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Sample records for 18o fractionation factors

  1. Factors determining δ13C and δ18O fractionation in aragonitic otoliths of marine fish

    NASA Astrophysics Data System (ADS)

    Thorrold, Simon R.; Campana, Steven E.; Jones, Cynthia M.; Swart, Peter K.

    1997-07-01

    Fish otoliths are aragonitic accretions located within the inner ear of teleost fish. The acellular nature of otoliths, along with taxon-specific shapes, chronological growth increments, and abundance in the fossil record suggest that the stable isotope chemistry of these structures may be unique recorders of environmental conditions experienced by fish in both modern and ancient water masses. To assess the factors determining δ 13C and δ 18O fractionation in fish otoliths, we reared Atlantic croaker ( Micropogonias undulatus) larvae under controlled environmental conditions. Metabolic effects apparently generated large isotopic disequilibria in the δ 13C values of M. undulatus otoliths. We found evidence of a negative regression between δ 13C- carbonate-δ 13C water (δ 13C) and temperature: δ 13C = -1.78 - 0.18 T °C However, this relationship was aliased to a degree by a positive correlation between δ 13C and somatic growth and otolith precipitation rates. Oxygen isotopes were deposited close to equilibrium with the ambient water. The relationship between temperature and the 18O/ 16O fractionation factor (α) was determined empirically to be: 1000 ln α = 18.56(10 3T K -1) - 32.54 The fractionation factor was not affected by either otolith precipitation or fish growth rates. Reconstruction of water temperature histories should, therefore, be possible from the δ 18O values of M. undulatus otoliths with a precision of 1°C, providing the δ 18O of the ambient water can be estimated.

  2. Experimental studies of alunite: I. 18O-16O and D-H fractionation factors between alunite and water at 250-450°C

    USGS Publications Warehouse

    Stoffregen, Roger E.; Rye, Robert O.; Wasserman, Michael D.

    1994-01-01

    We have determined oxygen and hydrogen isotope fractionation factors between alunite and water over a temperature range of 250-450??C by reacting synthetic natroalunite with 0.7 m K2SO4 -0.1 to 0.65 m H2SO4 solutions to produce K-rich alunite. From 88 to 95% alkali and isotope exchange were observed in most of these experiments, and the partial equilibrium method was used to compute equilibrium fractionation factors. Least-squares fits of the data give 103 In ??alunite(so4)-H2O = 3.09 ( 106 T2 (K)) - 2.94 and 103 In ??alunite(OH)-H2O = 2.28 ( 106 T2 (K)) - 3.90. The intramineral 18O- 16O fractionation factor 103 In ??alunite(so4-OH site) is given by the expression 0.8 ( 106 T2 (K)) + 0.96. The alunite-water D-H fractionation factor ranges from -19 at 450??C to -6 at 250??C and does not appear to be strongly dependent on temperature. Runs with alkali exchange in the opposite direction were used to obtain 18O- 16O and D-H fractionation factors between natroalunite (mol% Na = 70-75) and water at 350-450??C. These indicate that mol% Na has negligible effect on the fractionation factors over this temperature range. Measured 18O-16O and D-H fractionation factors between alunite and 1.0 m KCl -0.5 m H2SO4 fluids also agree within 2?? with the values obtained from the K2SO4-H2SO4 fluids. However, experiments with alunite and distilled water at 400??C gave a value of 103 In ??alunite(SO4)-H2O of 0.0, compared with a value of 3.9 obtained at this temperature with K2SO4- and H2SO4-bearing fluids. This suggests that changes in fluid composition can affect alunite-water 18O-16O fractionation factors. Reconnaissance experiments with fine-grained natural natroalunite demonstrate that alunite-water D-H exchange can occur by hydrogen diffusion, although this process is generally not significant in the experiments with coarser grained synthetic alunites. ?? 1994.

  3. Factors Influencing the Stable Oxygen and Hydrogen Isotopic Composition (δ 18O and δ D) of a Subarctic Freshwater Lake Ecosystem

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Wooller, M. J.

    2005-12-01

    Previous studies have shown that the stable oxygen and hydrogen isotopic compositions (δ 18O and δD) in various animal tissues can be used to examine past climates and animal migration pattern. Little attention has been paid to the relative roles of diet and water influencing the overall δ 18O and δD of animal tissues in freshwater ecosystems. It is unclear whether different trophic levels in a freshwater lake ecosystem have an identical relationship to the water that surrounds them. The δ18O and δD values of animal tissues may be controlled by numerous different factors, including metabolic and biosynthetic isotopic fractionation and variations of δ 18O and δD in the food available. We began to examine these issues by analyzing the δ 18O and δD throughout a freshwater aquatic ecosystem at Smith Lake in Alaska. We collected samples representing primary producers and consumers (primary and secondary). Samples included green algae, various aquatic plants, such as Nuphar variegatum (water lily), Polygonum amphibium (water smartweed), Carex utriculata (sedge), Utricularia vulgaris (common bladderwort), Typha latifolia (common cattail), and a range of aquatic invertebrates, including Chironomus. sp (midge), Zygoptera (damselfly), Anisoptera (dragonfly), Dytiscidae (diving beetle) and Euhirudinea (leeches). The δ 18O and δD of Smith Lake water were ~-13.5e and -129.0e, respectively, and we present the δ 18O and δD of the rest of the ecosystem relative to these data. For instance, the δ 18O of chironomus sp. was ~12.1, which is greater than the of the lake water. Preliminary results suggest the extent of the fractionation between δ 18O of chironomids vs. lake water δ 18O is consistent with previous studies. Our data provide an insight into the range of variations that could be expected within a single freshwater ecosystem.

  4. A novel isotopic fractionation during dissolved oxygen consumption in mesopelagic waters inferred from observation and model simulation of dissolved oxygen δ18O in open oceanic regions

    NASA Astrophysics Data System (ADS)

    Nakayama, N.; Oka, A.; Gamo, T.

    2012-12-01

    Oxygen isotopic ratio (δ18O) of dissolved oxygen is a useful for bioactive tracer of the subsurface aphotic (mesopelagic) ocean since it varies nonlinearly related to oxygen consumption via stoichiometry of organic matter decomposition. Therefore, along with global circulation model (GCM), observed δ18O and their vertical/geographical distribution can be effectively used to quantitatively determine how marine biological and ocean physical processes contribute to varying dissolved oxygen (DO) concentration in the ocean, in particular mesopelagic zone where pronounced biological activity alters DO concentration significantly. In the central north Pacific Ocean and Indian Ocean, including Arabian Sea, one of the few regions in the open ocean which has oxygen minimum zone (OMZ, a layer with severely depleted DO), vertical profiles of DO and δ18O were observed. These observed data are compared with a GCM simulation in which a constant isotopic fractionation factor of DO by marine biological respiration and a fixed Redfield molar ratio between P and O are assumed. Even in the Arabian Sea OMZ, relationship between DO and δ18O was found to be similar to those observed in other open oceans, indicating that no specific oxygen consumption process occurred in the OMZ. Using the GCM model, we attempted to reproduce the observed overall relationship between DO and δ18O, but it failed when we adopted the previously reported isotopic fractionation factor: Discrepancy became larger when oxygen saturation level decreased, in particular in thermocline water (at 20% oxygen saturation level, modeled δ18O was heavier than observed values by +7‰). Sensitivity simulations with the GCM model revealed that (1) simply changing the intensity of oxygen consumption by respiration/organic matter decomposition nor physical processes (diffusion and/or advection) could explain the observed relationship between DO and δ18O, (2) applying a smaller isotopic fractionation for deep waters

  5. Comment on "Stoll H. et al. (2015): Interpretation of orbital scale variability in mid-latitude speleothem δ18O: Significance of growth rate controlled kinetic fractionation effects. Quat. Sci. Rev. 127, 215-228"

    NASA Astrophysics Data System (ADS)

    Dreybrodt, Wolfgang

    2016-06-01

    Stoll et al. (2015) have recently proposed that kinetic growth rate dependence of the oxygen isotope fractionation factor imprints an 18O isotope signal into the calcite precipitated to stalagmites. In their work growth rates of five stalagmites are related to negative offsets of δ18O from its equilibrium value. They report: "In the stalagmites contemplated here, growth rates of 4 - 80 μm year-1are equivalent to deposition rates of 3.4·10-9to 6.9·10-8 mol m-2 s-1assuming a density of calcite of 2.71 g/cm3."

  6. Interpretation of orbital scale variability in mid-latitude speleothem δ18O: Significance of growth rate controlled kinetic fractionation effects

    NASA Astrophysics Data System (ADS)

    Stoll, Heather; Mendez-Vicente, Ana; Gonzalez-Lemos, Saul; Moreno, Ana; Cacho, Isabel; Cheng, Hai; Edwards, R. Lawrence

    2015-11-01

    Oxygen isotopes have been the most widely used climate indicator in stalagmites, applied to reconstruct past changes in rainfall δ18O and cave temperature. However, the δ18O signal in speleothems may also be influenced by variable kinetic fractionation effects, here conceived broadly as fractionation effects not arising from temperature variation. The regional reproducibility of speleothem δ18O signals has been proposed as a way to distinguish the δ18O variations arising directly from changes rainfall δ18O and cave temperature, from variations due to kinetic effects which may nonetheless be influenced by climate. Here, we compare isotopic records from 5 coeval stalagmites from two proximal caves in NW Spain covering the interval 140 to 70 ka, which experienced the same primary variations in temperature and rainfall δ18O, but exhibit a large range in growth rates and temporal trends in growth rate. Stalagmites growing at faster rates near 50 μm/yr have oxygen isotopic ratios over 1‰ more negative than coeval stalagmites with very slow (5 μm/yr) growth rates. Because growth rate variations also occur over time within any given stalagmite, the measured oxygen isotopic time series for a given stalagmite includes both climatic and kinetic components. Removal of the kinetic component of variation in each stalagmite, based on the dependence of the kinetic component on growth rate, is effective at distilling a common temporal evolution of among the oxygen isotopic records of the multiple stalagmites. However, this approach is limited by the quality of the age model. For time periods characterized by very slow growth and long durations between dates, the presence of crypto-hiatus may result in average growth rates which underestimate the instantaneous speleothem deposition rates and which therefore underestimate the magnitude of kinetic effects. The stacked growth rate-corrected speleothem δ18O is influenced by orbital scale variation in the cave temperature and

  7. Determination of {sup 16}O and {sup 18}O sensitivity factors and charge-exchange processes in low-energy ion scattering

    SciTech Connect

    Tellez, H.; Chater, R. J.; Fearn, S.; Symianakis, E.; Kilner, J. A.; Brongersma, H. H.

    2012-10-08

    Quantitative analysis in low-energy ion scattering (LEIS) requires an understanding of the charge-exchange processes to estimate the elemental sensitivity factors. In this work, the neutralization of He{sup +} scattered by {sup 18}O-exchanged silica at energies between 0.6 and 7 keV was studied. The process is dominated by Auger neutralization for E{sub i} < 0.8 keV. An additional mechanism starts above the reionization threshold. This collision-induced neutralization becomes the dominant mechanism for E{sub i} > 2 keV. The ion fractions P{sup +} were determined for Si and O using the characteristic velocity method to quantify the surface density. The {sup 18}O/{sup 16}O sensitivity ratio indicates an 18% higher sensitivity for the heavier O isotope.

  8. Oxygen isotopes in synthetic goethite and a model for the apparent pH dependence of goethite-water 18O/ 16O fractionation

    NASA Astrophysics Data System (ADS)

    Yapp, Crayton J.

    2007-03-01

    Goethite synthesis experiments indicate that, in addition to temperature, pH can affect the measured value of the 18O/ 16O fractionation factor between goethite and water ( αG-W). A simple model was developed which expresses αG-W in terms of kinetic parameters associated with the growth of goethite from aqueous solution. The model predicts that, at a particular temperature, the range of pH over which αG-W changes as pH changes is expected to be comparatively small (˜3 pH "units") relative to the range of pH values over which goethite can crystallize (pH from ˜1 to 14). Outside the range of sensitivity to pH, αG-W is predicted to be effectively constant (for constant temperature) at either a low-pH αG-W value or a high-pH αG-W value. It also indicates that the values of αG-W at high pH will be disequilibrium values. Values of αG-W for goethite crystallized at low pH may approach, but probably do not attain, equilibrium values. For goethite synthesized at values of pH from ˜1 to 2, data from two different laboratories define the following equation for the temperature dependence of 1000 ln αG-W ( T in degrees Kelvin) 1000lnα={1.66×106}/{T2}-12.6 Over the range of temperatures from 0 to 120°C, values of 1000 ln αG-W from Eq. (IV) differ by ⩽0.1‰from those of a published equation [Yapp C.J., 1990. Oxygen isotopes in iron (III) oxides. 1. Mineral-water fractionation factors. Chem. Geol.85, 329-335]. Therefore, interpretations of data from natural goethites using the older equation are not changed by use of Eq. (IV). Data from a synthetic goethite suggest that the temperature dependence of 1000 ln αG-W at low pH as expressed in Eq. (IV) may be valid for values of pH up to at least 6. This result and the model prediction of an insensitivity of αG-W to pH over a larger range of pH values could explain the observation that Eq. (IV) yields values of αG-W which mimic most 18O/ 16O fractionations measured to date in natural goethites.

  9. 13C and 18O fractionation effects on open splits and on the ion source in continuous flow isotope ratio mass spectrometry.

    PubMed

    Elsig, Joachim; Leuenberger, Markus C

    2010-05-30

    Measurements of carbon and oxygen isotopes of CO(2) by continuous flow isotope ratio mass spectrometry are widely used in environmental studies and climate change research. Yet, there are remaining problems associated with the reproducibility of measurements, in particular when high precision is required and/or the amount of sample material is limited. Isotopic fractionations in open splits and nonlinear effects occurring in the mass spectrometer due to different sample amounts alter the results. In this study, we discuss the influence and the origin of these two effects and propose procedures for preventing their impact. Fractionation in the open split can be related to diffusion of CO(2) and can lead to shifted delta-values when measuring a sample gas against a reference gas injected via different open splits. We present a method, where such fractionations can be minimized by adjusting either the position of the capillaries or the flow rates involved or both. The nonlinear peak area dependence of delta(13)C measurements for small sample sizes can be explained by adsorption/desorption processes in the ionization chamber or its vicinity. For constant amplitudes, the magnitude of the nonlinearity only depends on the amount of CO(2) entering the ion source. This nonlinearity can be eliminated by a small additional flux of a conditioning gas fed to the mass spectrometer. The best results were obtained when using carbon monoxide. For the adsorption process in the mass spectrometer we found a fractionation factor of 0.982 +/- 0.005 for delta(13)C and 1.002 +/- 0.004 for delta(18)O. PMID:20411581

  10. Coordinated Isotopic and Mineral Characterization of Highly Fractionated 18O-Rich Silicates in the Queen Alexandra Range 99177 CR3 Chondrite

    NASA Technical Reports Server (NTRS)

    Nguyen, A. N.; Keller, L. P.; Messenger, S.; Rahman, Z.

    2016-01-01

    Carbonaceous chondrites contain a mixture of solar system condensates, pre-solar grains, and primitive organic matter. Each of these materials record conditions and processes in different regions of the solar nebula, on the meteorite parent body, and beyond the solar system. Oxygen isotopic studies of meteorite components can trace interactions of distinct oxygen isotopic reservoirs in the early solar system and secondary alteration processes. The O isotopic compositions of the earliest solar system condensates fall along a carbonaceous chondrite anhydrous mineral (CCAM) line of slope approximately 1 in a plot of delta 17O against delta 18O. This trend is attributed to mixing of material from 16O-poor and 16O-rich reservoirs. Secondary processing can induce mass-dependent fractionation of the O isotopes, shifting these compositions along a line of slope approximately 0.52. Substantial mass-dependent fractionation of O isotopes has been observed in secondary minerals in CAIs, calcite, and FUN inclusions. These fractionations were caused by significant thermal or aqueous alteration. We recently reported the identification of four silicate grains with extremely fractionated O isotopic ratios (delta 18O equals 37 - 55 per mille) in the minimally altered CR3 chondrite QUE 99177. TEM analysis of one grain indicates it is a nebular condensate that did not experience substantial alteration. The history of these grains is thus distinct from those of the aforementioned fractionated materials. To constrain the origin of the silicate grains, we conducted further Mg and Fe isotopic studies and TEM analyses of two grains.

  11. Fractionation of Oxygen Isotopes by Thermal Ionization Mass Spectrometry Inferred from Simultaneous Measurement of (17)O/(16)O and (18)O/(16)O Ratios and Implications for the (182)Hf-(182)W Systematics.

    PubMed

    Trinquier, Anne

    2016-06-01

    Accurate (182)Hf-(182)W chronology of early planetary differentiation relies on highly precise and accurate tungsten isotope measurements. WO3(-) analysis by negative thermal ionization mass spectrometry requires W(17)O(16)O2(-), W(17)O2(16)O(-), W(18)O(16)O2(-), W(17)O3(-), W(17)O(18)O(16)O(-), and W(18)O2(16)O(-) isotopologue interference corrections on W(16)O3(-) species ( Harper et al. Geochim. Cosmochim. Acta 1996 , 60 , 1131 ; Quitté et al. Geostandard. Newslett. 2002 , 26 , 149 ; Trinquier et al. Anal. Chem. 2016 , 88 , 1542 ; Touboul et al. Nature 2015 , 520 , 530 ; Touboul et al. Int. J. Mass Spectrom. 2012 , 309 , 109 ). In addition, low ion beam intensity counting statistics combined with Faraday cup detection noise limit the precision on the determination of (18)O/(16)O and (17)O/(16)O relative abundances. Mass dependent variability of (18)O/(16)O over the course of an analysis and between different analyses calls for oxide interference correction on a per integration basis, based on the in-run monitoring of the (18)O/(16)O ratio ( Harper et al. Geochim. Cosmochim. Acta 1996 , 60 , 1131 ; Quitté et al. Geostandard. Newslett. 2002 , 26 , 149 ; Trinquier et al. Anal. Chem. 2016 , 88 , 1542 ). Yet, the (17)O/(16)O variation is normally not being monitored and, instead, inferred from the measured (18)O/(16)O variation, assuming a δ(17)O-δ(18)O Terrestrial Fractionation Line ( Trinquier et al. Anal. Chem. 2016 , 88 , 1542 ). The purpose of the present study is to verify the validity of this assumption. Using high resistivity amplifiers, (238)U(17)O2 and (238)U(18)O2 ion beams down to 1.6 fA have been monitored simultaneously with (235,238)U(16)O2 species in a uranium certified reference material. This leads to a characterization of O isotope fractionation by thermal ionization mass spectrometry in variable loading and running conditions (additive-to-sample ratio, PO2 pressure, presence of ionized metal and oxide species). Proper determination of O

  12. High Resolution δ18O and δ13C Records of AMS 14C Dated Stalagmites From Jinlun and Yilingyan Caves in Guangxi, China: Climate Variability and Controlling Factors in the Monsoonal Region During the Past 2300 Years

    NASA Astrophysics Data System (ADS)

    Li, H. C.; Lien, W. Y.; Mii, H. S.; Jiang, G. H.; Chou, C. Y.; Chou, P. J.

    2015-12-01

    Jinlun Cave in Mashan County and Yilingyan Cave in Wuming County are ~120km and ~60km north of Nanning in Guangxi Province under influence of both Indian Monsoon and North Western Pacific Monsoon. Several stalagmites have been dated by AMS 14C dating method since 230Th/U is not applicable due to very low U contents. Twenty (20) AMS 14C dates on Stalagmite JL20131005-10 (10-cm long) show "Bomb carbon curve", spanning the past 60 years. Lamination counting further confirms the chronology. Thirty nine (39) AMS 14C dates on Stalagmite JL20131005-12 (33-cm long) reveal 2300-year continuous growth. Stalagmite YLY20130727-12 (10-cm long) from Yilingyan Cave covers a continuous record of past 2300 years. All studied stalagmites in the caves contain low dead carbon fractions. The annual resolution δ18O and δ13C records obtained from the stalagmites allow us to compare the stalagmite δ18O records with the instrumental rainfall and temperature records, Pacific Decadal Oscillation (PDO), Southern Oscillation Index (SOI), and Sunspot variation, etc. The δ18O and δ13C records exhibit relatively good correlation throughout the time, indicating climatic control on vegetation change. Based on the high-resolution δ18O and δ13C records, we interpret that dry climatic conditions and poor vegetation coverage during periods of AD1880~1850, 1700~1600, 1460~1320, 1210~1280, 860~750, 540~420, 300~220, and AD100~0 shown by increased δ18O and δ13C. The δ18O and δ13C were strongly depleted during the Medieval Warm Period (MWP between AD900 and AD1100) and Current Warm Period (CWP, since AD1900), reflecting strongly increased East Asian Summer Monsoon. After AD1900, the δ13C decreased about 6‰, perhaps indicating human impact on surface vegetation. The δ18O records from the study area are comparable to the published WX42B δ18O record of Wanxiang Cave (Zhang et al., 2008) except for the period of AD1400~1850. Our study suggests that AMS 14C dating is an alternative method for

  13. Predicting animal δ18O: Accounting for diet and physiological adaptation

    NASA Astrophysics Data System (ADS)

    Kohn, Matthew J.

    1996-12-01

    Theoretical predictions and measured isotope variations indicate that diet and physiological adaptation have a significant impact on animals δ18O and cannot be ignored. A generalized model is therefore developed for the prediction of animal body water and phosphate δ18O to incorporate these factors quantitatively. Application of the model reproduces most published compositions and compositional trends for mammals and birds. A moderate dependence of animal δ18O on humidity is predicted for drought-tolerant animals, and the correlation between humidity and North American deer bone composition as corrected for local meteoric water is predicted within the scatter of the data. In contrast to an observed strong correlation between kangaroo δ18O and humidity ( Δδ 18O/Δh ˜ 2.5 ± 0.4‰/10% r.h.), the predicted humidity dependence is only 1.3 - 1.7‰/10% r.h., and it is inferred that drinking water in hot dry areas of Australia is enriched in 18O over rainwater. Differences in physiology and water turnover readily explain the observed differences in δ18O for several herbivore genera in East Africa, excepting antelopes. Antelope models are more sensitive to biological fractionations, and adjustments to the flux of transcutaneous water vapor within experimentally measured ranges allows their δ18O values to be matched. Models of the seasonal changes of forage composition for two regions with dissimilar climates show that significant seasonal variations in animal isotope composition are expected, and that animals with different physiologies and diets track climate differently. Analysis of different genera with disparate sensitivities to surface water and humidity will allow the most accurate quantification of past climate changes.

  14. Predicting animal δ18O: Accounting for diet and physiological adaptation

    NASA Astrophysics Data System (ADS)

    Kohn, Matthew J.

    1996-12-01

    Theoretical predictions and measured isotope variations indicate that diet and physiological adaptation have a significant impact on animals δ18O and cannot be ignored. A generalized model is therefore developed for the prediction of animal body water and phosphate δ18O to incorporate these factors quantitatively. Application of the model reproduces most published compositions and compositional trends for mammals and birds. A moderate dependence of animal δ18O on humidity is predicted for drought-tolerant animals, and the correlation between humidity and North American deer bone composition as corrected for local meteoric water is predicted within the scatter of the data. In contrast to an observed strong correlation between kangaroo δ18O and humidity (Δδ18O/Δh ∼ 2.5± 0.4‰/10%r.h.), the predicted humidity dependence is only 1.3 - 1.7‰/10% r.h., and it is inferred that drinking water in hot dry areas of Australia is enriched in 18O over rainwater. Differences in physiology and water turnover readily explain the observed differences in δ18O for several herbivore genera in East Africa, excepting antelopes. Antelope models are more sensitive to biological fractionations, and adjustments to the flux of transcutaneous water vapor within experimentally measured ranges allows their δ18O values to be matched. Models of the seasonal changes of forage composition for two regions with dissimilar climates show that significant seasonal variations in animal isotope composition are expected, and that animals with different physiologies and diets track climate differently. Analysis of different genera with disparate sensitivities to surface water and humidity will allow the most accurate quantification of past climate changes.

  15. A conceptual model for interpreting δ18O and δD biomarker records from terrestrial archives

    NASA Astrophysics Data System (ADS)

    Zech, Michael; Tuthorn, Mario; Detsch, Florian; Rozanski, Kazimierz; Zech, Roland; Zöller, Ludwig; Zech, Wolfgang; Glaser, Bruno

    2013-04-01

    The natural abundances of stable oxygen (18O/16O) and hydrogen isotopes (D/H) are valuable proxies for reconstructing paleoclimate history on global as well as on regional scale. While stable isotope analyses of sedimentary leaf wax-derived n-alkanes enables establishing δD biomarker records, we recently developed a method based on compound-specific δ18O analyses of hemicellulose sugars (Zech and Glaser, 2009), which now additionally allows establishing δ18O biomarker records from soil/sedimentary organic matter of terrestrial archives. Here we present a conceptual model for interpreting combined δ18O and δD biomarker records (Zech et al., submitted). Based on this model, we suggest that both δ18O and δD biomarker records primarily reflect the isotopic composition of paleoprecipitation modified by evaporative isotope enrichment of leaf water during transpiration. Considering biosynthetic fractionation factors allows reconstructing from combined δ18O and δD biomarker records the leaf water isotopic composition and the deuterium excess of the leaf water. The deuterium excess may serve as proxy for evaporative enrichment and allows reconstructing relative humidity using a Craig-Gordon model. Furthermore, the model allows calculating δ18O of the plant source water (δ18Osource water), which can be assumed to primarily reflect δ18O of paleoprecipitation. Hence, paleoclimatic conclusions in terms of temperature can be drawn in high latitude study areas and precipitation amount can be reconstructed in monsoon regions. Zech, M., Glaser, B., 2009. Compound-specific δ18O analyses of neutral sugars in soils using GC-Py-IRMS: problems, possible solutions and a first application. Rapid Commun. Mass Spectrom. 23, 3522-3532. Zech et al., 2013. A 220 ka terrestrial δ18O and deuterium excess biomarker record from an eolian permafrost paleosol sequence, NE-Siberia. Submitted to Chemical Geology.

  16. δ18O analysis of individual carbohydrates - a new method for GC-pyrolysis-IRMS

    NASA Astrophysics Data System (ADS)

    Lehmann, Marco M.; Fischer, Maria; Zech, Michael; Siegwolf, Rolf T. W.; Saurer, Matthias

    2015-04-01

    Measuring the oxygen isotopic composition (δ18O) of various plant tissues is a widely used tool to investigate biochemical and physiological processes. While we have a good understanding about the hydrological cycle in plants with an evaporative enrichment in 18O in leaf water, we still lack knowledge about the biochemical link between the oxygen atoms in leaf water, leaf assimilates, and stem cellulose and associated isotope fractionations. Especially, the influence of different environmental factors on δ18O of individual carbohydrates (i.e. sugars) and thus on δ18O of cellulose is not fully resolved. A better understanding of these processes may improve climatic reconstructions of tree-ring studies about past environmental conditions. However, further progress in this topic is limited since a precise and reliable method to determine δ18O of individual sugars has not been available yet. With our new approach we attempt to overcome this issue by establishing a new methylation derivatization method suitable for GC-pyrolysis -IRMS. A methyl group (CH3) was thereby added to all hydroxyl groups of a sugar (e.g., glucose, fructose, and sucrose) during a catalyzed one-pot reaction overnight in acetonitrile with methyl iodide (CH3-I) and silver oxide, making them amenable for GC analysis. First results show a very good precision for δ18O of sucrose, but also δ18O of other high-abundant sugars such as glucose and fructose could be measured for the first time. We successfully analyzed a standard mix of all three sugars and determined various other carbohydrates not only related to plant sciences (e.g. mannitol, lactose), showing promising δ18O results. First tests with real plant samples were performed to make this method available for determining δ18O of individual carbohydrates of diverse plant tissues. In future, this new methylation derivatization method should allow us analyzing plant samples of different field sites and of lab experiments to investigate the

  17. High-Precision Tungsten Isotopic Analysis by Multicollection Negative Thermal Ionization Mass Spectrometry Based on Simultaneous Measurement of W and (18)O/(16)O Isotope Ratios for Accurate Fractionation Correction.

    PubMed

    Trinquier, Anne; Touboul, Mathieu; Walker, Richard J

    2016-02-01

    Determination of the (182)W/(184)W ratio to a precision of ± 5 ppm (2σ) is desirable for constraining the timing of core formation and other early planetary differentiation processes. However, WO3(-) analysis by negative thermal ionization mass spectrometry normally results in a residual correlation between the instrumental-mass-fractionation-corrected (182)W/(184)W and (183)W/(184)W ratios that is attributed to mass-dependent variability of O isotopes over the course of an analysis and between different analyses. A second-order correction using the (183)W/(184)W ratio relies on the assumption that this ratio is constant in nature. This may prove invalid, as has already been realized for other isotope systems. The present study utilizes simultaneous monitoring of the (18)O/(16)O and W isotope ratios to correct oxide interferences on a per-integration basis and thus avoid the need for a double normalization of W isotopes. After normalization of W isotope ratios to a pair of W isotopes, following the exponential law, no residual W-O isotope correlation is observed. However, there is a nonideal mass bias residual correlation between (182)W/(i)W and (183)W/(i)W with time. Without double normalization of W isotopes and on the basis of three or four duplicate analyses, the external reproducibility per session of (182)W/(184)W and (183)W/(184)W normalized to (186)W/(183)W is 5-6 ppm (2σ, 1-3 μg loads). The combined uncertainty per session is less than 4 ppm for (183)W/(184)W and less than 6 ppm for (182)W/(184)W (2σm) for loads between 3000 and 50 ng. PMID:26751903

  18. Magmatic ^18O in Zircons From Gabbros and Serpentinized Peridotite at the Mid-Atlantic Ridge (ODP Leg 153)

    NASA Astrophysics Data System (ADS)

    Cavosie, A. J.; Kita, N. T.; Valley, J. W.

    2005-12-01

    Zircons from gabbros and serpentinized ultramafic rocks from the Mid-Atlantic Ridge near the Kane Transform (MARK area) drilled during Leg 153 of the Ocean Drilling Program were analyzed for δ18O in situ in rock chips by ion microprobe. The gabbros contain clinopyroxene, plagioclase, apatite, Fe-oxides, with zircon occurring primarily along grain boundaries and as inclusions in other minerals (e.g. plagioclase). The mineralogy of the serpentinites is more complex, as they are comprised predominantly of a serpentine matrix that is cross-cut by multiple generations of intrusions, including zircon-bearing magmas emplaced as cm- to mm-scale gabbroic dikes and also lower temperature hydrothermal veins. The gabbroic dikes were pervasively altered at greenschist facies conditions, leaving zircon ± apatite as the only preserved magmatic phases. In some serpentinites it is difficult to distinguish altered magmatic veins from lower temperature hydrothermal veins. Zircons in serpentinite and gabbroic samples yield average δ18O values of 4.94±0.80‰ VSMOW (2 SD, N=33 analyses on 12 grains). This value would be in high temperature, magmatic equilibrium with MORB if δ18O (WR) ~ 5.3‰, or mantle peridotite if δ18O (Ol) = ~4.8‰. Equilibrium fractionation factors for δ18O between zircon-water (Zrc-H2O) were calculated by combining fractionation factors for Zrc-quartz (Valley et al. 2003) and quartz-H2O (Clayton et al., 1972; Matsuhisa et al., 1979). Over the temperature range of the calibrated fractionation factors (i.e. 500-800°C), calculated δ18O (zircon) values would be < 1 ‰ for zircon in equilibrium with previously measured MARK hydrothermal fluids (e.g. δ18O = 2.3‰). Zircon in equilibrium with seawater with δ18O = 0.0‰ would have 2.3‰ lower values. We note that extrapolation of the Zrc-H2O fractionation factors to temperatures below the calibrations of Zrc-Qtz and Qtz-H2O (e.g. <500°C) does not yield a typical mineral-water `crossover' at lower

  19. Constraints on the factors controlling 13C-18O bond abundances in biologically precipitated carbonates from measurements of marine calcifiers cultured at variable temperature, pH, and salinity

    NASA Astrophysics Data System (ADS)

    Conchas, T. E.; Eagle, R.; Eiler, J. M.; Ries, J. B.; Freitas, P. S.; Hiebenthal, C.; Wanamaker, A. D.; Tripati, A. K.

    2012-12-01

    Marine mollusks and corals are widely used as archives of past climate change; oxygen isotopic composition (δ18O value) of their carbonate minerals is perhaps the most commonly used proxy to reconstruct paleoclimate from these marine calcifiers. However, oxygen isotope paleothermometry of mollusks and corals is complicated by non-equilibrium "vital effects" and variations in seawater pH changes, both of which influence the net fractionation of oxygen isotopes between carbonate and water. Carbonate "clumped isotope" thermometry is an emerging approach that potentially addresses these ambiguities. Here we report measurements of abundance of 13C-18O bonds (described by the measured parameter Δ47) in a variety of marine calcifiers cultured under controlled conditions. Previous studies on biologically precipitated samples such as foraminifera, coccoliths, and corals have shown that Δ47 values are related to calcification temperature with a relationship that is generally similar to inorganic carbonate. However, the influence of effects other than temperature has not been extensively studied and little work has been done to explore the potential for small non-equilibrium effects in cultured specimens that were grown under controlled conditions. In this study, we report δ18O and Δ47 measurements of mollusk specimens that were cultured at several temperatures ranging from 5 to 25°C, as well as different pH and salinity values. We also report data for other marine calcifiers including the temperate coral species Oculina arbuscula and the coralline red algae Neogoniolithon sp., that were cultured at a single temperature but variable pH.

  20. Oxygen isotope fractionation factors between anhydrite and water from 100 to 550°C

    NASA Astrophysics Data System (ADS)

    Chiba, Hitoshi; Kusakabe, Minoru; Hirano, Shin-Ichi; Matsuo, Sadao; Somiya, Shigeyuki

    1981-03-01

    Oxygen isotope exchange between anhydrite and water was studied from 100 to 550°C, using the partial equilibrium method. The exchange rate was extremely low in NaCl solution. In the lower-temperature range, acid solutions were used to produce sufficient reaction to determine the oxygen isotope fractionation factors. The fractionation factors obtained in the present study are definitely different from those given by Lloyd [8]. They are similar to those for the HSO 4--water system studied by Mizutani and Rafter [19], and are consistently 2‰ higher than those of the barite-water system by Kusakabe and Robinson [5]. The temperature dependence of the oxygen isotope fractionation factors was calculated by the least squares method in which the weight was taken to be inversely proportional to the experimental error. The fractionation is given by: 10 3lnαanhydrite-water=3.21×(10 3/T) 2-4.72 Available δ 18O values of natural anhydrite were used to test the validity of this expression. It is shown that this newly revised geothermometer can be successfully applied to natural hydrothermal anhydrite.

  1. Determination of δ18O and δ15N in Nitrate

    USGS Publications Warehouse

    Revesz, K.; Böhlke, J.K.; Yoshinari, T.

    1997-01-01

    The analyses of both O and N isotopic compositions of nitrate have many potential applications in studies of nitrate sources and reactions in hydrology, oceanography, and atmospheric chemistry, but simple and precise methods for these analyses have yet to be developed. Testing of a new method involving reaction of potassium nitrate with catalyzed graphite (C + Pd + Au) at 520 °C resulted in quantitative recovery of N and O from nitrate as free CO2, K2CO3, and N2. The δ18O values of nitrate reference materials were obtained by analyzing both the CO2 and K2CO3 from catalyzed graphite combustion. Provisional values of δ18OVSMOW for the internationally distributed KNO3 reference materials IAEA-N3 and USGS-32 were both equal to +22.7 ± 0.5‰. Because the fraction of free CO2 and the isotopic fractionation factor between CO2 and K2CO3 were constant in the combustion products, the δ18O value of KNO3 could be calculated from measurements of the δ18O of free CO2. Thus, δ18OKNO3 = aδ18Ofree CO2 − b, where a and b were equal to 0.9967 and 3.3, respectively, for the specific conditions of the experiments. The catalyzed graphite combustion method can be used to determine δ18O of KNO3 from measurements of δ18O of free CO2 with reproducibility on the order of ±0.2‰ or better if local reference materials are prepared and analyzed with the samples. Reproducibility of δ15N was ±0.1‰ after trace amounts of CO were removed.

  2. Numerical experiments on the impacts of surface evaporation and fractionation factors on stable isotopes in precipitation

    NASA Astrophysics Data System (ADS)

    Zhang, Xinping; Guan, Huade; Zhang, Xinzhu; Zhang, Wanjun; Yao, Tianci

    2016-06-01

    The isotope enabled atmospheric water balance model is applied to examine the spatial and temporal variations of δ18O in precipitation, amount effect and meteoric water lines (MWL) under four scenarios with different fractionation nature and surface evaporation inputs. The experiments are conducted under the same weather forcing in the framework of the water balance and stable water isotope balance. Globally, the spatial patterns of mean δ18O and global MWLs simulated by four simulation tests are in reasonably good agreement with the Global Network of Isotopes in Precipitation observations. The results indicate that the assumptions of equilibrium fractionation for simulating spatial distribution in mean annual δ18O and the global MWL, and kinetic fractionation in simulating δ18O seasonality are acceptable. In Changsha, four simulation tests all reproduce the observed seasonal variations of δ18O in precipitation. Compared with equilibrium fractionation, the depleted degree of stable isotopes in precipitation is enhanced under kinetic fractionation, in company with a decrease of isotopic seasonality and inter-event variability. The alteration of stable isotopes in precipitation caused by the seasonal variation of stable isotopes in vapour evaporated from the surface is opposite between cold and warm seasons. Four simulations all produce the amount effect commonly observed in monsoon areas. Under kinetic fractionation, the slope of simulated amount effect is closer to the observed one than other scenarios. The MWL for warm and humid climate in monsoon areas are well simulated too. The slopes and intercepts of the simulated MWLs decrease under kinetic fractionation.

  3. Oxygen isotope systematics of the Banda Arc: low δ 18O despite involvement of subducted continental material in magma genesis

    NASA Astrophysics Data System (ADS)

    Vroon, P. Z.; Lowry, D.; van Bergen, M. J.; Boyce, A. J.; Mattey, D. P.

    2001-02-01

    This study reports new laser fluorination oxygen isotope data for 60 volcanic rocks and 15 sediments distributed over the whole length of the Banda Arc, eastern Indonesia. The melt oxygen isotope values (δ 18O melt) were calculated from phenocryst δ 18O data using theoretical and empirical mineral-melt fractionation factors. The δ 18O melt of individual volcanic centers within the arc varies between 5.57 and 6.54‰, except for Serua (δ 18O melt = 6.13-7.48‰) and Ambon (δ 18O melt = 8.12-8.38‰). These δ 18O melt values are up to 2‰ lower than new and previously published oxygen isotope data obtained on whole-rock powders by conventional methods. We attribute this discrepancy to post-emplacement low-temperature alteration and/or to a systematic deviation of the bulk analysis. Sediment δ 18O wr (calculated from the δ 18O carbonate and silica fractions, both measured conventionally) range between 12.9 and 24.2‰. The low δ 18O melt values (excluding Serua and Ambon) overlap with the mantle range, and are in agreement with simple two-component source-mixing models that predict 1-5% addition of subducted continental material to a depleted MORB-type source in the sub-arc mantle. This percentage is consistent with previous models based on Sr-Nd-Pb-Th-He-Hf isotope data. However, correlations between incompatible trace-element ratios and oxygen isotope systematics requires involvement of partial melts derived from subducted continental material as the major slab component rather than bulk addition. The contribution of hydrous fluids, from both subducted altered oceanic crust and continental material is probably of minor importance. Magma-mantle wedge interaction models could account for the observed low δ 18O signatures, but predicted effects are difficult to distinguish from models without mantle-wedge interaction. Assimilation of arc-crust material is thought to be important for the high δ 18O melt values of Serua and Ambon. AFC modelling suggests up to

  4. Preferential formation of 13C- 18O bonds in carbonate minerals, estimated using first-principles lattice dynamics

    NASA Astrophysics Data System (ADS)

    Schauble, Edwin A.; Ghosh, Prosenjit; Eiler, John M.

    2006-05-01

    that carbonate internal equilibration temperatures can be recovered from acid-generated CO 2 if abundances of isotopologues with mass 44-47 can be measured to sufficient precision. We have also calculated 18O/ 16O and 13C/ 12C reduced partition function ratios for carbonate minerals, and find them to be in good agreement with experiments and empirical calibrations. Carbon and oxygen isotope fractionation factors in hypothetical 40Mg—magnesite and 40Ba—witherite indicate that M 2+-cation mass does not contribute significantly to equilibrium isotopic fractionations between carbonate minerals.

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

    USGS Publications Warehouse

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

    2003-01-01

    Despite a rapidly growing literature on analytical methods and field applications of O isotope-ratio measurements of NO3- in environmental studies, there is evidence that the reported data may not be comparable because reference materials with widely varying ?? 18O values have not been readily available. To address this problem, we prepared large quantities of two nitrate salts with contrasting O isotopic compositions for distribution as reference materials for O isotope-ratio measurements: USGS34 (KNO3) with low ??18O and USGS35 (NaNO3) with high ??18O and 'mass-independent' ??17O. The procedure used to produce USGS34 involved equilibration of HNO3 with 18O-depleted meteoric water. Nitric acid equilibration is proposed as a simple method for producing laboratory NO3- reference materials with a range of ??18O values and normal (mass-dependent) 18O: 17O:16O variation. Preliminary data indicate that the equilibrium O isotope-fractionation factor (??) between [NO 3-] and H2O decreases with increasing temperature from 1.0215 at 22??C to 1.0131 at 100??C. USGS35 was purified from the nitrate ore deposits of the Atacama Desert in Chile and has a high 17O:18O ratio owing to its atmospheric origin. These new reference materials, combined with previously distributed NO3- isotopic reference materials IAEA-N3 (=IAEA-NO-3) and USGS32, can be used to calibrate local laboratory reference materials for determining offset values, scale factors, and mass-independent effects on N and O isotope-ratio measurements in a wide variety of environmental NO 3- samples. Preliminary analyses yield the following results (normalized with respect to VSMOW and SLAP, with reproducibilities of ??0.2-0.3???, 1??): IAEA-N3 has ??18O = +25.6??? and ??17O = +13.2??? USGS32 has ?? 18O = +25.7??? USGS34 has ??18O = -27. 9??? and ??17O = -14.8??? and USGS35 has ?? 18O = +57.5??? and ??17O = +51.5???.

  6. Climatological significance of δ18O in north Tibetan ice cores

    NASA Astrophysics Data System (ADS)

    Yao, Tandong; Thompson, Lonnie G.; Mosley-Thompson, Ellen; Zhihong, Yang; Xingping, Zhang; Lin, Ping-Nan

    1996-12-01

    Oxygen isotopic ratios (δ18O) of precipitation samples collected over several years at three meteorological stations on the northern Tibetan Plateau were used to conduct the first investigation of the relationship between δ18O and contemporaneous air temperatures (Ta). Inferring past temperatures from δ18O measured in recently acquired Tibetan ice cores necessitates establishing whether a δ18O-Ta relationship exists. For each station a strong temporal relationship is found between δ18O and Ta, particularly for monthly averages which remove synoptic-scale influences such as changes in condensation level, condensation temperature, and moisture sources. Moisture source is identified as a major factor in the spatial distribution of δ18O, but air temperature determines the temporal fluctuations of δ18O at individual sites on the northern Tibetan Plateau. The 30-year records of annually averaged δ18O from three different ice coring sites are not correlated significantly with contemporaneous air temperature records from their closest meteorological station (150 to 200 km). However, since 1960 the three air temperature records reveal a modest warming trend, while the three contemporaneous δ18O records show a modest 18O enrichment.

  7. Simulating speleothem growth in the laboratory: Determination of stable isotope fractionation factors during precipitation of speleothem calcite

    NASA Astrophysics Data System (ADS)

    Hansen, Maximilian; Schöne, Bernd R.; Spötl, Christoph; Scholz, Denis

    2016-04-01

    We present laboratory experiments aiming to understand the processes affecting the δ13C and δ18O values of speleothems during precipitation of calcite from a thin layer of solution. In particular, we determined the precipitation rates and the isotope fractionation factors in dependence of several parameters, such as temperature, cave pCO2 and supersaturation with respect to calcite. The experiments were performed in a climate box in order to simulate cave conditions and to control them during the experiments[1]. In the experiments, a thin film of a CaCO3-CO2-H2O-solution supersaturated with respect to calcite flew down an inclined marble surface or a sand-blasted borosilicate glass plate, and the drip water was sampled at different distances and, thus, residence times on the plate. Subsequently, pH, electrical conductivity and the δ13C and δ18O values of the dissolved inorganic carbon (DIC) as well as the precipitated CaCO3 were determined. In addition, we determined the stable isotope values of the drip water and the atmosphere inside the box during the experiments. This enabled the identification of carbon and oxygen isotope fractionation factors between all carbonate species. The experiments were conducted at 10, 20 and 30 ° C, a pCO2 of 1000 and 3000 ppmV and with a Ca2+ concentration of 2 and 5 mmol/l. We observed an exponential decay of conductivity with increasing distance of flow documenting progressive precipitation of calcite confirming previous observations[2]. The corresponding time constants of precipitation range from 180 to 660 s. Both the δ13C and δ18O values show a progressive increase along the flow path. The enrichment of the δ13C values seems to be strongly influenced by kinetic isotope fractionation, whereas the δ18O values are in the range of isotopic equilibrium. The fractionation between the precipitated CaCO3 and DIC is between -1 and - 6.5 ‰ for carbon isotopes (13ɛ) and between -1.5 and -3 ‰ for oxygen isotopes (18ɛ). The

  8. Determination of Mineral-Specific Clumped Isotope Acid Digestion Fractionation Factors Using Heating Experiments and Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Henry, D.; Tang, J.; Mosenfelder, J. L.; Eagle, R.; Tripati, A.

    2014-12-01

    Clumped isotope thermometry involves the determination of formation temperatures of carbonates from the fraction of isotopologues containing multiple rare isotopes (oxygen-18 and carbon-13). At high temperatures, the abundance of these isotopologues should be stochastic. At lower temperatures, there is a tendency for heavy isotopes to form bonds with each other. However, spectroscopic determination of isotope ratios with high precision is difficult in solids, and so 13C-18O bond abundance is not measured in the solid phase. Instead, analysis of carbonates is performed using gas source mass spectrometry, by reacting the carbonate samples with phosphoric acid and measuring the evolved CO2 gas. As an oxygen atom is lost during the conversion of CO32- groups to CO2, this reaction is hypothesized to result in mineral and acid digestion temperature-dependent fractionation. In order to quantify this fractionation between CO32- and CO2, this experiment seeks to determine acid fractionation factors for carbonate samples of varying composition by randomizing samples through intense heating and comparing analyte CO2 measured composition to the expected composition for a stochastically distributed sample. From this analysis, future carbonate measurements can be calibrated to account for acid digestion fractionation.

  9. The role of soil processes in δ18O terrestrial climate proxies

    NASA Astrophysics Data System (ADS)

    Kanner, Lisa C.; Buenning, Nikolaus H.; Stott, Lowell D.; Timmermann, Axel; Noone, David

    2014-03-01

    A paleoclimate interpretation of a terrestrial hydrologic proxy such as the δ18O of tree cellulose or speleothem calcite may be biased or misinterpreted if the isotopic composition of the soil water from which the proxy originated undergoes isotopic exchange or fractionation. In this study, we use a global isotope-enabled land surface model to investigate how the δ18O of precipitation may be altered in a soil column due to evaporation and vertical moisture transport. In order to assess how precipitation and evaporation contribute to the soil water isotopic variability, we compare seasonal and interannual changes in simulated xylem water δ18O within a control simulation and in a suite of sensitivity experiments where the effects of precipitation δ18O, water vapor δ18O, and soil water evaporation are independently removed. The simulations, carried out for the period 1979 to 2004, reveal that in semiarid regions, such as the southwest United States, the seasonal cycle in xylem water δ18O is strongly affected by evaporative loss during the dry season and evaporation can also constitute as much as 50% of the interannual δ18O variance. Additional simulations, including soil water tagging experiments, indicate that upward fluxes of soil water occur during drier periods. For soil water δ18O profiles that are isotopically more depleted in 18O at depth, this imparts a low isotopic signature to xylem water δ18O during such dry intervals. Hence, without taking into account vertical moisture transport in the soils, low δ18O years could be misinterpreted as wet conditions (due to decreased evaporative enrichment) when instead drier conditions are equally as likely.

  10. The role of effective leaf mixing length in the relationship between the δ18 O of stem cellulose and source water across a salinity gradient.

    PubMed

    Ellsworth, Patricia V; Ellsworth, Patrick Z; Anderson, William T; Sternberg, Leonel S L

    2013-01-01

    Previous mangrove tree ring studies attempted, unsuccessfully, to relate the δ(18) O of trunk cellulose (δ(18) O(CELL) ) to the δ(18) O of source water (δ(18) O(SW) ). Here, we tested whether biochemical fractionation associated with one of the oxygen in the cellulose glucose moiety or variation in leaf water oxygen isotope fractionation (Δ(LW) ) can interfere with the δ(18) O(SW) signal as it is recorded in the δ(18) O(CELL) of mangrove (saltwater) and hammock (freshwater) plants. We selected two transects experiencing a salinity gradient, located in the Florida Keys, USA. The δ(18) O(CELL) throughout both transects did not show the pattern expected based on that of the δ(18) O(SW) . We found that in one of the transects, biochemical fractionation interfered with the δ(18) O(SW) signal, while in the other transect Δ(LW) differed between mangrove and hammock plants. Observed differences in Δ(LW) between mangroves and hammocks were caused by a longer effective leaf mixing length (L) of the water pathway in mangrove leaves compared to those of hammock leaves. Changes in L could have caused the δ(18) O(CELL) to record not only variations in the δ(18) O(SW) but also in Δ(LW) making it impossible to isolate the δ(18) O(SW) signal. PMID:22716972

  11. Chironomid δ ^{18}O and \\delta$D as Paleoclimate Proxies: Progress and Puzzles

    NASA Astrophysics Data System (ADS)

    Axford, Y.; Miller, G. H.; Wooller, M. J.; Francis, D.; Geirsdottir, A.; Wang, Y.; Sauer, P. E.

    2004-12-01

    An increasing number of paleolimnological studies are aimed at reconstructing lakewater isotopic composition, and thus (in appropriate hydrologic settings) the isotopic composition of paleo-precipitation. Records of \\delta18O and δ D of paleo-precipitation are used to infer changes in climate, including changes in site temperature and storm tracks. This study investigates the viability of using the \\delta18O and δ D of subfossil chironomid head capsules preserved in lake sediments to reconstruct lakewater isotopic composition. Chironomids (Chironomidae, or non-biting midges) spend much of their life cycle as aquatic larvae, and their chitinous larval head capsules are well preserved in many lake sediments. Wooller et al. (2004) demonstrated that chironomid \\delta18O and precipitation \\delta18O are strongly correlated along a transect from Greenland to Vermont (n=4, r2=0.96). The goal of the current research is to further investigate the relationships between mean annual temperature (MAT) and the stable isotopic composition (\\delta18O and δ D) of chironomids, lakewater, and precipitation. We have analyzed more than 100 samples from lakes in Iceland and Arctic Canada, including surface sediments from a transect of lakes representing a broad modern climatic gradient. Results confirm a correlation between chironomid \\delta18O and both lakewater \\delta18O and MAT. Chironomid δ D also correlates with lakewater δ D and MAT. On the other hand, preliminary results suggest differences in isotopic fractionation between taxa. Ongoing experiments are aimed at evaluating taxonomic differences and refining our methodology.

  12. Reconstructing relative humidity from plant delta18O and deltaD as deuterium deviations from the global meteoric water line.

    PubMed

    Voelker, Steven L; Brooks, J Renée; Meinzer, Frederick C; Roden, John; Pazdur, Anna; Pawelczyk, Slawomira; Hartsough, Peter; Snyder, Keirith; Plavcová, Lenka; Santrůcek, Jirí

    2014-07-01

    Cellulose delta18O and deltaD can provide insights on climates and hydrological cycling in the distant past and how these factors differ spatially. However, most studies of plant cellulose have used only one isotope, most commonly delta18O, resulting in difficulties partitioning variation in delta18O of precipitation vs. evaporative conditions that affect leaf water isotopic enrichment. Moreover, observations of pronounced diurnal differences from conventional steady-state model predictions of leaf water isotopic fractionation have cast some doubt on single isotope modeling approaches for separating precipitation and evaporation drivers of cellulose delta18O or deltaD. We explore a dual isotope approach akin to the concept of deuterium-excess (d), to establish deuterium deviations from the global meteoric water line in leaf water (deltad(l)) as driven by relative humidity (RH). To demonstrate this concept, we survey studies of leaf water delta18O and deltaD in hardwood vs. conifer trees. We then apply the concept to cellulose delta18O and deltaD using a mechanistic model of cellulose delta18O and deltaD to reconstruct deuterium deviations from the global meteoric water line (deltad(c)) in Quercus macrocarpa, Q. robur, and Pseudotsuga menziesii. For each species, deltad(c) showed strong correlations with RH across sites. deltad(c) agreed well with steady-state predictions for Q. macrocarpa, while for Q. robur, the relationship with RH was steeper than expected. The slope of deltad(c) vs. RH of P. menziesii was also close to steady-state predictions, but deltad(c) were more enriched than predicted. This is in agreement with our leaf water survey showing conifer deltad(l) was more enriched than predicted. Our data reveal that applications of this method should be appropriate for reconstructing RH from cellulose delta18O and deltaD after accounting for differences between hardwoods and conifers. Hence, deltad(c) should be useful for understanding variability in RH

  13. The origin of high δ18O zircons: marbles, megacrysts, and metamorphism

    NASA Astrophysics Data System (ADS)

    Cavosie, Aaron J.; Valley, John W.; Kita, Noriko T.; Spicuzza, Michael J.; Ushikubo, Takayuki; Wilde, Simon A.

    2011-11-01

    The oxygen isotope ratios (δ18O) of most igneous zircons range from 5 to 8‰, with 99% of published values from 1345 rocks below 10‰. Metamorphic zircons from quartzite, metapelite, metabasite, and eclogite record δ18O values from 5 to 17‰, with 99% below 15‰. However, zircons with anomalously high δ18O, up to 23‰, have been reported in detrital suites; source rocks for these unusual zircons have not been identified. We report data for zircons from Sri Lanka and Myanmar that constrain a metamorphic petrogenesis for anomalously high δ18O in zircon. A suite of 28 large detrital zircon megacrysts from Mogok (Myanmar) analyzed by laser fluorination yields δ18O from 9.4 to 25.5‰. The U-Pb standard, CZ3, a large detrital zircon megacryst from Sri Lanka, yields δ18O = 15.4 ± 0.1‰ (2 SE) by ion microprobe. A euhedral unzoned zircon in a thin section of Sri Lanka granulite facies calcite marble yields δ18O = 19.4‰ by ion microprobe and confirms a metamorphic petrogenesis of zircon in marble. Small oxygen isotope fractionations between zircon and most minerals require a high δ18O source for the high δ18O zircons. Predicted equilibrium values of Δ18O(calcite-zircon) = 2-3‰ from 800 to 600°C show that metamorphic zircon crystallizing in a high δ18O marble will have high δ18O. The high δ18O zircons (>15‰) from both Sri Lanka and Mogok overlap the values of primary marine carbonates, and marbles are known detrital gemstone sources in both localities. The high δ18O zircons are thus metamorphic; the 15-25‰ zircon values are consistent with a marble origin in a rock-dominated system (i.e., low fluid(external)/rock); the lower δ18O zircon values (9-15‰) are consistent with an origin in an external fluid-dominated system, such as skarn derived from marble, although many non-metasomatized marbles also fall in this range of δ18O. High δ18O (>15‰) and the absence of zoning can thus be used as a tracer to identify a marble source for high δ18O

  14. Age differences between Atlantic and Pacific benthic d18O change at terminations

    NASA Astrophysics Data System (ADS)

    Lisiecki, L. E.; Raymo, M. E.

    2007-12-01

    Because a large fraction of benthic δ18O change is due to global ice volume change, benthic δ18O is often used as stratigraphic tool to place marine records on a common age model and as a proxy for the timing of ice volume/sea level change. These applications require the assumptions that δ18O change is rapidly transmitted throughout the deep ocean and that the effects of hydrographic changes are in phase with ice volume. Recently, Skinner and Shackleton [2005] found that the timing of benthic δ18O change at the last termination differed by 4500 years between two sites in the Atlantic and Pacific. Based on Mg/Ca paleothermometry, they argued that these age discrepancies resulted from a late temperature increase in the Pacific and millennial-scale circulation changes in the Atlantic. Do these results imply that benthic δ18O change may not accurately record the timing of terminations? We compare benthic δ18O records from 34 sites in the Atlantic and Pacific to evaluate the impact of ocean mixing rates and deep water changes on the relative timing of terminations recorded in benthic δ18O. Statistical analysis of sedimentation rates derived from the alignment of benthic δ18O suggests an Atlantic lead over Pacific benthic δ18O change for all terminations of the last 600 kyr. The magnitude of sedimentation rate change suggests an average termination age difference of 1000-1500 years between the Atlantic and Pacific, consistent with or slightly greater than the delay expected due to ocean mixing rates, given that most glacial meltwater probably enters the North Atlantic.

  15. Evaluating the source of streamwater nitrate using δ15N and δ18O in nitrate in two watersheds in New Hampshire, USA

    USGS Publications Warehouse

    Pardo, Linda H.; Kendall, Carol; Pett-Ridge, Jennifer; Chang, Cecily C.Y.

    2004-01-01

    The natural abundance of nitrogen and oxygen isotopes in nitrate can be a powerful tool for identifying the source of nitrate in streamwater in forested watersheds, because the two main sources of nitrate, atmospheric deposition and microbial nitrification, have distinct δ18O values. Using a simple mixing model, we estimated the relative fractions in streamwater derived from these sources for two forested watersheds with markedly different streamwater nitrate outputs. In this study, we monitored δ15N and δ18O of nitrate biweekly in atmospheric deposition and in streamwater for 20 months at the Hubbard Brook Experimental Forest, New Hampshire, USA (moderate nitrogen export), and monthly in streamwater at the Bowl Research Natural Area, New Hampshire, USA (high nitrogen export). For rain, δ18O values ranged from +47 to +77‰ (mean: +58‰) and δ15N from −5 to +1‰ (mean: −3‰); for snow, δ18O values ranged from +52 to +75‰ (mean: +67‰) and δ15N from −3 to +2‰ (mean: −1‰). Streamwater nitrate, in contrast to deposition, had δ18O values between +12 and +33‰ (mean: +18‰) and δ15N between −3 and +6‰ (mean: 0‰). Since nitrate produced by nitrification typically has δ18O values ranging from −5 to +15‰, our field data suggest that most of the nitrate lost from the watersheds in streamflow was nitrified within the catchment. Our results confirm the importance of microbial nitrogen transformations in regulating nitrogen losses from forested ecosystems and suggest that hydrologic storage may be a factor in controlling catchment nitrate losses.

  16. Isotope fractionations factors of N2O production and reduction by denitrification: a. Laboratory incubation studies using N2O reductase inhibition

    NASA Astrophysics Data System (ADS)

    Well, Reinhard; Weymann, Daniel; Lewicka-Szczebak, Dominika; Rohe, Lena; Flessa, Heinz

    2013-04-01

    Isotopologue signatures of N2O such as δ18O, average δ15N (δ15Nbulk) and 15N site preference (SP = difference in δ15N between the central and peripheral N positions of the asymmetric N2O molecule) can be used to constrain the atmospheric N2O budget and to characterize N2O turnover processes. However, the use of this approach to study N2O dynamics in soils requires knowledge of isotopologue fractionation factors (?) for the various partial processes involved, e.g. N2O production by nitrification or denitrification, and N2O reduction by denitrification. Here we present results from laboratory incubations of soils and aquifer material to determine ?gf N2O production (?prod) and N2O reduction to N2 (?red) during denitrification. ?prod for δ18O, δ15Nbulk and SP was obtained by anaerobic incubation of NO3- amended soils when N2O reduction was inhibited by 10 kPa acetylene. ?red of the respective signatures was derived by comparing treatments with and without inhibition of N2O reduction. We investigated samples from 4 mineral soils, one organic soil and from a sandy aquifer. The mineral soils were incubated under unsaturated conditions in closed or open systems, the organic and aquifer samples as homogenized slurries in a closed system. Results of fractionation factors, process rates and incubation conditions will be presented and discussed in view of previous studies and theoretical considerations.

  17. Characterization of Growing Bacterial Populations in McMurdo Dry Valley Soils through Stable Isotope Probing with 18O-water

    PubMed Central

    Schwartz, Egbert; Buelow, Heather N.; Gooseff, Michael N.; Barrett, John E.; Okie, Jordan G.; Takacs-Vesbach, Cristina D.; Van Horn, David J.

