosarcoma during fractionated irradiation

    International Nuclear Information System (INIS)

    Zywietz, Friedrich; Reeker, Wolfram; Kochs, Eberhard

    1995-01-01

    Purpose: To quantify the changes in tumor oxygenation in the course of a fractionated radiation treatment extending over 4 weeks. Methods and Materials: Rhabdomyosarcomas R1H of the rat were irradiated with 60 Co-γ-rays with a total dose of 60 Gy, given in 20 fractions over 4 weeks. Oxygen partial pressure (pO 2 ) in tumors was measured at weekly intervals using polarographic needle probes in combination with a microprocessor-controlled device (pO 2 -Histograph/KIMOC). The pO 2 measurements were carried out in anesthetized animals under mechanical ventilation and in respiratory and hemodynamic steady state. Tumor pO 2 values were correlated to the arterial oxygen pressure p a O 2 , arterial pCO 2 , and pH determined with a blood gas analyzer. Results: Tumor oxygenation did not change significantly during the 3 weeks of irradiation (up to 45 Gy), from a median pO 2 of 23 ± 2 mmHg in untreated controls to 19 ± 4 mmHg after the third week. The decrease of the number of pO 2 values between 0 and 5 mmHg indicated that an improved oxygenation in the tumors occurred. However, with increasing radiation dose (fourth week, 60 Gy) a significant decrease in tumor oxygenation to a median pO 2 of 8 ± 2 mmHg and a rapid increase in the frequency of pO 2 values (35 ± 4%) between 0 and 5 mmHg was found. Conclusion: Improved oxygenation in rhabdomyosarcomas R1H was only present in the early phase of the fractionated irradiation. Radiation doses above 45 Gy led to a considerable decrease of tumor oxygenation in the later phase of irradiation

  14. 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.

  15. 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

  16. Caution on the storage of waters and aqueous solutions in plastic containers for hydrogen and oxygen stable isotope analysis.

    Science.gov (United States)

    Spangenberg, Jorge E

    2012-11-30

    The choice of containers for storage of aqueous samples between their collection, transport and water hydrogen ((2)H) and oxygen ((18)O) stable isotope analysis is a topic of concern for a wide range of fields in environmental, geological, biomedical, food, and forensic sciences. The transport and separation of water molecules during water vapor or liquid uptake by sorption or solution and the diffusive transport of water molecules through organic polymer material by permeation or pervaporation may entail an isotopic fractionation. An experiment was conducted to evaluate the extent of such fractionation. Sixteen bottle-like containers of eleven different organic polymers, including low and high density polyethylene (LDPE and HDPE), polypropylene (PP), polycarbonate (PC), polyethylene terephthalate (PET), and perfluoroalkoxy-Teflon (PFA), of different wall thickness and size were completely filled with the same mineral water and stored for 659 days under the same conditions of temperature and humidity. Particular care was exercised to keep the bottles tightly closed and prevent loss of water vapor through the seals. Changes of up to +5‰ for δ(2)H values and +2.0‰ for δ(18)O values were measured for water after more than 1 year of storage within a plastic container, with the magnitude of change depending mainly on the type of organic polymer, wall thickness, and container size. The most important variations were measured for the PET and PC bottles. Waters stored in glass bottles with Polyseal™ cone-lined PP screw caps and thick-walled HDPE or PFA containers with linerless screw caps having an integrally molded inner sealing ring preserved their original δ(2)H and δ(18)O values. The carbon, hydrogen, and oxygen stable isotope compositions of the organic polymeric materials were also determined. The results of this study clearly show that for precise and accurate measurements of the water stable isotope composition in aqueous solutions, rigorous sampling and

  17. 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

  18. Carbon and oxygen isotope compositions of the carbonate facies

    Indian Academy of Sciences (India)

    The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleopro- terozoic to the Neoproterozoic period.Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies.However,the ...

  19. 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.

  20. 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

  1. Controls of oxygen isotope ratios of nitrate formed during nitrification in soils

    International Nuclear Information System (INIS)

    Mayer, B.; Bollwerk, S.M.; Vorhoff, B.; Mansfeldt, T.; Veizer, J.

    1999-01-01

    The isotopic composition of nitrate is increasingly used to determine sources and transformations of nitrogen in terrestrial and aquatic ecosystems. Oxygen isotope ratios of nitrate appear to be particularly useful, since they allow the differentiation between nitrate from atmospheric deposition (δ 18 O nitrate between +25 and +70 per mille), nitrate from fertilizers (δ 18 O nitrate +23 per mille), and nitrate derived from nitrification processes in soils (δ 18 O nitrate 3 molecule derive from H 2 O (with negative δ 18 O values dependent upon location) and one oxygen derives from atmospheric O 2 (δ 18 O = +23.5 per mille).. The objective of this study was to experimentally determine the extent to which water oxygen controls the δ 18 O value of nitrate, which is formed during nitrification in soils

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

    Directory of Open Access Journals (Sweden)

    Nurgul Balci

    2017-08-01

    Full Text Available Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62− and elemental sulfur (S° to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6 by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4 from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2. During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4

  3. 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.

  4. Simulated oxygen isotopes in cave drip water and speleothem calcite in European caves

    Directory of Open Access Journals (Sweden)

    A. Wackerbarth

    2012-11-01

    Full Text Available Interpreting stable oxygen isotope18O records from stalagmites is still one of the complex tasks in speleothem research. Here, we present a novel model-based approach, where we force a model describing the processes and modifications of δ18O from rain water to speleothem calcite (Oxygen isotope Drip water and Stalagmite Model – ODSM with the results of a state-of-the-art atmospheric general circulation model enhanced by explicit isotope diagnostics (ECHAM5-wiso. The approach is neither climate nor cave-specific and allows an integrated assessment of the influence of different varying climate variables, e.g. temperature and precipitation amount, on the isotopic composition of drip water and speleothem calcite.

    First, we apply and evaluate this new approach under present-day climate conditions using observational data from seven caves from different geographical regions in Europe. Each of these caves provides measured δ18O values of drip water and speleothem calcite to which we compare our simulated isotope values. For six of the seven caves modeled δ18O values of drip water and speleothem calcite are in good agreement with observed values. The mismatch of the remaining caves might be caused by the complexity of the cave system, beyond the parameterizations included in our cave model.

    We then examine the response of the cave system to mid-Holocene (6000 yr before present, 6 ka climate conditions by forcing the ODSM with ECHAM5-wiso results from 6 ka simulations. For a set of twelve European caves, we compare the modeled mid-Holocene-to-modern difference in speleothem calcite δ18O to available measurements. We show that the general European changes are simulated well. However, local discrepancies are found, and might be explained either by a too low model resolution, complex local soil-atmosphere interactions affecting evapotranspiration or by cave specific factors

  5. Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia

    Science.gov (United States)

    Brookman, Tom H.; Ambrose, Stanley H.

    2012-09-01

    Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C3 and C4 vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ13C and δ18O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north-south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.

  6. 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.

  7. Laser Spectroscopic Analysis of Liquid Water Samples for Stable Hydrogen and Oxygen Isotopes

    International Nuclear Information System (INIS)

    2009-01-01

    Stable isotope ratios of hydrogen and oxygen are tracers of choice for water cycle processes in hydrological, atmospheric and ecological studies. The use of isotopes has been limited to some extent because of the relatively high cost of isotope ratio mass spectrometers and the need for specialized operational skills. Here, the results of performance testing of a recently developed laser spectroscopic instrument for measuring stable hydrogen and oxygen isotope ratios of water samples are described, along with a procedure for instrument installation and operation. Over the last four years, the IAEA Water Resources Programme conducted prototype and production model testing of these instruments and this publication is the outcome of those efforts. One of the main missions of the IAEA is to promote the use of peaceful applications of isotope and nuclear methods in Member States and this publication is intended to facilitate the use of laser absorption based instruments for hydrogen and oxygen stable isotope analyses of liquid water samples for hydrological and other studies. The instrument uses off-axis integrated cavity output spectroscopy to measure absolute abundances of 2 HHO, HH 18 O, and HHO via laser absorption. Test results using a number of natural and synthetic water standards and samples with a large range of isotope values demonstrate adequate precision and accuracy (e.g. precisions of 1 per mille for δ 2 H and 0.2 per mille for δ 18 O). The laser instrument has much lower initial and maintenance costs than mass spectrometers and is substantially easier to operate. Thus, these instruments have the potential to bring about a paradigm shift in isotope applications by enabling researchers in all fields to measure isotope ratios by themselves. The appendix contains a detailed procedure for the installation and operation of the instrument. Using the procedure, new users should be able to install the instrument in less than two hours. It also provides step

  8. Oxygen isotope variations in phosphate of biogenic apatites. Pt.1

    International Nuclear Information System (INIS)

    Kolodny, Y.; Luz, B.; Navon, O.

    1983-01-01

    The major advantage of the oxygen in phosphate isotope paleothermometry is that it is a system which records temperatures with great sensitivity while bone (and teeth) building organisms are alive, and the record is nearly perfectly preserved after death. Fish from seven water bodies of different temperatures (3-23 0 C) and different delta 18 O (values - 16 to + 3) of the water were analysed. The delta 18 O values of the analysed PO 4 vary from 6 to 25. The system passed the following tests: (a) the temperature deduced from isotopic analyses of the sequence of fish from Lake Baikal are in good agreement with the temperatures measured in the thermally stratified lake; (b) the isotopic composition of fish bone phosphate is not influenced by the isotopic composition of the phosphate which is fed to the fish, but only by temperature and water composition. Isotopic analysis of fossil fish in combination with analysis of mammal bones should be a useful tool in deciphering continental paleoclimates. (orig.)

  9. Holocene climate variability revealed by oxygen isotope analysis of Sphagnum cellulose from Walton Moss, northern England

    Science.gov (United States)

    Daley, T. J.; Barber, K. E.; Street-Perrott, F. A.; Loader, N. J.; Marshall, J. D.; Crowley, S. F.; Fisher, E. H.

    2010-07-01

    Stable isotope analyses of Sphagnum alpha-cellulose, precipitation and bog water from three sites across northwestern Europe (Raheenmore, Ireland, Walton Moss, northern England and Dosenmoor, northern Germany) over a total period of 26 months were used to investigate the nature of the climatic signal recorded by Sphagnum moss. The δ18O values of modern alpha-cellulose tracked precipitation more closely than bog water, with a mean isotopic fractionation factor αcellulose-precipitation of 1.0274 ± 0.001 (1 σ) (≈27‰). Sub-samples of isolated Sphagnum alpha-cellulose were subsequently analysed from core WLM22, Walton Moss, northern England yielding a Sphagnum-specific isotope record spanning the last 4300 years. The palaeo-record, calibrated using the modern data, provides evidence for large amplitude variations in the estimated oxygen isotope composition of precipitation during the mid- to late Holocene. Estimates of palaeotemperature change derived from statistical relationships between modern surface air temperatures and δ18O precipitation values for the British Isles give unrealistically large variation in comparison to proxies from other archives. We conclude that use of such relationships to calibrate mid-latitude palaeo-data must be undertaken with caution. The δ18O record from Sphagnum cellulose was highly correlated with a palaeoecologically-derived index of bog surface wetness (BSW), suggesting a common climatic driver.

  10. Scavenging of oxygen vacancies at modulation-doped oxide interfaces: Evidence from oxygen isotope tracing

    DEFF Research Database (Denmark)

    Chen, Yunzhong; Döbeli, M.; Pomjakushina, E.

    2017-01-01

    , the mechanisms underlying the extreme mobility enhancement remain elusive. Herein, we used 18O isotope exchanged SrTi18O3 as substrates to create 2DEG at room temperature with and without the LSMO buffer layer. By mapping the oxygen profile across the interface between STO18 and disordered LaAlO3 or yttria...

  11. 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)

  12. Preparation and use of nitrogen (2) oxide of special purity for production of oxygen and nitrogen isotopes

    International Nuclear Information System (INIS)

    Polevoj, A.S.

    1989-01-01

    Problems related with production of oxygen and nitrogen isotopes by means of low-temperature rectification of nitrogen (2) oxide are analyzed. Special attention, in particular, is payed to the techniques of synthesis and high purification of initial NO, utilization of waste flows formed during isotope separation. Ways to affect the initial isotope composition of nitrogen oxide and the rate of its homogeneous-isotope exchange, which provide for possibility of simultaneous production of oxygen and nitrogen isotopes by means of NO rectification, are considered. Description of a new technique for high purification of nitrogen oxide, prepared at decomposition of nitric acid by sulfurous anhydride, suggested by the author is presented

  13. USGS42 and USGS43: Human-hair stable hydrogen and oxygen isotopic reference materials and analytical methods for forensic science and implications for published measurement results

    Science.gov (United States)

    Coplen, T.B.; Qi, H.

    2012-01-01

    Because there are no internationally distributed stable hydrogen and oxygen isotopic reference materials of human hair, the U.S. Geological Survey (USGS) has prepared two such materials, USGS42 and USGS43. These reference materials span values commonly encountered in human hair stable isotope analysis and are isotopically homogeneous at sample sizes larger than 0.2 mg. USGS42 and USGS43 human-hair isotopic reference materials are intended for calibration of δ(2)H and δ(18)O measurements of unknown human hair by quantifying (1) drift with time, (2) mass-dependent isotopic fractionation, and (3) isotope-ratio-scale contraction. While they are intended for measurements of the stable isotopes of hydrogen and oxygen, they also are suitable for measurements of the stable isotopes of carbon, nitrogen, and sulfur in human and mammalian hair. Preliminary isotopic compositions of the non-exchangeable fractions of these materials are USGS42(Tibetan hair)δ(2)H(VSMOW-SLAP) = -78.5 ± 2.3‰ (n = 62) and δ(18)O(VSMOW-SLAP) = +8.56 ± 0.10‰ (n = 18) USGS42(Indian hair)δ(2)H(VSMOW-SLAP) = -50.3 ± 2.8‰ (n = 64) and δ(18)O(VSMOW-SLAP) = +14.11 ± 0.10‰ (n = 18). Using recommended analytical protocols presented herein for δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) measurements, the least squares fit regression of 11 human hair reference materials is δ(2)H(VSMOW-SLAP) = 6.085δ(2)O(VSMOW-SLAP) - 136.0‰ with an R-square value of 0.95. The δ(2)H difference between the calibrated results of human hair in this investigation and a commonly accepted human-hair relationship is a remarkable 34‰. It is critical that readers pay attention to the δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) of isotopic reference materials in publications, and they need to adjust the δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) measurement results of human hair in previous publications, as needed, to ensure all results on are on the same scales.

  14. Dual temperature effects on oxygen isotopic ratio of shallow-water coral skeleton: Consequences on seasonal and interannual records

    Science.gov (United States)

    Juillet-Leclerc, A.; Reynaud, S.

    2009-04-01

    Oxygen isotopic ratio from coral skeleton is regarded for a long time as promising climate archives at seasonal scale. Although in isotopic disequilibrium relative to seawater, it is supposed to obey to the isotope thermometer. Indeed, coral oxygen isotopic records are strongly temperature dependent, but d18O-temperature calibrations derived from different corals are highly variable. The isotope thermometer assumption does not take into account vital effects due to biogenic origin of the mineral. Corals are animals living in symbiosis with algae (zooxanthellae). Interactions between symbiont photosynthesis and coral skeleton carbonation have been abundantly observed but they remain poorly understood and the effects of photosynthesis on coral growth and skeleton oxygen ratio are ignored. Coral cultured under two light conditions enabled to relate metabolic parameters and oxygen isotopic variability with photosynthetic activity. By examining responses provided by each colony they revealed that photosynthesis significantly affected d18O, by an opposite sense compared with the sole temperature influence. Since temperature and light changes are associated during seasonal variations, this complicates the interpretation of seasonal record. Additionally, this complexity is amplified because photosynthetic activity is also directly impacted by temperature variability. Thus, the annual isotopic amplitude due to the "physical" temperature influence is partly compensated through photosynthesis. Similar opposite effect is also shown by extension rate of the cultured colonies. First, we will examine and quantify consequences of photosynthesis on growth rate and oxygen isotopic signature, from cultured corals. Second, we will consider the consequences of this vital effect on data series, at seasonal and interannual time scales.

  15. Isotopic-spectral determination of hydrogen, nitrogen, oxygen and carbon in semiconductor materials

    International Nuclear Information System (INIS)

    Dudich, G.K.; Eremeev, V.A.; Li, V.N.; Nemets, V.M.

    1981-01-01

    Techniques of low-temperature isotopic-spectral determination of impurities of hydrogen, nitrogen, oxygen and carbon in semiconductor materials Bi, Ge, Pb tellurides are developed. The techniques include selection into special vessel with the known volume (exchanger) of sample analyzed, dosed introduction into exchanger of rare isotope of the element determined ( 2 H, 15 N, 18 O, 13 C) in the form of isotope-containing gas, balancing of the determined element isotopes in the system sample-isotope, containing gas, spectroscopic, determination of its isotope composition in gaseous phase of the system and calculation of the amount of the element determined in the sample. The lower boundaries of the amounts determined constitute 10 -7 , 10 -7 , 10 -6 and 10 -5 mass % respectively when sample of 20 g are used [ru

  16. 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.

  17. Survival and Neurodevelopmental Outcomes of Preterms Resuscitated With Different Oxygen Fractions

    NARCIS (Netherlands)

    Boronat, Nuria; Aguar, Marta; Rook, Denise; Iriondo, Martin; Brugada, María; Cernada, María; Nuñez, Antonio; Izquierdo, Montserrat; Cubells, Elena; Martinez, María; Parra, Anna; van Goudoever, Hans; Vento, Máximo

    2016-01-01

    Stabilization of preterm infants after birth frequently requires oxygen supplementation. At present the optimal initial oxygen inspiratory fraction (Fio2) for preterm stabilization after birth is still under debate. We aimed to compare neurodevelopmental outcomes of extremely preterm infants at 24

  18. Using Oxygen and Carbon Isotopic Signatures in Order to Infer Climatic and Dietary Information in Roman Edessa, Greece

    Science.gov (United States)

    Michael, Dimitra-Ermioni; Dotsika, Elissavet

    2017-12-01

    Even though many isotopic studies have been conducted on ancient populations from Greece for the purpose of dietary reconstruction; mostly through carbon and nitrogen isotopic signals of bone collagen, less attention has been given to the utility of apatite signatures (oxygen and carbon) as dietary and palaeoenvironmental tools. Moreover, until recently the isotopic signal of tooth enamel for both the purposes of environmental and dietary reconstructions has been rarely assessed in ancient Greek societies. Therefore, the present study aims to provide with novel isotopic information regarding Edessa; a town in Northern Greece, during the Roman period. The current study primarily aims to explore the possible differentiation between the present climatic conditions in Edessa in relation to those occurring at the Roman period. Secondly, this study aims to reveal the significant utility of enamel isotopic signatures (carbon and oxygen) in palaeoenvironmental and palaeodietary studies regarding ancient human remains. The isotopic analyses have been conducted at the Stable Isotope and Radiocarbon Unit of INN, NCSR “Demokritos”. The population of Roman Edessa (2nd-4th c. AD) consists of 22 individuals, providing with 19 bone samples and 16 enamel ones. The mean enamel oxygen value is at -7.7 ±1.1 %0, the bone apatite mean oxygen value at -9.2 ±1.9 %0, and finally the mean carbon enamel value is at -11.7 ±1.2 %0. Oxygen values probably indicate that Edessa had a cooler climate during the Roman times in relation to present conditions, even though more research should be carried out in order to be more certain. In addition, the possible existence of non-local individuals has been revealed through the oxygen teeth enamel-bone apatite spacing. Finally, the carbon enamel signature has pointed out possible differentiations between the adult and the juvenile diet. Based on Edessa’s findings, the stated study strongly encourages the enamel oxygen and carbon isotopic signals

  19. The common property of isotope anomalies in meteorites

    International Nuclear Information System (INIS)

    Robert, F.

    2004-01-01

    The treatment proposed to account for the non-mass-dependent isotopic fractionation effect observed for oxygen isotopes during the synthesis of ozone (Robert and Camy-Peyret 2001) is applied to other chemical elements. A numerical treatment to calculate isotopic reaction rate ratios is proposed. This treatment yields non-mass-dependent isotopic effects in other chemical elements, qualitatively similar to those observed in some of the high temperature minerals found in the carbonaceous meteorites. This treatment may reflect the numerical consequences of an unrecognized quantum mechanical effect, linked to a property of chemical reactions involving indistinguishable isotopes. (author)

  20. Normalization of stable isotope data for carbonate minerals: implementation of IUPAC guideline

    Science.gov (United States)

    Kim, Sang-Tae; Coplen, Tyler B.; Horita, Juske

    2015-01-01

    Carbonate minerals provide a rich source of geochemical information because their δ13C and δ18O values provide information about surface and subsurface Earth processes. However, a significant problem is that the same δ18O value is not reported for the identical carbonate sample when analyzed in different isotope laboratories in spite of the fact that the International Union of Pure and Applied Chemistry (IUPAC) has provided reporting guidelines for two decades. This issue arises because (1) the δ18O measurements are performed on CO2 evolved by reaction of carbonates with phosphoric acid, (2) the acid-liberated CO2 is isotopically fractionated (enriched in 18O) because it contains only two-thirds of the oxygen from the solid carbonate, (3) this oxygen isotopic fractionation factor is a function of mineralogy, temperature, concentration of the phosphoric acid, and δ18O value of water in the phosphoric acid, (4) researchers may use any one of an assortment of oxygen isotopic fractionation factors that have been published for various minerals at various reaction temperatures, and (5) it sometimes is not clear how one should calculate δ18OVPDB values on a scale normalized such that the δ18O value of SLAP reference water is −55.5 ‰ relative to VSMOW reference water.

  1. Multiple taxon multiple locality approach to providing oxygen isotope evidence for warm-blooded theropod dinosaurs

    Science.gov (United States)

    Fricke, Henry C.; Rogers, Raymond R.

    2000-09-01

    Oxygen isotope ratios of fossil remains of coexisting taxa from several different localities can be used to help investigate dinosaur thermoregulation. Focusing on the Late Cretaceous, oxygen isotope ratios of crocodile tooth enamel from four separate localities exhibit less of a decrease with latitude than do ratios of tooth enamel from coexisting theropod dinosaurs. A shallower latitudinal gradient for crocodiles is consistent with how oxygen isotope ratios should vary for heterothermic animals having body temperatures coupled with their environments (“cold blooded”), while a steeper gradient for theropods is consistent with how these ratios should vary for homeothermic animals having constant body temperatures independent of their environments (“warm blooded”). This inferred homoethermy in theropods is likely due to higher rates of metabolic heat production relative to crocodiles and is not an artifact of body size.

  2. Oxygen isotope separation by isotopically selective infrared multiphoton dissociation of 2,3-dihydropyran

    International Nuclear Information System (INIS)

    Yokoyama, Atsushi; Ohba, Hironori; Akagi, Hiroshi; Yokoyama, Keiichi; Saeki, Morihisa; Katsumata, Keiichi

    2008-01-01

    Oxygen isotopic selectivity on infrared multiphoton dissociation of 2,3-dihydropyran has been studied by the examination of the effects of excitation frequency, laser fluence, and gas pressure on the dissociation probability of 2,3-dihydropyran and isotopic composition of products. Oxygen-18 was enriched in a dissociation product: 2-propenal. The enrichment factor of 18 O and the dissociation probability were measured at laser frequency between 1033.5 and 1057.3 cm -1 ; the laser fluence of 2.2 - 2.3 J/cm 2 ; and the 2,3-dihydropyran pressure of 0.27 kPa. The dissociation probability decreases as the laser frequency being detuned from the absorption peak of 2,3-dihydropyran around 1081 cm -1 . On the other hand, the enrichment factor increases with detuning the frequency. The enrichment factor of 18 O increases with increasing the 2,3-dihydropyran pressure at the laser fluence below 3 J/cm 2 and the laser frequency of 1033.5 cm -1 , whereas the yield of 2-propenal decreases with increasing the pressure. Very high enrichment factor of 751 was obtained by the irradiation of 0.53 kPa of 2,3-dihydropyran at 2.1 J/cm 2 . (author)

  3. Inner Retinal Oxygen Extraction Fraction in Response to Light Flicker Stimulation in Humans

    Science.gov (United States)

    Felder, Anthony E.; Wanek, Justin; Blair, Norman P.; Shahidi, Mahnaz

    2015-01-01

    Purpose Light flicker has been shown to stimulate retinal neural activity, increase blood flow, and alter inner retinal oxygen metabolism (MO2) and delivery (DO2). The purpose of the study was to determine the change in MO2 relative to DO2 due to light flicker stimulation in humans, as assessed by the inner retinal oxygen extraction fraction (OEF). Methods An optical imaging system, based on a modified slit lamp biomicroscope, was developed for simultaneous measurements of retinal vascular diameter (D) and oxygen saturation (SO2). Retinal images were acquired in 20 healthy subjects before and during light flicker stimulation. Arterial and venous D (DA and DV) and SO2 (SO2A and SO2V) were quantified within a circumpapillary region. Oxygen extraction fraction was defined as the ratio of MO2 to DO2 and was calculated as (SO2A − SO2V)/SO2A. Reproducibility of measurements was assessed. Results Coefficients of variation and intraclass correlation coefficients of repeated measurements were <5% and ≥0.83, respectively. During light flicker stimulation, DA, DV , and SO2V significantly increased (P ≤ 0.004). Oxygen extraction fraction was 0.37 ± 0.08 before light flicker and significantly decreased to 0.31 ± 0.07 during light flicker (P = 0.001). Conclusions Oxygen extraction fraction before and during light flicker stimulation is reported in human subjects for the first time. Oxygen extraction fraction decreased during light flicker stimulation, indicating the change in DO2 exceeded that of MO2. This technology is potentially useful for the detection of changes in OEF response to light flicker in physiological and pathological retinal conditions. PMID:26469748

  4. Oxygen isotope analysis of plant water without extraction procedure

    International Nuclear Information System (INIS)

    Gan, K.S.; Wong, S.C.; Farquhar, G.D.; Yong, J.W.H.

    2001-01-01

    Isotopic analyses of plant water (mainly xylem, phloem and leaf water) are gaming importance as the isotopic signals reflect plant-environment interactions, affect the oxygen isotopic composition of atmospheric O 2 and CO 2 and are eventually incorporated into plant organic matter. Conventionally, such isotopic measurements require a time-consuming process of isolating the plant water by azeotropic distillation or vacuum extraction, which would not complement the speed of isotope analysis provided by continuous-flow IRMS (Isotope-Ratio Mass Spectrometry), especially when large data sets are needed for statistical calculations in biological studies. Further, a substantial amount of plant material is needed for water extraction and leaf samples would invariably include unenriched water from the fine veins. To measure sub-microlitre amount of leaf mesophyll water, a new approach is undertaken where a small disc of fresh leaf is cut using a specially designed leaf punch, and pyrolysed directly in an IRMS. By comparing with results from pyrolysis of the dry matter of the same leaf, the 18 O content of leaf water can be determined without extraction from fresh leaves. This method is validated using a range of cellulose-water mixtures to simulate the constituents of fresh leaf. Cotton leaf water δ 18 O obtained from both methods of fresh leaf pyrolysis and azeotropic distillation will be compared. The pyrolysis technique provides a robust approach to measure the isotopic content of water or any volatile present in a homogeneous solution or solid hydrous substance

  5. Low-temperature aqueous alteration on the CR chondrite parent body: Implications from in situ oxygen-isotope analyses

    Science.gov (United States)

    Jilly-Rehak, Christine E.; Huss, Gary R.; Nagashima, Kazu; Schrader, Devin L.

    2018-02-01

    The presence of hydrated minerals in chondrites indicates that water played an important role in the geologic evolution of the early Solar System; however, the process of aqueous alteration is still poorly understood. Renazzo-like carbonaceous (CR) chondrites are particularly well-suited for the study of aqueous alteration. Samples range from being nearly anhydrous to fully altered, essentially representing snapshots of the alteration process through time. We studied oxygen isotopes in secondary-minerals from six CR chondrites of varying hydration states to determine how aqueous fluid conditions (including composition and temperature) evolved on the parent body. Secondary minerals analyzed included calcite, dolomite, and magnetite. The O-isotope composition of calcites ranged from δ18O ≈ 9 to 35‰, dolomites from δ18O ≈ 23 to 27‰, and magnetites from δ18O ≈ -18 to 5‰. Calcite in less-altered samples showed more evidence of fluid evolution compared to heavily altered samples, likely reflecting lower water/rock ratios. Most magnetite plotted on a single trend, with the exception of grains from the extensively hydrated chondrite MIL 090292. The MIL 090292 magnetite diverges from this trend, possibly indicating an anomalous origin for the meteorite. If magnetite and calcite formed in equilibrium, then the relative 18O fractionation between them can be used to extract the temperature of co-precipitation. Isotopic fractionation in Al Rais carbonate-magnetite assemblages revealed low precipitation temperatures (∼60 °C). Assuming that the CR parent body experienced closed-system alteration, a similar exercise for parallel calcite and magnetite O-isotope arrays yields "global" alteration temperatures of ∼55 to 88 °C. These secondary mineral arrays indicate that the O-isotopic composition of the altering fluid evolved upon progressive alteration, beginning near the Al Rais water composition of Δ17O ∼ 1‰ and δ18O ∼ 10‰, and becoming increasingly

  6. Stable isotope deltas: Tiny, yet robust signatures in nature

    Science.gov (United States)

    Brand, Willi A.; Coplen, Tyler B.

    2012-01-01

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

  7. 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)

  8. 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.

  9. 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.

  10. Oxygen isotopic abundances in calcium- aluminum-rich inclusions from ordinary chondrites: implications for nebular heterogeneity.

    Science.gov (United States)

    McKeegan, K D; Leshin, L A; Russell, S S; MacPherson, G J

    1998-04-17

    The oxygen isotopic compositions of two calcium-aluminum-rich inclusions (CAIs) from the unequilibrated ordinary chondrite meteorites Quinyambie and Semarkona are enriched in 16O by an amount similar to that in CAIs from carbonaceous chondrites. This may indicate that most CAIs formed in a restricted region of the solar nebula and were then unevenly distributed throughout the various chondrite accretion regions. The Semarkona CAI is isotopically homogeneous and contains highly 16O-enriched melilite, supporting the hypothesis that all CAI minerals were originally 16O-rich, but that in most carbonaceous chondrite inclusions some minerals exchanged oxygen isotopes with an external reservoir following crystallization.

  11. 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

  12. 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

  13. The impact of including spatially longitudinal heterogeneities of vessel oxygen content and vascular fraction in 3D tumor oxygenation models on predicted radiation sensitivity.

    Science.gov (United States)

    Lagerlöf, Jakob H; Kindblom, Jon; Bernhardt, Peter

    2014-04-01

    Oxygen distribution models have been used to analyze the influences of oxygen tensions on tissue response after radiotherapy. These distributions are often generated assuming constant oxygen tension in the blood vessels. However, as red blood cells progress through the vessels, oxygen is continuously released into the plasma and the surrounding tissue, resulting in longitudinally varying oxygen levels in the blood vessels. In the present study, the authors investigated whether a tumor oxygenation model that incorporated longitudinally varying oxygen levels would provide different predictions of necrotic fractions and radiosensitivity compared to commonly used models with a constant oxygen pressure. Our models simulated oxygen diffusion based on a Green's function approach and oxygen consumption according to the Michaelis-Menten equation. The authors constructed tumor models with different vascular fractions (VFs), from which they generated depth oxygenation curves and a look-up table of oxygen pressure gradients. The authors evaluated models of spherical tumors of various sizes, from 1 to 10(4) mg. The authors compared the results from a model with constant vessel oxygen (CVO) pressure to those from models with longitudinal variations in oxygen saturation and either a constant VF (CVF) or variable VF (VVF) within the tumor tissue. The authors monitored the necrotic fractions, defined as tumor regions with an oxygen pressure below 1 mmHg. Tumor radiation sensitivity was expressed as D99, the homogeneous radiation dose required for a tumor control probability of 0.99. In the CVO saturation model, no necrosis was observed, and decreasing the VF could only decrease the D99 by up to 10%. Furthermore, the D99 vs VF dependence was similar for different tumor masses. Compared to the CVO model, the extended CVF and VVF models provided clearly different results, including pronounced effects of VF and tumor size on the necrotic fraction and D99, necrotic fractions ranging

  14. 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

  15. Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

    Science.gov (United States)

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

    2012-01-01

    Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation

  16. Sunlight creates oxygenated species in water-soluble fractions of Deepwater horizon oil

    Energy Technology Data Exchange (ETDEWEB)

    Ray, Phoebe Z. [Department of Chemistry, University of New Orleans, New Orleans, LA 70148 (United States); Chen, Huan [National High Magnetic Field Laboratory, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005 (United States); Podgorski, David C. [National High Magnetic Field Laboratory, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005 (United States); Future Fuels Institute, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005 (United States); McKenna, Amy M. [National High Magnetic Field Laboratory, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005 (United States); Tarr, Matthew A., E-mail: mtarr@uno.edu [Department of Chemistry, University of New Orleans, New Orleans, LA 70148 (United States)

    2014-09-15

    Graphical abstract: Sunlight oxygenates petroleum. - Highlights: • Oxidation seen in water-soluble oil fraction after exposure to simulated sunlight. • Oxygen addition occurred across a wide range of carbon number and DBE. • Oil compounds were susceptible to addition of multiple oxygens to each molecule. • Results provide understanding of fate of oil on water after exposure to sunlight. - Abstract: In order to assess the impact of sunlight on oil fate, Macondo well oil from the Deepwater Horizon (DWH) rig was mixed with pure water and irradiated with simulated sunlight. After irradiation, the water-soluble organics (WSO) from the dark and irradiated samples were extracted and characterized by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Liquid–liquid extraction yielded two fractions from dark and irradiated water/oil mixtures: acidic WSOs (negative-ion electrospray (ESI)), and base/neutral WSOs (positive-ion ESI) coupled to FT-ICR MS to catalog molecular-level transformations that occur to Macondo-derived WSOs after solar irradiation. Such direct measure of oil phototransformation has not been previously reported. The most abundant heteroatom class detected in the irradiated WSO acid fractions correspond to molecules that contain five oxygens (O{sub 5}), while the most abundant acids in the dark samples contain two oxygen atoms per molecule (O{sub 2}). Higher-order oxygen classes (O{sub 5}–O{sub 9}) were abundant in the irradiated samples, but <1.5% relative abundance in the dark sample. The increased abundance of higher-order oxygen classes in the irradiated samples relative to the dark samples indicates that photooxidized components of the Macondo crude oil become water-soluble after irradiation. The base/neutral fraction showed decreased abundance of pyridinic nitrogen (N{sub 1}) concurrent with an increased abundance of N{sub 1}O{sub x} classes after irradiation. The predominance of higher

  17. Isotope and chemical tracers in groundwater hydrology

    International Nuclear Information System (INIS)

    Kendall, C.; Stewart, M.K.; Morgenstern, U.; Trompetter, V.

    1999-01-01

    The course sessions cover: session 1, Fundamentals of stable and radioactive isotopes; session 2, Stable oxygen and hydrogen isotopes in hydrology: background, examples, sampling strategy; session 3, Catchment studies using oxygen and hydrogen isotopes: background - the hydrologic water balance, evapotranspiration - the lion's share, runoff generation - new water/old water fractions, groundwater recharge - the crumbs; session 4, Isotopes in catchment hydrology: survey of applications, future developments; session 5, Applications of tritium in hydrology: background and measurement, interpretation, examples; session 6, Case studies using mixing models: Hutt Valley groundwater system, an extended mixing model for simulating tracer transport in the unsaturated zone; session 7, Groundwater dating using CFC concentrations: background, sampling and measurement, use and applications; session 8, Groundwater dating with carbon-14: background, sampling and measurement, use and applications; session 9, NZ case studies: Tauranga warm springs, North Canterbury Plains groundwater; session 10, Stable carbon and nitrogen isotopes: background and examples, biological applications of C-N-S isotopes; session 11, New developments in isotope hydrology: gas isotopes, compound specific applications, age dating of sediments etc; session 12, NZ case studies: North Canterbury Plains groundwater (continued), Waimea Plains groundwater. (author). refs., figs

  18. 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.

  19. Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis.

    Science.gov (United States)

    Hitzfeld, Kristina L; Gehre, Matthias; Richnow, Hans-Hermann

    2017-05-01

    In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS 18 O/ 16 O monitoring for future method development is proposed.

  20. Stratigraphy on Oxygen and Carbon Isotope of Paciran Formation East Java

    International Nuclear Information System (INIS)

    Premonowati; R P Koesoemadinata; Harsono-Pringgoprawiro; Wahyoe-S-Hantoro

    2004-01-01

    Paleotemperature fluctuation in tropical zone (centennial and decad al scale) has been known. It's based on stable isotopic analysis from each of unconformity zones. Those boundaries have derived on reef units of shallows marine reef complex of Paciran Formation, Tuban area in Northeast Java Basin. From 25 samples have been choosen on undeformed calcite and analyzed by oxygen and carbon stable isotope. It used to validizing a sea level changes during the formation to Reef 1 to Reef 17 from Paciran formation with sea surface temperature (SST) since 4 Ma until now. On early forming of Reef 1 to Reef 3 (since 4 Ma - 2,88 Ma), sea level occurred marine flooding surface. Since the formation of reef 4 (2,59 Ma) to Reef 8 (1,4 Ma) occurred stagnant temperature and almost to warmer condition. Then, δ 18 O have arise up drastically to 5 0/00 and shows warmer condition to Reef 8 formation, in contrary, the sea level have been arised to Reef 10 formation (0,7 Ma). The temperature have been fluctuated between 0,5 o and 1 o C until the formation of Reef 17 (Early Holocene) and continued to Reef 17 formation at 2 o C based on the rapidity sampling of Po rites sp. Wholly, in centennial scale, since the formation of Reef 4 (2,59 Ma) to Reef 17 (1 Ma), the curve of oxygen stable isotope shows decrease or cooler condition. Those condition have conducted to sea level drop since the formation to Reef 7 and Reef 8. There are 4 periods of interglacial since the formation of Reef 4. The warmer condition indicated since the formation of Reef 9, Reef 11 and Reef 17. Recently, a curve of oxygen isotopes reveals warmer drastically or sea level have been arisen. (author)

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

    Science.gov (United States)

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

    2011-01-01

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

  2. 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

  3. Quasi-free one nucleon knockout reactions on neutron-rich oxygen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Atar, Leyla; Aumann, Thomas [TU Darmstadt, Darmstadt (Germany); GSI, Darmstadt (Germany); Bertulani, Carlos [Texas A and M University-Commerce, Commerse (United States); Paschalis, Stefanos [TU Darmstadt, Darmstadt (Germany); Nociforo, Chiara [GSI, Darmstadt (Germany); Collaboration: R3B-Collaboration

    2015-07-01

    Recent experiments have shown a reduction of spectroscopic strengths to about 60-70% for stable nuclei. When going to drip lines this tendency is changing, loosely bound nucleons have spectroscopic strengths close unity while deeply bound nucleons have a large reduction of the strength. We aim to make a systematic study of spectroscopic factors (SF) of the Oxygen isotopes using quasi-free (p,2p) and (p,pn) knockout reactions in inverse kinematics. Quasi-free knockout reactions are a direct tool to study the occupancy and the location of valance and deeply bound single particle states. The Oxygen isotopes offer a large variation of separation energies which will allow us to obtain a qualitative and quantitative understanding of SF in a large variation of isospin asymmetry. For this we performed an experiment at the R3B-LAND setup at the GSI with secondary beams containing {sup 14-24}O. The {sup 16-18}O and {sup 21-23}O isotopes have been analyzed and the preliminary results will be presented. The results include the partial cross sections, gamma ray spectra of the residual fragments in coincidence, and the SF obtained via comparison with theory.

  4. Classifying Acute Respiratory Distress Syndrome Severity: Correcting the Arterial Oxygen Partial Pressure to Fractional Inspired Oxygen at Altitude.

    Science.gov (United States)

    Pérez-Padilla, Rogelio; Hernández-Cárdenas, Carmen Margarita; Lugo-Goytia, Gustavo

    2016-01-01

    In the well-known Berlin definition of acute respiratory distress syndrome (ARDS), there is a recommended adjustment for arterial oxygen partial pressure to fractional inspired oxygen (PaO2/FIO2) at altitude, but without a reference as to how it was derived.

  5. 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.)

  6. Effects of must concentration techniques on wine isotopic parameters.

    Science.gov (United States)

    Guyon, Francois; Douet, Christine; Colas, Sebastien; Salagoïty, Marie-Hélène; Medina, Bernard

    2006-12-27

    Despite the robustness of isotopic methods applied in the field of wine control, isotopic values can be slightly influenced by enological practices. For this reason, must concentration technique effects on wine isotopic parameters were studied. The two studied concentration techniques were reverse osmosis (RO) and high-vacuum evaporation (HVE). Samples (must and extracted water) have been collected in various French vineyards. Musts were microfermented at the laboratory, and isotope parameters were determined on the obtained wine. Deuterium and carbon-13 isotope ratios were studied on distilled ethanol by nuclear magnetic resonance (NMR) and isotope ratio mass spectrometry (IRMS), respectively. The oxygen-18 ratio was determined on extracted and wine water using IRMS apparatus. The study showed that the RO technique has a very low effect on isotopic parameters, indicating that this concentration technique does not create any isotopic fractionation, neither at sugar level nor at water level. The effect is notable for must submitted to HVE concentration: water evaporation leads to a modification of the oxygen-18 ratio of the must and, as a consequence, ethanol deuterium concentration is also modified.

  7. Isotopic Zonation Within Sulfate Evaporite Mineral Crystals Reveal Quantitative Paleoenvironment Details

    Science.gov (United States)

    Coleman, M.; Rhorssen, M.; Mielke, R. E.