    2014-01-01

    Soil microbial communities of the McMurdo Dry Valleys, Antarctica (MDV) contain representatives from at least fourteen bacterial phyla. However, given low rates of microbial activity, it is unclear whether this richness represents functioning rather than dormant members of the community. We used stable isotope probing (SIP) with 18O-water to determine if microbial populations grow in MDV soils. Changes in the microbial community were characterized in soils amended with H2 18O and H2 18O-organic matter. Sequencing the 16S rRNA genes of the heavy and light fractions of the bacterial community DNA show that DNA of microbial populations was labeled with 18O-water, indicating these microorganisms grew in the MDV soils. Significant differences existed in the community composition of the heavy and light fractions of the H2 18O and H2 18O-organic matter amended samples (Anosim P<0.05 of weighted Unifrac distance). Control samples and the light DNA fraction of the H2 18O amended samples were dominated by representatives of the phyla Deinococcus-Thermus, Proteobacteria, Planctomyces, Gemmatimonadetes, Actinobacteria and Acidobacteria, whereas Proteobacteria were more prevalent in the heavy DNA fractions from the H2 18O-water and the H2 18O-water-organic matter treatments. Our results indicate that SIP with H2 18O can be used to distinguish active bacterial populations even in this low organic matter environment. PMID:24785369

  18. Variations in the Yangze River outflow in the last 7 ky deduced from δ18O and Mg/Ca in the northern East China Sea

    NASA Astrophysics Data System (ADS)

    Kubota, Y.; Kimoto, K.; Tada, R.; Yokoyama, Y.

    2014-12-01

    The East Asian summer monsoon (EASM) system is involved in hydrological cycle, and latent heat and energy transport, thus plays a significant role in global climate system. Observation records of the precipitation (~50-year long) are not long enough to reveal the frequency and extremity of the EASM precipitation. Therefore, quantitative reconstruction of the past precipitation changes using geological records is necessary. The δ18O of seawater (δ18Ow), an indirect indicator of sea surface salinity, in the northern East China Sea (ECS) is reconstructed for the last 7 kyr using paired Mg/Ca ratio and δ18O of planktic foraminiferal tests. According to modern observation, inter-annual variations in sea surface salinity during summer in the northern part of the ECS are mainly controlled by the discharge from the Yangtze River, which reflects summer rainfall in the drainage area of the Yangtze River. Thus, changes in the summer sea surface salinity in the northern ECS are interpreted as reflecting variations in the East Asian summer monsoon (EASM) precipitation in South China. This interpretation is confirmed by the relationship between salinity in the northern ECS and the discharge from the Yangtze River during wet season (May-October) based on the observational salinity data from 1951 to 1995. We calculate a fraction of the Yangtze River freshwater by using two endmembers, freshwater δ18O and seawater δ18O. During the last 7 ky, the freshwater fraction varies between 5% and 0% on multi-centennial to millennial-scale. However, there is no long-term trend from the middle Holocene that is commonly known in Chinese speleothem δ18O. Our record suggests that changes in summer insolation in the Northern Hemisphere do not seem to impact on changes in summer precipitation in the Yangtze Basin. Instead, other factors such as inter-seasonal migration speed of the monsoon front likely control on the precipitation in the Yangtze Basin even in the long time scale.

  19. Modeling the signal transfer of sea water δ18O to the δ18O of atmospheric oxygen using a diagnostic box model for the terrestrial and marine biosphere

    NASA Astrophysics Data System (ADS)

    Leuenberger, Markus C.

    1997-11-01

    We make use of a simple diagnostic box model to determine the sensitivities of the influencing parameters for the isotopic signal transfer of seawater oxygen to atmospheric oxygen. We calculate the δ18O of atmospheric oxygen from prescribed oxygen fluxes of the living and dead biomes on land and in the ocean, respectively. The model is driven by an assumed (experiment 1) or measured (experiments 2 and 3) temporal seawater δ18O signal and a land biomass estimation. In experiment 1, we calculated the required changes of several model parameters in order to study fast variations of δ18O of atmospheric oxygen as seen in the Greenland Ice Core Project (GRIP) ice at depths assigned to the Eemian time period. Our calculations support evidence of stratigraphic problems at these depths in the GRIP ice core. In experiment 2, we adjusted the model output, which was driven by the benthic seawater δ18O record from V19-30, to the measured Greenland Ice Sheet Project 2 δ18O record of atmospheric oxygen for the last 110,000 years, by varying the model parameter. Single and multi-parameter matchings were performed. The results for single-parameter runs exceed the uncertainty ranges for most of the parameters, while multiparameter variations are well within these ranges. The model calculations are most sensitive to the land respiration factor. Our results support the findings of Van de Water et al. [1994] that the fractionations associated with biomes activities were most probably lower during cold periods, which could point to a combination of fractionations with different temperature dependencies. The model results indicate periods of higher marine biological activity during the ice age than today. Temporal variations of the model parameters show a double peak around 10000 and 8000 years ago, which could be associated with meltwater pulses, as shown in experiment 3. However, they are hardly the well-known Fairbanks [Fairbanks et al., 1992] pulses since these occur 3000 to

  20. Two-neutron transfer analysis of the 16O(18O,16O)18O reaction

    NASA Astrophysics Data System (ADS)

    Ermamatov, M. J.; Cappuzzello, F.; Lubian, J.; Cubero, M.; Agodi, C.; Carbone, D.; Cavallaro, M.; Ferreira, J. L.; Foti, A.; Garcia, V. N.; Gargano, A.; Lay, J. A.; Lenzi, S. M.; Linares, R.; Santagati, G.; Vitturi, A.

    2016-08-01

    Recently a quantitative description of the two-neutron transfer reaction 12C(18O,16O)14C was performed and the measured cross sections were successfully reproduced [M. Cavallaro et al., Phys. Rev. C 88, 054601 (2013), 10.1103/PhysRevC.88.054601]. This task was accomplished by combining nuclear structure calculations of spectroscopic amplitudes and a full quantum description of the reaction mechanism. Verification of such a theoretical approach to other heavy nuclear systems is mandatory in order to use (18O,16O ) reactions to assess pair configurations in nuclear states. In this work we apply this methodology to the 16O(18O,16O)18O reaction at 84 MeV. Experimental angular distributions for the two-neutron transfer to the ground state and 21+ state of 18O were obtained using the MAGNEX spectrometer at INFN-LNS. The roles of one- and two-step processes are analyzed under the exact finite range coupled reaction channel and the second order distorted wave Born approximation. We conclude that the one-step transfer mechanism is dominant in this system.

  1. Effect of temperature on the oxygen isotope composition of carbon dioxide (δ18O) prepared from carbonate minerals by reaction with polyphosphoric acid: An example of the rhombohedral CaCO 3-MgCO 3 group minerals

    NASA Astrophysics Data System (ADS)

    Crowley, Stephen F.

    2010-11-01

    Measurement of the ratio of 18O to 16O in CO 2(δ18O) produced from rhombohedral carbonate minerals in the compositional range CaCO 3-MgCO 3 by reaction with polyphosphoric acid (PPA), at temperatures of between 25 and 110 °C, shows that values of δ18O are linearly correlated ( r o > 0.99) with the reciprocal of absolute reaction temperature (K/ T). This observation is consistent with earlier studies documenting the effect of temperature on the kinetic fractionation of oxygen isotopes between parent carbonate and product CO 2 and H 2O during acid decomposition. However, analysis of the resultant data reveals: (1) a progressive increase in dδ18O/dT-1 with increasing Mg content, and (2) a significant variation in dδ18O/dT-1 between individual samples of carbonate of identical lattice symmetry and similar chemical composition. The overall increase in gradient with increasing Mg content is assumed to reflect cation radius dependent factors that control the bonding environment at the interface between the metal cation exposed at the surface of the reacting carbonate solid and a H 2CO 3 transitional species during disproportionation of H 2CO 3 to CO 2 and H 2O ("cluster model" of Guo et al., 2009). Phase-specific variations in dδ18O/dT-1 might result from differences in lattice structure variables (e.g., degree of lattice distortion, extent of positional disorder, and non-ideal mixing of substituent cations where carbonates depart from end-member compositions). Lattice structure variables may be dependent on geochemical conditions pertaining at the time of carbonate precipitation (e.g., biosynthetic versus inorganic precipitates) and suggests that dδ18O/dT-1 has the potential to vary, within limits, in response to both the chemical composition and structure of each carbonate sample. Because the oxygen isotope composition of carbonate minerals (δ18O) measured on the VPDB scale is defined by the oxygen isotope composition of CO 2 prepared from NBS19 (calcite) by

  2. Isolating relative humidity: dual isotopes d18O and dD as deuterium deviations from the global meteoric water line

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cellulose d18O and dD can provide insights on climates and hydrological cycling in the distant past and how these factors differ spatially. However, most studies of plant cellulose have used only one isotope, most commonly d18O, resulting in difficulties partitioning variation in d18O of precipitati...

  3. A 220 ka terrestrial δ18O and deuterium excess biomarker record from an eolian permafrost paleosol sequence, NE-Siberia

    NASA Astrophysics Data System (ADS)

    Tuthorn, Mario; Zech, Michael; Detsch, Florian; Rozanski, Kazimierz; Zech, Roland; Zöller, Ludwig; Zech, Wolfgang; Glaser, Bruno

    2013-04-01

    The natural abundances of stable oxygen (18O/16O) and hydrogen isotopes (D/H) are valuable proxies of climate changes in the past. Yet, to date no continuous δ18O and only few δD records are available from loess-paleosol sequences. Taking advantage of a recently developed method based on compound-specific δ18O analyzes of hemicellulose sugar biomarkers in soils (Zech and Glaser, 2009), we here present a first terrestrial δ18O biomarker record from an eolian permafrost paleosol sequence in NE-Siberia that covers the last ~220 ka. The δ18O values of the hemicellulose biomarkers arabinose and xylose range from 22.5 to 32.8‰ and from 21.3 to 31.9‰, respectively, and reveal systematic glacial - interglacial shifts. The modern topsoil and the interglacial paleosols exhibit more positive δ18O values, whereas the glacial paleosols are characterized by more negative δ18O values. This is in agreement with the δD record obtained for sedimentary n-alkane leaf wax biomarkers. We present a conceptual model for interpreting the combined δ18O and δD biomarker record. Based on this model, we suggest that both our δ18O and the δD record primarily reflect the temperature-controlled isotopic composition of paleoprecipitation modified by evaporative isotope enrichment of leaf water during transpiration. Considering fractionation factors during sugar and n-alkane biomarker biosynthesis allows reconstructing the leaf water isotopic composition and the deuterium excess of the leaf water. The deuterium excess may serve as proxy for evaporative enrichment and allows calculating relative humidity using a Craig-Gordon model. Accordingly, relative humidity in NE-Siberia was higher during marine isotope stage (MIS) 6 compared to MIS 2, 4 and 5d and thus could help explaining the much larger extent of the Late Saalian glaciation compared to the Weichselian glaciations. Using the Craig-Gordon model, we also calculated δ18O of the plant source water (δ18Osource water), which can

  4. Tracing atmospheric moisture from precipitation δ18O to climate proxy using an isotope enabled land surface model

    NASA Astrophysics Data System (ADS)

    Kanner, L.; Buenning, N. H.; Stott, L. D.; Timmermann, A.

    2013-12-01

    A paleoclimate interpretation of a terrestrial hydrologic proxy such as the δ18O of tree cellulose or speleothem calcite may be biased or misinterpreted if the isotopic composition of the soil water from which the proxy originated undergoes isotopic exchange or fractionation. In this study, we use a global isotope-enabled land surface model (IsoLSM) to investigate how the δ18O of precipitation may be altered in a soil column due to evaporation and vertical moisture flux. In order to assess how precipitation and evaporation contribute the soil water isotopic variability, we compare seasonal and interannual changes in simulated xylem water δ18O within a control simulation and in a suite of experiments where the effect of precipitation δ18O, water vapor δ18O, and ground water evaporation are independently removed. The simulations, carried out for 1979 to 2004, reveal that in semi-arid regions, such as the southwest United States, the seasonal cycle in xylem water δ18O is strongly affected by evaporative loss during the dry season and this can constitute as much as 50% of the interannual δ18O variance. Additional simulations, including soil water tagging experiments, indicate that upward fluxes of soil water occur during drier periods. For soil water δ18O profiles that are isotopically more depleted in 18O at depth, this imparts a low isotopic signature to xylem water δ18O during such dry intervals. Hence, without taking into account moisture flux processes, an isotopic proxy could be misinterpreted as wet conditions (due to decreased evaporative enrichment) for low δ18O years when instead drier conditions are equally as likely. Using IsoLSM simulated xylem water and leaf water δ18O, offline calculations of cellulose δ18O compare well with observations in diverse climatic regimes. Thus, the driving mechanisms on soil water δ18O identified in this study, and in particular the important role of evaporation on seasonal and interannual timescales, may

  5. Online high-precision delta(2)H and delta(18)O analysis in water by pyrolysis.

    PubMed

    Lu, Feng H

    2009-10-01

    A method for online simultaneous delta(2)H and delta(18)O analysis in water by high-temperature conversion is presented. Water is injected by using a syringe into a high-temperature carbon reactor and converted into H(2) and CO, which are separated by gas chromatography (GC) and carried by helium to the isotope ratio mass spectrometer for hydrogen and oxygen isotope analysis. A series of experiments was conducted to evaluate several issues such as sample size, temperature and memory effects. The delta(2)H and delta(18)O values in multiple water standards changed consistently as the reactor temperature increased from 1150 to 1480 degrees C. The delta(18)O in water can be measured at a lower temperature (e.g. 1150 degrees C) although the precision was relatively poor at temperatures <1300 degrees C. Memory effects exist for delta(2)H and delta(18)O between two waters, and can be reduced (to <1%) with proper measures. The injection of different amounts of water may affect the isotope ratio results. For example, in contrast to small injections (100 nL or less) from small syringes (e.g. 1.2 microL), large injections (1 microL or more) from larger syringes (e.g. 10 microL) with dilution produced asymmetric peaks and shifts of isotope ratios, e.g. 4 per thousand for delta(2)H and 0.4 per thousand for delta(18)O, probably resulting from isotope fractionation during dilution via the ConFlo interface. This method can be used to analyze nanoliter samples of water (e.g. 30 nL) with good precision of 0.5 per thousand for delta(2)H and 0.1 per thousand for delta(18)O. This is important for geosciences; for instance, fluid inclusions in ancient minerals may be analyzed for delta(2)H and delta(18)O to help understand the formation environments. PMID:19714707

  6. Influence of glacial meltwater on equilibrium process of two Tibetan lakes indicated by δ18O

    NASA Astrophysics Data System (ADS)

    Gao, J.

    2009-12-01

    δ18O measurements based on systematic sampling and isotopic model have been adopted to study the affects of glacial meltwater in two lake basins (Lakes Yamdrok-tso and Puma Yum-tso) at two different elevations on the southern Tibetan Plateau. Temporally, δ18O values in precipitation and lake water display a seasonal fluctuation in both lakes. Spatially, δ18O values in the two lake basins increase by 10‰ from the termini of glaciers to the lake shores, by about 1‰ from the lakeshores to the lake center, by 0.4‰ from the water surface to depth in these lakes. The obvious annual δ18O variations indicate that lake water mixes sufficient in a short time. Model results show that glacial meltwater is an important factor on lake water equilibrium process. Equilibrium δ18O values decrease 0.8‰ for Yamdrok-tso Lake and 0.6‰ for Puma Yum-tso Lake when contributions of glacial meltwater to these lakes shrink by 60%. δ18O increases rapidly during the initial stages and then it takes a long time to approach the equilibrium value. The modeled results also show that the surface lake water temperature has only a little impact on this process.

  7. Diachronous benthic δ18O responses during late Pleistocene terminations

    NASA Astrophysics Data System (ADS)

    Lisiecki, Lorraine E.; Raymo, Maureen E.

    2009-09-01

    Benthic δ18O is often used as a stratigraphic tool to place marine records on a common age model and as a proxy for the timing of ice volume/sea level change. However, Skinner and Shackleton (2005) found that the timing of benthic δ18O change at the last termination differed by 3900 years between one Atlantic site and one Pacific site. These results suggest that benthic δ18O change may not always accurately record the timing of deglaciation. We compare benthic δ18O records from 20 Atlantic sites and 14 Pacific sites to evaluate systematic differences in the timing of terminations in benthic δ18O. Analysis of sedimentation rates derived from the alignment of benthic δ18O suggests a statistically significant Atlantic lead over Pacific benthic δ18O change during the last six terminations. We estimate an average Pacific benthic δ18O lag of 1600 years for Terminations 1-5, slightly larger than the delay expected from ocean mixing rates given that most glacial meltwater probably enters the North Atlantic. We additionally find evidence of ˜4000-year Pacific δ18O lags at approximately 128 ka and 330 ka, suggesting that stratigraphic correlation of δ18O has the potential to generate age model errors of several thousand years during terminations. A simple model demonstrates that these lags can be generated by diachronous temperature changes and do not require slower circulation rates. Most importantly, diachronous benthic δ18O responses must be taken into account when comparing Atlantic and Pacific benthic δ18O records or when using benthic δ18O records as a proxy for the timing of ice volume change.

  8. A precise method for the analysis of d18O of dissolved inorganic phosphate in seawater

    USGS Publications Warehouse

    McLaughlin, K.; Silva, S.; Kendall, C.; Stuart-Williams, Hilary; Paytan, A.

    2004-01-01

    A method for preparation and analysis of the oxygen isotope composition (d18O) of dissolved inorganic phosphate (DIP) has been developed and preliminary results for water samples from various locations are reported. Phosphate is extracted from seawater samples by coprecipitation with magnesium hydroxide. Phosphate is further purified through a series of precipitations and resin separation and is ultimately converted to silver phosphate. Silver phosphate samples are pyrolitically decomposed to carbon monoxide and analyzed for d18O. Silver phosphate samples weighing 0.7 mg (3.5 mol oxygen) can be analyzed routinely with an average standard deviation of about 0.3. There is no isotope fractionation during extraction and blanks are negligible within analytical error. Reproducibility was determined for both laboratory standards and natural samples by multiple analyses. A comparison between filtered and unfiltered natural seawater samples was also conducted and no appreciable difference was observed for the samples tested. The d18O values of DIP in seawater determined using this method range from 18.6 to 22.3, suggesting small but detectable natural variability in seawater. For the San Francisco Bay estuary DIP d18O is more variable, ranging from 11.4 near the San Joaquin River to 20.1 near the Golden Gate Bridge, and was well correlated with salinity, phosphate concentration, and d18O of water.

  9. Tooth Enamel δ13C and δ18O Variations in Modern and Archaeological Horses From Northern Kazakhstan as Indicators of Regional Climate

    NASA Astrophysics Data System (ADS)

    Sikora, M. T.; Rosenmeier, M. F.; Stacy, E. M.; Olsen, S. L.

    2007-12-01

    In this study, the oxygen and carbon isotope values of tooth enamel were measured in forty-one modern and twenty-three Copper Age (3600 - 3100 B.C.) horse specimens from the grassland steppe region of northern Kazakhstan. Modern tooth enamel δ13C and δ18O values were compared with the carbon isotopic compositions of local vegetation and the δ18O values of meteoric waters. Tooth enamel isotope values within the Copper Age specimens (attributed to the so-called Botai culture) were, in turn, compared with modern samples. Average carbon isotopic values within modern bulk tooth enamel samples ranged between -13.7 and -12.0‰ (VPDB). This suggests that the diet of modern northern Kazakhstani horses is comprised almost entirely of C3 plants (considering enamel-diet fractionation factors) consistent with documented grassland compositions within the region. The observed amplitude of δ13C variations within individual teeth (typically less than ~2‰) suggests only minimal seasonal variation in the δ13C of grasses attributed to heat and water stress. Alternatively, the minimal seasonal changes observed within intra-tooth δ13C values may be the direct result of fodder provisioning. Ingested water δ18O values derived from oxygen isotope ratios within bulk tooth enamel samples appear statistically indistinguishable from estimates of regional precipitation, suggesting that Kazakhstani horse tooth enamel δ18O measurements may be used as a direct estimate of the oxygen isotopic composition of meteoric waters. Intra-tooth oxygen isotopic variations therefore reflect the pronounced seasonal variability in precipitation δ18O values tied to temperature changes and amount effects observed annually within Kazakhstan. However, these intra-tooth isotopic variations exhibit slightly reduced amplitudes relative to meteoric water values, suggesting that horses likely consume water from buffered sources such as lakes and wells. Average bulk tooth enamel δ13C values within

  10. Calibration of speleothem δ18O records against hydroclimate instrumental records in Central Brazil

    NASA Astrophysics Data System (ADS)

    Moquet, J. S.; Cruz, F. W.; Novello, V. F.; Stríkis, N. M.; Deininger, M.; Karmann, I.; Santos, R. Ventura; Millo, C.; Apaestegui, J.; Guyot, J.-L.; Siffedine, A.; Vuille, M.; Cheng, H.; Edwards, R. L.; Santini, W.

    2016-04-01

    δ18O in speleothems is a powerful proxy for reconstruction of precipitation patterns in tropical and sub-tropical regions. The aim of this study is to calibrate the δ18O record of speleothems against historical precipitation and river discharge data in central Brazil, a region directly influenced by the Southern Atlantic Convergence Zone (SACZ), a major feature of the South American Monsoon System (SAMS). The present work is based on a sub-annual resolution speleothem record covering the last 141 years (the period between the years 1870 and 2011) from a cave in central Brazil. The comparison of this record with instrumental hydroclimate records since 1921 allows defining a strong relationship between precipitation variability and stable oxygen isotope ratios from speleothems. The results from a monitoring program of climatic parameters and isotopic composition of rainfall and cave seepage waters performed in the same cave, show that the rain δ18O variability is dominated by the amount effect in this region, while δ18O drip water remains almost constant over the monitored period (1.5 years). The δ18O of modern calcite, on the other hand, shows clear seasonal variations, with more negative values observed during the rainy season, which implies that other factors also influence the isotopic composition of carbonate. However, the relationship between δ18O of carbonate deposits and rainwater is supported by the results from the comparison between speleothem δ18O records and historical hydroclimate records. A significant correlation between speleothem δ18O and monsoon rainfall variability is observed on sub-decadal time scales, especially for the monsoon period (DJFM and NDJFM), once the rainfall record have been smoothed with a 7-9 years running mean. This study confirms that speleothem δ18O is directly associated with monsoon rainfall variability in central Brazil. The relationship between speleothem δ18O records and hydroclimatic historical records allows

  11. Li sbnd δ 18O sbnd SiO 2 systematics in volcanic rocks and mafic lower crustal granulite xenoliths

    NASA Astrophysics Data System (ADS)

    Mengel, K.; Hoefs, J.

    1990-11-01

    Li sbnd δ 18O sbnd SiO 2 relationships have been examined for suites of spilitized basaltic rocks (DSDP 504B; Xigaze Ophiolite; Blanco Fracture Zone; Greater Caucasus; Rhenohercynian Fold Belt) and intra-plate evolved tholeiites (Northern Hessian Depression and Vogelsberg, W Germany; Mount Falla, Transantarctic Mountains). Relative to unaltered MORB and intra-plate primary olivine tholeiites, both the spilitic rocks and the evolved tholeiites are characterized by Li and 18O enrichment. For the spilitic rocks, Li and 18O enrichment is accompanied by a loss of SiO 2 as a result of seawater hydrothermal alteration, whereas the evolved tholeiites have gained SiO 2, Li and 18O from fractionation of mafic phases and assimilation of crustal rocks. On Li vs. SiO 2 and δ 18O vs. SiO 2 diagrams, the two rock groups plot largely in distinct fields, suggesting the possibility of so distinguishing between such lithologies in the ancient rock record. Mafic granulite xenoliths from the Northern Hessian Depression have elevated Li and 18O abundances at low SiO 2 contents. Even after correction for extraction of felsic components, their Li sbnd δ 18O sbnd SiO 2 signatures plot within the field of spilitic protoliths, suggesting that the lower crust in this region contains relics of spilitic rocks from a former oceanic crust.

  12. Large and unexpected enrichment in stratospheric 16O13C18O and its meridional variation

    PubMed Central

    Yeung, Laurence Y.; Affek, Hagit P.; Hoag, Katherine J.; Guo, Weifu; Wiegel, Aaron A.; Atlas, Elliot L.; Schauffler, Sue M.; Okumura, Mitchio; Boering, Kristie A.; Eiler, John M.

    2009-01-01

    The stratospheric CO2 oxygen isotope budget is thought to be governed primarily by the O(1D)+CO2 isotope exchange reaction. However, there is increasing evidence that other important physical processes may be occurring that standard isotopic tools have been unable to identify. Measuring the distribution of the exceedingly rare CO2 isotopologue 16O13C18O, in concert with 18O and 17O abundances, provides sensitivities to these additional processes and, thus, is a valuable test of current models. We identify a large and unexpected meridional variation in stratospheric 16O13C18O, observed as proportions in the polar vortex that are higher than in any naturally derived CO2 sample to date. We show, through photochemical experiments, that lower 16O13C18O proportions observed in the midlatitudes are determined primarily by the O(1D)+CO2 isotope exchange reaction, which promotes a stochastic isotopologue distribution. In contrast, higher 16O13C18O proportions in the polar vortex show correlations with long-lived stratospheric tracer and bulk isotope abundances opposite to those observed at midlatitudes and, thus, opposite to those easily explained by O(1D)+CO2. We believe the most plausible explanation for this meridional variation is either an unrecognized isotopic fractionation associated with the mesospheric photochemistry of CO2 or temperature-dependent isotopic exchange on polar stratospheric clouds. Unraveling the ultimate source of stratospheric 16O13C18O enrichments may impose additional isotopic constraints on biosphere–atmosphere carbon exchange, biosphere productivity, and their respective responses to climate change. PMID:19564595

  13. 18O enrichment in phosphorus pools extracted from soybean leaves.

    PubMed

    Pfahler, Verena; Dürr-Auster, Thilo; Tamburini, Federica; Bernasconi, M Stefano; Frossard, Emmanuel

    2013-01-01

    The objective of this study was to investigate the isotopic composition of oxygen bound to phosphate (δ(18)O-PO(4)) in different phosphorus (P) pools in plant leaves. As a model plant we used soybean (Glycine max cv Toliman) grown in the presence of ample P in hydroponic cultures. The leaf blades were extracted with 0.3 M trichloroacetic acid (TCA) and with 10 M nitric acid. These extractions allowed measurement of the TCA-soluble reactive P (TCA P) that is rapidly cycled within the cell and the total leaf P. The difference between total leaf P and TCA P yielded the structural P which includes organic P compounds not extractable by TCA. P uptake and its translocation and transformation within the soybean plants lead to an (18)O enrichment of TCA P (δ(18)O-PO(4) between 16.9 and 27.5‰) and structural P (δ(18)O-PO(4) between 42.6 and 68.0 ‰) compared with 12.4‰ in the phosphate in the nutrient solution. δ(18)O values of phosphate extracted from soybean leaves grown under optimal conditions are greater than the δ(18)O-PO(4) values of the provided P source. Furthermore, the δ(18)O-PO(4) of TCA P seems to be controlled by the δ(18)O of leaf water and the activity of inorganic pyrophosphatase or other pyrophosphatases. PMID:23106517

  14. Analyses of FT spectra of C2V ozone isotopologues in the 4500-5700 cm-1 region: 16O18O16O, 18O16O18O and 18O3

    NASA Astrophysics Data System (ADS)

    Barbe, A.; De Backer, M.-R.; Starikova, E.; Thomas, X.; Tyuterev, Vl. G.

    2014-12-01

    This work continues the systematic investigation of high resolution infrared spectra of 18O enriched ozone isotopologues in the 4500-6300 cm-1 spectral range. So far, the 16O18O16O and 18O16O18O spectra have been recorded and analysed using Fourier Transform Spectrometer (FTS) below 5000 cm-1 and using high sensitivity Cavity Ring-Down Spectroscopy above 6000 cm-1. In order to fill the gap between 5000 and 6000 cm-1, new infrared spectra were recorded with the Reims FTS. The analyses of the 2ν1+ν2+3ν3 band of 16O18O16O and of the 5ν3, ν1+2ν2+3ν3 and ν1+5ν3 bands of 18O16O18O are reported. New ν1+2ν2+3ν3 and ν1+5ν3 bands of 18O3 were also observed and analysed. Observed line positions were fitted using effective Hamiltonian models accounting for the dark state perturbations. The derived band centres and rotational constants are in a good agreement with new theoretical calculations from the molecular potential function.

  15. W18O49 Nanowires as Ultraviolet Photodetector

    PubMed Central

    2010-01-01

    Photodetectors in a configuration of field effect transistor were fabricated based on individual W18O49 nanowires. Evaluation of electrical transport behavior indicates that the W18O49 nanowires are n-type semiconductors. The photodetectors show high sensitivity, stability and reversibility to ultraviolet (UV) light. A high photoconductive gain of 104 was obtained, and the photoconductivity is up to 60 nS upon exposure to 312 nm UV light with an intensity of 1.6 mW/cm2. Absorption of oxygen on the surface of W18O49 nanowires has a significant influence on the dark conductivity, and the ambient gas can remarkably change the conductivity of W18O49 nanowire. The results imply that W18O49 nanowires will be promising candidates for fabricating UV photodetectors. PMID:20671789

  16. δ18O and δ13C values of modern brachiopod shells

    NASA Astrophysics Data System (ADS)

    Carpenter, Scott J.; Lohmann, Kyger C.

    1995-09-01

    Researchers have not rigorously tested the hypothesis that calcite from modern brachiopod shells is precipitated in oxygen isotope equilibrium with ambient seawater. Isotopic variability at the intraspecimen and intertaxon levels has not been examined. Without such data for modern brachiopods, similar data from ancient brachiopods cannot be accurately interpreted. In this study, a survey is made of δ18O and δ13C values of Terebratulid, Rhynchonellid, Thecideidine, and Craniacean brachiopods from Antarctica, the Bay of Fundy, Curacao, Japan, New Zealand, Norway, Puget Sound, Palau, Sicily, and South Africa. This suite of samples provides a wide range of taxonomic levels, temperatures, salinities, and depositional environments for evaluating the degree of isotopic equilibrium attained during precipitation of brachiopod calcite. New data indicate that modem brachiopod calcite is not always precipitated in oxygen and carbon isotope equilibrium with ambient seawater. Calcite from the primary layer and specialized shell structures (hinge, brachidium, foramen, interarea, muscle scars) are depleted in both 18O and 13C, a characteristic of biological fractionation or "vital" effects often found in other calcerous, marine organisms. Our findings suggest that these portions of the brachiopod shell should be avoided during sampling of ancient brachiopods. Secondary layer calcite, the material most often analyzed in ancient brachiopods, has higher δ18O and δ13C values which approach and sometimes correspond with predicted equilibrium values. Therefore, secondary layer calcite is the most suitable portion of the brachiopod shell for use as an ancient seawater proxy. Although near equilibrium precipitation in secondary layer calcite is encouraging to those studying the isotopic composition of ancient oceans, these data come with caveats. Large intraspecimen variability in the δ18O values of secondary layer calcite (±1‰ in some samples) limits the use of brachiopods as

  17. The enigma of effective pathlength for 18O enrichment in leaf water of conifers

    NASA Astrophysics Data System (ADS)

    Roden, J. S.; Kahmen, A.; Buchmann, N. C.; Siegwolf, R. T.

    2013-12-01

    The stable isotopes of oxygen (δ18O) in tree ring cellulose provide valuable proxy information about past environments and climate. Mechanistic models have been used to clarify the important drivers of isotope fractionation and help interpret δ18O variation in tree rings. A critical component to these models is an estimate of leaf water enrichment. However, standard models seldom accurately predict 18O enrichment in conifer needles and Péclet corrections often require effective pathlengths (L) that seem unreasonable from the perspective of needle morphology (>0.5 m). To analyze the potential role of path length on the Péclet effect in conifers we carried out experiments in controlled environment chambers. We exposed seedlings of six species of conifer (Abies alba, Larix decidua, Picea abies, Pinus cembra, P. sylvestris, Taxus bacata), that differ in needle morphology, to four different vapor pressure deficits (VPD), in order to modify transpiration rates (E) and leaf water 18O enrichment. Environmental and δ18O data (leaf, stem and chamber water vapor) were collected to parameterize leaf water models. Cross-sections of needles were sampled for an analysis of needle anatomy. Conifer needles have a single strand of vascular tissue making pathlength determinations through anatomical assessments possible. The six species differed in mesophyll distance (measured from endodermis to epidermis) and cell number, with Pinus and Picea species having the shortest distance and Abies and Taxus the longest (flat needle morphology). Other anatomical measures (transfusion distance, cell size etc.) did not differ significantly. A suberized strip was apparent in the endodermis of all species except Taxus and Abies. Conifer needles have a large proportion (from 0.2 to 0.4) of needle cross-sectional area in vascular tissues that may not be subject to evaporative enrichment. As expected, leaf water δ18O and E responded strongly to VPD and standard models (Craig

  18. Abrupt shift in δ18O values at Medicine Lake volcano (California, USA)

    USGS Publications Warehouse

    Donnelly-Nolan, J. M.

    1998-01-01

     Oxygen-isotope analyses of lavas from Medicine Lake volcano (MLV), in the southern Cascade Range, indicate a significant change in δ18O in Holocene time. In the Pleistocene, basaltic lavas with <52% SiO2 averaged +5.9‰, intermediate lavas averaged +5.7‰, and silicic lavas (≥63.0%SiO2) averaged +5.6‰. No analyzed Pleistocene rhyolites or dacites have values greater than +6.3‰. In post-glacial time, basalts were similar at +5.7‰ to those erupted in the Pleistocene, but intermediate lavas average +6.8‰ and silicic lavas +7.4‰ with some values as high as +8.5‰. The results indicate a change in the magmatic system supplying the volcano. During the Pleistocene, silicic lavas resulted either from melting of low-18O crust or from fractionation combined with assimilation of very-low-18O crustal material such as hydrothermally altered rocks similar to those found in drill holes under the center of the volcano. By contrast, Holocene silicic lavas were produced by assimilation and/or wholesale melting of high-18O crustal material such as that represented by inclusions of granite in lavas on the upper flanks of MLV. This sudden shift in assimilant indicates a fundamental change in the magmatic system. Magmas are apparently ponding in the crust at a very different level than in Pleistocene time.

  19. Theoretical Calibration on the 13C-18O Clumped Isotope Thermometer

    NASA Astrophysics Data System (ADS)

    Tang, M.; Zhang, S. T.; LIU, Q.; Liu, Y.

    2014-12-01

    The kinetic isotope effect (KIE) arisen from phosphoric acid digestion of carbonates has been noticed since the beginning of stable isotope geochemistry. However, the molecular level details of this reaction have not been fully understood yet. Equilibrium 13C-18O clumped isotope distribution in carbonates has been suggested as a new thermometer for surface temperature systems; nevertheless, existing Δ47-T relationships calibrated by several different groups are incompatible, generating substantial confusions and debates about those variations. Here we propose a new molecular-level mechanism with three parallel pathways for the phosphoric acid digestion of carbonates. We show that the KIE of such reaction can be different if the relative contributions of the three parallel pathways are changed. This new mechanism abandons completely a previously proposed molecular mechanism (i.e., Guo et al., 2009) and can explain (at least partly) why the Δ47-T relationships provided by different groups are different. Together with a re-calculated equilibrium clumped isotope fractionation factors of carbonate minerals using a new volume-variable-cluster-model method with higher theoretical-level treatments and higher-order anharmonic corrections, we present a theoretical (equilibrium + KIE) Δ47-T relationship for carbonates. Our theoretical calibration line is with large variations due to considering possible changes of relative contributions of the three parallel pathways and different carbonate mineral used. For minimizing the variation, we suggest using the same amount of sample, the same mineral and the same temperature of phosphoric acid digestion for this experiment.

  20. Influence of glacial meltwater and humidity on evaporation of two Tibetan lakes indicated by delta 18O

    NASA Astrophysics Data System (ADS)

    Gao, J.

    2009-04-01

    delta 18O and model results are adopted to study the affects of glacial meltwater and relative humidity in two lake basins (Lakes Yamdrok-tso and Puma Yum-tso) at two different elevations on the southern Tibetan Plateau. Temporally, the lake water delta 18O of Yamdrok-tso Lake displays a seasonal fluctuation, whereas the lake water delta 18O is stable in Puma Yum-tso Lake in whole year. Spatially, the delta 18O value in Yamdrok-tso Lake is 2‰ higher than that in Puma Yum-tso Lake. delta 18O values in the two lake basins increase by 10‰ from the termini of glaciers to the lake shores, by about 1‰ from the lakeshores to the lake center, by 0.4‰ from the water surface to depth in these lakes. The largest difference, from the terminus of the Qiangyong Glacier to the depth of 35 m, is 14.1‰ and demonstrates the importance of glacial meltwater. Evaporation alters the changes of delta 18O in the two lake basins. Model results show that relative humidity is a major controlling factor of evaporation. delta 18O values of both Yamdrok-tso and Puma Yum-tso Lakes are at their steady condition, but Puma Yum-tso Lake has taken a longer time to approach the current condition, which might be attributed to higher humidity and more glacial meltwater at the lake.

  1. Constraining the origin of the Messinian gypsum deposits using coupled measurement of δ^{18}O$/δD in gypsum hydration water and salinity of fluid inclusions

    NASA Astrophysics Data System (ADS)

    Evans, Nicholas P.; Gázquez, Fernando; McKenzie, Judith A.; Chapman, Hazel J.; Hodell, David A.

    2016-04-01

    We used oxygen and hydrogen isotopes of gypsum hydration water (GHW) coupled with salinity deduced from ice melting temperatures of primary fluid inclusions in the same samples (in tandem with 87Sr/86Sr, δ34S and other isotopic measurements) to determine the composition of the mother fluids that formed the gypsum deposits of the Messinian Salinity Crisis from shallow and intermediate-depth basins. Using this method, we constrain the origin of the Messinian Primary Lower Gypsum (PLG) of the Sorbas basin (Betic foreland) and both the Upper Gypsum (UG) and the Lower Gypsum of the Sicilian basin. We then compare these results to measurements made on UG recovered from the deep Ionian and Balearic basins drilled during DSDP Leg 42A. The evolution of GHW δ18O/δD vs. salinity is controlled by mixing processes between fresh and seawater, coupled with the degree of evaporation. Evaporation and subsequent precipitation of gypsum from fluids dominated by freshwater will result in a depressed 87Sr/86Sr values and different trajectory in δ18O/δD vs. salinity space compared to fluids dominated by seawater. The slopes of these regression equations help to define the end-members from which the fluid originated. For example, salinity estimates from PLG cycle 6 in the Sorbas basin range from 18 to 51ppt, and after correction for fractionation factors, estimated δ18O and δD values of the mother water are low (-2.6 < δ18O < 2.7‰ ; -16.2 < δD < 15.8‰). The intercepts of the regression equations (i.e. at zero salinity) are within error of the average isotope composition of the modern precipitation and groundwater in this region of SE Spain. This indicates there was a significant contribution of meteoric water during gypsum deposition, while 87Sr/86Sr (0.708942 < 87Sr/86Sr < 0.708971) indicate the ions originated from the dissolution of previously marine evaporites. Gypsum from cycle 2 displays similar mother water values (-2.4 < δ18O < 2.4‰ ; -13.2 < δD < 17.0‰) to

  2. δ18O water isotope in the iLOVECLIM model (version 1.0) - Part 1: Implementation and verification

    NASA Astrophysics Data System (ADS)

    Roche, D. M.

    2013-03-01

    A new 18O stable water isotope scheme is developed for three components of the iLOVECLIM coupled climate model: atmospheric, oceanic and land surface. The equations required to reproduce the fractionation of stable water isotopes in the simplified atmospheric model ECBilt are developed consistently with the moisture scheme. Simplifications in the processes are made to account for the simplified vertical structure including only one moist layer. Implementation of these equations together with a passive tracer scheme for the ocean and a equilibrium fractionation scheme for the land surface leads to the closure of the (isotopic-)water budget in our climate system. Following the implementation, verification of the existence of usual δ18O to climatic relationships are performed for the Rayleigh distillation, the Dansgaard relationship and the δ18O-salinity relationship. Advantages and caveats of the approach taken are outlined.

  3. Immunogenic dialyzable factor derived from a ribosomal fraction of Salmonella typhimurium. I. Preparation of the protective dialyzable factor from the ribosomal fraction by the freeze-thaw procedure.

    PubMed

    Kita, E; Matsuura, H; Masuda, S; Tomihata, S; Kashiba, S

    1983-01-01

    The preparation, properties, and immunogenicity of the dialyzable factor from a ribosomal fraction of Salmonella typhimurium are described. The ribosomal fraction was purified to eliminate O-antigenic components, by affinity chromatography (Sepharose-anti-O antibody conjugates used as immunoadsorbent). The dialyzable factor was obtained in the concentrated dialysate of the purified ribosomal fraction which was alternately frozen in dry-ice acetone and thawed in an 80 C water bath, for a total of five or six cycles. When this preparation was tested for its ability to protect mice against challenge with 1,000 LD50 of the homologous bacteria, it afforded 100% protection at a dose equivalent to 5.0 micrograms of RNA. The protection conferred by this factor was mainly cell mediated but immune serum enhanced this immunity despite the fact that no antibodies were detected in it. The protective activity of this factor was sensitive to RNase digestion but resistant to proteolytic enzymes. Ion exchange chromatography of this factor with DEAE-Sephadex A-25 (in 7 M Urea-0.02 M Tris-HCl buffer, pH 7.5) resulted in a single A260 peak which was found to be immunogenic. Chemical analysis of this peak after it was concentrated and desalted revealed that this immunogenic fraction was composed mainly of mixed nucleotides. The data indicate that protective immunity conferred by a ribosomal vaccine is associated with RNA but may not require the intact RNA molecule. PMID:6346023

  4. Ultrathin W18O49 nanowire assemblies for electrochromic devices.

    PubMed

    Liu, By Jian-Wei; Zheng, Jing; Wang, Jin-Long; Xu, Jie; Li, Hui-Hui; Yu, Shu-Hong

    2013-08-14

    Ordered W18O49 nanowire thin films were fabricated by Langmuir-Blodgett (LB) technique in the presence of poly(vinyl pyrrolidone) coating. The well-organized monolayer of W18O49 nanowires with periodic structures can be readily used as electrochromic sensors, showing reversibly switched electrochromic properties between the negative and positive voltage. Moreover, the electrochromism properties of the W18O49 nanowire films exhibit significant relationship with their thickness. The coloration/bleaching time was around 2 s for the W18O49 nanowire monolayer, which is much faster than the traditional tungsten oxide nanostructures. Moreover, the nanowire devices display excellent stability when color switching continues, which may provide a versatile and promising platform for electrochromism device, smart windows, and other applications. PMID:23869487

  5. Late Holocene hydroclimate change inferred from δ18O of lake sediments, Lost River Range, Idaho

    NASA Astrophysics Data System (ADS)

    Krueger, C. R.; Finney, B. P.; Shapley, M.

    2012-12-01

    High-resolution paleohydrological records are needed to assess the frequency and magnitude of past droughts in Idaho and the northern Rocky Mountain region, but are scarce in this semi-arid region. Sediments from Lost Keys Pond (LKP) can be used to reconstruct hydroclimate. LKP is closed to surface outflow and is therefore sensitive to precipitation minus evaporation; surface water is enriched in δ18O compared to the local meteoric waters. In summer 2011 several sediment cores were collected from LKP using a square rod piston corer; the focus of this analysis is an 82-cm Bolivia core. This core contains thinly banded to laminated, authigenic carbonate mud, a recorder of lake δ18O at the time of deposition. This core was sampled for δ18O and /δ13C at 0.5 cm intervals, and the <20 um fraction was isolated to avoid any detrital carbonate. Based on the current age model, sampling at this interval records sub-decadal (5-10 year) hydroclimate variability. The δ18O signal recovered has 5‰ variability over the length of the record, including several major fluctuations in last 1,000 years. During this period, several major dry and wet periods have been recorded occurring over multidecadal timescales, with a trend toward increasing aridity. The δ18O and δ13C records in the lowest decimeter are divergent and mirror each other, above this interval isotopic records have strong covariance. This pattern may be indicative of a change from surface outflow to no surface outflow conditions. The age model is being refined to better assess how this record correlates with other regional records, and ultimately improve our understanding of past atmospheric circulation.

  6. Leaf cellulose δD and δ 18O trends with elevation differ in direction among co-occurring, semiarid plant species

    NASA Astrophysics Data System (ADS)

    Terwilliger, Valery J.; Betancourt, Julio L.; Leavitt, Steven W.; Van de water, Peter K.

    2002-11-01

    The potential to reconstruct paleoclimate from analyses of stable isotopes in fossil leaf cellulose could be enhanced by adequate calibration. This potential is likely to be particularly great in mid-latitude deserts, where a rich store of fossil leaves is available from rodent middens. Trends in δD and δ 18O of leaf cellulose were examined for three species growing across climatic gradients caused by elevation and slope aspect in southeastern Utah, USA. The species differed in morphology ( Pinus edulis vs. Yucca glauca), photosynthetic pathway (C 3Y. glauca vs. CAM Yucca baccata) or both ( P. edulis vs. Y. baccata). The δD LCN (leaf cellulose nitrate) and δ 18O LC (leaf cellulose) values of P. edulis decreased with elevation. Stem water δD values either increased (in spring) or did not change with elevation (in summer). Needle water δD values usually decreased with elevation and differed greatly with leaf age. These results suggest that δ cellulose values of P. edulis record the effects of climate on the isotopic composition of leaf water but not climate effects on meteoric water. In contrast to P. edulis, δD LCN values of Y. glauca increased with elevation. The δ 18O LC values of Y. glauca also increased with elevation but less significantly and only on south-facing slopes. The δ cellulose values in both P. edulis and Y. glauca were most significantly related to changes in temperature, although temperature and precipitation were negatively correlated in the study area. Where all three species co-occurred, their δD LCN values differed but their δ 18O LC values were the same. The disparity in δD LCN between Y. baccata and the other species corresponds to differences in biochemical fractionations associated with photosynthetic pathway. Biochemical fractionations may also contribute to differences between the two C 3 species. Knowledge of factors affecting responses of individual plant species to environment may be required to infer climate from δD LCN

  7. Direct Synthesis of ESBO Derivatives-18O Labelled with Dioxirane

    PubMed Central

    Tommasi, Immacolata; Fusco, Caterina

    2013-01-01

    This work addresses a new approach developed in our laboratory, consisting in the application of isolated dimethyldioxirane (DDO, 1a) labelled with 18O for synthesis of epoxidized glyceryl linoleate (Gly-LLL, 2). We expect that this work could contribute in improving analytical methods for the determination of epoxidized soybean oil (ESBO) in complex food matrices by adopting an 18O-labelled-epoxidized triacylglycerol as an internal standard. PMID:24163617

  8. Leaf cellulose δD and δ18O trends with elevation differ in direction among co-occurring, semiarid plant species

    USGS Publications Warehouse

    Terwilliger, Vallery J.; Betancourt, Julio L.; Leavitt, Steven W.; Van De Water, Peter K.

    2002-01-01

    The potential to reconstruct paleoclimate from analyses of stable isotopes in fossil leaf cellulose could be enhanced by adequate calibration. This potential is likely to be particularly great in mid-latitude deserts, where a rich store of fossil leaves is available from rodent middens. Trends in ??D and ??18O of leaf cellulose were examined for three species growing across climatic gradients caused by elevation and slope aspect in southeastern Utah, USA. The species differed in morphology (Pinus edulis vs. Yucca glauca), photosynthetic pathway (C3 Y. glauca vs. CAM Yucca baccata) or both (P. edulis vs. Y. baccata). The ??DLCN (leaf cellulose nitrate) and ??18OLC (leaf cellulose) values of P. edulis decreased with elevation. Stem water ??D values either increased (in spring) or did not change with elevation (in summer). Needle water ??D values usually decreased with elevation and differed greatly with leaf age. These results suggest that ?? cellulose values of P. edulis record the effects of climate on the isotopic composition of leaf water but not climate effects on meteoric water. In contrast to P. edulis, ??DLCN values of Y. glauca increased with elevation. The ??18O LC values ofc Y. glauca also increased with elevation but less significantly and only on south-facing slopes. The ?? cellulose values in both P. edulis and Y. glauca were most significantly related to changes in temperature, although temperature and precipitation were negatively correlated in the study area. Where all three species co-occurred, their ??DLCN values differed but their ??18O LC values were the same. The disparity in ??DLCN between Y. baccata and the other species corresponds to differences in biochemical fractionations associated with photosynthetic pathway. Biochemical fractionations may also contribute to differences between the two C3 species. Knowledge of factors affecting responses of individual plant species to environment may be required to infer climate from ??DLCN and ??18OLC

  9. First results from a novel methodological approach for δ18O analyses of sugars using GC-Py-IRMS

    NASA Astrophysics Data System (ADS)

    Zech, Michael; Saurer, Matthias; Tuthorn, Mario; Rinne, Katja; Werner, Roland; Juchelka, Dieter; Siegwolf, Rolf; Glaser, Bruno

    2013-04-01

    statistically not significant) for δ18O of sucrose (n = 7) and bulk δ18O (R = 0.62), δ13C of sucrose (R = 0.55) and maximum day temperature (R = 0.58) and negative correlation for δ18O of sucrose and cloudiness (R = -0.80). This highlights the great potential of compound-specific δ18O analyses of sucrose for (paleo-) plimate studies. Zech, M., Glaser, B., 2009. Compound-specific d18O analyses of neutral sugars in soils using GC-Py-IRMS: problems, possible solutions and a first application. RCM 23, 3522-3532. Zech, M., Tuthorn, M., Glaser, B., Amelung, W., Huwe, B., Zech, W., Zöller, L., Löffler, J., 2013. Natural abundance of 18O of sugar biomarkers in topsoils along a climate transect over the Central Scandinavian Mountains, Norway. JPNSS, in press. Zech, M., Werner, R., Juchelka, D., Kalbitz, K., Buggle, B., Glaser, B., 2012. Absence of oxygen isotope fractionation/exchange of (hemi-) cellulose derived sugars during litter decomposition. Org Geochem 42, 1470-1475.

  10. Speleothem calcite farmed in situ: Modern calibration of δ 18O and δ 13C paleoclimate proxies in a continuously-monitored natural cave system

    NASA Astrophysics Data System (ADS)

    Tremaine, Darrel M.; Froelich, Philip N.; Wang, Yang

    2011-09-01

    changes in cave ventilation due to dissolution fissures and ceiling collapse creating and plugging ventilation windows. Farmed calcite δ 18O was found to exhibit a +0.82 ± 0.24‰ offset from values predicted by both theoretical calculations and laboratory-grown inorganic calcite. Unlike δ 13C CaCO3, oxygen isotopes showed no ventilation effects, i.e. Δδ 18O CaCO3 appears to be a function of growth temperature only although we cannot rule out a small effect of (unmeasured) gradients in relative humidity (evaporation) accompanying ventilation. Our results support the findings of other cave investigators that water-calcite fractionation factors observed in speleothem calcite are higher that those measured in laboratory experiments. Cave and laboratory calcite precipitates may differ mainly in the complex effects of kinetic isotope fractionation. Combining our data with other recent speleothem studies, we find a new empirical relationship for cave-specific water-calcite oxygen isotope fractionation across a range of temperatures and cave environments: 1000lnα=16.1103T-1-24.6 with a fractionation temperature dependence of Δδ 18O/Δ T = -0.177‰/°C, lower than the currently accepted -0.206‰/°C.

  11. Influence of glacial meltwater on water balance processes of two Tibetan lakes indicated by δ18O

    NASA Astrophysics Data System (ADS)

    Gao, J.; Itpcas

    2011-12-01

    δ18O measurements based on systematic sampling and isotopic modeling have been adopted to study the affects of glacial meltwater in two lake basins (Lakes Yamdrok-tso and Puma Yum-tso) at two different elevations on the southern Tibetan Plateau. Temporally, δ18O values in precipitation and lake water display a seasonal fluctuation in both lakes. Spatially, δ18O values in the two lake basins increase by 10% from the termini of glaciers to the lake shores, by about 1% from the lakeshores to the lake center, by 0.4% from the water surface to depth in these lakes. The obvious annual δ18O variations indicate that lake water mixes sufficiently in a short time. Model results show that glacial meltwater is an important factor on lake water balance process. Equilibrium δ18O values decrease 0.8% for Yamdrok-tso Lake and 0.6% for Puma Yum-tso Lake when contributions of glacial meltwater to these lakes shrink by 60%. δ18O ratios increase rapidly during the initial stages and take a relatively longer time to approach the equilibrium value. The modeled results also show that the surface lake water temperature has a minimal impact on this process.
    Dr. Jing Gao

  12. Elastic and inelastic scattering of 16O and 18O ions from 64Zn at energies near the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Salém-Vasconcelos, S.; Takagui, E. M.; Bechara, M. J.; Koide, K.; Dietzsch, O.; Bairrio Nuevo, A., Jr.; Takai, H.

    1994-08-01

    Coulomb-nuclear interference effects were investigated in the inelastic scattering of 16O and 18O by 64Zn. Measurements of elastic and inelastic angular distributions of 18O were performed at a laboratory energy of 49 MeV, over the angular range from θlab~30° to 85°. The excitation functions of 16O and 18O ions were measured at incident energies between 29 and 46 MeV at θlab=174°. The experimental angular distributions show structures which are more pronounced for projectile excitation than for target excitation. The interference minimum for the excitation of the 18O first 2+ state was found to be shifted towards forward angles by approximately 5° (c.m.) with respect to the distorted-wave Born approximation calculations and by approximately 3.5° (c.m.) with respect to the coupled-channels calculations. A pronounced Coulomb-nuclear interference minimum was seen in the excitation of 64Zn(2+) state by inelastic scattering of 16O projectiles, whereas no pronounced minimum was observed in target excitation by 18O projectiles. The elastic scattering data were analyzed with the optical model. The inelastic differential cross sections for the excitation of the first 2+ states in the target and in the 18O projectile were analyzed using the distorted-wave Born approximation and also the coupled-channels approach with collective form factors.

  13. Oxygen isotope fractionation in double carbonates.

    PubMed

    Zheng, Yong-Fei; Böttcher, Michael E

    2016-01-01

    Oxygen isotope fractionations in double carbonates of different crystal structures were calculated by the increment method. Synthesis experiments were performed at 60 °C and 100 °C to determine oxygen and carbon isotope fractionations involving PbMg[CO3]2. The calculations suggest that the double carbonates of calcite structure are systematically enriched in (18)O relative to those of aragonite and mixture structures. Internally consistent oxygen isotope fractionation factors are obtained for these minerals with respect to quartz, calcite and water at a temperature range of 0-1200 °C. The calculated fractionation factors for double carbonate-water systems are generally consistent with the data available from laboratory experiments. The experimentally determined fractionation factors for PbMg[CO3]2, BaMg[CO3]2 and CaMg[CO3]2 against H2O not only fall between fractionation factors involving pure carbonate end-members but are also close to the calculated fractionation factors. In contrast, experimentally determined carbon isotope fractionation factors between PbMg[CO3]2 and CO2 are much closer to theoretical predictions for the cerussite-CO2 system than for the magnesite-CO2 system, similar to the fractionation behavior for BaMg[CO3]2. Therefore, the combined theoretical and experimental results provide insights into the effects of crystal structure and exchange kinetics on oxygen isotope partitioning in double carbonates. PMID:25393769

  14. Oxygen isotope ratios (18O/16O) of hemicellulose-derived sugar biomarkers in plants, soils and sediments as paleoclimate proxy I: Insight from a climate chamber experiment

    NASA Astrophysics Data System (ADS)

    Zech, Michael; Mayr, Christoph; Tuthorn, Mario; Leiber-Sauheitl, Katharina; Glaser, Bruno

    2014-02-01

    enrichment of leaf water. Finally, we present a conceptual model for the interpretation of δ18Ohemicellulose records and propose that a combined δ18Ohemicellulose and δ2Hn-alkane biomarker approach is promising for disentangling δ18Oprecipitation variability from evapotranspirative 18O enrichment variability in future paleoclimate studies. One major factor influencing δ18Ohemicellulose is the oxygen isotopic composition of the plant source water (Fig. 4). Basically, it depends on δ18Oprecipitation which can vary over time due to temperature, amount and/or source effects (Dansgaard, 1964; Rozanski et al., 1993; Araguas-Araguas et al., 2000). While it is generally accepted that the uptake of water by roots is not associated with a 18O fractionation (Wershaw et al., 1966; Dawson et al., 2002), other factors may need careful consideration. For instance, the uptake of ground water depleted in 18O by deep rooting plants versus uptake of soil water enriched in 18O by evaporation (Fig. 4), seasonality of δ18Oprecipitation (growing season) (see also our companion study presented by Tuthorn et al., 2014) or uptake of permafrost meltwater (Sugimoto et al., 2002). A second major influencing factor is evapotranspirative 18O enrichment of leaf water (Fig. 4). It is most rigorously controlled by relative air humidity (Fig. 3A), whereas the direct physical effect of temperature on evapotranspirative 18O enrichment is much smaller (Fig. 3B). However, temperature can indirectly exert influence via plant physiological reactions, namely by affecting the transpiration rate which strongly controls δ18Oleaf water due to the Péclet effect at least under very arid climatic conditions (Fig. 3C). While this effect is highlighted in the here presented climate chamber study with an automatic irrigation system, the relevance of the temperature and the Péclet effect in paleoclimate studies where water supply is actually often limited is presumably considerably lower than the relevance of

  15. Determination of the delta(18O/16O)of Water: RSIL Lab Code 489

    USGS Publications Warehouse

    Revesz, Kinga; Coplen, Tyler

    2008-01-01

    The purpose of the technique described by the Reston Stable Isotope Laboratory (RSIL) lab code 489 is to present a method to determine the delta(180/160), abbreviated as delta-180, of water. This delta-18O measurement of water also is a component of National Water Quality Laboratory (NWQL in USGS) schedules 1142 and 1172. Water samples are loaded into glass sample containers on a vacuum manifold to equilibrate gaseous CO2 at constant temperature (25 deg C) with water samples. After loading water samples on the vacuum manifold, air is evacuated through capillary to avoid evaporation, and CO2 is added. The samples are shaken to increase the equilibration rate of water and CO2. When isotopic equilibrium has been attained, an aliquot of CO2 is extracted sequentially from each sample container, separated from water vapor by means of a dry ice trap, and introduced into a dual-inlet isotope-ratio mass spectrometer (DI-IRMS) for determination of the delta-18O value. There is oxygen isotopic fractionation between water and CO2, but it is constant at constant temperature. The DI-IRMS is a DuPont double-focusing mass spectrometer. It has a double collector. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other ion beams are collected in the front collector. The instrument is capable of measuring mass/charge (m/z) 44 and 45 or 44 and 46 by changing the ion-accelerating voltage under computer control. The ion beams from these m/z values are as follows: m/z 44=CO2=12C16O16O, m/z 45=CO2=13C16O16O primarily, and m/z 46 = CO2=12C16O18O primarily. The data acquisition and control software calculates delta-18O values.

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

    NASA Astrophysics Data System (ADS)

    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 < -22.7‰) the residual sulfate showed an increase of the sulfate δ 18O close to the values of the enriched water of +700‰. In the experiments with δ 18O-depleted water, the oxygen isotope values in the residual sulfate stayed fairly constant for strains Desulfovibrio desulfuricans, Desulfobacca acetoxidans and Desulfonatronovibrio hydrogenovorans. However, strain TRM1, which exhibits the lowest sulfur isotope fractionation factor ( ɛS < -38.7‰) showed slightly decreasing δ 18O values. Our results give strong evidence that

  17. Oxygen isotope fractionation in phosphates: the role of dissolved complex anions in isotope exchange.

    PubMed

    Zheng, Yong-Fei

    2016-01-01

    Oxygen isotope fractionation factors for phosphates were calculated by means of the increment method. The results suggest that Ag3PO4 and BiPO4 are enriched in (18)O relative to AgPO4, and the three phosphates are consistently depleted in (18)O relative to Ba3[PO4]2; fluorapatite and chlorapatite exhibit a similar behaviour of oxygen isotope fractionation with consistent enrichment of (18)O relative to hydroxyapatite. The valence, radii and coordination of metal cations play a quantitative role in dictating the (18)O/(16)O partitioning in these phosphates of different compositions. The calculated fractionation factors for the Ag3PO4-H2O system are in agreement with experimental determinations derived from enzyme-catalysed isotope exchange between dissolved inorganic phosphate and water at the longest reaction durations at low temperatures. This demonstrates that the precipitated Ag3PO4 has completely captured the oxygen isotope fractionation in the dissolved inorganic phosphate. The calculated fractionation factors for the F/Cl-apatite-water systems are in agreement with the enzyme-catalysed experimental fractionations for the dissolved phosphate-water system at the longest reaction durations but larger than fractionations derived from bacteria-facilitated exchange and inorganic precipitation experiments as well as natural observations. For the experimental calibrations of oxygen isotope fractionation involving the precipitation of dissolved phosphate species from aqueous solutions, the fractionation between precipitate and water is primarily dictated by the isotope equilibration between the dissolved complex anions and water prior to the precipitation. Therefore, the present results provide a quantitative means to interpret the temperature dependence of oxygen isotope fractionation in inorganic and biogenic phosphates. PMID:25587823

  18. (16) O/(18) O Exchange of Aldehydes and Ketones caused by H2 (18) O in the Mechanistic Investigation of Organocatalyzed Michael, Mannich, and Aldol Reactions.

    PubMed

    Hayashi, Yujiro; Mukaiyama, Takasuke; Benohoud, Meryem; Gupta, Nishant R; Ono, Tsuyoshi; Toda, Shunsuke

    2016-04-18

    Organocatalyzed Michael, Mannich, and aldol reactions of aldehydes or ketones, as nucleophiles, have triggered several discussions regarding their reaction mechanism. H2 (18) O has been utilized to determine if the reaction proceeds through an enamine or enol mechanism by monitoring the ratio of (18) O incorporated into the final product. In this communication, we describe the risk of H2 (18) O as an evaluation tool for this mechanistic investigation. We have demonstrated that exchange of (16) O/(18) O occurs in the aldehyde or ketone starting material, caused by the presence of H2 (18) O and amine catalysts, before the Michael, Mannich, and aldol reactions proceed. Because the newly generated (18) O starting aldehydes or ketones and (16) O water affect the incorporation ratio of (18) O in the final product, the use of H2 (18) O would not be appropriate to distinguish the mechanism of these organocatalyzed reactions. PMID:26841358

  19. Multinucleon transfer study in 206Pb(18O,x ) at energies above the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Sonika, Roy, B. J.; Parmar, A.; Pal, U. K.; Kumawat, H.; Jha, V.; Pandit, S. K.; Parkar, V. V.; Ramachandran, K.; Mahata, K.; Pal, A.; Santra, S.; Mohanty, A. K.; Sekizawa, K.

    2015-08-01

    Single- and multi-nucleon transfer reactions, namely, 206Pb(18O,20O), 206Pb(18O,19O), 206Pb(18O,17O), 206Pb(18O,16O), 206Pb(18O,18N), 206Pb(18O,17N), 206Pb(18O,16N), 206Pb(18O,15N), 206Pb(18O,14N), 206Pb(18O,16C), 206Pb(18O,15C), 206Pb(18O,14C), 206Pb(18O,13C), 206Pb(18O,12C), 206Pb(18O,12B), 206Pb(18O,11B), 206Pb(18O,10B), 206Pb(18O,10Be), and 206Pb(18O,9Be), have been studied at an incident 18O energy of 139 MeV. The total kinetic energy loss (TKEL) spectrum and angular distribution of reaction products have been measured. The Q value and angle integrated cross sections are deduced. Angular distributions for the elastically scattered 18O particles are also measured. Fully microscopic time-dependent Hartree-Fock (TDHF) calculations, based on the independent single-nucleon transfer mode, have been carried out and are compared with experimental data of multinucleon transfer reactions. The TDHF calculations provide reasonable agreement with the experimental data for cases where one- and two-nucleon transfer is involved; the discrepancy is large for multinucleon transfer reactions. The effect of particle evaporation on the production cross sections has been studied. Inclusion of particle evaporation effects, though improving the results, could not reproduce the measured cross sections. Possible origins of these discrepancies are discussed.

  20. The influence of temperature, pH, and growth rate on the δ18O composition of inorganically precipitated calcite

    NASA Astrophysics Data System (ADS)

    Watkins, James M.; Hunt, Jonathan D.; Ryerson, Frederick J.; DePaolo, Donald J.

    2014-10-01

    The oxygen isotope composition of carbonate minerals varies with temperature as well as other environmental variables. For carbonates that precipitate slowly, under conditions that approach thermodynamic equilibrium, the temperature-dependence of 18O uptake is the dominant signal and the measured 18O content can be used as a paleotemperature proxy. In the more common case where carbonate minerals grow in a regime where they are not in isotopic equilibrium with their host solution, their oxygen isotope compositions are a convolution of multiple environmental variables. Here we present results from calcite growth experiments demonstrating the occurrence of large (>2‰) non-equilibrium oxygen isotope effects under conditions relevant to biogenic calcite growth and many natural inorganic systems. We show that these non-equilibrium effects vary systematically with pH and crystal growth rate. An isotopic ion-by-ion crystal growth model quantifies the competing roles of temperature, pH, and growth rate, and provides a general description of calcite-water oxygen isotope fractionation under non-equilibrium conditions. The crystal growth model results show that (1) there are both equilibrium and kinetic contributions to calcite oxygen isotopes at biogenic growth rates, (2) calcite does not directly inherit the oxygen isotope composition of DIC even at fast growth rates, (3) there is a kinetically controlled variation of about 1‰ per pH unit between pH=7.7 and 9.3 at constant growth rate for inorganic calcite as well as biogenic calcite, and (4) extreme light isotope enrichments in calcite in alkaline environments are likely due to disequilibrium among DIC species in aqueous solution. The model can be extended to 13C uptake into carbonates as well as clumped isotopes but additional data are needed to constrain the kinetic fractionation factors for carbon isotopes. The experimental and model results constitute an important step in separating the relative influence of

  1. Experimental determination of the Si isotope fractionation factor between liquid metal and liquid silicate

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    The conditions of core formation and the abundances of the light elements in Earth's core remain debated. Silicon isotope fractionation provides a tool contributing to this subject. We present experimentally determined Si isotope fractionation factors between liquid metal and liquid silicate at 1450 °C and 1750 °C, which allow calibrating the temperature dependence of Si isotope fractionation. Experiments were performed in a centrifuging piston cylinder at 1 GPa, employing both graphite and MgO capsules. Tin was used to lower the melting temperature of the metal alloys for experiments performed at 1450 °C. Tests reveal that neither Sn nor C significantly affects Si isotope fractionation. An alkaline fusion technique was employed to dissolve silicate as well as metal phases prior to ion exchange chemistry and mass spectrometric analysis. The results show that metal is consistently enriched in light isotopes relative to the silicate, yielding average metal-silicate fractionation factors of -1.48±0.08‰ and -1.11±0.14‰ at 1450 °C and 1750 °C, respectively. The temperature dependence of equilibrium Si isotope fractionation between metal and silicate can thus be described as Δ30SiMetal-Silicate=-4.42(±0.05)×106/T2. The Si isotope equilibrium fractionation is thus about 1.7 times smaller than previously proposed on the basis of experiments. A consequence of this smaller fractionation is that the calculated difference between the Si isotope composition of the bulk Earth and that of the bulk silicate Earth generated by core formation is smaller than previously thought. It is therefore increasingly difficult to match the Si isotope composition of the bulk silicate Earth with that of chondrites for metal-silicate equilibration temperatures above ∼2500 K. This suggests that Si isotopes were more sensitive to the early stages of core formation when low oxygen fugacities allowed significant incorporation of Si into metal.

  2. Temporal and spatial distributions of δ18O and δ2H in precipitation in Romania

    NASA Astrophysics Data System (ADS)

    Nagavciuc, Viorica; Bădăluță, Carmen-Andreea; Perșoiu, Aurel

    2015-04-01

    Stable isotope ratios of meteoric water have an important role in climatic, paleoclimatic, hydrological and meteorological studies. While such data are available from most of Europe, so far, in Romania (East Central Europe), no systematic study of the stable isotopic composition of precipitation exists. In this context, the aim of this study is to analyze the isotopic composition of rainwater, its temporal and spatial distribution, the identification of the main factors influencing these variations and the creation of the first map of spatial distribution of stable isotopes in precipitation in Romania. Between March 2012 and March 2014 we have collected monthly samples from 22 stations in Romania, which were subsequently analyzed for their δ18O and δ2H at the Stable Isotopes Laboratory, Stefan cel Mare University, Suceava, Romania. Precipitation in W and NW Romania plot along the GMWL, while those in the East are slightly below it, on an evaporative trend. The LMWL for Romania is defined as δ2H=7,27*δ18O + 6,92. The W-E gradient in the distribution of δ18O and δ2H are less marked than the N-S ones, with local influences dominating in areas of strong evaporation (intramountain basins, rain-shadow areas etc). In SW, and especially in autumn and winter, Meditteranean cyclones carry moisture from the Eastern Mediterranean, the δ18O and δ2H values in precipitation in the area plotting between the GMWL and the Eastern Mediterranean Meteoric Water Line. The isotopic composition of rainwater in Romania correlates well with air temperature, and is influenced to a lesser extent by other factors such as the amount of precipitation, topography configuration, the effect of continentalism and season of the year.

  3. Intraseasonal Variability of δ18O of Precipitation in The Indonesia Maritime Continent

    NASA Astrophysics Data System (ADS)

    Belgaman, H. A.; Ichiyanagi, K.; Tanoue, M.; Suwarman, R.; Yoshimura, K.; Mori, S.; Yamanaka, M. D.; Kurita, N.; Syamsudin, F.

    2014-12-01

    The Indonesian maritime continent (IMC) consists of many islands in a warm pool of sea water and is located between two great oceans—the Pacific Ocean and Indian Ocean, and two major continents—the Asian and Australian continents. This tropical region also influenced by many regional and local climate and weather phenomenon which causes high spatial and temporal rainfall variability. These factors may produce unique variability of isotopic precipitation. The isotopic content (d18O and dD) in precipitation have been known to have important role for reconstructing the atmospheric circulation, hydrological cycle, and paleoclimate. Using daily data from six observation station across the IMC (Bukit tinggi, Jambi, Denpasar, Makasar, Manado, and Palau Island), the variability of δ18O was explored. Observation times for each station were different. Bukit Tinggi (GAW) was from Jan. 2001 - Mar. 2010, Jambi (JMB) was from Apr. 2001 - Dec. 2005, Denpasar (DPS), Makassar (MKS), Manado (MND) were from Nov. 2002 - Mar. 2010, and Palau Island (PLL) was from Dec. 2001 - May 2007. Daily average value of δ18O were -7.57‰, -5.41‰, -3.15‰, -6.12‰, -5.49‰ and -4.26‰ for GAW, JMB, DPS, MKS, MND and PLL respectively. Daily value of δ18O in GAW has the lowest value compare with the other station was because the location of GAW station located at high altitude. High correlation of variability of δ18O and Madden-Julian Oscillation (MJO) was observed at western part of the IMC (GAW and JMB), and northern part of the IMC (MKS, MND, and PLL), meanwhile δ18O variability at DPS was less correlated with MJO compare with other stations. Preliminary result from Color Moisture Analysis (CMA) model revealed that precipitable water at GAW and JMB stations was mostly occupied by water vapor evaporated from the Indian Ocean. However, precipitable water at other stations was mostly composed of water vapor evaporated from the Java Sea and the Pacific Ocean. These findings indicate

  4. The Impact of Clouds on Ecosystem-Atmosphere CO18O Exchanges in the U.S. Great Plains

    NASA Astrophysics Data System (ADS)

    Still, C. J.; Riley, W. J.; Biraud, S. C.; Noone, D. C.; Berry, J. A.

    2005-12-01

    The downward excursion in δ18O of atmospheric CO2 observed during the 1990s and the large interannnual variability characteristic of this isotopologue are not understood. We hypothesize that these variations in δ18O of atmospheric CO2 may be linked to global-scale variations in cloud cover and its influence on biosphere-atmosphere CO18O exchanges. Recent work has demonstrated the influence of clouds on canopy photosynthesis through increases in the diffuse radiation fraction and relative humidity, combined with decreases in leaf temperature. In concert, these alterations tend to increase canopy photosynthesis, which should also increase CO18O fluxes. However, photosynthetic CO18O fluxes also depend on the δ18O of leafwater, and enhanced cloudiness should decrease the δ18O of leafwater by enhancing relative humidity. Thus, the net impact of differing cloud cover on biosphere-atmosphere CO18O exchanges is difficult to predict. To capture these contrasting effects, we employed a comprehensive ecosystem isotope model (ISOLSM) in the southern great plains region of Oklahoma and Kansas. This region is particularly amenable for such a study because of the density of cloud property and radiation measurements. The region contains natural and agricultural ecosystems representing a variety of photosynthetic pathways and growth forms, including tallgrass prairie pastures, broadleaf forests, and crops. To drive the model across the entire region, we used Mesonet meteorological data collected at 120 stations in 2004, as well as precipitation δ18O values from the National Atmospheric Deposition Program network. LAI profiles from 2004 were derived from MODIS data. Our results suggest a large impact of clouds on photosynthetic CO2 and CO18O fluxes across this region. In an unstressed broadleaf deciduous forest (LAI=6.3), three sequential midsummer days with contrasting cloud cover illustrate this impact. Julian Day 222 is sunny, JD 223 is partly cloudy, and JD 224 is very

  5. Computing the Partial Fraction Decomposition of Rational Functions with Irreducible Quadratic Factors in the Denominators

    ERIC Educational Resources Information Center

    Man, Yiu-Kwong

    2012-01-01

    In this note, a new method for computing the partial fraction decomposition of rational functions with irreducible quadratic factors in the denominators is presented. This method involves polynomial divisions and substitutions only, without having to solve for the complex roots of the irreducible quadratic polynomial or to solve a system of linear…

  6. Mechanisms linking metabolism of Helicobacter pylori to 18O and 13C-isotopes of human breath CO2

    PubMed Central

    Som, Suman; De, Anulekha; Banik, Gourab Dutta; Maity, Abhijit; Ghosh, Chiranjit; Pal, Mithun; Daschakraborty, Sunil B.; Chaudhuri, Sujit; Jana, Subhra; Pradhan, Manik

    2015-01-01

    The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 (18O) and carbon-13 (13C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of 18O/16O and 13C/12C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of 18O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of 18O in breath CO2 were manifested in individuals without the infections. In contrast, the 13C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to 13C-enriched glucose uptake, whereas a distinguishable change of breath 13C/12C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the 18O and 13C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath 12C18O16O and 13C16O16O can be used as potential molecular biomarkers to distinctively track the pathogenesis of Helicobacter pylori and also for eradication purposes and thus may open new perspectives into the pathogen’s physiology along with isotope-specific non-invasive diagnosis of the infection. PMID:26039789

  7. δ18O and chemical composition of Libyan Desert Glass, country rocks, and sands: New considerations on target material

    NASA Astrophysics Data System (ADS)

    Longinelli, Antonio; Sighinolfi, Giampaolo; de Michele, Vincenzo; Selmo, Enricomaria

    2011-02-01

    Oxygen isotope and chemical measurements were carried out on 25 samples of Libyan Desert Glass (LDG), 21 samples of sandstone, and 3 of sand from the same area. The δ18O of LDG samples range from 9.0‰ to 11.9‰ (Vienna Standard Mean Ocean Water [VSMOW]); some correlations between isotope data and typological features of the LDG samples are pointed out. The initial δ18O of a bulk parent material may be slightly increased by fusion due to the loss of isotopically light pore water with no isotope exchange with oxygen containing minerals. Accordingly, the δ18O of the bulk parent material of LDG may have been about 9.0 ± 1‰ (VSMOW). The measured bulk sandstone and sand samples have δ18O values ranging from 12.6‰ to 19.5‰ and are consequently ruled out as parent materials, matching the results of previous studies. However, separated quartz fractions have δ18O values compatible with the LDG values suggesting that the modern surface sand inherited quartz from the target material. This hypothesis fits previous findings of lechatelierite and baddeleyite in these materials. As the age of the parent material reported in previous studies is Pan-African, we measured the δ18O values of bulk rock and quartz from intrusives of Pan-African age and the results obtained were compatible with the LDG values. The main element abundances (Fe, Mg, Ca, K, Na) in our LDG samples conform to previous estimates; Fe, Mg, and K tend to be higher in heterogeneous samples with dark layers. The hypothesis of a low-altitude airburst involving silica-rich surface materials deriving from weathered intrusives of Pan-African age, partially melted and blown over a huge surface by supersonic winds matches the results obtained.

  8. Cr isotope fractionation factors for Cr(VI) reduction by a metabolically diverse group of bacteria

    NASA Astrophysics Data System (ADS)

    Basu, Anirban; Johnson, Thomas M.; Sanford, Robert A.

    2014-10-01

    Reduction of Cr(VI) is an important process that determines the geochemical behavior, mobility and bioavailability of Cr in both terrestrial and marine environments. Many metabolically diverse microorganisms possess Cr(VI) reduction capacity. Cr(VI) reduction fractionates Cr isotopes and thus 53Cr/52Cr ratios can be used to monitor Cr(VI) reduction and redox conditions. The magnitude of isotopic fractionation (ε) for a variety of microbial reduction mechanisms must be known for accurate interpretation of observed shifts in 53Cr/52Cr ratios. We determined isotopic fractionation factors for Cr(VI) reduction by metal reducers Geobacter sulfurreducens and Shewanella sp. strain NR, a denitrifying soil bacterium Pseudomonas stutzeri DCP-Ps1, and a sulfate reducer Desulfovibrio vulgaris. All bacteria investigated in this study produced significant Cr isotope fractionation. The fractionation (ε) for G. sulfurreducens, Shewanella sp. (NR), P. stutzeri DCP-Ps1, and D. vulgaris were -3.03‰ ± 0.12‰, -2.17‰ ± 0.22‰, -3.14‰ ± 0.13‰, and -3.01‰ ± 0.11‰, respectively. Despite differences in microbial strains in this study, the ε did not vary significantly except for Shewanella sp. (NR). Our results suggest that strong isotopic fractionation is induced during Cr(VI) reduction under electron donor poor (∼300 μM) conditions.

  9. Mg/Ca and δ18O in the calcite of benthic foraminifera: does size matter?

    NASA Astrophysics Data System (ADS)

    de Nooijer, Lennart; Bijma, Jelle; -Jan Reichart, Gert; Hathorne, Ed

    2010-05-01

    Mg/Ca and del-18O are popular proxies for past sea water temperatures, ice volume and, together, salinity. The biological control that foraminifera have over calcification results in precipitation of calcium carbonate that has an isotope and element composition that is very different from those of inorganically precipitated calcium carbonates. Indications for an effect of ontogeny (i.e. size of a specimen) on the fractionation of oxygen isotopes are contradictory, while for the incorporation of most (trace) elements, data are lacking. The causes of size-based variability in element incorporation and isotope fractionation need to be understood and quantified in order to reliably use them as paleoproxies. In this study, we present Mg/Ca and oxygen isotope data from cultured specimens of the benthic foraminifer Ammonia tepida. When asexual reproduction takes place in this species, 50-300 genetically identical juveniles (i.e. clones) are produced. These juveniles are cultured at constant temperature, carbonate chemistry, salinity, etc to determine inter- and intra-specimen variability in Mg/Ca, Ba/Ca and Sr/Ca. From the same groups of clones, del-18O was determined from specimens with different sizes. Results show that the variability differs greatly between the analysed elements (e.g. relatively constant for Sr and Ba, variable for Mg) and isotopes, underscoring the need for a biological understanding of foraminiferal calcification pathways.

  10. Effects of environmental and biotic factors on carbon isotopic fractionation during decomposition of soil organic matter

    NASA Astrophysics Data System (ADS)

    Wang, Guoan; Jia, Yufu; Li, Wei

    2015-06-01

    Decomposition of soil organic matter (SOM) plays an important role in the global carbon cycle because the CO2 emitted from soil respiration is an important source of atmospheric CO2. Carbon isotopic fractionation occurs during SOM decomposition, which leads to 12C to enrich in the released CO2 while 13C to enrich in the residual SOM. Understanding the isotope fractionation has been demonstrated to be helpful for studying the global carbon cycle. Soil and litter samples were collected from soil profiles at 27 different sites located along a vertical transect from 1200 to 4500 m above sea level (a.s.l.) in the south-eastern side of the Tibetan Plateau. Their carbon isotope ratios, C and N concentrations were measured. In addition, fiber and lignin in litter samples were also analyzed. Carbon isotope fractionation factor (α) during SOM decomposition was estimated indirectly as the slope of the relationship between carbon isotope ratios of SOM and soil C concentrations. This study shows that litter quality and soil water play a significant role in isotope fractionation during SOM decomposition, and the carbon isotope fractionation factor, α, increases with litter quality and soil water content. However, we found that temperature had no significant impact on the α variance.

  11. Insulin-Like Growth Factor-1 Preserves Salivary Gland Function After Fractionated Radiation

    SciTech Connect

    Limesand, Kirsten H.; Avila, Jennifer L.; Victory, Kerton; Chang, Hui-Hua; Shin, Yoon Joo; Grundmann, Oliver; Klein, Rob R.

    2010-10-01

    Purpose: Radiotherapy for head-and-neck cancer consists of fractionated radiation treatments that cause significant damage to salivary glands leading to chronic salivary gland dysfunction with only limited prevention and treatment options currently available. This study examines the feasibility of IGF-1 in preserving salivary gland function following a fractionated radiation treatment regimen in a pre-clinical model. Methods and Materials: Mice were exposed to fractionated radiation, and salivary gland function and histological analyses of structure, apoptosis, and proliferation were evaluated. Results: In this study, we report that treatment with fractionated doses of radiation results in a significant level of apoptotic cells in FVB mice after each fraction, which is significantly decreased in transgenic mice expressing a constitutively active mutant of Akt1 (myr-Akt1). Salivary gland function is significantly reduced in FVB mice exposed to fractionated radiation; however, myr-Akt1 transgenic mice maintain salivary function under the same treatment conditions. Injection into FVB mice of recombinant insulin-like growth factor-1 (IGF-1), which activates endogenous Akt, suppressed acute apoptosis and preserved salivary gland function after fractionated doses of radiation 30 to 90 days after treatment. FVB mice exposed to fractionated radiation had significantly lower levels of proliferating cell nuclear antigen-positive salivary acinar cells 90 days after treatment, which correlated with a chronic loss of function. In contrast, FVB mice injected with IGF-1 before each radiation treatment exhibited acinar cell proliferation rates similar to those of untreated controls. Conclusion: These studies suggest that activation of IGF-1-mediated pathways before head-and-neck radiation could modulate radiation-induced salivary gland dysfunction and maintain glandular homeostasis.

  12. /sup 18/O + /sup 12/C fusion-evaporation reaction

    SciTech Connect

    Heusch, B; Beck, C; Coffin, J P; Freeman, R M; Gallmann, A; Haas, F; Rami, F; Wagner, P; Alburger, D E

    1980-01-01

    A study of the /sup 18/O + /sup 12/C fusion evaporation reaction has been undertaken for 2 reasons: to make a systematic study of the formation cross section for each individual evaporation residue over a broad excitation energy region in the compound nucleus /sup 30/Si:30 to 62 MeV; and to compare all results to fusion-evaporation calculations done in the framework of the Hauser-Feschbach statistical model.

  13. Negative δ 18O values in Allan Hills 84001 carbonate: Possible evidence for water precipitation on mars

    NASA Astrophysics Data System (ADS)

    Holland, G.; Saxton, J. M.; Lyon, I. C.; Turner, G.

    2005-03-01

    The Martian meteorite ALH84001 contains ˜1% by weight of carbonate formed by secondary processes on the Martian surface or in the shallow subsurface. The major form of this carbonate is chemically and isotopically zoned rosettes which have been well documented elsewhere. This study concentrates upon carbonate regions ˜200 μm across which possess previously unobserved magnesium rich inner cores, interpreted here as rosette fragments, surrounded by a later stage cement containing rare Ca-rich carbonates (up to Ca 81Mg 07Fe 04Mn 07) intimately associated with feldspar. High spatial resolution ion probe analyses of Ca-rich carbonate surrounding rosette fragments have δ 18O V-SMOW values as low as -10 ‰. These values are not compatible with deposition from a global Martian atmosphere invoked to explain ALH84001 rosettes. The range of δ 18O values are also incompatible with a fluid that has equilibrated with the Martian crust at high temperature or from remobilisation of carbonate of rosette isotopic composition. At Martian atmospheric temperatures, the small CO 2(gas)-CO 2(ice) fractionation makes meteoric CO 2 an unlikely source for -10 ‰ carbonates. In contrast, closed system Rayleigh fractionation of H 2O can generate δ 18O H2O -30 ‰, as observed at high latitudes on Earth. We suggest that atmospheric transport and precipitation of H 2O in a similar fashion to that on Earth provides a source of suitably 18O depleted water for generation of carbonate with δ 18O V-SMOW = -10 ‰.

  14. Oxygen and chlorine isotopic fractionation during perchlorate biodegradation: Laboratory results and implications for forensics and natural attenuation studies

    USGS Publications Warehouse

    Sturchio, N.C.; Böhlke, J.K.; Beloso, A.D., Jr.; Streger, S.H.; Heraty, L.J.; Hatzinger, P.B.

    2007-01-01

    Perchlorate is a widespread environmental contaminant having both anthropogenic and natural sources. Stable isotope ratios of O and Cl in a given sample of perchlorate may be used to distinguish its source(s). Isotopic ratios may also be useful for identifying the extent of biodegradation of perchlorate, which is critical for assessing natural attenuation of this contaminant in groundwater. For this approach to be useful, however, the kinetic isotopic fractionations of O and Cl during perchlorate biodegradation must first be determined as a function of environmental variables such as temperature and bacterial species. A laboratory study was performed in which the O and Cl isotope ratios of perchlorate were monitored as a function of degradation by two separate bacterial strains (Azospira suillum JPLRND and Dechlorospirillum sp. FBR2) at both 10??C and 22??C with acetate as the electron donor. Perchlorate was completely reduced by both strains within 280 h at 22??C and 615 h at 10??C. Measured values of isotopic fractionation factors were ??18O = -36.6 to -29.0??? and ??37Cl = -14.5 to -11.5???, and these showed no apparent systematic variation with either temperature or bacterial strain. An experiment using 18O-enriched water (??18O = +198???) gave results indistinguishable from those observed in the isotopically normal water (??18O = -8.1???) used in the other experiments, indicating negligible isotope exchange between perchlorate and water during biodegradation. The fractionation factor ratio ??18O/??37Cl was nearly invariant in all experiments at 2.50 ?? 0.04. These data indicate that isotope ratio analysis will be useful for documenting perchlorate biodegradation in soils and groundwater. The establishment of a microbial fractionation factor ratio (??18O/??37Cl) also has significant implications for forensic studies. ?? 2007 American Chemical Society.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Long-Term Results and Prognostic Factors of Fractionated Strontium-90 Eye Applicator for Pterygium

    SciTech Connect

    Arruda Viani, Gustavo Stefano, Eduardo Jose; Fendi, Ligia Issa de; Carrara Fonseca, Ellen

    2008-11-15

    Purpose: To evaluate the long-term safety, effectiveness, and prognostic factors of fractionated postoperative {beta}-irradiation. Methods and Materials: Between 1993 and 2005, 623 patients with 737 pterygium lesions were treated with a strontium-90 eye applicator after surgical excision. The median follow-up period was 60 months (range, 6.7-139.5). Of the 737 lesions, 644 were primary and 93 were recurrences after surgical removal alone. Fractionated radiotherapy (RT) to a total dose of 35 Gy in five to seven fractions was used. Results: A total of 73 local pterygium recurrences (9.9%) were noted. Of the recurrent cases, 80% were noted within 3 years after treatment. The 5- and 10-year probability of local control was 90% and 88%, respectively. The multivariate analysis for all cases demonstrated that gender, age, total radiation dose, recurrent pterygia, and interval between surgery and RT affected the overall local control rate. Late toxicities that might have been associated with strontium-90 RT included scleromalacia (scleral thinning) in nine eyes, adhesion of the eyelids in eight, cataracts in six, and scleral ulcer in five eyes. Conclusion: Fractionated strontium-90 RT to a total dose of approximately 35 Gy in five to seven fractions results in a similar local control rate as higher doses in other series, with an acceptable complication rate.

  17. Oxygen isotope fractionation in divalent metal carbonates

    USGS Publications Warehouse

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

    1969-01-01

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

  18. Southwest U.S. Paleoclimate Over the Past 30,000 Years: Insights from Speleothem δ18O and Growth Rate Time Series

    NASA Astrophysics Data System (ADS)

    Meyer, K. J.; FENG, W.; Banner, J. L.; James, E.; Musgrove, M.

    2011-12-01

    A 30 ky growth rate and high-resolution δ18O time series from a central Texas (TX) speleothem provides new insights when integrated with recently published speleothem δ18O and growth rate records from New Mexico (NM) and Arizona (AZ), along with Gulf of Mexico (GOM) foraminifera δ18O records. This comparison enables a regional assessment of factors which may control temporal variations in rainfall amount and moisture sources in the Southwestern U.S. The three speleothem locations (TX, NM, AZ) span ~ 1,200 km. A regional east-to-west decrease in speleothem δ18O values of up to 9 % is observed throughout the record. This is the same direction of regional decrease as in modern rainfall. This suggests 1) mixing of moisture from two sources, Pacific moisture (low δ18O), and GOM moisture (high δ18O), and 2) that these two sources have contributed moisture to the region for most of the last 30 ky. Prior to 15 ka, relatively large magnitude, millennial-scale oscillations (up to ~3 %) occur in the NM δ18O record while the TX and AZ records show smaller variations (~1 %). Starting at ~ 15 ka, both AZ and NM records show a rapid increase in δ18O values, whereas TX shows a decrease prior to a rapid increase. This dip in the TX δ18O record approximately corresponds with δ18O shifts in the GOM that have been attributed to glacial melt water inputs. All three records show peaks in growth rate between 15 and 12 ka, and significant decreases in growth rate in the Holocene. The speleothem δ18O time series appear to reflect changes in rainfall amount and composition. The correspondence of the TX and GOM records implicates GOM moisture composition as the major control on Late Pleistocene to Holocene TX precipitation δ18O values. NM and AZ, by contrast, apparently received varying proportions of Pacific and GOM sources over this time period. Periods of high δ18O values in the NM and AZ records, when combined with relative high growth rates, may suggest increased overall

  19. Strong coupling of centennial-scale changes of Asian monsoon and soil processes derived from stalagmite δ18O and δ13C records, southern China

    NASA Astrophysics Data System (ADS)

    Liu, Dianbing; Wang, Yongjin; Cheng, Hai; Edwards, R. Lawrence; Kong, Xinggong; Li, Ting-Yong

    2016-05-01

    The paleoclimate application of speleothem δ13C is influenced by site-specific processes. Here we present four stalagmite δ13C records from two caves in southern China, covering early and late Marine Isotope Stage (MIS) 3 and the Holocene, to investigate the spatio-temporal pattern of calcite δ13C changes and the relationship with Asian monsoon (AM) variability. In each growth period, precessional- to millennial-scale changes are clear in the δ18O record. In contrast, millennial variability is absent in the δ13C record, which characterizes persistent centennial oscillations. However, centennial-scale δ18O variations agree well with those of δ13C, with a larger amplitude in δ13C changes (about twice that of δ18O). This suggests that soil humidity balance associated with regional hydrological circulations is important for these centennial δ13C changes, although evaporation-related kinetic fractionation can induce concurrent enrichments in δ18O and δ13C. In frequency, the detrended δ18O and δ13C records are coupled at a periodicity of about 300 yr during the last glacial period and 150 yr during the Holocene. Those centennial-scale δ13C variations are generally consistent with Greenland temperature variability, indicating a climate response over broad regions. Thus, strong co-variation of δ18O and δ13C records should have a climatic origin, even if it is amplified by kinetic effects.

  20. Strong coupling of centennial-scale changes of Asian monsoon and soil processes derived from stalagmite δ18O and δ13C records, southern China

    NASA Astrophysics Data System (ADS)

    Liu, Dianbing; Wang, Yongjin; Cheng, Hai; Edwards, R. Lawrence; Kong, Xinggong; Li, Ting-Yong

    2016-05-01

    The paleoclimate application of speleothem δ13C is influenced by site-specific processes. Here we present four stalagmite δ13C records from two caves in southern China, covering early and late Marine Isotope Stage (MIS) 3 and the Holocene, to investigate the spatio-temporal pattern of calcite δ13C changes and the relationship with Asian monsoon (AM) variability. In each growth period, precessional- to millennial-scale changes are clear in the δ18O record. In contrast, millennial variability is absent in the δ13C record, which characterizes persistent centennial oscillations. However, centennial-scale δ18O variations agree well with those of δ13C, with a larger amplitude in δ13C changes (about twice that of δ18O). This suggests that soil humidity balance associated with regional hydrological circulations is important for these centennial δ13C changes, although evaporation-related kinetic fractionation can induce concurrent enrichments in δ18O and δ13C. In frequency, the detrended δ18O and δ13C records are coupled at a periodicity of about 300 yr during the last glacial period and 150 yr during the Holocene. Those centennial-scale δ13C variations are generally consistent with Greenland temperature variability, indicating a climate response over broad regions. Thus, strong co-variation of δ18O and δ13C records should have a climatic origin, even if it is amplified by kinetic effects.

  1. Factors Leading to Variability of Emission Factors, Single Scattering Albedo, and Elemental Carbon Fraction from Biofuel Emissions

    NASA Astrophysics Data System (ADS)

    Roden, C. A.; Bond, T. C.; Conway, S.; Osorto Pinel, B.; Maccarty, N.

    2006-12-01

    In a three-year study of field and laboratory emissions of traditional and improved biofuel cookstoves, we found that field measured particulate emissions of actual cooking events average 2.5 times those of reproduced lab emissions. Emission factors are highly dependent on the care and skill of the operator, and the resulting combustion; these do not appear to be accurately reproduced in the lab. The single scatter albedo (SSA) of the emissions is very low in both lab and field measurements, averaging about 0.3 for lab tests and around 0.5 for field tests, indicating that the primary particles are climate warming. In Honduras, improved stoves generally had lower emission factors than traditional stoves. Over the course of 3 summers we have measured field emissions from traditional cookstoves, relatively-new improved cookstoves, and "broken-in" improved cookstoves. For improved stoves, the presence of a chimney generally resulted in lower emission factors but left the SSA unaffected. Traditional cookstoves had an average PM emission factor of 8.5 g/kg significantly larger than previous studies. Particulate emission factors for improved cookstoves without and with chimneys averaged about 5.7 g/kg and 3.5 g/kg respectively. The elemental carbon (EC) fraction of PM varied significantly between individual tests, but averaged about 25% for each of the categories. Wood type affects on the PM emission factor, the SSA of the emissions and EC fraction. During our 2006 field measurements, we performed multiple emission measurements on the same stove while varying the fuel. Pine wood generally produced more PM than oak per kilogram of fuel. Additionally, Ocote, a resinous pitch pine often used in Central America for lighting fires, produces emissions which have a very low SSA and high EC fraction. We present the elemental carbon fraction and mass emission factors for different type of stoves and testing conditions. We summarize the characteristics of the particles emitted

  2. Three Millimeter Molecular Line Observations of Sagittarius B2. II. High-Resolution Studies of C 18O, HNCO, NH 2CHO, and HCOOCH 3

    NASA Astrophysics Data System (ADS)

    Kuan, Yi-Jehng; Snyder, Lewis E.

    1996-10-01

    High-resolution imaging of C18O, HNCO, NR2CHO, and RCOOCH3 in Sgr B2 are presented in this study. The C18O emission comes mainly from the Sgr B2(M) and Sgr B2(N) dense cores and the western gas clump RNO(M). Toward Sgr B2(M), the C18O column density is 2 times higher and the fractional abundance is 80 times higher than toward Sgr B2(N). In HNO(M), the narrow line width implies that the C18O emission arises from the diffuse gas. The complex molecules NR2CHO and HCOOCR3 were detected only toward the Sgr B2(N) core. The HNCO K-1 = 2 emission is detected only in Sgr B2(N) and is attributed to efficient radiative pumping, which indicates the significant presence of far-infrared field and warm dust grains. Only 4% of the HNCO was found in the K-1 = 0 ladders in Sgr B2(N). The nondetection of the K-1 = 2 emission toward Sgr B2(M) is caused by excitation and low abundance. In contrast, the HNCO K-1 = 0 emission comes mainly from the extended gas component: the far northern region and HNCO(SW). For the K-1 = 0 transitions, Trot = ˜7 K. The low Trot and the apparent ubiquity of RNCO suggest that abundant HNCO exists in the Sgr B2 envelope. The HNCO K-1 = 0 emission unveiled two spatially extended velocity components; the velocity gap between them covers the same LSR velocities of the Sgr B2 dense cores. If HNCO is formed via surface reactions, the pervasive detection of HNCO in the outer edges of Sgr B2 cloud core leads to the cloud-cloud collision postulate. A north-south C18O bipolar structure was seen in Sgr B2(M) centered at the compact H II region F. The bipolar structure appears asymmetric and thus favors the outflow interpretation. The sharp outer edges of the C18O line profiles of the two lobes further support the outflow picture. The estimated outflow age is ˜2±1 x 104 yr, and the total mass is ˜1700 Msun. The outflow masses for the blue and red lobes are <360 Msun and <410 Msun, respectively. The mass-loss rate is thus <0.037 Msun yr-1. The detection of

  3. Effects of formalin and ethanol preservation on otolith delta18O stable isotope signatures.

    PubMed

    Storm-Suke, A; Dempson, J B; Caron, F; Power, M

    2007-01-01

    The use of preserved otoliths for stable isotope analysis assumes handling and preservation procedures do not alter the isotopic composition of the otolith. Otoliths from wild and hatchery-reared salmonids (brook charr, Salvelinus fontinalis, and Atlantic salmon, Salmo salar) were used to test for possible delta(18)O preservation effects in ethanol and formalin preservation experiments at varying temperatures. Analysis of variance (ANOVA) demonstrated a significant interaction effect between species and preservative during preservation. Possible causes for the observed effect are discussed in relation to species-specific differences in otolith chemistry related to growth and environment including: (1) chemical mechanisms of dissolution-recrystallisation involving the precipitation of secondary minerals within and at the otolith surface; (2) adsorption of ions at available binding sites on the otolith surface; and (3) isotopic exchange during otolith surface dissolution and/or reprecipitation processes. Differential occurrence of vaterite and aragonite in otoliths is believed to account for some of the observed effects as a result of otolith density differences. Isotopic exchange is also argued to cause much of the observed variation in species-specific preservation effects. Biologically, study findings imply that preserved otoliths should not be used for baseline paleoclimatic or individual fish thermal reconstructions, or the development of delta(18)O-fractionation equations, without the prior use of pilot studies to determine preservation effects. PMID:17245794

  4. Paleomagnetic and Clay δ18O Ages for Weathering in Northwestern NSW, Australia

    NASA Astrophysics Data System (ADS)

    Smith, M. L.; Pillans, B. J.

    2005-12-01

    There is a complex history of erosion, deposition, tectonism and weathering relating to the Surat, Eromanga and Murray/Darling Basins in northwestern New South Wales. In this study we use paleomagnetic and δ18O measurements to demonstrate that the weathering history dates extends back to the Permain. Paleomagnetic dating of hematitic regolith profiles yields ages for the terminal stages of deep chemical weathering, often corresponding to drying out of a profile. Previous work identified two major periods of weathering across the Australian continent during the Tertiary. This study extends the data in the eastern part of the continent, and reveals several stages of weathering from the Jurassic through to the latest Tertiary, including the two Tertiary weathering events, at ~60-30 Ma, and ~3-12 Ma. A possible Jurassic weathering episode is recorded from two sites at Cobar. A 100 Ma weathering event is recorded in samples from Cobar and the Broken Hill Region, which is a new weathering event recorded from Australian regolith samples. Clay δ18O compositions reflect the chemical makeup of groundwaters active during weathering and clay formation. There is a predictable relationship between δ18O and age of authigenic clays in regolith profiles in Australia. Clay δ18O ages from this study range from Permian through to Late Tertiary. The two oldest ages represent inheritance of some fraction of clay from the weathered host lithology. Samples from White Cliffs, Cobar and Lightning Ridge yield Oligo-Miocene ages. Another sample from the Cobar region yields a Mio-Pliocene age. The results presented provide evidence for multiple periods of deep weathering across NW NSW, from the Jurassic through the Pliocene. Clay formation in weathering profiles occurs under humid conditions, whilst hematite formation occurs at the terminal stages of intense chemical weathering, at the end of periods of humid climatic regimes. When the results are combined, they indicate periods of humid

  5. Probabilistic sequence alignment of Late Pleistocene benthic δ18O data

    NASA Astrophysics Data System (ADS)

    Lawrence, C.; Lin, L.; Lisiecki, L. E.; Stern, J.

    2013-12-01

    The stratigraphic alignment of ocean sediment cores plays a vital role in paleoceanographic research because it is used to develop mutually consistent age models for climate proxies measured in these cores. The most common proxy used for alignment is the The stratigraphic alignment of ocean sediment cores plays a vital role in paleoceanographic research because it is used to develop mutually consistent age models for climate proxies measured in these cores. The most common proxy used for alignment is the δ18O of calcite from benthic or planktonic foraminifera because a large fraction of δ18O variance derives from the global signal of ice volume. To date, alignment has been performed either by manual, qualitative comparison or by deterministic algorithms (Martinson, Pisias et al. Quat. Res. 27 1987; Lisiecki and Lisiecki Paleoceanography 17, 2002; Huybers and Wunsch, Paleoceanography 19, 2004). Here we present a probabilistic sequence alignment algorithm which provides 95% confidence bands for the alignment of pairs of benthic δ18O records. The probabilistic algorithm presented here is based on a hidden Markov model (HMM) (Levinson, Rabiner et al. Bell Systems Technical Journal, 62,1983) similar to those that have been used extensively to align DNA and protein sequences (Durbin, Eddy et al. Biological Sequence Analysis, Ch. 4, 1998). However, here the need to the alignment of sequences stems from expansion and/or contraction in the records due to changes in sedimentation rates rather than the insertion or deletion of residues. Transition probabilities that are used in this HMM to model changes in sedimentation rates are based on radiocarbon estimates of sedimentation rates. The probabilistic algorithm considers all possible alignments with these predefined sedimentation rates. Exact calculations are completed using dynamic programming recursions. The algorithm yields the probability distributions of the age at each point in the record, which are probabilistically

  6. Glacial-interglacial shifts in global and regional precipitation δ18O

    NASA Astrophysics Data System (ADS)

    Jasechko, S.; Lechler, A.; Pausata, F. S. R.; Fawcett, P. J.; Gleeson, T.; Cendón, D. I.; Galewsky, J.; LeGrande, A. N.; Risi, C.; Sharp, Z. D.; Welker, J. M.; Werner, M.; Yoshimura, K.

    2015-03-01

    Previous analyses of past climate changes have often been based on site-specific isotope records from speleothems, ice cores, sediments and groundwaters. However, in most studies these dispersed records have not been integrated and synthesized in a comprehensive manner to explore the spatial patterns of precipitation isotope changes from the last ice age to more recent times. Here we synthesize 88 globally-distributed groundwater, cave calcite, and ice core isotope records spanning the last ice age to the late-Holocene. Our data-driven review shows that reconstructed precipitation δ18O changes from the last ice age to the late-Holocene range from -7.1‰ (ice age δ18O < late-Holocene δ18O) to +1.8‰ (ice age δ18O > late-Holocene δ18O) with wide regional variability. The majority (75%) of reconstructions have lower ice age δ18O values than late-Holocene δ18O values. High-magnitude, negative glacial-interglacial precipitation δ18O shifts (ice age δ18O < late-Holocene δ18O by more than 3‰) are common at high latitudes, high altitudes and continental interiors. Conversely, lower-magnitude, positive glacial-interglacial precipitation δ18O shifts (ice age δ18O > late-Holocene δ18O by less than 2‰) are most common along subtropical coasts. Broad, global patterns of glacial-interglacial precipitation δ18O shifts are consistent with stronger-than-modern isotopic distillation of air masses during the last ice age, likely impacted by larger global temperature differences between the tropics and the poles. Further, to complement our synthesis of proxy-record precipitation δ18O, we compiled isotope enabled general circulation model simulations of recent and last glacial maximum climate states. Simulated precipitation δ18O from five general circulation models show better inter-model and model-observation agreement in the sign of δ18O changes from the last ice age to present day in temperate and polar regions than in the tropics. Further model precipitation

  7. Simultaneous Measurement of δ2H, δ17O, and δ18O in H2O using a Commercial Cavity Ringdown Spectrometer

    NASA Astrophysics Data System (ADS)

    Dominguez, G.; Salvo, C.; Gormally, J.

    2012-12-01

    Quantifying the abundance of oxygen and hydrogen isotopes found in H2O from natural systems and laboratory experiments can be used to better understand physical-chemical processes. While much attention has traditionally been paid to 18O/16O and D/H ratios in natural samples, advances in the precision of mass-spectrometric techniques have exploited small differences in the relative changes of 18O/16O and 17O/16O ratios that are induced by different photochemical and chemical processes such as diffusion and evaporation. In recent years, commercial instruments employing infrared spectroscopy have been shown to be capable of resolving 18O/16O ratios in H2O samples with precisions that are comparable to traditional IRMS techniques. Here we show that, with a modest amount of work, a widely distributed commercial water vapor spectroscopic instrument designed for the determination of {{18}O/{16}^O} and D/H ratios in samples (Picarro L2120-i) can be used to also be used to simultaneously determine the 17O/16O ratio of water samples. Using this instrument, we performed simple evaporation experiments to determine the effect of H2O evaporation (T=40-70C) on the relative ratios of 17O/16O and 18O/16O of residual water. Our results agree with Angert et al. (2004) theoretical prediction for this fractionation. In addition, our results confirm that relative changes in 18O/16O vs. D/H for evaporative conditions follow a slope that is significantly less than 8 (δ 18O vs. D/H) , the value expected for equilibrium conditions. This technique should prove helpful for acquiring data on the multi-isotopic fractionation induced by physical-chemical processes such as evaporation and diffusion in field and laboratory investigations.

  8. δ18O water isotope in the iLOVECLIM model (version 1.0) - Part 1: Implementation and verification

    NASA Astrophysics Data System (ADS)

    Roche, D. M.

    2013-09-01

    A new 18O stable water isotope scheme is developed for three components of the iLOVECLIM coupled climate model: atmospheric, oceanic and land surface. The equations required to reproduce the fractionation of stable water isotopes in the simplified atmospheric model ECBilt are developed consistently with the moisture scheme. Simplifications in the processes are made to account for the simplified vertical structure including only one moist layer. Implementation of these equations together with a passive tracer scheme for the ocean and a equilibrium fractionation scheme for the land surface leads to the closure of the (isotopic-) water budget in our climate system. Following the implementation, verification of the existence of usual δ18O to climatic relationships are performed for the Rayleigh distillation, the Dansgaard relationship and the δ18O -salinity relationship. Advantages and caveats of the approach taken are outlined. The isotopic fields simulated are shown to reproduce most expected oxygen-18-climate relationships with the notable exception of the isotopic composition in Antarctica.

  9. What controls precipitation δ18O in the southern Tibetan Plateau at seasonal and intra-seasonal scales? A case study at Lhasa and Nyalam

    NASA Astrophysics Data System (ADS)

    Gao, Jing; Masson-Delmotte, Valérie; Risi, Camille; He, You; Yao, Tandong

    2013-10-01

    Understanding the spatial and temporal controls of precipitation δ18O in the southern Tibetan Plateau of central Asia is necessary for paleoclimate reconstructions from the wealth of regional archives (ice cores, lake sediments, tree ring cellulose, and speleothems). While classical interpretations of such records were conducted in terms of local precipitation, simulations conducted with atmospheric general circulation models enabled with water stable isotopes have suggested that past changes in south Asia precipitation δ18O may be driven by remote processes linked to moisture transport. Studies conducted at the event scale can provide constraints to assess the drivers of precipitation δ18O and the validity of simulated mechanisms. Here, we take advantage of new event precipitation δ18O monitored from January 2005 to December 2007 at two southern Tibetan Plateau stations (Lhasa and Nyalam). The drivers of daily to seasonal variations are investigated using statistical relationships with local and regional temperature, precipitation amount and convective activity based on in situ data and satellite products. The strongest control on precipitation δ18O at Lhasa during the monsoon season at event and seasonal scales is provided by the integrated regional convective activity upstream air mass trajectories, cumulated over several days. In contrast, the integrated convection appears to be the main driver of precipitation δ18O at Nyalam only in July and August, and the situation is more complex in other months. Local climate variables can only account for a small fraction of the observed δ18O variance, with significant differences between both stations. This study offers a better constraint on climate archives interpretation in the southern Tibetan Plateau. The daily data presented here also provides a benchmark to evaluate the capacity of isotopically enabled atmospheric general circulation models (iGCMs) to simulate the response of precip! itation δ18O to

  10. Symmetry and structure tests in 18O and 18Ne

    SciTech Connect

    Choudry, S. N.; Orce, J. N.; Varadarajan, V.; Lesher, S.; Bandyopadhyay, D.; Mukhopadhyay, S.; McEllistrem, M. T.; Yates, S. W.

    2006-03-13

    Isospin (T) symmetry assumes charge symmetry and charge independence are explicit in nuclear structure. Whereas charge independence implies the nn, np and pp interactions are the same, charge symmetry states that the nn and pp interactions are equal. The latt lowbar er approximate symmetry is experimentally verified by the comparison of the excited levels lying at about the same energy in light mirror nuclei. Both of these symmetries are broken by the electromagnetic interaction. The neutron facility at the University of Kentucky provides a unique opportunity to examine charge independence, and in particular, charge symmetry from the reduced electromagnetic transition probabilities and neutron scattering cross sections. Here, we use the isospin formalism by Bernstein, Brown and Madsen, which relates the proton and neutron matrix elements, M p and M n respectively, for equivalent excited states in T=1 mirror nuclei (Tz = +/-1). The nucleus 18O has been studied using the (n,n') reaction in order to measure the neutron cross sections of the 2{sup +}{sub 1}, T=1 state. Using the previously determined proton matrix elements for the Tz = -1 mirror nucleus (18Ne), along with the determination of the neutron matrix element in 18O from neutron scattering, allows an experimental test of charge symmetry in the A=18 mirror system.

  11. Comparisons of observed and modelled lake δ18O variability

    NASA Astrophysics Data System (ADS)

    Jones, Matthew D.; Cuthbert, Mark O.; Leng, Melanie J.; McGowan, Suzanne; Mariethoz, Gregoire; Arrowsmith, Carol; Sloane, Hilary J.; Humphrey, Kerenza K.; Cross, Iain

    2016-01-01

    With the substantial number of lake sediment δ18O records published in recent decades, a quantitative, process-based understanding of these systems can increase our understanding of past climate change. We test mass balance models of lake water δ18O variability against five years of monthly monitoring data from lakes with different hydrological characteristics, in the East-Midlands region of the UK, and the local isotope composition of precipitation. These mass balance models can explain up to 74% of the measured lake water isotope variability. We investigate the sensitivity of the model to differing calculations of evaporation amount, the amount of groundwater, and to different climatic variables. We show there is only a small range of values for groundwater exchange flux that can produce suitable lake water isotope compositions and that variations in evaporation and precipitation are both required to produce recorded isotope variability in lakes with substantial evaporative water losses. We then discuss the potential for this model to be used in a long-term, palaeo-scenario. This study demonstrates how long term monitoring of a lake system can lead to the development of robust models of lake water isotope compositions. Such systematics-based explanations allow us to move from conceptual, to more quantified reconstructions of past climates and environments.

  12. Constraining Holocene hydrological changes in the Carpathian-Balkan region using speleothem δ18O and pollen-based temperature reconstructions

    NASA Astrophysics Data System (ADS)

    Drăguşin, V.; Staubwasser, M.; Hoffmann, D. L.; Ersek, V.; Onac, B. P.; Veres, D.

    2014-07-01

    Here we present a speleothem isotope record (POM2) from Ascunsă Cave (Romania) that provides new data on past climate changes in the Carpathian-Balkan region from 8.2 ka until the present. This paper describes an approach to constrain the effect of temperature changes on calcite δ18O values in stalagmite POM2 over the course of the middle Holocene (6-4 ka), and across the 8.2 and 3.2 ka rapid climate change events. Independent pollen temperature reconstructions are used to this purpose. The approach combines the temperature-dependent isotope fractionation of rain water during condensation and fractionation resulting from calcite precipitation at the given cave temperature. The only prior assumptions are that pollen-derived average annual temperature reflects average cave temperature, and that pollen-derived coldest and warmest month temperatures reflect the range of condensation temperatures of rain above the cave site. This approach constrains a range of values between which speleothem δ18O changes should be found if controlled only by surface temperature variations at the cave site. Deviations of the change in δ18Ocspel values from the calculated temperature-constrained range of change are interpreted towards large-scale variability of climate-hydrology. Following this approach, we show that an additional ∼0.6‰ enrichment of δ18Oc in the POM2 stalagmite was caused by changing hydrological patterns in SW Romania across the middle Holocene, most likely comprising local evaporation from the soil and an increase in Mediterranean moisture δ18O. Further, by extending the calculations to other speleothem records from around the entire Mediterranean basin, it appears that all eastern Mediterranean speleothems recorded a similar isotopic enrichment due to changing hydrology, whereas all changes recorded in speleothems from the western Mediterranean are fully explained by temperature variation alone. This highlights a different hydrological evolution between

  13. Human transcription factors contain a high fraction of intrinsically disordered regions essential for transcriptional regulation.

    PubMed

    Minezaki, Yoshiaki; Homma, Keiichi; Kinjo, Akira R; Nishikawa, Ken

    2006-06-16

    Human transcriptional regulation factors, such as activators, repressors, and enhancer-binding factors are quite different from their prokaryotic counterparts in two respects: the average sequence in human is more than twice as long as that in prokaryotes, while the fraction of sequence aligned to domains of known structure is 31% in human transcription factors (TFs), less than half of that in bacterial TFs (72%). Intrinsically disordered (ID) regions were identified by a disorder-prediction program, and were found to be in good agreement with available experimental data. Analysis of 401 human TFs with experimental evidence from the Swiss-Prot database showed that as high as 49% of the entire sequence of human TFs is occupied by ID regions. More than half of the human TFs consist of a small DNA binding domain (DBD) and long ID regions frequently sandwiching unassigned regions. The remaining TFs have structural domains in addition to DBDs and ID regions. Experimental studies, particularly those with NMR, revealed that the transactivation domains in unbound TFs are usually unstructured, but become structured upon binding to their partners. The sequences of human and mouse TF orthologues are 90.5% identical despite a high incidence of ID regions, probably reflecting important functional roles played by ID regions. In general ID regions occupy a high fraction in TFs of eukaryotes, but not in prokaryotes. Implications of this dichotomy are discussed in connection with their functional roles in transcriptional regulation and evolution. PMID:16697407

  14. Sample Artefacts in δ15N and δ18O of Nitrate in the atmosphere

    NASA Astrophysics Data System (ADS)

    Seguin, A.; Norman, A. L.

    2009-12-01

    Nitrate is one of the major inorganic anions in aerosols. Recently nitrogen and oxygen isotopes in nitrates have been used to trace sources and chemical processes in the atmosphere. High volume samplers are used in order to gain enough material for isotope analysis, but artefacts can occur when measuring with this technique. Besides retaining NO3 from aerosol, gaseous HNO3 can be absorbed on the filter increasing the reported values of nitrate reported. Alternatively; when elevated temperatures are present in the atmosphere, nitrate is volatized in the form of NH3NO3 which would lead to an underestimation of nitrogen on the filter [Schaap et al., 2004]. The artefacts from high volume sampling may cause inaccuracies in the reported isotope values due to isotope fractionation or different initial isotope values between gaseous HNO3 and particulate nitrate. High volume samplers were deployed on board a ship in the summer of 2003 jointly with the Canadian Surface Ocean - Lower Atmosphere Study (SOLAS). A quartz filter was positioned on a high volume sampler. A cellulose acetate filter treated with potassium carbonate and glycerol was placed underneath the quartz filter. The cellulose acetate filter is designed to catch sticky gaseous (such as SO2) but was also found to catch a nitrogen gas species (most probable HNO3 and/or NH3NO3). Analysis of isotopic composition of nitrate for both nitrogen and oxygen was carried out on selected samples by the denitrifier method. Values ranged between -4 and +1‰ for δ15N and between +49 and +66‰ for δ18O for quartz filter. The nitrogen gas species had ranges between -11 and -0‰ for δ15N and between +44 and +62‰ for δ18O. Average differences between the aerosol (caught on the quartz filter) and the nitrogen gas species (on the cellulose acetate filter) were 3±4 ‰ for δ15N and 10±7 ‰ for δ18O. These values are examined to find insights in possible fractionation in the nitrate collection method currently used in

  15. The influence of void fraction on the submerged perforated sheet hydraulic friction factor

    NASA Astrophysics Data System (ADS)

    Blinkov, V. N.; Elkin, I. V.; Emelianov, D. A.; Melikhov, V. I.; Melikhov, O. I.; Nerovnov, A. A.; Nikonov, S. M.; Parfenov, Yu. V.

    2015-07-01

    The results from an experimental investigation of two-phase flow motion through a submerged perforated sheet (SPS) obtained at the Elektrogorsk Research Center test facility are presented. The test facility, the test section of which is a transverse "cutout" from the full-scale PGV-1000 steam generator with the models of vessel internals, is described in detail. The procedure for carrying out trial startups is outlined, and the system of instrument and control devices is described. The SPS used in all experimental modes of operation had the perforation ratio (the hole area to the sheet area ratio) equal to 5.7%. The pressure in the system was around 7 MPa, and the flow rate of supplied steam was varied from 4.23 to 7.94 t/h, which corresponded to the steam velocity at the evaporation surface equal to 0.15-0.29 m/s. Distributions of pressure difference across the SPS and void fractions under the SPS and above it are obtained. The SPS hydraulic friction factor for a two-phase flow is determined as a result of processing the experimental data. A correction for two-phase nature of the flow for the SPS operating conditions is determined by comparing the obtained SPS hydraulic friction factor for a two-phase flow with the SPS hydraulic friction factor to single-phase flow of steam. It is shown that this correction can be either greater than unity (at low void fractions) or less than unity (at high void fractions).

  16. Planktic δ18O records in the northern South China Sea: MIS 5.5 vs MIS 1

    NASA Astrophysics Data System (ADS)

    Sarnthein, M.; Sadatzki, H.

    2012-04-01

    Benthic δ18O records show peak and average levels for Marine Isotope Stage (MIS) 5.5, which are 0.1-0.2 ‰ lighter than during MIS 1, a shift that largely results from changes in global ice volume. In planktic δ18O records of the northern South China Sea this trend may grow by 0.1-0.2 ‰ due to both a rise in sea surface temperatures (SST) during MIS 5.5 and enhanced freshwater input. On the other hand, dominant sources of atmospheric humidity may alter from the far distant equatorial Indian (18O depleted) to the nearby West Pacific Ocean (18O enriched), thus significantly influencing the δ18O value of the monsoon-controlled freshwater discharge to the South China Sea (Pausata et al., 2011), and accordingly, the local planktic δ18O signal of surface waters. We tested the role of these possibly opposed factors by means of planktic δ18O records with centennial-scale resolution at ODP Site 1144 (2040 m w.d.; Bühring et al., 2004) and MD05-2904 (2070 m w.d.; Ge et al., 2010). In contrast to an expected 18O depletion for MIS 5.5 of 0.3 ‰, the pertinent core sections were 18O enriched by 0.4 ‰ as compared to MIS 1. This positive shift may either suggest a major and dominant switch in atmosph¬eric water supply from Indian to nearby West Pacific sources or exhibit a loss of the sediment section crucial for MIS 5.5, that is a distinct stratigraphic gap. Highly resolved δ18O records obtained for comparison from three sediment cores retrieved nearby at much greater water depths (ODP Sites 1145, 1146; Core 17924) clearly show for MIS-5.5 the expected δ18O level that is slightly lighter than that of MIS 1, in harmony with increased SST (He et al., 2008), and thus support the hiatus model. It is also corroborated by large fields of (modern) erosional furrows which are generated by a vigorous inflow of Upper Pacific Deepwater passing along the continental slope off Hong Kong near 2350 m w.d. During interglacial MIS 5.5, this current had probably moved upslope by

  17. Vascular endothelial growth factor assessment in different blood fractions of gastrointestinal cancer patients and healthy controls.

    PubMed

    Ranieri, Girolamo; Coviello, Maria; Chiriatti, Annalisa; Stea, Baldassarre; Montemurro, Severino; Quaranta, Michele; Dittadi, Ruggero; Paradiso, Angelo

    2004-02-01

    Vascular endothelial growth factor (VEGF) is known to play a central role in tumour angiogenesis. Up to now inconclusive data have been published on the clinical-biological significance of circulating VEGF and on the most suitable blood fraction for measuring it. The aims of this pilot study were to assess VEGF in blood compartments of 16 healthy control volunteers and 56 gastrointestinal cancer patients, prospectively collected, to identify the most suitable blood fraction for the determination of VEGF and to evaluate its possible clinical-biological significance. Samples of serum (S) and plasma (P) in both sodium citrate (SC) and sodium citrate-theophylline-adenosine-dipyridamole (CTAD) were collected from venous blood. After the centrifugation and separation methods VEGF levels were detected by ELISA in: S, plasma-platelets poor (P-PP), plasma-activated platelets rich (P-APR) and blood-lysed whole (B-LW). The best differentiation between healthy control volunteers and cancer patients in VEGF level was seen for P-APRCTAD (mean value: 278 pg/ml vs 77 pg/ml; p=0.0036 by t-test). No significant correlation among the blood fractions of VEGF analysed and clinical-pathological features was found. Our data suggest that P-APRCTAD blood fraction, obtained according to well standardised conditions, could represent the most suitable compartment for the assessment of VEGF. We suggest that VEGF levels in P-APRCTAD could play a role as an angiogenic marker of malignant gastrointestinal transformation. Further studies on a larger series of patients and healthy controls with the same experimental methodological conditions are required to confirm our preliminary conclusions. PMID:14719080

  18. A 16 ka lacustrine 18O record from High Himalaya reflecting the Indian Monsoon variability

    NASA Astrophysics Data System (ADS)

    Zech, M.; Tuthorn, M.; Zech, R.; Schlütz, F.; Zech, W.; Glaser, B.

    2012-04-01

    Establishing 18O records using organic matter of lake sediments is so far complicated due to analytical challenges. Based on the results obtained by a novel analytical method, the so-called compound-specific delta18O-analysis of hemicellulose monosaccharides (Zech, M. and Glaser, B., 2009. Rapid Communications in Mass Spectrometry 23, 3522-3532), we here present a first well-dated continuous late glacial lacustrine 18O record from High Himalayan lake sediments. Our 18O record, which reflects a coupled hydrological and thermal control, reveals the late glacial Indian Summer Monsoon variability depicting the Bölling/Alleröd and the Younger Dryas. Thus, it closely resembles the 18O records of South Asian speleothems and Greenland ice cores. We hence conclude that our novel 18O method enables regional paleoclimate reconstructions and that our 18O record highlights the previously suggested teleconnections between the Indian and the East Asian Monsoon and Greenland temperatures.