    2008-12-01

    Isotopic variations measured within a single crystal of hydrated magnesium sulfate are greater than 30 permil for delta 2-H, almost 10 permil for δ18O in water of hydration; and greater than 3 permil in sulfate oxygen. These results are interpreted to indicate the relative humidity of the system during evaporation (15 to 20 percent in this test case) and constrain the volume of water involved. The theoretical basis of this system is the isotopic fractionation between the species in solution and those precipitated as evaporite salts. Precipitation preferentially accumulates more of the heavy isotopes of sulfur and oxygen in mineral sulfate, relative to sulfate in solution. During the course of mineral growth this leads to successive depletion of the respective heavier isotopes in the residual brine reflected in a parallel trend in successive precipitates or even in successive zones within a single crystal. The change in isotopic composition at any one time during the process, relative to the initial value, can be described by an isotopic version of the Rayleigh Fractionation equation, depending only on the extent of the completion of the process and the relevant fractionation factor. Evaporation preferentially removes isotopically lighter hydrogen and oxygen leading to successive extents of enrichment in the respective heavier isotopes in the residual water. However, the relative effects on hydrogen and oxygen isotopes differs as function of relative humidity [1]. ALL OF THESE CHANGES ARE PRESERVED IN THE MINERAL ISOTOPE COMPOSITIONS. We precipitated barium sulfate from epsomite or gypsum samples, which was reduced at 1450°C in the presence of graphite and glassy carbon in a Finnigan TC/EA to produce CO for O isotopic analysis in a Finnigan 253 mass spectrometer, while a separate subsample was oxidized to SO2 in a Costech Elemental Analyzer. However, to make progress with this approach we needed to make a large number of measurements of hydration water and so we

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. The geochemistry of the stable isotopes of silicon

    International Nuclear Information System (INIS)

    Douthitt, C.B.

    1982-01-01

    One hundred thirty two new measurements of the relative abundances of the stable isotopes of silicon in terrestrial materials are presented. The total variation of delta 30 Si found is 6.2 parts per thousand, centered on the mean of terrestrial mafic and ultramafic igneous rocks, delta 30 Si = -0.4 parts per thousand. Igneous rocks show limited variation; coexisting minerals exhibit small, systematic silicon isotopic fractionations that are roughly 1/3 the magnitude of concomitant oxygen isotopic fractionations at 1150 0 C. In both igneous minerals and rocks, delta 30 Si shows a positive correlation with silicon content, as does delta 18 O. Opal from both sponge spicules and sinters is light, with delta 30 Si = -2.3 and -1.4 parts per thousand respectively. Large delta 30 Si values of both positive and negative sign are reported for the first time from clay minerals, opaline phytoliths, and authigenic quartz. All highly fractionated samples were precipitated from solution at low temperatures; however, aqueous silicon is not measurably fractionated relative to quartz at equilibrium. A kinetic isotope fractionation of approximately 3.5 parts per thousand is postulated to occur during the low temperature precipitation of opal and, possibly, poorly ordered phyllosilicates, with the silicate phase being enriched in 28 Si. This fractionation, coupled with a Rayleigh precipitation model, is capable of explaining most non-magmatic delta 30 Si variations. (author)

  13. Isotope effects in photo dissociation of ozone with visible light

    Science.gov (United States)

    Früchtl, Marion; Janssen, Christof; Röckmann, Thomas

    2014-05-01

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

  14. Oxygen isotopic analyses of individual planktic foraminifera species: Implications for seasonality in the western Arabian Sea

    Digital Repository Service at National Institute of Oceanography (India)

    Naidu, P.D.; Niitsuma, N.; Naik, S.S.

    The variation of stable isotopes between individual shells of planktic foraminifera of a given species and size may provide short-term seasonal insight on Paleoceanography. In this context, oxygen isotope analyses of individual Globigerinoides...

  15. 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

  16. Multiple stable isotope fronts during non-isothermal fluid flow

    Science.gov (United States)

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

    2018-02-01

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

  17. Measurement of infiltration rates in urban sewer systems by use of oxygen isotopes.

    Science.gov (United States)

    De Bénédittis, J; Bertrand-Krajewski, J L

    2005-01-01

    The paper presents the principle of a method to measure infiltration rates in sewer systems based on the use of oxygen isotopes and its application in Lyon (France). In the urban area of Lyon, significant differences in delta 18O that can reach 3 per thousand are observed between the oxygen isotopic compositions of groundwater originating from Rhone, Saone and from their associated alluvial aquifers. Drinking water supplying Lyon results mainly from pumping in the Rhone alluvial aquifer. Therefore, in some areas, the difference of isotopic composition between wastewater resulting from the consumption of drinking water and local groundwater can be used to measure infiltration in sewer systems. The application in the catchment of Ecully shows that the infiltration flow rate presents strong fluctuations at an hourly scale: it varies between 15 and 40 m3/h. This variability could be explained by non-constant discharges of pumping and by variations of the water level in the sewer.

  18. Stable isotope hydrology. Deuterium and oxygen-18 in the water cycle

    International Nuclear Information System (INIS)

    Gat, J.R.; Gonfiantini, R.

    1981-01-01

    This monograph is mainly intended for hydrologists, hydrogeologists and geochemists who want to become acquainted, rapidly but in some detail, with the theoretical background of stable isotope fractionation in natural physico-chemical processes involving fresh water, with the isotopic differences actually encountered in natural waters and with their use for practical hydrological purposes. Throughout the monograph, and in particular in the last chapter, a series of examples are discussed, giving the results obtained with stable isotope techniques in current hydrological and hydrogeological investigations or, more generally, in water resources exploration and assessment. One chapter is also dedicated to the techniques for measuring D/H and 18 O/ 16 O ratios in water

  19. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-07-01

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

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  2. Geochemistry of the stable isotopes of silicon

    Energy Technology Data Exchange (ETDEWEB)

    Douthitt, C B [California Inst. of Tech., Pasadena (USA). Div. of Geological and Planetary Sciences

    1982-08-01

    One hundred thirty two new measurements of the relative abundances of the stable isotopes of silicon in terrestrial materials are presented. The total variation of delta/sup 30/Si found is 6.2 parts per thousand, centered on the mean of terrestrial mafic and ultramafic igneous rocks, delta/sup 30/Si = -0.4 parts per thousand. Igneous rocks show limited variation; coexisting minerals exhibit small, systematic silicon isotopic fractionations that are roughly 1/3 the magnitude of concomitant oxygen isotopic fractionations at 1150/sup 0/C. In both igneous minerals and rocks, delta/sup 30/Si shows a positive correlation with silicon content, as does delta/sup 18/O. Opal from both sponge spicules and sinters is light, with delta/sup 30/Si = -2.3 and -1.4 parts per thousand respectively. Large delta/sup 30/Si values of both positive and negative sign are reported for the first time from clay minerals, opaline phytoliths, and authigenic quartz. All highly fractionated samples were precipitated from solution at low temperatures; however, aqueous silicon is not measurably fractionated relative to quartz at equilibrium. A kinetic isotope fractionation of approximately 3.5 parts per thousand is postulated to occur during the low temperature precipitation of opal and, possibly, poorly ordered phyllosilicates, with the silicate phase being enriched in /sup 28/Si. This fractionation, coupled with a Rayleigh precipitation model, is capable of explaining most non-magmatic delta/sup 30/Si variations.

  3. 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

  4. 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

  5. The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions

    Science.gov (United States)

    Keller, Lindsay P.; McKeegan, K. D.; Sharp, Z. D.

    2012-01-01

    MIL 090001 is a large (>6 kg) carbonaceous chondrite that was classified as a member of the CV reduced subgroup (CVred) that was recovered during the 2009-2010 ANSMET field season [1]. Based on the abundance of refractory inclusions and the extent of aqueous alteration, Keller [2] suggested a CV2 classification. Here we report additional mineralogical and petrographic data for MIL 090001, its whole-rock oxygen isotopic composition and ion microprobe analyses of individual phases. The whole rock oxygen isotopic analyses show that MIL 090001 should be classified as a CR chondrite.

  6. 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.

  7. 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.

  8. Estimating of gas transfer velocity using triple isotopes of dissolved oxygen.

    Digital Repository Service at National Institute of Oceanography (India)

    Sarma, V.V.S.S.; Abe, O.; Honda, M.; Saino, T.

    variations in oxygen isotopes are found to be higher than the direct estimations at low wind speed (<5 m s sup(-1)) and lower at high wind speeds (>13 m s sup(-1)) and showed significant spatial variability. The method presented here can be used to derive...

  9. 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.

  10. Comparison of interglacial warm events since the marine oxygen isotope stage 11

    Digital Repository Service at National Institute of Oceanography (India)

    Oba, T.; Banakar, V.K.

    Large numbers of oxygen isotopic curves of benthic foraminifcral tests from deep-sea sediment cores have been published. The curves are well-established reliable proxies for past climate and relative sea level fluctuations. In order to understand...

  11. Forensic applications of nitrogen and oxygen isotopes in tracing nitrate sources in urban environments

    Science.gov (United States)

    Silva, S.R.; Ging, P.B.; Lee, R.W.; Ebbert, J.C.; Tesoriero, A.J.; Inkpen, E.L.

    2002-01-01

    Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington. In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing ??15N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urban areas. ?? Published by Elsevier Science Ltd. on behalf of AEHS.

  12. 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

  13. Carbon isotope effects associated with Fenton-like degradation of toluene: Potential for differentiation of abiotic and biotic degradation

    International Nuclear Information System (INIS)

    Ahad, Jason M.E.; Slater, Greg F.

    2008-01-01

    Hydrogen peroxide (H 2 O 2 )-mediated oxygenation to enhance subsurface aerobic biodegradation is a frequently employed remediation technique. However, it may be unclear whether observed organic contaminant mass loss is caused by biodegradation or chemical oxidation via hydroxyl radicals generated during catalyzed Fenton-like reactions. Compound-specific carbon isotope analysis has the potential to discriminate between these processes. Here we report laboratory experiments demonstrating no significant carbon isotope fractionation during Fenton-like hydroxyl radical oxidation of toluene. This implies that observation of significant isotopic fractionation of toluene at a site undergoing H 2 O 2 -mediated remediation would provide direct evidence of biodegradation. We applied this approach at a field site that had undergone 27 months of H 2 O 2 -mediated subsurface oxygenation. Despite substantial decreases (> 68%) in groundwater toluene concentrations carbon isotope signatures of toluene (δ 13 C tol ) showed no significant variation (mean = - 27.5 ±0.3 per mille, n = 13) over a range of concentrations from 11.1 to 669.0 mg L -1 . Given that aerobic degradation by ring attack has also been shown to result in no significant isotopic fractionation during degradation, at this site we were unable to discern the mechanism of degradation. However, such differentiation is possible at sites where aerobic degradation by methyl group attack results in significant isotopic fractionation

  14. Planetary fertility during the past 400 ka based on the triple isotope composition of O2 in trapped gases from the Vostok ice core

    Science.gov (United States)

    Blunier, T.; Bender, M. L.; Barnett, B.; von Fisher, J. C.

    2012-01-01

    The productivity of the biosphere leaves its imprint on the isotopic composition of atmospheric oxygen. Ultimately atmospheric oxygen, through photosynthesis, originates from seawater. Fractionations during the passage from seawater to atmospheric O2 and during respiration are mass dependent, affecting δ17O about half as much as δ18O. An "anomalous" (also termed mass independent) fractionation process changes δ17O about 1.7 times as much as δ18O during isotope exchange between O2 and CO2 in the stratosphere. The relative rates of biological O2 production and stratospheric processing determine the relationship between δ17O and δ18O of O2 in the atmosphere. Variations of this relationship thus allow us to estimate changes in the rate of mass dependent O2 production by photosynthesis vs. the rate of mass independent O2-CO2 exchange in the stratosphere. However, the analysis of the 17O anomaly is complicated because each hydrological and biological process influencing δ17O and δ18O fractionates 17O and 18O in slightly different proportions. In this study we present oxygen data covering the last 400 kyr from the Vostok ice core. We reconstruct oxygen productivities from the triple isotope composition of atmospheric oxygen with a box model. Our steady state model for the oxygen cycle takes into account fractionation during photosynthesis and respiration of the land and ocean biosphere as well as fractionation when oxygen passes through the stratosphere. We consider changes of fractionation factors linked to climate variations taking into account the span of estimates of the main factors affecting our calculations. We find that ocean oxygen productivity was likely elevated relative to modern during glacials. However, this increase probably did not fully compensate for a reduction in land ocean productivity resulting in a slight reduction in total oxygen production during glacials.

  15. Sulfur Isotope Trends in Archean Microbialite Facies Record Early Oxygen Production and Consumption

    Science.gov (United States)

    Zerkle, A.; Meyer, N.; Izon, G.; Poulton, S.; Farquhar, J.; Claire, M.

    2014-12-01

    The major and minor sulfur isotope composition (δ34S and Δ33S) of pyrites preserved in ~2.65-2.5 billion-year-old (Ga) microbialites record localized oxygen production and consumption near the mat surface. These trends are preserved in two separate drill cores (GKF01 and BH1-Sacha) transecting the Campbellrand-Malmani carbonate platform (Ghaap Group, Transvaal Supergroup, South Africa; Zerkle et al., 2012; Izon et al., in review). Microbialite pyrites possess positive Δ33S values, plotting parallel to typical Archean trends (with a Δ33S/δ34S slope of ~0.9) but enriched in 34S by ~3 to 7‰. We propose that these 34S-enriched pyrites were formed from a residual pool of sulfide that was partially oxidized via molecular oxygen produced by surface mat-dwelling cyanobacteria. Sulfide, carrying the range of Archean Δ33S values, could have been produced deeper within the microbial mat by the reduction of sulfate and elemental sulfur, then fractionated upon reaction with O2 produced by oxygenic photosynthesis. Preservation of this positive 34S offset requires that: 1) sulfide was only partially (50­­-80%) consumed by oxidation, meaning H2S was locally more abundant (or more rapidly produced) than O2, and 2) the majority of the sulfate produced via oxidation was not immediately reduced to sulfide, implying either that the sulfate pool was much larger than the sulfide pool, or that the sulfate formed near the mat surface was transported and reduced in another part of the system. Contrastingly, older microbialite facies (> 2.7 Ga; Thomazo et al., 2013) appear to lack these observed 34S enrichments. Consequently, the onset of 34S enrichments could mark a shift in mat ecology, from communities dominated by anoxygenic photosynthesizers to cyanobacteria. Here, we test these hypotheses with new spatially resolved mm-scale trends in sulfur isotope measurements from pyritized stromatolites of the Vryburg Formation, sampled in the lower part of the BH1-Sacha core. Millimeter

  16. Palmyra Island Monthly Oxygen Isotope Data (delta 18O) for 1886-1998

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Palmyra Island Monthly Coral Oxygen Isotope Data. 112-yr, monthly-resolved coral record from Palmyra Island (5 deg 52 min N, 162 deg 8 min W). The coral was drilled...

  17. LBA-ECO CD-02 Carbon, Nitrogen, Oxygen Stable Isotopes in Organic Material, Brazil

    Data.gov (United States)

    National Aeronautics and Space Administration — This data set reports the measurement of stable carbon, nitrogen, and oxygen isotope ratios in organic material (plant, litter and soil samples) in forest canopy...

  18. LBA-ECO CD-02 Carbon, Nitrogen, Oxygen Stable Isotopes in Organic Material, Brazil

    Data.gov (United States)

    National Aeronautics and Space Administration — ABSTRACT: This data set reports the measurement of stable carbon, nitrogen, and oxygen isotope ratios in organic material (plant, litter and soil samples) in forest...

  19. 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

  20. Effects of carbogen plus fractionated irradiation on KHT tumor oxygenation

    International Nuclear Information System (INIS)

    Fenton, Bruce M.

    1997-01-01

    Background and purpose: Numerous studies have demonstrated improvements in the oxygenation of tumor cells following both irradiation and carbogen breathing. The current studies were initiated to measure the combined effects of carbogen inhalation plus single and multi-dose irradiation on tumor oxygen availability, to better define the underlying physiological relationships. Materials and methods: Using KHT murine sarcomas, radiation was delivered to the tumor-bearing legs of non-anesthetized mice. Tumors were quick-frozen prior to or following single or multifraction irradiation and carbogen breathing, and intravascular HbO 2 saturation profiles were determined cryospectrophotometrically. Results: HbO 2 levels for blood vessels located near the tumor surface initially decreased following 10 Gy irradiation, then increased and remained elevated. Interior HbO 2 levels remained unchanged. Following 2.5 Gy, HbO 2 changes were minimal. At 24 h following 10 Gy, HbO 2 levels were significantly increased compared to non-irradiated controls, and carbogen breathing produced no additional benefit. At 24 h following five fractions of 2 Gy, HbO 2 levels throughout the tumor volume were significantly higher in carbogen breathing animals than in air breathing controls. Conclusions: Although peripheral blood vessels demonstrated substantial improvements in oxygenation following irradiation, oxygen availability nearer the tumor center remained at very low levels. The utility of carbogen in enhancing tumor oxygen availability was maintained following five clinically relevant fractions. At higher doses, radiation-induced enhancements in HbO 2 levels overshadowed the carbogen effect. For either air or carbogen breathing, a decrease in the percentage of vessels with very low oxygen content did not appear to be a major factor in the reoxygenation of the KHT tumor

  1. INVESTIGATION OF DISSOLVED SULPHATE IN VARIOUS GEOTHERMAL FIELDS OF SUMATRA USING OXYGEN AND SULPHUR ISOTOPES

    Directory of Open Access Journals (Sweden)

    E. Ristin Pujiindiyati

    2010-06-01

    Full Text Available There are at least 30 high temperature systems; eleven active volcanoes, five degassing volcanoes and one caldera volcano controlled by Sumatra Fault Zone over a length of 1700 km. To understand this geothermal field system, some information about geochemistry including isotope composition in its fluid is needed. Sulphur-34 and oxygen-18 isotopes in dissolved sulphate pair have been used to determine the origin of acidic fluid of sulphate and to evaluate the process involved. The fluids from eight hot springs, two fumaroles, four deep wells and crater have been collected in along Sumatra geothermal fields. Sulphur-34 (d 34S (SO4, 0/00 CDT and oxygen-18 (d 18O (SO4, 0/00 SMOW in sulphate is analyzed according to Robinson-Kusakabe and Rafter method, respectively. The d 34S (SO4 values from Sibayak wells are more enriched of 16.8 0/00 to 18.2 0/0 that may indicate the dissolution of anhydrite minerals or isotope partitioning in hydration of SO2. The d 34S (SO4 values from two fumaroles (Pusuk Bukit - North Sumatra and Rantau Dadap - South Sumatra are at depleted value of -0.150/00 and 1.80/00, those are close to d 34S from magmatic sulphur.  In general, the d 34S (SO4 of springs spread in a wide range of 5.250/00 to14.20/00 and show a mixing process between atmospheric sulphate and sulphate from deep wells. The d 18O (SO4 from wells exhibits depleted value around -3.60/00 suggesting that 87.5% of sulphate oxygen is derived from groundwater oxygen and 12.5% is derived from atmospheric molecular oxygen in sulphide oxidation reaction. In the other hand, hot springs (except Semurup, crater and fumaroles have enriched value of d 18O (SO4. These enriched values suggest that a higher percentage of atmospherically derived oxygen compared to those from the depth.   Keywords: isotope, geothermal, Sumatra

  2. 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.

  3. Modelling and Mapping Oxygen-18 Isotope Composition of Precipitation in Spain for Hydrologic and Climatic Applications

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez-Arevalo, J.; Diaz-Teijeiro, M. F. [Centro de Estudios y Experimentacion de Obras Publicas (CEDEX), Madrid (Spain); Castano, S. [Geological Survey of Spain (IGME), Madrid (Spain)

    2013-07-15

    A simple multiple regression model based on two geographic factors (latitude and elevation) has been developed that reproduces reasonably well the spatial distribution of the current mean oxygen-18 isotope composition in precipitation over spain. In a preliminary analysis, additional geographic and climatic factors do not improve the performance of the model. A continuous digital map of oxygen-18 isotope composition in precipitation has been produced by combining the polynomial model with a digital elevation model using GIS tools. Application of the resulting map to several groundwater case studies in spain has shown it to be useful as a reference of the input function to recharge. Further validation of the model, and further testing of its usefulness in surface hydrology and climatic studies, is ongoing through comparison of model results with isotope data from the GNIP database and from isotope studies in hydrogeology and climate change taking place in spain. (author)

  4. Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters

    Science.gov (United States)

    Sun, Jing; Kobayashi, Tatsuaki; Strosnider, William H. J.; Wu, Pan

    2017-08-01

    Karst water resources, which are extremely sensitive to mining activities, are critical for the support of human societies and ecological systems in many regions worldwide. In order to determine the sources and fate of dissolved sulfate in low-pH karst waters, hydrochemical variations of karst waters with and without acid mine drainage (AMD) impacts were investigated along with stable isotope dynamics. As expected, hydrochemical characteristics and isotopic compositions of the AMD and AMD-downstream water (ADW) were dramatically different from that of the non-AMD-impacted water (NAW). The sources of sulfur isotopes in sulfate were predominantly pyrite oxidation for the AMD and ADW, and atmospheric deposition for the NAW. Based on the general isotope-balance model, the relative proportions of sulfate oxygen derived from water and air were calculated. The mean proportion of sulfate oxygen derived from water in ADW was roughly double that of AMD. This suggests that the sulfate associated with AMD is predominantly influenced by aerobic pyrite oxidation, while that of ADW is likely affected by the dissolution of pyrite under anaerobic conditions in reservoir sediment. This observation was coincident with the noted variations of hydrochemical characteristics and was supported by principal component analysis. These results provide a better understanding of how stable isotopes of sulfate and water can be used to track mining contamination in karst aquifers, which could benefit remediation planning for these distinctive systems.

  5. 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.

  6. Oxygen isotope geochemistry of The Geysers reservoir rocks, California

    Energy Technology Data Exchange (ETDEWEB)

    Gunderson, Richard P.; Moore, Joseph N.

    1994-01-20

    Whole-rock oxygen isotopic compositions of Late Mesozoic graywacke, the dominant host rock at The Geysers, record evidence of a large liquid-dominated hydrothermal system that extended beyond the limits of the present steam reservoir. The graywackes show vertical and lateral isotopic variations that resulted from gradients in temperature, permeability, and fluid composition during this early liquid-dominated system. All of these effects are interpreted to have resulted from the emplacement of the granitic "felsite" intrusion 1-2 million years ago. The {delta}{sup 18}O values of the graywacke are strongly zoned around a northwest-southeast trending low located near the center of and similar in shape to the present steam system. Vertical isotopic gradients show a close relationship to the felsite intrusion. The {delta}{sup 18}O values of the graywacke decrease from approximately 15 per mil near the surface to 4-7 per mil 300 to 600 m above the intrusive contact. The {delta}{sup 18}O values then increase downward to 8-10 per mil at the felsite contact, thereafter remaining nearly constant within the intrusion itself. The large downward decrease in {delta}{sup 18}O values are interpreted to be controlled by variations in temperature during the intrusive event, ranging from 150{degree}C near the surface to about 425{degree}C near the intrusive contact. The upswing in {delta}{sup 18}O values near the intrusive contact appears to have been caused by lower rock permeability and/or heavier fluid isotopic composition there. Lateral variations in the isotopic distributions suggests that the effects of temperature were further modified by variations in rock permeability and/or fluid-isotopic composition. Time-integrated water:rock ratios are thought to have been highest within the central isotopic low where the greatest isotopic depletions are observed. We suggest that this region of the field was an area of high permeability within the main upflow zone of the liquid

  7. Temperature evolution and the oxygen isotope composition of Phanerozoic oceans from carbonate clumped isotope thermometry

    Science.gov (United States)

    Henkes, Gregory A.; Passey, Benjamin H.; Grossman, Ethan L.; Shenton, Brock J.; Yancey, Thomas E.; Pérez-Huerta, Alberto

    2018-05-01

    Surface temperature is among the most important parameters describing planetary climate and habitability, and yet there remains considerable debate about the temperature evolution of the Earth's oceans during the Phanerozoic Eon (541 million years ago to present), the time during which complex metazoan life radiated on Earth. Here we critically assess the emerging record of Phanerozoic ocean temperatures based on carbonate clumped isotope thermometry of fossil brachiopod and mollusk shells, and we present new data that fill important gaps in the Late Paleozoic record. We evaluate and reject the hypothesis that solid-state reordering of 13C-18O bonds has destroyed the primary clumped isotope temperature signal of most fossils during sedimentary burial at elevated temperatures. The resulting Phanerozoic record, which shows a general coupling between tropical seawater temperatures and atmospheric carbon dioxide (CO2) levels since the Paleozoic, indicates that tropical temperatures during the icehouse climate of the Carboniferous period were broadly similar to present (∼25-30 °C), and suggests that benthic metazoans were able to thrive at temperatures of 35-40 °C during intervals of the early and possibly the latest Paleozoic when CO2 levels were likely 5-10× higher than present-day values. Equally important, there is no resolvable trend in seawater oxygen isotope ratios (δ18 O) over the past ∼500 million years, indicating that the average temperature of oxygen exchange between seawater and the oceanic crust has been high (∼270 °C) since at least the early Paleozoic, which points to mid-ocean ridges as the dominant locus of water-rock interaction over the past half-billion years.

  8. Oxygen isotopes in garnet and accessory minerals to constrain fluids in subducted crust

    Science.gov (United States)

    Rubatto, Daniela; Gauthiez-Putallaz, Laure; Regis, Daniele; Rosa Scicchitano, Maria; Vho, Alice; Williams, Morgan

    2017-04-01

    Fluids are considered a fundamental agent for chemical exchanges between different rock types in the subduction system. Constraints on the sources and pathways of subduction fluids thus provide crucial information to reconstruct subduction processes. Garnet and U-Pb accessory minerals constitute some of the most robust and ubiquitous minerals in subducted crust and can preserve multiple growth zones that track the metamorphic evolution of the sample they are hosted in. Microbeam investigation of the chemical (major and trace elements) and isotopic composition (oxygen and U-Pb) of garnet and accessory minerals is used to track significant fluid-rock interaction at different stages of the subduction system. This approach requires consideration of the diffusivity of oxygen isotopes particularly in garnet, which has been investigated experimentally. The nature of the protolith and ocean floor alteration is preserved in relict accessory phases within eclogites that have been fully modified at HP conditions (e.g. Monviso and Dora Maira units in the Western Alps). Minerals in the lawsonite-blueschists of the Tavsanli zone in Turkey record pervasive fluid exchange between mafic and sedimentary blocks at the early stage of subduction. High pressure shear zones and lithological boundaries show evidence of intense fluid metasomatism at depth along discontinuities in Monviso and Corsica. In the UHP oceanic crust of the Zermatt-Saas Zone, garnet oxygen isotopes and tourmaline boron isotopes indicate multistage fluid infiltration during prograde metamorphism. Localized exchanges of aqueous fluids are also observed in the subducted continental crust of the Sesia-Lanzo Zone. In most cases analyses of distinct mineral zones enable identification of multiple pulses of fluids during the rock evolution.

  9. Oxygen isotope signature of UV degradation of glyphosate and phosphonoacetate: Tracing sources and cycling of phosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Sandy, Edward H. [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Department of Chemistry, University of Sierra Leone, Freetown (Sierra Leone); Blake, Ruth E., E-mail: ruth.blake@yale.edu [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Chang, Sae Jung [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Jun, Yao, E-mail: yaojun@ustb.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Yu, Chan [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China)

    2013-09-15

    Highlights: • Phosphonate (phon) hydrolysis by UVR (1.2 kW) attained ≥90% completion in 84 h. • Isotope study reveals both ambient H{sub 2}O and O{sub 2} involvements in phon C-P bond cleavage. • Mechanistic models proposed for phon C-P bond cleavage based on O-isotope analysis. • Model equations used to calculate δ{sup 18}O{sub P-org} of original phon P-moiety-useful as a tracer. • Study shows relevance in tracing phon sources and cycling in the environment. -- Abstract: The degradation of phosphonates in the natural environment constitutes a major route by which orthophosphate (Pi) is regenerated from organic phosphorus and recently implicated in marine methane production, with ramifications to environmental pollution issues and global climate change concerns. This work explores the application of stable oxygen isotope analysis in elucidating the C-P bond cleavage mechanism(s) of phosphonates by UV photo-oxidation and for tracing their sources in the environment. The two model phosphonates used, glyphosate and phosphonoacetic acid were effectively degraded after exposure to UV irradiation. The isotope results indicate the involvement of both ambient water and atmospheric oxygen in the C-P bond cleavage and generally consistent with previously posited mechanisms of UV-photon excitation reactions. A model developed to calculate the oxygen isotopic composition of the original phosphonate P-moiety, shows both synthetic phosphonates having distinctly lower values compared to naturally derived organophosphorus compounds. Such mechanistic models, based on O-isotope probing, are useful for tracing the sources and reactions of phosphonates in the environment.

  10. Oxygen isotope systematics of chondrules in the Murchison CM2 chondrite and implications for the CO-CM relationship

    Science.gov (United States)

    Chaumard, Noël; Defouilloy, Céline; Kita, Noriko T.

    2018-05-01

    High-precision oxygen three-isotope measurements of olivine and pyroxene were performed on 29 chondrules in the Murchison CM2 chondrite by secondary ion mass spectrometry (SIMS). The oxygen isotope ratios of analyzed chondrules all plot very close to the primitive chondrule minerals (PCM) line. In each of 24 chondrules, the olivine and/or pyroxene grains analyzed show indistinguishable oxygen isotope ratios. Exceptions are minor occurrences of isotopically distinguished relict olivine grains, which were found in nine chondrules. The isotope homogeneity of these phenocrysts is consistent with a co-magmatic crystallization of olivine and pyroxene from the final chondrule melts and a significant oxygen isotope exchange between the ambient gas and the melts. Homogeneous type I chondrules with Mg#'s of 98.9-99.5 have host chondrule Δ17O values ranging from -6.0‰ to -4.1‰, with one exception (Δ17O: -1.2‰; Mg#: 99.6). Homogeneous chondrules with Mg#'s poor H2O ice (∼0.3-0.4× the CI dust; Δ17O > 0‰) and at dust enrichments of ∼300-2000×. Regarding the Mg# and oxygen isotope ratios, the chondrule populations sampled by CM and CO chondrites are similar and indistinguishable. The similarity of these 16O-rich components in CO and CM chondrites is also supported by the common Fe/Mn ratio of olivine in type II chondrules. Although they accreted similar high-temperature silicates, CO chondrites are anhydrous compared to CM chondrites, suggesting they derived from different parent bodies formed inside and outside the snow line, respectively. If chondrules in CO and CM chondrites formed at the same disk locations but the CM parent body accreted later than the CO parent body, the snow line might have crossed the common chondrule-forming region towards the Sun between the time of the CO and CM parent bodies accretion.

  11. 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

  12. Heterogenous Oxygen Isotopic Composition of a Complex Wark-Lovering Rim and the Margin of a Refractory Inclusion from Leoville

    Science.gov (United States)

    Simon, J. I.; Matzel, J. E. P.; Simon, S. B.; Weber, P. K.; Grossman, L.; Ross, D. K.; Hutcheon, I. D.

    2014-01-01

    Wark-Lovering (WL) rims [1] surrounding many refractory inclusions represent marker events in the early evolution of the Solar System in which many inclusions were exposed to changes in pressure [2], temperature [3], and isotopic reservoirs [4-7]. The effects of these events can be complex, not only producing mineralogical variability of WL rims [2], but also leading to mineralogical [8-10] and isotopic [7, 11, 12] changes within inclusion interiors. Extreme oxygen isotopic heterogeneity measured in CAIs has been explained by mixing between distinct oxygen gas reservoirs in the nebula [13]. Some WL rims contain relatively simple mineral layering and/or are isotopically homogeneous [14, 15]. As part of a larger effort to document and understand the modifications observed in some CAIs, an inclusion (L6) with a complex WL rim from Leoville, a member of the reduced CV3 subgroup was studied. Initial study of the textures and mineral chemistry was presented by [16]. Here we present NanoSIMS oxygen isotopic measurements to complement these petrologic observations.

  13. 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

  14. 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

  15. Oxygen isotopic ratios of quartz from wind-erosive soils of southwestern United States in relation to aerosol dust

    Energy Technology Data Exchange (ETDEWEB)

    Sridhar, K.; Jackson, M.L.; Clayton, R.N.; Gillette, D.A.; Hawley, J.W.

    1978-01-01

    The oxygen isotopic ratios (expressed as parts per thousand relative to mean ocean water, SMOW, delta/sup 18/O) of the quartz from 13 soils undergoing much wind erosion during the study period of 1972-1975 in four southwestern states and from comparison areas were determined. The delta/sup 18/O for quartz from eight Texas (TX) and Arizona (AZ) soils range from 13.0 to 15.9 /sup 0///sub 00/. The quartz of the sands and silts coarser than 20 ..mu..m from three of the soils had delta/sup 18/O values ranging from 13.1 to 15.1 /sup 0///sub 00/, characteristic of an ultimate igneous-metamorphic origin. The delta/sup 18/O values increase greatly with decreasing particle size of quartz from three soils ranging from loamy fine sand to loam to clay in texture. The delta/sup 18/O of the 1-10 ..mu..m quartz fraction (aerosol size) ranged from 19.2 to 20.2 /sup 0///sub 00/ (19.55 +- 0.28 /sup 0///sub 00/; +- sigma) for the thirteen soils most affected by dust storms. The oxygen isotopic ratios of 1-10 ..mu..m quartz from three Hawaiian soils and two sediments from Lake Waiau occurring at 3,970 m altitude on the Mauna Kea summit on the Island of Hawaii give a delta/sup 18/O mean of 18.3 +- 0.2 /sup 0///sub 00/.

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

    Science.gov (United States)

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

    2016-08-01

    Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ(15)NNO2- and δ(18)ONO2-, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of "Candidatus Nitrosocaldus." The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ(18)O value of nitrite produced from ammonia oxidation varied with the δ(18)O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ(18)ONO2- in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of

  17. 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)

  18. Isotopic exchange between CO2 and H2O and labelling kinetics of photosynthetic oxygen

    International Nuclear Information System (INIS)

    Gerster, Richard

    1971-01-01

    The reaction of carbon dioxide with water has been studied by measuring the rate of oxygen exchange between C 18 O 2 and H 2 16 O. The mathematical treatment of the kinetics allows to determine with accuracy the diffusion flow between the gas and the liquid phase, in the same way as the CO 2 hydration rate. The velocity constant of this last process, whose value gives the in situ enzymatic activity of carbonic anhydrase, has been established in the case of chloroplast and Euglena suspensions and of aerial leaves. The study of the isotopic exchange between C 18 O 2 and a vegetable submitted to alternations of dark and light has allowed to calculate the isotopic abundance of the metabolized CO 2 whose value has been compared to that of the intracellular water and that of photosynthetic oxygen. In addition, a new method using 13 C 18 O 2 gives the means to measure with accuracy eventual isotopic effects. The labelling kinetics of the oxygen evolved by Euglena suspensions whose water has been enriched with 18 O have been established at different temperatures. (author) [fr

  19. Preliminary study on the characteristics of carbon and oxygen isotopes in the Shiziping geothermal field groundwater in Emei Mountain

    International Nuclear Information System (INIS)

    Yu Xiujing; Jia Shuyuan

    2000-01-01

    Emei Mountain is a well-known scenic tourism spot in China. In order to promote the development of tourist trade, the authors have explored the hydrothermal water in Emei Mountain. At the beginning of 1998, the hydrothermal water was successfully drilled from the Shiziping geothermal field. In the process of prospecting the hydrothermal water, the authors adopted the geochemical method such as carbon and oxygen isotopes. The result indicates that the groundwater of different genetic types has different constitution characteristics of carbon and oxygen isotopes. This provides the important basis for finding out the forming conditions of underground hydrothermal water. So, it is prospective to study the growth characteristics of hydrothermal water with the carbon and oxygen isotopes of HCO 3 in groundwater

  20. Covariance of oxygen and hydrogen isotopic composition in plant water: Species effects

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, L.W.; DeNiro, M.J. (Univ. of California, Los Angeles (United States))

    1989-12-01

    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species-specific factors on leaf water enrichment of D and {sup 18}O have not been studied for different plants growing together. To learn whether leaf water enrichment patterns and processes for D and {sup 18}O are different for individual species growing under the same environmental conditions the authors tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show high sloped (m in the leaf water equation {delta}D = m {delta}{sup 18}O + b) than in C{sub 3} plants. They determined the relationships between the stable hydrogen ({delta}D) and oxygen ({delta}{sup 18}O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes.

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

    Science.gov (United States)

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

    2016-07-01

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

  2. 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)

  3. 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

  4. 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...

  5. Search for Fractionally Charged Nuclei in High-Energy Oxygen-Lead Collisions

    CERN Multimedia

    2002-01-01

    We propose to use stacks of CR-39 plastic track detectors to look for fractionally charged projectile fragments produced in collisions of high-energy oxygen, sulfur, and calcium nuclei with a lead target. The expected charge resolution is @s^z~=~0.06e for fragments with 17e/3~@$<$~Z~@$<$~23e/3. We request that two target + stack assemblies be exposed to 1~x~10|5 oxygen nuclei at maximum available energy.

  6. Stable isotope fractionation at a glacial hydrothermal field: implications for biogeochemistry and biosignatures on Mars

    Science.gov (United States)

    Cousins, C.; Bowden, R.; Fogel, M.; Cockell, C.; Crawford, I.; Gunn, M.; Karlsson, M. T.; Thorsteinsson, T.

    2012-12-01

    Hydrothermal environments that arise through the interaction between volcanogenic heat and glacial ice are ideal sites for understanding microbial biogeochemical processes on Earth, and also potentially on Mars where similar volcano-cryosphere interactions are thought to have occurred in the past. The Kverkfjöll subglacial basaltic volcano in central Iceland is geographically isolated, with little influence from flora, fauna, and human activity. Major environmental inputs include geothermal heat, meltwater from ice and snow, and outgassing of CO2, H2S, and SO2. Large physiochemical gradients exist, from steaming fumaroles and boiling hydrothermal pools, to frozen geothermal ground and glacial ice. Stable isotope measurements of total organic carbon, total sulphur, and total nitrogen were coupled with metagenomic analysis of the residing microbial communities, with the aim to identify biogeochemical relationships and processes operating within the Kverkfjöll geothermal environment, and also to identify any isotopic biosignatures that could be preserved within geothermal sediments. This study focused on a variety of samples taken along a hot spring stream that fed into a large ice-confined geothermal lake. Samples analysed range from unconsolidated hot spring sediments, well-developed microbial mats, and dissolved sulphate from hot spring fluids. From the anoxic spring source, the stream water increases in dissolved oxygen, decreases in temperature, yet maintains a pH of ~4. The spring environment is dominated by dissolved sulphate (~2.3 mM), with lower levels of nitrate (~50 μM), phosphorus (~5μM), and ammonium (~1.5 μM). Stable S isotope analysis reveals a fractionation of ~3.2 ‰ between sediment sulphide (as pyrite; δ34S ~0‰), and dissolved water sulphate (δ34S ~3.2 ‰) consistently along the hot spring stream, indicating the presence of an active sulphur cycle, although not one dominated by sulphate reduction (e.g. very negative sulphide δ34S). This

  7. Sulphur isotope variations in the atmosphere

    International Nuclear Information System (INIS)

    Newman, L.; Krouse, H.R.; Grinenko, V.A.

    1991-01-01

    The measurement of the isotope ratios of sulphur and oxygen can in principal be used to assess sulphur inputs into, transformation within, and removal from the atmosphere. Major inputs arise from both anthropogenic and biogenic activities. Transformations arise from oxidation, neutralization, and other chemical reactions. Advection causes dilution and the main removal processes are dry deposition (governed by gravitation and diffusion) and rain. The admixture of sources can be discerned from their isotopic signatures whereas transformations and removal can be followed from the isotopic fractionation that might occur. In this chapter, the atmospheric sulphur cycle and the associated chemistry are summarized. Also presented is information on natural isotopic variations and fundamental concepts relating to the use of isotopic data to delineate anthropogenic S in the atmosphere. Examples of successful applications of these concepts are given. Finally, consideration is given to the potential of using isotopically enriched sulphur to study transport and transformation of atmospheric S compounds. Refs, figs and tabs

  8. Ras Umm Sidd Oxygen Isotope (delta 18O) Data for 1750 to 1995

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Ras Umm Sidd bimonthly coral oxygen isotope data (coral core RUS-95). Notes on the data: File (Ras Umm Sidd d18O.txt.) includes columns for Year AD (bimonthly...

  9. 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

  10. 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

  11. Modelling and Mapping Oxygen-18 Isotope Composition of Precipitation in Spain for Hydrologic and Climatic Applications

    International Nuclear Information System (INIS)

    Rodriguez-Arevalo, J.; Diaz-Teijeiro, M.F.; Castano, S.

    2011-01-01

    A simple multiple regression model based on two geographic factors (latitude and elevation) has been developed that reproduces reasonably well the spatial distribution of the current mean oxygen-18 isotope composition in precipitation over Spain. In a preliminary analysis, additional geographic and climatic factors do not improve the performance of the model. A continuous digital map of oxygen-18 isotope composition in precipitation has been produced by combining the polynomial model with a Digital Elevation Model using GIS tools. Application of the resulting map to several case studies in Spain has shown it to be useful as a reference of the isotope input function to groundwater recharge and surface runoff. The results obtained so far show a good fit between modelled stable isotope values and those measured in surface and ground waters from different aquifers and recharge areas. The GIS tools applied to a continuous digital layer of spatial isotope are able to provide accurate information at detailed scales that are not affordable by other means. Further validation of the model, and further testing of its usefulness in surface hydrology and climatic studies, is going on.