  19. 2H and 18O Freshwater Isoscapes of Scotland

    NASA Astrophysics Data System (ADS)

    Meier-Augenstein, Wolfram; Hoogewerff, Jurian; Kemp, Helen; Frew, Danny

    2013-04-01

    Scotland's freshwater lochs and reservoirs provide a vital resource for sustaining biodiversity, agriculture, food production as well as for human consumption. Regular monitoring of freshwaters by the Scottish Environment Protection Agency (SEPA) fulfils legislative requirements with regards to water quality but new scientific methods involving stable isotope analysis present an opportunity combining these mandatory monitoring schemes with fundamental research to inform and deliver on current and nascent government policies [1] through gaining a greater understanding of Scottish waters and their importance in the context of climate change, environmental sustainability and food security. For example, 2H and 18O isoscapes of Scottish freshwater could be used to underpin research and its applications in: • Climate change - Using longitudinal changes in the characteristic isotope composition of freshwater lochs and reservoirs as proxy, isoscapes will provide a means to assess if and how changes in temperature and weather patterns might impact on precipitation patterns and amount. • Scottish branding - Location specific stable isotope signatures of Scottish freshwater have the potential to be used as a tool for provenancing and thus protecting premium Scottish produce such as Scottish beef, Scottish soft fruit and Scottish Whisky. During 2011 and 2012, with the support of SEPA more than 110 samples from freshwater lochs and reservoirs were collected from 127 different locations across Scotland including the Highlands and Islands. Here we present the results of this sampling and analysis exercise isotope analyses in form of 2H and 18O isoscapes with an unprecedented grid resolution of 26.5 × 26.5 km (or 16.4 × 16.4 miles). [1] Adaptation Framework - Adapting Our Ways: Managing Scotland's Climate Risk (2009): Scotland's Biodiversity: It's in Your Hands - A strategy for the conservation and enhancement of biodiversity in Scotland (2005); Recipe For Success - Scotland

  20. Microbial, Physical and Chemical Drivers of COS and 18O-CO2 Exchange in Soils

    NASA Astrophysics Data System (ADS)

    Meredith, L. K.; Boye, K.; Whelan, M.; Pang, E.; von Sperber, C.; Brueggemann, N.; Berry, J. A.; Welander, P. V.

    2015-12-01

    Carbonyl sulfide (COS) and the oxygen isotope composition (δ18O) of CO2 are potential tools for differentiating the contributions of photosynthesis and respiration to the balance of global carbon cycling. These processes are coupled at the leaf level via the enzyme carbonic anhydrase (CA), which hydrolyzes CO2 in the first biochemical step of the photosynthetic pathway (CO2 + H2O ⇌ HCO3- + H+) and correspondingly structural analogue COS (COS + H2O → CO2 + H2S). CA also accelerates the exchange of oxygen isotopes between CO2 and H2O leading to a distinct isotopic imprint [1]. The biogeochemical cycles of these tracers include significant, yet poorly characterized soil processes that challenge their utility for probing the carbon cycle. In soils, microbial CA also hydrolyze COS and accelerate O isotope exchange between CO2 and soil water. Soils have been observed to emit COS by undetermined processes. To account for these soil processes, measurements are needed to identify the key microbial, chemical, and physical factors. In this study, we survey COS and δ18O exchange in twenty different soils spanning a variety of biomes and soil properties. By comparing COS fluxes and δ18O-CO2 values emitted from moist soils we investigate whether the same types of CA catalyze these two processes. Additionally, we seek to identify the potential chemical drivers of COS emissions by measuring COS fluxes in dry soils. These data are compared with soil physical (bulk density, volumetric water content, texture), chemical (pH, elemental analysis, sulfate, sulfur K-edge XANES), and microbial measurements (biomass and phylogeny). Furthermore, we determine the abundance and diversity of CA-encoding genes to directly link CA with measured soil function. This work will define the best predictors for COS fluxes and δ18O-CO2 values from our suite of biogeochemical measurements. The suitability of identified predictor variables can be tested in follow-up studies and applied for modeling

  1. SIMS δ18O and U isotope analyses of opal speleothems: potential for reconstruction of net infiltration and implications for paleoclimate studies

    NASA Astrophysics Data System (ADS)

    Oster, J. L.; Maher, K.; Kitajima, K.; Valley, J. W.; Rogers, B.

    2012-12-01

    Past environmental changes are often reconstructed using records of oxygen isotope variability (δ18O) in soil minerals and speleothems. However, δ18O may be influenced by a combination of environmental factors including rainfall amount, temperature, and moisture source. Variations in initial uranium isotopic values ((234U/238U)0) reflect changes in net infiltration—precipitation minus evapotranspiration (P-ET)—and thus provide a paleoclimate proxy that is sensitive to changes in rainfall. Combined investigation of (234U/238U)0 and δ18O in the same materials could provide records of variations in P-ET and allow differentiation of the influence of effective moisture on δ18O values from other factors such as moisture source. Opal speleothems from a talus cave at Pinnacles National Monument (PNM) in the central California Coast Ranges have high U concentrations (75-4000 ppm) that permit the development of a 230Th-U chronology and (234U/238U)0 record using in situ secondary ion mass spectrometry (SIMS) on the same spatial scale as a record of δ18O variability also produced using SIMS techniques. Modern rainfall δ18O at PNM displays a negative correlation with relative humidity but is also linked to moisture source. Combined high spatial resolution records of speleothem (234U/238U)0 and δ18O from PNM should allow independent investigation of potential changes in rainfall and moisture source in central California. 230Th-U opal ages of the PNM speleothem, measured using the Stanford/USGS SHRIMP-RG at ~50 μm spatial resolution, suggest a growth interval of 15.7 to 2.7 ka, with some possible depositional shifts to calcite. The δ18O of the PNM speleothem was measured at 10 μm spatial resolution using the CAMECA 1280 at the WiscSIMS facility. Typical precision on individual δ18O measurements was 0.3 ‰, and δ18O in coeval material varied by 0.2 ‰ on average. An age model for the δ18O data was constructed using 230Th ages and cathodoluminescence imaging. Age

  2. A 240 ka terrestrial 18O record from a NE-Siberian loess-like permafrost paleosol-sequence based on a novel analytical 18O method

    NASA Astrophysics Data System (ADS)

    Tuthorn, M.; Zech, M.; Detsch, F.; Juchelka, D.; Kalbitz, K.; Mayr, C.; Werner, R.; Zech, R.; Zech, W.; Glaser, B.

    2012-04-01

    Recently, we developed a novel analytical tool for paleoclimate research based on compound-specific delta18O analyses of hemicellulose-derived monosaccharides using gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) (Zech and Glaser, 2009. Rapid Communications in Mass Spectrometry 23, 3522-3532). This method overcomes extraction, purification and hygroscopicity problems of so far applied cellulose methods based on TC/EA-IRMS delta18O analyses and allows establishing 18O records from sedimentary organic matter. Taking advantage of plant samples from a climate chamber experiment we can demonstrate that our novel method yields similar results like cellulose for plant material. Furthermore, we demonstrate using 18O-enriched water that the hydroxyl-groups of hemicelluloses are not prone to oxygen exchange reactions (Zech et al., 2012. Organic Geochemistry 42, 1470-1475). Ongoing methodological improvements will be shortly reported. By applying our novel 18O method to a loess-like permafrost paleosol-sequence we established a presumably 240 ka terrestrial 18O record for NE-Siberia. While the modern topsoil and the interglacial/-stadial paleosols reveal more positive delta18O values, the glacial paleosols reveal more negative delta18O values. The 18O variability is generally confirmed by a respective deltaD record which is based on sedimentary plant leafwax-derived n-alkanes. This finding suggests that our high-latitude 240 ka terrestrial 18O and D/H record from NE-Siberia reflects the temperature-dependent isotopic composition of precipitation and the increased isotopic enrichment of leaf-water during interglacials/-stadials.

  3. Fractionation studies on a factor in linseed meal protecting against selenosis in chicks.

    PubMed

    Jensen, L S; Chang, C H

    1976-03-01

    Growth rate of Single Combe White Leghorn cockerels fed a casein-gelatin-glucose diet was significantly depressed at two weeks when 10 p.p.m. or more selenium was added to the diet. When 20% linseed meal was included in the diet, growth was not reduced with 10 p.p.m. selenium and only slightly reduced with 20 p.p.m. selenium. Including 20% soybean meal failed to modify the toxicity. Levels of 5 and 10% linseed meal were less effective in counteracting selenosis than was 20%. Fractionation studies showed that a protective factor in linseed meal was extracted by methanol and ethanol and was not destroyed by autoclaving. Ashing the ethanol extract destroyed its activity. The factor was readily extracted by chlorform:methanol (2:1) but less effectively by acetone and diethyl ether. Washed chloroform:methanol extract was inactive but the washings contained the factor. Concentrates of the factor were active at less than 1% of the dry matter of the diet. The results of these studies show that linseed meal contains a heat stable, organic, polar factor that modified selenium toxicity in the chick. PMID:947092

  4. δ18O and δ13C Analysis in Tree Rings of Pterocarpus angolensis Growing in Zimbabwe

    NASA Astrophysics Data System (ADS)

    McLeran, K.; Schoof, J. T.; Lefticariu, L.; Therrell, M.

    2015-12-01

    Instrumental weather records in southern Africa are largely limited to the last 100 years and documentary weather-related data are rare prior to the 1800s, hindering our understanding of the natural and/or anthropogenic factors that influence climate variability over this region. Measuring stable isotopes ratios (commonly 13C/12C and 18O/16O) in tree rings can provide a good proxy for extending climate data beyond the instrumental record. The objective of this study is to characterize historical variations in the climatology underlying extreme climatic events in Zimbabwe using instrumental climate records (precipitation and temperature) and a multi-proxy approach (ring width, δ18O, and δ13C) for dendroclimatic proxy reconstructions. A 90-year (1900-1990) δ18O and δ13C tree ring record using four Pterocarpus angolensis samples is being developed and compared to tree ring width, monthly, seasonal, and annual precipitation totals, meteoric water δ18O values, and mean monthly and seasonal temperature. Preliminary results indicate significant correlations between the average δ18O record and the previous year December precipitation totals (r=0.41, p<0.0001), current year January precipitation totals (r=0.45, p<0.0001), and combined total precipitation for the previous year November and December and current year January (r=0.57, p<0.0001). Furthermore, we find that the δ18O values are strongly influenced by maximum temperature during the previous year December (r=0.39, p=0.0001) and current year January (r=0.40, p=0.0001), and average maximum temperature during the months of the previous year December and current year January and February (r=0.47, p<0.001). We thus present one of the first studies to integrate a multi-proxy approach to investigate historical climate variability in southern Africa using ring widths, and tree ring δ18O and δ13C values of trees growing in Zimbabwe.

  5. Measuring hourly 18O and 2H fluxes in a mixed hardwood forest using an integrated cavity output spectrometer

    NASA Astrophysics Data System (ADS)

    Wang, L.; Caylor, K.; Dragoni, D.

    2008-12-01

    The 18O and 2H of water vapor can be used to investigate couplings between biological processes (e.g., photosynthesis or transpiration) and hydrologic processes (e.g., evaporation) and therefore serve as powerful tracers in hydrological cycles. A typical method for determining δ18O and δ2H fluxes in landscapes is a 'Keeling Plot' approach, which uses field-collected vapor samples coupled with a traditional isotope ratio mass spectrometer to infer the isotopic composition of evapotranspiration. However, fractionation accompanying inefficient vapor trapping can lead to large measurement uncertainty and the intensive laboring involved in cold-trap make it almost impossible for continuous measurements. Over the last 3-4 years a few groups have developed continuous approaches for measuring δ18O and δ2H that use laser absorption spectroscopy (LAS) to achieve accuracy levels similar to lab-based mass spectrometry methods. Unfortunately, most LAS systems need cryogenic cooling, constant calibration to a reference gas, and substantial power requirements, which make them unsuitable for long-term field deployment at remote field sites. In this research, we tested out a new LAS--based water vapor isotope analyzer (WVIA, Los Gatos Research, Inc, Mountain View, CA) based on Integrated Cavity Output Spectroscopy (ICOS) and coupled this instrument with a flux gradient system. The WVIA was calibrated bi- weekly using a dew point generator and water with known δ18O and δ2H signatures. The field work was performed at Morgan-Monroe State Forest Ameriflux tower site (central Indiana) between August 8 and August 27, 2008. The combination method was able to produce hourly δ18O and δ2H fluxes data with reproducibility similar to lab-based mass spectrometry methods. Such high temporal resolution data were also able to capture signatures of canopy and bare soil evaporation to individual rainfall events. The use of the ICOS water vapor analyzer within a gradient system has the

  6. Latitudinal temperature gradient during the Cretaceous Upper Campanian-Middle Maastrichtian: δ 18O record of continental vertebrates

    NASA Astrophysics Data System (ADS)

    Amiot, Romain; Lécuyer, Christophe; Buffetaut, Eric; Fluteau, Frédéric; Legendre, Serge; Martineau, François

    2004-09-01

    Latitudinal variations in model biogenic apatite δ18O values were calculated using fractionation equations of vertebrates and weighted rainfall δ18O values along with mean annual air temperatures provided by IAEA-WMO meteorological stations. The reference equation obtained was used to compute a continental temperature gradient for the Late Campanian-Middle Maastrichtian interval by using published and new δ18O values of phosphate from vertebrates. Samples are mainly tooth enamel from crocodilians and dinosaurs that lived at paleolatitudes ranging from 83-9+4°N (Alaska) to 32±3°S (Madagascar). The temperature gradient was less steep (0.4±0.1 °C/°latitude) than the present-day one (0.6 °C/°latitude) with temperatures that decreased from about 30 °C near the equator to about -5 °C at the poles. Above 30° of paleolatitude, air temperatures were higher than at present. The validity of these results is discussed by comparison with climatic criteria inferred from paleontological, paleobotanical and sedimentological data. The latitudinal distribution of oxygen isotope compositions of continental vertebrates is potentially a powerful tool for quantifying Mesozoic terrestrial climates.

  7. Determining long and short hyporheic flow paths in Antarctic streams by comparing evaporative enrichment of D and 18O

    NASA Astrophysics Data System (ADS)

    Gooseff, M. N.; McKnight, D. M.

    2001-12-01

    In glacial meltwater streams of the Dry Valleys, Antarctica, streambeds are composed of porous alluvium, allowing the development of extensive, well-defined hyporheic zones. Stream water and subsurface water from the adjoining saturated alluvium were sampled for major ions and stable isotopes (D and 18O) in order to discritize the hyporheic zone based on variations in residence times. Subsurface water was more enriched in heavier isotopes and had higher solute content than water in the stream. Downstream surface water D and 18O enrichment rates were greater than could be accounted for by direct surface water evaporation, based on data from an evaporation pan experiment. Subsurface samples collected from wells farther from the edge of the open channel, at the upland edge of the hyporheic zone were the most enriched in D and 18O. These results suggest greater fractionation in lateral hyporheic water due to longer residence times at the edges of the hyporheic zone, and that hyporheic mixing may account for the stream water enrichment rates. Inverse modeling results using OTIS confirm the influence of exchange on stream water. These findings show that the hyporheic zones have areas of rapid stream water exchange, where "fast" biogeochemical reactions may influence water chemistry, and areas of very slow exchange in which any magnitude of chemical reaction rate may affect water chemistry.

  8. Scale dependence of environmental and physiological correlates of δ18O and δ13C in the magnesium calcite skeletons of bamboo corals (Gorgonacea; Isididae)

    NASA Astrophysics Data System (ADS)

    Thresher, Ronald E.; Neil, Helen

    2016-08-01

    We examine in detail δ18O and δ13C in the calcite internodes of bamboo corals as potential proxies of physiological and environmental variability, through (a) a "core top" calibration that includes specimens from a wide range of habitats and environmental conditions and (b) a comparison of high resolution serial point analyses along radial growth axes of a sub-set of specimens with each other, with instrumental temperature and salinity records, with growth rates and with a nominal skeletal proxy for temperature (Mg/Ca) in the same specimens. At the whole-of-specimen level, δ18O and the intercept of the strong within-specimen regression of δ18O against δ13C correlates highly with ambient temperatures at slopes that are identical to those reported for other marine biogenic carbonates (-0.22 per °C). δ13C varies predominantly with apparent specimen-mean growth rate. It also correlates with the slope of the within-specimen covariance between δ18O and δ13C, which in turn is distributed bi-modally among specimens and linked to differences in apparent growth rates. Within-specimens, variability in δ13C, and to a lesser extent δ18O, correlates between specimens collected in the same region and differs between regions, implying an environmental effect, but the factors involved for either isotope ratio are unclear. Correlations between δ18O and temperature (and Mg/Ca) range from positive to negative among specimens and appear to vary over time even within specimens. The mismatch between the consistent temperature-dependence of δ18O at the whole-of-specimen level and the mixed relationship within-specimens can be reconciled by assuming an unknown temperature-dependent factor affecting δ18O during the growth of Isidid calcite. The contrast between the results of the "core top" temperature calibration for δ18O, which are consistent with studies of other carbonates, and the apparently more complex suite of factors affecting both δ13C and δ18O within specimens

  9. Relation between D/H ratios and 18O /16O ratios in cellulose from linen and maize - Implications for paleoclimatology and for sindonology

    NASA Astrophysics Data System (ADS)

    DeNiro, Michael J.; Sternberg, Leonel D.; Marino, Bruno D.; Druzik, James R.

    1988-09-01

    The 18O /16O ratios of cellulose and the D/H ratios of cellulose nitrate were determined for linen, a textile produced from the fibers of the flax plant Linum usitatissimum, and for maize ( Zea mays) from a variety of geographic locations in Europe, the Middle East, and North and South America. The regression lines of δD values on δ 18O values had slopes of 5.4 and 5.8 for the two species. Statistical analysis of results reported in the only other study in which samples of a single species (the silver fir Abies pindrow) that grew under a variety of climatic conditions were analyzed yielded slopes of ~6 when δD values of cellulose nitrate were regressed on δ 18O values of cellulose. The occurrence of this previously unrecognized relationship in three species suggests it may obtain in other plants as well. Determining the basis for this relationship, which is not possible given current understanding of fractionation of the isotopes of oxygen and hydrogen by plants, should lead to increased understanding of how D/H and 18O /16O ratios in cellulose isolated from fossil plants are related to paleoclimates. The separation of most linen samples from Europe from those originating in the Middle East when δD values are plotted against δ 18O values suggests it may be possible to use the isotope ratios of cellulose prepared from the Shroud of Turin to resolve the controversy concerning its geographic origin.

  10. Linear model describing three components of flow in karst aquifers using 18O data

    USGS Publications Warehouse

    Long, A.J.; Putnam, L.D.

    2004-01-01

    The stable isotope of oxygen, 18O, is used as a naturally occurring ground-water tracer. Time-series data for ??18O are analyzed to model the distinct responses and relative proportions of the conduit, intermediate, and diffuse flow components in karst aquifers. This analysis also describes mathematically the dynamics of the transient fluid interchange between conduits and diffusive networks. Conduit and intermediate flow are described by linear-systems methods, whereas diffuse flow is described by mass-balance methods. An automated optimization process estimates parameters of lognormal, Pearson type III, and gamma distributions, which are used as transfer functions in linear-systems analysis. Diffuse flow and mixing parameters also are estimated by these optimization methods. Results indicate the relative proximity of a well to a main conduit flowpath and can help to predict the movement and residence times of potential contaminants. The three-component linear model is applied to five wells, which respond to changes in the isotopic composition of point recharge water from a sinking stream in the Madison aquifer in the Black Hills of South Dakota. Flow velocities as much as 540 m/d and system memories of as much as 71 years are estimated by this method. Also, the mean, median, and standard deviation of traveltimes; time to peak response; and the relative fraction of flow for each of the three components are determined for these wells. This analysis infers that flow may branch apart and rejoin as a result of an anastomotic (or channeled) karst network.

  11. Characteristics of the meltwater field from a large Antarctic iceberg using δ18O

    NASA Astrophysics Data System (ADS)

    Helly, John J.; Vernet, Maria; Murray, Alison E.; Stephenson, Gordon R.

    2015-03-01

    Large tabular icebergs represent a disruptive influence on a stable water column when drifting in the open ocean. This is a study of one iceberg, C18A, encountered in the Powell Basin in the Weddell Sea in March 2009, formed from iceberg C18 (76×7 km) originating from the Ross Ice Shelf in May 2002. C18A was lunate in shape with longest dimensions of 31 km×7 km×184 m. The meltwater field from C18A was characterized using δ18O from water samples collected near C18A (Near-field, 0.4-2 km) and contrasted with a Far-field comprised of samples from an Away site (19 km from C18A), a Control site (70 km away), and a region populated with small icebergs (Iceberg Alley, 175 km away). The in-sample fractions of meteoric water were calculated relative δ18O in iceberg ice and Weddell Deep Water and converted to meteoric water height (m) and a percentage within 100 m depth bins. The Near-field and Far-field difference from surface to 200 m was 0.51±0.28%. The concentration of meteoric water dropped to approximately half that value below 200 m, approximate keel depth of the iceberg, although detectable to 600 m. From surface to 600 m, the overall difference was statistically significant (P<0.0001). From this, we estimate the Near-field volume astern of the iceberg (0.16 km3d-1) as a continuous source of meteoric water.

  12. Factors affecting measurement of channel thickness in asymmetrical flow field-flow fractionation.

    PubMed

    Dou, Haiyang; Jung, Euo Chang; Lee, Seungho

    2015-05-01

    Asymmetrical flow field-flow fractionation (AF4) has been considered to be a useful tool for simultaneous separation and characterization of polydisperse macromolecules or colloidal nanoparticles. AF4 analysis requires the knowledge of the channel thickness (w), which is usually measured by injecting a standard with known diffusion coefficient (D) or hydrodynamic diameter (dh). An accurate w determination is a challenge due to its uncertainties arising from the membrane's compressibility, which may vary with experimental condition. In the present study, influence of factors including the size and type of the standard on the measurement of w was systematically investigated. The results revealed that steric effect and the particles-membrane interaction by van der Waals or electrostatic force may result in an error in w measurement. PMID:25817708

  13. N2O and δ15N-N2O and δ18O-N2O from polar ice cores: interpretable data for interglacials

    NASA Astrophysics Data System (ADS)

    Bock, Michael; Schmitt, Jochen; Seth, Barbara; Beck, Jonas; Fischer, Hubertus

    2014-05-01

    Ice cores provide a wealth of information on climate change. For instance, the history of the atmospheric greenhouse gas N2O can be reconstructed using air entrapped in polar ice cores. N2O has several sources in both terrestrial and marine ecosystems, predominantly wetland soils and oxygen minimum zones in the ocean. N2O records generally follow the climatic changes during the glacial-interglacial cycles with higher N2O mixing ratios during warmer climate stages. However, the underlying processes driving these changes are difficult to identify from N2O mixing ratios alone. Additional information on the individual sources and sinks are provided by stable isotope measurements. The emission fluxes of the dominant N2O sources are ascribed to several pathways (nitrification, denitrification), with characteristic fractionation factors for the nitrogen and oxygen isotope signatures of the generated N2O (δ15N-N2O and δ18O-N2O). In the end, the individual proportions of pathways are responsible for distinct δ15N-N2O and δ18O-N2O for the average terrestrial and marine sources. Here, we present new ice core measurements of δ15N-N2O and δ18O-N2O covering the Holocene, MIS 5 and MIS 11. For the past 15 kyrs the δ15N-N2O record shows a continuous decrease starting at 15 kyrs to about 6 kyrs; during the past 6 kyrs δ15N-N2O remains rather constant. The resemblance with a recently published global reconstruction of bulk δ15N is remarkable (McLauchlan et al. 2013, Nature). Taken at face value this could mean that mainly the terrestrial source signature changed rather than a shift in the relative proportions of the terrestrial and marine source. The integrity of N2O ice core records relies on the assumption that the measurements truly represent the past atmosphere. However, comparative analyses of different ice cores from the same age intervals show offsets in the N2O mixing ratios among the records. One likely assumption is that higher mixing ratios are due to in

  14. Differences in the fractional abundances of carbohydrates of natural and recombinant human tissue factor

    PubMed Central

    Krudysz-Amblo, Jolanta; Jennings, Mark E; Matthews, Dwight E; Mann, Kenneth G; Butenas, Saulius

    2011-01-01

    Tissue factor (TF) is a single polypeptide integral membrane glycoprotein composed of 263 residues and is essential to life in its role as the initiator of blood coagulation. Objective Previously we have shown that the activity of the natural placental TF (pTF) and the recombinant TF (rTF) from Sf9 insect cells is different (Krudysz-Amblo, J. et al(2010) J. Biol. Chem. 285, 3371–3382). In this study, using mass spectrometry, we show by quantitative analysis that the extent of glycosylation varies on each protein. Results Fractional abundance, of each glycan composition at each of the three glycosylation sites, reveals the most pronounced difference to be at asparagine (Asn) 11. This residue is located in the region of extensive TFfactor VIIa (FVIIa) interaction. Carbohydrate fractional abundance at Asn11 revealed that glycosylation in the natural placental TF is much more prevalent (~76%) than in the recombinant protein (~20%). The extent of glycosylation on Asn124 and Asn137 is similar in the two proteins, despite the pronounced differences in the carbohydrate composition. Additionally, 77% of rTF exists as TF des-1, 2 (missing the first two amino acids from the N-terminus). In contrast, only 31% of pTF is found in the des-1, 2 form. Conclusion These observations may attribute to the difference in the ability of TF-FVIIa complex to activate factor X (FX). Structural and functional comparison of the recombinant and natural protein advances our understanding and knowledge on the biological activity of TF. PMID:21172408

  15. Diffusion length history over the last 16 ka based on a high resolution δ18O record from NGRIP. Implications for glaciological and paleoclimatic studies.

    NASA Astrophysics Data System (ADS)

    Gkinis, Vasileios; Simonsen, Sebastian B.; Buchardt, Susanne L.; Vinther, Bo M.; White, James W. C.

    2013-04-01

    The Holocene epoch as seen in the water isotopic records of polar ice cores is described by a relatively stable climate characterized by minimal fluctuations in temperature. Arguably, the most commonly used proxy in ice core studies, the ratios of water's stable isotopes, provide an insight in past temperatures via a linear relationship with temperature, commonly referred to as the isotope slope. However, the validity of this slope has been extensively debated. Based on borehole thermometry and gas isotope fractionation studies, it has been shown that temperature changes over the Bølling - Allerød and Younger Dryas transitions as well as several interstadial events have been underestimated by the water isotope slope. Additionally, isotopic artifacts related to ice sheet elevation changes, apparent between 6 and 10 ka b2k, result in a poor or even absent representation of the Holocene climatic optimum in the δ18O record from Greenland ice cores, contrary to what other paleoclimatic records from Northern latitudes indicate. In this study we present ongoing work on the use of the firn isotopic diffusion lengths as a high resolution proxy of the snow and firn temperature. Our reconstruction is based on the high resolution δ18O dataset from NGRIP. Water isotope diffusion is a process that occurs after deposition of the precipitation and takes place in the porous space of the firn until the close off depth. Assuming a diffusivity parameterization and based on a densification and strain rate history, it is possible to investigate the effects of temperature and accumulation on the diffusion length. By inverting the model we produce a temperature reconstruction for the last 15 ka. This temperature signal is independent of factors like the water vapor source location and temperature, the intensity of the atmospheric inversion over the deposition site and the presence or not of clear sky precipitation. In order for the reconstruction to reproduce the long term climate

  16. Late-Glacial to Late-holocene Shifts in Global Precipitation Delta(sup 18)O

    NASA Technical Reports Server (NTRS)

    Jasechko, S.; Lechler, A.; Pausata, F.S.R.; Fawcett, P.J.; Gleeson, T.; Cendon, D.I.; Galewsky, J.; LeGrande, A. N.; Risi, C.; Sharp, Z. D.; Welker, J. M.; Werner, M.; Yoshimura, K.

    2015-01-01

    Reconstructions of Quaternary climate are often based on the isotopic content of paleo-precipitation preserved in proxy records. While many paleo-precipitation isotope records are available, few studies have synthesized these dispersed records to explore spatial patterns of late-glacial precipitation delta(sup 18)O. Here we present a synthesis of 86 globally distributed groundwater (n 59), cave calcite (n 15) and ice core (n 12) isotope records spanning the late-glacial (defined as 50,000 to 20,000 years ago) to the late-Holocene (within the past 5000 years). We show that precipitation delta(sup 18)O changes from the late-glacial to the late-Holocene range from -7.1% (delta(sup 18)O(late-Holocene) > delta(sup 18)O(late-glacial) to +1.7% (delta(sup 18)O(late-glacial) > delta(sup 18)O(late-Holocene), with the majority (77) of records having lower late-glacial delta(sup 18)O than late-Holocene delta(sup 18)O values. High-magnitude, negative precipitation delta(sup 18)O shifts are common at high latitudes, high altitudes and continental interiors.

  17. Monsoon influence on planktic δ18O records from the South China Sea

    NASA Astrophysics Data System (ADS)

    Wang, Pinxian; Li, Qianyu; Tian, Jun; He, Juan; Jian, Zhimin; Ma, Wentao; Dang, Haowen

    2016-06-01

    While the benthic δ18O records from many South China Sea sites mimic the SPECMAP/LR04 standard, their paired planktic δ18O curves differ by comparable values at negative peaks corresponding to interstadials, especially between MIS 5.1, 5.3, 5.5, 6.5, and 7.3. Similar planktic δ18O records also occur in some other low-latitude oceans under monsoon influence. Because neither temperature nor salinity effects can fully account for the variations of such δ18O records after derivation from the SPECMAP/LR04 standard, variations in the rain water δ18O affected by regional hydroclimate changes are considered to have played an important role. In contrast to the SPECMAP/LR04 standard δ18O curve prevailed by 100-kyr cycles, these regional planktic δ18O curves are distinguished by 20-kyr precession signal, showing partial similarity to the δ18O records of atmospheric oxygen in polar ice-core bubbles and in stalagmite calcite. We speculate that the common features of these three independent δ18O records are indicative of the effect of evolving hydrological cycling driven by monsoon circulation in low latitudes.

  18. The Study of the Groundwater by Using the 34S and 18O of the Sulphates-S18O4 Isotopes

    NASA Astrophysics Data System (ADS)

    Awad, Sadek

    The stable isotope of the sulphur atom (34S) and the 18O of the sulphates (S18O4) give information about the type of the mineralisation of the groundwater existing during the water seepage. The decrease of the concentrations in dissolved SO42- (meq/L) versus the increase of δ18O (‰ vs. SMOW) of the sulphates (S18O42-) confirms a partial reduction of the dissolved sulphates in the water. The Under-saturated waters versus the gypsum do not cause the precipitations of the sulphates. The study of δ34S (‰ CD) vs. Cl- (mg/L) indicates high variations in δ34S (‰ CD) for weak difference in the Cl- (mg/L) content, this is due to the reduction of the dissolved sulphates. Concerning the Jurassic water in Lebanon, an oxidation of the sulphide can take place.

  19. Diagnostic value and influencing factors of fractional exhaled nitric oxide in suspected asthma patients

    PubMed Central

    Wang, Yubo; Li, Li; Han, Rui; Lei, Wenhui; Li, Zhongyan; Li, Kunlin; Kang, Jun; Chen, Hengyi; He, Yong

    2015-01-01

    Objective: To explore the critical value and possible influencing factors of fractional exhaled nitric oxide (FeNO) in suspected asthma patients. Methods: 923 suspected asthmatics consecutively referred to our hospital during December 2012 to July 2014 were selected. All cases were carried out FeNO measurement at first; next, spirometry, bronchoprovocation tests or bronchodilation tests were used to confirm or exclude asthma. Receiver operating characteristic curve (ROC) was used to determine the best cut-off value of FeNO for asthma diagnosis. Results: In bronchoprovocation test, 125 cases were diagnosed as asthma, other 283 were non-asthmatics. FeNO levels of asthmatics were significantly higher than non-asthmatics (median, 64.8 ppb vs. 27.9 ppb, P < 0.01). In this group of patients, 64 ppb was the best cut-off value of FeNO to identify asthma with sensitivity of 52.0% and specificity of 94.35%. In bronchodilation test, 185 patients were diagnosed as asthma, other 330 were non-asthmatics. FeNO levels of asthmatics were significantly higher than non-asthmatics (median, 60.6 ppb vs. 29.05 ppb, P < 0.01). In bronchodilation test patients, 41 ppb was the best cut-off value of FeNO to identify asthma with sensitivity of 72.43% and specificity of 74.85%. Influencing factors analysis showed that sex was an independent factor affecting patients’ FeNO level. Conclusion: FeNO was an effective auxiliary diagnosis method for bronchial asthma. 64 ppb and 41 ppb was the best cut-off value of FeNO to identify asthma in bronchoprovocation test or bronchodilation test, respectively. Sex was an independent factor affecting patients’ FeNO level. PMID:26191266

  20. Neurite-promoting factor in conditioned medium from RN22 Schwannoma cultures: bioassay, fractionation, and properties.

    PubMed

    Manthorpe, M; Varon, S; Adler, R

    1981-09-01

    On polyornithine (PORN) substrata dissociated 8-day chick embryo ciliary ganglionic neurons will survive if the culture medium is supplemented with Ciliary neuronotrophic Factor. However, neuritic growth will not occur unless the substratum is derivatized with a PORN-bindable Neurite Promoting Factor (PNPF). In this preliminary study we report that soluble PNPF can be (1) assayed by a convenient in vitro system; (2) obtained in relatively large amounts from serum-free media conditioned over RN22 Schwannoma cultures; (3) concentrated by using Amicon XM100 ultrafiltration; and (4) separated from nearly all of the non-active protein by using ion-exchange chromatography. The partially purified PNPF can be concentrated using XM100 and is heat- and protease-sensitive. In the course of these fractionation studies we observed in some cases a concentration-dependent interference with the expression of PNPF activity in the bioassay; we propose graphical methods to permit the simultaneous determination of PNPF and the extent of such interference. Different treatments that affected the interference property did not always affect PNPF activity in a reciprocal manner, leaving open the possibility that the interference with PNPF activity results from reversible alteration of the PNPF molecule, or that there exists a separate interfering agent. PMID:7276956

  1. Optimization of the safety factor profile for high noninductive current fraction discharges in DIII-D

    NASA Astrophysics Data System (ADS)

    Ferron, J. R.; Holcomb, C. T.; Luce, T. C.; Politzer, P. A.; Turco, F.; White, A. E.; DeBoo, J. C.; Doyle, E. J.; Hyatt, A. W.; La Haye, R. J.; Murakami, M.; Petrie, T. W.; Petty, C. C.; Rhodes, T. L.; Zeng, L.

    2011-06-01

    In order to assess the optimum q profile for discharges in DIII-D with 100% of the current driven noninductively (fNI = 1), the self-consistent response of the plasma profiles to changes in the q profile was studied in high fNI, high βN discharges through a scan of qmin and q95 at two values of βN. As expected, both the bootstrap current fraction, fBS, and fNI increased with q95. The temperature and density profiles were found to broaden as either qmin or βN is increased. A consequence is that fBS does not continue to increase at the highest values of qmin. A scaling function that depends on qmin, q95, and the peaking factor for the thermal pressure was found to represent well the fBS/βN inferred from the experimental profiles. The changes in the shapes of the density and temperature profiles as βN is increased modify the bootstrap current density (JBS) profile from peaked close to the axis to relatively flat in the region between the axis and the H-mode pedestal. Therefore, significant externally driven current density in the region inside the H-mode pedestal is required in addition to JBS in order to match the profiles of the noninductive current density (JNI) to the desired total current density (J). In this experiment, the additional current density was provided mostly by neutral beam current drive with the neutral-beam-driven current fraction 40-90% of fBS. The profiles of JNI and J were most similar at qmin ≈ 1.35-1.65, q95 ≈ 6.8, where fBS is also maximum, establishing this q profile as the optimal choice for fNI = 1 operation in DIII-D with the existing set of external current drive sources.

  2. The fractionation factors of stable carbon and hydrogen isotope ratios for VOCs

    NASA Astrophysics Data System (ADS)

    Kawashima, H.

    2014-12-01

    Volatile organic compounds (VOCs) are important precursors of ozone and secondary organic aerosols in the atmosphere, some of which are carcinogenic, teratogenic, or mutagenic. VOCs in ambient air originate from many sources, including vehicle exhausts, gasoline evaporation, solvent use, natural gas emissions, and industrial processes, and undergo intricate chemical reactions in the atmosphere. To develop efficient air pollution remediation strategies, it is important to clearly identify the emission sources and elucidate the reaction mechanisms in the atmosphere. Recently, stable carbon isotope ratios (δ13C) of VOCs in some sources and ambient air have been measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). In this study, we measured δ13C and stable hydrogen isotope ratios (δD) of atmospheric VOCs by using the gas chromatography/thermal conversion/isotope ratio mass spectrometry coupled with a thermal desorption instrument (TD-GC/TC/IRMS). The wider δD differences between sources were found in comparison with the δ13C studies. Therefore, determining δD values of VOCs in ambient air is potentially useful in identifying VOC sources and their reactive behavior in the atmosphere. However, to elucidate the sources and behavior of atmospheric VOCs more accurately, isotopic fractionation during atmospheric reaction must be considered. In this study, we determined isotopic fractionation of the δ13C and δD values for the atmospheric some VOCs under irradiation conditions. As the results, δ13C for target all VOCs and δD for most VOCs were increasing after irradiation. But, the δD values for both benzene and toluene tended to decrease as irradiation time increased. We also estimated the fractionation factors for benzene and toluene, 1.27 and 1.05, respectively, which differed from values determined in previous studies. In summary, we were able to identify an inverse isotope effect for the δD values of benzene and toluene

  3. The role of vascular endothelial growth factor in fractional laser resurfacing with the carbon dioxide laser.

    PubMed

    Jiang, Xia; Ge, Hongmei; Zhou, Chuanqing; Chai, Xinyu; Ren, Qiu Shi

    2012-05-01

    The aim of this study was to analyze the role of vascular endothelial growth factor (VEGF) in mechanisms of cutaneous remodeling induced by fractional CO(2) laser treatment. The dorsal skin of Kunming mice was exposed to a single-pass fractional CO(2) laser treatment. Biopsies were taken 1 h, and 1, 3, 7, 14, 28 and 56 days after treatment. Skin samples VEGF expression was evaluated by immunohistochemistry and ELISA, fibroblasts by hematoxylin-eosin staining, and types I and III collagen by ELISA. Staining for VEGF was found in many types of cell including fibroblasts. The amount of VEGF in the skin of laser-treated areas had increased significantly compared to that in the control areas on days 1 and 3 (P < 0.05, P < 0.01, respectively), then decreased by day 7 after treatment and returned to the baseline level. The number of fibroblasts in the skin of the laser-treated areas had increased significantly compared to that in control areas on days 3, 7, 14, 28 and 56 after irradiation (P < 0.05, P < 0.01, P < 0.01, P < 0.01, P < 0.01, respectively). The amount of type I collagen was significantly higher in the skin of the laser-treated areas compared to that in control areas from day 28 to day 56 (P < 0.05, respectively), and type III collagen was significantly higher from day 3 to day 56 (P < 0.05, P < 0.05, P < 0.05, P < 0.05, P < 0.01, respectively). There was a positive correlation between the level of VEGF and fibroblast proliferation early stage after laser treatment (r = 0.853, P < 0.01), but there was no correlation after the first week (r = -0.124, P > 0.05). The amounts of type I and III collagen showed no significant correlations with the expression of VEGF in the late stages after laser treatment (r = 0.417, P > 0.05 and r = 0.340, P > 0.05, respectively). The results suggest that VEGF might be mainly involved in the early stages of wound healing, including the stages

  4. What do benthic δ13C and δ18O data tell us about Atlantic circulation during Heinrich Stadial 1?

    NASA Astrophysics Data System (ADS)

    Oppo, Delia W.; Curry, William B.; McManus, Jerry F.

    2015-04-01

    Approximately synchronous with the onset of Heinrich Stadial 1 (HS1), δ13C decreased throughout most of the upper (~1000-2500 m) Atlantic, and at some deeper North Atlantic sites. This early deglacial δ13C decrease has been alternatively attributed to a reduced fraction of high-δ13C North Atlantic Deep Water (NADW) or to a decrease in the NADW δ13C source value. Here we present new benthic δ18O and δ13C records from three relatively shallow (~1450-1650 m) subpolar Northeast Atlantic cores. With published data from other cores, these data form a depth transect (~1200-3900 m) in the subpolar Northeast Atlantic. We compare Last Glacial Maximum (LGM) and HS1 data from this transect with data from a depth transect of cores from the Brazil Margin. The largest LGM-to-HS1 decreases in both benthic δ13C and δ18O occurred in upper waters containing the highest NADW fraction during the LGM. We show that the δ13C decrease can be explained entirely by a lower NADW δ13C source value, entirely by a decrease in the proportion of NADW relative to Southern Ocean Water, or by a combination of these mechanisms. However, building on insights from model simulations, we hypothesize that reduced ventilation due to a weakened but still active Atlantic Meridional Overturning Circulation also contributed to the low δ13C values in the upper North Atlantic. We suggest that the benthic δ18O gradients above ~2300 m at both core transects indicate the depth to which heat and North Atlantic deglacial freshwater had mixed into the subsurface ocean by early HS1.

  5. EFFECT OF HIGH-ENERGY RESONANCES ON THE {sup 18}O(p, {alpha}){sup 15}N REACTION RATE AT AGB AND POST-AGB RELEVANT TEMPERATURES

    SciTech Connect

    La Cognata, M.; Spitaleri, C.; Mukhamedzhanov, A. M.

    2010-11-10

    The {sup 18}O(p, {alpha}){sup 15}N reaction is of great importance in several astrophysical scenarios, as it influences the production of key isotopes such as {sup 19}F, {sup 18}O, and {sup 15}N. Fluorine is synthesized in the intershell region of asymptotic giant branch (AGB) stars, together with s-elements, by {alpha} radiative capture on {sup 15}N, which in turn is produced in the {sup 18}O proton-induced destruction. Peculiar {sup 18}O abundances are observed in R-Coronae Borealis stars, having {sup 16}O/{sup 18}O {approx}< 1, hundreds of times smaller than the galactic value. Finally, there is no definite explanation of the {sup 14}N/{sup 15}N ratio in pre-solar grains formed in the outer layers of AGB stars. Again, such an isotopic ratio is influenced by the {sup 18}O(p, {alpha}){sup 15}N reaction. In this work, a high accuracy {sup 18}O(p, {alpha}){sup 15}N reaction rate is proposed, based on the simultaneous fit of direct measurements and of the results of a new Trojan Horse experiment. Indeed, current determinations are uncertain because of the poor knowledge of the resonance parameters of key levels of {sup 19}F. In particular, we have focused on the study of the broad 660 keV 1/2{sup +} resonance corresponding to the 8.65 MeV level of {sup 19}F. Since {Gamma} {approx} 100-300 keV, it determines the low-energy tail of the resonant contribution to the cross section and dominates the cross section at higher energies. Here, we provide a reaction rate that is a factor of two larger above T {approx} 0.5 10{sup 9} K based on our new improved determination of its resonance parameters, which could strongly influence present-day astrophysical model predictions.

  6. Calibration of δ13C and δ18O measurements in CO2 using Off-axis Integrated Cavity Output Spectrometer (ICOS)

    NASA Astrophysics Data System (ADS)

    Joseph, Jobin; Külls, Christoph

    2014-05-01

    The δ13C and δ18O of CO2 has enormous potential as tracers to study and quantify the interaction between the water and carbon cycles. Isotope ratio mass spectrometry (IRMS) being the conventional method for stable isotopic measurements, has many limitations making it impossible for deploying them in remote areas for online or in-situ sampling. New laser based absorption spectroscopy approaches like Cavity Ring Down Spectroscopy (CRDS) and Integrated Cavity Output Spectroscopy (ICOS) have been developed for online measurements of stable isotopes at an expense of considerably less power requirement but with precision comparable to IRMS. In this research project, we introduce a new calibration system for an Off- Axis ICOS (Los Gatos Research CCIA-36d) for a wide range of varying concentrations of CO2 (800ppm - 25,000ppm), a typical CO2 flux range at the plant-soil continuum. The calibration compensates for the concentration dependency of δ13C and δ18O measurements, and was performed using various CO2 standards with known CO2 concentration and δC13 and δO18 values. A mathematical model was developed after the calibration procedure as a correction factor for the concentration dependency of δ13C and δ18O measurements. Temperature dependency of δ13C and δ18O measurements were investigated and no significant influence was found. Simultaneous calibration of δ13C and δ18O is achieved using this calibration system with an overall accuracy of (~ 0.75±0.24 ‰ for δ13C, ~ 0.81 ±0.26‰ for δ18O). This calibration procedure is found to be appropriate for making Off-Axis ICOS suitable for measuring CO2 concentration and δ13C and δ18O measurements at atmosphere-plant-soil continuum.

  7. The δ2H and δ18O of tap water from 349 sites in the United States and selected territories

    USGS Publications Warehouse

    Coplen, Tyler B.; Landwehr, Jurate M.; Qi, Haiping; Lorenz, Jennifer M.

    2013-01-01

    Because the stable isotopic compositions of hydrogen (δ2H) and oxygen (δ18O) of animal (including human) tissues, such as hair, nail, and urine, reflect the δ2H and δ18O of water and food ingested by an animal or a human and because the δ2H and δ18O of environmental waters vary geographically, δ2H and δ18O values of tap water samples collected in 2007-2008 from 349 sites in the United States and three selected U.S. territories have been measured in support of forensic science applications, creating one of the largest databases of tap water δ2H and δ18O values to date. The results of replicate isotopic measurements for these tap water samples confirm that the expanded uncertainties (U = 2μc) obtained over a period of years by the Reston Stable Isotope Laboratory from δ2H and δ18O dual-inlet mass spectrometric measurements are conservative, at ±2‰ and ±0.2 ‰, respectively. These uncertainties are important because U.S. Geological Survey data may be needed for forensic science applications, including providing evidence in court cases. Half way through the investigation, an isotope-laser spectrometer was acquired, enabling comparison of dual-inlet isotope-ratio mass spectrometric results with isotope-laser spectrometric results. The uncertainty of the laser-based δ2H measurement results for these tap water samples is comparable to the uncertainty of the mass spectrometric method, with the laser-based method having a slightly lower uncertainty. However, the δ18O uncertainty of the laser-based method is more than a factor of ten higher than that of the dual-inlet isotoperatio mass spectrometric method.

  8. Compound specific 13C- and 18O-isotope analysis of organic aerosols

    NASA Astrophysics Data System (ADS)

    Blees, Jan; Saurer, Matthias; Siegwolf, Rolf T. W.; Dommen, Josef; Baltensperger, Urs

    2014-05-01

    . Elements other than carbon may provide valuable additional information. Here we report on the development of methods for the analysis of stable carbon and oxygen isotope ratios of organic compounds in aerosols, through GC-combustion-irMS and GC-pyrolysis-irMS. We apply these analyses to environmental aerosol samples and samples of smog-chamber experiments, with the aim of identifying isotopic signatures of sources and pathways. We will pay special attention to derivatisation techniques - notably alternatives to the often-used trimethylsilyl derivatives in GC-pyrolysis-irMS for δ18O analysis - and to compound separation and identification. We present initial data of combined δ13C and δ18O studies on (secondary) organic aerosol samples, and their added value for source apportionment studies.

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

    USGS Publications Warehouse

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

    2009-01-01

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

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

    SciTech Connect

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

    2009-01-01

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

  11. Fractionation of Nitrous Oxide Isotopomers in the Stratosphere: Enrichment Factors and the Effects of Transport and Mixing

    NASA Astrophysics Data System (ADS)

    Griffith, D. W.; Toon, G. C.; Sen, B.; Blavier, J.

    2002-05-01

    We have measured vertical profiles of the mixing ratios of the four most abundant isotopomers of nitrous oxide, 14N14N16O, 14N15N16O, 15N14N16O, and 14N14N18O, by remote sensing during 11 balloon flights of the JPL MkIV Fourier transform interferometer. The measurements span from the tropopause to around 30 km at northern mid-high latitudes between 1992 and 2000, and include two polar vortex flights in the 1999-2000 winter. We present a flight-by-flight analysis of the vertical profiles and enrichment factors and compare them with other recently published profiles and laboratory measurements. The observed profiles adhere well to a Rayleigh distillation model above 20-24 km, consistent with an irreversible sink process for N2O, but we observe some deviation from strictly Rayleigh behaviour in the profiles in the lower stratosphere. By correlation with profiles of CH4 measured from the same spectra, we find these deviations to be consistent with the effects of atmospheric transport and mixing processes.

  12. A 300-year Vietnam hydroclimate and ENSO variability record reconstructed from tree ring δ18O

    NASA Astrophysics Data System (ADS)

    Sano, Masaki; Xu, Chenxi; Nakatsuka, Takeshi

    2012-06-01

    A tree ring δ18O chronology is developed for the past 300 years (1705-2004) using 6 cypress trees from northern Vietnam to reconstruct long-term hydroclimatic variations in the summer monsoon season. To the best of our knowledge, this is the first well-replicated tree ringδ18O chronology from Southeast Asia, as well as the longest yet produced. Response analyses reveal that tree ring δ18O is significantly correlated with temperature, precipitation, and the Palmer Drought Severity Index (PDSI) during the period May-October, with highest correlation to the PDSI. Our δ18O chronology accounts for 44% of the PDSI variance, and is in good agreement with a 52-year tree ringδ18O chronology from northern Laos (r = 0.77), indicating that regional hydroclimatic signals are well recorded in the δ18O data. Spatial correlation analyses with global sea surface temperatures suggest that the tropical Pacific plays an important role in modulating hydroclimate over the study region. Further, the δ18O chronology correlates significantly with El Niño-Southern Oscillation (ENSO)-related indices, and is therefore used to reconstruct the annual Multivariate ENSO Index. Because previously published ENSO reconstructions are based mainly on proxy records originating from North America and/or the tropical Pacific, the future development of a tree ringδ18O network from mainland Southeast Asia could lead to an independent and more robust reconstruction of ENSO variability.

  13. A ‘hidden’ 18O-enriched reservoir in the sub-arc mantle

    PubMed Central

    Liu, Chuan-Zhou; Wu, Fu-Yuan; Chung, Sun-Lin; Li, Qiu-Li; Sun, Wei-Dong; Ji, Wei-Qiang

    2014-01-01

    Plate subduction continuously transports crustal materials with high-δ18O values down to the mantle wedge, where mantle peridotites are expected to achieve the high-δ18O features. Elevated δ18O values relative to the upper mantle value have been reported for magmas from some subduction zones. However, peridotites with δ18O values significantly higher than the well-defined upper mantle values have never been observed from modern subduction zones. Here we present in-situ oxygen isotope data of olivine crystals in Sailipu mantle xenoliths from South Tibet, which have been subjected to a long history of Tethyan subduction before the India-Asia collision. Our data identify for the first time a metasomatized mantle that, interpreted as the sub-arc lithospheric mantle, shows anomalously enriched oxygen isotopes (δ18O = +8.03 ± 0.28 ‰). Such a high-δ18O mantle commonly does not contribute significantly to typical island arc basalts. However, partial melting or contamination of such a high-δ18O mantle is feasible to account for the high-δ18O signatures in arc basalts. PMID:24577190

  14. A 'hidden' 18O-enriched reservoir in the sub-arc mantle.

    PubMed

    Liu, Chuan-Zhou; Wu, Fu-Yuan; Chung, Sun-Lin; Li, Qiu-Li; Sun, Wei-Dong; Ji, Wei-Qiang

    2014-01-01

    Plate subduction continuously transports crustal materials with high-δ(18)O values down to the mantle wedge, where mantle peridotites are expected to achieve the high-δ(18)O features. Elevated δ(18)O values relative to the upper mantle value have been reported for magmas from some subduction zones. However, peridotites with δ(18)O values significantly higher than the well-defined upper mantle values have never been observed from modern subduction zones. Here we present in-situ oxygen isotope data of olivine crystals in Sailipu mantle xenoliths from South Tibet, which have been subjected to a long history of Tethyan subduction before the India-Asia collision. Our data identify for the first time a metasomatized mantle that, interpreted as the sub-arc lithospheric mantle, shows anomalously enriched oxygen isotopes (δ(18)O = +8.03 ± 0.28 ‰). Such a high-δ(18)O mantle commonly does not contribute significantly to typical island arc basalts. However, partial melting or contamination of such a high-δ(18)O mantle is feasible to account for the high-δ(18)O signatures in arc basalts. PMID:24577190

  15. Data-model comparison of soil-water δ18O at a temperate site in N. Spain with implications for interpreting speleothem δ18O

    NASA Astrophysics Data System (ADS)

    Comas-Bru, Laia; McDermott, Frank

    2015-11-01

    An understanding of how seasonal and longer-term δ18O signals in meteoric precipitation (δ18Op) are modified by percolation through soils is essential to link temporal changes in speleothem δ18O to surface climatic conditions. This study focuses on modifications that occur in a relatively thick soil above a temperate cave site (La Garma, N. Spain). Monthly soil-water δ18O (δ18Osw) values at a depth of 60 cm through the year are only 14% of the range in δ18Op, implying substantial homogenisation and attenuation of seasonal signals. A striking feature is that δ18Osw values at 60 cm depth are lowest in summer and highest in winter, the opposite (anti-phase) to that observed in rainfall. Soil-water residence times of up to circa 6 months in the upper 60 cm of soil, and a matrix flow, piston-type infiltration behaviour with mixing are inferred. Evaporative effects on recovered soil-water δ18O are minimal at this wet temperate site, in contrast with published results from arid and semi-arid sites. A soil-water model is presented to estimate monthly δ18Osw as a function of air temperature and δ18Op, incorporating effects such as variations in the amount of infiltrated water, changes in the ratio between evaporation and transpiration, mixing with antecedent soil moisture and small enrichments in 18O linked to evaporation and summer moisture deficits. Our model reproduces the observed δ18Osw results, and produces δ18O outputs in excellent agreement with δ18O data for two monitored drip-water sites at La Garma cave that exhibit seasonal δ18O variability. We conclude that simple evapotranspiration models that permit infiltration during months that have a positive hydrological balance only, tend to underestimate summer rainfall contributions. Overall, the study provides an improved framework for predicting δ18Osw trends at temperate sites such as La Garma that have a relatively thick soil cover, as well as for understanding seasonal ranges and trends in δ18O in

  16. Analysis of δ15N and δ18O to differentiate NO3- sources in runoff at two watersheds in the Catskill Mountains of New York

    NASA Astrophysics Data System (ADS)

    Burns, Douglas A.; Kendall, Carol

    2002-05-01

    To quantify the movement of atmospheric nitrogen deposition through two forested watersheds in the Catskill Mountains of New York, dual-isotope analysis (δ15N and δ18O) was used to differentiate NO3- derived from precipitation from NO3- derived by microbial nitrification and to quantify the contributions of these sources to NO3- in drainage waters. Samples of stream water, soil water, precipitation, snowmelt, and O-horizon soil were collected during the March and April snowmelt period of 1994 and throughout an 18-month period from August 1995 through February 1997. The mean δ18O-NO3- value of precipitation was +50.5‰, whereas the mean values for stream water and soil water were +17.7‰ and +23.6‰, respectively. The mean δ15N-NO3- of precipitation was -0.2‰, that of soil water was +1.4‰, and that of stream water was +2.3‰ these values showed greater overlap among the three different waters than did the δ18O-NO3- values, indicating that δ15N-NO3- was not as useful for source separation. Soil water δ18O-NO3- values decreased, and δ15N-NO3- values increased, from the O to the B and C horizons, but most of the differences among horizons were not statistically significant. Nitrate derived by nitrification in incubated soil samples had a wide range of δ15N-NO3- values, from +1.5‰ to +16.1‰, whereas δ18O-NO3- values ranged more narrowly, from +13.2‰ to +16.0‰. Values of δ18O-NO3- indicated that NO3- in stream water is mainly derived from nitrification. Only during a high-flow event that exceeded the annual flood was precipitation a major contributor to stream water NO3-. Values of δ18O-NO3- and δ15N-NO3- changed at differing rates as NO3- cycled through these watersheds because δ18O-NO3- values change sharply through the incorporation of oxygen from ambient water and gas during nitrification, whereas δ15N-NO3- values change only incrementally through fractionation during biocycling processes. The results of this study show that most NO3

  17. Water - Isotope - Map (δ 18O, δ 2H, 3H) of Austria: Applications, Extremes and Trends

    NASA Astrophysics Data System (ADS)

    Wyhlidal, Stefan; Kralik, Martin; Benischke, Ralf; Leis, Albrecht; Philippitsch, Rudolf

    2016-04-01

    The isotopic ratios of oxygen and hydrogen in water (2H/1H and 18O/16O) are important tools to characterise waters and their cycles. This starts in the atmosphere as rain or snow and continues in surface water and ends in shallow groundwater as well as in deep groundwater. Tritium formed by natural cosmic radiation in the upper atmosphere and in the last century by tests of thermonuclear bombs in the atmosphere, is characterised by its radioactive decay with a half-life of 12.32 years and is an ideal age-marker during the last 60 years. To determine the origin and mean age of waters in many projects concerning water supply, engineering and scientific projects in the last 45 years on more than 1,350 sites, more than 40,000 isotope measurements were performed in Austria. The median value of all sites of oxygen-18 is δ 18O -10.7 ‰ and for hydrogen-2 δ 2H -75 ‰. As the fractionation is mainly temperature dependent the lowest negative values are observed in winter precipitation (oxygen-18 as low as δ 18O -23 ‰) and in springs in the mountain regions (δ 18O -15.1 ‰). In contrast the highest values were observed in summer precipitation (up to δ 18O - 0.5 ‰) and in shallow lakes in the Seewinkel (up to δ 18O + 5 ‰). The isotopic ratios of the Austrian waters are also influenced by the origin of the evaporated water masses. Therefore the precipitation in the region south of the main Alpine crest (East-Tyrol, Carinthia and South-East Styria) is approximately 1 ‰ higher in δ 18O-values than sites at the same altitude in the northern part. This is most probably caused by the stronger influence of precipitation from the mediterranean area. The median value of all 1,120 sampling sites of decay corrected (2015) tritium measurements is 6.2 tritium units (TU). This is somewhat smaller than the median value of all precipitation stations with 7.2 TU. This can be explained by the fact that in most cases in groundwater the median value has been reduced by decay

  18. Freshwater fluxes in the Weddell Gyre: results from δ18O.

    PubMed

    Brown, Peter J; Meredith, Michael P; Jullion, Loïc; Naveira Garabato, Alberto; Torres-Valdés, Sinhue; Holland, Paul; Leng, Melanie J; Venables, Hugh

    2014-07-13

    Full-depth measurements of δ(18)O from 2008 to 2010 enclosing the Weddell Gyre in the Southern Ocean are used to investigate the regional freshwater budget. Using complementary salinity, nutrients and oxygen data, a four-component mass balance was applied to quantify the relative contributions of meteoric water (precipitation/glacial input), sea-ice melt and saline (oceanic) sources. Combination of freshwater fractions with velocity fields derived from a box inverse analysis enabled the estimation of gyre-scale budgets of both freshwater types, with deep water exports found to dominate the budget. Surface net sea-ice melt and meteoric contributions reach 1.8% and 3.2%, respectively, influenced by the summer sampling period, and -1.7% and +1.7% at depth, indicative of a dominance of sea-ice production over melt and a sizable contribution of shelf waters to deep water mass formation. A net meteoric water export of approximately 37 mSv is determined, commensurate with local estimates of ice sheet outflow and precipitation, and the Weddell Gyre is estimated to be a region of net sea-ice production. These results constitute the first synoptic benchmarking of sea-ice and meteoric exports from the Weddell Gyre, against which future change associated with an accelerating hydrological cycle, ocean climate change and evolving Antarctic glacial mass balance can be determined. PMID:24891394

  19. Freshwater fluxes in the Weddell Gyre: results from δ18O

    PubMed Central

    Brown, Peter J.; Meredith, Michael P.; Jullion, Loïc; Naveira Garabato, Alberto; Torres-Valdés, Sinhue; Holland, Paul; Leng, Melanie J.; Venables, Hugh

    2014-01-01

    Full-depth measurements of δ18O from 2008 to 2010 enclosing the Weddell Gyre in the Southern Ocean are used to investigate the regional freshwater budget. Using complementary salinity, nutrients and oxygen data, a four-component mass balance was applied to quantify the relative contributions of meteoric water (precipitation/glacial input), sea-ice melt and saline (oceanic) sources. Combination of freshwater fractions with velocity fields derived from a box inverse analysis enabled the estimation of gyre-scale budgets of both freshwater types, with deep water exports found to dominate the budget. Surface net sea-ice melt and meteoric contributions reach 1.8% and 3.2%, respectively, influenced by the summer sampling period, and −1.7% and +1.7% at depth, indicative of a dominance of sea-ice production over melt and a sizable contribution of shelf waters to deep water mass formation. A net meteoric water export of approximately 37 mSv is determined, commensurate with local estimates of ice sheet outflow and precipitation, and the Weddell Gyre is estimated to be a region of net sea-ice production. These results constitute the first synoptic benchmarking of sea-ice and meteoric exports from the Weddell Gyre, against which future change associated with an accelerating hydrological cycle, ocean climate change and evolving Antarctic glacial mass balance can be determined. PMID:24891394

  20. Predicting Effects of Cations (Mg, Ca, Na, and K) on 13C-18O Clumping in Dissolved Inorganic Carbon Species and Implications for Carbonate Geothermometry

    NASA Astrophysics Data System (ADS)

    Hill, P. S.; Tripati, A.; Schauble, E. A.