  12. Myocardial oxygen extraction fraction measured using bolus inhalation of 15O-oxygen gas and dynamic PET

    NARCIS (Netherlands)

    Lubberink, Mark; Wong, YY; Raijmakers, P. G.; Huisman, Marc C.; Schuit, Robert C.; Luurtsema, Geert; Boellaard, Ronald; Knaapen, P; Vonk-Noordegraaf, Anton; Lammertsma, Adriaan A.

    Abstract The aim of this study was to determine the accuracy of oxygen extraction fraction (OEF) measurements using a dynamic scan protocol after bolus inhalation of 15O2. The method of analysis was optimized by investigating potential reuse of myocardial blood flow (MBF), perfusable tissue

  13. Validation of chlorine and oxygen isotope ratio analysis to differentiate perchlorate sources and to document perchlorate biodegradation

    Science.gov (United States)

    Paul B. Hatzinger,; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua

    2013-01-01

    Increased health concerns about perchlorate (ClO4-) during the past decade and subsequent regulatory considerations have generated appreciable interest in source identification. The key objective of the isotopic techniques described in this guidance manual is to provide evidence concerning the origin of ClO4- in soils and groundwater and, more specifically, whether that ClO4- is synthetic or natural. Chlorine and oxygen isotopic analyses of ClO4- provide the primary direct approach whereby different sources of ClO4- can be distinguished from each other. These techniques measure the relative abundances of the stable isotopes of chlorine (37Cl and 35Cl) and oxygen (18O, 17O, and 16O) in ClO4- using isotope-ratio mass spectrometry (IRMS). In addition, the relative abundance of the radioactive chlorine isotope 36Cl is measured using accelerator mass spectrometry (AMS). Taken together, these measurements provide four independent quantities that can be used to distinguish natural and synthetic ClO4- sources, to discriminate different types of natural ClO4-, and to detect ClO4- biodegradation in the environment. Other isotopic, chemical, and geochemical techniques that can be applied in conjunction with isotopic analyses of ClO4- to provide supporting data in forensic studies are also described.

  14. In-situ, high pressure and temperature experimental determination of hydrogen isotope fractionation between coexisting hydrous melt and silicate-saturated aqueous fluid

    Science.gov (United States)

    Mysen, B. O.

    2012-12-01

    Hydrogen isotope fractionation between water-saturated silicate melt and silicate-saturated aqueous fluid has been determined experimentally, in-situ with the samples in the 450-800C and 101-1567 MPa temperature and pressure range, respectively. The temperatures are, therefore higher than those where hydrogen bonding in fluids and melts is important [1]. The experiments were conducted with a hydrothermal diamond anvil cell (HDAC) as the high-temperature/-pressure tool and vibrational spectroscopy to determine D/H fractionation. Compositions were along the haploandesite join, Na2Si4O9 - Na2(NaAl)4O9 [Al/(Al+Si)=0-0.1], and a 50:50 (by volume) H2O:D2O fluid mixture as starting material. Platinum metal was used to enhance equilibration rate. Isotopic equilibrium was ascertained by using variable experimental duration at given temperature and pressure. In the Al-free Na-silicate system, the enthalpy change of the (D/H) equilibrium of fluid is 3.1±0.7 kJ/mol, whereas for coexisting melt, ΔH=0 kJ/mol within error. With Al/(Al+Si)=0.1, ΔH=5.2±0.9 kJ/mol for fluid and near 0 within error for coexisting melt melt. For the exchange equilibrium between melt and fluid, H2O(melt)+D2O(fluid)=H2O(fluid)+D2O(melt), the ΔH=4.6±0.7 and 6.5±0.7 kJ/mol for the two Al-free and Al-bearing compositions, respectively, respectively. The D/H equilibration within fluids and melts and, therefore, D/H partitioning between coexisting fluid and melt reflect the influence of dissolved H2O(D2O) in melts and dissolved silicate components in H2O(D2O) fluid on their structure. The positive temperature- and pressure-dependence of silicate solubility and on silicate structure in silicate-saturated aqueous fluid governs the D/H fractionation in the fluid because increasing silicate solute concentration in fluid results in silicate polymerization [2]. These structural effects may be analogous to observed solute-dependent oxygen isotope fractionation between brine and CO2 [3]. In the temperature

  15. 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.

  16. 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

  17. Oxygen isotopes from biogenic apatites suggest widespread endothermy in Cretaceous dinosaurs

    Science.gov (United States)

    Amiot, Romain; Lécuyer, Christophe; Buffetaut, Eric; Escarguel, Gilles; Fluteau, Frédéric; Martineau, François

    2006-06-01

    The much debated question of dinosaur thermophysiology has not yet been conclusively solved despite numerous attempts. We used the temperature-dependent oxygen isotope fractionation between vertebrate body water (δ 18O body water) and phosphatic tissues (δ 18O p) to compare the thermophysiology of dinosaurs with that of non-dinosaurian ectothermic reptiles. Present-day δ 18O p values of vertebrate apatites show that ectotherms have higher δ 18O p values than endotherms at high latitudes due to their lower body temperature, and conversely lower δ 18O p values than endotherms at low latitudes. Using a data set of 80 new and 49 published δ 18O p values, we observed similar and systematic differences in δ 18O p values (Δ 18O) between four groups of Cretaceous dinosaurs (theropods, sauropods, ornithopods and ceratopsians) and associated fresh water crocodiles and turtles. Expressed in terms of body temperatures ( Tb), these Δ 18O values indicate that dinosaurs maintained rather constant Tb in the range of endotherms whatever ambient temperatures were. This implies that high metabolic rates were widespread among Cretaceous dinosaurs belonging to widely different taxonomic groups and suggest that endothermy may be a synapomorphy of dinosaurs, or may have been acquired convergently in the studied taxa.

  18. Application of oxygen and hydrogen isotopes of waters in Tengchong hydrothermal systems of China

    International Nuclear Information System (INIS)

    Shen Minzi; Hou Fagao; Lin Ruifen; Ni Baoling

    1988-01-01

    This paper summarizes the results obtained for hydrothermal systems in Tengchong by using deuterium, oxygen-18 and tritium as natural tracers. On the basis of deuterium and oxygen-18 analyses of 69 thermal springs and some other meteoric, surface and underground water samples it has been confirmed that all geothermal waters are originally meteoric, but the δD of hot spring waters is often lighter than that of local surface and underground waters. It seems that the recharging water is from higher elevations and far from the thermal areas. The differences in oxygen-18 and deuterium contents between thermal springs and deep thermal waters have been calculated for single-stage steam separation from 276 deg. C to 96 deg. C. The oxygen isotope shift of deep thermal water produced by water-rock reactions is of 1.57 per mille and part of the observed oxygen isotope shift of thermal springs seems to have occurred due to subsurface boiling. The tritium content ( 18 O three subsurface processes would have been distinguished, they are subsurface boiling, mixing-subsurface boiling and subsurface boiling-mixing. The springs formed by subsurface boiling have tritium content of less than 5 TU. The tritium content of 5-10 TU is for springs formed by mixing-subsurface boiling and 10-20 TU is for subsurface boiling-mixing. The tritium content of geothermal water in Hot Sea, geothermal field seems higher than that of the Geysers U.S.A. and Wairakei N.Z. It would show that the circulation time of the thermal water in Hot Sea geothermal system is not so long, the reservoir is quite good with percolation and the recharging water is sufficiently enough. The most important applications of oxygen and hydrogen isotopes of water in geothermal study are in two ways, as tracers of water origins and as tracers of reservoir processes. This paper discussed these two aspects of Tengchong hydrothermal systems. 6 refs, 6 figs, 5 tabs

  19. Oxygen isotopic tracing study of the dry thermal oxidation of 6H SiC

    International Nuclear Information System (INIS)

    Vickridge, I.C.; Ganem, J.-J.; Battistig, G.; Szilagyi, E.

    2000-01-01

    The (0 0 0 1) and (0 0 0 1-bar) faces of 6H SiC have been oxidised sequentially at 1100 deg. C and 100 mbar in ultra-dry oxygen of natural isotopic concentration and in ultra-dry oxygen highly enriched in 18 O. Measurement of the 18 O isotopic concentration profiles by nuclear resonance profiling with the narrow resonance at 151 keV in 18 O(p,α) 15 N shows that on the carbon-terminated face (0 0 0 1-bar) the oxidation mechanism is rather similar to that observed on Si(1 0 0), but that on the silicon-terminated face (0 0 0 1) the surface isotopic exchange and oxide formation are superposed. The surface exchange observed during a third dry oxidation, in 16 O 2 , is very similar in magnitude and spatial extent on Si(1 0 0), and the two 6H SiC faces, suggesting that at least near the surface the nature and composition of the three oxides are very similar

  20. Oxygen isotopic tracing study of the dry thermal oxidation of 6H SiC

    Energy Technology Data Exchange (ETDEWEB)

    Vickridge, I.C. E-mail: vickridge@gps.jussieu.fr; Ganem, J.-J.; Battistig, G.; Szilagyi, E

    2000-03-01

    The (0 0 0 1) and (0 0 0 1-bar) faces of 6H SiC have been oxidised sequentially at 1100 deg. C and 100 mbar in ultra-dry oxygen of natural isotopic concentration and in ultra-dry oxygen highly enriched in {sup 18}O. Measurement of the {sup 18}O isotopic concentration profiles by nuclear resonance profiling with the narrow resonance at 151 keV in {sup 18}O(p,{alpha}){sup 15}N shows that on the carbon-terminated face (0 0 0 1-bar) the oxidation mechanism is rather similar to that observed on Si(1 0 0), but that on the silicon-terminated face (0 0 0 1) the surface isotopic exchange and oxide formation are superposed. The surface exchange observed during a third dry oxidation, in {sup 16}O{sub 2}, is very similar in magnitude and spatial extent on Si(1 0 0), and the two 6H SiC faces, suggesting that at least near the surface the nature and composition of the three oxides are very similar.

  1. Isotopic homogeneity of iron in the early solar nebula.

    Science.gov (United States)

    Zhu, X K; Guo, Y; O'Nions, R K; Young, E D; Ash, R D

    2001-07-19

    The chemical and isotopic homogeneity of the early solar nebula, and the processes producing fractionation during its evolution, are central issues of cosmochemistry. Studies of the relative abundance variations of three or more isotopes of an element can in principle determine if the initial reservoir of material was a homogeneous mixture or if it contained several distinct sources of precursor material. For example, widespread anomalies observed in the oxygen isotopes of meteorites have been interpreted as resulting from the mixing of a solid phase that was enriched in 16O with a gas phase in which 16O was depleted, or as an isotopic 'memory' of Galactic evolution. In either case, these anomalies are regarded as strong evidence that the early solar nebula was not initially homogeneous. Here we present measurements of the relative abundances of three iron isotopes in meteoritic and terrestrial samples. We show that significant variations of iron isotopes exist in both terrestrial and extraterrestrial materials. But when plotted in a three-isotope diagram, all of the data for these Solar System materials fall on a single mass-fractionation line, showing that homogenization of iron isotopes occurred in the solar nebula before both planetesimal accretion and chondrule formation.

  2. 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....

  3. 18O isotopic tracer studies of silicon oxidation in dry oxygen

    International Nuclear Information System (INIS)

    Han, C.J.

    1986-01-01

    Oxidation of silicon in dry oxygen has been an important process in the integrated circuit industry for making gate insulators on metal-oxide-semiconductory (MOS) devices. This work examines this process using isotopic tracers of oxygen to determine the transport mechanisms of oxygen through silicon dioxide. Oxides were grown sequentially using mass-16 and mass-18 oxygen gas sources to label the oxygen molecules from each step. The resulting oxides are analyzed using secondary ion mass spectrometry (SIMS). The results of these analyses suggest two oxidant species are present during the oxidation, each diffuses and oxidizes separately during the process. A model from this finding using a sum of two linear-parabolic growth rates, each representing the growth rate from one of the oxidants, describes the reported oxidation kinetics in the literature closely. A fit of this relationship reveals excellent fits to the data for oxide thicknesses ranging from 30 A to 1 μm and for temperatures ranging from 800 to 1200 0 C. The mass-18 oxygen tracers also enable a direct observation of the oxygen solubility in the silicon dioxide during a dry oxidation process. The SIMS profiles establish a maximum solubility for interstitial oxygen at 1000 0 C at 2 x 10 20 cm -3 . Furthermore, the mass-18 oxygen profiles show negligible network diffusion during an 1000 0 C oxidation

  4. Ocean Ridges and Oxygen

    Science.gov (United States)

    Langmuir, C. H.

    2014-12-01

    The history of oxygen and the fluxes and feedbacks that lead to its evolution through time remain poorly constrained. It is not clear whether oxygen has had discrete steady state levels at different times in Earth's history, or whether oxygen evolution is more progressive, with trigger points that lead to discrete changes in markers such as mass independent sulfur isotopes. Whatever this history may have been, ocean ridges play an important and poorly recognized part in the overall mass balance of oxidants and reductants that contribute to electron mass balance and the oxygen budget. One example is the current steady state O2 in the atmosphere. The carbon isotope data suggest that the fraction of carbon has increased in the Phanerozoic, and CO2 outgassing followed by organic matter burial should continually supply more O2 to the surface reservoirs. Why is O2 not then increasing? A traditional answer to this question would relate to variations in the fraction of burial of organic matter, but this fraction appears to have been relatively high throughout the Phanerozoic. Furthermore, subduction of carbon in the 1/5 organic/carbonate proportions would contribute further to an increasingly oxidized surface. What is needed is a flux of oxidized material out of the system. One solution would be a modern oxidized flux to the mantle. The current outgassing flux of CO2 is ~3.4*1012 moles per year. If 20% of that becomes stored organic carbon, that is a flux of .68*1012 moles per year of reduced carbon. The current flux of oxidized iron in subducting ocean crust is ~2*1012 moles per year of O2 equivalents, based on the Fe3+/Fe2+ ratios in old ocean crust compared to fresh basalts at the ridge axis. This flux more than accounts for the incremental oxidizing power produced by modern life. It also suggests a possible feedback through oxygenation of the ocean. A reduced deep ocean would inhibit oxidation of ocean crust, in which case there would be no subduction flux of oxidized

  5. Applications of stable Isotope ratios determinations in fruit juice authentication

    International Nuclear Information System (INIS)

    Magdas, Dana Alina; Dehelean, Adriana; Voica, Cezara; Puscas, Romulus

    2010-01-01

    Full text: Adulteration of a product consists in making it impure by fraudulent addition of a foreign or inferior substance. The result is either an alteration of the product and of its quality or a falsification. The falsification is a voluntary act with the intention of abuse. The falsification may be more or less sophisticated and its sophistication as well as its costs increases with the improvement of analytical methods. Vacuum concentration with aroma does not affect the chemical composition of fruit juices and therefore the determination of deuterium (D) and oxygen-18 content in waters is the most confident procedure for differentiating between a natural single strength juice and a juice rediluted from a concentrate. This technique is based on the fact that when absorbed by a plant, the rainwater or the irrigation water is fractionated by evapotranspiration, and enriched in the heavy isotopes (deuterium and oxygen-18) with respect to the light isotope (hydrogen and oxygen-16, respectively). It is known that climatic conditions affect the isotope content of rain waters and therefore that of fruit juices waters: the warmer climate, the higher the deuterium and oxygen-18 contents in water. Rainwater and tap water have nearly the same isotopic content and the water of fruit juices derived from concentrate by dilution with tap water has an isotopic content close to that of tap water. This makes it easy to distinguish diluted concentrates from the isotopically more enriched water of authentic single strength juice. In this study, single strength juice, in Romanian fruits, were investigated by mean of stable isotope measurements (oxygen, hydrogen and carbon) in order to offer a discussion basis for the authenticity of some fruit juices currently available on Romanian market. (authors)

  6. 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.

  7. Stable carbon isotope response to oceanic anoxic events

    International Nuclear Information System (INIS)

    Hu Xiumian; Wang Chengshan; Li Xianghui

    2001-01-01

    Based on discussion of isotope compositions and fractionation of marine carbonate and organic carbon, the author studies the relationship between oceanic anoxic events and changes in the carbon isotope fractionation of both carbonate and organic matter. During the oceanic anoxic events, a great number of organisms were rapidly buried, which caused a kind of anoxic conditions by their decomposition consuming dissolved oxygen. Since 12 C-rich organism preserved, atmosphere-ocean system will enrich relatively of 13 C. As a result, simultaneous marine carbonate will record the positive excursion of carbon isotope. There is a distinctive δ 13 C excursion during oceanic anoxic events in the world throughout the geological time. In the Cenomanian-Turonian anoxic event. this positive excursion arrived at ∼0.2% of marine carbonate and at ∼0.4% of organic matter, respectively. Variations in the carbon isotopic compositions of marine carbonate and organic carbon record the changes in the fraction of organic carbon buried throughout the geological time and may provide clues to the changes in rates of weathering and burial of organic carbon. This will provide a possibility of interpreting not only the changes in the global carbon cycle throughout the geological time, but also that in atmospheric p CO 2

  8. Deciphering the iron isotope message of the human body

    Science.gov (United States)

    Walczyk, Thomas; von Blanckenburg, Friedhelm

    2005-04-01

    Mass-dependent variations in isotopic composition are known since decades for the light elements such as hydrogen, carbon or oxygen. Multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS) and double-spike thermal ionization mass spectrometry (TIMS) permit us now to resolve small variations in isotopic composition even for the heavier elements such as iron. Recent studies on the iron isotopic composition of human blood and dietary iron sources have shown that lighter iron isotopes are enriched along the food chain and that each individual bears a certain iron isotopic signature in blood. To make use of this finding in biomedical research, underlying mechanisms of isotope fractionation by the human body need to be understood. In this paper available iron isotope data for biological samples are discussed within the context of isotope fractionation concepts and fundamental aspects of human iron metabolism. This includes evaluation of new data for body tissues which show that blood and muscle tissue have a similar iron isotopic composition while heavier iron isotopes are concentrated in the liver. This new observation is in agreement with our earlier hypothesis of a preferential absorption of lighter iron isotopes by the human body. Possible mechanisms for inducing an iron isotope effect at the cellular and molecular level during iron uptake are presented and the potential of iron isotope effects in human blood as a long-term measure of dietary iron absorption is discussed.

  9. Oxygenation as a driver of the Great Ordovician Biodiversification Event

    Science.gov (United States)

    Edwards, Cole T.; Saltzman, Matthew R.; Royer, Dana L.; Fike, David A.

    2017-12-01

    The largest radiation of Phanerozoic marine animal life quadrupled genus-level diversity towards the end of the Ordovician Period about 450 million years ago. A leading hypothesis for this Great Ordovician Biodiversification Event is that cooling of the Ordovician climate lowered sea surface temperatures into the thermal tolerance window of many animal groups, such as corals. A complementary role for oxygenation of subsurface environments has been inferred based on the increasing abundance of skeletal carbonate, but direct constraints on atmospheric O2 levels remain elusive. Here, we use high-resolution paired bulk carbonate and organic carbon isotope records to determine the changes in isotopic fractionation between these phases throughout the Ordovician radiation. These results can be used to reconstruct atmospheric O2 levels based on the O2-dependent fractionation of carbon isotopes by photosynthesis. We find a strong temporal link between the Great Ordovician Biodiversification Event and rising O2 concentrations, a pattern that is corroborated by O2 models that use traditional carbon-sulfur mass balance. We conclude that that oxygen levels probably played an important role in regulating early Palaeozoic biodiversity levels, even after the Cambrian Explosion.

  10. 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.

  11. 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.

  12. 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

  13. Oxygen isotope study of the Long Valley magma system, California: isotope thermometry and convection in large silicic magma bodies

    Science.gov (United States)

    Bindeman, Ilya; Valley, John

    2002-07-01

    Products of voluminous pyroclastic eruptions with eruptive draw-down of several kilometers provide a snap-shot view of batholith-scale magma chambers, and quench pre-eruptive isotopic fractionations (i.e., temperatures) between minerals. We report analyses of oxygen isotope ratio in individual quartz phenocrysts and concentrates of magnetite, pyroxene, and zircon from individual pumice clasts of ignimbrite and fall units of caldera-forming 0.76 Ma Bishop Tuff (BT), pre-caldera Glass Mountain (2.1-0.78 Ma), and post-caldera rhyolites (0.65-0.04 Ma) to characterize the long-lived, batholith-scale magma chamber beneath Long Valley Caldera in California. Values of δ18O show a subtle 1‰ decrease from the oldest Glass Mountain lavas to the youngest post-caldera rhyolites. Older Glass Mountain lavas exhibit larger ( 1‰) variability of δ18O(quartz). The youngest domes of Glass Mountain are similar to BT in δ18O(quartz) values and reflect convective homogenization during formation of BT magma chamber surrounded by extremely heterogeneous country rocks (ranging from 2 to +29‰). Oxygen isotope thermometry of BT confirms a temperature gradient between "Late" (815 °C) and "Early" (715 °C) BT. The δ18O(quartz) values of "Early" and "Late" BT are +8.33 and 8.21‰, consistent with a constant δ18O(melt)=7.8+/-0.1‰ and 100 °C temperature difference. Zircon-melt saturation equilibria gives a similar temperature range. Values of δ18O(quartz) for different stratigraphic units of BT, and in pumice clasts ranging in pre-eruptive depths from 6 to 11 km (based on melt inclusions), and document vertical and lateral homogeneity of δ18O(melt). Worldwide, five other large-volume rhyolites, Lava Creek, Lower Bandelier, Fish Canyon, Cerro Galan, and Toba, exhibit equal δ18O(melt) values of earlier and later erupted portions in each of the these climactic caldera-forming eruptions. We interpret the large-scale δ18O homogeneity of BT and other large magma chambers as evidence

  14. Devonian climate and reef evolution: Insights from oxygen isotopes in apatite

    Science.gov (United States)

    Joachimski, M. M.; Breisig, S.; Buggisch, W.; Talent, J. A.; Mawson, R.; Gereke, M.; Morrow, J. R.; Day, J.; Weddige, K.

    2009-07-01

    Conodonts, microfossils composed of carbonate-fluor apatite, are abundant in Palaeozoic-Triassic sediments and have a high potential to preserve primary oxygen isotope signals. In order to reconstruct the palaeotemperature history of the Devonian, the oxygen isotope composition of apatite phosphate was measured on 639 conodont samples from sequences in Europe, North America and Australia. The Early Devonian (Lochkovian; 416-411 Myr) was characterized by warm tropical temperatures of around 30 °C. A cooling trend started in the Pragian (410 Myr) with intermediate temperatures around 23 to 25 °C reconstructed for the Middle Devonian (397-385 Myr). During the Frasnian (383-375 Myr), temperatures increased again with temperatures to 30 °C calculated for the Frasnian-Famennian transition (375 Myr). During the Famennian (375-359 Myr), surface water temperatures slightly decreased. Reconstructed Devonian palaeotemperatures do not support earlier views suggesting the Middle Devonian was a supergreenhouse interval, an interpretation based partly on the development of extensive tropical coral-stromatoporoid communities during the Middle Devonian. Instead, the Devonian palaeotemperature record suggests that Middle Devonian coral-stromatoporoid reefs flourished during cooler time intervals whereas microbial reefs dominated during the warm to very warm Early and Late Devonian.

  15. Using Oxygen Isotopic Values in Order to Infer Palaeoclimatic Differences between Northern and Central-Southern Greece

    Science.gov (United States)

    Michael, Dimitra-Ermioni; Dotsika, Elissavet

    2017-12-01

    Even though isotopic analyses have been extensively implemented on human skeletal remains for the purpose of dietary reconstruction, less attention has been given to the ingested water and thus to the investigation of palaeoclimatic conditions. In particular, oxygen isotopic fingerprinting has never been applied on human skeletal remains from Greece for the abovementioned purpose before. The basic aim of the present study is to compare climatic conditions from two ancient populations, deriving from two different ecological locations; Edessa (Greek Macedonia; 2nd-4th c. AD) and Thebes (Sterea Hellas, 13th-14th c. AD). Oxygen values in Edessa are at -7.69 ±1.13 ‰ and -9.18 ±1.88 ‰ for tooth enamel and bone apatite respectively. On the other hand, oxygen signals in Thebes are at -5.8 ±2.16 ‰ and -9.23 ±1.3 % for the enamel and bone apatite respectively. The utility of oxygen isotopic signatures for the purpose of palaeoclimatic investigation lies on the fact that the ratio of 18 to 16O of meteoric precipitation, expressed as δ18O per mill (‰), relative to the international standard (vSMOW) varies geographically by temperature, humidity, evaporation, distance to the sea, altitude and latitude. Therefore, results as expected, point out that Edessa do presents more negative enamel isotopic values in relation to Thebes, however the noted difference is not observed for the bone apatite samples. The lack of bone apatite differentiation between sites could be attributed to cultural diversity (particularly in Thebes), shift in dietary habits due to migration or social status, climatic fluctuations within each site or to possible diagenetic alteration of bone apatite samples.

  16. Seasonality of bottom water temperature in the northern North Sea reconstructed from the oxygen isotope composition of the bivalve Arctica islandica

    Science.gov (United States)

    Trofimova, Tamara; Andersson, Carin; Bonitz, Fabian

    2017-04-01

    The seasonality of temperature changes is an important characteristic of climate. However, observational data for the ocean are only available for the last 150 year from a limited number of locations. Prior to 18th century information is only available from proxy reconstructions. The vast majority of such reconstructions depend on land-based archives, primarily from dendrochronology. Established marine proxy records for the ocean, especially at high latitudes, are both sparsely distributed and poorly resolved in time. Therefore, the identification and development of proxies for studying key ocean processes at sub-annual resolution that can extend the marine instrumental record is a clear priority in marine climate science. In this study, we have developed a record of early Holocene seasonal variability of bottom water temperature from the Viking Bank in the northern most North Sea. This area is of a particular interest since the hydrography is controlled by the inflow of Atlantic water. The reconstruction is based on the oxygen isotope composition of the growth increments in two sub-fossil shells of Arctica islandica (Bivalvia), dated to 9600-9335 cal. yr BP. By combining radiocarbon dating and sclerochronological techniques a floating chronology spanning over 200 years was constructed. Using the chronology as an age model, oxygen isotope measurements from 2 shells were combined into a 22-years long record. The results from this oxygen isotope record are compared with stable oxygen isotope profiles from modern shells to estimate changes in the mean state and seasonality between present and early Holocene. Shell-derived oxygen isotope values together with ice-volume corrected oxygen isotope values for the seawater were used to calculate bottom-water temperatures on a sub-annual time-scale. Preliminary results of the reconstructed early Holocene bottom water temperature indicate higher seasonality and lower minimum temperature compared to the present.

  17. 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.

  18. Measurement of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen

    International Nuclear Information System (INIS)

    Wiedenbeck, M.E.; Greiner, D.E.; Bieser, F.S.; Crawford, H.J.; Heckman, H.H.; Lindstrom, P.J.

    1979-06-01

    The results of an investigation of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen (E approx. 80 to 230 MeV/amu) made using the U.C. Berkeley HKH instrument aboard the ISEE-3 spacecraft are reported. The combination of high mass resolution and a large statistical sample makes possible a precise determination of the relative isotopic abundances for these elements. In local interplanetary space we find: 13 C/C = 0.067 +- 0.008, 15 N/N = 0.54 +- 0.03, 17 O/O 18 O/O = 0.019 +- 0.003

  19. Magnesium and Titanium Isotopic Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende: It Is Fun

    Science.gov (United States)

    Liu, M.-C.; Keller, L. P.; McKeegan, K. D.

    2016-01-01

    Introduction: Hibonite-rich refractory inclusions are among the first solids that formed in the solar nebula, and thus provide constraints on the earliest environment in the Solar System. An unusual hibonite-perovskite inclusion from Allende, SHAL, consists of a large (approximately 500 by 200 microns) single hibonite crystal and coexisting blocky perovskite (approximately 200 microns in size). The hibonite is characterized by chemical and oxygen isotopic compositions similar to those in the FUN (Fractionated and Unknown Nuclear anomalies) inclusion HAL. However, the rare earth element (REE) patterns measured at different spots of SHAL hibonite are highly variable, ranging from Group II-like (light REEs enriched relative to heavy REEs) to Group III-like (relatively flat with slight Eu depletions), but overall contrast largely with that of HAL, especially in the Ce and Yb abundances. This implies that SHAL hibonite formed and underwent distillation processes under more reducing conditions. Interestingly, the accompanying perovskite has uniform, unfractionated oxygen isotopic compositions (averaging delta (sup 17) O equals delta (sup 18) O equals -7 per mille) and REE abundances that are completely different from those of SHAL hibonite. This has been interpreted that perovskite and hibonite may not be co-genetic. Here we performed Al-Mg and Ti isotopic measurements of SHAL hibonite and perovskite to determine if the FUN characteristics are observed in these two isotope systems, and to further constrain the origin and evolution of SHAL. Results: Isotopic measurements of Al-Mg and Ti in SHAL were performed on the UCLA CAMECA ims-1290 ion microprobe by following the analytical protocols described in [1]. The Al-Mg and Ti data obtained in both terrestrial standards and SHAL hibonite and perovskite are shown below. Both SHAL hibonite and perovskite, despite very high (sup 27) Al to (sup 24) Mg ratios, are devoid of (sup 26) Mg excesses that can be attributed to the decay

  20. Charge state distribution studies of pure and oxygen mixed krypton ECR plasma - signature of isotope anomaly and gas mixing effect.

    Science.gov (United States)

    Kumar, Pravin; Mal, Kedar; Rodrigues, G

    2016-11-01

    We report the charge state distributions of the pure, 25% and 50% oxygen mixed krypton plasma to shed more light on the understanding of the gas mixing and the isotope anomaly [A. G. Drentje, Rev. Sci. Instrum. 63 (1992) 2875 and Y Kawai, D Meyer, A Nadzeyka, U Wolters and K Wiesemann, Plasma Sources Sci. Technol. 10 (2001) 451] in the electron cyclotron resonance (ECR) plasmas. The krypton plasma was produced using a 10 GHz all-permanent-magnet ECR ion source. The intensities of the highly abundant four isotopes, viz. 82 Kr (~11.58%), 83 Kr (~11.49%), 84 Kr (~57%) and 86 Kr (17.3%) up to ~ +14 charge state have been measured by extracting the ions from the plasma and analysing them in the mass and the energy using a large acceptance analyzer-cum-switching dipole magnet. The influence of the oxygen gas mixing on the isotopic krypton ion intensities is clearly evidenced beyond +9 charge state. With and without oxygen mixing, the charge state distribution of the krypton ECR plasma shows the isotope anomaly with unusual trends. The anomaly in the intensities of the isotopes having quite closer natural abundance, viz. 82 Kr, 86 Kr and 83 Kr, 86 Kr is prominent, whereas the intensity ratio of 86 Kr to 84 Kr shows a weak signature of it. The isotope anomaly tends to disappear with increasing oxygen mixing in the plasma. The observed trends in the intensities of the krypton isotopes do not follow the prediction of linear Landau wave damping in the plasma. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  1. 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

  2. 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.

  3. 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

  4. Oxygen isotope regional pattern in granitoids from the Cachoeirinha Belt, northeast Brazil

    International Nuclear Information System (INIS)

    Sial, A.N.

    1984-01-01

    Four groups of granitoids are present within the Cachoeirinha belt and in the adjacent migmatitic basement, between 37 0 and 40 0 W long. and 7 0 and 8 0 15' S lat., States of Pernambuco and Paraiba: a) K 2 O - enriched, very porphyritic; b) a calc-alkalic slightly porphyritic group; c) group with trondjemitic affinities; and d) peralkalic group. Petrology and oxygen isotope geochemistry for over 100 samples from these groups were studied. Almost all plutons for which 5 or more samples were analyzed, exhibit a total range of gamma 18 O less than 2% o. A broad range of mean oxygen isotope composition is observed, varying from 6.93 to 12.79% o. There is a systematic regional trend in which the calc-alkalic granitoids (conceicao-type) found within the Cachoeirinha space are the most 18 O - enriched rocks (10.6 to 12.9% o) while the lowest mean gamma 18 O values (4.5 to 9.7% o) are found in the K 2 O - enriched granitoids (Itaporanga-type). Intermediate gamma 18 O values were recorded in the bodies with trondhjemitic affinities (8.9 to 9.8% o) which intruded metasediments of the Salgueiro Group and in the peralkalic granitoids of Catingueira (8.1 to 9.8% o) which intruded Cachoeirinha metamorphics. Among the potassic granitoids, mean gamma 18 O increases from Bodoco to Itaporanga (from west to east). As a whole, the W.R. gamma 18 O of these plutons correlate with the type of grade of metamorphism of the host rocks and, therefore, with the tectonic framework, increasing from those which intruded the gneiss-migmatites to those which intruded the low-grade metamorphics of the Cachoeirinha Group. The possible origin of each rock group is discussed in light of the oxygen isotope geochemistry. (Author) [pt

  5. 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.

  6. 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.

  7. Oxygen Isotopes Archived in Subfossil Chironomids: Advancing a Promising Proxy for Lake Water Isotopes

    Science.gov (United States)

    Lasher, G. E.; Axford, Y.; Blair, N. E.

    2017-12-01

    Oxygen isotopes measured in subfossil chironomid head capsules (aquatic insect remains) in lake sediments are beginning to offer paleoclimate insights from previously under-studied areas of the world. Since the first published pilot study demonstrated the potential of chironomid δ18O to record lake water δ18O (Wooller et al., 2004), subsequent work has refined our understanding of this proxy: confirming via lab cultures that growth water controls head capsule δ18O (Wang et al., 2009), refining laboratory pretreatment protocols, and further validating the method by demonstrating strong agreement between carbonate and chironomid-derived paleo-isotope records (Verbruggen et al., 2009, 2010, 2011). However, outstanding questions remain, including the seasonality of chironomid growth, possible species-dependent vital effects, and diagenetic effects on the protein-chitin complex that comprise chironomid cuticles. To address some of these questions, we summarize available data from paired modern chironomid-lake water δ18O values from around the world and discuss climatic and environmental factors affecting chironomid isotopic signatures. We also present new data on the resistance of these subfossils to diagenesis and degradation throughout the late Quaternary using Fourier Transform Infrared Spectroscopy (FT-IR) and Pyrolysis Gas Chromatography Mass Spectrometry (Py-GC/MS) of chironomid remains up to >100,000 years old. As chironomids are nearly ubiquitous in lakes globally and, we argue, molecularly stable through glacial and interglacial cycles, this proxy has the potential to greatly expand the spatial and temporal resolution of Quaternary paleo-isotopes and thus climate records. In addition to reviewing and presenting new methodological advances, we also present applications of chironomid δ18O from millennial- to centennial-scale Holocene Greenland lake records.

  8. Oxygen isotope variations at the margin of a CAI records circulation within the solar nebula.

    Science.gov (United States)

    Simon, Justin I; Hutcheon, Ian D; Simon, Steven B; Matzel, Jennifer E P; Ramon, Erick C; Weber, Peter K; Grossman, Lawrence; DePaolo, Donald J

    2011-03-04

    Micrometer-scale analyses of a calcium-, aluminum-rich inclusion (CAI) and the characteristic mineral bands mantling the CAI reveal that the outer parts of this primitive object have a large range of oxygen isotope compositions. The variations are systematic; the relative abundance of (16)O first decreases toward the CAI margin, approaching a planetary-like isotopic composition, then shifts to extremely (16)O-rich compositions through the surrounding rim. The variability implies that CAIs probably formed from several oxygen reservoirs. The observations support early and short-lived fluctuations of the environment in which CAIs formed, either because of transport of the CAIs themselves to distinct regions of the solar nebula or because of varying gas composition near the proto-Sun.

  9. Properties of thin films deposited from HMDSO/O2 induced remote plasma: Effect of oxygen fraction

    International Nuclear Information System (INIS)

    Saloum, S.; Naddaf, M.; Al-Khaled, B.

    2008-01-01

    Thin films deposited from hexamethyle disiloxane (HMDSO)/O 2 mixture excited in a radio-frequency hollow cathode discharge system have been investigated for their structural, optical and corrosive properties as a function of oxygen fraction χo 2 (χo 2 =0, 0.38, 0.61, 0.76 and 0.90). It is found that the effect of oxygen fraction on films properties is related to O 2 dissociation degree (αd) behavior in pure oxygen plasma. αd has been investigated by actinometry optical emission spectroscopy (AOES) combined with double langmuir probe measurements, a maximum of O 2 dissociation degree of 15% has been obtained for 50 sccm flow rate of O 2 (χo 2 =0.61 in HMDSO/O 2 plasma). Fourier transform infrared spectroscopy (FTIR) and optical measurements showed that the behavior of both identified IR group densities and deposition rate as a function of oxygen fraction is similar to that of O 2 dissociation degree. The inorganic nature of the films depends significantly on oxygen fraction, the best inorganic structure of deposited films has been obtained for 62% HMDSO content in the mixture HMDSO/O 2 (χo 2 =0.38). The refractive index for deposited films from pure HMDSO(χo 2 =0) has been found to be higher than that of films deposited from HMDSO/O 2 mixture. In HMDSO/O 2 plasma, it has a behavior similar to that of deposition rate, and it is comparable to that of quartz. The effect of oxygen fraction on the corrosive properties of thin films deposited on steel has been investigated. It is found that the measured corrosion current density in 0.1 M KCI solution decreases with the addition of O 2 to HMDSO plasma, and it is minimum for χo 2 =0.38. (author)

  10. Hydrogen and oxygen stable isotope ratios of milk in the United States.

    Science.gov (United States)

    Chesson, Lesley A; Valenzuela, Luciano O; O'Grady, Shannon P; Cerling, Thure E; Ehleringer, James R

    2010-02-24

    Models of hydrogen and oxygen incorporation in human tissues recognize the impact of geographic location on the isotopic composition of fluid intake, but inputs can include nonlocal beverages, such as milk. Milk and cow drinking water were collected from dairies, and commercially available milk was purchased from supermarkets and fast food restaurants. It was hypothesized that milk water delta(2)H and delta(18)O values record geographic location information. Correlations between milk water isotope ratios and purchase location tap water were significant. However, the amount of variation in milk delta(2)H and delta(18)O values explained by tap water was low, suggesting a single estimation of fluid input isotope ratios may not always be adequate in studies. The delta(2)H and delta(18)O values of paired milk and cow drinking water were related, suggesting potential for geographical origin assignment using stable isotope analysis. As an application example, milk water delta(18)O values were used to predict possible regions of origin for restaurant samples.

  11. 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

  12. Increased long-term mortality after a high perioperative inspiratory oxygen fraction during abdominal surgery

    DEFF Research Database (Denmark)

    Meyhoff, Christian Sylvest; Jorgensen, Lars N; Wetterslev, Jørn

    2012-01-01

    A high perioperative inspiratory oxygen fraction (80%) has been recommended to prevent postoperative wound infections. However, the most recent and one of the largest trials, the PROXI trial, found no reduction in surgical site infection, and 30-day mortality was higher in patients given 80% oxygen...

  13. Digesting the data - Effects of predator ingestion on the oxygen isotopic signature of micro-mammal teeth

    Science.gov (United States)

    Barham, Milo; Blyth, Alison J.; Wallwork, Melinda D.; Joachimski, Michael M.; Martin, Laure; Evans, Noreen J.; Laming, Belinda; McDonald, Bradley J.

    2017-11-01

    Biogenic minerals such as dental apatite have become commonly analysed archives preserving geochemical indicators of past environmental conditions and palaeoecologies. However, post-mortem, biogenic minerals are modified due to the alteration/replacement of labile components, and recent moves to utilise micro-mammal tooth δ18O signatures for refined Cenozoic terrestrial palaeoclimate reconstructions has lacked consideration of the chemical effects of predator digestion. Here, the physical and chemical condition of laboratory-raised mouse (Mus musculus) teeth have been investigated in conjunction with their bulk phosphate and tissue-specific δ18O values prior, and subsequent, to ingestion and excretion by various predator species (owls, mammals and a reptile). Substantial variability (up to 2‰) in the δ18O values of both undigested teeth and those ingested by specific predators suggests significant natural heterogeneity of individual prey δ18O. Statistically distinct, lower δ18O values (∼0.7‰) are apparent in teeth ingested by barn owls compared to undigested controls as a result of the chemically and enzymatically active digestive and waste-pellet environments. Overall, dentine tissues preserve lower δ18O values than enamel, while the greatest modification of oxygen isotope signals is exhibited in the basal enamel of ingested teeth as a result of its incompletely mineralised state. However, recognition of 18O-depletion in chemically purified phosphate analyses demonstrates that modification of original δ18O values is not restricted to labile oxygen-bearing carbonate and organic phases. The style and magnitude of digestive-alteration varies with predator species and no correlation was identified between specific physical or minor/trace-element (patterns or concentrations) modification of ingested teeth and disruption of their primary oxygen isotope values. Therefore, there is a current lack of any screening tool for oxygen isotope disruption as a result

  14. In situ oxygen isotope compositions in olivines of different types of cosmic spherules: An assessment of relationships to chondritic particles

    Digital Repository Service at National Institute of Oceanography (India)

    Rudraswami, N.G.; ShyamPrasad, M.; Jones, R.H.; Nagashima, K.

    bearing cosmic spherules (Rudraswami et al., 2015b). In addition, some Mg-rich relict olivine grains are very 16O-rich, with 17O ranging from −21.9 to -18.7‰, similar to oxygen isotopic compositions observed in calcium aluminium rich inclusions (CAIs... isotope analyses of the olivine grains are provided in Appendix B and Table 1, respectively. 5    Four scoriaceous spherules namely, AAS62-61-P64, AAS62-9-P43, AAS62-9-P51 and AAS62-9- P54 were identified for oxygen isotope studies (Fig. 1a...

  15. Evidence for oxygenic photosynthesis half a billion years before the Great Oxidation Event

    Science.gov (United States)

    Planavsky, Noah J.; Asael, Dan; Hofmann, Axel; Reinhard, Christopher T.; Lalonde, Stefan V.; Knudsen, Andrew; Wang, Xiangli; Ossa Ossa, Frantz; Pecoits, Ernesto; Smith, Albertus J. B.; Beukes, Nicolas J.; Bekker, Andrey; Johnson, Thomas M.; Konhauser, Kurt O.; Lyons, Timothy W.; Rouxel, Olivier J.