    2014-12-01

    13C-18O bond abundance in carbonates is becoming more widely used as a geothermometer; this proxy is affected by various environmental factors. Here we report the influence of cations (Mg2+, Ca2+, Na+, and K+) at high concentrations (~2 mol/liter) on the isotopologue composition of the DIC pool. Clumped isotope fractionation in CO32- groups of dissolved species and carbonate minerals is reported using the notation Δ63 corresponding mainly to the enrichment in per mil of Hx13C18O16O2x-2 (plus Hx12C18O17O 16Ox-2, Hx12C17O17O 17Ox-2, and Hx13C17O17O 16Ox-2) above the amount expected for a random distribution of isotopes among all CO32-, HCO3- and H2CO3 isotopologues. The Δ63 of a solution of dissolved inorganic carbon (DIC) depends upon the relative abundances of each DIC species (CO2(aq) or H2CO3, HCO3-, and CO32-) since each DIC species has a distinct equilibrium clumped isotope signature. These abundances depend primarily upon solution pH and secondarily upon temperature and salinity (fresh water vs. sea water vs. brine). Solvated DIC species with additional ions and the composite DIC solutions were modeled as a series of supermolecular clusters, each with a single DIC molecule, an added cation, and 21 to 32 surrounding H2O molecules. As in our previous work (Hill et al., 2014, GCA 125, 610-652), we developed electronic structure models at different levels of theory to ensure the best possible reliability at reasonable computational efficiency. Overall, the models predict that common aqueous cations will slightly increase the 13C-18O clumping signature of both individual DIC species and the total DIC pool at a given pH, salinity, and temperature. Predicted Δ63values are also dependent upon cation concentration. The perturbing effect of Mg2+ > Ca2+ > K+ > Na+. Dissolved cations increase the clumped crossover pH (pH at which the composite Δ63 of the DIC pool equals the Δ63 of calcite at equilibrium). Our models predict that a DIC solution of low to moderate p

  1. Seasonal-Resolution δ18O in Speleothems by Ion Microprobe: Revealing Asian Monsoon Dynamics

    NASA Astrophysics Data System (ADS)

    Orland, I. J.; Edwards, R. L.; Cheng, H.; Kozdon, R.; Valley, J. W.

    2014-12-01

    Over the last decade, ion microprobe analysis of speleothems (cave carbonates) has increased the temporal resolution of their oxygen isotope (δ18O) paleoclimate proxy records. Recent improvements in methodology, standardization, and imaging at the WiscSIMS lab make it possible to examine sub-annual patterns of δ18O variability at 10-µm-scale, revealing new seasonal paleoenvironmental information. We applied this technique to an important suite of Chinese stalagmites with conventional drill-sampled δ18O records that reflect changes in Asian Monsoon dynamics across the last deglaciation. Seasonal-resolution δ18O analyses in the Chinese stalagmites reveal regular patterns of annual δ18O variability. Quantitative assessment of the patterns identifies two important components in the δ18O records. First, the source and rainout histories of water vapors that ultimately yield rainfall over China play a primary role in determining the δ18O value of speleothem calcite year-round. Second, intra-annual patterns of calcite δ18O variability indicate that the annual proportion of monsoon precipitation changes systematically during the last deglaciation; the annual proportion of monsoon rainfall is greater during the Holocene and Bølling-Allerød than during the Younger Dryas. This is the first time these components have been characterized in any speleothem δ18O record of monsoon dynamics because seasonal δ18O variability is lost by conventional drill-sampling. Ion microprobe analysis of speleothems can also produce year-by-year records of δ18O across abrupt climate change events. At the Younger Dryas-Holocene transition in a Kulishu Cave stalagmite, which spanned 16 years at 11.53 ky BP, there is a relatively smooth decrease in year-round δ18O(calcite). In contrast, the intra-annual δ18O patterns indicate that the increase in the annual proportion of monsoon rainfall across this transition is stochastic, implying that this record can distinguish the regional

  2. Oxygen isotope fractionation between aragonite and seawater: Developing a novel kinetic oxygen isotope fractionation model

    NASA Astrophysics Data System (ADS)

    Wang, Zhengrong; Gaetani, Glenn; Liu, Chao; Cohen, Anne

    2013-09-01

    Oxygen isotope fractionation factors between aragonite and seawater are studied at T = 25-55 °C and pH = 7.4-8.1 in a set of 'free-drift' precipitation experiments with various CO2-degassing rates (0-75 cc/min). The measured fractionation factors correlate weakly with degassing rate, but strongly with temperature in the following form (R2 = 0.998): 1000lnα=22.5(±0.5)(103/T)-46.1(±1.6) where α is the fractionation factor and T is the temperature in Kelvin. Along with results from previous studies, these experiments help calibrate two extreme cases of a new kinetic model - extremely fast (e.g., during spontaneous precipitation) and slow aragonite precipitation processes (e.g., during slow 'free-drift' precipitation experiments) - at pH >7.5, T = 0-55 °C and salinity = ˜5-39.6‰. The model assumes little isotopic fractionation between DIC species and aragonite during their attachment and detachment on aragonite surfaces at low temperatures and the δ18O value of aragonite equals the average δ18O value of all contributing DIC species. During the fast precipitation of aragonite, the contribution of each DIC species to the δ18O value of aragonite is proportional to its concentration, whereas in a slow precipitation process when the system reaches a steady state, the contribution is determined by both its concentration and a modifying factor. Although the physical meaning of this modifying factor depends on the method of derivation and other assumptions made, three different derivations based on precipitation/dissolution kinetics, isotope exchange reactions, and isotope disequilibrium among DIC species all lead to the same formulation. At pH >7.5, the natural logarithm of the modifying factor (k) for adjusting the contribution of the bicarbonate ion relative to the carbonate ion is calibrated, using experimental data covering a range of temperature, salinity, pH, and precipitation rate, as follows: lnk=(2.22±0.08)×(pH-pH)+{(846±78)·S-(40.3±2.1)×103}/{RT

  3. Assessment of source apportionment by Positive Matrix Factorization analysis on fine and coarse urban aerosol size fractions

    NASA Astrophysics Data System (ADS)

    Karanasiou, A. A.; Siskos, P. A.; Eleftheriadis, K.

    This study was conducted in order to investigate the differences observed in source profiles in the urban environment, when chemical composition parameters from different aerosol size fractions are subjected to factor analysis. Source apportionment was performed in an urban area where representative types of emission sources are present. PM 10 and PM 2 samples were collected within the Athens Metropolitan area and analysed for trace elements, inorganic ions and black carbon. Analysis by two-way and three-way Positive Matrix Factorization was performed, in order to resolve sources from data obtained for the fine and coarse aerosol fractions. A difference was observed: seven factors describe the best solution in PMF3 while six factors in PMF2. Six factors derived from PMF3 analysis correspond to those described by the PMF2 solution for the fine and coarse particles separately. These sources were attributed to road dust, marine aerosol, soil, motor vehicles, biomass burning, and oil combustion. The additional source resolved by PMF3 was attributed to a different type of road dust. Combustion sources (oil combustion and biomass burning) were correctly attributed by PMF3 solely to the fine fraction and the soil source to the coarse fraction. However, a motor vehicle's contribution to the coarse fraction was found only by three-way PMF. When PMF2 was employed in PM 10 concentrations the optimum solution included six factors. Four source profiles corresponded to the previously identified as vehicles, road dust, biomass burning and marine aerosol, while two could not be clearly identified. Source apportionment by PMF2 analysis based solely on PM 10 aerosol composition data, yielded unclear results, compared to results from PMF2 and PMF3 analyses on fine and coarse aerosol composition data.

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

    PubMed

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

    2011-01-14

    The formation of six ozone isotopomers and isotopologues, (16)O(16)O(16)O, (18)O(18)O(18)O, (16)O(16)O(18)O, (18)O(18)O(16)O, (16)O(18)O(16)O, and (18)O(16)O(18)O, has been studied in electron-irradiated solid oxygen (16)O(2) and (18)O(2) (1 ∶ 1) ices at 11 K. Significant isotope effects were found to exist which involved enrichment of (18)O-bearing ozone molecules. The heavy (18)O(18)O(18)O species is formed with a factor of about six higher than the corresponding (16)O(16)O(16)O isotopologue. Likewise, the heavy (18)O(18)O(16)O species is formed with abundances of a factor of three higher than the lighter (16)O(16)O(18)O counterpart. No isotope effect was observed in the production of (16)O(18)O(16)O versus(18)O(16)O(18)O. Such studies on the formation of distinct ozone isotopomers and isotopologues involving non-thermal, non-equilibrium chemistry by irradiation of oxygen ices with high energy electrons, as present in the magnetosphere of the giant planets Jupiter and Saturn, may suggest that similar mechanisms may contribute to the (18)O enrichment on the icy satellites of Jupiter and Saturn such as Ganymede, Rhea, and Dione. In such a Solar System environment, energetic particles from the magnetospheres of the giant planets may induce non-equilibrium reactions of suprathermal and/or electronically excited atoms under conditions, which are quite distinct from isotopic enrichments found in classical, thermal gas phase reactions. PMID:21079822

  5. Antinutritional factors and functionality of protein-rich fractions of industrial guar meal as affected by heat processing.

    PubMed

    Nidhina, N; Muthukumar, S P

    2015-04-15

    Proximate composition analysis and antinutritional factor composition of different fractions of industrial guar meal: raw churi (IRC), heated churi (IHC), final churi (IFC) and guar korma (IGK) were studied and compared. Protein content was found to be very high in IGK (52.7%) when compared to the churi fractions (32-33%) and the trypsin inhibitor activities were found to be negligible in all the fractions (0.58-1.8 mg/g). Single fraction (IGK) was selected for further studies, based on the protein content. The antinutritional factors of selected fractions were significantly reduced by different heat treatments. Heat treatments significantly increased the water absorbing capacity of IGK, but reduced the nitrogen solubility, emulsifying and foaming capacity. Highest L(∗) value was observed for boiled IGK, highest a(∗) and b(∗) values for roasted IGK, during colour measurement. FTIR spectral analysis revealed the presence several aromatic groups in IGK and slight modifications in the molecular structure during heat treatments. PMID:25466107

  6. Late-glacial to late-Holocene shifts in global precipitation δ18O

    NASA Astrophysics Data System (ADS)

    Jasechko, S.; Lechler, A.; Pausata, F. S. R.; Fawcett, P. J.; Gleeson, T.; Cendón, D. I.; Galewsky, J.; LeGrande, A. N.; Risi, C.; Sharp, Z. D.; Welker, J. M.; Werner, M.; Yoshimura, K.

    2015-10-01

    Reconstructions of Quaternary climate are often based on the isotopic content of paleo-precipitation preserved in proxy records. While many paleo-precipitation isotope records are available, few studies have synthesized these dispersed records to explore spatial patterns of late-glacial precipitation δ18O. Here we present a synthesis of 86 globally distributed groundwater (n = 59), cave calcite (n = 15) and ice core (n = 12) isotope records spanning the late-glacial (defined as ~ 50 000 to ~ 20 000 years ago) to the late-Holocene (within the past ~ 5000 years). We show that precipitation δ18O changes from the late-glacial to the late-Holocene range from -7.1 ‰ (δ18Olate-Holocene > δ18Olate-glacial) to +1.7 ‰ (δ18Olate-glacial > δ18Olate-Holocene), with the majority (77 %) of records having lower late-glacial δ18O than late-Holocene δ18O values. High-magnitude, negative precipitation δ18O shifts are common at high latitudes, high altitudes and continental interiors (δ18Olate-Holocene > δ18Olate-glacial by more than 3 ‰). Conversely, low-magnitude, positive precipitation δ18O shifts are concentrated along tropical and subtropical coasts (δ18Olate-glacial > δ18Olate-Holocene by less than 2 ‰). Broad, global patterns of late-glacial to late-Holocene precipitation δ18O shifts suggest that stronger-than-modern isotopic distillation of air masses prevailed during the late-glacial, likely impacted by larger global temperature differences between the tropics and the poles. Further, to test how well general circulation models reproduce global precipitation δ18O shifts, we compiled simulated precipitation δ18O shifts from five isotope-enabled general circulation models simulated under recent and last glacial maximum climate states. Climate simulations generally show better inter-model and model-measurement agreement in temperate regions than in the tropics, highlighting a need for further research to better understand how inter-model spread in

  7. 18O 16O ratios in cherts associated with the saline lake deposits of East Africa

    USGS Publications Warehouse

    O'Neil, J.R.; Hay, R.L.

    1973-01-01

    The cherts formed from sodium silicate precursors in East African saline, alkaline lakes have ??18O values ranging from 31.1 to 44.1. The ??18O values correlate in general with lake salinities as inferred from geologic evidence, indicating that most chert was formed from its precursor in contact with lake water trapped at the time of deposition. A few of the analyzed cherts probably formed in contact with dilute meteoric water. From the widely varying ??18O values we conclude that precursors were transformed to chert in fluids of widely varying salinity and aNa+/aH+ ratio. ?? 1973.

  8. Protease- and Acid-catalyzed Labeling Workflows Employing 18O-enriched Water

    PubMed Central

    Klingler, Diana; Hardt, Markus

    2013-01-01

    Stable isotopes are essential tools in biological mass spectrometry. Historically, 18O-stable isotopes have been extensively used to study the catalytic mechanisms of proteolytic enzymes1-3. With the advent of mass spectrometry-based proteomics, the enzymatically-catalyzed incorporation of 18O-atoms from stable isotopically enriched water has become a popular method to quantitatively compare protein expression levels (reviewed by Fenselau and Yao4, Miyagi and Rao5 and Ye et al.6). 18O-labeling constitutes a simple and low-cost alternative to chemical (e.g. iTRAQ, ICAT) and metabolic (e.g. SILAC) labeling techniques7. Depending on the protease utilized, 18O-labeling can result in the incorporation of up to two 18O-atoms in the C-terminal carboxyl group of the cleavage product3. The labeling reaction can be subdivided into two independent processes, the peptide bond cleavage and the carboxyl oxygen exchange reaction8. In our PALeO (protease-assisted labeling employing 18O-enriched water) adaptation of enzymatic 18O-labeling, we utilized 50% 18O-enriched water to yield distinctive isotope signatures. In combination with high-resolution matrix-assisted laser desorption ionization time-of-flight tandem mass spectrometry (MALDI-TOF/TOF MS/MS), the characteristic isotope envelopes can be used to identify cleavage products with a high level of specificity. We previously have used the PALeO-methodology to detect and characterize endogenous proteases9 and monitor proteolytic reactions10-11. Since PALeO encodes the very essence of the proteolytic cleavage reaction, the experimental setup is simple and biochemical enrichment steps of cleavage products can be circumvented. The PALeO-method can easily be extended to (i) time course experiments that monitor the dynamics of proteolytic cleavage reactions and (ii) the analysis of proteolysis in complex biological samples that represent physiological conditions. PALeO-TimeCourse experiments help identifying rate-limiting processing

  9. The Fractionation of Nitrogen Isotopes in Macroalgae during the Assimilation of Nitrate and Ammonium as a Function of Concentration

    NASA Astrophysics Data System (ADS)

    Swart, Peter; Evans, Sam; Altabet, Mark

    2013-04-01

    In order to determine the amount of fractionation of 15N and 18O during the assimilation of NO3- in marine macro-benthic algae, two species (Ulva sp. and Agardhiella sp.) were grown in a wide range of concentrations of NO3- (2-500 μM). Two types of experiments were performed, one in which the concentration of NO3- was allowed to decrease as it was assimilated by the algae over a 24 hours period and the water and nutrients then restored to the original concentrations and a second set in which the concentration was maintained at a low steady state value by means of a syringe pump. The effective fractionation factor during assimilation was determined by measuring the δ15N of the (i) new algal growth produced, and (ii) measuring the δ15N and δ18O of the NO3- in the free drift experiments which were left for 0, 12, 24, and 48 hours. The fractionation of 15N and 18O was modeled using a Rayleigh distillation model. The results indicate that the fractionation factor during assimilation for NO3- is dependent upon the concentration of NO3- in both species of algae and approaches unity at concentrations of less than 10 μM. The change in the fractionation factor with respect to concentration is the greatest at lower concentrations (1-10 μM). There is also evidence that the fractionation factor falls below unity at very low concentrations. Determinations of the assimilation factor made using the δ15N of the NO3- and the solid algal material provided statistically the same result. At normal marine concentrations of NO3-, fractionation during assimilation can be considered to be negligible. However, at higher concentrations, fractionation during assimilation will lead to isotopic enrichment of the δ15N of the NO3- pool regardless of the δ15N of the source. In addition, to changing the relationship in fractionation relative to concentration, the relationship between the δ15N and δ18O also varies, with values close to unity at higher concentrations and decreasing at

  10. 12CO, 13CO and C18O observations along the major axes of nearby bright infrared galaxies

    NASA Astrophysics Data System (ADS)

    Tan, Qing-Hua; Gao, Yu; Zhang, Zhi-Yu; Xia, Xiao-Yang

    2011-07-01

    We present simultaneous observations of 12CO, 13CO and C18O J = 1-0 emission in 11 nearby (cz < 1000km s-1) bright infrared galaxies. Both 12CO and 13CO are detected in the centers of all the galaxies, except for 13CO in NGC 3031. We have also detected C18O, CS J = 2-1 and HCO+ J = 1-0 emission in the nuclear regions of M82 and M51. These are the first systematical extragalactic detections of 12CO and its isotopes from the PMO 14m telescope. We have conducted half-beam-spaced mapping of M82 over an area of 4' × 2.5' and major axis mapping of NGC 3627, NGC 3628, NGC 4631 and M51. The radial distributions of 12CO and 13 CO in NGC 3627, NGC 3628 and M51 can be well fitted by an exponential profile. The 12CO/13CO intensity ratio, Script R, decreases monotonically with the galactocentric radius in all mapped sources. The average Script R in the center and disk of the galaxies are 9.9±3.0 and 5.6±1.9, respectively, much lower than the peculiar Script R(~24) found in the center of M82. The intensity ratios of 13CO/C18O, 13CO/HCO+ and 13CO/CS (either our or literature data) show little variation with galactocentric radius, in sharp contrast with the greatly varied Script R. This supports the notion that the observed gradient in Script R could be the result of the variations of the physical conditions across the disks. The H2 column density derived from C18O shows that the Galactic standard conversion factor (X-factor) overestimates the amount of the molecular gas in M82 by a factor of ~2.5. These observations suggest that the X-factor in active star-forming regions (i.e., nuclear regions) should be lower than that in normal star-forming disks and the gradient in Script R can be used to trace the variations of the X-factor.

  11. Speleothem record of the last 180 ka in Villars cave (SW France): Investigation of a large δ18O shift between MIS6 and MIS5

    NASA Astrophysics Data System (ADS)

    Wainer, K.; Genty, D.; Blamart, D.; Daëron, M.; Bar-Matthews, M.; Vonhof, H.; Dublyansky, Y.; Pons-Branchu, E.; Thomas, L.; van Calsteren, P.; Quinif, Yves; Caillon, N.

    2011-01-01

    The Vil-car-1 flowstone core from Villars cave (SW France) provides one of the first European speleothem records extending back to 180 ka, based on U-Th TIMS and MC-ICP-MS measurements. The core offers a continuous record of Termination II and the Last Interglacial. The penultimate deglaciation is characterized by a prominent 5‰ depletion in calcite δ18O. Determining which specific environmental factors controlled such a large oxygen isotopic shift offers the opportunity to assess the impact of various factors influencing δ18O variations in speleothem calcite. Oxygen isotope analyses of fluid inclusions indicate that drip water δ18O remained within a very narrow range of ±1‰ from Late MIS6 to the MIS5 δ18O optimum. The possibility of such a stable behaviour is supported by simple calculations of various effects influencing seepage water δ18O. Although this could suggest that the isotopic shift in calcite is mainly driven by temperature increase, attempts to quantify the temperature shift from Late MIS6 to the MIS5 δ18O optimum by assuming an equilibrium relationship between calcite and fluid inclusion δ18O yield unreasonably high estimates of ˜20 °C warming and Late MIS6 cave temperatures below 0 °C; this suggests that the flowstone calcite precipitated out of thermodynamic equilibrium at this site. Using a method proposed by Guo et al. (submitted for publication) combining clumped isotope measurements, fluid inclusion and modern calcite δ18O analyses, it is possible to quantitatively correct for isotopic disequilibrium and estimate absolute paleotemperatures. Although the precision of these absolute temperature reconstructions is limited by analytical uncertainties, the temperature rise between Late MIS6 and the MIS5 optimum can be robustly constrained between 13.2 ± 2.6 and 14.6 ± 2.6 °C (1σ), consistent with existing estimates from Western Europe pollen and sea-surface temperature records.

  12. Investigating spatially coherent changes in European speleothem δ18O time-series

    NASA Astrophysics Data System (ADS)

    Deininger, Michael; McDermott, Frank; Mangini, Augusto; Schröder-Ritzrau, Andrea; Fohlmeister, Jens; Scholz, Denis; Winterhalder, Sophie

    2013-04-01

    Speleothems can provide valuable archives of past environmental conditions on the continents. They can be dated precisely using U-Series disequilibria techniques, or in some cases by lamina counting. Oxygen isotope ratios in speleothem calcite are widely used to infer past climatic conditions. In general speleothem δ18O values are typically dominated by the δ18O signal of the precipitation above a cave site. Therefore, coeval speleothems represent different parts of the same hydrological cycle and should, consequently record spatially coherent δ18O variations. Here we present a new study, in which speleothem δ18O time-series from different locations in Europe are collated to investigate coherent δ18O variations, applying principal component analysis (PCA). The temporal focus of our study was the past 2,000 years, an interval that includes two relatively strong phases of climate change, namely the Medieval Warm Period (MWP) and the Little Ice Age (LIA). The first of two time slices investigated covers the interval from 2.0 until 0.8 ka BP (BP = 1950 cal. years) and the second, the period from 1.2 to 0.05 ka BP. The seven speleothem δ18O time-series, which were tested for spatial coherence during the analysed time slices originate from caves in Austria, Germany, Ireland, Romania, Northern Spain, Sweden and Northern Turkey, respectively. The 1st principal component (PC 1) derived for the first time slice (2.0-0.8 ka BP) explains 36.0 ± 8.9 % (1-sigma) of the total variance (TEV) and is anti-correlated with the speleothem δ18O time-series in Central, Northern and Eastern Europe, including Turkey and correlated with the speleothem δ18O time-series from Ireland and Northern Spain. The mean Spearman rank coefficient between PC 1 with the speleothem δ18O time-series is +/- 0.6, respectively. For the second time slice (1.2-0.05 ka BP) the 1st PC (TEV = 30.9 ± 4.3 %) shows a significant correlation with the speleothem δ18O time-series from Austria, Germany

  13. Discrimination against C18O16O during photosynthesis and the oxygen isotope ratio of respired CO2 in boreal forest ecosystems

    NASA Astrophysics Data System (ADS)

    Flanagan, Lawrence B.; Brooks, J. Renee; Varney, Gregory T.; Ehleringer, James R.

    1997-03-01

    Our objective was to analyze factors that influence changes in the oxygen isotope ratio (δ18O) of atmospheric CO2 within boreal forest ecosystems. We made measurements in the three major forest types (black spruce, jack pine, and aspen) at the southern and northern ends of the boreal forest in central Canada. This research was part of a larger study, the Boreal Ecosystem-Atmosphere Study (BOREAS). In terrestrial ecosystems the δ18O value of atmospheric CO2 is strongly influenced by isotope effects that occur during photosynthesis and respiration. Of primary importance is an equilibrium isotope effect that occurs between oxygen in CO2 and oxygen in soil water and plant chloroplast water. During the equilibrium reaction the oxygen isotope ratio of CO2 becomes enriched in 18O relative to that of water. We measured seasonal changes in the oxygen isotope ratio of (1) water input to the ecosystems (precipitation), (2) water taken up by the major plant species from the soil (plant stem water), and (3) water in plant leaves. We used this information in calculations of isotope discrimination during photosynthesis and soil respiration. Discrimination against C18O16O during photosynthetic gas exchange (ΔA) (influenced by equilibration with chloroplast water) averaged approximately 21‰ at midday and was similar for all forest types. In contrast, CO2 released during plant and soil respiration had an average δ18O value of -14.4‰ but was less depleted in 18O than would be expected for respired CO2 in isotopic equilibrium with soil water. This effect was most pronounced in black spruce sites because of the extensive coverage of moss on the ground surface and the observation that water in the upper moss layers can have an oxygen isotope ratio substantially different from water in deeper soil layers.

  14. East Asian Summer Monsoon variations in the past 12.5 ka: High-resolution δ18O record from a precisely dated aragonite stalagmite in central China

    NASA Astrophysics Data System (ADS)

    Zhang, Hui-Ling; Yu, Ke-Fu; Zhao, Jian-Xin; Feng, Yue-Xing; Lin, Yu-Shi; Zhou, Wei; Liu, Guo-Hui

    2013-09-01

    Due to possible aragonite to calcite transformation resulting in alteration in isotopic signatures and a bias in age-dating, aragonite speleothems are often excluded from paleoclimatic archives. However, aragonite stalagmites contain ppm-level uranium content, making them much easier to date, achieving higher age-dating precisions than calcite stalagmites. In this regard, provided aragonite-to-calcite transformation did not occur, aragonite stalagmites are potentially well suited for Holocene climate research, given their climate proxies can be placed into a better constrained chronological framework. In this paper, we present high-precision U/Th dates and O isotopic time series for a 82 cm long, continuous growth aragonite stalagmite, LH2, from Lianhua Cave, Hunan Province, China, and discuss East Asian Summer Monsoon (EASM) variability for the last 12.5 ka BP (before present). The U/Th-dated δ18O sequence with a mean 16-year resolution and the growth rate pattern of LH2 show that EASM experienced a strengthening stage, a strong stage and a weakening stage during the last 12.5 ka. During the YD (12.5-11.5 ka BP), heavy δ18O values and low growth rate indicate a weak monsoon period. During the Preboreal (from ∼11.5 to 10.6 ka BP), δ18O values decreased dramatically (∼1.94‰) reflecting abrupt strengthening of the monsoon. From 10.6 to 4.2 ka BP, the record is characterized by the lightest δ18O values and high growth rates, suggesting a strong monsoon period. The summer monsoon weakened substantially after 4.2 ka BP, as inferred from gradually increasing δ18O values and decreasing growth rate. Overall, the intensity of the EASM is regulated by summer insolation at 30°N during the last 12.5 ka. Although oxygen isotope fractionation is different between aragonite-H2O and calcite-H2O because of Rayleigh Fractionation Law, the overall temporal pattern of δ18O values from aragonite stalagmite LH2 is concordant with other high-resolution Holocene calcite

  15. Oxygen isotope fractionation in travertine-depositing pools at Baishuitai, Yunnan, SW China: Effects of deposition rates

    NASA Astrophysics Data System (ADS)

    Sun, Hailong; Liu, Zaihua; Yan, Hao

    2014-05-01

    Travertine δ18O values can be used to reconstruct paleo-temperatures if the oxygen isotope fractionation factors between travertine and water are accurately understood. For this purpose, the δ18O values of pool travertine and its parent water, and the deposition rates of the calcite were investigated at Baishuitai (Yunnan, SW China) over the course of the full hydrological year, April 23 2006-April 25 2007. The results show that the travertine-water isotope fractionation factors are close to the commonly accepted equilibrium line of Kim and O'Neil (1997). This differs from the results obtained by Yan et al. (2012) who found that the oxygen isotope fractionation factors in the travertine-depositing pools were close to the line suggested as equilibrium relationship by Coplen (2007). The average calcite deposition rate (2.30 mg cm-2 d-1) in the present study is six times larger than that (0.38 mg cm-2 d-1) in Yan et al. (2012). If slower calcite precipitation leads to equilibrium oxygen isotopic fractionation, then the results of this study support the results of Coplen (2007) that indicate that the equilibrium fractionation factor may be greater than the commonly accepted one derived by Kim and O'Neil (1997). The relationship between oxygen isotope fractionation factor and calcite deposition rate in our study also agrees with the results of Dietzel et al. (2009) who found that the kinetic-isotope effect favors preferential incorporation of 16O in solid calcite as the calcite deposition rate increases. There was a threshold for calcite precipitation rate control on oxygen isotopic equilibrium. In our case of travertine-depositing pools, when the calcite deposition rate was lower than 0.38 mg cm-2 d-1, oxygen isotopic equilibrium between calcite and water was attained. Therefore, calcite deposition rate is a potentially important consideration when using δ18O in natural carbonates as a proxy for terrestrial and ocean temperature.

  16. Coupled measurement of δ18O/δD in gypsum hydration water and salinity of fluid inclusions in gypsum: A novel tool for reconstructing parent water chemistry and depositional environment

    NASA Astrophysics Data System (ADS)

    Evans, Nick; Gázquez, Fernando; Turchyn, Alexandra; Chapman, Hazel; Hodell, David

    2015-04-01

    The measurement of oxygen and hydrogen isotopes in gypsum hydration water (CaSO4•2H2O) is a powerful tool to determine the isotopic composition of the parent fluid from which gypsum precipitated. To be useful, however, the hydration water must retain its original isotope signal and not have undergone postdepositional exchange. We developed a novel method to ascertain whether hydration waters have secondarily exchanged by coupling oxygen and hydrogen isotopes of gypsum hydration water with the salinities of fluid inclusions. Salinity is obtained through microthermometric analysis of the same gypsum crystals measured for hydration water by freezing the sample and then measuring the melting point of the fluid inclusions. We apply the method to Messinian gypsum deposits of Cycle 6 within the Yesares Member, Río de Aguas section, Sorbas Basin (SE Spain). After correction of oxygen and hydrogen isotopes of gypsum hydration water for fractionation factors, the estimated range of the mother water is -1.8o to 2.8o for δ18O and -12.5o to 16.3o for δD. In the same samples, estimated salinity of primary fluid inclusions range from 18 to 51ppt. Salinity is highly correlated with δ18O and δD, yielding an r2 of 0.88 and 0.87, respectively. The intercepts of the regression equations (i.e., at zero salinity) define the isotope composition of the freshwater endmember, and average -4.4±1.3o for δ18O and -28.9±8.7o for δD. These values are within error of the average isotope composition of precipitation and groundwater data from the local region of Almería today (-4.3o and -22.2o for δ18O and δD, respectively). This agreement provides strong evidence that the gypsum hydration water has retained its isotope composition and has not undergone postdepositional exchange. Furthermore, the isotope and salinity values indicate a significant contribution of meteoric water during gypsum deposition. This observation contrasts with sulfur and oxygen isotopes in sulfate (21.9 > δ34S

  17. Global isoscapes for δ18O and δ2H in precipitation: improved prediction using regionalized climatic regression models

    NASA Astrophysics Data System (ADS)

    Terzer, S.; Wassenaar, L. I.; Araguás-Araguás, L. J.; Aggarwal, P. K.

    2013-11-01

    A regionalized cluster-based water isotope prediction (RCWIP) approach, based on the Global Network of Isotopes in Precipitation (GNIP), was demonstrated for the purposes of predicting point- and large-scale spatio-temporal patterns of the stable isotope composition (δ2H, δ18O) of precipitation around the world. Unlike earlier global domain and fixed regressor models, RCWIP predefined 36 climatic cluster domains and tested all model combinations from an array of climatic and spatial regressor variables to obtain the best predictive approach to each cluster domain, as indicated by root-mean-squared error (RMSE) and variogram analysis. Fuzzy membership fractions were thereafter used as the weights to seamlessly amalgamate results of the optimized climatic zone prediction models into a single predictive mapping product, such as global or regional amount-weighted mean annual, mean monthly, or growing-season δ18O/δ2H in precipitation. Comparative tests revealed the RCWIP approach outperformed classical global-fixed regression-interpolation-based models more than 67% of the time, and clearly improved upon predictive accuracy and precision. All RCWIP isotope mapping products are available as gridded GeoTIFF files from the IAEA website (www.iaea.org/water) and are for use in hydrology, climatology, food authenticity, ecology, and forensics.

  18. Global isoscapes for δ18O and δ2H in precipitation: improved prediction using regionalized climatic regression models

    NASA Astrophysics Data System (ADS)

    Terzer, S.; Wassenaar, L. I.; Araguás-Araguás, L. J.; Aggarwal, P. K.

    2013-06-01

    A Regionalized Climatic Water Isotope Prediction (RCWIP) approach, based on the Global Network for Isotopes in Precipitation (GNIP), was demonstrated for the purposes of predicting point- and large-scale spatiotemporal patterns of the stable isotope compositions of water (δ2H, δ18O) in precipitation around the world. Unlike earlier global domain and fixed regressor models, RCWIP pre-defined thirty-six climatic cluster domains, and tested all model combinations from an array of climatic and spatial regressor variables to obtain the best predictive approach to each cluster domain, as indicated by RMSE and variogram analysis. Fuzzy membership fractions were thereafter used as the weights to seamlessly amalgamate results of the optimized climatic zone prediction models into a single predictive mapping product, such as global or regional amount-weighted mean annual, mean monthly or growing-season δ18O/δ2H in precipitation. Comparative tests revealed the RCWIP approach outperformed classical global-fixed regression-interpolation based models more than 67% of the time, and significantly improved upon predictive accuracy and precision. All RCWIP isotope mapping products are available as gridded GeoTIFF files from the IAEA website (www.iaea.org/water) and are for use in hydrology, climatology, food authenticity, ecology, and forensics.

  19. A multi-model-proxy comparison study to refine the climatic interpretations of a speleothem δ18O record

    NASA Astrophysics Data System (ADS)

    Jex, C.; Phipps, S. J.; Baker, A.; Bradley, C.; Scholz, D.

    2012-12-01

    Speleothem δ18O (δ18Ospel) is arguably one of the best proxies for understanding seasonal groundwater recharge dynamics on all timescales, and therefore for inferring past changes in regional hydroclimate. Statistical relationships between δ18Ospel and the amount of seasonally effective precipitation or its isotopic composition may be demonstrated at cave sites where there is a reliable seasonally distinct composition of δ18O of precipitation (δ18Opptn). This is often the case where recharge is driven by spring snow-melt, seasonal soil moisture excess, or in monsoonal regimes with distinct changes in moisture source. We suggest that there are also three main areas of uncertainty that need to be addressed with any individual record of δ18Ospel. Here we present the results of a multi-model-proxy comparison using a published record of δ18Ospel from Turkey that has grown over the last 500 years in order to quantify these three main areas of uncertainty. First, we assess the stability of previously observed relationships between local climate parameters and regional circulation dynamics over the last 1ka using the CSIRO Mk3L climate system model [Phipps et al., 2011] in order to estimate the variability of δ18Opptn that could be explained by internal climate variability alone. Second, we estimate the variability in δ18Odw that could be explained by storage and routing of water in the karst aquifer over the last 1 ka using the temperature and precipitation output of a three-member ensemble of transient simulations and synthetic δ18Opptn for this location, to drive the KarstFor karst systems model [Baker et al., 2012]. Finally, we estimate the variability in δ18Ospel that may be attributed to kinetic fractionation processes associated with non-equilibrium CaCO3 formation for this cave system [Scholz et al., 2009]. Baker, A., C. Bradley, S. J. Phipps, M. Fischer, I. J. Fairchild, L. Fuller, C. Spötl, and C. Azcurra (2012), Millennial-length forward models and

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  1. Stable Isotope (18O, 2H) and Arsenic Distribution in the Shallow Aquifers in Araihazar, Bangladesh

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Datta, S.; Stute, M.; Dhar, R.; Hoque, M. A.; Rahman, M. W.; Ahmed, K. M.; Schlosser, P.; van Geen, A.

    2005-12-01

    Recent estimates indicate that in Bangladesh alone, an estimated 50 million people have been exposed to Arsenic levels that exceed the WHO guideline of 10 μgL-1 for drinking water by up to two orders of magnitude. There is still debate on what processes control the spatial heterogeneity of dissolved As concentrations. One recent suggestion has been that surface waters enriched in labile organic matter and transferred to greater depths by irrigation pumping may be an important factor. We have monitored for a year the oxygen and hydrogen isotopic composition of precipitation in Dhaka, Bangladesh, and of surface waters and groundwaters in a 25 km2 study area in Araihazar, 20 km east of Dhaka. The data show a large spatial and temporal heterogeneity, with δ18O covering a range of up to 12 ‰. The isotopic composition of precipitation falls on the global meteoric water line (GMWL), while most surface waters collected from rivers, ponds and irrigated rice fields plot below and to the right of the meteoric water line, suggesting that evaporation is an important mechanism in this system. Surface waters show a strong evaporative enrichment during the dry season of up to 10 ‰ in δ18O and then show increased mixing with precipitation during the wet season. The groundwater isotopic composition obtained at 6 multi level well sites covers the range between the GMWL and moderately evaporated surface waters. These data indicate that some groundwaters are recharged directly by precipitation while others show evidence of recharge from evaporated surface waters during the wet and at the beginning of the dry season. For several well nests, the sources of groundwater vary in a systematic way as a function of depth. Highly evaporated irrigation water from rice fields in the dry season does not seem to contribute much to groundwater recharge. The degree of evaporation expressed as deuterium excess does not correlate with As concentrations in the groundwater samples. This finding

  2. Low-(18)O Silicic Magmas: Why Are They So Rare?

    SciTech Connect

    Balsley, S.D.; Gregory, R.T.

    1998-10-15

    LOW-180 silicic magmas are reported from only a small number of localities (e.g., Yellowstone and Iceland), yet petrologic evidence points to upper crustal assimilation coupled with fractional crystallization (AFC) during magma genesis for nearly all silicic magmas. The rarity of 10W-l `O magmas in intracontinental caldera settings is remarkable given the evidence of intense 10W-l*O meteoric hydrothermal alteration in the subvolcanic remnants of larger caldera systems. In the Platoro caldera complex, regional ignimbrites (150-1000 km3) have plagioclase 6180 values of 6.8 + 0.1%., whereas the Middle Tuff, a small-volume (est. 50-100 km3) post-caldera collapse pyroclastic sequence, has plagioclase 8]80 values between 5.5 and 6.8%o. On average, the plagioclase phenocrysts from the Middle Tuff are depleted by only 0.3%0 relative to those in the regional tuffs. At Yellowstone, small-volume post-caldera collapse intracaldera rhyolites are up to 5.5%o depleted relative to the regional ignimbrites. Two important differences between the Middle Tuff and the Yellowstone 10W-180 rhyolites elucidate the problem. Middle Tuff magmas reached water saturation and erupted explosively, whereas most of the 10W-l 80 Yellowstone rhyolites erupted effusively as domes or flows, and are nearly devoid of hydrous phenocrysts. Comparing the two eruptive types indicates that assimilation of 10W-180 material, combined with fractional crystallization, drives silicic melts to water oversaturation. Water saturated magmas either erupt explosively or quench as subsurface porphyrins bejiire the magmatic 180 can be dramatically lowered. Partial melting of low- 180 subvolcanic rocks by near-anhydrous magmas at Yellowstone produced small- volume, 10W-180 magmas directly, thereby circumventing the water saturation barrier encountered through normal AFC processes.

  3. /sup 18/O as a core plus two valence neutrons: A three-body Faddeev calculation

    SciTech Connect

    Ueta, K.; Miyake, H.; Mizukami, A.

    1983-01-01

    The nucleus /sup 18/O is studied assuming a three-body model: two neutrons outside an inert core of /sup 16/O: and solving the Faddeev equations. The calculated spectrum is in good agreement with experiment.

  4. Relation between D/H ratios and sup 18 O/ sup 16 O ratios in cellulose from linen and maize--Implications for paleoclimatology and for sindonology

    SciTech Connect

    DeNiro, M.J.; Sternberg, L.D.; Marino, B.D. ); Druzik, J.R. )

    1988-09-01

    The {sup 18}O/{sup 16}O ratios of cellulose and the D/H ratios of cellulose nitrate were determined for linen, a textile produced from the fibers of the flax plant Linum usitatissimum, and for maize (Zea mays) from a variety of geographic locations in Europe, the Middle East, and North and South America. The regression lines of {delta}D values on {delta}{sup 18}O values had slopes of 5.4 and 5.8 for the two species. Statistical analysis of results reported in the only other study in which samples of a single species that grew under a variety of climatic conditions were analyzed yielded slopes of {approximately}6 when {delta}D values of cellulose nitrate were regressed on {delta}{sup 18}O values of cellulose. The occurrence of this previously unrecognized relationship in three species suggests it may obtain in other plants as well. Determining the basis for this relationship, which is not possible given current understanding of fractionation of the isotopes of oxygen and hydrogen by plants, should lead to increased understanding of how D/H and {sup 18}O/{sup 16}O ratios in cellulose isolated from fossil plants are related to paleoclimates. The separation of most linen samples from Europe from those originating in the Middle East when {delta}D values are plotted against {delta}{sup 18}O values suggests it may be possible to use the isotope ratios of cellulose prepared from the Shroud of Turin to resolve the controversy concerning its geographic origin.

  5. Body composition among Sri Lankan infants by 18*O dilution method and the validity of anthropometric equations to predict body fat against 18*O dilution

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Body composition indicators provide a better guidance for growth and nutritional status of the infants. This study was designed to (1) measure the body composition of the Sri Lankan infants using a reference method, the 18*O dilution method; (2) calculate the body fat content of the infants using pu...

  6. Dentine oxygen isotopes (δ (18)O) as a proxy for odontocete distributions and movements.

    PubMed

    Matthews, Cory J D; Longstaffe, Fred J; Ferguson, Steven H

    2016-07-01

    Spatial variation in marine oxygen isotope ratios (δ (18)O) resulting from differential evaporation rates and precipitation inputs is potentially useful for characterizing marine mammal distributions and tracking movements across δ (18)O gradients. Dentine hydroxyapatite contains carbonate and phosphate that precipitate in oxygen isotopic equilibrium with body water, which in odontocetes closely tracks the isotopic composition of ambient water. To test whether dentine oxygen isotope composition reliably records that of ambient water and can therefore serve as a proxy for odontocete distribution and movement patterns, we measured δ (18)O values of dentine structural carbonate (δ (18) OSC) and phosphate (δ (18) OP) of seven odontocete species (n = 55 individuals) from regional marine water bodies spanning a surface water δ (18)O range of several per mil. Mean dentine δ (18) OSC (range +21.2 to +25.5‰ VSMOW) and δ (18) OP (+16.7 to +20.3‰) values were strongly correlated with marine surface water δ (18)O values, with lower dentine δ (18) OSC and δ (18) OP values in high-latitude regions (Arctic and Eastern North Pacific) and higher values in the Gulf of California, Gulf of Mexico, and Mediterranean Sea. Correlations between dentine δ (18) OSC and δ (18) OP values with marine surface water δ (18)O values indicate that sequential δ (18)O measurements along dentine, which grows incrementally and archives intra- and interannual isotopic composition over the lifetime of the animal, would be useful for characterizing residency within and movements among water bodies with strong δ (18)O gradients, particularly between polar and lower latitudes, or between oceans and marginal basins. PMID:27547302

  7. On the enigmatic similarity in Greenland δ18O between the Oldest and Younger Dryas

    NASA Astrophysics Data System (ADS)

    Pausata, Francesco S. R.; Löfverström, Marcus

    2015-12-01

    The last deglaciation (20.0-10.0 kyr B.P.) was punctuated by two major cooling events affecting the Northern Hemisphere: the Oldest Dryas (OD; 18.0-14.7 kyr B.P.) and the Younger Dryas (YD; 12.8-11.5 kyr B.P.). Greenland ice core δ18O temperature reconstructions suggest that the YD was as cold as the OD, despite a 50 ppmv increase in atmospheric CO2, while modeling studies suggest that the YD was approximately 4-5°C warmer than the OD. This discrepancy has been surmised to result from changes in the origin of the water vapor delivered to Greenland; however, this hypothesis has not been hitherto tested. Here we use an atmospheric circulation model with an embedded moisture-tracing module to investigate atmospheric processes that may have been responsible for the similar δ18O values during the OD and YD. Our results show that the summer-to-winter precipitation ratio over central Greenland in the OD is twice as high as in the YD experiment, which shifts the δ18O signal toward warmer (summer) temperatures (enriched δ18O values and it accounts for ~45% of the expected YD-OD δ18O difference). A change in the inversion (cloud) temperature relationship between the two climate states further contributes (~20%) to altering the δ18O-temperature-relation model. Our experiments also show a 7% decrease of δ18O-depleted precipitation from distant regions (e.g., the Pacific Ocean) in the OD, hence further contributing (15-20%) in masking the actual temperature difference. All together, these changes provide a physical explanation for the ostensible similarity in the ice core δ18O temperature reconstructions in Greenland during OD and YD.

  8. /sup 18/O-studies on the mechanism of action of 5-oxoprolinase

    SciTech Connect

    Li, L.; Seddon, A.P.; Meister, A.

    1986-05-01

    When the reaction catalyzed by bacterial 5-oxoprolinase was carried out to 80% of completion in /sup 18/O-enriched H/sub 2/O, /sup 18/O was found in the P/sub i/ and glutamate (..gamma..-COOH) products and also in amide carbonyl oxygen of the residual 5-oxoproline. Some glutamate molecules contained 2 atoms of /sup 18/O (..gamma..-COOH). In similar studies with component A alone, /sup 18/O was incorporated into P/sub i/ but not into 5-oxoproline. When enzyme isolated from rat kidney was run in /sup 18/O-enriched H/sub 2/O, isotope was found in the residual 5-oxoproline, glutamate and P/sub i/. Some glutamate contained 2 ..gamma..-carboxyl /sup 18/O atoms and di-labeling of P/sub i/ was also observed. The results obtained with 5-oxoprolinase isolated from kidney and bacteria are thus comparable. The reversibility of the reaction catalyzed by the bacterial enzyme (A + B) was carefully examined and no reversibility was observed. The labeling patterns observed are consistent with a mechanism in which the phosphorylated enol form of 5-oxoproline is hydrated and converted to ..gamma..-glutamyl phosphate which is hydrolyzed at phosphate to give glutamate. A detailed mechanism consistent with these data will be presented.

  9. Regional Scale High Resolution δ18O Prediction in Precipitation Using MODIS EVI

    PubMed Central

    Huang, Cho-Ying; Wang, Chung-Ho; Lin, Shou-De; Lo, Yi-Chen; Huang, Bo-Wen; Hatch, Kent A.; Shiu, Hau-Jie; You, Cheng-Feng; Chang, Yuan-Mou; Shen, Sheng-Feng

    2012-01-01

    The natural variation in stable water isotope ratio data, also known as water isoscape, is a spatiotemporal fingerprint and a powerful natural tracer that has been widely applied in disciplines as diverse as hydrology, paleoclimatology, ecology and forensic investigation. Although much effort has been devoted to developing a predictive water isoscape model, it remains a central challenge for scientists to generate high accuracy, fine scale spatiotemporal water isoscape prediction. Here we develop a novel approach of using the MODIS-EVI (the Moderate Resolution Imagining Spectroradiometer-Enhanced Vegetation Index), to predict δ18O in precipitation at the regional scale. Using a structural equation model, we show that the EVI and precipitated δ18O are highly correlated and thus the EVI is a good predictor of precipitated δ18O. We then test the predictability of our EVI-δ18O model and demonstrate that our approach can provide high accuracy with fine spatial (250×250 m) and temporal (16 days) scale δ18O predictions (annual and monthly predictabilities [r] are 0.96 and 0.80, respectively). We conclude the merging of the EVI and δ18O in precipitation can greatly extend the spatial and temporal data availability and thus enhance the applicability for both the EVI and water isoscape. PMID:23029053

  10. Regional scale high resolution δ18O prediction in precipitation using MODIS EVI.

    PubMed

    Chan, Wei-Ping; Yuan, Hsiao-Wei; Huang, Cho-Ying; Wang, Chung-Ho; Lin, Shou-De; Lo, Yi-Chen; Huang, Bo-Wen; Hatch, Kent A; Shiu, Hau-Jie; You, Cheng-Feng; Chang, Yuan-Mou; Shen, Sheng-Feng

    2012-01-01

    The natural variation in stable water isotope ratio data, also known as water isoscape, is a spatiotemporal fingerprint and a powerful natural tracer that has been widely applied in disciplines as diverse as hydrology, paleoclimatology, ecology and forensic investigation. Although much effort has been devoted to developing a predictive water isoscape model, it remains a central challenge for scientists to generate high accuracy, fine scale spatiotemporal water isoscape prediction. Here we develop a novel approach of using the MODIS-EVI (the Moderate Resolution Imagining Spectroradiometer-Enhanced Vegetation Index), to predict δ(18)O in precipitation at the regional scale. Using a structural equation model, we show that the EVI and precipitated δ(18)O are highly correlated and thus the EVI is a good predictor of precipitated δ(18)O. We then test the predictability of our EVI-δ(18)O model and demonstrate that our approach can provide high accuracy with fine spatial (250×250 m) and temporal (16 days) scale δ(18)O predictions (annual and monthly predictabilities [r] are 0.96 and 0.80, respectively). We conclude the merging of the EVI and δ(18)O in precipitation can greatly extend the spatial and temporal data availability and thus enhance the applicability for both the EVI and water isoscape. PMID:23029053

  11. Calibration of sclerosponge oxygen isotope records to temperature using high-resolution δ 18O data

    NASA Astrophysics Data System (ADS)

    Rosenheim, Brad E.; Swart, Peter K.; Willenz, Philippe

    2009-09-01

    A revised calibration is presented relating the oxygen isotope composition of the aragonite-secreting sclerosponge Ceratoporella nicholsoni, oxygen isotope composition of seawater, and ambient water temperature. This new relationship has been obtained using high-resolution δ 18O data measured in sclerosponges from the Bahamas and Jamaica compared to ambient temperature measurements and δ 18O values of seawater from the two locations, both measured and published. New data improve an existing calibration which was determined using measurements of salinity rather than directly measured δ 18O values of the seawater and was composed of measurements from different species of sclerosponge and other aragonite-secreting organisms. The updated calibration ( n = 12, r2 = 0.95) is: T(°C)=16.1(±3.1)-[6.5(±1.1)](δ-δ), where T is temperature in degrees Celsius, δ arag is the δ 18O value of aragonite normalized to VPDB, and δ sw is the δ 18O value of water normalized to VSMOW. This calibration improves accuracy and precision of Caribbean sclerosponges for reconstructions of temperature as well as δ 18O values of seawater.

  12. Application of δ(18)O, δ(13)CDIC, and major ions to evaluate micropollutant sources in the Bay of Vidy, Lake Geneva.

    PubMed

    Halder, Janine; Pralong, Charles; Bonvin, Florence; Lambiel, Frederic; Vennemann, Torsten W

    2016-01-01

    Waters were sampled monthly from a profile at the wastewater outlet and a reference point in the Bay of Vidy (Lake Geneva) for a year. The samples were analyzed for (18)O/(16)O of water, (13)C/(12)C of dissolved inorganic carbon (DIC), major ions, and selected micropollutant concentrations. δ(18)O values, combined with the major ion concentrations, allowed discharged waste and storm-drainage water to be traced within the water column. On the basis of δ(18)O values, mole fractions of wastewater (up to 45 %), storm-drainage (up to 16 %), and interflowing Rhône River water (up to 34 %) could be determined. The results suggest that the stormwater fractions do not influence micropollutant concentrations in a measurable way. In contrast, the Rhône River interflow coincides with elevated concentrations of Rhône River-derived micropollutants in some profiles. δ(13)C values of DIC suggest that an increase in micropollutant concentrations at the sediment-water interface could be related to remineralization processes or resuspension. PMID:25358053

  13. An automated technique for measuring deltaD and delta18O values of porewater by direct CO2 and H2 equilibration.

    PubMed

    Koehler, G; Wassenaar, L I; Hendry, M J

    2000-11-15

    The stable-oxygen and -hydrogen isotopic values (deltaD, delta18O) of porewater in geologic media are commonly determined on water obtained by extraction techniques such as centrifugation, mechanical squeezing, vacuum heating and cryogenic microdistillation, and azeotropic distillation. Each of these techniques may cause isotopic fractionation as part the extraction process and each is laborious. Here we demonstrate a new approach to obtain automated, high-precision deltaD and delta18O measurements of porewater in geologic sediments by direct H2- and CO2-porewater equilibration using a modified commercial CO2-water equilibrator. This technique provides an important and cost-effective improvement over current extraction methods, because many samples can be rapidly analyzed with minimal handling, thereby reducing errors and potential for isotopic fractionation. The precision and accuracy of direct H2- and CO2-porewater equilibration is comparable to or better than current porewater extraction methods. Finally, the direct equilibration technique allows investigators to obtain high-resolution (cm scale) porewater deltaD and delta18O profiles using cores from individual boreholes, eliminating the need for costly piezometers or conventional porewater extractions. PMID:11101245

  14. High resolution δ17O-δ18O as a single mineral thermometer

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Sengupta, S.; Pack, A.

    2014-12-01

    The equilibrium relationship α17O/16Oa-b = (α18O/16Oa-b)θ makes the analysis of δ17O redundant for most terrestrial applications. However the θ term varies with temperature, so that ultra-high precision δ17O data provide additional information not available from δ18O alone. If the δ18O and δ17O values of formation water covary in a known way (e.g., meteoric water, ocean water), then a unique solution for both temperature and the δ18O of the formation fluids can be obtained from the combined δ18O-δ17O mineral values. The paired δ18O-δ17O values are in essence a single mineral thermometer. Unlike clumped isotopes or combined δ18O-δD data, the δ18O and δ17O values of a mineral have identical 'diagenetic potential', and will only be altered with a high F/R ratio. We have made an empirical determination of the temperature dependence on θ = -710/T2 + 0.5305 using Pleistocene diatom data from ODP Leg 177, Site 1093 (δ18O = 39.610, δ17O = 20.536‰), which is almost identical to Pack and Herwartz (EPSL, 2014). Application to ancient cherts gives the following results: The δ18O-δ17O values of cherts vary systematically with age, from Archean to Proterozoic to Phanerozoic. The Archean cherts are incompatible with modern seawater under any temperature conditions. Instead they have equilibrated with water of δ18O= -10±3 (‰ vs SMOW) at 50 to 70°C. These data support a lighter ocean in the Archean by ~5‰. Proterozoic cherts equilibrated at 35-50°C with meteoric water of -8±3‰ and Phanerozoic cherts equilibrated with mixed meteoric water/ocean water at similar temperatures and higher δ18O values (-3±3‰). The δ18O values of lacustrine diatoms from the Valles Caldera, NM, vary by over 20‰ between glacial and interglacial times. The combined δ18O-δ17O values of interglacial diatoms give T= ~12°C, δ18Ometeoric water = -9‰. A glacial age diatom sample gives T=<10°C, δ18Ometeoric water = -20‰. These data could not be obtained from the

  15. Pervasive and Persistent Large-Volume, low delta 18O Silicic Magma Generation at the Yellowstone Hotspot, 12.7-10.5 Ma: Ion Microprobe Analyses of Zircon in the Cougar Point Tuff

    NASA Astrophysics Data System (ADS)

    Cathey, H. E.; Nash, B. P.; Valley, J. W.; Kita, N.; Ushikubo, T.; Spicuzza, M.

    2007-12-01

    volumes at the time of eruption has been documented previously by polymodal assemblages of glass and pyroxene compositions in several units and is consistent with the zircon δ18O data. Temporal patterns of variation in δ18O over the sequence of eruptions are consistent with zircon core inheritance from unerupted residual magmas and/or remelting of solidified remains of earlier CPT magma reservoirs that were depleted in 18O by hydrothermal alteration. Oxygen isotopes in bulk quartz separates measured by laser fluorination range in δ18O from 1.3 to 4.5‰, and temporal variations in quartz track those of average δ18O in zircon rims in each unit, and thus are consistent with a comagmatic origin with zircon. From the fourth eruption in the sequence to the tenth, average δ18O in quartz (=3.4, sd=0.4) and zircon rims (=0.9, sd=0.5) does not change appreciably from one eruption to the next. Measured Delta (Qz-Zrc) values using δ18O in zircon rims range from 1.8-2.6, and most fractionations are consistent with predictions based on mineral thermometry. First order estimates of the averageδ18O of the total eruptive volume (i.e. 7000 km3) range from 2.4 to 3.4‰, making the Cougar Point Tuff the largest volume of low δ18O magma known.

  16. Tracking water pathways in steep hillslopes by δ18O depth profiles of soil water

    NASA Astrophysics Data System (ADS)

    Mueller, Matthias H.; Alaoui, Abdallah; Kuells, Christoph; Leistert, Hannes; Meusburger, Katrin; Stumpp, Christine; Weiler, Markus; Alewell, Christine

    2014-11-01

    Assessing temporal variations in soil water flow is important, especially at the hillslope scale, to identify mechanisms of runoff and flood generation and pathways for nutrients and pollutants in soils. While surface processes are well considered and parameterized, the assessment of subsurface processes at the hillslope scale is still challenging since measurement of hydrological pathways is connected to high efforts in time, money and personnel work. The latter might not even be possible in alpine environments with harsh winter processes. Soil water stable isotope profiles may offer a time-integrating fingerprint of subsurface water pathways. In this study, we investigated the suitability of soil water stable isotope (δ18O) depth profiles to identify water flow paths along two transects of steep subalpine hillslopes in the Swiss Alps. We applied a one-dimensional advection-dispersion model using δ18O values of precipitation (ranging from -24.7 to -2.9‰) as input data to simulate the δ18O profiles of soil water. The variability of δ18O values with depth within each soil profile and a comparison of the simulated and measured δ18O profiles were used to infer information about subsurface hydrological pathways. The temporal pattern of δ18O in precipitation was found in several profiles, ranging from -14.5 to -4.0‰. This suggests that vertical percolation plays an important role even at slope angles of up to 46°. Lateral subsurface flow and/or mixing of soil water at lower slope angles might occur in deeper soil layers and at sites near a small stream. The difference between several observed and simulated δ18O profiles revealed spatially highly variable infiltration patterns during the snowmelt periods: The δ18O value of snow (-17.7 ± 1.9‰) was absent in several measured δ18O profiles but present in the respective simulated δ18O profiles. This indicated overland flow and/or preferential flow through the soil profile during the melt period. The applied

  17. Hydrological shifts in seawater δ18O in southwest tropical Pacific since 1649 CE

    NASA Astrophysics Data System (ADS)

    DeLong, K. L.; Quinn, T. M.; Taylor, F. W.; Lin, K.; Shen, C. C.

    2014-12-01

    Here we present monthly resolved coral δ18O, δ13C, and Sr/Ca determinations from Porites lutea colonies offshore of Amédée Island, New Caledonia (22º28.8'S, 166º27.9'E) to investigate sea surface temperature (SST) and δ18O of seawater (δ18Osw) variability in the southwest tropical Pacific from 1649-1999 CE. Coral δ18O varies with SST and δ18Osw, which varies with oceanic and hydrologic processes whereas coral Sr/Ca varies with SST because Sr and Ca in seawater are invariant on centennial time scales. Comparison of coral δ18O-SST and Sr/Ca-SST anomalies reveals a persistent +0.3‰ divergence in coral δ18O prior to 1936 CE suggesting a shift in hydrology in which relatively 18O rich surface waters are present as the result of more evaporation than precipitation. Coral δ18O variations from 1649-1936 CE contain interannual to bidecadal variations larger than those observed from 1936-1999 CE and in the coral Sr/Ca-SST reconstruction, suggesting hydrological shifts on those time scales. Long-term coral δ13C variations provide a record of anthropogenic CO2 uptake in the ocean. Coral δ13C records reveal a shift to lower values (Δ=-0.9‰) starting ~1850 CE, a shift greater than that observed in corals from Fiji. The rate of change varies but approaches a constant rate from 1945-1980 CE and then increases from 1980-2000 CE.

  18. The "Flood of the Century" as Isotopic Fingerprint in Canopy d18O Signatures

    NASA Astrophysics Data System (ADS)

    Seibt, U.; Wingate, L.; Berry, J. A.

    2006-12-01

    The d18O composition of water and CO2 exchange at smaller scales (leaf and ecosystem) can be affected by changes in environmental conditions at larger (regional) scales. During a sampling campaign in a beech forest in Germany in August 2002, we encountered such a large scale change when dry sunny weather was followed by a large storm system with heavy rains leading to floods across Europe. During the first, sunny period, bulk leaf water d18O was -1 permil at night and 7 permil at mid-day. Foliage CO2 exchange had positive values of 18O discrimination during photosynthesis (10-30 permil) and nocturnal respiration (11 permil). The second period had frequent rains and mostly diffuse light, with reduced foliage water fluxes but similar carbon fluxes. Canopy vapour d18O decreased at least 2 permil, and leaf water then reflected isotopic exchange with this depleted vapour due to the high humidity. Hence, bulk leaf water was substantially more depleted at night (-8 permil) and showed virtually no evaporative enrichment during the day (-5 permil). Values of 18O discrimination during CO2 exchange were small or even negative for photosynthesis (-2 to 6 permil) but larger for nocturnal respiration (23-39 permil). Model simulations indicated that the small positive foliage isoflux during the day was offset by the negative isoflux at night. As a consequence, the d18O of CO2 in canopy air decreased from -0.3 permil during the sunny period to -3 permil during the wet period. The d18O signatures of canopy water and CO2 thus reflected the transition from local water to the regional regime of depleted water deposited across the area by the storm.

  19. Synthesis and Microwave Dielectric Properties of A16V18O61 (A = Ba, Sr and Ca) Ceramics for LTCC Applications

    NASA Astrophysics Data System (ADS)

    Suresh, E. K.; Prasad, K.; Arun, N. S.; Ratheesh, R.