    2014-04-01

    The early Earth was characterized by the absence of oxygen in the ocean-atmosphere system, in contrast to the well-oxygenated conditions that prevail today. Atmospheric concentrations first rose to appreciable levels during the Great Oxidation Event, roughly 2.5-2.3 Gyr ago. The evolution of oxygenic photosynthesis is generally accepted to have been the ultimate cause of this rise, but it has proved difficult to constrain the timing of this evolutionary innovation. The oxidation of manganese in the water column requires substantial free oxygen concentrations, and thus any indication that Mn oxides were present in ancient environments would imply that oxygenic photosynthesis was ongoing. Mn oxides are not commonly preserved in ancient rocks, but there is a large fractionation of molybdenum isotopes associated with the sorption of Mo onto the Mn oxides that would be retained. Here we report Mo isotopes from rocks of the Sinqeni Formation, Pongola Supergroup, South Africa. These rocks formed no less than 2.95 Gyr ago in a nearshore setting. The Mo isotopic signature is consistent with interaction with Mn oxides. We therefore infer that oxygen produced through oxygenic photosynthesis began to accumulate in shallow marine settings at least half a billion years before the accumulation of significant levels of atmospheric oxygen.

  16. Chemical and Oxygen Isotopic Composition of Roman and Late Antique Glass from Northern Greece

    Directory of Open Access Journals (Sweden)

    Alberta Silvestri

    2017-01-01

    Full Text Available The present paper emphasizes the importance of measuring the oxygen isotopic and chemical compositions of ancient glass, in order to constrain some features such as age, raw materials, and production technologies and to identify the “fingerprint” of local productions. In this context, thirty-nine Roman and late Antique glass samples and eight chert samples from northern Greece were selected and analysed for their oxygen isotopic and chemical compositions. Results show that the majority of glass samples are produced using natron as flux and have δ18O values of about 15.5‰, plus or minus a few tenths of one per mil, suggesting that raw materials probably come from Levantine area. Four samples are heavily enriched in 18O, and their chemical composition clearly shows that they were made with soda plant ash as flux. Isotopic and chemical data of Greek chert samples support the hypothesis of local production of the above samples. About half of the glass samples have chemical compositions, which allow their age to be constrained to the late Antique period. For the remaining glass, similarities with literature compositional groups are reported and discussed.

  17. 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.

  18. Interpreting isotopic analyses of microbial sulfate reduction in oil reservoirs

    Science.gov (United States)

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

    2013-12-01

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

  19. 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

  20. Removal method of fluorescent dyes as pretreatment for measurement of major ion concentrations and hydrogen and oxygen isotopic ratios

    International Nuclear Information System (INIS)

    Nakata, Kotaro; Hasegawa, Takuma; Kashiwaya, Koki; Kodama, Hiroki; Miyajima, Tohru

    2011-01-01

    The major ion concentration and isotope ratio of hydrogen and oxygen can provide important information for migration of groundwater. Sometimes, quantitative estimation of these chemical and isotopic characteristics of solution is necessary for groundwater containing fluorescent dyes, which are used in drilling borehole and tracer experiments. However, sometimes correct estimation is disturbed by dyes and they become a cause of troubles for measurement equipments. Thus development of method to remove dyes is required so that the characteristics of groundwater can be estimated without the negative effect of dyes on measurement or equipments. In this study, removal of four representative dyes (Uranin, Eosin, Naphthalenesulfonic acid sodium(NAP) and Amino G acid potassium salt (AG)) was investigated. Uranin and Eosin were found to be removed by non-ionic synthetic resin: HP2MG. 99.99% of the dyes were removed from initial solutions containing dyes with 10 mg/L after contact with resin, while the contact had little effect on ion concentrations and oxygen and hydrogen isotope ratios. Thus the chemical and isotopic characteristics of groundwater samples containing Uranin and Eosin can be obtained by using the HP2MG resin. On the other hand, the NAP and AG were found to be difficult to remove by the HP2MG resin but they were able to be removed by anion exchange resin (Dowex 1x8). Though contact of solution with Dowex 1x8 did not affect cation concentrations and hydrogen and oxygen isotope ratios, anion concentrations were changed by the contact. Therefore the Dowex 1x8 is only applicable to estimation of the cation concentrations and isotope ratio of hydrogen and oxygen. When both anion and cation concentrations from the samples were necessary, Uranin or Eosin were recommended as a tracer in drilling or tracer experiments. (author)

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

    Science.gov (United States)

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

    2017-03-01

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

  2. Kalahari groundwaters: Their hydrogen, carbon and oxygen isotopes

    International Nuclear Information System (INIS)

    Mazor, E.; Verhagen, B.T.; Sellschop, J.P.F.; Robins, N.S.; Hutton, L.G.

    1974-01-01

    Tritium and 14 C measurements have revealed several cases of post-nuclear bomb-test rain recharge of local groundwaters, along with values indicating recharge over larger, yet hydrologically active, time scales. In general, recharge seems to follow rain distribution in being more intense in the northern rather than in the southern Kalahari. Initial δ 13 C values vary over a wide range and reveal some correlation to pH and chemical composition of the water. They cannot be used to correct for fossil carbon dilution in 14 C-age calculations. Radiocarbon-deduced ages range from recent to 30,000 years. Stable hydrogen and oxygen isotopes indicate recharge from direct rain infiltration. (author)

  3. Significance of Isotopically Labile Organic Hydrogen in Thermal Maturation of Organic Matter

    Energy Technology Data Exchange (ETDEWEB)

    Arndt Schimmelmann; Maria Mastalerz

    2010-03-30

    Isotopically labile organic hydrogen in fossil fuels occupies chemical positions that participate in isotopic exchange and in chemical reactions during thermal maturation from kerogen to bitumen, oil and gas. Carbon-bound organic hydrogen is isotopically far less exchangeable than hydrogen bound to nitrogen, oxygen, or sulfur. We explore why organic hydrogen isotope ratios express a relationship with organic nitrogen isotope ratios in kerogen at low to moderate maturity. We develop and apply new techniques to utilize organic D/H ratios in organic matter fractions and on a molecular level as tools for exploration for fossil fuels and for paleoenvironmental research. The scope of our samples includes naturally and artificially matured substrates, such as coal, shale, oil and gas.

  4. Covariance of oxygen and hydrogen isotopic compositions in plant water: species effects

    International Nuclear Information System (INIS)

    Cooper, L.W.; DeNiro, M.J.

    1989-01-01

    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species—specific factors on leaf water enrichment of D and 18 O have not been studied for different plants growing together. Accordingly, to learn whether leaf water enrichment patterns and processes for D and 18 O are different for individual species growing under the same environmental conditions we tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show higher slopes (m in the leaf water equation °D = m ° 18 O + b) than in C 3 plants. We determined the relationships between the stable hydrogen (°D) and oxygen (° 18 O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. Slopes (m in the above leaf water equation) ranged from 1.50 to 3.21, compared to °8 for meteoric water, but differences in slope could not be attributed to carboxylation pathway (CAM vs. C 3 ) nor climate (coastal California vs. Sonoran Desert). Higher slopes were correlated with greater overall ranges of leaf water enrichment of D and 18 O. Water in plants with higher slopes also differed most from unaltered meteoric water. Leaf water isotope ratios in plants with lower slopes were better correlated with temperature and humidity. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes

  5. Growth patterns of an intertidal gastropod as revealed by oxygen isotope analysis

    Science.gov (United States)

    Bean, J. R.; Hill, T. M.; Guerra, C.

    2007-12-01

    The size and morphology of mollusk shells are affected by environmental conditions. As a result, it is difficult to assess growth rate, population age structure, shell morphologies associated with ontogenetic stages, and to compare life history patterns across various environments. Oxygen isotope analysis is a useful tool for estimating minimum ages and growth rates of calcium carbonate secreting organisms. Calcite shell material from members of two northern California populations of the intertidal muricid gastropod Acanthinucella spirata was sampled for isotopic analysis. Individual shells were sampled from apex to margin, thus providing a sequential record of juvenile and adult growth. A. spirata were collected from a sheltered habitat in Tomales Bay and from an exposed reef in Bolinas. Abiotic factors, such as temperature, wave exposure, and substrate consistency, and biotic composition differ significantly between these sites, possibly resulting in local adaptations and variation in life history and growth patterns. Shell morphology of A. spirata changes with age as internal shell margin thickenings of denticle rows associated with external growth bands are irregularly accreted. It is not known when, either seasonally and/or ontogentically, these thickenings and bands form or whether inter or intra-populational variation exists. Preliminary results demonstrate the seasonal oxygen isotopic variability present at the two coastal sites, indicating 5-6 degC changes from winter to summertime temperatures; these data are consistent with local intertidal temperature records. Analysis of the seasonal patterns indicate that: 1) differences in growth rate and seasonal growth patterns at different ontogenetic stages within populations, and 2) differences in growth patterns and possibly age structure between the two A. spirata populations. These findings indicate that isotopic analyses, in addition to field observations and morphological measurements, are necessary to

  6. Temperature measurements of Transdanubian Mesozoic rocks by the oxygen isotope method

    International Nuclear Information System (INIS)

    Cornides, I.; Csaszar, G.; Haas, J.; Jochane Edelenyi, E.

    1979-01-01

    Subjected to paleotemperature measurements with the use of oxygen and carbon isotopes were Upper Triassic, Jurassic and Cretaceous sedimentary rocks and their fossils from the Transdanubian Central Mountains, the Mecsek and the Villany Mts. In determining formation temperature, an important parameter of the environment of formation, the authors relied on the fact that the oxygen isotope composition of calcium carbonate precipitating from its aqueous solution deviates, in dependence on the temperature of the solution concerned, from that of the water. Consequently, the temperature of the water of the one-time seas must have been recorded by the 18 O/ 16 O ratio in the calcite of fossils or sediments. The results reported indicate smaller changes in temperature as compared to international results. In the Jurassic the values of temperature remain consistently below those quoted for Swiss and French territories, being around the values reported from/sroe/thern Germany. These u curves have their maxima in the Toarcian, Aalenian, sediments for which unfortunately no Hungarian results are available. The few results of Cretaceous belemnites are values higher than their international counterparts. The high temperature value obtained for the Albian correlates very well with the formation of rocks known from this stratigraphic stage (red clays, bauxites). (A.L.)

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. Constraints on the nature of the projectile using siderophile elements and triple-oxygen isotopes: Zhamanshin impact structure, Kazakhstan

    Czech Academy of Sciences Publication Activity Database

    Jonášová, Šárka; Ackerman, Lukáš; Žák, Karel; Skála, Roman; Magna, T.; Pack, A.; Deutsch, A.

    2016-01-01

    Roč. 51, SI, Supplement 1 (2016), A358-A358 ISSN 1086-9379. [Annual Meeting of the Meteoritical Society /79./. 07.08.2016-12.08.2016, Berlin] Institutional support: RVO:67985831 Keywords : impact glass * irghizites * geochemistry * meteoritic component * siderophile elements * osmium isotopes * triple-oxygen Isotopes * Zhamanshin Subject RIV: DD - Geochemistry

  12. Oxygen isotope studies of the Salton Sea geothermal field

    International Nuclear Information System (INIS)

    Olson, E.R.

    1978-01-01

    Interbedded shales and sandstones were drilled to a depth of 1588 metres in Sinclair Number Four Well, Salton Sea Geothermal Field. Bottom hole temperatures are approximately 290 0 C. The oxygen dels of hydrothermal and detrital calcite have a systematic relationship at any depth in the geothermal reservoir. Typical values are: vein calcite, +6 0 / 00 ; calcite in white sandstone, +10 0 / 00 ; calcite in dark gray shale, +11 0 / 00 ; calcite in light gray shale, +17 0 / 00 ; calcite in red-brown shale, +20 0 / 00 . This succession represents decreasing water-rock interaction that is also indicated by the clay mineralogy of the shales. Permeability has a marked effect on the equilibration of water and rocks at any given temperature. Original differences in permeability have resulted in partial preservation of original detrital sedimentary compositions. The fluids in the Salton Sea Geothermal Field are probabaly partially evaporated Colorado River water, and their oxygen del values vary as much as 4 0 / 00 throughout the field. Truesdell's (1974) data suggest that dissolved salts may make the water oxygen activity del as much as 6 0 / 00 greater than the concentration del in the geothermal reservoir. Such an uncertainty is a serious impediment to precise isotope geothermometry in this system.(auth.)

  13. 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.

  14. Discrepancies between measured changes of radiobiological hypoxic fraction and oxygen tension monitoring using two assay systems

    International Nuclear Information System (INIS)

    Sasai, K.; Brown, J.M.

    1994-01-01

    This study was conducted to assess the ability of computerized pO 2 histography to measure changes in tumor oxygenation produced by low oxygen breathing. Female syngeneic C3H/Km mice bearing SCC VII/St carcinomas were used in these experiments. Changes in tumor oxygenation produced by the mice breathing 10% oxygen were assessed with computerized pO2 histography, 3 H-misonidazole binding, and the paired survival curve assay of radiosensitivity. The hypoxic cell fraction of the tumors in mice breathing 10% oxygen was 3.1 times higher than that of tumors in mice breathing normal air determined by an in vivo-in vitro clonogenic assay. Binding of radiolabeled misonidazole to the tumors in mice breathing 10% oxygen was also significantly higher than that to tumors in mice breathing normal air (p 2 value for the tumor. The number of pO 2 readings lower than 5 mmHg in the tumor was not affected by the 10% oxygen breathing. These findings indicate that increases in radiobiological hypoxic fraction produced by lower blood oxygen levels may not correlate well with the results of polarographic measurements of tumor pO 2 levels. 29 refs., 4 figs., 1 tab

  15. Isotopic mixing in carbon monoxide catalyzed by zinc oxide

    International Nuclear Information System (INIS)

    Carnisio, G.; Garbassi, F.; Petrini, G.; Parravano, G.

    1978-01-01

    The rate of the isotopic mixing in CO has been studied at 300 0 C, for CO partial pressures from 6 to 100 Torr and a total pressure of 250 Torr on ZnO catalysts. Significant deviations from a first-order rate in p/sub co/ were found. The rate of oxygen exchange between ZnO and gas-phase CO was also measured and the results were employed to calculate the fraction of surface sites active for the CO isotopic mixing. Values on the order of 0.001 were found. The turnover rate and surface collision efficiency varied between 0.7 and 107 min -1 and 0.13 and 2.24 x 10 -8 , respectively. H 2 additions to CO increased the rate of isotopic mixing, whereas the rate of H 2 + D 2 was decreased by the presence of CO. The H 2 + D 2 rate was faster than that of isotopic mixing in CO, but as the ratio p/sub H 2 //p/sub co/ decreased the rates became about equal. It is argued that on ZnO samples, in which the rate of CO isotopic mixing and the rate of ZnO--CO oxygen exchange were influenced in a similar manner by the CO pressure, the isotopic mixing in CO took place via the ZnO oxygen, while oxide oxygen participation was not kinetically significant for ZnO samples in which the two reactions had different kinetics. The crucial factor controlling the path followed by the isotopic mixing in CO seems to be the surface Zn/O ratio, since a close correlation was found between the former and the reaction kinetics of the CO isotopic mixing reaction. Solid-state conditions which may vary the Zn/O surface ratio (foreign additions) are indicated. The implications of these findings to the problem of product selectivity from CO-H 2 mixtures reacting on metal oxide surfaces are discussed

  16. Measurement of Soot Volume Fraction and Temperature for Oxygen-Enriched Ethylene Combustion Based on Flame Image Processing

    Directory of Open Access Journals (Sweden)

    Weijie Yan

    2017-05-01

    Full Text Available A method for simultaneously visualizing the two-dimensional distributions of temperature and soot volume fraction in an ethylene flame was presented. A single-color charge-coupled device (CCD camera was used to capture the flame image in the visible spectrum considering the broad-response spectrum of the R and G bands of the camera. The directional emissive power of the R and G bands were calibrated and used for measurement. Slightly increased temperatures and reduced soot concentration were predicted in the central flame without self-absorption effects considered, an iterative algorithm was used for eliminating the effect of self-absorption. Nine different cases were presented in the experiment to demonstrate the effects of fuel mass flow rate and oxygen concentration on temperature and soot concentration in three different atmospheres. For ethylene combustion in pure-air atmosphere, as the fuel mass flow rate increased, the maximum temperature slightly decreased, and the maximum soot volume fraction slightly increased. For oxygen fractions of 30%, 40%, and 50% combustion in O2/N2 oxygen-enhanced atmospheres, the maximum flame temperatures were 2276, 2451, and 2678 K, whereas combustion in O2/CO2 atmospheres were 1916, 2322, and 2535 K. The maximum soot volume fractions were 4.5, 7.0, and 9.5 ppm in oxygen-enriched O2/N2 atmosphere and 13.6, 15.3, and 14.8 ppm in oxygen-enriched O2/CO2 atmosphere. Compared with the O2/CO2 atmosphere, combustion in the oxygen-enriched O2/N2 atmosphere produced higher flame temperature and larger soot volume fraction. Preliminary results indicated that this technique is reliable and can be used for combustion diagnosis.

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

    Science.gov (United States)

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

    2015-06-01

    Mesoscale eddies in Oxygen Minimum Zones (OMZs) have been identified as important fixed nitrogen (N) loss hotspots that may significantly impact both the global rate of N-loss as well as the ocean's N isotope budget. They also represent "natural tracer experiments" with intensified biogeochemical signals that can be exploited to understand the large-scale processes that control N-loss and associated isotope effects (ɛ; the ‰ deviation from 1 in the ratio of reaction rate constants for the light versus heavy isotopologues). We observed large ranges in the concentrations and N and O isotopic compositions of nitrate (NO3-), nitrite (NO2-), and biogenic N2 associated with an anticyclonic mode-water eddy in the Peru OMZ during two cruises in November and December 2012. In the eddy's center where NO3- was nearly exhausted, we measured the highest δ15N values for both NO3- and NO2- (up to ~70‰ and 50‰) ever reported for an OMZ. Correspondingly, N deficit and biogenic N2-N concentrations were also the highest near the eddy's center (up to ~40 µmol L-1). δ15N-N2 also varied with biogenic N2 production, following kinetic isotopic fractionation during NO2- reduction to N2 and, for the first time, provided an independent assessment of N isotope fractionation during OMZ N-loss. We found apparent variable ɛ for NO3- reduction (up to ~30‰ in the presence of NO2-). However, the overall ɛ for N-loss was calculated to be only ~13-14‰ (as compared to canonical values of ~20-30‰) assuming a closed system and only slightly higher assuming an open system (16-19‰). Our results were similar whether calculated from the disappearance of DIN (NO3- + NO2-) or from the appearance of N2 and changes in isotopic composition. Further, we calculated the separate ɛ values for NO3- reduction to NO2- and NO2- reduction to N2 of ~16-21‰ and ~12‰, respectively, when the effect of NO2- oxidation could be removed. These results, together with the relationship between N and O of NO

  18. 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.

  19. Isotopes of carbon and oxygen in the carbonate impurities of coal have potential as palaeoenvironmental indicators

    International Nuclear Information System (INIS)

    Verhagen, B.T.; Falcon, R.M.

    1990-01-01

    The nature and systematics of impurities such as carbonates need to be established in order to understand their provenance in coal seams with reference to mining, beneficiation and ultimately their elimination or reduction. To this end, mineralogical and carbon-13 and oxygen-18 isotopic studies were undertaken on carbonate occurrences in coal from the eastern Transvaal highveld. Isotopic variations of considerable amplitude and individual values of extreme ''lightness'' are to be found in the carbonates in coal of the Witbank and adjacent basins. The observed isotopic ratios have a clear bearing on the nature and origins of the carbonates. 1 tab., 1 fig

  20. Assessing Pyrite-Derived Sulfate in the Mississippi River with Four Years of Sulfur and Triple-Oxygen Isotope Data.

    Science.gov (United States)

    Killingsworth, Bryan A; Bao, Huiming; Kohl, Issaku E

    2018-05-17

    Riverine dissolved sulfate (SO 4 2- ) sulfur and oxygen isotope variations reflect their controls such as SO 4 2- reduction and reoxidation, and source mixing. However, unconstrained temporal variability of riverine SO 4 2- isotope compositions due to short sampling durations may lead to mischaracterization of SO 4 2- sources, particularly for the pyrite-derived sulfate load. We measured the sulfur and triple-oxygen isotopes (δ 34 S, δ 18 O, and Δ' 17 O) of Mississippi River SO 4 2- with biweekly sampling between 2009 and 2013 to test isotopic variability and constrain sources. Sulfate δ 34 S and δ 18 O ranged from -6.3‰ to -0.2‰ and -3.6‰ to +8.8‰, respectively. Our sampling period captured the most severe flooding and drought in the Mississippi River basin since 1927 and 1956, respectively, and a first year of sampling that was unrepresentative of long-term average SO 4 2- . The δ 34 S SO4 data indicate pyrite-derived SO 4 2- sources are 74 ± 10% of the Mississippi River sulfate budget. Furthermore, pyrite oxidation is implicated as the dominant process supplying SO 4 2- to the Mississippi River, whereas the Δ' 17 O SO4 data shows 18 ± 9% of oxygen in this sulfate is sourced from air O 2 .

  1. Mass independent isotope effects and their observations in nature

    International Nuclear Information System (INIS)

    Thiemens, M.H.

    2002-01-01

    In 1983, Thiemens and Heidenreich reported the first chemically produced mass independent isotope effect. A significant feature of the fractionation was that it identically produced the isotopic relation observed in the calcium-aluminum inclusions in the Allende meteorite. This δ 17 O=δ 18 O composition had previously been thought to represent a nucleosynthetic component as no chemical process was capable of producing a mass independent isotopic composition. It now appears nearly certain that the meteoritic oxygen isotopic anomalies were produced by chemical, rather than nuclear, processes. Since oxygen is the major element in stony planets this represents a major event in the formation of the solar system. In a recent review (Thiemens, 1999), it has been shown that mass independent isotopic compositions are pervasive in the Earth's atmosphere. Molecules which have been demonstrated to possess mass independent isotopic compositions include: O 2 , O 3 , CO 2 , CO, and N 2 O. In each case, the specific nature of the mass independent isotopic composition has provided details of their atmospheric chemistry that could not have been obtained by any other measurement technique. Most recently, solid materials have been observed to possess mass independent isotopic composition. In this paper, these observations are briefly discussed. These solid reservoirs include: 1) carbonates and sulphates from Mars, 2) terrestrial aerosol sulphate, 3) sulphides and sulphates from the Earth, ranging in time from 3.8 to 2.2 billion years before present, 4) sulphates from the Namibian desert and 5) the Antartic Dry Valleys. The information obtained from these measurements is extraordinarily wide ranging, extending from understanding the history of Martian atmosphereregolith interaction to the evolution of the oxygen in the Earth's earliest atmosphere. As was the case for gas phase species, this information and insight could not have been obtained by any other measurement technique

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

    Science.gov (United States)

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

    2004-01-01

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

  3. Permafrost oxygen isotope ratios and chronology of three cores from Antarctica

    International Nuclear Information System (INIS)

    Stuiver, M.; Yang, I.C.; Denton, G.H.

    1976-01-01

    It is stated that permafrost core sediments, associated with the last intrusion of the Ross Ice Shelf in the New Harbour region, were deposited in marine (0 - 85 m deep) as well as freshwater environments (100 - 125 m). Oxygen isotope ratio measurements on these cores provide palaeoclimatic information and show that the extension of the Ross Ice Shelf predates 150,000 yr BP, whereas the radiocarbon date of its retreat is about 5,800 yr b.p. (author)

  4. 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...

  5. 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.

  6. The oxygen isotope effect on the in-plane penetration depth in cuprate superconductors

    International Nuclear Information System (INIS)

    Khasanov, R; Shengelaya, A; Morenzoni, E; Conder, K; Savic, I M; Keller, H

    2004-01-01

    Muon spin rotation (μSR) studies of the oxygen isotope ( 16 O/ 18 O) effect (OIE) on the in-plane magnetic field penetration depth λ ab in cuprate high-temperature superconductors (HTS) are presented. First, the doping dependence of the OIE on the transition temperature T c in various HTS is briefly discussed. It is observed that different cuprate families show similar doping dependences of the OIE on T c . Then, bulk μSR, low-energy μSR, and magnetization studies of the total and site-selective OIE on λ ab are described in some detail. A substantial OIE on λ ab was observed in various cuprate families at all doping levels, suggesting that cuprate HTS are non-adiabatic superconductors. The experiments clearly demonstrate that the total OIE on T c and λ ab arise from the oxygen sites within the superconducting CuO 2 planes, demonstrating that the phonon modes involving the movement of planar oxygen are dominantly coupled to the supercarriers. Finally, it is shown that the OIE on T c and λ ab exhibit a relation that appears to be generic for different families of cuprate HTS. The observation of these unusual isotope effects implies that lattice effects play an essential role in cuprate HTS and have to be considered in any realistic model of high-temperature superconductivity

  7. Preservation of Fe Isotope Proxies in the Rock Record

    Science.gov (United States)

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

    2005-12-01

    Fe ratios for re-crystallized magnetite from BIFs of the Biwabik iron formation that have apparent oxygen-isotope (quartz-magnetite) temperatures between 270 and 800 oC span a significant portion of the range measured in lower-grade BIFs from South Africa and Australia. d56Fe values for Biwabik magnetite vary from -0.2 to +0.7 per mil, whereas magnetite from the Dales Gorge member of the Brockman iron formation and the Kuruman iron formation has d56Fe values that lie between -1.2 and +1.3 per mil. Iron isotope fractionations between magnetite and Fe silicates (greenalite, hedenbergite, and fayalite) in the Biwabik iron formation regularly decrease with increasing oxygen-isotope temperatures, approaching the zero fractionation expected at igneous temperatures; apparent magnetite-Fe silicate fractionations range from +0.2 per mil at 650 oC to +0.5 per mil at 300 oC, lying close to those predicted using the revised beta factors of Polyakov et al. (2005, Goldschmidt). During closed-system Fe isotope exchange during metamorphism, the overall range in d56Fe values for magnetite will remain relatively constant, although it may shift to higher d56Fe values relative to primary (low-temperature) magnetite due to the non-zero magnetite-Fe silicate fractionation factor at moderate temperature ranges. If the mineral parageneis is known, and some assumptions regarding primary mineralogy can be made, these small corrections may be made to successfully infer the original Fe isotope compositions of sedimentary minerals and rocks that have been subjected to metamorphism.

  8. Stable isotopic investigations of early development in extant and fossil chambered cephalopods I. Oxygen isotopic composition of eggwater and carbon isotopic composition of siphuncle organic matter in Nautilus

    Science.gov (United States)

    Crocker, Kimberley C.; DeNiro, Michael J.; Ward, Peter D.

    1985-12-01

    Eggwaters from the chambered cephalopod Nautilus are depleted in both 18O and deuterium relative to ambient seawater. Eggwaters from six other species, including the related chambered cephalopod Sepia, do not show such depletion. These observations indicate that the previously observed step towards more positive δ 18O values in calcium carbonate laid down after Nautilus hatches, relative to carbonate precipitated prior to hatching, can be explained by equilibration of the carbonate with water in the egg before hatching and with seawater after hatching. The presence of an oxygen isotope difference between eggwater and seawater for Nautilus and its absence for Sepia suggest that hatching will be recorded in the δ 18O values of shell carbonates for some but not all extinct and extant chambered cephalopods. The δ 13C values of the organic fraction of the siphuncle in Nautilus do not show any consistent pattern with regard to the time of formation before or after hatching. This observation suggests that the minimum in δ 13C values previously observed for calcium carbonate precipitated after Nautilus hatches is not caused by a change in food sources once the animal becomes free-swimming, as has been suggested.

  9. 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.

  10. Isotope exchange in oxide-containing catalyst

    Science.gov (United States)

    Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

    1989-01-01

    A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

  11. The isotopic composition of valves and organic tissue of diatoms grown in steady state cultures under varying conditions of temperature, light and nutrients. Implications for the interpretation of oxygen isotopes from sedimentary biogenic opal as proxies of environmental variations

    Energy Technology Data Exchange (ETDEWEB)

    Kowalczyk, K

    2006-05-15

    The oxygen isotopes of diatomaceous silica from marine and freshwater sediments are frequently used as indicators of the palaeotemperature development, particularly in cases where calcareous microfossils are rare or absent. With regard to terrestrial waters it is unknown whether or not palaeotemperature scale can be used in a limnic ecosystem. Due to the fact that the seasonal variations in lakes are larger than in oceans, specific problems arise when working with freshwater sediments. Thus, an understanding of the contribution of the various factors (e.g. temperature, light nutrients, competition) influencing the formation of isotope signals in biogenic opal is a prerequisite for the accurate interpretation of environmental processes. Since it is impossible to examine the influence of a single parameter under natural ecosystem conditions due to permanent changes of the environment, laboratory experiments with single diatom species are needed. Therefore, the aim of this study was to investigate the correlation between the oxygen isotope variations in biogenic opal and different environmental parameters using steady state cultures with diatoms. It should be examined whether or not the different diatom species grown under identical conditions show equal oxygen isotope ratios (species relationship), if variations of the water temperature induce variations of the oxygen isotope ratio (relationship with temperature), variable parameters such as light intensity and nitrate concentration influence the isotope ratio, and if vital effects (e.g. growth rate) lead to variations of the oxygen isotope ratio. (orig.)

  12. The isotopic composition of valves and organic tissue of diatoms grown in steady state cultures under varying conditions of temperature, light and nutrients. Implications for the interpretation of oxygen isotopes from sedimentary biogenic opal as proxies of environmental variations

    International Nuclear Information System (INIS)

    Kowalczyk, K.

    2006-05-01

    The oxygen isotopes of diatomaceous silica from marine and freshwater sediments are frequently used as indicators of the palaeotemperature development, particularly in cases where calcareous microfossils are rare or absent. With regard to terrestrial waters it is unknown whether or not palaeotemperature scale can be used in a limnic ecosystem. Due to the fact that the seasonal variations in lakes are larger than in oceans, specific problems arise when working with freshwater sediments. Thus, an understanding of the contribution of the various factors (e.g. temperature, light nutrients, competition) influencing the formation of isotope signals in biogenic opal is a prerequisite for the accurate interpretation of environmental processes. Since it is impossible to examine the influence of a single parameter under natural ecosystem conditions due to permanent changes of the environment, laboratory experiments with single diatom species are needed. Therefore, the aim of this study was to investigate the correlation between the oxygen isotope variations in biogenic opal and different environmental parameters using steady state cultures with diatoms. It should be examined whether or not the different diatom species grown under identical conditions show equal oxygen isotope ratios (species relationship), if variations of the water temperature induce variations of the oxygen isotope ratio (relationship with temperature), variable parameters such as light intensity and nitrate concentration influence the isotope ratio, and if vital effects (e.g. growth rate) lead to variations of the oxygen isotope ratio. (orig.)

  13. Temperatures and isotopic evolution of silicic magmas, Taupo Volcanic Zone and Coromandel, New Zealand

    International Nuclear Information System (INIS)

    Blattner, P.; Rui-Zhong H.; Graham, I.J.; Houston-Eleftheriadis, C.

    1996-01-01

    A new set of oxygen and strontium isotope data on rhyolitic lavas and ignimbrites of the Taupo Volcanic Zone (TVZ) and the Coromandel Peninsula provides new limits for petrogenic models. For oxygen isotopes, the rock matrix is frequently altered, so that values for magma need to be phenocryst based. Within TVZ a trend towards more negative δ 1 8O values for more recent magmas appears likely (average before about 1 Ma and for Coromandel near 8.0 per mille; after 1 Ma near 7.5 per mille). This could indicate the gradual removal of supracrustal contaminants from the zones of magma accumulation and extrusion. Similar trends within Coromandel cannot yet be resolved. A generally positive correlation is found for oxygen and strontium isotopes of magmas. Most magmas have a limited range of isotopic values, which then becomes a fingerprint (e.g., the Mamaku, Matahina, and Waiotapu Ignimbrites). A narrow range of eruption temperatures of 880 ± 60 o C is derived from quartz-plagioclase fractionations of 0.98 ± 0.25 per mille δ 1 8O values of quartz and feldspar phenocrysts are sufficiently low to suggest interaction between surface water and magma. However, large negative oxygen isotope anomalies (such as known from Yellowstone), could be no more than partially concealed by the isotopically less depleted meteoric water of New Zealand, and have not yet been found in New Zealand. (authors). 45 refs., 6 figs., 3 tabs

  14. Water relations link carbon and oxygen isotope discrimination to phloem sap sugar concentration in eucalyptus globulus

    International Nuclear Information System (INIS)

    Cernusak, L.A.; Farquhar, G.D.; Arthur, D.J; Pate, J.S.

    2002-01-01

    Full text: The carbon isotope ratio of phloem sap sugars has been previously observed to correlate strongly with the phloem sap sugar concentration in Eucalyptus globulus. We hypothesized that the correspondence between these two parameters results from co-linearity in their responses to variation in plant water potential. Carbon isotope discrimination is expected to decrease with decreasing plant water potential due to the influence of stomatal conductance on the ratio of intercellular to ambient CO 2 , concentrations (c 1 /c a ). Conversely, we expected the phloem sap sugar concentration to increase with decreasing plant water potential, thereby maintaining positive turgor pressure within the sieve tubes. The study comprised 40 individual Eucalyptus globulus trees growing in three plantations situated on opposing ends of a rainfall gradient in southwestern Australia. A strong correlation was observed between the carbon isotope ratio in phloem sap sugars and phloem sap sugar concentration. Carbon isotope discrimination correlated positively with shoot water potential, whereas phloem sap sugar concentration correlated negatively with shoot water potential. The relationship between carbon isotope discrimination measured in phloem sap sugars collected from the stem and c 1 /c a measured instantaneously on subtending leaves was close to that theoretically predicted. Accordingly, a strong, negative relationship was observed between instantaneous c 1 /c a and the phloem sap sugar concentration. Oxygen isotope discrimination in phloem sap sugars also correlated strongly with phloem sap sugar concentration. A theoretical model suggested that the observed variation in stomatal conductance was sufficient to account for the variation observed in oxygen isotope discrimination across the study. Results strongly support the contention that water relations form a mechanistic link between phloem sap sugar concentration and both instantaneous and integrated measures of the

  15. Submaximal oxygen uptake kinetics, functional mobility, and physical activity in older adults with heart failure and reduced ejection fraction

    OpenAIRE

    Hummel, Scott L; Herald, John; Alpert, Craig; Gretebeck, Kimberlee A; Champoux, Wendy S; Dengel, Donald R; Vaitkevicius, Peter V; Alexander, Neil B

    2016-01-01

    Background Submaximal oxygen uptake measures are more feasible and may better predict clinical cardiac outcomes than maximal tests in older adults with heart failure (HF). We examined relationships between maximal oxygen uptake, submaximal oxygen kinetics, functional mobility, and physical activity in older adults with HF and reduced ejection fraction. Methods Older adults with HF and reduced ejection fraction (n = 25, age 75 ? 7 years) were compared to 25 healthy age- and gender-matched cont...

  16. The impact of moisture sources on the oxygen isotope composition of precipitation at a continental site in central Europe

    Science.gov (United States)

    Krklec, Kristina; Domínguez-Villar, David; Lojen, Sonja

    2018-06-01

    The stable isotope composition of precipitation records processes taking place within the hydrological cycle. Potentially, moisture sources are important controls on the stable isotope composition of precipitation, but studies focused on this topic are still scarce. We studied the moisture sources contributing to precipitation at Postojna (Slovenia) from 2009 to 2013. Back trajectory analyses were computed for the days with precipitation at Postojna. The moisture uptake locations were identified along these trajectories using standard hydrometeorological formulation. The moisture uptake locations were integrated in eight source regions to facilitate its comparison to the monthly oxygen isotope composition (δ18O values) of precipitation. Nearly half of the precipitation originated from continental sources (recycled moisture), and >40% was from central and western Mediterranean. Results show that moisture sources do not have a significant impact on the oxygen isotope composition at this site. We suggest that the large proportion of recycled moisture originated from transpiration rather than evaporation, which produced water vapour with less negative δ18O values. Thus the difference between the oceanic and local vapour source was reduced, which prevented the distinction of the moisture sources based on their oxygen isotope signature. Nevertheless, δ18O values of precipitation are partially controlled by climate parameters, which is of major importance for paleoclimate studies. We found that the main climate control on Postojna δ18O values of precipitation is the surface temperature. Amount effect was not recorded at this site, and the winter North Atlantic Oscillation (NAO) does not impact the δ18O values of precipitation. The Western Mediterranean Oscillation (WeMO) was correlated to oxygen stable isotope composition, although this atmospheric pattern was not a control. Instead we found that the link to δ18O values results from synoptic scenarios affecting We

  17. An X-ray, EPMA, and oxygen isotope study of vermiculitized micas in the ultramafic rocks at Askos, Macedonia, Greece

    International Nuclear Information System (INIS)

    Tsirambides, A.; Michailidis, K.

    1999-01-01

    40% with the biotite percentage dominating in the mixed phase. Lower abundances (20-40%) of biotite/smectite and chlorite/vermiculite occur in both finer fractions (2-20 and <2 μm) of all vermiculitic samples. Vermiculite/smectite is very abundant in the <2 μm fractions of most vermiculitic samples. The DTA curves of the samples analyzed are characteristic of Mg-vermiculites. The electron microprobe analyses show a gradual K leaching from precursor mica with increasing degree of weathering. Oxygen isotope results confirm this assumption. Initially, hydrothermal fluids derived from the neighboring granitic intrusions, were responsible for the micatization of the primary minerals of the ultramafic bodies. Hydrothermal activity was also responsible for the partial formation of corrensite. Consequently, water moving downwards was very important for the formation of the vermiculite and other clay mineral mixed-layer phases through the alteration of micas and chlorite. The low relief and the long-lasting tectonic stability of the area were essential for the development of a significant thickness of the vermiculite zones. These vermiculites have properties desirable in certain building, agriculture, and horticulture products. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  18. Isotopes in the earth sciences

    Energy Technology Data Exchange (ETDEWEB)

    Bowen, Robert

    1988-01-01

    This book examines significant aspects of isotope applications in geology and geochemistry commencing with basic matters, such as atomic structure, stable nuclides and their fractionation, as well as the various decay modes of unstable nuclides. Modern mass spectrometry techniques including electrostatic tandem accelerators are followed by a review of radioisotope dating technology. The relatively new method using the rare earth elements samarium and neodymium are covered. Other geochronometers, applicable to both rocks and minerals not dateable otherwise, are included. A review is given of isotopes in the atmosphere, hydrosphere and lithosphere of the Earth. Those of oxygen and hydrogen together with the cosmogenic radionuclides tritium and radiocarbon are discussed in relation to the biosphere. The role of isotopes of carbon, nitrogen and sulphur is described and extended to fossil fuels and rocks as well as meteorites. Related themes such as Phanerozoic oceans, oceanic palaeothermometry, snow and ice stratigraphy and geothermal waters are covered. The field of isotopic palaeoecology is discussed. Radioactive wastes, their accumulation, dangers and disposal are investigated with especial reference to their environmental impacts.

  19. Metagenomic analysis of size-fractionated picoplankton in a marine oxygen minimum zone

    OpenAIRE

    Ganesh, Sangita; Parris, Darren J; DeLong, Edward F; Stewart, Frank J

    2013-01-01

    Marine oxygen minimum zones (OMZs) support diverse microbial communities with roles in major elemental cycles. It is unclear how the taxonomic composition and metabolism of OMZ microorganisms vary between particle-associated and free-living size fractions. We used amplicon (16S rRNA gene) and shotgun metagenome sequencing to compare microbial communities from large (>1.6 μm) and small (0.2–1.6 μm) filter size fractions along a depth gradient in the OMZ off Chile. Despite steep vertical redox ...

  20. Oxygen isotope mapping and evaluation of paleo-hydrothermal systems associated with synvolcanic intrusion and VMS deposits

    International Nuclear Information System (INIS)

    Taylor, B.E

    2001-01-01

    Whole-rock oxygen isotope mapping provides a useful method for the delineation and quantitative evaluation of paleo-hydrothermal systems associated with syn-volcanic intrusions and volcanic-associated massive sulfide (VMS) deposits. During the course of a four-year study of regional alteration systems associated with VMS Deposits, four syn-volcanic intrusive complexes in Canada were mapped using stable isotope techniques. The complexes included Noranda, Quebec; Clifford-Ben Nevis, Ontario; Snow Lake, Manitoba, and Sturgeon Lake, Ontario. This study was regional in extent, involving large areas and large numbers of whole-rock samples: Noranda (625 km 2 ;≥600 samples, plus others (total = 1198); Sturgeon Lake (525 km 2 ; 452 samples); Clifford-Ben Nevis (160 km 2 ; 251 samples); and Snow Lake (84 km 2 ; 575 samples). Isotopic data on whole-rock carbonates and hydrous minerals were also collected. The regional isotopic studies were carried out in concert with other studies on mineral assemblages and mineral composition, and on associated intrusive and extrusive rocks. The Clifford-Ben Nevis area was selected as a control area, in as much as it contains no known VMS deposits; all other areas are well-known, productive VMS districts. Oxygen isotope maps are, in a sense, thermal maps, illustrating the paleo-distribution of heat and fluids, and offering a potential aid to exploration. The isotopic data may be contoured to reveal zones of 18 O depletion and enrichment, relative to unaltered rocks. Zones of δ 18 O≤60% comprise rocks that have reacted with seawater at high (e.g., 300+ o C) temperatures. The volume of foot-wall rocks isotopically-depleted by water/rock interaction during the life of one or more episodes of submarine hydrothermal activity is proportional to the amount of heat available from the syn-volcanic intrusive center. These altered rocks comprise the reaction zone often inferred to have supplied metals and other constituents for the VMS deposits