    2016-06-01

    Low-temperature co-firable A16V18O61 (A = Ba, Sr, Ca) ceramics have been prepared through the solid state ceramic route. The structural features of these ceramics have been studied using the x-ray diffraction (XRD) technique. The existence of the A16V18O61 (A = Ba, Sr, Ca) ceramic phase was confirmed through laser Raman spectroscopic studies. Scanning electron microscopy analysis revealed a dense microstructure for the ceramics with closely packed polygonal grains. Among the samples studied, Ba16V18O61 ceramic was prepared in the ultralow sintering temperature of 620°C for 1 h, which can be co-firable with an aluminium electrode. XRD and electron dispersive spectroscopy analyses showed that the samples under study have excellent compatibility with metal electrodes. The microwave dielectric properties measured using a vector network analyzer revealed that A16V18O61 (A = Ba, Sr, Ca) ceramics have excellent unloaded quality factors.

  20. Hydrogen and oxygen isotope fractionation between brucite and aqueous NaCl solutions from 250 to 450°C

    USGS Publications Warehouse

    Saccocia, Peter J.; Seewald, Jeffrey S.; Shanks, Wayne C., III

    1998-01-01

    Hydrogen and oxygen isotope fractionation factors between brucite and aqueous NaCl solutions (1000lnαbr-sw) have been calibrated by experiment from 250 to 450°C at 0.5 Kb. For D/H fractionation, 1000lnα br-sw values are as follows: −32 ± 6‰ (250°C, 3.2 wt% NaCl), −21 ± 2‰ (350°C, 10.0 wt% NaCl), and −22 ± 2‰ (450°C, 3.2 wt% NaCl), indicating that brucite is depleted in D relative to coexisting aqueous NaCl solutions. These results are in good agreement with previous D/H fractionation factors determined in the brucite-water system, indicating that any effects of dissolved salt on D/H fractionation are relatively small, particularly in solutions with near seawater salinity. The maximum salt effect (+4‰) was observed in 10.0 wt% NaCl solutions at 350°C, suggesting that the addition of dissolved NaCl increases the amount of deuterium fractionated into mineral structures. For 18O/16O fractionation, 1000lnαbr-sw values in 3.0 wt% NaCl solutions are −6.0 ± 1.3‰, −5.6 ± 0.7‰ and −4.1 ± 0.2‰, at 250, 350, and 450°C, respectively, and −5.8 ± 0.6‰ in 10.0 wt % NaCl at 350°C. These data indicate that brucite is depleted in 18O relative to coexisting aqueous NaCl solutions and that the degree of depletion decreases slightly with increasing temperature and is not strongly dependent on salinity. We calculated 18O/16O brucite-water fractionation factors from available calibrations of the salt-effect on 18O/16O fractionation between coexisting phases. The resulting values were fit to the following equation that is valid from 250 to 450°C 1000ln αbr-w = 9.54 × 106T−2 − 3.53 × 104T−1 + 26.58 where T is temperature in Kelvins. These new data have been used to improve the prediction of 18O/16O fractionation factors in the talc-water and serpentine-water systems by modifying existing empirical bond-water models. The results of this analysis indicate that the δ18O composition of talc-brucite and serpentine

  1. How much 18O-depleted rhyolite in the Snake River Plain?

    NASA Astrophysics Data System (ADS)

    Boroughs, S.; Bonnichsen, B.; Wolff, J.; Godchaux, M.; Larson, P.

    2006-12-01

    Oxygen isotope ratios were determined on quartz and feldspar phenocryst separates from 41 silicic units in the central Snake River Plain (CSRP), Owyhee-Humbolt (OH) region, and McDermitt caldera complex (MC), in southwestern Idaho. These rhyolites represent volcanism from a large scale, time transgressive, melting event that progressed from southern Oregon/northern Nevada to the Yellowstone Volcanic Plateau (YVP) from ~17 Ma to present. All CSRP/OH volcanic units erupted between ~14 Ma and 6 Ma have anomalously low δ18O values of less than 4‰ and represent a vast region of δ18O depleted rhyolites (>30,000 km2), from W113.5° to W117° and N42° to N43°. The units are dominantly densely welded ignimbrites and voluminous lava flows with minor non- welded deposits. The area of low δ18O rhyolites is bounded by rhyolites with more common signatures (6-11‰) in the ~17-16 Ma MC to the southwest, and by the 10.5-11.5 Ma Western Snake River Plain rhyolites to the northwest (7-10‰). Also, two significantly older units in the CSRP, the Rough Mountain and Jarbidge rhyolites, which both appear to be caldera infill, returned values of 7- 8‰. Samples from the MC are variable, from 6-11‰, but within the typical range for silicic magmas. We attribute the upper range of values (> 8.5‰) to either mild low temperature hydration/alteration after emplacement or the incorporation of a small component of high δ18O sedimentary material into some of the MC magmas. There seems to be little correlation between δ18O and geographic position within the region of depleted δ18O signatures, although the highest δ18O values, around 3.8‰ , are found in units at the eastern and western margins. Also, there is no significant correlation between eruptive style and magmatic δ18O values. It is generally accepted that δ18O values in fresh silicic igneous rocks below ~5.5‰ must be the result of high temperature interaction between meteoric water and the magma or source rock during

  2. Holocene tropical South American hydroclimate revealed from a decadally resolved lake sediment δ 18O record

    NASA Astrophysics Data System (ADS)

    Bird, Broxton W.; Abbott, Mark B.; Rodbell, Donald T.; Vuille, Mathias

    2011-10-01

    Oxygen isotope ratios of authigenic calcite (δ 18O cal) measured at annual to decadal resolution from Laguna Pumacocha document Andean precipitation variability during the last 11,200 years. Modern limnological data show that Pumacocha δ 18O cal reflects the average annual isotopic composition of the lake's surface waters (δ 18O lw), and that δ 18O lw tracks the isotopic composition of precipitation (δ 18O precip), which is largely controlled by the intensity of the South American summer monsoon (SASM). Based on these relationships we use down-core δ 18O cal measurements as a proxy for δ 18O precip that varies with the intensity of SASM precipitation. Pumacocha δ 18O cal increased rapidly between 11,200 and 10,300 yr B.P. from - 14.5‰ to - 10.5‰, reaching a maximum of - 10.3‰ by 9800 yr B.P. After 9800 yr B.P., δ 18O cal underwent a long-term decrease that tracked increasing Southern Hemisphere summer insolation, suggesting that enhanced SASM precipitation was linked to precessional forcing. Higher-frequency trends did not follow insolation and therefore represent other variability in the climate system. Millennial-scale trends from Pumacocha strongly resemble those from lower-resolution tropical Andean ice and lake core isotopic records, particularly the Huascaran ice core, and low elevation speleothems. These relationships suggest that tropical Andean isotopic records reflect variations in precipitation intensity related to precessional forcing rather than tropical temperatures. They also demonstrate a coherent pattern of SASM variability, although with differences between low elevation and Andean records during the late Glacial to Holocene transition and the late Holocene. Centennial and decadal SASM precipitation variability is also apparent. Reduced SASM rainfall occurred from 10,000-9200, 7000-5000, 1500-900 yr B.P. and during the last 100 years. Intensifications of the SASM occurred at 5000, 2200-1500, and 550-130 yr B.P. with the amplitude of

  3. Comparison of River Water and Precipitation δ18O Across the 48 Contiguous United States

    NASA Astrophysics Data System (ADS)

    Dutton, A. L.; Wilkinson, B. H.; Welker, J. M.; Lohmann, K. C.

    2002-12-01

    A variety of proxies for ancient meteoric precipitation δ18O have been employed to reconstruct paleoclimates including compositions of glacial ice, speleothems, pedogenic carbonate and hematite, authigenic clay minerals, lacustrine carbonate, meteoric cements, and biogenic hardparts such as teeth, otoliths, and bivalve shells. Because many of these techniques rely upon the assumption that the isotopic composition of the surface or groundwater is analogous to that of precipitation in the same locality, we have undertaken a quantitative comparison of the oxygen isotope (δ18O) composition of modern river water and precipitation across the entire U. S. using data from the USGS gauging stations, U. S. Network for Isotopes in Precipitation, and data compiled from the literature. We have generated maps of modern mean annual δ18O for both precipitation and river water across the 48 contiguous United States using latitude and elevation as our primary predictors of stable isotope composition while also incorporating regional and local deviations from this simple model based on available isotopic data. Differences between precipitation and river water compositions were calculated at each grid point (spaced at 30 arc seconds) to generate a final map that displays regions where river water δ18O is similar to, or significantly offset from local precipitation δ18O. Additional maps depicting seasonal and extreme values for river water and precipitation were also constructed. Across most of the Great Plains, river water δ18O is significantly more positive than precipitation, while throughout much of the western United States river water is depleted in 18O compared to local precipitation. One of the most salient features that emerged from this comparison is the "catchment effect" for the river water. Because river water samples are largely derived from precipitation that occurs upstream of the sample localities (i.e., at higher elevations), river water δ18O values are lower

  4. The {sup 18}O(d,p){sup 19}O reaction and the ANC method

    SciTech Connect

    Burjan, V.; Hons, Z.; Kroha, V.; Mrázek, J.; Piskoř, Š.; Mukhamedzhanov, A. M.; Trache, L.; Tribble, R. E.; La Cognata, M.; Lamia, L.; Pizzone, G. R.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Spartà, R.; Spitaleri, C.; Gulino, M.; Tumino, A.

    2014-05-09

    The neutron capture rate {sup 18}O(n,γ){sup 19}O is important for analysis of nucleosynthesis in inhomogeneous Big Bang models and also for models of processes in massive red giant stars and AGB stars. Angular distributions of the {sup 18}O(d,p){sup 19}O reaction were measured at a deuteron energy of 16.3 MeV in NPI in Řež, Czech Republic, with the aim to determine Asymptotic Normalization Coefficients which can then be used for indirect determination of the direct contribution to the {sup 18}O(n,γ){sup 19}O process. In the experiment, the gas target with {sup 18}O isotope of high purity 99.9 % was used thus eliminating any contaminating reactions. Reaction products were measured by the set of 8 ΔE-E telescopes consisting of thin and thick silicon surface-barrier detectors. Angular distributions of proton transfers corresponding to 6 levels of {sup 19}O up to the 4.1093 MeV excitation energy were determined. The analysis of angular distributions in the angular range from 6 to 64 degree including also the angular distribution of elastically scattered deuterons was carried out by means of ECIS and DWUCK codes. From the determined ANCs the direct contribution to the radiative capture {sup 18}O(n,γ){sup 19}O was deduced and compared with existing direct measurements.

  5. Secondary sup 18 O isotope effects for hexokinase-catalyzed phosphoryl transfer from ATP

    SciTech Connect

    Jones, J.P.; Weiss, P.M.; Cleland, W.W. )

    1991-04-16

    Secondary {sup 18}O isotope effects in the {gamma}-position of ATP have been measured on phosphoryl transfer catalyzed by yeast hexokinase in an effort to deduce the structure of the transition state. The isotope effects were measured by the remote-label method with the exocyclic amino group of adenine as the remote label. With glucose as substrate, the secondary {sup 18}O isotope effect per {sup 18}O was 0.9987 at pH 8.2 and 0.9965 at pH 5.3, which is below the pK of 6.15 seen in the V/K profile for MgATP. With the slow substrate 1,5-anhydro-D-glucitol, the value was 0.9976 at pH 8.2. While part of the inverse nature of the isotope effect may result from an isotope effect on binding, the more inverse values when catalysis is made more rate limiting by decreasing the pH or switching to a slower substrate suggest a dissociative transition state for phosphoryl transfer, in agreement with predictions from model chemistry. The {sup 18}O equilibrium isotope effect for deprotonation of HATP{sup 3{minus}} is 1.0156, while Mg{sup 2+} coordination to ATP{sup 4{minus}} does not appear to be accompanied by an {sup 18}O isotope effect larger than 1.001.

  6. A Nonpolar Blueberry Fraction Blunts NADPH Oxidase Activation in Neuronal Cells Exposed to Tumor Necrosis Factor

    PubMed Central

    Gustafson, Sally J.; Dunlap, Kriya L.; McGill, Colin M.; Kuhn, Thomas B.

    2012-01-01

    Inflammation and oxidative stress are key to the progressive neuronal degeneration common to chronic pathologies, traumatic injuries, and aging processes in the CNS. The proinflammatory cytokine tumor necrosis factor-alpha (TNF-α) orchestrates cellular stress by stimulating the production and release of neurotoxic mediators including reactive oxygen species (ROS). NADPH oxidases (NOX), ubiquitously expressed in all cells, have recently emerged as pivotal ROS sources in aging and disease. We demonstrated the presence of potent NOX inhibitors in wild Alaska bog blueberries partitioning discretely into a nonpolar fraction with minimal antioxidant capacity and largely devoid of polyphenols. Incubation of SH-SY5Y human neuroblastoma cells with nonpolar blueberry fractions obstructed the coalescing of lipid rafts into large domains disrupting NOX assembly therein and abolishing ROS production characteristic for TNF-α exposure. These findings illuminate nutrition-derived lipid raft modulation as a novel therapeutic approach to blunt inflammatory and oxidative stress in the aging or diseased CNS. PMID:22530077

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

    USGS Publications Warehouse

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

    2009-01-01

    reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (18O/37Cl, 18O/15N) derived from homogeneous laboratory systems (e.g. pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion. ?? CSIRO 2009.

  8. Limited Boron Isotopic Variation Between Caldera-Forming and Post-Caldera Low-δ 18O Rhyolites from Yellowstone Caldera

    NASA Astrophysics Data System (ADS)

    Schmitt, A. K.

    2004-12-01

    Post-collapse rhyolites from within Yellowstone caldera show prominent excursions to δ 18O values (VSMOW) as low as ˜0 ‰ that provide strong evidence for significant non-lithospheric oxygen input into magmas, presumably via infiltration of meteoric waters (1). Very little, however, is known about the behavior of other stable isotope systems, such as boron, in low δ 18O rhyolites and their potential for unraveling the mechanisms by which brines and magmas interact. Ion microprobe measurements of quartz-hosted melt inclusions from two low-δ 18O rhyolite flows (South Biscuit Basin SBB and Middle Biscuit Basin MBB) yielded average δ 11B values (NIST SRM 951) of -1.5 and -0.9 ‰ , respectively. These values overlap within error with those for glassy obsidian matrix from SBB and MBB. Melt inclusions from two caldera-forming tuff eruptions (Lava Creek Tuff LCT and Huckleberry Ridge Tuff HRT), known to have 'normal' oxygen isotopic compositions, also yielded indistinguishable δ 11B values of -1.8 ‰ . Recent petrologic studies (1) suggested that bulk remelting of hydrothermally altered volcanic rocks, specifically HRT, in the down-dropped roof of the magma chamber produced the low-δ 18O magmas. The lack of strong boron isotopic variations (within ±2‰ ) between 'normal' and low-δ 18O rhyolites, however, contrasts with published evidence for strong 11B-depletion in hydrothermal altered rhyolite encountered in Yellowstone drill-wells (δ 11B = -9.7 ‰ ; 2). This implies that boron isotopic fractionation due to interaction with hydrothermal fluids was either absent in the source region of the SBB and MBB magmas, or became masked due to subsequent processes. From preliminary mixing calculations it is concluded that assimilation of 11B- and 18O-depleted rocks by fresh rhyolite recharge could be a compositionally and thermally viable alterative to bulk remelting. (1) I. N. Bindeman and J. W. Valley (2001) J Petrol 42, 1491-1517; (2) M. R. Palmer and N. C. Sturchio

  9. Stable Oxygen (δ 18O) and Carbon (δ 13C) Isotopes in the Skeleton of Bleached and Recovering Corals From Hawaii

    NASA Astrophysics Data System (ADS)

    Rodrigues, L. J.; Grottoli, A. G.

    2004-12-01

    Coral skeletal stable oxygen isotopes (δ 18O) reflect changes in seawater temperature and salinity, while stable carbon isotopes (δ 13C) reflect a combination of both metabolic (photosynthesis and feeding) and kinetic fractionation. Together, the two isotopic signatures may be used as a proxy for past bleaching events. During bleaching, increased seawater temperatures often contribute to a decline in zooxanthellae and/or chlorophyll concentrations, resulting in a decrease in photosynthesis. We experimentally investigated the effect of bleaching and subsequent recovery on the δ 13C and δ 18O values of coral skeleton. Fragments from two coral species (Montipora capitata and Porites compressa) from Kaneohe Bay, Hawaii were bleached in outdoor tanks by raising the seawater temperature to 30° C. Additional fragments from the same parent colonies were maintained at ambient seawater temperatures (27° C) in separate tanks as controls. After one month in the tanks, a subset of the fragments was frozen and all remaining fragments were placed back on the reef to recover. All coral fragments were analyzed for their skeletal δ 13C and δ 18O compositions at five time intervals: before, immediately after, 1.5, 4, and 8 months after bleaching. In addition, rates of photosynthesis, calcification, and heterotrophy were also measured. Immediately after bleaching, δ 18O decreased in bleached M. capitata relative to controls, reflecting their exposure to increased seawater temperatures. During recovery, δ 18O values in the treatment M. capitata were not different from the controls. In P. compressa, δ 18O did not significantly differ in bleached and control corals at any time during the experiment. Immediately after bleaching, δ 13C decreased in the bleached fragments of both species relative to controls reflecting decreased photosynthetic rates. However, during recovery δ 13C in both species was greater in bleached than control fragments despite photosynthesis remaining

  10. A high-resolution Sr/Ca and [delta][sup 18]O coral record from the Great Barrier Reef, Australia, and the 1982-1983 El Nino

    SciTech Connect

    McCulloch, M.T.; Gagan, M.K.; Mortimer, G.E.; Chivas, A.R. ); Isdale, P.J. )

    1994-06-01

    A high-resolution (near weekly) Sr/Ca and oxygen isotopic record is presented for a coral from the Pandora Reef in the Great Barrier Reef (GBR) of Australia during the period of 1978 to 1984. The records are well correlated except for periods of high rainfall when river runoff has significantly modified the [delta][sup 18]O value of seawater. Using the Sr/Ca temperature calibration of De Villiers et al., the Sr/Ca records exhibit seasonally controlled cyclical SST (sea surface temperature) variations of from [approximately] 21 to [approximately] 28[degrees]C. During the very strong El Nino of 1982-1983, the Sr/CA systematics indicate a sharp drop in the winter SST to [approximately] 18.5[degrees]C. This represents a temperature anomaly of -3[degrees]C which is approximately twice that given by the [delta][sup 18]O variations, suggesting an [approximately] x2 amplification of the anomaly by the Sr/Ca system, possibly due to the increasing dominance of inorganically controlled aragonite-seawater fractionation. The oxygen isotope systematics show the combined effects of both temperature and changing seawater [delta][sup 18]O values, the latter reflecting the influx of [sup 18]O-depleted runoff during periods of high rainfall. Due to the extremely low ([approximately] 10[sup [minus]3]) Sr and Ca contents of river runoff relative to seawater, it is possible to use the Sr/Ca thermometer to calculate temperatures independent of major floods and hence deconvolve the combined effects in the oxygen isotopic record of variable temperature and the [delta][sup 18]O value of seawater. Using this approach it is possible to quantitatively reproduce the volume of runoff from the Burdekin River during the periods of major flooding that occurred in early 1979 and 1981. The results of this study demonstrate that the combined use of high-resolution Sr/Ca and [delta][sup 18]O systematics in scleractinian corals is a powerful tool for providing quantitative constraints on past climate.

  11. In vivo studies on the binding of heparin and its fractions with platelet factor 4

    SciTech Connect

    Walz, D.A.; Hung, G.L.

    1985-01-01

    PF4 has a half-life in plasma of less than 3 minutes, and its rapid clearance appears to be a function of binding to the vascular endothelium. Once bound to the endothelium, PF4 can be released by heparin in a time-dependent manner; recovery is greater the sooner heparin is administered following PF4 infusion. This heparin-induced release of PF4 can be abolished if the heparin is first complexed with hexadimethrine bromide. Likewise, this heparin-induced release of PF4 is dependent upon the type of heparin used; low molecular weight heparin fractions and fragments do not cause the PF4 rebound seen with intact heparin. Thus, it would appear that low molecular weight forms of heparin are advantageous in that their in vivo administration would not be mediated by such platelet modulators as PF4.

  12. 18O/16O in CO2 evolved from goethite during some unusually rapid solid state α-FeOOH to α-Fe2O3 phase transitions: Test of an exchange model for possible use in oxygen isotope analyses of goethite

    NASA Astrophysics Data System (ADS)

    Yapp, Crayton J.

    2015-12-01

    The initial ∼60% of an isothermal vacuum dehydration of goethite can commonly be approximated by first order kinetics. Also, natural goethites contain small amounts of an Fe(CO3)OH component in apparent solid solution. The 18O/16O of CO2 evolved from the Fe(CO3)OH during isothermal vacuum dehydrations is related to the 18O/16O of the goethite by an apparent fractionation factor (αapp) that is, in turn, correlated with a first order rate constant, |m|. A kinetic exchange model predicts that αapp should decrease as |m| increases for a range of |m| that corresponds to relatively slow rates of dehydration. This pattern has been observed in published results. In contrast, for rapid rates of dehydration, αapp is predicted to increase with increasing |m|. Isothermal vacuum dehydrations of two natural goethites had unusually large values of |m| and provided serendipitous tests of this rapid-rate prediction. For these experiments, the measured values of αapp were consistent with patterns of variation predicted by the model. This allowed an estimate of the activation energy (E2) of a model parameter, K2, which is the rate constant for oxygen isotope exchange between CO2 and H2O during the solid-state goethite to hematite phase transition. The estimated value of E2 is only ∼9 kJ/mol. Heterogeneous catalysis tends to decrease the activation energies of gas reactions. Consequently, the inferred value of E2 suggests that goethite and/or hematite catalyze oxygen isotope exchange between CO2 and H2O during the solid-state phase change. Yield, δ13C, and δ18O values are routinely measured for increments of CO2 evolved from the Fe(CO3)OH component during isothermal vacuum dehydration of goethite. Model-predicted values of αapp can be combined with plateau δ18O values of the evolved CO2 to estimate the δ18O of the goethite with a less than optimal, but potentially useful, precision of about ±0.8‰. Therefore, a single analytical procedure (incremental dehydration

  13. Isotopic Study ( 18O, 2H) of the Ground Water in the Bekaa's plain (Lebanon)

    NASA Astrophysics Data System (ADS)

    Awad, S.

    The stable isotopes of the water molecule (18O, 2H) give informations about the paleoclimate existing during the water seepage and about the recharge conditions of the groundwater. The effects of the Orography, the Continentality, and the origin of the masses of air have an effect on the isotopic abundance of the precipitations (rain + snow) in Lebanon. An evaporation of the recharge water exists in the atmosphere, with a mixing between the deep water and the shallow ones. The sea water has an isotopic abundance at 0 ‰ (SMOW: Standard Mean Ocean Water) for δ2H et δ18O, the Mediterranean Sea is at the origin of the rains which fall on the studied area, and which do not keep the isotopic abundances of the sea because the high mountains that they cross during their movement. This high altitude causes an impoverishment of the water of the rain on heavy isotope (18O).

  14. Minimization of sample requirement for delta18O in benzoic acid.

    PubMed

    Hagopian, William M; Jahren, A Hope

    2010-09-15

    The measurement of the oxygen stable isotope content in organic compounds has applications in many fields, ranging from paleoclimate reconstruction to forensics. Conventional High-Temperature Conversion (HTC) techniques require >20 microg of O for a single delta(18)O measurement. Here we describe a system that converts the CO produced by HTC into CO(2) via reduction within a Ni-furnace. This CO(2) is then concentrated cryogenically, and 'focused' into the isotope ratio mass spectrometry (IRMS) source using a low-flow He carrier gas (6-8 mL/min). We report analyses of benzoic acid (C(7)H(6)O(2)) reference materials that yielded precise delta(18)O measurement down to 1.3 microg of O, suggesting that our system could be used to decrease sample requirement for delta(18)O by more than an order of magnitude. PMID:20740528

  15. Low-temperature synthesis and electrical transport properties of W 18O 49 nanowires

    NASA Astrophysics Data System (ADS)

    Shi, Songlin; Xue, Xinyu; Feng, Ping; Liu, Yonggang; Zhao, Heng; Wang, Taihong

    2008-01-01

    W 18O 49 nanowires are simply synthesized by the reaction between water vapor and tungsten powders in tube furnace at a low temperature of 600 °C. The nanowires have diameters of 20-50 nm, lengths several micrometers. XRD, TEM and SAED results show that the nanowires are of single crystalline monoclinic W 18O 49 structures with the growth direction [0 1 0]. The growth mechanism is analyzed. We investigate the temperature dependence electrical transport properties of individual W 18O 49 nanowires. The conductivity is 2.58 Ω -1 cm -1 at 290 K and 42.35 Ω -1 cm -1 at 500 K, respectively. And the electron activation energy is calculated to be about 0.26 eV.

  16. Latitudinal gradients in greenhouse seawater δ(18) O: evidence from Eocene sirenian tooth enamel.

    PubMed

    Clementz, Mark T; Sewall, Jacob O

    2011-04-22

    The Eocene greenhouse climate state has been linked to a more vigorous hydrologic cycle at mid- and high latitudes; similar information on precipitation levels at low latitudes is, however, limited. Oxygen isotopic fluxes track moisture fluxes and, thus, the δ(18)O values of ocean surface waters can provide insight into hydrologic cycle changes. The offset between tropical δ(18)O values from sampled Eocene sirenian tooth enamel and modern surface waters is greater than the expected 1.0 per mil increase due to increased continental ice volume. This increased offset could result from suppression of surface-water δ(18)O values by a tropical, annual moisture balance substantially wetter than that of today. Results from an atmospheric general circulation model support this interpretation and suggest that Eocene low latitudes were extremely wet. PMID:21512030

  17. Method for determination of .sup.18 O/.sup.16 O and .sup.2 H/.sup.1 H ratios and .sup.3 H (tritium) concentrations of xylem waters and subsurface waters using time series sampling

    SciTech Connect

    Smith, Brian; Menchaca, Leticia

    1999-01-01

    A method for determination of .sup.18 O/.sup.16 O and .sup.2 H/.sup.1 H ratios and .sup.3 H concentrations of xylem and subsurface waters using time series sampling, insulating sampling chambers, and combined .sup.18 O/.sup.16 O, .sup.2 H/.sup.1 H and .sup.3 H concentration data on transpired water. The method involves collecting water samples transpired from living plants and correcting the measured isotopic compositions of oxygen (.sup.18 O/.sup.16 O) and hydrogen (.sup.2 H/.sup.1 H and/or .sup.3 H concentrations) to account for evaporative isotopic fractionation in the leafy material of the plant.

  18. Method for determination of {sup 18}O/{sup 16}O and {sup 2}H/{sup 1}H ratios and {sup 3}H (tritium) concentrations of xylem waters and subsurface waters using time-series sampling

    SciTech Connect

    1999-11-09

    This application describes a method for the determination of {sup 18}O/{sup 16}O and {sup 2}H/{sup 1}H ratios and {sup 3}H concentrations of xylem and subsurface waters using time-series sampling, insulating sampling chambers, and combined {sup 18}O/{sup 16}O, {sup 2}H/{sup 1}H and {sup 3}H concentration data on transpired water. The method involves collecting water samples transpired from living plants and correcting the measured isotopic compositions of oxygen ({sup 18}O/{sup 16}O) and hydrogen ({sup 2}H/{sup 1}H and/or {sup 3}H concentrations) to account for evaporative isotopic fractionation in the leafy material of the plant.

  19. French summer droughts since 1326 AD: a reconstruction based on tree ring cellulose δ18O

    NASA Astrophysics Data System (ADS)

    Labuhn, I.; Daux, V.; Girardclos, O.; Stievenard, M.; Pierre, M.; Masson-Delmotte, V.

    2015-11-01

    The reconstruction of droughts is essential for the understanding of past drought dynamics, and can help evaluate future drought scenarios in a changing climate. This article presents a reconstruction of summer droughts in France based on annually resolved, absolutely dated chronologies of oxygen isotope ratios (δ18O) in tree ring cellulose from Quercus spp. Samples were taken from living trees and timber wood from historic buildings at two sites: Fontainebleau (48° 23' N, 2° 40' E; 1326-2000 AD) and Angoulême (45° 44' N, 0° 18' E; 1360-2004 AD). Cellulose δ18O from these sites proved to be a good proxy of summer climate, as the trees were sensitive to temperature and moisture availability. However, offsets in average δ18O values between tree cohorts necessitated a correction before joining them to the final chronologies. Using the corrected δ18O chronologies, we developed models based on linear regression to reconstruct drought, expressed by the standardized precipitation evapotranspiration index (SPEI). The significant correlations between the SPEI and cellulose δ18O (r ≈ -0.70), as well as the verification of the models by independent data support the validity of these reconstructions. At both sites, recent decades are characterized by increasing drought. Fontainebleau displays dominantly wetter conditions during earlier centuries, whereas the current drought intensity is not unprecedented in the Angoulême record. While the δ18O chronologies at the two studied sites are highly correlated during the 19th and 20th century, there is a significant decrease in the correlation coefficient between 1550 and 1800 AD, which indicates either a weaker climate sensitivity of the tree ring proxies during this period, or a more heterogeneous climate in the north and the south of France. Future studies of tree ring isotope networks might reveal if the seasonality and spatial patterns of past droughts can explain this decoupling.

  20. δ 18O of ethanol in wine and spirits for authentication purposes.

    PubMed

    Perini, Matteo; Camin, Federica

    2013-06-01

    Since 1986 the European Union has established official isotopic analysis methods for detecting the illegal addition of sugar and water to wine and to enable geographical traceability. In this paper we investigate the possibility of using analysis of the 18O/16O stable isotope ratio (expressed as δ 18O) of ethanol to improve detection of the watering of wine and to determine the origin of ethanol. Sixty-nine authentic wine samples from all over Italy, 59 spirits from fruit and cereals, 5 chemically synthesized ethanols, one concentrated and rectified must, one beet and one cane sugar, one fresh must, and 6 waters with increasing δ 18O values were considered. Ethanol was recovered by distillation, using a Cadiot spinning band column, following the official OIV methods. The residual water was trapped by storing the distillate for at least 24 h on a molecular sieve. The 18O/16O ratio was measured using a pyrolyser interfaced with an isotope ratio mass spectrometer. The δ (-18)O of ethanol is significantly related to the δ 18O of the fermentation water and can be considered as a reliable internal reference. The values ranged from +24‰ to +36‰ in wine (years 2008 to 2012), +10‰ to +26‰ in fruit and cereal distillates, and from -2‰ to +12‰ in synthetic ethanol. The method was shown to be effective in improving detection of the watering of wine and determining the origin of ethanol (from grapes, other fruit, or synthesis), but not in detecting the addition of cane or beet sugar to wine. PMID:23772705

  1. Homogeneous /sup 18/O enrichment of the Marcy Anorthosite Massif, Adirondack Mountains, New York

    SciTech Connect

    Morrison, J.; Valley, J.W.

    1985-01-01

    The Marcy Anorthosite Massif in the Adirondack Mountains, New York, is a composite intrusion that was metamorphosed to granulite facies at approx. 1.1 Ga. The massif is dominantly anorthosite but ranges from anorthosite (1-10% mafics) to oxide-rich pyroxenite layers (up to 98% mafics). In the St Regis Quad (SRQ) systematic variations in the percentage of mafics (POM) roughly parallel the foliation and increase toward the contacts (Davis, 1971). In 47 SRQ samples studied the POM varies from 2-25%; garnet ranges from 0-11%, pyroxene from <1-16% and oxides from <1-8%. Percent phenocrysts varies between 1-80. The Port Kent-Westport Unit (PKW) and an associated hybrid unit show significantly greater textural variability. The POM Varies from 1-50%; garnet ranges from 0-18%, pyroxene from 0-15%, oxides from 0-3% and phenocrysts vary from 0-80%. A total of 28 unaltered plagioclase phenocrysts have been analyzed for delta/sup 18/O: in 13 SRQ samples delta/sup 18/O = 9.0-9.8 (x=9.4. sigma=0.2) and in 15 samples from the PKW and hybrid units values of delta/sup 18/O=8.5-10.5 (x=9.5.sigma0.5). No correlations exist between the modal parameters and delta/sup 18/O. The results from SRQ demonstrate an extreme homogeneity suggesting for the first time a pristine magmatic character which is supported by the virtual absence of metasedimentary inclusions. This contrasts with PKW where inclusions are common and delta/sup 18/O values are more heterogeneous. Further analyses will evaluate the possibility of an anomalous source region as a cause of the /sup 18/O enrichment in the anorthosite.

  2. Direct evidence for the origin of low-18O silicic magmas: quenched samples of a magma chamber's partially-fused granitoid walls, Crater Lake, Oregon

    USGS Publications Warehouse

    Bacon, C.R.; Adami, L.H.; Lanphere, M.A.

    1989-01-01

    Partially fused granitoid blocks were ejected in the climactic eruption of Mount Mazama, which was accompanied by collapse of Crater Lake caldera. Quartz, plagioclase, and glass in the granitoids have much lower ??18O values (-3.4 to +4.9???) than any fresh lavas of Mount Mazama and the surrounding region (+5.8 to +7.0???). Oxygen isotope fractionation between phases in granitoids is consistent with equilibrium at T ??? 900??C following subsolidus exchange with hydrothermal fluids of meteoric origin. Assimilation of ??? 10-20% of material similar to these granitoids can account for the O and Sr isotopic compositions of lavas and juvenile pyroclasts derived from the climactic magma chamber, many of which have ??18O values ??? 0.5??? or more lower than comparable lavas of Mount Mazama. The O isotope data provide the only clear evidence for such assimilation because the mineralogy and chemical and radiogenic isotopic compositions of the granitoids (dominantly granodiorite) are similar to those of erupted juvenile magmas. The granitoid blocks from Crater Lake serve as direct evidence for the origin of 18O depletion in large, shallow silicic magma bodies. ?? 1989.

  3. Characterization of the water chemistry, sediment (13)C and (18)O compositions of Kolleru Lake-a Ramsar wetland in Andhra Pradesh, India.

    PubMed

    Das Sharma, Subrata; Sujatha, D

    2016-07-01

    The chemistry of surface water sampled at different locations of the Kolleru Lake in Andhra Pradesh (India) show heterogeneous variability. The concentrations of dissolved sodium and chloride ions, total dissolved solids (TDS) together with high conductivity documented in water samples are indicative of mixing of saline seawater. This interpretation is further corroborated by enriched δ(18)O compositions of the carbonate fraction of the surface sediments collected at the same locations (as that of water) of the lake, and fairly good positive correlations of δ(18)O -Na(+) and δ(18)O-TDS. The saline water intrusion into the lake appears to be resulted due to its near stagnant to dry condition with reduced inflow and outflow. Such dry condition facilitated seawater intrusion into the lake due to several reasons: (i) proximity of lake to the sea (~35 km), (ii) overexploitation of fresh groundwater for agriculture as well as livestock farming, and (iii) incursion of tidal seawater (high sea waves) through Upputeru River, which is directly linked to the sea. We also document highly heterogeneous distribution of certain potentially toxic metal ions like chromium, copper, manganese, and zinc in the lake waters. Indiscriminate disposal of domestic and industrial effluents around the lake appears to be responsible for the presence of potentially toxic heavy metals. Based on these results, we finally suggest some measures for environmental rehabilitation of the lake and its surroundings. PMID:27312252

  4. An estimation of the 18O / 16O ratio of UT/LMS ozone based on artefact CO in air sampled during CARIBIC flights

    NASA Astrophysics Data System (ADS)

    Gromov, S.; Brenninkmeijer, C. A. M.

    2015-02-01

    An issue of O3-driven artefact production of O3 in the upper troposphere/lowermost stratosphere (UT/LMS) air analysed in the CARIBIC-1 project is being discussed. By confronting the CO mixing and isotope ratios obtained from different analytical instrumentation, we (i) reject natural/artificial sampling and mixing effects as possible culprits of the problem, (ii) ascertain the chemical nature and quantify the strength of the contamination, and (iii) demonstrate successful application of the isotope mass-balance calculations for inferring the isotope composition of the contamination source. The δ18O values of the latter indicate that the oxygen is very likely being inherited from O3. The δ13C values hint at reactions of trace amounts of organics with stratospheric O3 that could have yielded the artificial CO. While the exact contamination mechanism is not known, it is clear that the issue pertains only to the earlier (first) phase of the CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) project. Finally, estimated UT/LMS ozone δ18O values are lower than those observed in the stratosphere within the same temperature range, suggesting that higher pressures (240-270 hPa) imply lower isotope fractionation controlling the local δ18O(O3) value.

  5. Recording of El Niño in ice core δ18O records from Nevado Huascarán, Peru

    NASA Astrophysics Data System (ADS)

    Henderson, K. A.; Thompson, L. G.; Lin, P.-N.

    1999-01-01

    The 68-year monthly resolved time series of δ18O from ice cores retrieved from the glaciated col of Nevado Huascarán, Peru (9°S, 77°W, 6050 m) reflects climate variability over Amazonia and the western tropical Atlantic. Over the 25-year period (1968-1993) of midtroposphere observations, the interannual variations in Huascarán δ18O relate closely with the zonal wind variations over tropical South America at the 500 hPa level. Additionally, there is some evidence that the spatial distribution of temperature anomalies in the western tropical Atlantic has influence on the 500 hPa circulation and hence the isotopic fractionation of moisture advected across Amazonia. During El Niño warming, the moisture convergence axis over the Atlantic Ocean is commonly diverted northward, leading to unusual warm and dry conditions over northeast Brazil, and 18O-enriched snowfall at Huascarán. This enrichment phase is enhanced when the peak Pacific warming occurs during the first half of the calendar year, coincident with the wet season over Amazonia. Approximately 12 months later, the El Niño demise is affiliated with a reprisal of strong trade wind circulation, and the resultant cool, pluvial environment over Amazonia triggers a reversal to strongly depleted isotope anomalies.

  6. Reaction-dependent spin population and evidence of breakup in {sup 18}O

    SciTech Connect

    Hojman, D.; Pacheco, A.J.; Testoni, J.E.; Davidson, J.; Davidson, M.; Cardona, M.A.; Fernandez-Niello, J.O.; Kreiner, A.J.; Arazi, A.; Capurro, O.A.; Marti, G.V.; Bazzacco, D.; Lenzi, S.M.; Lunardi, S.; Alvarez, C. Rossi; Ur, C.; Burlon, A.; Debray, M.E.; De Angelis, G.; De Poli, M.

    2006-04-15

    Angular distributions and angular correlations have been measured for the emission of one and two {alpha}-particles in the {sup 18}O+{sup 207,208}Pb,{sup 209}Bi reactions at several beam energies above the Coulomb barrier. The results rule out fusion evaporation as the main reaction mechanism for the channels involving {alpha}-particle emission and support the interpretation of the breakup of the {sup 18}O projectiles into at least {sup 14}C+{alpha} and {sup 10}Be+{sup 8}Be before fusion.

  7. Excitation Function for the 74Se(18O,p3n) Reaction

    SciTech Connect

    Gates, Jacklyn; Dragojevic, Irena; Dvorak, Jan; Ellison, Paul; Gregorich, Kenneth; Stavsetra, Liv; Nitsche, Heino

    2009-02-02

    The 74Se(18O,p3n)88gNb excitation function was measured and a maximum cross section of 495+-5 mb was observed at and 18O energy of 74.0 MeV. Experimental cross sections were compared to theoretical calculations using the computer code ALICE-91 and the values were found to be in good agreement. The half life of 88gNb was determined to be around 14.56+-0.11 min.

  8. ({sup 18}O,{sup 18}Ne) double charge-exchange with MAGNEX

    SciTech Connect

    Bondí, M.; Cappuzzello, F.; Nicolosi, D.; Tropea, S.; Agodi, C.; Carbone, D.; Cavallaro, M.; Cunsolo, A.; De Napoli, M.; Foti, A.

    2014-05-09

    An experimental study concerning Double Gamow-Teller (DGT) modes in ({sup 18}O,{sup 18}Ne) Double Charge-Exchange reactions has been very recently performed at INFN-LNS laboratory in Catania. The experiment was performed using a {sup 40}Ca solid target and a {sup 18}O Cyclotron beam at 270 MeV incident energy. Charged ejectiles produced in the reaction were momentum analyzed and identified by MAGNEX spectrometer at very forward angles. Preliminary results are presented in the present paper.

  9. Coral δ18O stratigraphy from the West Pacific Warm Pool, Palau

    NASA Astrophysics Data System (ADS)

    Osborne, M. C.; Dunbar, R. B.; Mucciarone, D. A.; Sanchez-Cabeza, J.

    2009-12-01

    High-resolution paleoenvironmental records obtained from coral cores are powerful tools for assessing pre-instrumental ENSO behavior on interannual to centennial time scales, but the scarcity of such records limits the robust assessment of natural ENSO variability prior to the start of widespread instrumental monitoring. Here we present new δ18O stratigraphies from four cores sampled from two Porites lutea corals collected in the Republic of Palau during December 2008. Palau lies in the West Pacific Warm Pool (WPWP), a region characterized by warm annual sea surface temperatures (SSTs) and intense atmospheric convection. Variations in the expanse of the WPWP are tightly linked to ENSO dynamics. The δ18O composition of coral skeletal material is determined by the δ18O of seawater as well as SST, and the strong positive correlation between SSTs and precipitation in the WPWP region generally exerts an additive effect on coral δ18O. During strong El Niño events, positive δ18O anomalies in coral aragonite should result from increased salinity and decreased SSTs in Palau, whereas negative δ18O anomalies are expected during La Niña conditions. Overall the δ18O variability in our stratigraphies is consistent between all four cores, though we note small discrepancies attributed to uncertainties in cross-correlation, local environmental variation, and potential vital effects. We compare our analyses with available instrumental data and argue that seasonal climate variations in Palau are evident in our coral stratigraphies. Based on this assertion, these data can be used for age model constructions as well as for climate analyses in the time and frequency domains. Our estimates of coral growth rates are ~1.5 cm/yr, yielding ~70 years of record from coral U-1/U-2 and ~25 years from coral U-3/U-4. With continued analyses we expect to provide coral-based climate time series of ~180 yrs in length from core U-2. We also provide evidence that periods of strong ENSO

  10. Enhancing the Accuracy of Carbonate δ18O and δ13C Measurements by SIMS

    NASA Astrophysics Data System (ADS)

    Orland, I. J.; Kozdon, R.; Linzmeier, B.; Wycech, J.; Sliwinski, M.; Kitajima, K.; Kita, N.; Valley, J. W.

    2015-12-01

    The precision and accuracy of carbonate δ18O & δ13C analysis by multicollector SIMS is well established if standards match samples in structure and major/minor element chemistry. However, low-T- and bio-carbonates used to construct paleoclimate archives can include complex internal structures and some samples analyzed at WiscSIMS (and other SIMS labs) have a consistent, sample-dependent offset between average SIMS δ18O measurements and bulk δ18O analyses by phosphoric-acid digestion. The offset is typically <1‰, but recent work has discovered samples where the offset is greater — up to 1.8‰ (average SIMS δ18O values < corresponding conventional measurements). Notably, δ13C offsets have not been observed even in samples with a δ18O offset. We conducted tests to characterize the δ18O offset in different low-T carbonate materials. Multiple potential causes were examined: perhaps the measured offset is real and conventional analyses include material that SIMS excludes (and vice versa); analytical errors and inter-lab (mis)calibration; depth-profiling effects; porosity; and the effects of variable minor element composition. One explanation implicates water and/or organic matter within carbonate that is ionized during SIMS analysis, but sometimes removed for bulk analysis. Two diagnostic tools help monitor such contaminants during SIMS analysis: 1) simultaneous measurement of [16O1H], and 2) secondary ion yield. Offsets of 0.3 to 1.8‰ in δ18O correlate to [16O1H] for 7 studies of Nautilus, foraminifera, pteropods and speleothems. Offsets were not observed in all foraminifera. For Nautilus, foraminifera, otoliths, and speleothems we also tested pre-treatment techniques (e.g. vacuum roasting, hydrogen peroxide), for which there is no agreed procedure in conventional bulk analyses. For SIMS analyses, pre-treatments had varied influence on the δ18O value, [16O1H], the concentration of "organic markers" like 12C14N and 31P, and mineralogy (of aragonite

  11. Determination of the δ15N and δ18O of nitrate in solids; RSIL lab code 2897

    USGS Publications Warehouse

    Coplen, Tyler B.; Qi, Haiping; Revesz, Kinga; Casciotti, Karen; Hannon, Janet E.

    2007-01-01

    The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2897 is to determine the δ15N and δ18O of nitrate (NO3-) in solids. The NO3- fraction of the nitrogen species is dissolved by water (called leaching) and can be analyzed by the bacterial method covered in RSIL lab code 2900. After leaching, the δ15N and δ18O of the dissolved NO3- is analyzed by conversion of the NO3- to nitrous oxide (N2O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of NO3- to N2O, which follows the pathway shown in equation 1: NO3- → NO2- → NO → 1/2 N2O (1) Because the bacteria Pseudomonas aureofaciens lack N2O reductive activity, the reaction stops at N2O, unlike the typical denitrification reaction that goes to N2. After several hours, the conversion is complete, and the N2O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO4)2), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N2O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge (m/z) of the N2O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N2O = 14N14N16O; m/z = 45 = N2O = 14N15N16O or 14N14N17O; m/z = 46 = N2O = 14N14N18O. The 17O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ15N values are reported.

  12. Review of Exculsive B to D(*,**)Lnu Decays: Branching Fractions, Form-Factors And |V(Cb|

    SciTech Connect

    Snyder, A.E.; /SLAC

    2007-04-02

    This paper reviews semileptonic decays of B-mesons to states containing charm mesons, i.e., D, D*, D** and possible non-resonant D{sup (*)}{eta}{pi} states as well. The paper covers measurement of branching fractions, form-factors and, most importantly, the magnitude of the CKM matrix element V{sub cb}. I will not attempt a comprehensive review, but will concentrate on reasonably fresh results and consider mostly exclusive measurements. I will also comment on the consistency of the results and what needs to be done to resolve the apparent conflicts.

  13. Seasonal Variations in δ18O of Inflowing River Water, Lake Water, Sediment Trap Material and Ostracod Shells of Lake Nam Co and its Catchment (Tibet, China) — a Proxy Calibration Study

    NASA Astrophysics Data System (ADS)

    Daut, G.; Wang, J.; Ju, J.; Plessen, B.; Fürstenberg, S.; Baade, J.; Frenzel, P.; Haberzettl, T.; Maeusbacher, R.; Zhu, L.

    2014-12-01

    δ18O is a very common proxy used in palaeoclimate studies all over the world, but for most parts of the world and especially the Tibetan Plateau modern studies that trace the pathway of this isotope from sink to source are lacking. In this study, financed by the BMBF (German Ministry of Science and Education, Project CADY), we present data that fill this gap. The study was performed in the terminal lake Nam Co, the biggest lake on the central Tibetan Plateau and its catchment. Water of the main tributaries to the lake, lake water at three different stations and from different water depths, bulk carbonate collected from different water depths with sediment traps and shells of living ostracods were collected for one year at lake Nam Co in approx. monthly intervals and analyzed for their δ18O values. The inflowing river waters mainly reflect the precipitation and show regional as well as seasonal variations depending on their location and on Monsoon or Westerly season but are in general on the global meteoric waterline. The lake water shows only minor vertical and spatial variations and is clearly off the meteoric waterline due to strong evaporation effects in this terminal lake. δ18O values of the bulk carbonate of sediment collected in sediment traps show only minor vertical and spatial variations during the year and the δ18O offset compared to the lake water is with around 1 ‰ quite small. Most probably this is attributed to chemical fractionation during formation of monohydrocalcite in the water column. In contrast δ18O values of ostracod shells are significant heavier than the lake water indicating isotopic fractionation (vital effect) during shell formation. In addition a seasonal variability is visible. The data of this proxy calibration study give now for the first time the opportunity to validate δ18O proxy data measured on core material from Lake Nam Co for their palaeoclimatic significance.

  14. δ18O and δ13C Values in Living and Holocene Brachiopods and the Relationship with Oceanographic Variability across Australia's Vast Southern Shelf

    NASA Astrophysics Data System (ADS)

    Dhillon, R.

    2015-12-01

    Carbon and oxygen isotopic compositions of brachiopods are commonly used to reconstruct secular changes in ocean chemistry through the Phanerozoic but few studies have focused on the variations that occur laterally and concurrently across a single vast depositional system. Previous studies have identified significant isotopic variability to occur within an individual stratigraphic layer and the scatter in values has been attributed to diagenesis, non-equilibrium fractionation effects, and variability in oceanography. In order to further investigate these hypotheses, this study evaluates the δ18O and δ13C values from 346 living and Holocene brachiopods collected from surficial sediments across the latitude-parallel southern Australian shelf, a lateral distance of ~3000 km. Modern oceanographic measurements were used to calculate the range in δ18O values of calcite precipitated in apparent equilibrium with ambient seawater. A total of 84% of δ18O values from brachiopod samples (n = 684) fall within the range of calculated equilibrium calcite and accurately record a combination of normal shelf water conditions, winter downwelling across the shelf, and local summer upwelling. Most δ18O outliers are attributed to seasonal upwelling (90 of 108 outliers) and imply that either upwelling occurred in an area that has not been well established as an upwelling zone, or it occurred in a known upwelling area but the intensity was greater than previously measured. The δ13C values of brachiopods increase with increasing depth, which is the opposite of what is reported elsewhere. This unusual δ13C trend is caused by deeper slope currents being sourced from surface water southwest of Tasmania, an area with relatively high δ13C of DIC. The δ13C values of living specimens are consistently lower by 0.5-1.0‰ than most dead specimens, which is attributed to the decrease in δ13C values in the carbon cycle due to combustion of isotopically light fossil fuels over the last 200

  15. Unveiling stomata 24/7: can we use carbonyl sulfide (COS) and oxygen isotopes (18O) to constrain estimates of nocturnal transpiration across different evolutionary plant forms?

    NASA Astrophysics Data System (ADS)

    Gimeno, Teresa E.; Ogee, Jerome; Bosc, Alexander; Genty, Bernard; Wohl, Steven; Wingate, Lisa

    2015-04-01

    Numerous studies have reported a continued flux of water through plants at night, suggesting that stomata are not fully closed. Growing evidence indicates that this nocturnal flux of transpiration might constitute an important fraction of total ecosystem water use in certain environments. However, because evaporative demand is usually low at night, nocturnal transpiration fluxes are generally an order of magnitude lower than rates measured during the day and perilously close to the measurement error of traditional gas-exchange porometers. Thus estimating rates of stomatal conductance in the dark (gnight) precisely poses a significant methodological challenge. As a result, we lack accurate field estimates of gnight and how it responds to different atmospheric drivers, indicating the need for a different measurement approach. In this presentation we propose a novel method to obtain detectable and robust estimates of gnight. We will demonstrate using mechanistic theory how independent tracers including the oxygen isotope composition of CO2 (δ18O) and carbonyl sulfide (COS) can be combined to obtain robust estimates of gnight. This is because COS and CO18O exchange within leaves are controlled by the light insensitive enzyme carbonic anhydrase. Thus, if plant stomata are open in the dark we will continue to observe COS and CO18O exchange. Using our theoretical model we will demonstrate that the exchange of these tracers can now be measured using advances in laser spectrometry techniques at a precision high enough to determine robust estimates of gnight. We will also present our novel experimental approach designed to measure simultaneously the exchange of CO18O and COS alongside the conventional technique that relies on measuring the total water flux from leaves in the dark. Using our theoretical approach we will additionally explore the feasibility of our proposed experimental design to detect variations in gnight during drought stress and across a variety of plant

  16. Digoxin in Heart Failure with a Reduced Ejection Fraction: A Risk Factor or a Risk Marker.

    PubMed

    Konstantinou, Dimitrios M; Karvounis, Haralambos; Giannakoulas, George

    2016-01-01

    Digoxin is one of the oldest compounds used in cardiovascular medicine. Nevertheless, its mechanism of action and most importantly its clinical utility have been the subject of an endless dispute. Positive inotropic and neurohormonal modulation properties are attributed to digoxin, and it was the mainstay of heart failure therapeutics for decades. However, since the institution of β-blockers and aldosterone antagonists as part of modern heart failure medical therapy, digoxin prescription rates have been in free fall. The fact that digoxin is still listed as a valid therapeutic option in both American and European heart failure guidelines has not altered clinicians' attitude towards the drug. Since the publication of original Digitalis Investigation Group trial data, a series of reports based predominately on observational studies and post hoc analyses have raised concerns about the clinical efficacy and long-term safety of digoxin. In the present review, we will attempt a critical appraisal of the available clinical evidence regarding the efficacy and safety of digoxin in heart failure patients with a reduced ejection fraction. The methodological issues, strengths, and limitations of individual studies will be highlighted. PMID:26959501

  17. Volumetric Properties of the Mixture Propenenitrile C3H3N + C8H18O Octan-1-ol (VMSD1211, LB4554_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Propenenitrile C3H3N + C8H18O Octan-1-ol (VMSD1211, LB4554_V)' providing data from direct low-pressure dilatometric measurement of molar excess volume at variable mole fraction and constant temperature.

  18. Behavior of isotope (18O/16O, 234U/238U) systems during the formation of uranium deposits of the "sandstone" type

    NASA Astrophysics Data System (ADS)

    Golubev, V. N.; Dubinina, E. O.; Chernyshev, I. V.; Ikonnikova, T. A.

    2016-01-01

    The uneven character of the distribution of 18O/16O and 234U/238U values was established in the vertical cross section of the productive sequence of the Dybryn uranium deposit (Vitim uranium-ore region, Buryatia). Both a deficiency and an excess of 234U in relation to the equilibrium 234U/238U ratio in the vertical sequence may provide evidence for the extremely low rate of the infiltration water flow. The behavior of oxygen isotope characteristics for different size fractions of terrigenous rocks provides evidence for active uranium redistribution and openness of the isotope system of this element during interaction of terrigenous-sedimentary rocks with infiltration waters.

  19. A first Late Glacial and Early Holocene coupled 18O and 2H biomarker isotope record from Gemuendener Maar, Germany

    NASA Astrophysics Data System (ADS)

    Zech, Michael; Bromm, Tobias; Hepp, Johannes; Benesch, Marianne; Sirocko, Frank; Glaser, Bruno; Zech, Roland

    2015-04-01

    During the last years, we developed a method for compound-specific d18O analyses of hemicellulose-derived sugars from plants, soils and sediment archives (Zech and Glaser, 2009; Zech et al., 2014). The coupling of respective d18O sugar results with d2H alkane results from paleosol and sediment climate archives proved to be a valuable innovative approach towards quantitative paleoclimate reconstruction (Hepp et al., 2014; Zech et al., 2013). Here we present a first coupled d18O sugar and d2H alkane biomarker record obtained for Late Glacial and Early Holocene sediments from the Gemuendener Maar in the Eifel, Germany. The d18O sugar biomarker record resembles the d18O ice core records of Greenland. The coupling with the d2H alkane biomarker results allows drawing further more quantitative paleocimate information in terms of (i) paleohumidity and (ii) d18O of paleoprecipitation.

  20. Equilibrium and kinetic Si isotope fractionation factors and their implications on Si isotope distributions in the Earth's surface environments

    NASA Astrophysics Data System (ADS)

    Tang, M.; Zhang, S.; Liu, Y.

    2015-12-01

    Several important equilibrium Si isotope fractionation factors among minerals, organic molecules and the H4SiO4 solution are complemented to facilitate explanation of distributions of Si isotope in the Earth's surface environments. The results reveal that heavy Si isotopes will be significantly enriched in the secondary silicate minerals in comparison to aqueous H4SiO4. On the contrary, quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution. The extent of 28Si-enrichment in hyper-coordinated organosilicon complexes is found the largest. In addition, the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer is calculated and the result supports previous statement that highly 28Si-enrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations. With equilibrium Si isotope fractionation factors provided here, Si isotope distributions in many surface systems of the Earth can be explained. For example, the change of bulk soil δ30Si can be predicted as a concave pattern with respect to weathering degree, with the minimum value where allophane completely dissolves and the total amount of sesqui-oxides and poorly crystalline minerals reaches its maximum. When well-crystallized clays start to precipitate from pore solutions under equilibrium conditions, the bulk soil δ30Si will increase again and reach a constant value. Similarly, the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain δ30Si variations in the ground water profile. Equilibrium Si isotope fractionations among quadra-coordinated organosilicon complexes and the H4SiO4 solution may also shed the light on the Si isotope distributions in Si-accumulating plants.

  1. Aquatic sediments pollution estimate using the metal fractionation, secondary phase enrichment factor calculation, and used statistical methods.

    PubMed

    Sakan, Sanja; Popović, Aleksandar; Anđelković, Ivan; Đorđević, Dragana

    2016-06-01

    The sequential extraction procedure of the European Community Bureau of Reference (BCR) was applied for the fractionation of Cd, Cr, Cu, Ni, Pb, Zn, Fe, Mn, and V in the Serbian river sediments. The aim of this paper was to describe a new approach in detection of anthropogenic elements in sediments, related to the Serbian river courses in order to assess their metal contamination. For sediment pollution evaluation, the risk assessment code (RAC) and the secondary phase enrichment factor (KSPEF) were used. Metal fractionation showed more easily mobilized forms predominant for copper, zinc, cadmium, manganese, and lead, which can be one of the indicators for anthropogenic source input. Chromium, nickel, iron, and vanadium found in the residual fraction indicate these metals may be an indicator for natural sources input. Based on RAC classification, results of sediments show no risk (Cr and V), low risk (Ni, Pb, and Fe), medium risk (Cu), high risk (Cd and Zn), and very high risk (Mn). The mean values of KSPEF were Cd > Cu > Zn > Ni > Mn > Pb > Fe > Cr > V, decreasing scale of no to moderately severe enrichment. The sediments were found to be contaminated by heavy metals to various extents, mostly Cd, Cu, and Zn. Research has shown the importance of KSPEF in quantifying degree of metal enrichment in sediments using results of sequential extraction. With the application of this factor, which is not frequently used in the scientific literature, the results obtained with sequential extraction can be used not only for assessment of mobility but also to quantify the metal pollution. PMID:26385383

  2. Seasonal variations of water uptake by Achnatherum splendens in Lake Qinghai watershed, based on δD and δ18O

    NASA Astrophysics Data System (ADS)

    Huawu, W.

    2014-12-01

    Water availability is a key ecological factor for plant growth and distribution in arid and semi-arid region. To reveal the characteristics of water uptake patterns by Achnatherum splendens and how it response to changes of water conditions in Lake Qinghai watershed, we analyzed isotopic concentrations (δD and δ18O) of plant stem water and soil water, groundwater and precipitation under the natural and drought treatment habitats. Water uptake by A.splendens was analyzed by direct comparison and multi-source mixing model calculating the plant-use proportions from diverse soil depths. The results showed that large fluctuations were found in the soil moisture and the isotopic contents of soil water in the surface soil layers, directly influenced by precipitation and evaporation. The slope and intercept of evaporative soil water line was evidently smaller than local meteoric water line indicating that the isotopic contents from soil water experienced stronger evaporation fractionation processes; The isotopic concentrations of stem were scattered along the evaporative soil water line exhibiting that the possible water sources extracted from soil water. Water uptake by A.splendens mainly absorbed surface soil water ( 45.1% from 0-10cm in June) at the early growth stage. Large precipitation events significantly impacted the whole soil water content and isotopic contents and resulted in the differences of plant-use proportions by A.splendens were minimal during August and September, which revealed that the roots of A.splendens extracted various depth of soil water when soil availability water was high. Under the drought treatment conditions, A.splendens largely used the surface soil water (0-30cm) in the early July. The absorbed depth transmitted to deep soil layers while the surface soil moisture decreased. However, the acquired depth by A.splendens again shifted from deep to surface soil layers when surface soil moisture sharply increased after the irrigation.

  3. Devils Hole, Nevada, δ18O record extended to the mid-Holocene

    USGS Publications Warehouse

    Winograd, Isaac J.; Landwehr, Jurate M.; Coplen, Tyler B.; Sharp, Warren D.; Riggs, Alan C.; Ludwig, Kenneth R.; Kolesar, Peter T.

    2006-01-01

    The mid-to-late Pleistocene Devils Hole δ18O record has been extended from 60,000 to 4500 yr ago. The new δ18O time series, in conjunction with the one previously published, is shown to be a proxy of Pacific Ocean sea surface temperature (SST) off the coast of California. During marine oxygen isotope stages (MIS) 2 and 6, the Devil Hole and SST time series exhibit a steady warming that began 5000 to > 10,000 yr prior to the last and penultimate deglaciations. Several possible proximate causes for this early warming are evaluated. The magnitude of the peak δ18O or SST during the last interglacial (LIG) is significantly greater (1 per mill and 2 to 3°C, respectively) than the peak value of these parameters for the Holocene; in contrast, benthic δ18O records of ice volume show only a few tenths per mill difference in the peak value for these interglacials. Statistical analysis provides an estimate of the large shared information (variation) between the Devils Hole and Eastern Pacific SST time series from ∼ 41 to ∼ 2°N and enforces the concept of a common forcing among all of these records. The extended Devils Hole record adds to evidence of the importance of uplands bordering the eastern Pacific as a source of archives for reconstructing Pacific climate variability.

  4. 18O and 226Ra in the Minjiang River estuary, China and their hydrological implications

    NASA Astrophysics Data System (ADS)

    Liu, Huatai; Guo, Zhanrong; Gao, Aiguo; Yuan, Xiaojie; Zhang, Bin

    2016-05-01

    In this work, the 2H, 18O and 226Ra values in groundwater and surface water in the Minjiang River estuary were investigated in the dry and wet seasons. The δ18O values in the dry season were always higher than those in the wet season in both groundwater and surface water because of the presence of evaporation in the water cycle process. During the dry season, the δ18O values in groundwater on the southern bank of the Minjiang River are much higher than those on the northern bank because evaporation is more intense in the farmland of the southern bank than in the urbanized northern bank. The δ18O values in the estuarine water exhibit a good positive correlation with salinity, with a coefficient of 0.96 (p = 0.05) in both seasons. The 226Ra activities in the estuarine water increase with increasing salinity because of desorption from riverine suspended particles. The 226Ra activity reaches a peak value at a salinity of 20.5. Based on a three-endmember model, the average proportions of the estuarine water are calculated to be 0.02 for groundwater, 0.39 for river water and 0.59 for seawater. From this mixing ratio, the groundwater discharge into the estuary is estimated to be 9.31 × 106 m3 d-1 in the wet season.

  5. A foraminiferal δ(18)O record covering the last 2,200 years.

    PubMed

    Taricco, Carla; Alessio, Silvia; Rubinetti, Sara; Vivaldo, Gianna; Mancuso, Salvatore

    2016-01-01

    Thanks to the precise core dating and the high sedimentation rate of the drilling site (Gallipoli Terrace, Ionian Sea) we were able to measure a foraminiferal δ(18)O series covering the last 2,200 years with a time resolution shorter than 4 years. In order to support the quality of this data-set we link the δ(18)O values measured in the foraminifera shells to temperature and salinity measurements available for the last thirty years covered by the core. Moreover, we describe in detail the dating procedures based on the presence of volcanic markers along the core and on the measurement of (210)Pb and (137)Cs activity in the most recent sediment layers. The high time resolution allows for detecting a δ(18)O decennial-scale oscillation, together with centennial and multicentennial components. Due to the dependence of foraminiferal δ(18)O on environmental conditions, these oscillations can provide information about temperature and salinity variations in past millennia. The strategic location of the drilling area makes this record a unique tool for climate and oceanographic studies of the Central Mediterranean. PMID:27328303

  6. The. delta. sup 18 O record of Phanerozoic abiotic marine calcite cements

    SciTech Connect

    Lohmann, K.C.; Walker, J.C.G. )

    1989-04-01

    Monomineralic, abiotic marine cements formed in low-latitude Phanerozoic reefs provide the direction and amplitude of secular variation of {delta}{sup 13}C and {delta}{sup 18}O in marine calcite and defines two end member compositions - 580 to 360 my ({minus}7 to {minus}5{per thousand}{delta}{sup 18}O{sub PDB}) and 360 to present ({minus}3 to 0{per thousand}{delta}{sup 18}O{sub PDB}). Sampling of the Devono-Carboniferous transition (375-320 my) at several global sites reveals a rapid change in carbonate isotopic compositions. Bracketed within Fammenian to Early Visean-aged strata, a 7 to 15 my time interval, this shift corresponds to a 2% offset in mean {delta}{sup 13}C and 3-4% offset in {delta}{sup 18}O. The abruptness of such change, and its overall correlation with variations in {sup 87}Sr/{sup 86}Sr, {delta}{sup 34}S, {delta}{sup 13}C, and Li/Al ratios in marine sediments suggests a primary offset in marine water composition.

  7. Patterns of d18O in fish tissues in two Oregon Coast range streams

    EPA Science Inventory

    We are using stable isotopes of C, N, O and S (H planned) to study the ecology of coho salmon in streams of the Oregon Coast Range. As part of this work we have examined changes in d18O in coho salmon juveniles (from eggs to smolting) and sculpin (from 0.5 to 20 gm.). For fish...

  8. Loggerhead turtle movements reconstructed from 18O and 13C profiles from commensal barnacle shells

    NASA Astrophysics Data System (ADS)

    Killingley, John S.; Lutcavage, Molly

    1983-03-01

    Commensal barnacles, Chelonibia testudinaria, from logger-head turtles have 18O and 13C variations in their calcitic shells that record the environments in which the turtles live. Isotopic profiles from the barnacle shells can thus be interpreted to reconstruct movements of the host turtle between open ocean and brackish-water regimes.

  9. Sub-barrier capture reactions with 16,18O and 40,48Ca beams

    NASA Astrophysics Data System (ADS)

    Sargsyan, V. V.; Adamian, G. G.; Antonenko, N. V.; Scheid, W.; Zhang, H. Q.

    2013-05-01

    Various sub-barrier capture reactions with 16,18O and 40,48Ca are treated within the quantum diffusion approach. The role of neutron transfer in these capture reactions is discussed. The quasielastic and capture barrier distributions are analyzed and compared with the recent experimental data.

  10. A foraminiferal δ18O record covering the last 2,200 years

    PubMed Central

    Taricco, Carla; Alessio, Silvia; Rubinetti, Sara; Vivaldo, Gianna; Mancuso, Salvatore

    2016-01-01

    Thanks to the precise core dating and the high sedimentation rate of the drilling site (Gallipoli Terrace, Ionian Sea) we were able to measure a foraminiferal δ18O series covering the last 2,200 years with a time resolution shorter than 4 years. In order to support the quality of this data-set we link the δ18O values measured in the foraminifera shells to temperature and salinity measurements available for the last thirty years covered by the core. Moreover, we describe in detail the dating procedures based on the presence of volcanic markers along the core and on the measurement of 210Pb and 137Cs activity in the most recent sediment layers. The high time resolution allows for detecting a δ18O decennial-scale oscillation, together with centennial and multicentennial components. Due to the dependence of foraminiferal δ18O on environmental conditions, these oscillations can provide information about temperature and salinity variations in past millennia. The strategic location of the drilling area makes this record a unique tool for climate and oceanographic studies of the Central Mediterranean. PMID:27328303

  11. Simulation of 18O in precipitation by the regional circulation model REMOiso

    NASA Astrophysics Data System (ADS)

    Sturm, Kristof; Hoffmann, Georg; Langmann, Bärbel; Stichler, Willibald

    2005-11-01

    The first results of a regional circulation model REMOiso fitted with water isotope diagnostics are compared with various isotope series from central Europe. A 2 year case study is conducted from March 1997 to February 1999 centred over Europe, analysing daily and monthly measurements. Isotope signals over Europe are dominated by the typical isotopic effects such as temperature, continental and altitude effects, both on annual and seasonal scales. These well-known isotopic effects are successfully reproduced by REMOiso, using two different boundary data sets. In a first simulation, the European Centre for Medium-range Weather Forecasts (ECMWF) analyses serve as boundary conditions, where water isotopes were parameterized by a simple temperature dependence. In a second simulation, boundary conditions both for climatic and isotopic variables are taken from the ECHAMiso general circulation model output. The comparison of both simulations shows a very high sensitivity of the simulated 18O signal to boundary conditions. The ECMWF-nested simulation shows an average offset of -4.5 in mean 18O values and exaggerated seasonal amplitude. The ECHAM-nested simulation represents correctly the observed mean 18O values, although with a dampened seasonality. REMOiso's isotope module is further validated against daily 18O measurements at selected stations (Nordeney, Arkona and Hohenpeissenberg) situated in Germany. Copyright

  12. sup 13 C and sup 18 O isotopic disequilibrium in biological carbonates: I. Patterns

    SciTech Connect

    McConnaughey, T. )

    1989-01-01

    Biological carbonates frequently precipitate out of {sup 18}O and {sup 13}C equilibrium with ambient waters. Two patterns of isotopic disequilibrium are particularly common. Kinetic disequilibria, so designated because they apparently result from kinetic isotope effects during CO{sub 2} hydration and hydroxylation, involve simultaneous depletions of {sup 18}O and {sup 13}C as large as 4{per thousand} and 10 to 15{per thousand}, respectively. Rapid skeletogenesis favors strong kinetic effects, and approximately linear correlations between skeletal {delta}{sup 18}O and {delta}{sup 13}C are common in carbonates showing mainly the kinetic pattern. Metabolic effects involve additional positive or negative modulation of skeletal {delta}{sup 13}C, reflecting changes in the {delta}{sup 13}C of dissolved inorganic carbon, caused mainly by photosynthesis and respiration. Kinetic isotope disequilibria tend to be fairly consistent in rapidly growing parts of photosynthetic corals, and time dependent isotopic variations therefore reflect changes in environmental conditions. {delta}{sup 18}O variations from Galapagos corals yields meaningful clues regarding seawater temperature, while {delta}{sup 13}C variations reflect changes in photosynthesis, modulated by cloudiness.

  13. Permo-Pennsylvanian palaeotemperatures from Fe-Oxide and phyllosilicate δ18O values

    NASA Astrophysics Data System (ADS)

    Tabor, Neil J.

    2007-01-01

    The oxygen isotope composition of fossil roots that have been permineralized by hematite are presented from eight different stratigraphic levels spanning the Upper Pennsylvanian and Lower Permian strata of north-central Texas. Hematite δ18O values range from - 0.4% to 3.7%. The most negative δ18O values occur in the upper Pennsylvanian strata, and there is a progressive trend toward more positive δ18O values upward through the lower Permian strata. This stratigraphic pattern is similar in magnitude and style to δ18O values reported for penecontemporaneous authigenic palaeosol phyllosilicates and calcites, suggesting that all three minerals record similar paragenetic histories that are probably attributed to temporal palaeoenvironmental changes across the Late Pennsylvanian and Early Permian landscapes. Palaeotemperature estimates based on paired δ18O values between penecontemporaneous hematite and phyllosilicate samples suggest these minerals co-precipitated at relatively low temperatures that are consistent with a supergene origin in a low-latitude soil-forming environment. Hematite-phyllosilicate δ18O pairs indicate (1) relatively low soil temperatures (˜ 24 ± 3 °C) during deposition of the upper Pennsylvanian strata followed by (2) a considerable rise in soil temperatures (˜ 35-37 ± 3 °C) during deposition of the lowermost Permian strata. Significantly, δD and δ18O values of contemporaneous phyllosilicates provide single mineral palaeotemperature estimates that are analytically indistinguishable from temperature estimates based on hematite-phyllosilicate oxygen isotope pairs. The results between the two temperature-proxy methods suggest that the inferred large temperature change across the Upper Pennsylvanian-Lower Permian boundary might be taken seriously. If real, such a significant climate change would have undoubtedly had far-reaching ecological effects within this region of Pangaea. Notably, there are important lithological and palaeobotanical

  14. Assessing modern climatic controls on southern Sierra Nevada precipitation and speleothem δ18O

    NASA Astrophysics Data System (ADS)

    McCabe-Glynn, S. E.; Johnson, K. R.; Berkelhammer, M. B.

    2012-12-01

    Precipitation in the southwestern United States (SW US) is highly seasonal and exhibits inter-annual to inter-decadal variability. A 1154-year δ18O time series obtained from a southwestern Sierra Nevada Mountain stalagmite from Crystal Cave, CRC-3, (36.58°N; 118.56°W; 1540 m) reveals substantial decadal to multi-decadal variability closely linked to the Pacific Decadal Oscillation (PDO), and more specifically, to sea surface temperatures (SSTs) in the Kuroshio Extension region, which impact the atmospheric trajectory and isotopic composition of moisture reaching the study site. The instrumental portion of the CRC-3 δ18O time series suggests that more negative precipitation δ18O values are delivered from higher latitudes during positive phases of the PDO and/or when SSTs in the Kuroshio Extension region are anomalously cool, such as during La Niña events. In order to improve our understanding of the controls on speleothem δ18O in this region, we have conducted a detailed modern study of the climate, hydrology, and stable isotopic composition of meteoric waters (precipitation and drip water) at the cave. Here we present Crystal Cave drip logger results from 2010 to 2012, the isotopic composition of North American Deposition Program precipitation samples collected from 2001 to 2012 from several locations near our site including Ash Mountain (ASM), Sequoia National Park-Giant Forest (Ca75), and Yosemite National Park (Ca99), and isotopic composition of cave drip water and glass plate calcite. We also compare the δ18O values in the precipitation to satellite imagery, NCAR/NCEP data, and NOAA Hysplit Model backward trajectories between the sites. Results indicate that this site is particularly sensitive to "Pineapple Express" type storms, a persistent flow of atmospheric moisture and heavy rainfall extending from near the Hawaiian Islands to the coast of North America, which average about twice as much precipitation as other storms in the Sierra Nevada during

  15. Evidence for a universal pathway of abscisic acid biosynthesis in higher plants from sup 18 O incorporation patterns

    SciTech Connect

    Zeevaart, J.A.D.; Heath, T.G.; Gage, D.A. )

    1989-12-01

    Previous labeling studies of abscisic acid (ABA) with {sup 18}O{sub 2} have been mainly conducted with water-stressed leaves. In this study, {sup 18}O incorporation into ABA of stressed leaves of various species was compared with {sup 18}O labeling of ABA of turgid leaves and of fruit tissue in different stages of ripening. In stressed leaves of all six species investigated, avocado (Persea americana), barley (Hordeum vulgare), bean (Phaseolus vulgaris), cocklebur (Xanthium strumarium), spinach (Spinacia oleracea), and tobacco (Nicotiana tabacum), {sup 18}O was most abundant in the carboxyl group, whereas incorporation of a second and third {sup 18}O in the oxygen atoms on the ring of ABA was much less prominent after 24 h in {sup 18}O{sub 2}. ABA from turgid bean leaves showed significant {sup 18}O incorporation, again with highest {sup 18}O enrichment in the carboxyl group. On the basis of {sup 18}O-labeling patterns observed in ABA from different tissues it is concluded that, despite variations in precusor pool sizes and intermediate turnover rates, there is a universal pathway of ABA biosynthesis in higher plants which involves cleavage of a larger precursor molecule, presumably an oxygenated carotenoid.

  16. Linking water and carbon fluxes in a Mediterranean oak woodland using a combined flux and ?18O partitioning approach

    NASA Astrophysics Data System (ADS)

    Dubbert, M.; Piayda, A.; Costa e Silva, F.; Correia, A.; Pereira, J. S.; Cuntz, M.; Werner, C.

    2013-12-01

    Water is one of the key factors driving ecosystem productivity, especially in water-limited ecosystems, where global climate change is expected to intensify drought and alter precipitation patterns. One such ecosystem is the ';Montado', where two vegetation layers respond differently to drought: oak trees avoid drought due to their access to deeper soil layers and ground water while herbaceous plants, surviving the summer in the form of seeds. We aimed at 1) quantifying the impact of the understory herbaceous vegetation on ecosystem carbon and water fluxes throughout the year, 2) determining the driving environmental factors for evapotranspiration (ET) and net ecosystem exchange (NEE) and 3) disentangling how ET components of the ecosystem relate to carbon dioxide exchange. We present one year data set comparing modeled and measured stable oxygen isotope signatures (δ18O) of soil evaporation, confirming that the Craig and Gordon equation leads to good agreement with measured δ18O of evaporation (Dubbert et al. 2013). Partitioning ecosystem ET and NEE into its three sources revealed a strong contribution of soil evaporation (E) and herbaceous transpiration (T) to ecosystem ET during spring and fall. In contrast, soil respiration (R) and herbaceous net carbon gain contributed to a lesser amount to ecosystem NEE during spring and fall, leading to consistently smaller water use efficiencies (WUE) of the herbaceous understory compared to the cork-oaks. Here, we demonstrate that the ability to assess ET, NEE and WUE independent of soil evaporation dynamics enables the understanding of the mechanisms of the coupling between water and carbon fluxes and their responses to drought. Dubbert, M., Cuntz, M., Piayda, A., Maguas, C., Werner, C., 2013: Partitioning evapotranspiration - Testing the Craig and Gordon model with field measurements of oxygen isotope ratios of evaporative fluxes. J Hydrol. a) Oxygen isotope signatures of soil evaporation on bare soil plots calculated

  17. 13C-18O bonding (Δ47) in deep-sea corals: a calibration study

    NASA Astrophysics Data System (ADS)

    Kimball, J. B.; Tripati, A.; Dunbar, R. B.; Eagle, R.

    2013-12-01

    Deep-sea corals are a potentially valuable archive of temperature in intermediate and deep waters, regions for which a paucity of temperature data exists. These archives could give valuable insight into the natural variability of areas of the ocean that play an active role in large-scale climate dynamics. Due to significant 'vital effects' (i.e., non-equilibrium mineral compositions) in δ18O, however, deep-sea coral have been challenging to develop as a paleotemperature proxy. Clumped-isotope paleothermometry is a new method that may circumvent some of the known complications with δ18O paleotemperature analysis in deep-sea coral. This geothermometer is based on the ordering of heavy 13C-18O ';clumps' in carbonate minerals. Initial calibration studies have shown that the method is independent from the solution chemistry of the precipitating fluids as well as 'vital effects' in deep-sea corals and other types of carbonates. Some kinetic effects have been observed in tropical corals and speleothems. Here we report new data in order to further develop clumped isotopes as a paleothermometer in deep-sea corals as well as to investigate taxon-specific effects. 13C-18O bond ordering was analyzed in live-collected scleractinian (Enallopsammia sp.) and gorgonian (Isididae and Coralliidae) deep-sea corals. We determined mass 47 anomalies in samples (Δ47), which refers to the parts per thousand excess of 13C-18O-16O in CO2 produced on acid digestion of a sample, relative to the amount predicted to be present if isotopes were randomly distributed amongst all CO2 isotopologues. Measured Δ47 values were compared to in situ temperatures and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects.

  18. FT-IR spectra of 18O-, and 13C-enriched CO2 in the ν3 region: High accuracy frequency calibration and spectroscopic constants for 16O12C18O, 18O12C18O, and 16O13C16O

    NASA Astrophysics Data System (ADS)

    Elliott, Ben M.; Sung, Keeyoon; Miller, Charles E.

    2015-06-01

    In this report, we extend our Fourier transform infrared (FT-IR) spectroscopy measurements of CO2 in the ν3 region (2200-2450 cm-1, 65-75 THz) to the 18O-, and 13C-substituted isotopologues, using the JPL Bruker IFS-125HR Fourier Transform Spectrometer (JPL-FTS). High quality (S/N ∼ 2000) spectra were obtained separately for each of the 18O-, and 13C-isotopically enriched samples. The absolute wavenumber accuracies were better than 3 × 10-6 cm-1 (∼100 kHz) for strong, isolated transitions, calibrated against the highest accuracy reported CO and 16O12C16O (626) frequency measurements. The JPL-FTS performance and calibration procedure is shown to be reliable and consistent, achievable through vigorous maintenance of the optical alignment and regular monitoring of its instrumental line shape function. Effective spectroscopic constant fits of the 00011 ← 00001 fundamental bands for 16O12C18O (628), 18O12C18O (828), and 16O13C16O (636) were obtained with RMS residuals of 2.9 × 10-6 cm-1, 2.8 × 10-6 cm-1, and 2.9 × 10-6 cm-1, respectively. The observed bands encompassed 79 lines over the Jmax range of P67/R67, 47 lines over P70/R62, and 60 lines over P70/R70 for 628, 828, and 636, respectively. These results complement our recent work on the 17O-enriched isotopologues (Elliott et al., 2014), providing additional high-quality frequency measurements for atmospheric remote sensing applications.

  19. First Principles Calculation on Equilibrium Si Isotope Fractionation Factors and its Implementation on Si Isotope Distributions in Earth Surface Environments

    NASA Astrophysics Data System (ADS)

    Liu, Y.; He, H. T.; Zhu, C.

    2014-12-01

    Several important equilibrium Si isotope fractionation factors are calculated here. We use a so-called volume-variable-cluster-model (VVCM) method for solids and the "water-droplet" method for aqueous species for isotope fractionation calculation at the same quantum chemistry level. The calculation results show that several silicate minerals, such as quartz, feldspar, kaolinite, etc., all enrich heavy Si isotopes relative to aqueous H4SiO4 and can be up to 3.3‰ at 25°C, different from most field observations. Meanwhile stable organosilicon complexes can enrich even lighter Si isotopes than aqueous H4SiO4. For explaining the difference between the calculation results and field observations, we calculate the kinetic isotope effect (KIE) associated with the formation of amorphous silica, and find that amorphous silica will enrich extremely light Si isotopes. From amorphous silica to crystalline quartz, the structural adjustment & transition needs getting rid of small amount of Si to re-organize the structure. Light Si isotopes will be preferentially lost and let the final crystalline quartz with a little bit more heavy Si isotopes. However, such late-stage Si heavy isotope enrichment cannot erase the total isotopic signal, crystalline quartz still inherit much light Si isotopic composition from amorphous quartz. That is the reason for the discrepancy between the calculation results and the field observations, because the formation of amorphous quartz is under a non-equilibrium process but theoretical calculations are for equilibrium isotope fractionations. With accurate equilibrium fractionation factors provided here, Si isotope distributions in earth surface environments including soil, groundwater and plants can be further interpreted. We find that δ30Si variations in soil are mainly driven by secondary minerals precipitation and adsorption. Also, bulk soil δ30Si maybe have a parabolic distribution with soil age, with a minimum value at where allophane is

  20. Analysis of δ15N and δ18O to differentiate NO3- sources in runoff at two watersheds in the Catskill Mountains of New York

    USGS Publications Warehouse

    Burns, Douglas A.; Kendall, Carol

    2002-01-01

    To quantify the movement of atmospheric nitrogen deposition through two forested watersheds in the Catskill Mountains of New York, dual-isotope analysis (δ15N and δ18O) was used to differentiate NO3− derived from precipitation from NO3− derived by microbial nitrification and to quantify the contributions of these sources to NO3− in drainage waters. Samples of stream water, soil water, precipitation, snowmelt, and O-horizon soil were collected during the March and April snowmelt period of 1994 and throughout an 18-month period from August 1995 through February 1997. The mean δ18O-NO3− value of precipitation was +50.5‰, whereas the mean values for stream water and soil water were +17.7‰ and +23.6‰, respectively. The mean δ15N-NO3− of precipitation was −0.2‰, that of soil water was +1.4‰, and that of stream water was +2.3‰; these values showed greater overlap among the three different waters than did the δ18O-NO3− values, indicating that δ15N-NO3− was not as useful for source separation. Soil water δ18O-NO3− values decreased, and δ15N-NO3− values increased, from the O to the B and C horizons, but most of the differences among horizons were not statistically significant. Nitrate derived by nitrification in incubated soil samples had a wide range of δ15N-NO3− values, from +1.5‰ to +16.1‰, whereas δ18O-NO3− values ranged more narrowly, from +13.2‰ to +16.0‰. Values of δ18O-NO3− indicated that NO3− in stream water is mainly derived from nitrification. Only during a high-flow event that exceeded the annual flood was precipitation a major contributor to stream water NO3−. Values of δ18O-NO3− and δ15N-NO3− changed at differing rates as NO3− cycled through these watersheds because δ18O-NO3− values change sharply through the incorporation of oxygen from ambient water and gas during nitrification, whereas δ15N-NO3− values change only incrementally through fractionation during biocycling

  1. An assessment of the isotopic (2H/18O) integrity of water samples collected and stored by unattended precipitation totalizers

    NASA Astrophysics Data System (ADS)

    Terzer, Stefan; Wassenaar, Leonard I.; Douence, Cedric; Araguas-Araguas, Luis

    2016-04-01

    The IAEA-WMO Global Network of Isotopes in Precipitation (GNIP) provides worldwide δ18O and δ2H data for numerous hydrological and climatological studies. The traditional GNIP sample collection method relies on weather station operators to accumulate precipitation obtained from manual rain gauges. Over the past decades, widespread weather station automatization resulted in the increased use of unattended precipitation totalizers that accumulate and store the rainwater in the field for up to one month. Several low-tech measures were adopted to prevent in situ secondary evaporative isotopic enrichment (SEE) of totalized water samples (i.e. disequilibrium isotopic fractionation after precipitation is stored in the collection device). These include: (a) adding a 0.5-1 cm floating layer of paraffin oil to the totalizer bottle, (b) using an intake tube leading from the collection funnel and submerged to the bottom of the totalizer bottle, or (c) placing a table tennis ball in the funnel aiming to reduce evaporation of the collected water from the receiving bottle to the atmosphere. We assessed the isotopic integrity of stored rainwater samples for three totalizers under controlled settings: each aforementioned totalizer was filled with a 100 or 500 mL of isotopically known water and installed in the field with the intake funnels sheltered to prevent rainwater collection. Potential evapotranspiration (PET) was obtained from on-site meteorological recordings. Stored evaporative loss from each totalizer was evaluated on a monthly basis; gravimetrically and by analysing δ18O and δ2H of the stored water, for a period of 6 months and a cumulative PET of ˜500 mm. The gravimetric and isotope results revealed that for smaller water volumes (100 ml, corresponding to ca. 5 mm of monthly precipitation), negligible isotope enrichment (δ18O) was observed in the paraffin-oil based totalizer, whereas unacceptable evaporative isotope effects were observed for the ball

  2. Factors controlling the growth rate, carbon and oxygen isotope variation in modern calcite precipitation in a subtropical cave, Southwest China

    NASA Astrophysics Data System (ADS)

    Pu, Junbing; Wang, Aoyu; Shen, Licheng; Yin, Jianjun; Yuan, Daoxian; Zhao, Heping

    2016-04-01

    A prerequisite for using cave speleothems to reconstruct palaeoenvironmental conditions is an accurate understanding of specific factors controlling calcite growth, in particular the isotopic partitioning of oxygen (δ18O) and carbon (δ13C) which are the most commonly used proxies. An in situ monitoring study from April 2008 to September 2009 at Xueyu Cave, Chongqing, SW China, provides insight into the controls on calcite growth rates, drip water composition, cave air parameters and δ18O and δ13C isotopic values of modern calcite precipitation. Both cave air PCO2 and drip water hydrochemical characteristics show obvious seasonality driven by seasonal changes in the external environment. Calcite growth rates also display clear intra-annual variation, with the lowest values occurring during wet season and peak values during the dry season. Seasonal variations of calcite growth rate are primarily controlled by variations of cave air PCO2 and drip water rate. Seasonal δ18O-VPDB and δ13C-VPDB in modern calcite precipitates vary, with more negative values in the wet season than in the dry season. Strong positive correlation of δ18O-VPDB vs. δ13C-VPDB is due to simultaneous enrichment of both isotopes in the calcite. This correlation indicates that kinetic fractionation occurs between parent drip water and depositing calcite, likely caused by the variations of cave air PCO2 and drip rate influenced by seasonal cave ventilation. Kinetic fractionation amplifies the equilibrium fractionation value of calcite δ18O (by ∼1.5‰) and δ13C (by ∼1.7‰), which quantitatively reflects surface conditions during the cave ventilation season. These results indicate that the cave monitoring of growth rate and δ18O and δ13C of modern calcite precipitation are necessary in order to use a speleothem to reconstruct palaeoenvironment.

  3. Environmental and biological controls on size-specific δ13C and δ18O in recent planktonic foraminifera

    NASA Astrophysics Data System (ADS)

    Ezard, Thomas H. G.; Edgar, Kirsty M.; Hull, Pincelli M.

    2015-03-01

    As living organisms, planktonic foraminifera are not passive tracers of the environment. Their test geochemistry—arguably the single most important resource for paleoceanographic research—reflects the combined signal of environmental, biological, and preservational processes. For most species, comparisons of test stable isotopic composition within and among taxa provide the primary means for disentangling the relative influences of these different processes. Here we test the foundations of our paleoceanographic interpretations with the first quantitative comparison of the determinants of carbon and oxygen isotopic variation across multiple ocean basins, studies, and species by re-analyzing size-specific data collated from the literature. We find clear evidence of species-specific biological effects (i.e., vital effects), as the intercepts of size-specific carbon and oxygen isotopic compositions differ significantly among species. Trends in body size and isotopic composition, particularly in dinoflagellate bearing taxa, suggest that much of the size-dependent isotopic variation observed in death assemblages (i.e., core tops and sediments) relates to factors influencing the maximum size obtained by adults rather than ontogeny. The presence and type of photosymbiont hosted (dinoflagellate, chrysophyte, or none) were a major factor affecting species- and size-specific δ18O values. In contrast, size-related trends in δ13C values were driven by depth habitat (mixed layer, thermocline, subthermocline), symbiont ecology and whether the assemblage was alive or dead when sampled. On this broad geographic and oceanographic scale, ocean basin and biome had a significant effect on δ18O and δ13C values . Our analysis and its model-averaged predictions provide a quantitative basis for interpreting size-specific isotopic variation in 22 species of modern macroperforate planktonic foraminifera. We conclude by highlighting existing data gaps and outstanding questions of the

  4. Coherency of European speleothem δ18O records linked to North Atlantic ocean circulation

    NASA Astrophysics Data System (ADS)

    Deininger, Michael; McDermott, Frank

    2016-04-01

    Speleothem δ18O records can provide valuable information about past continental environmental and climatic conditions. In recent decades a European speleothem network has been assembled that allows us to reconstruct past climate variability in both space and time. In particular climate variability during the Holocene was investigated by these studies. The Holocene is thus an ideal period to apply sophisticated statistical methods to derive spatio-temporal pattern of common climate variability in the European speleothem record. Here we evaluate a compilation of 10 speleothem δ18O records covering the last 4.5 ka for their shared variability. The selected speleothem δ18O records must satisfy certain quality criteria to be included: (i) a robust age model; (ii) a temporal intra-sampling resolution of smaller than 30 years; and (iii) the record should be published. A Monte Carlo based Principal Component Analysis (MC-PCA) that accounts for uncertainties in individual speleothem age models and for the different and varying temporal resolutions of each speleothem δ18O record was used for this purpose. Our MC-PCA approach allows not only the identification of temporally coherent changes in δ18O records, but it also facilitates their depiction and evaluation spatially. The compiled speleothem δ18O records span almost the entire European continent (with the exception of the circum-Mediterranean region) ranging from the western Margin of the European continent (stalagmite CC-3, Ireland) to Northern Turkey (SO-1) and from Northern Italy (CC-26) to Norway (FM-3). For the MC-PCA analysis, the 4.5 ka period was sub-divided into eight 1 ka long time windows that overlap the subsequent time window by 500 years to allow a comparison of the temporal evolution of the common signal. In this study we only interpreted the 1st principal component (PC) that depict the spatio-temporal pattern with the highest explained variability of all speleothem δ18O records. Our MC-PCA results

  5. Down Core Oxygen Isotopic Measurements Of Diatom δ18O From The Guaymas Basin, Gulf Of California

    NASA Astrophysics Data System (ADS)

    Menicucci, A. J.; Spero, H. J.; Thunell, R.

    2015-12-01

    The Guaymas Basin (GB), Gulf of California (27º53'N, 111º40'W ), is an evaporative basin, with sea surface temperatures (SST) varying between ~30oC (summer) and ~15oC (winter). Productivity is controlled mostly by seasonal upwelling starting in fall (early November) and extending into spring. We are currently analyzing δ18Odiatom from a boxcore (BC-43) using microfluorination (Menicucci, et al. 2013). This boxcore was previously analyzed for UK '37 alkenones and 210Pb activity (Goni, et al. 2001). Residual BC-43 material was sampled at ~2cm intervals. Samples were cleaned to isolate diatoms from other sediments, then equilibrated in water with δ18Owater = +85‰ for 70 hours at 21oC prior to vacuum dehydroxylation and microfluorination. The latter equilibration was done to account for fractionation between covalently bound O and OH- groups during vacuum dehydroxylation, preserving the original δ18Odiatom value. We present δ18Odiatom data from BC-43 samples covering 27cm, equivalent to >225 years of sediment accumulation. δ18O data are converted to temperature (T) based on an existing calibration (Leclerc and Labeyrie 1987). Our data suggest δ18Odiatom values record a T range of 22-18oC, corresponding to the mixed layer depth and the chlorophyll maximum during the fall bloom. These T values are offset from SST data by a mean of 5oC for the same sample intervals. However, δ18Odiatom values from the most recent samples suggest a ~2oC increase in diatom T relative to SST during the last 35 years. This subsurface warming may be due to decreased fall upwelling, increased mixed layer and chlorophyll maximum depths, and/or the timing of the peak diatom bloom. Such correlations are being investigated and the latest results will be presented. Goni, M. A., et al. (2001). Oceanographic considerations for the application of the alkenone-based paleotemperature U-37(K ') index in the Gulf of California. Geochimica Et Cosmochimica Acta 65: 545-557. Leclerc, A. J. and L

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

    SciTech Connect

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

    2012-01-15

    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.

  7. Transcription Factor EB Is Selectively Reduced in the Nuclear Fractions of Alzheimer's and Amyotrophic Lateral Sclerosis Brains

    PubMed Central

    Wang, Hongjie

    2016-01-01

    Multiple studies suggest that autophagy is strongly dysregulated in Alzheimer's disease (AD) and amyotrophic lateral sclerosis (ALS), as evidenced by accumulation of numerous autophagosomes, lysosomes with discontinuous membranes, and aggregated proteins in the patients' brains. Transcription factor EB (TFEB) was recently discovered to be a master regulator of lysosome biogenesis and autophagy. To examine whether aberrant autophagy in AD and ALS is due to alterations in TFEB expression, we systematically quantified the levels of TFEB in these brains by immunoblotting. Interestingly, cytoplasmic fractions of AD brains showed increased levels of normalized (to tubulin) TFEB only at Braak stage IV (61%, p < 0.01). Most importantly, normalized (to lamin) TFEB levels in the nuclear fractions were consistently reduced starting from Braak stage IV (52%, p < 0.01), stage V (67%, p < 0.01), and stage VI (85%, p < 0.01) when compared to normal control (NC) brains. In the ALS brains also, nuclear TFEB levels were reduced by 62% (p < 0.001). These data suggest that nuclear TFEB is selectively lost in ALS as well as AD brains, in which TFEB reduction was Braak-stage-dependent. Taken together, the observed reductions in TFEB protein levels may be responsible for the widely reported autophagy defects in these disorders. PMID:27433468

  8. Fraction Reduction through Continued Fractions

    ERIC Educational Resources Information Center

    Carley, Holly

    2011-01-01

    This article presents a method of reducing fractions without factoring. The ideas presented may be useful as a project for motivated students in an undergraduate number theory course. The discussion is related to the Euclidean Algorithm and its variations may lead to projects or early examples involving efficiency of an algorithm.

  9. Large-Scale Multiplexed Quantitative Discovery Proteomics Enabled by the Use of an 18O-Labeled “Universal” Reference Sample

    PubMed Central

    Qian, Wei-Jun; Liu, Tao; Petyuk, Vladislav A.; Gritsenko, Marina A.; Petritis, Brianne O.; Polpitiya, Ashoka D.; Kaushal, Amit; Xiao, Wenzhong; Finnerty, Celeste C.; Jeschke, Marc G.; Jaitly, Navdeep; Monroe, Matthew E.; Moore, Ronald J.; Moldawer, Lyle L.; Davis, Ronald W.; Tompkins, Ronald G.; Herndon, David N.; Camp, David G.; Smith, Richard D.

    2009-01-01

    The quantitative comparison of protein abundances across a large number of biological or patient samples represents an important proteomics challenge that needs to be addressed for proteomics discovery applications. Herein, we describe a strategy that incorporates a stable isotope 18O-labeled ″universal″ reference sample as a comprehensive set of internal standards for analyzing large sample sets quantitatively. As a pooled sample, the 18O-labeled ″universal″ reference sample is spiked into each individually processed unlabeled biological sample and the peptide/protein abundances are quantified based on 16O/18O isotopic peptide pair abundance ratios that compare each unlabeled sample to the identical reference sample. This approach also allows for the direct application of label-free quantitation across the sample set simultaneously along with the labeling-approach (i.e., dual-quantitation) since each biological sample is unlabeled except for the labeled reference sample that is used as internal standards. The effectiveness of this approach for large-scale quantitative proteomics is demonstrated by its application to a set of 18 plasma samples from severe burn patients. When immunoaffinity depletion and cysteinyl-peptide enrichment-based fractionation with high resolution LC-MS measurements were combined, a total of 312 plasma proteins were confidently identified and quantified with a minimum of two unique peptides per protein. The isotope labeling data was directly compared with the label-free 16O-MS intensity data extracted from the same data sets. The results showed that the 18O reference-based labeling approach had significantly better quantitative precision compared to the label-free approach. The relative abundance differences determined by the two approaches also displayed strong correlation, illustrating the complementary nature of the two quantitative methods. The simplicity of including the 18O-reference for accurate quantitation makes this

  10. The timing of termination I in benthic δ18O of the Atlantic, Pacific, and Mediterranean basins

    NASA Astrophysics Data System (ADS)

    Konijnendijk, T.

    2014-12-01

    Terminations used to be regarded as effectively globally synchronous events. As such they were used (amongst other features) in aligning cores by Lisiecki and Raymo (2005) in their widely accepted global benthic stack. Skinner and Shackleton (2005) showed, however, that this assumption of synchronicity may not hold. In a detailed study of the last glacial-interglacial transition, an Atlantic record from the Iberian Margin and a record from the deep eastern equatorial Pacific - both dated by 14C for a solid, independent age estimate - show a significant discrepancy in timing: ~4,000 years. Indeed, in 2009 Lisiecki and Raymo published a separate reconstruction for the Atlantic and Pacific records in their stack, and found indications for diachronous termination signals for the last five terminations. We compared the Atlantic and Pacific records of Skinner and Shackleton (2005) to the benthic isotope record of ODP site 968 in the eastern Mediterranean published by Ziegler et al. (2010), to see how the Mediterranean record feeds into this discussion. The age model for this record is constrained by the carbon dated boundaries of saproprel 1 as well as correlation to the radiometrically dated cave record of Sanbao-Hulu (Wang et al., 2008). The benthic δ18O record of ODP site 968 resembles the Pacific record much more than the geographically closer Iberian Margin record. This raises questions: whether the Late Glacial/Early Holocene benthic record of MD99-2334K on the Iberian Margin is representative of Atlantic benthic δ18O; what oceanographic factors could have influenced the benthic δ18O of the sites involved; whether there is, after all, a globally synchronous, two-step deglaciation in the Mediterranean, Atlantic, and Pacific basins. Lisiecki and Raymo, 2005. DOI: 10.1029/2004PA001071 Lisiecki and Raymo, 2005. DOI: 10.1029/2009PA001732 Skinner and Shackleton, 2005: DOI: 10.1016/j.quascirev.2004.11.008 Wang et al. 2008: doi:10.1038/nature06692. Ziegler et al., 2010

  11. Physical factors determining the fraction of stored energy recoverable from hydrothermal convection systems and conduction-dominated areas

    USGS Publications Warehouse

    Nathenson, Manuel

    1975-01-01

    This report contains background analyses for the estimates of Nathenson and Muffler (1975) of geothermal resources in hydrothermal convection systems and conduction-dominated areas. The first section discusses heat and fluid recharge potential of geothermal reservoirs. The second section analyzes the physical factors that determine the fraction of stored energy obtainable at the surface from a geothermal reservoir. Conversion of heat to electricity and the use of geothermal energy for direct-heating applications are discussed in the last two sections. Nathenson, Manuel, and Muffler, L.J.P., 1975, Geothermal resources in hydrothermal convection systems and conduction dominated areas, in White, D.E., and Williams, D.L., eds., Assessment of the Geothermal Resources of the United States--1975: U.S. Geological Survey Circular 726, p. 104-121, available at http://pubs.er.usgs.gov/usgspubs/cir/cir726

  12. δ18O comparisons of coral cores in the western tropical Pacific, Palau

    NASA Astrophysics Data System (ADS)

    Johnston, E.; Osborne, M. C.

    2010-12-01

    Certain corals secrete calcium carbonate exoskeletons that can record changes in ocean water temperature and salinity when tested for δ18O by mass spectrometry. Records from these corals provide insight into the chemistry of the seas for times when instrumental records were not available. The composition of δ18O in coral calcium carbonate reflects both the temperature of the water and the δ18O composition of the water the corals were growing in. Calcium carbonate that is relatively high in 18O indicates that the corals were growing in ocean water with cooler temperatures and/ or higher salinity due to decreased precipitation or increased evaporation. On the other hand, a decrease in 18O indicates warmer and/ or less saline waters. Broadly speaking, changes in evaporation and precipitation are linked to El Niño/La Niña and Southern Oscillation cycles (ENSO) in the tropical Pacific. Palau, an archipelago in the western tropical Pacific, is greatly affected during El Niño years by abnormally cool waters and decreased rainfall. The opposite conditions are common during La Niña. In 2000, two coral cores were collected in a lagoon in Ngaragebal, Palau by Japanese researchers (7°24.30.3” N, 134°26’53.1”E; Iijima et. Al, 2003). Later, in 2008, two different cores of the same species were collected in the same lagoon in Ngaragebal, Palau by a separate group of scientists (7°24.386”N, 134°26.115”E). Here I compare overlapping δ18O data from the two research groups to create a correlation coefficient which will reveal how closely related the data sets are. Due to it’s location inside a lagoon, unlike other coral collection sites which may be more exposed to open ocean conditions, data from Ngaragebal could be capturing a local signal. However, if data from multiple sites around Palau are similar, this gives us confidence in our interpretations of long term trends. Also, by comparing Ngaragebel data from two different research groups, we can test for

  13. French summer droughts since 1326 CE: a reconstruction based on tree ring cellulose δ18O

    NASA Astrophysics Data System (ADS)

    Labuhn, Inga; Daux, Valérie; Girardclos, Olivier; Stievenard, Michel; Pierre, Monique; Masson-Delmotte, Valérie

    2016-05-01

    The reconstruction of droughts is essential for the understanding of past drought dynamics and can help evaluate future drought scenarios in a changing climate. This article presents a reconstruction of summer droughts in France based on annually resolved, absolutely dated chronologies of oxygen isotope ratios (δ18O) in tree ring cellulose from Quercus spp. Samples were taken from living trees and timber wood from historic buildings at two sites: Fontainebleau (48°23' N, 2°40' E; 1326-2000 CE) and Angoulême (45°44' N, 0°18' E; 1360-2004 CE). Cellulose δ18O from these sites proved to be a good proxy of summer climate, as the trees were sensitive to temperature and moisture availability. However, offsets in average δ18O values between tree cohorts necessitated a correction before joining them to the final chronologies. Using the corrected δ18O chronologies, we developed models based on linear regression to reconstruct drought, expressed by the standardized precipitation evapotranspiration index (SPEI). The significant correlations between the SPEI and cellulose δ18O (r ≈ -0.70), as well as the verification of the models by independent data support the validity of these reconstructions. At both sites, recent decades are characterized by increasing drought. Fontainebleau displays dominantly wetter conditions during earlier centuries, whereas the current drought intensity is not unprecedented in the Angoulême record. While the δ18O chronologies at the two studied sites are highly correlated during the 19th and 20th centuries, there is a significant decrease in the correlation coefficient between 1600 and 1800 CE, which indicates either a weaker climate sensitivity of the tree ring proxies during this period, or a more heterogeneous climate in the north and the south of France. Future studies of tree ring isotope networks might reveal if the seasonality and spatial patterns of past droughts can explain this decoupling. A regional drought reconstruction

  14. Paleoclimatic Inferences From a High Resolution Bristlecone Pine δ18O Chronology

    NASA Astrophysics Data System (ADS)

    Berkelhammer, M.; Stott, L.

    2007-12-01

    This study presents a comprehensive high resolution 400-year chronology of tree-ring α cellulose δ18O values of Pinus longaeva (Bristlecone Pine) from the White Mountains of California. The δ18OVSMOW stratigraphy exhibits a distinctive bidecadal oscillation during the 20th century with peak excursions of 4‰. The cellulosic δ18O values appear to correlate both with growing season temperatures and the isotopic composition of regional precipitation. Because there is not a good instrumental record of δ18O in precipitation for this region, the latter statistic was estimated by calculating the percentage of each year's precipitation that had a subtropical origin by the use of daily NCEP Reanalysis data and a recently developed catalog of Pineapple Express storms. The subtropical influence on the region exhibits large interannual variability, ranging from years where no such storm occurs to years where close to 15% of the total water budget has a subtropical origin. Precipitation in this region falls predominately during the winter months and the growing season is restricted to late spring through early fall, so it can be stated that the average annual δ18O value integrates a distinct summer and winter signal. The δ18O variability during the instrumental period is dwarfed by a dramatic enrichment (~10‰) in cellulosic δ18O values between 1905 and 1855 AD. This mid 19th century isotopic shift correlates with major climatic changes across the Northern Hemisphere that have been documented in a wide-range of proxy records. Both the magnitude and direction of the Bristlecone Pine isotopic excursion suggest it is not likely the result of post-Little Ice Age warming but rather a major change in the dominant storm tracks striking this region. We hypothesize that the large isotopic shift in the mid-19th century is evidence for a change in mean storm trajectories brought about by a more southerly position of the mid-latitude jet and changes in the strength and zonality

  15. Prevalence and Risk Factors of Heart Failure with Preserved Ejection Fraction: A Population-Based Study in Northeast China

    PubMed Central

    Guo, Liang; Guo, Xiaofan; Chang, Ye; Yang, Jun; Zhang, Limin; Li, Tan; Sun, Yingxian

    2016-01-01

    Background: Heart failure with preserved ejection fraction (HFpEF) has attracted increasing attention worldwide. We aimed to estimate the prevalence of HFpEF and analyze its correlates in a sample of residents of northeast China; Methods: A population-based study of 2230 participants ≥35 years old was conducted in rural areas of Liaoning Province from January 2012 through August 2013. Information about lifestyle and other potential risk factors was obtained. HFpEF was diagnosed according to the recommendations of European Society of Cardiology; Results: The overall prevalence of HFpEF was 3.5% (1.8% in men and 4.9% in women). The prevalence of HFpEF increased with age in both genders and was greater in women than in men for every age group. Multivariable logistic regression analysis found that female gender (OR, 3.575; 95% CI, 1.761–7.256), hypertension (OR, 3.711; 95% CI, 2.064–6.674), and history of heart disease (2.086; 95% CI, 1.243–3.498) were associated factors for prevalent HFpEF; Conclusions: In a general population from rural northeast China, we found that female gender, hypertension, and history of heart disease were risk factors for prevalent HFpEF. PMID:27483300

  16. Effects of comprehensive function of factors on retention behavior of microparticles in gravitational field-flow fractionation.

    PubMed

    Guo, Shuang; Qiu, Bai-Ling; Zhu, Chen-Qi; Yang, Ya-Ya Gao; Wu, Di; Liang, Qi-Hui; Han, Nan-Yin

    2016-09-15

    Gravitational field-flow fractionation (GrFFF) is a useful technique for separation and characterization for micrometer-sized particles. Elution behavior of micrometer-sized particles in GrFFF was researched in this study. Particles in GrFFF channel are subject to hydrodynamic lift forces (HLF), fluid inertial forces and gravity, which drive them to different velocities by carrier flow, resulting in a size-based separation. Effects of ionic strength, flow rate and viscosity as well as methanol were investigated using polystyrene latex beads as model particles. This study is devoted to experimental verification of the effect of every factor and their comprehensive function. All experiments were performed to show isolated influence of every variable factor. The orthogonal design test was used to evaluate various factors comprehensively. Results suggested that retention ratio of particles increases with increasing flow rate or the viscosity of carrier liquid by adjusting external forces acting on particles. In addition, retention ratio increases as ionic strength decreases because of decreased electrostatic repulsion between particles and channel accumulation wall. As far as methanol, there is no general trend due to the change of both density and viscosity. On the basis of orthogonal design test it was found that viscosity of carrier liquid plays a significant role in determining resolution of micrometer-sized particles in GrFFF. PMID:27447927

  17. Attached, unattached fraction of progeny concentrations and equilibrium factor for dose assessments from (222)Rn and (220)Rn.

    PubMed

    Singh, Parminder; Saini, Komal; Mishra, Rosaline; Sahoo, Bijay Kumar; Bajwa, Bikramjit Singh

    2016-08-01

    In this study, measurements of indoor radon ((222)Rn), thoron ((220)Rn) and their equilibrium equivalent concentration (EEC) were carried out in 96 dwellings from 22 different villages situated in Hamirpur district, Himachal Pradesh, India, by using LR-115 type II-based pinhole twin cup dosimeters and deposition-based progeny sensors (DRPS/DTPS). The annual average indoor (222)Rn and (220)Rn concentrations observed in these dwellings were 63.82 and 89.59 Bq/m(3), respectively, while the average EEC (attached + unattached) for (222)Rn and (220)Rn was 29.28 and 2.74 Bq/m(3). For (222)Rn (f Rn) and (220)Rn (f Tn), the average values of unattached fraction were 0.11 and 0.09, respectively. The equilibrium factors for radon (F Rn) and thoron (F Tn) varied from 0.12 to 0.77 with an average of 0.50, and from 0.01 to 0.34 with an average of 0.05, respectively. The annual inhalation dose due to mouth and nasal breathing was calculated using dose conversion factors and unattached fractions. The indoor annual effective doses for (222)Rn (AEDR) and (220)Rn (AEDT) were found to be 1.92 and 0.83 mSv a(-1), respectively. The values of (222)Rn/(220)Rn concentrations and annual effective doses obtained in the present study are within the safe limits as recommended by the International Commission on Radiological Protection for indoor dwelling exposure conditions. PMID:27289385

  18. Direct measurement of the boron isotope fractionation factor: Reducing the uncertainty in reconstructing ocean paleo-pH

    NASA Astrophysics Data System (ADS)

    Nir, Oded; Vengosh, Avner; Harkness, Jennifer S.; Dwyer, Gary S.; Lahav, Ori

    2015-03-01

    The boron isotopic composition of calcium carbonate skeletons is a promising proxy method for reconstructing paleo-ocean pH and atmospheric CO2 from the geological record. Although the boron isotope methodology has been used extensively over the past two decades to determine ancient ocean-pH, the actual value of the boron isotope fractionation factor (εB) between the two main dissolved boron species, 11B(OH)3 and 10B(OH)-4, has remained uncertain. Initially, εB values were theoretically computed from vibrational frequencies of boron species, resulting in a value of ∼ 19 ‰. Later, spectrophotometric pH measurements on artificial seawater suggested a higher value of ∼ 27 ‰. A few independent theoretical models also pointed to a higher εB value. Here we provide, for the first time, an independent empirical fractionation factor (εB = 26.0 ± 1.0 ‰ ; 25 °C), determined by direct measurements of B(OH)3 in seawater and other solutions. Boric acid was isolated by preferential passage through a reverse osmosis membrane under controlled pH conditions. We further demonstrate that applying the Pitzer ion-interaction approach, combined with ion-pairing calculations, results in a more accurate determination of species distribution in aquatic solutions of different chemical composition, relative to the traditional two-species boron-system approach. We show that using the revised approach reduces both the error in simulating ancient atmospheric CO2 (by up to 21%) and the overall uncertainty of applying boron isotopes for paleo-pH reconstruction. Combined, this revised methodology lays the foundation for a more accurate determination of ocean paleo-pH through time.

  19. Endogenous and environmental factors influence the dietary fractionation of 13C and 15N in hissing cockroaches Gromphadorhina portentosa.

    PubMed

    McCue, Marshall D

    2008-01-01

    Since DeNiro and Epstein's discovery that the (13)C and (15)N isotopic signatures of animals approximate those of their respective diets, the measurement of stable isotope signatures has become an important tool for ecologists studying the diets of wild animals. This study used Madagascar hissing cockroaches (Gromphadorhina portentosa) to examine several preexisting hypotheses about the relationship between the isotopic composition of an animal and its diet. Contrary to my predictions, the results revealed that the tissues of adult cockroaches raised for two generations on a diet of known isotopic composition did not demonstrate enrichment of heavy stable isotopes. Moreover, the (15)N signatures of cockroaches were neither influenced by periods of rapid growth (i.e., 300-fold increase in dry body mass over 120 d) nor by imposed periods of starvation lasting up to 80 d. The offspring born to mothers raised on known diets were enriched in (15)N. Diet-switching experiments showed that turnover times of (13)C were highly correlated with age and ranged from 9 to 10 d to 60 to 75 d in subadults and adults, respectively. Adults subjected to diet switches differed from the subadults in that the adults achieved equilibrated isotopic signatures that were shifted approximately 1.0 per thousand toward their respective original diets. Lipid fractions of adult cockroaches averaged 2.9 per thousand more depleted in (13)C than in lipid-free fractions, but no changes in (13)C were observed in aging adults. Exposure to reduced ambient temperature from 33 degrees C to 23 degrees C over 120 d did not influence isotopic signatures of tissues. Overall, the results of this study reveal that different endogenous and exogenous factors can influence the isotopic signatures of cockroaches. These findings reinforce the need to conduct controlled studies to further examine environmental factors that influence the relationships between the isotopic signatures of animals and their diets. PMID

  20. Neglected role of hookah and opium in gastric carcinogenesis: a cohort study on risk factors and attributable fractions.

    PubMed

    Sadjadi, Alireza; Derakhshan, Mohammad H; Yazdanbod, Abbas; Boreiri, Majid; Parsaeian, Mahbubeh; Babaei, Masoud; Alimohammadian, Masoomeh; Samadi, Fatemeh; Etemadi, Arash; Pourfarzi, Farhad; Ahmadi, Emad; Delavari, Alireza; Islami, Farhad; Farzadfar, Farshad; Sotoudeh, Masoud; Nikmanesh, Arash; Alizadeh, Behrooz Z; de Bock, Geertruida H; Malekzadeh, Reza

    2014-01-01

    A recent study showed an association between hookah/opium use and gastric cancer but no study has investigated the relationship with gastric precancerous lesions. We examined the association between hookah/opium and gastric precancerous lesions and subsequent gastric cancer. In a population-based cohort study, 928 randomly selected, healthy, Helicobacter pylori-infected subjects in Ardabil Province, Iran, were followed for 10 years. The association between baseline precancerous lesions and lifestyle risk factors (including hookah/opium) was analyzed using logistic regression and presented as odds ratios (ORs) and 95% confidence intervals (CIs). We also calculated hazard ratios (HRs) and 95% CIs for the associations of lifestyle risk factors and endoscopic and histological parameters with incident gastric cancers using Cox regression models. Additionally, the proportion of cancers attributable to modifiable risk factors was calculated. During 9,096 person-years of follow-up, 36 new cases of gastric cancer were observed (incidence rate: 3.96/1,000 persons-years). Opium consumption was strongly associated with baseline antral (OR: 3.2; 95% CI: 1.2-9.1) and body intestinal metaplasia (OR: 7.3; 95% CI: 2.5-21.5). Opium (HR: 3.2; 95% CI: 1.4-7.7), hookah (HR: 3.4; 95% CI: 1.7-7.1) and cigarette use (HR: 3.2; 95% CI: 1.4-7.5), as well as high salt intake, family history of gastric cancer, gastric ulcer and histological atrophic gastritis and intestinal metaplasia of body were associated with higher risk of gastric cancer. The fraction of cancers attributable jointly to high salt, low fruit intake, smoking (including hookah) and opium was 93% (95% CI: 83-98). Hookah and opium use are risk factors for gastric cancer as well as for precancerous lesions. Hookah, opium, cigarette and high salt intake are important modifiable risk factors in this high-incidence gastric cancer area. PMID:23797606

  1. Oxygen isotope ratios (18O/16O) of hemicellulose-derived sugar biomarkers in plants, soils and sediments as paleoclimate proxy II: Insight from a climate transect study

    NASA Astrophysics Data System (ADS)

    Tuthorn, Mario; Zech, Michael; Ruppenthal, Marc; Oelmann, Yvonne; Kahmen, Ansgar; Valle, Héctor Francisco del; Wilcke, Wolfgang; Glaser, Bruno

    2014-02-01

    control on evaporative 18O enrichment of leaf water and thus δ18Ohemicellulose, whereas the effect of temperature changes is of minor importance. While oxygen exchange and degradation effects seem to be negligible, further factors needing consideration when interpreting δ18Ohemicellulose values obtained from (paleo-)soils are evaporative 18O enrichment of soil water, seasonality effects, wind effects and in case of abundant stem/root-derived organic matter input a partial loss of the evaporative 18O enrichment of leaf water. Overall, our results prove that compound-specific δ18O analyses of hemicellulose biomarkers in soils and sediments are a promising tool for paleoclimate research. However, disentangling the two major factors influencing δ18Ohemicellulose, namely δ18Oprec and relative air humidity controlled evaporative 18O enrichment of leaf water, is challenging based on δ18O analyses alone. Although oxygen in hemicelluloses derives from water and thus ultimately from precipitation, the hemicellulose biomarkers arabinose, fucose and xylose do not simply reflect δ18Oprec but rather δ18Oleaf water. The correlation between measured δ18Ohemicellulose and modeled δ18Oleaf water is highly significant (r = 0.81, p < 0.001, n = 20). This finding can be attributed to the evaporative 18O enrichment of leaf water during transpiration. Model sensitivity tests using a Péclet-modified Craig-Gordon (PMCG) model corroborate that relative air humidity is a very rigorous climate parameter influencing δ18Oleaf water, whereas temperature is of minor importance. While oxygen exchange and degradation effects on δ18O values of hemicelluloses sugar biomarkers seem to be negligible (Zech et al., 2012), further effects that need to be considered when interpreting δ18Ohemicellulose values obtained from (paleo-)soils are evaporative 18O enrichment of soil water, seasonality effects, wind effects and in case of abundant stem/root-derived organic matter input a partial loss of the

  2. Oxygen isotope ratios (18O/16O) of hemicellulose-derived sugar biomarkers in plants, soils and sediments as paleoclimate proxy II: Insight from a climate transect study

    NASA Astrophysics Data System (ADS)

    Tuthorn, Mario; Zech, Michael; Ruppenthal, Marc; Oelmann, Yvonne; Kahmen, Ansgar; Valle, Héctor Francisco del; Wilcke, Wolfgang; Glaser, Bruno

    2014-02-01

    control on evaporative 18O enrichment of leaf water and thus δ18Ohemicellulose, whereas the effect of temperature changes is of minor importance. While oxygen exchange and degradation effects seem to be negligible, further factors needing consideration when interpreting δ18Ohemicellulose values obtained from (paleo-)soils are evaporative 18O enrichment of soil water, seasonality effects, wind effects and in case of abundant stem/root-derived organic matter input a partial loss of the evaporative 18O enrichment of leaf water. Overall, our results prove that compound-specific δ18O analyses of hemicellulose biomarkers in soils and sediments are a promising tool for paleoclimate research. However, disentangling the two major factors influencing δ18Ohemicellulose, namely δ18Oprec and relative air humidity controlled evaporative 18O enrichment of leaf water, is challenging based on δ18O analyses alone. Although oxygen in hemicelluloses derives from water and thus ultimately from precipitation, the hemicellulose biomarkers arabinose, fucose and xylose do not simply reflect δ18Oprec but rather δ18Oleaf water. The correlation between measured δ18Ohemicellulose and modeled δ18Oleaf water is highly significant (r = 0.81, p < 0.001, n = 20). This finding can be attributed to the evaporative 18O enrichment of leaf water during transpiration. Model sensitivity tests using a Péclet-modified Craig-Gordon (PMCG) model corroborate that relative air humidity is a very rigorous climate parameter influencing δ18Oleaf water, whereas temperature is of minor importance. While oxygen exchange and degradation effects on δ18O values of hemicelluloses sugar biomarkers seem to be negligible (Zech et al., 2012), further effects that need to be considered when interpreting δ18Ohemicellulose values obtained from (paleo-)soils are evaporative 18O enrichment of soil water, seasonality effects, wind effects and in case of abundant stem/root-derived organic matter input a partial loss of the

  3. Characterization of surface and ground water δ18O seasonal variation and its use for estimating groundwater residence times

    USGS Publications Warehouse

    Reddy, Michael M.; Schuster, Paul F.; Kendall, Carol; Reddy, Micaela B.

    2006-01-01

    18O is an ideal tracer for characterizing hydrological processes because it can be reliably measured in several watershed hydrological compartments. Here, we present multiyear isotopic data, i.e. 18O variations (δ18O), for precipitation inputs, surface water and groundwater in the Shingobee River Headwaters Area (SRHA), a well-instrumented research catchment in north-central Minnesota. SRHA surface waters exhibit δ18O seasonal variations similar to those of groundwaters, and seasonal δ18O variations plotted versus time fit seasonal sine functions. These seasonal δ18O variations were interpreted to estimate surface water and groundwater mean residence times (MRTs) at sampling locations near topographically closed-basin lakes. MRT variations of about 1 to 16 years have been estimated over an area covering about 9 km2 from the basin boundary to the most downgradient well. Estimated MRT error (±0·3 to ±0·7 years) is small for short MRTs and is much larger (±10 years) for a well with an MRT (16 years) near the limit of the method. Groundwater transit time estimates based on Darcy's law, tritium content, and the seasonal δ18O amplitude approach appear to be consistent within the limits of each method. The results from this study suggest that use of the δ18O seasonal variation method to determine MRTs can help assess groundwater recharge areas in small headwaters catchments.

  4. The δ15N and δ18O values of N2O produced during the co-oxidation of ammonia by methanotrophic bacteria

    USGS Publications Warehouse

    Mandernack, Kevin W.; Mills, Christopher T.; Johnson, Craig A.; Rahn, Thomas; Kinney, Chad

    2009-01-01

    In order to determine if the δ15N and δ18O values of N2O produced during co-oxidation of NH4+ by methanotrophic (methane oxidizing) bacteria can be isotopically distinguished from N2O produced either by autotrophic nitrifying or denitrifying bacteria, we conducted laboratory incubation experiments with pure cultures of methanotrophic bacteria that were provided NH4Cl as an oxidation substrate. The N2O produced during NH4+ oxidation by methanotrophic bacteria showed nitrogen isotope fractionation between NH4+ and N2O (εN2O–NH4+) of − 48 and − 55‰ for Methylomonas methanica and Methylosinus trichosporium, OB3b respectively. These large fractionations are similar to those previously measured for autotrophic nitrifying bacteria and consistent with N2O formation by multiple rate limiting steps that include NH4+oxidation by the methane monooxygenase enzyme and reduction of NO2− to N2O. Consequently, N2O formed by NH4+ oxidation via methanotrophic or autotrophic nitrifying bacteria might generally be characterized by lower δ15NN2O values than that formed by denitrificaiton, although this also depends on the variability of δ15N of available nitrogen sources (e.g., NH4+, NO3−, NO2−). Additional incubations with M. trichosporium OB3b at high and low CH4 conditions in waters of different δ18O values revealed that 19–27% of the oxygen in N2O was derived from O2 with the remainder from water. The biochemical mechanisms that could explain this amount of O2 incorporation are discussed. The δ18O of N2O formed under high CH4 conditions was ~ + 15‰ more positive than that formed under lower CH4 conditions. This enrichment resulted in part from the incorporation of O2 into N2O that was enriched in 18O due to an isotope fractionation effect of − 16.1 ± 2.0‰ and − 17.5 ± 5.4‰ associated with O2 consumption during the high and low methane concentration incubations, respectively. Therefore, N2O formed by NH4+

  5. 13C and 18O of wood from the Roman siege rampart in Masada, Israel (Ad 70-73): Evidence for a less arid climate for the region

    NASA Astrophysics Data System (ADS)

    Yakir, Dan; Issar, Arie; Gat, Joel; Adar, Eilon; Trimborn, Peter; Lipp, Joseph

    1994-08-01

    The isotopic ratios 13C /12C and 18O /16O of cellulose from tamarix trees which were used by the Roman army as a groundwork of the siege-rampart of Masada ( AD 70-73) were compared with ratios measured in present-day tamarix trees growing in the Masada region and in central Israel. The ancient tamarix cellulose is depleted in both 13C and 18O compared to cellulose from trees growing in the Masada region today. Similar trends were observed on comparing modern tamarix trees growing in the Negev Desert with those growing in the temperate climate of central Israel. Considering the factors that can contribute to the observed changes in isotopic composition, we conclude that the ancient trees enjoyed less arid environmental conditions during their growth compared to contemporary trees in this desert region. This report demonstrates the potential in using combined 18O and 13C analyses of archeological plant material as independent indication of regional climatic change in desert areas (where conventional isotopic analyses, such as in tree rings, are impractical).

  6. Simultaneous 13C/12C and (18)O/(16)O isotope ratio measurements on CO2 based on off-axis integrated cavity output spectroscopy.

    PubMed

    Jost, Hans-Jürg; Castrillo, Antonio; Wilson, H William

    2006-03-01

    A prototype off-axis integrated cavity output spectrometer (OA-ICOS) utilizing two identical cavities together with a near-infrared (1.63 microm) external cavity tunable diode laser is described. The two-cavity design-one for a reference gas and one for a sample gas-takes advantage of classical double-beam infrared spectrometer characteristics in reducing uncertainties due to laser scan or power instabilities and major temperature variations by a factor of three or better compared with a single-cavity scheme. This is the first OA-ICOS instrument designed to determine 13C/12C and (18)O/(16)O ratios from CO2 rotation/vibration fine structure in three different combination bands. Preliminary results indicate that at 0.8 Hz a precision of 3.3 and 2.8 per thousand is obtained for delta13C and delta(18)O, respectively, over a period of 10 h and a pure CO2 gas sample at 26 hPa. By averaging 100 spectra over a subset of the data, we achieved a precision of 1.6 and 0.8 \\permil\\ for delta13C and delta(18)O, respectively. PMID:16500753

  7. Influence of carbonic anhydrase activity in terrestrial vegetation on the 18O content of atmospheric CO2.

    PubMed

    Gillon, J; Yakir, D

    2001-03-30

    The oxygen-18 (18O) content of atmospheric carbon dioxide (CO2) is an important indicator of CO2 uptake on land. It has generally been assumed that during photosynthesis, oxygen in CO2 reaches isotopic equilibrium with oxygen in 18O-enriched water in leaves. We show, however, large differences in the activity of carbonic anhydrase (which catalyzes CO2 hydration and 18O exchange in leaves) among major plant groups that cause variations in the extent of 18O equilibrium (theta(eq)). A clear distinction in theta(eq) between C3 trees and shrubs, and C4 grasses makes atmospheric C18OO a potentially sensitive indicator to changes in C3 and C4 productivity. We estimate a global mean theta(eq) value of approximately 0.8, which reasonably reconciles inconsistencies between 18O budgets of atmospheric O2 (Dole effect) and CO2. PMID:11283366

  8. Influence of Carbonic Anhydrase Activity in Terrestrial Vegetation on the 18O Content of Atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Gillon, Jim; Yakir, Dan

    2001-03-01

    The oxygen-18 (18O) content of atmospheric carbon dioxide (CO2) is an important indicator of CO2 uptake on land. It has generally been assumed that during photosynthesis, oxygen in CO2 reaches isotopic equilibrium with oxygen in 18O-enriched water in leaves. We show, however, large differences in the activity of carbonic anhydrase (which catalyzes CO2 hydration and 18O exchange in leaves) among major plant groups that cause variations in the extent of 18O equilibrium (θeq). A clear distinction in θeq between C3 trees and shrubs, and C4 grasses makes atmospheric C18OO a potentially sensitive indicator to changes in C3 and C4 productivity. We estimate a global mean θeq value of ~0.8, which reasonably reconciles inconsistencies between 18O budgets of atmospheric O2 (Dole effect) and CO2.

  9. ENSO flavors in a tree-ring δ18O record of Tectona grandis from Indonesia

    NASA Astrophysics Data System (ADS)

    Schollaen, K.; Karamperidou, C.; Krusic, P. J.; Cook, E. R.; Helle, G.

    2014-10-01

    Indonesia's climate is dominated by the equatorial monsoon system, and has been linked to El Niño-Southern Oscillation (ENSO) events that often result in extensive droughts and floods over the Indonesian archipelago. In this study we investigate ENSO-related signals in a tree-ring δ18O record (1900-2007) of Javanese teak. Our results reveal a clear influence of Warm Pool (central Pacific) El Niño events on Javanese tree-ring δ18O, and no clear signal of Cold Tongue (eastern Pacific) El Niño events. These results are consistent with the distinct impacts of the two ENSO flavors on Javanese precipitation, and illustrate the importance of considering ENSO flavors when interpreting palaeoclimate proxy records in the tropics.

  10. ENSO flavors in a tree-ring δ18O record of Tectona grandis from Indonesia

    NASA Astrophysics Data System (ADS)

    Schollaen, K.; Karamperidou, C.; Krusic, P.; Cook, E.; Helle, G.

    2015-10-01

    Indonesia's climate is dominated by the equatorial monsoon system, and has been linked to El Niño-Southern Oscillation (ENSO) events that often result in extensive droughts and floods over the Indonesian archipelago. In this study we investigate ENSO-related signals in a tree-ring δ18O record (1900-2007) of Javanese teak. Our results reveal a clear influence of Warm Pool (central Pacific) El Niño events on Javanese tree-ring δ18O, and no clear signal of Cold Tongue (eastern Pacific) El Niño events. These results are consistent with the distinct impacts of the two ENSO flavors on Javanese precipitation, and illustrate the importance of considering ENSO flavors when interpreting palaeoclimate proxy records in the tropics, as well as the potential of palaeoclimate proxy records from appropriately selected tropical regions for reconstructing past variability of. ENSO flavors.

  11. Identification of Highly Fractionated (18)O-Rich Silicate Grains in the Queen Alexandra Range 99177 CR3 Chondrite

    NASA Technical Reports Server (NTRS)

    Nguyen, A. N.; Keller, L. P.; Messenger, S.; Rahman, Z.

    2015-01-01

    Carbonaceous chondrites contain a mixture of solar system condensates, presolar grains, and primitive organic matter. The CR3 chondrite QUE 99177 has undergone minimal al-teration [1], exemplified by abundant presolar silicates [2, 3] and anomalous organic matter [4]. Oxygen isotopic imaging studies of this meteorite have focused on finding submicrometer anomalous grains in fine-grained regions of thin sections. Here we present re-sults of an O isotopic survey of larger matrix grains.

  12. 34S/32S and 18O/16O ratios of dissolved sulfate from interstitial water samples above gas hydrate bearing sediments of IODP Expedition 311, Cascadia

    NASA Astrophysics Data System (ADS)

    Wortmann, U. G.; Chernyavsky, B. M.; Torres, M. E.; Kastner, M.

    2008-12-01

    Microbially mediated sulfate reduction affects the isotopic composition of dissolved and solid sulfur species in marine sediments. Although several details of the fractionation process remain controversial, the overall process is well understood and can be described as the sum of several mass dependent fractionations during the stepwise reduction of sulfate to sulfide. Experiments and field data show that the 18O/16O of sulfate is also modified in the presence of sulfate-reducing microorganisms. Here we use a reaction transport model to analyze these processes and to constrain the rates of organotrophic versus methanotrophic sulfate reduction. Our results show that even in cases where sulfate concentrations decline in a linear fashion, up to 50% of all sulfate is consumed by organotrophic sulfate reduction.

  13. Reducing uncertainty in the climatic interpretations of speleothem δ18O

    NASA Astrophysics Data System (ADS)

    Jex, C. N.; Phipps, S. J.; Baker, A.; Bradley, C.

    2013-05-01

    We explore two principal areas of uncertainty associated with paleoclimate reconstructions from speleothem δ18O (δ18Ospel): potential non-stationarity in relationships between local climate and larger-scale atmospheric circulation, and routing of water through the karst aquifer. Using a δ18Ospel record from Turkey, the CSIRO Mk3L climate system model and the KarstFOR karst hydrology model, we confirm the stationarity of relationships between cool season precipitation and regional circulation dynamics associated with the North Sea-Caspian pattern since 1 ka. Stalagmite δ18O is predicted for the last 500 years, using precipitation and temperature output from the CSIRO Mk3L model and synthetic δ18O of precipitation as inputs for the KarstFOR model. Interannual variability in the δ18Ospel record is captured by KarstFOR, but we cannot reproduce the isotopically lighter conditions of the sixteenth to seventeenth centuries. We argue that forward models of paleoclimate proxies (such as KarstFOR) embedded within isotope-enabled general circulation models are now required.

  14. Significant recent warming over the northern Tibetan Plateau from ice core δ18O records

    NASA Astrophysics Data System (ADS)

    An, W.; Hou, S.; Zhang, W.; Wang, Y.; Liu, Y.; Wu, S.; Pang, H.

    2016-02-01

    Stable oxygen isotopic records in ice cores provide valuable information about past temperature, especially for regions with scarce instrumental measurements. This paper presents the δ18O result of an ice core drilled to bedrock from Mt. Zangser Kangri (ZK), a remote area on the northern Tibetan Plateau (TP). We reconstructed the temperature series for 1951-2008 from the δ18O records. In addition, we combined the ZK δ18O records with those from three other ice cores in the northern TP (Muztagata, Puruogangri, and Geladaindong) to reconstruct a regional temperature history for the period 1951-2002 (RTNTP). The RTNTP showed significant warming at 0.51 ± 0.07 °C (10 yr)-1 since 1970, a higher rate than the trend of instrumental records of the northern TP (0.43 ± 0.08 °C (10 yr)-1) and the global temperature trend (0.27 ± 0.03°C (10 yr)-1) at the same time. In addition, the ZK temperature record, with extra length until 2008, seems to suggest that the rapid elevation-dependent warming continued for this region during the last decade, when the mean global temperature showed very little change. This could provide insights into the behavior of the recent warming hiatus at higher elevations, where instrumental climate records are lacking.

  15. Implications of the 14C(α,γ)18O reaction for nonstandard big bang nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Gai, Moshe

    1992-06-01

    The thermonuclear burning rates for the 14C(α,γ)18O radiative capture reaction are calculated at temperatures (0.318O as would be deduced from the Yale-Michigan State University measurement of the beta-delayed alpha-particle emission of 18N and suggested by the Notre Dame-Caltech measurement of the nonresonant 14C(α,γ)18O cross section. The gamma widths of the proposed broad state is estimated using the Alhassid, Gai, and Bertsch sum rule, and an experimental study is proposed.

  16. Delta(18)O characteristics of lichens and their effects on evaporative processes of the subjacent soil.

    PubMed

    Hartard, Britta; Máguas, C; Lakatos, M

    2008-03-01

    The study presents first data on the delta(18)O performance of poikilohydrous lichen ground cover, and its potential impact on the isotopic composition of water fluxes arising from subjacent soil layers. As a model organism, the globally distributed lichen Cladina arbuscula was studied under laboratory conditions as well as in the field. During a desiccation experiment, delta(18)O of the lichen's thallus water and of its respired CO(2) became enriched by approximately 7 per thousand and followed a similar enrichment pattern to that expected from homoiohydrous, vascular plants. However, the observed degree of enrichment was lower in comparison to vascular plants due to (i) the lichen's inherent lower evaporative resistances; and (ii) a stronger effect of the more depleted surrounding water vapour. In lichens growing in their natural habitat, this specific pattern may show substantial variations depending on prevailing microclimatic conditions. Within a field study, thallus water delta(18)O of lichens principally proved to become more depleted when close to equilibration with the surroundings. It thereby strongly depended on the absorption of surrounding water vapour. Moreover, the results indicate that lichen mats substantially reduce evaporation rates arising from subjacent soil layers, and may alter the isotopic signal of vapour diffusing away from these layers into more depleted values. PMID:18320432

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

    NASA Astrophysics Data System (ADS)

    Liang, Y.; Blake, R. E.

    2002-12-01

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

  18. Regulation of adipogenesis by paracrine factors from adipose stromal-vascular fraction - a link to fat depot-specific differences.

    PubMed

    Meissburger, Bettina; Perdikari, Aliki; Moest, Hansjörg; Müller, Sebastian; Geiger, Matthias; Wolfrum, Christian

    2016-09-01

    Visceral and subcutaneous adipose tissue depots have distinct features and contribute differentially to the development of metabolic dysfunction. We show here that adipocyte differentiation in subcutaneous stromal-vascular fraction (SVF) is increased compared to visceral SVF, however this increased differentiation capacity seems not to be due to changes in the number of adipocyte precursor cells. Rather, we demonstrate that secreted heat-sensitive factors from the SVF can inhibit adipocyte differentiation and that this effect is higher in visceral than in subcutaneous SVF, suggesting that visceral SVF is a source of secreted factors that can inhibit adipocyte formation. In order to explore secreted proteins that potentially inhibit differentiation in visceral preadipocytes we analyzed the secretome of both SVFs which led to the identification of 113 secreted proteins with an overlap of 42%. Further expression analysis in both depots revealed 16 candidates that were subsequently analyzed in a differentiation screen using an adenoviral knockdown system. From this analysis we were able to identify two potential inhibitory candidates, namely decorin (Dcn) and Sparc-like 1 (Sparcl1). We could show that ablation of either candidate enhanced adipogenesis in visceral preadipocytes, while treatment of primary cultures with recombinant Sparcl1 and Dcn blocked adipogenesis in a dose dependent manner. In conclusion, our data suggests that the differences in adipogenesis between depots might be due to paracrine and autocrine feedback mechanisms which could in turn contribute to metabolic homeostasis. PMID:27317982

  19. The oxygen isotope composition of Karoo and Etendeka picrites: High δ18O mantle or crustal contamination?

    NASA Astrophysics Data System (ADS)

    Harris, Chris; le Roux, Petrus; Cochrane, Ryan; Martin, Laure; Duncan, Andrew R.; Marsh, Julian S.; le Roex, Anton P.; Class, Cornelia

    2015-07-01

    Oxygen isotope compositions of Karoo and Etendeka large igneous province (LIP) picrites and picrite basalts are presented to constrain the effects of crustal contamination versus mantle source variation. Olivine and orthopyroxene phenocrysts from lavas and dykes (Mg# 64-80) from the Tuli and Mwenezi (Nuanetsi) regions of the ca 180 Ma Karoo LIP have δ18O values that range from 6.0 to 6.7 ‰. They appear to have crystallized from magmas having δ18O values about 1-1.5 ‰ higher than expected in an entirely mantle-derived magma. Olivines from picrite and picrite basalt dykes from the ca 135 Ma Etendeka LIP of Namibia and Karoo-age picrite dykes from Dronning Maud Land, Antarctica, do not have such elevated δ18O values. A range of δ18O values from 4.9 to 6.0 ‰, and good correlations between δ18O value and Sr, Nd and Pb isotope ratios for the Etendeka picrites are consistent with previously proposed models of crustal contamination. Explanations for the high δ18O values in Tuli/Mwenezi picrites are limited to (1) alteration, (2) crustal contamination, and (3) derivation from mantle with an abnormally high δ18O. Previously, a variety of models that range from crustal contamination to derivation from the `enriched' mantle lithosphere have been suggested to explain high concentrations of incompatible elements such as K, and average ɛNd and ɛSr values of -8 and +16 in Mwenezi (Nuanetsi) picrites. However, the primitive character of the magmas (Mg# 73), combined with the lack of correlation between δ18O values and radiogenic isotopic compositions, MgO content, or Mg# is inconsistent with crustal contamination. Thus, an 18O-enriched mantle source having high incompatible trace element concentration and enriched radiogenic isotope composition is indicated. High δ18O values are accompanied by negative Nb and Ta anomalies, consistent with the involvement of the mantle lithosphere, whereas the high δ18O themselves are consistent with an eclogitic source. Magma δ18

  20. A method for calculating 16O/18O peptide ion ratios for the relative quantification of proteomes.

    PubMed

    Johnson, Kenneth L; Muddiman, David C

    2004-04-01

    A method is described for the identification and relative quantification of proteomes using accurate mass tags (AMT) generated by nLC-dual ESI-FT-ICR-MS on a 7T instrument in conjunction with stable isotope labeling using 16O/18O ratios. AMTs were used for putative peptide identification, followed by confirmation of peptide identity by tandem mass spectrometry. For a combined set of 58 tryptic peptides from bovine serum albumin (BSA) and human transferrin, a mean mass measurement accuracy of 1.9 ppm +/-0.94 ppm (CIM99%) was obtained. This subset of tryptic peptides was used to measure 16O/18O ratios of 0.36 +/- 0.09 (CIM99%) for BSA (micro = 0.33) and 1.48 +/- 0.47 (CIM99%) for transferrin (micro = 1.0) using a method for calculating 16O/18O ratios from overlapping isotopic multiplets arising from mixtures of 16O, 18O1, and 18O2 labeled C-termini. The model amino acid averagine was used to calculate a representative molecular formula for estimating and subtracting the contributions of naturally occurring isotopes solely as a function of peptide molecular weight. The method was tested against simulated composite 16O/18O spectra where peptide molecular weight, 16O/18O ratio, 18O1/18O2 ratios, and number of sulfur atoms were varied. Relative errors of 20% or less were incurred when the 16O/18O ratios were less than three, even for peptides where the number of sulfur atoms was over- or under-estimated. These data demonstrate that for biomarker discovery, it is advantageous to label the proteome representing the disease state with 18O; and the method is not sensitive to variations in 18O1/18O2 ratio. This approach allows a comprehensive differentiation of expression levels and tentative identification via AMTs, followed by targeted analysis of over- and under-expressed peptides using tandem mass spectrometry, for applications such as the discovery of disease biomarkers. PMID:15047049

  1. Analysis of Biogenic Silica and Quartz δ18O Utilizing TC/EA CF-IRMS

    NASA Astrophysics Data System (ADS)

    Menicucci, A. J.; Spero, H. J.; Matthews, J.

    2012-12-01

    Oxygen isotope ratio analyses of inorganic and biogenic silicates, and in particular δ18O values from diatoms, remain underutilized as a tool for paleoenvironmental reconstructions and mineralogical investigations. Measuring the δ18O in silicates is difficult and hazardous in comparison to measurements of carbonate minerals because fluorine reagents are typically utilized to break the covalent Si-O bonds. Necessary equipment to safely manipulate such materials is expensive and not readily available in most laboratories. This difficulty creates a practical limitation on paleoclimate investigations for many researchers to areas where more easily analyzed fossil material (i.e. carbonate fossils) is prevalent. This has resulted in a paucity of paleoclimate data in limnetic environments, continental interiors, and high latitude marine localities where carbonate fossils are sparse or non-existent. Measurements of δ18O from diatoms in areas where significant diatom populations exist are therefore highly desirable. Here we present a new technique to measure δ18O in silicates which is applicable to both biogenic silica and inorganic quartz samples. This new method utilizes polytetrafluoroethylene (PTFE) Teflon (C2F4) powder as a fluorine source. Over 100 inorganic quartz samples, including NBS-28, and 75 biogenic silica samples, both diatomite and fossil grass phytoliths, have been processed. These silicates span an approximate 30‰ range. Cleaned and purified samples are first dehydrated/dehydroxylated by heating to 1050oC under hard vacuum, and then loaded into silver foil sample boats. PTFE Teflon powder and graphite are added, and the samples are analyzed with a TC/EA furnace linked via continuous flow to an isotope ratio mass spectrometer (CF-IRMS). Samples are analyzed at 1450C. Mean sample yield is 92% (±8.6% at 1σ standard deviation). Teflon blanks combusted between silicates indicate no detectable silica remaining in the reaction column in between sample

  2. Reducing uncertainty in the climatic interpretations of speleothem ?18O (Invited)

    NASA Astrophysics Data System (ADS)

    Jex, C.; Phipps, S. J.; Baker, A.; Bradley, C.; Treble, P. C.

    2013-12-01

    Speleothem δ18O (δ18Ospel) is an excellent proxy for terrestrial palaeoclimate reconstruction. The δ18O of cave drip water from which a speleothem forms, records the isotopic composition of the water that infiltrates into the deep soil layers and the karst aquifer. Interpretations of δ18Ospel therefore depend upon adequate constraints on: i. the atmospheric controls on precipitation δ18O (δ18Op), and ii. the 'non-climatic' controls that dictate the nature and duration of transmission of this meteoric input through the karst aquifer and into the cave as drip water. Monitoring of cave systems and analysis of local and regional controls on modern day climate parameters and δ18Op are commonplace to aid interpretations of δ18Ospel, and to establish transfer functions between climatic parameters and δ18Ospel over instrumental time periods. However, subsequent climate reconstructions still depend upon two key assumptions: i. potential non-stationarity in the relationships between local climate and the larger-scale atmospheric circulation; and ii. routing of water through the karst aquifer. These are arguably the dominant sources of uncertainty in the climatic interpretations of δ18Ospel. We explore these two areas of uncertainty, using a δ18Ospel record from Turkey, the CSIRO Mk3L climate system model and the KarstFOR karst hydrology model. We confirm the stationarity of relationships between cool season precipitation and regional circulation dynamics associated with the North Sea - Caspian Pattern over the last 1000 years. Stalagmite δ18O is predicted for the last 500 years, using simulated precipitation and temperature from the CSIRO Mk3L model and synthetic precipitation δ18O as inputs to the KarstFOR model. Interannual variability in the δ18Ospel record is captured by KarstFOR, but we cannot reproduce the isotopically lighter conditions of the 16th to 17th Centuries. We argue that forward models of paleoclimate proxies (such as KarstFOR) embedded within

  3. Photorespiratory Rates in Wheat and Maize as Determined by 18O-Labeling 1

    PubMed Central

    de Veau, Edward J.; Burris, John E.

    1989-01-01

    A method was devised to quantify short-term photorespiratory rates in terrestrial plants using 18O-intermediates of the glycolate pathway, specifically glycolate, glycine, and serine. The pathway intermediates were isolated and analyzed on a GC/MS to determine molecular percent 18O-enrichment. Rates of glycolate synthesis were determined from 18O-labeling kinetics of the intermediates, derived rate equations, and nonlinear regression techniques. Glycolate synthesis in wheat (Triticum aestivum L.), a C3 plant, and maize (Zea mays L.), a C4 plant, was stimulated by high O2 concentrations and inhibited by high CO2 concentrations. The synthesis rates were 7.3, 2.1, and 0.7 micromoles per square decimeter per minute under a 21% O2 and 0.035% CO2 atmosphere for leaf tissue of wheat, maize seedlings, and 3-month-old maize, respectively. Photorespiratory CO2 evolution rates were estimated to be 27, 6, and 2%, respectively, of net photosynthesis for the three groups of plants under the above atmosphere. The results from maize tissue support the hypothesis that C4 plants photorespire, albeit at a reduced rate in comparison to C3 plants, and that the CO2/O2 ratio in the bundle sheath of maize is higher in mature tissue than in seedling tissue. The pool size of the three photorespiratory intermediates remained constant and were unaffected by changes in either CO2 or O2 concentrations throughout the 10-minute labeling period. This suggests that photorespiratory metabolism is regulated by other mechanism besides phosphoglycolate synthesis by ribulose-1,5-bisphosphate carboxylase/oxygenase, at least under short-term conditions. Other mechanisms could be alternate modes of synthesis of the intermediates, regulation of some of the enzymes of the photorespiratory pathway, or regulation of carbon flow between organelles involved in photorespiration. The glycolate pool became nearly 100% 18O-labeled under an atmosphere of 40% O2. This pool failed to become 100% 18O-enriched under

  4. Isotopologue fractionation during N(2)O production by fungal denitrification.

    PubMed

    Sutka, Robin L; Adams, Gerard C; Ostrom, Nathaniel E; Ostrom, Peggy H

    2008-12-01

    Identifying the importance of fungi to nitrous oxide (N2O) production requires a non-intrusive method for differentiating between fungal and bacterial N2O production such as natural abundance stable isotopes. We compare the isotopologue composition of N2O produced during nitrite reduction by the fungal denitrifiers Fusarium oxysporum and Cylindrocarpon tonkinense with published data for N2O production during bacterial nitrification and denitrification. The fractionation factors for bulk nitrogen isotope values for fungal denitrification were in the range -74.7 to -6.6 per thousand. There was an inverse relationship between the absolute value of the fractionation factors and the reaction rate constant. We interpret this in terms of variation in the relative importance of the rate constants for diffusion and enzymatic reduction in controlling the net isotope effect for N2O production during fungal denitrification. Over the course of nitrite reduction, the delta(18)O values for N2O remained constant and did not exhibit a relationship with the concentration characteristic of an isotope effect. This probably reflects isotopic exchange with water. Similar to the delta(18)O data, the site preference (SP; the difference in delta(15)N between the central and outer N atoms in N2O) was unrelated to concentration during nitrite reduction and, therefore, has the potential to act as a conservative tracer of production from fungal denitrification. The SP values of N2O produced by F. oxysporum and C. tonkinense were 37.1 +/- 2.5 per thousand and 36.9 +/- 2.8 per thousand, respectively. These SP values are similar to those obtained in pure culture studies of bacterial nitrification but quite distinct from SP values for bacterial denitrification. The large magnitude of the bulk nitrogen isotope fractionation and the delta(18)O values associated with fungal denitrification are distinct from bacterial production pathways; thus multiple isotopologue data holds much promise for

  5. Liquid-Vapor Equilibrium Isotopic Fractionation of Water. How well can classical water models predict it?

    SciTech Connect

    Chialvo, Ariel A; Horita, Juske

    2009-01-01

    The liquid-vapor equilibrium isotopic fractionation of water is determined by molecular-based simulation, via Gibbs Ensemble Monte Carlo and isothermal-isochoric molecular dynamics involving two radically different but realistic models, the extended simple point charge (SPC/E) and the Gaussian charge polarizable (GCP) models. The predicted temperature dependence of the liquid-vapor equilibrium isotopic fractionation factors for H 2 18O / H 2 16O, H 2 17O / H 2 16O, and 2H 1H 16O / 1H 2 16O are compared against the most accurate experimental datasets to assess the ability of these intermolecular potential models to describe quantum effects according to the Kirkwood-Wigner free energy perturbation ! 2 !expansion. Predictions of the vapor pressure isotopic effect for the H 2 18O / H 2 16O and H 2 17O / H 2 16O pairs are also presented in comparison with experimental data and two recently proposed thermodynamic modeling approaches. Finally, the simulation results are used to discuss some approximations behind the microscopic interpretation of isotopic fractionation based on the underlying roto-translational coupling.

  6. Method for selective recovery of PET-usable quantities of [.sup.18 F] fluoride and [.sup.13 N] nitrate/nitrite from a single irradiation of low-enriched [.sup.18 O] water

    DOEpatents

    Ferrieri, Richard A.; Schlyer, David J.; Shea, Colleen

    1995-06-13

    A process for simultaneously producing PET-usable quantities of [.sup.13 N]NH.sub.3 and [.sup.18 F]F.sup.- for radiotracer synthesis is disclosed. The process includes producing [.sup.13 N]NO.sub.2.sup.- /NO.sub.3.sup.- and [.sup.18 F]F.sup.- simultaneously by exposing a low-enriched (20%-30%) [.sup.18 O]H.sub.2 O target to proton irradiation, sequentially isolating the [.sup.13 N]NO.sub.2.sup.- /NO.sub.3.sup.- and [.sup.18 F]F.sup.- from the [.sup.18 O]H.sub.2 O target, and reducing the [.sup.13 N]NO.sub.2.sup.- /NO.sub.3.sup.- to [.sup.13 N]NH.sub.3. The [.sup.13 N]NH.sub.3 and [.sup.18 F]F.sup.- products are then conveyed to a laboratory for radiotracer applications. The process employs an anion exchange resin for isolation of the isotopes from the [.sup.18 O]H.sub.2 O, and sequential elution of [.sup.13 N]NO.sub.2.sup.- /NO.sub.3.sup.- and [ .sup.18 F]F.sup.- fractions. Also the apparatus is disclosed for simultaneously producing PET-usable quantities of [.sup.13 N]NH.sub.3 and [.sup.18 F]F.sup.- from a single irradiation of a single low-enriched [.sup.18 O]H.sub.2 O target.

  7. Ca isotope stratigraphy across the Cenomanian-Turonian OAE 2: Links between volcanism, seawater geochemistry, and the carbonate fractionation factor

    NASA Astrophysics Data System (ADS)

    Du Vivier, Alice D. C.; Jacobson, Andrew D.; Lehn, Gregory O.; Selby, David; Hurtgen, Matthew T.; Sageman, Bradley B.

    2015-04-01

    The Ca isotope composition of marine carbonate rocks offers potential to reconstruct drivers of environmental change in the geologic past. This study reports new, high-precision Ca isotope records (δ44/40Ca; 2σSD = ± 0.04 ‰) for three sections spanning a major perturbation to the Cretaceous ocean-climate system known as Ocean Anoxic Event 2 (OAE 2): central Colorado, USA (Portland #1 core), southeastern France (Pont d'Issole), and Hokkaido, Japan (Oyubari, Yezo Group). In addition, we generated new data for selected samples from Eastbourne, England (English Chalk), where a previous Ca isotope study was completed using different methodology (Blättler et al., 2011). Strata of the Yezo Group contain little carbonate (∼1 wt.% on average) and accordingly did not yield a clear δ44/40Ca signal. The Portland core and the Pont d'Issole section display comparable δ44/40Ca values, which increase by ∼ 0.10- 0.15 ‰ at the onset of OAE 2 and then decrease to near-initial values across the event. The Eastbourne δ44/40Ca values are higher than previously reported. They are also higher than the δ44/40Ca values for the Portland core and the Pont d'Issole section but define a similar pattern. According to a numerical model of the marine Ca cycle, elevated hydrothermal inputs have little impact on seawater δ44/40Ca values. Elevated riverine (chemical weathering) inputs produce a transient negative isotope excursion, which significantly differs from the positive isotope excursions observed in the Portland, Pont d'Issole, and Eastbourne records. A decrease in the magnitude of the carbonate fractionation factor provides the best explanation for a positive shift in δ44/40Ca values, especially given the rapid nature of the excursion. Because a decrease in the fractionation factor corresponds to an increase in the Ca/CO3 ratio of seawater, we tentatively attribute the positive Ca isotope excursion to transient ocean acidification, i.e., a reduction in the concentration of

  8. Fractionated stereotactic radiotherapy in patients with benign or atypical intracranial meningioma: Long-term experience and prognostic factors

    SciTech Connect

    Milker-Zabel, Stefanie . E-mail: stefanie_milker-zabel@med.uni-heidelberg.de; Zabel, Angelika; Schulz-Ertner, Daniela; Schlegel, Wolfgang; Wannenmacher, Michael; Debus, Juergen

    2005-03-01

    Purpose: To analyze our long-term experience and prognostic factors after fractionated stereotactic radiotherapy (FSRT) in patients with benign or atypical intracranial meningioma. Methods and materials: Between January 1985 and December 2001, 317 patients with a median age of 55.7 years were treated with FSRT for intracranial meningioma. The tumor distribution was World Health Organization (WHO) Grade 1 in 48.3%, WHO Grade 2 in 8.2%, and unknown in 43.5%. Of the 317 patients, 97 underwent RT as their primary treatment, 79 underwent postoperative RT (subtotal resection in 38 and biopsy only in 41), and 141 were treated for recurrent disease. The median target volume was 33.6 cm{sup 3} (range, 1.0-412.6 cm{sup 3}). The median total dose was 57.6 Gy at 1.8 Gy/fraction five times weekly. Results: The median follow-up was 5.7 years (range, 1.2-14.3 years). The overall local tumor control rate was 93.1% (295 of 317). Of the 317 patients, 72 had a partial response on CT/MRI and 223 (70.4%) remained stable. At a median of 4.5 years after FSRT, 22 patients (6.9%) had local tumor progression on MRI. Local tumor failure was significantly greater in patients with WHO Grade 2 meningioma (p < 0.002) than in patients with WHO Grade 1 or unknown histologic features. Patients treated for recurrent meningioma showed a trend toward decreased progression-free survival compared with patients treated with primary therapy, after biopsy, or after subtotal resection (p < 0.06). Patients with a tumor volume >60 cm{sup 3} had a recurrence rate of 15.5% vs. 4.3% for those with a tumor volume of {<=}60 cm{sup 3} (p < 0.001). In 42.9% of the patients, preexisting neurologic deficits improved. Worsening of preexisting neurologic symptoms occurred in 8.2%. Eight patients developed new clinical symptoms, such as reduced vision, trigeminal neuralgia, and intermittent tinnitus located at the side of the irradiated meningioma after FSRT. Conclusion: These data have demonstrated that FSRT is an

  9. Risk factors for chronic undernutrition among children in India: Estimating relative importance, population attributable risk and fractions.

    PubMed

    Corsi, Daniel J; Mejía-Guevara, Iván; Subramanian, S V

    2016-05-01

    Nearly 40% of the world's stunted children live in India and the prevalence of undernutrition has been persistently high in recent decades. Given numerous available interventions for reducing undernutrition in children, it is not clear of the relative importance of each within a multifactorial framework. We assess the simultaneous contribution of 15 known risk factors for child chronic undernutrition in India. Data are from the 3rd Indian National Family Health Survey (NFHS-3), a nationally representative cross-sectional survey undertaken in 2005-2006. The study population consisted of children aged 6-59 months [n = 26,842 (stunting/low height-for-age), n = 27,483 (underweight/low weight-for-age)]. Risk factors examined for their association with undernutrition were: vitamin A supplementation, vaccination, use of iodized salt, household air quality, improved sanitary facilities, safe disposal of stools, improved drinking water, prevalence of infectious disease, initiation of breastfeeding, dietary diversity, age at marriage, maternal BMI, height, education, and household wealth. Age/sex-adjusted and multivariable adjusted effect sizes (odds ratios) were calculated for risk factors along with Population Attributable Risks (PAR) and Fractions (PAF) using logistic regression. In the mutually adjusted models, the five most important predictors of childhood stunting/underweight were short maternal stature, mother having no education, households in lowest wealth quintile, poor dietary diversity, and maternal underweight. These five factors had a combined PAR of 67.2% (95% CI: 63.3-70.7) and 69.7% (95% CI: 66.3-72.8) for stunting and underweight, respectively. The remaining factors were associated with a combined PAR of 11.7% (95% CI: 6.0-17.4) and 15.1% (95% CI: 8.9-21.3) for stunting and underweight, respectively. Implementing strategies focused on broader progress on social circumstances and infrastructural domains as well as investments in nutrition specific

  10. The influence of clouds and diffuse radiation on ecosystem-atmosphere CO2 and CO18O exhanges

    SciTech Connect

    Still, C.J.; Riley, W.J.; Biraud, S.C.; Noone, D.C.; Buenning, N.H.; Randerson, J.T.; Torn, M.S.; Welker, J.; White, J.W.C.; Vachon, R.; Farquhar, G.D.; Berry, J.A.

    2009-05-01

    This study evaluates the potential impact of clouds on ecosystem CO{sub 2} and CO{sub 2} isotope fluxes ('isofluxes') in two contrasting ecosystems (a broadleaf deciduous forest and a C{sub 4} grassland), in a region for which cloud cover, meteorological, and isotope data are available for driving the isotope-enabled land surface model, ISOLSM. Our model results indicate a large impact of clouds on ecosystem CO{sub 2} fluxes and isofluxes. Despite lower irradiance on partly cloudy and cloudy days, predicted forest canopy photosynthesis was substantially higher than on clear, sunny days, and the highest carbon uptake was achieved on the cloudiest day. This effect was driven by a large increase in light-limited shade leaf photosynthesis following an increase in the diffuse fraction of irradiance. Photosynthetic isofluxes, by contrast, were largest on partly cloudy days, as leaf water isotopic composition was only slightly depleted and photosynthesis was enhanced, as compared to adjacent clear sky days. On the cloudiest day, the forest exhibited intermediate isofluxes: although photosynthesis was highest on this day, leaf-to-atmosphere isofluxes were reduced from a feedback of transpiration on canopy relative humidity and leaf water. Photosynthesis and isofluxes were both reduced in the C{sub 4} grass canopy with increasing cloud cover and diffuse fraction as a result of near-constant light limitation of photosynthesis. These results suggest that some of the unexplained variation in global mean {delta}{sup 18}O of CO{sub 2} may be driven by large-scale changes in clouds and aerosols and their impacts on diffuse radiation, photosynthesis, and relative humidity.

  11. A tree-ring cellulose δ18O-based July-October precipitation reconstruction since AD 1828, northwest Thailand

    NASA Astrophysics Data System (ADS)

    Xu, Chenxi; Pumijumnong, Nathsuda; Nakatsuka, Takeshi; Sano, Masaki; Li, Zhen

    2015-10-01

    A tree-ring δ18O chronology for the period 1828-2000 was developed from four Pinus merkusii trees, to find a reliable proxy for reconstructing precipitation in northwest Thailand. Inter-tree δ18O correlations were high during the entire period (r = 0.57-0.79). The tree-ring δ18O chronology shows significant negative correlations with regional July-October precipitation during the period 1901-2000 (r = -0.62) and with July-October river flow (r = -0.54), and is in good agreement with a shorter tree-ring δ18O chronology from living Pinus kesiya in northwest Thailand. The spatial correlation analysis between tree-ring δ18O and regional July-October precipitation also support that the tree-ring δ18O of P. merkusii is a promising proxy to reconstruct precipitation in northwest Thailand. The tree-ring δ18O-based July-October reconstruction, which accounts for 37.6% of the precipitation variance, shows a close relationship with El Niño-Southern Oscillation (ENSO) during the period 1871-2000, with the exception of during the past two decades; the exception may be related to the southeastward shift of the descending limb of Walker circulation and increased frequency of central Pacific ENSO.

  12. Factors controlling the carbon isotope fractionation of tetra- and trichloroethene during reductive dechlorination by Sulfurospirillum ssp. and Desulfitobacterium sp. strain PCE-S.

    PubMed

    Cichocka, Danuta; Siegert, Michael; Imfeld, Gwenaël; Andert, Janet; Beck, Kirsten; Diekert, Gabriele; Richnow, Hans-Hermann; Nijenhuis, Ivonne

    2007-10-01

    Carbon stable isotope fractionation of tetrachloroethene (PCE) and trichloroethene (TCE) was investigated during reductive dechlorination. Growing cells of Sulfurospirillum multivorans, Sulfurospirillum halorespirans, or Desulfitobacterium sp. strain PCE-S, the respective crude extracts and the abiotic reaction with cyanocobalamin (vitamin B(12)) were used. Fractionation of TCE (alphaC=1.0132-1.0187) by S. multivorans was more than one order of magnitude higher than values previously observed for tetrachloroethene (PCE) (alphaC=1.00042-1.0017). Similar differences in fractionation were observed during reductive dehalogenation by the close relative S. halorespirans with alphaC=1.0046-1.032 and alphaC=1.0187-1.0229 for PCE and TCE respectively. TCE carbon isotope fractionation (alphaC=1.0150) by the purified PCE-reductive dehalogenase from S. multivorans was more than one order of magnitude higher than fractionation of PCE (alphaC=1.0017). Carbon isotope fractionation of TCE by Desulfitobacterium sp. strain PCE-S (alphaC=1.0109-1.0122) as well as during the abiotic reaction with cyanocobalamin (alphaC=1.0154) was in a similar range to previously reported values for fractionation by mixed microbial cultures. In contrast with previous results with PCE, no effects due to rate limitations, uptake or transport of the substrate to the reactive site could be observed during TCE dechlorination. Our results show that prior to a mechanistic interpretation of stable isotope fractionation factors it has to be carefully verified how other factors such as uptake or transport affect the isotope fractionation during degradation experiments with microbial cultures. PMID:17908097

  13. East China Sea δ18O Record Detects Millennial-Scale Changes in the East Asian Summer Monsoon

    NASA Astrophysics Data System (ADS)

    Gleeman, E.; Clemens, S. C.; Lawman, A. E.; Kubota, Y.; Holbourn, A. E.; Martin, A.

    2015-12-01

    The East Asian Summer Monsoon (EASM) brings heavy summer rainfall to some of Asia's most densely-populated areas, impacting agricultural production and water resources. Sediment cores were recovered from International Ocean Drilling Program Site U1429 in the East China Sea (31° 37.04' N, 128° 59.50' E, 732 mbsl). This location receives runoff from the Yangtze River, which serves as a major drainage system for monsoon-induced precipitation. Hence, the δ18O record of planktonic foraminifera at Site U1429 reflects changes in regional, monsoon-driven salinity. The top 100 meters of core at Site U1429 were sampled at a preliminary resolution of 15 cm and processed to isolate the planktonic foraminifer Globigerinoides ruber for δ18O mass spectrometry analyses. Abrupt, millennial-scale regional climate variability in the EASM and its linkage to orbital forcings have been reconstructed using stratigraphic analysis of δ18O. The sub-orbital scale structure of the δ18O record over the past 400 kyr matches the structures of both the composite speleothem δ18O from eastern China (Sanbao and Hulu caves) and the planktonic δ18O record from northern South China Sea Site 1146. The similarities between these δ18O records indicate a strong regional response to monsoon forcing. Removal of the temperature component of the δ18O signal by using Mg/Ca (G. ruber) paleothermometry will provide a record of changes in the δ18O composition of seawater in response to Yangtze River runoff.

  14. Effect of photosynthesis on the abundance of 18O13C16O in atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Hofmann, Magdalena E. G.; Pons, Thijs L.; Ziegler, Martin; Lourens, Lucas J.; Röckmann, Thomas

    2016-04-01

    leaf so that the CO2 concentration at the outlet was 400 ppm and varied between 0.6 and 1.5 L min‑1. CO2 and H2O concentrations in air were monitored with an IRGA and air was sampled at the outlet with flasks. We found that the effect on Δ47 of the residual CO2 for the C3 species sunflower and ivy was proportional to the effect on δ18O of the residual CO2. The difference in Δ47 between the in- and outgoing CO2 was between -0.07 and 0.49‰ varying with the CO2 concentration in the chloroplasts relative to the bulk air (Cc/Ca). The Cc/Ca depends on conductance and photosynthetic activity, and was different for the two species and was manipulated with the light intensity. For the C4 species maize, a Δ47 value of -0.08±0.02‰ was observed. The slightly negative effect on Δ47may be related to its lower Cc/Ca ratio and possibly a lower carbonic anhydrase activity causing incomplete exchange with leaf water. We will discuss these results in light of the suggested fractionation processes and discuss the implication for the global Δ47 value of atmospheric CO2. References Affek H. P. and Eiler J. M., GCA 70, 1-12 (2006). Affek H. P., Xu X. and Eiler J. M., GCA 71, 5033-5043 (2007). Eiler J. M. and Schauble E., GCA 68, 4767-4777 (2004).

  15. Archean high δ18O Mg-diorite: crustal-derived melt hybridized with enriched mafic accumulated rocks

    NASA Astrophysics Data System (ADS)

    Wang, Dan; Guo, Jing-Hui

    2016-04-01

    The genesis of Mg-diorite or sanukitoids has significances to understand the crustal growth and tectonic style in Archean. The chemical compositions of minerals and rocks, whole-rock Sm-Nd isotope, zircon SIMS U-Pb ages and Hf-O isotopes of Zhulagou (ZLG) Mg-diorite and their mafic enclaves (Yinshan Block, North China Craton) were studied to place constraints on their sources and genesis, and therefore provide information about dynamic processes. The ~2520 Ma ZLG diorites have intermediate SiO2 (59.4-65.5 wt.%), high Mg# (49-52), Cr (90.4-438 ppm), Ni (15.0-95.9 ppm), Sr (436-882 ppm) and Ba (237-1206 ppm) contents with fractionated rare earth elements (REE, LaN/YbN = 9.1-40.5) and depleted high field-strength element (HFSE, e.g. Nb, Ta and Ti). These geochemical signatures are similar to those Archean high-Mg diorites and sanukitoids. However, they are sodic with low K2O/Na2O (0.14-0.49) ratios, exhibiting an affinity with Archean trondhjemite-tonalite-granodiorite (TTG). Abundant coeval amphibole-bearing mafic enclaves (~2525 Ma) are enclosed within the ZLG diorites. They display low SiO2 (46.5-50.3 wt.%) contents but high concentrations of MgO (9.0-14.5 wt.%), Cr (647-1946 ppm) and Ni (197-280 ppm). They are enriched in K2O (0.64-3.43 wt.%) and large ion lithophile element (LILE), depleted in Nb, Ta and Ti. Combined with their concave REE patterns and prominent negative Eu anomaly, we suggest that they are cumulates of the melt which probably derived from subduction-related Archean metasomatized mantle source. Mineral trace element modelling results, similar ɛNd(t) (+0.6 to +2.3) and δ18O(Zrc) values (~8.6-9.0 ‰) of the diorites and mafic enclaves, strongly reflect that they had experienced intense interaction and hybridization. Evolved whole-rock Nd isotopes (TDM = 2.80-2.70 Ga), variable zircon ɛHf (t) (-1.6 to +6.0) and high δ18O (~9.0 ‰) values of the diorites indicate that they most likely originated from melting of an older continental crust (≥ 2

  16. Reconstructing lake evaporation history and the isotopic composition of precipitation by a coupled δ18O-δ2H biomarker approach

    NASA Astrophysics Data System (ADS)

    Hepp, Johannes; Tuthorn, Mario; Zech, Roland; Mügler, Ines; Schlütz, Frank; Zech, Wolfgang; Zech, Michael

    2015-10-01

    Over the past decades, δ18O and δ2H analyses of lacustrine sediments became an invaluable tool in paleohydrology and paleolimnology for reconstructing the isotopic composition of past lake water and precipitation. However, based on δ18O or δ2H records alone, it can be challenging to distinguish between changes of the precipitation signal and changes caused by evaporation. Here we propose a coupled δ18O-δ2H biomarker approach that provides the possibility to disentangle between these two factors. The isotopic composition of long chain n-alkanes (n-C25, n-C27, n-C29, n-C31) were analyzed in order to establish a 16 ka Late Glacial and Holocene δ2H record for the sediment archive of Lake Panch Pokhari in High Himalaya, Nepal. The δ2Hn-alkane record generally corroborates a previously established δ18Osugar record reporting on high values characterizing the deglaciation and the Older and the Younger Dryas, and low values characterizing the Bølling and the Allerød periods. Since the investigated n-alkane and sugar biomarkers are considered to be primarily of aquatic origin, they were used to reconstruct the isotopic composition of lake water. The reconstructed deuterium excess of lake water ranges from +57‰ to -85‰ and is shown to serve as proxy for the evaporation history of Lake Panch Pokhari. Lake desiccation during the deglaciation, the Older Dryas and the Younger Dryas is affirmed by a multi-proxy approach using the Hydrogen Index (HI) and the carbon to nitrogen ratio (C/N) as additional proxies for lake sediment organic matter mineralization. Furthermore, the coupled δ18O and δ2H approach allows disentangling the lake water isotopic enrichment from variations of the isotopic composition of precipitation. The reconstructed 16 ka δ18Oprecipitation record of Lake Panch Pokhari is well in agreement with the δ18O records of Chinese speleothems and presumably reflects the Indian Summer Monsoon variability.

  17. Impact of Forest Fires on Tree-Ring δ13C and δ18O of Gmelinii Larch in the Permafrost Zone

    NASA Astrophysics Data System (ADS)

    Knorre, Anastasia; Kirdyanov, Alexander; Saurer, Matthias; Siegwolf, Rolf; Sidorova, Olga; Prokushkin, Anatoly

    2013-04-01

    Forest fire is one of the most important environmental factors which define forest ecosystem functioning in the continuous permafrost zone in the north of Siberia. Tree-ring width (TRW) and stable isotope (13C/12C and 18O/16O) chronologies from two Larix Gmelinii sites with initially different conditions (wet and dry) and characterized by different fire history (fires in 1852 at wet and 1896 at dry sites, respectively) were considered. It was found that the rate of tree radial growth is enlarged due to the increased depth of seasonally thawing soil layer after fire. This effect is well pronounced during the consequent 30-60 years after the fire event and the length of this period depends on the fire intensity and the type of post-fire ground vegetation. TRW and δ18O are identified to be the most sensitive parameters to the changes of tree growth condition after fire. Correlations between these tree-ring parameters from the two sites shift from significantly positive (r=0.40; p<0.05 for TRW and r=0.62; p<0.05 for δ18O) before to negative (r=-0.52; p<0.05 for TRW and r=-0.38; p<0.05 for δ18O) after fire. In ~30-40 years correlations return to be positive, and faster recovery for TRW than for δ18O is observed. Values of δ13C in tree-rings from the two sites are highly positively correlated (r=0.56; p<0.05) during all considered periods independently of the fire impact. This fact indicates that δ13C chronologies should be more adequate for climatic reconstruction in the region because of the climate signal consistency. However, comparative analyses of prior and post-fire climatic response of the dendrochronological parameters indicate sufficient? significant changes in tree-ring growth and isotopic ratio response to climate due to the increased demand of water for trees during the post-fire period (deeper seasonal retreat of permafrost). The results obtained imply a higher impact of forest fires on the permafrost ecosystem under projected climate change because

  18. Past break-monsoon conditions detectable by high resolution intra-annual δ18O analysis of teak rings

    NASA Astrophysics Data System (ADS)

    Managave, S. R.; Sheshshayee, M. S.; Borgaonkar, H. P.; Ramesh, R.

    2010-03-01

    Intra-annual variations in the cellulose oxygen isotopic composition (δ18O) of several annual growth rings of three teak (Tectona grandis L.F.) trees from central India show a clear seasonal cycle with higher values in the early and late growing seasons and lower values in the middle. This cycle is useful to identify growth occurring during different phases of the growing season. Relative humidity (RH) appears to control the intra-annual δ18O variations rather than rainfall, and therefore past break-monsoon conditions associated with lower RH, could be detected by high resolution sub-sampling of annual rings for δ18O analysis.

  19. Mapping the Hydrogen Bond Networks in the Catalytic Subunit of Protein Kinase A Using H/D Fractionation Factors.

    PubMed

    Li, Geoffrey C; Srivastava, Atul K; Kim, Jonggul; Taylor, Susan S; Veglia, Gianluigi

    2015-07-01

    Protein kinase A is a prototypical phosphoryl transferase, sharing its catalytic core (PKA-C) with the entire kinase family. PKA-C substrate recognition, active site organization, and product release depend on the enzyme's conformational transitions from the open to the closed state, which regulate its allosteric cooperativity. Here, we used equilibrium nuclear magnetic resonance hydrogen/deuterium (H/D) fractionation factors (φ) to probe the changes in the strength of hydrogen bonds within the kinase upon binding the nucleotide and a pseudosubstrate peptide (PKI5-24). We found that the φ values decrease upon binding both ligands, suggesting that the overall hydrogen bond networks in both the small and large lobes of PKA-C become stronger. However, we observed several important exceptions, with residues displaying higher φ values upon ligand binding. Notably, the changes in φ values are not localized near the ligand binding pockets; rather, they are radiated throughout the entire enzyme. We conclude that, upon ligand and pseudosubstrate binding, the hydrogen bond networks undergo extensive reorganization, revealing that the open-to-closed transitions require global rearrangements of the internal forces that stabilize the enzyme's fold. PMID:26030372

  20. Source identification of different size fraction of PM10 using factor analysis at residential cum commercial area of Nagpur city.

    PubMed

    Pipalatkar, P P; Gajghate, D G; Khaparde, V V

    2012-02-01

    Particulate size distribution of PM(10) and associated trace metal concentrations has been carried out in residential cum commercial area of Mahal at Nagpur city. Sampling for size fraction of particulate matter was performed during winter season using eight-stage cascade impactor with a pre-separator and toxic metals were analyzed using inductively coupled plasma-optical emission spectroscopy (ICP-OES). The average concentration of PM(10) and fine particulate matter (effective cut of aerodynamic diameter ≤2.2 μm) was found to be 300 and 136.7 μg/m(3), respectively which was exceeding limit of Central Pollution Control Board. Maximum mass concentration of 41 μg/m(3) in size range of 9.0-10.0 μm and minimum mass concentration of 19 μg/m(3) in size range 2.2-3.3 μm was observed. Metals (Sr, Ni and Zn) were found to large proportions in below 0.7 μm particle size and could therefore pass directly into the alveoli region of human respiratory system. Factor analysis results indicated combustion and vehicular emission as the dominant source in fine mode and resuspended dust was dominant in medium mode while crustal along with vehicular source was major in coarse mode of particulate matter. PMID:22033656

  1. Reconstructing climate processes driving variability in precipitation sources from mid to late Holocene speleothem δ18O records from the Southwest US

    NASA Astrophysics Data System (ADS)

    Wong, C. I.; Nusbaumer, J. M.; Banner, J.

    2015-12-01

    Independent co-variation of speleothem δ18O values and other moisture-sensitive speleothem proxies (e.g., growth rate, trace element concentrations) in recently published Holocene stalagmite records from Texas and New Mexico suggest a decoupling between precipitation amounts and precipitation sources over the southwest US. There is, however, limited understanding of the relation between precipitation sources and precipitation amounts and the climate processes governing variability in the region's precipitation sources. To address this, we use source water tags to track precipitation derived from Pacific and Atlantic Oceans during a simulation of modern (1975-2013) climate. We find distinct patterns in the spatial distribution of the fraction of Pacific-derived winter precipitation are associated with unique atmospheric states. High pressure ridging reflected by 500 hPa geopotential heights result in weaker zonal winds and stronger northerly winds over the western US. Under these conditions, Pacific-derived moisture propagates further to the east, and Atlantic-derived moisture is suppressed over southern US. Conversely, 500 hPa geopotential heights that are latitudinally streamline result in strong zonal winds across the entire US. Under these conditions, the fraction of West Pacific-derived precipitation is limited to higher latitudes, and the fraction of far East Pacific- and Atlantic-derived precipitation is enhanced across the Southwest and Southern US, respectively. Further analysis of this data set will assess the teleconnections that link the distinct atmospheric conditions over the US with the state of the ocean and atmosphere over the Pacific and Atlantic Oceans. The results will be applied to reconstructing variability in the climate dynamics governing moisture transport to the southwest US during the mid to late Holocene as reflected by speleothem δ18O records in the region.

  2. The effect of carbonic anhydrase on the kinetics and equilibrium of the oxygen isotope exchange in the CO2-H2O system: Implications for δ18O vital effects in biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Uchikawa, Joji; Zeebe, Richard E.

    2012-10-01

    equilibrium is nearly halved by the presence of 3.7 × 10-9 M of CA used for the experiments. Despite its significant influence on the oxygen isotope exchange kinetics, the equilibrium oxygen isotope fractionation between individual DIC species and H2O is unaffected by CA. Because many CaCO3-secreting organisms possess active CA, our findings imply that 18O equilibration of the CO2-H2O system is possible within realistic timescales of biogenic calcification.

  3. Thermal neutron capture cross sections for 16,171,18O and 2H

    NASA Astrophysics Data System (ADS)

    Firestone, R. B.; Revay, Zs.

    2016-04-01

    Thermal neutron capture γ -ray spectra for 16,17,18O and 2H have been measured with guided cold neutron beams from the Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRM II) reactor and the Budapest Research Reactor (BRR) on natural and O,1817 enriched D2O targets. Complete neutron capture γ -ray decay schemes for the 16,17,18O(n ,γ ) reactions were measured. Absolute transition probabilities were determined for each reaction by a least-squares fit of the γ -ray intensities to the decay schemes after accounting for the contribution from internal conversion. The transition probability for the 870.76-keV γ ray from 16O(n ,γ ) was measured as Pγ(871 )=96.6 ±0.5 % and the thermal neutron cross section for this γ ray was determined as 0.164 ±0.003 mb by internal standardization with multiple targets containing oxygen and stoichiometric quantities of hydrogen, nitrogen, and carbon whose γ -ray cross sections were previously standardized. The γ -ray cross sections for the O,1817(n ,γ ) and 2H(n ,γ ) reactions were then determined relative to the 870.76-keV γ -ray cross section after accounting for the isotopic abundances in the targets. We determined the following total radiative thermal neutron cross sections for each isotope from the γ -ray cross sections and transition probabilities; σ0(16O )=0.170 ±0.003 mb; σ0(17O )=0.67 ±0.07 mb; σ0(18O )=0.141 ±0.006 mb; and σ0(2H )=0.489 ±0.006 mb.

  4. Seasonal 18O variations and groundwater recharge for three landscape types in central Pennsylvania, USA

    NASA Astrophysics Data System (ADS)

    O'Driscoll, M. A.; DeWalle, D. R.; McGuire, K. J.; Gburek, W. J.

    2005-03-01

    Seasonal 18O variations in precipitation, soil water, snowmelt, spring flow and stream baseflow were analyzed to characterize seasonal dynamics of groundwater recharge in three central Pennsylvania catchments. The catchments represented three common landscape types: Valley and Ridge-shale (Mahantango Creek), Valley and Ridge-carbonate (Buffalo Run), and Appalachian Plateau-sandstone (Benner Run). Samples were collected on a biweekly basis from May 18, 1999 to May 9, 2000. Precipitation, soil water, and baseflow isotopic composition data indicated that a seasonal recharge bias existed for these catchments, most recharge occurred in the fall, winter, and spring months. An altitude effect of -0.16 to -0.32‰/100 m change in elevation was discernible in precipitation, soil water, and stream baseflow isotopic compositions. Soils effectively damped seasonal variations of recharge 18O composition after depths of 1.62-2.85 m. The greatest damping of the annual isotopic composition signal occurred in the shallow soil layers (0-15 cm). In these and similar landscapes with thick soils the annual isotopic composition signal may be completely damped prior to reaching the stream as baseflow. Isotopic variations measured in stream baseflow are more likely to be caused by the shallow flowpath water relatively close to the streams. Baseflow stable isotope variations found on the basins studied suggested that residence times for subsurface waters to reach channels were much longer than the annual seasonal cycle of 18O in precipitation. Damping depths were similar for the three different catchments but it is not certain how spatially variable damping depths were within each catchment. This information would be useful in determining areas within catchments that contribute to short term isotopic composition fluctuations within streams ('new water'). Predictive models that determine isotopic damping depth from meteorological, soil and vegetation/land-use data can help develop a better

  5. Tempered fractional calculus

    NASA Astrophysics Data System (ADS)

    Sabzikar, Farzad; Meerschaert, Mark M.; Chen, Jinghua

    2015-07-01

    Fractional derivatives and integrals are convolutions with a power law. Multiplying by an exponential factor leads to tempered fractional derivatives and integrals. Tempered fractional diffusion equations, where the usual second derivative in space is replaced by a tempered fractional derivative, govern the limits of random walk models with an exponentially tempered power law jump distribution. The limiting tempered stable probability densities exhibit semi-heavy tails, which are commonly observed in finance. Tempered power law waiting times lead to tempered fractional time derivatives, which have proven useful in geophysics. The tempered fractional derivative or integral of a Brownian motion, called a tempered fractional Brownian motion, can exhibit semi-long range dependence. The increments of this process, called tempered fractional Gaussian noise, provide a useful new stochastic model for wind speed data. A tempered fractional difference forms the basis for numerical methods to solve tempered fractional diffusion equations, and it also provides a useful new correlation model in time series.

  6. Tempered fractional calculus

    SciTech Connect

    Sabzikar, Farzad; Meerschaert, Mark M.; Chen, Jinghua

    2015-07-15

    Fractional derivatives and integrals are convolutions with a power law. Multiplying by an exponential factor leads to tempered fractional derivatives and integrals. Tempered fractional diffusion equations, where the usual second derivative in space is replaced by a tempered fractional derivative, govern the limits of random walk models with an exponentially tempered power law jump distribution. The limiting tempered stable probability densities exhibit semi-heavy tails, which are commonly observed in finance. Tempered power law waiting times lead to tempered fractional time derivatives, which have proven useful in geophysics. The tempered fractional derivative or integral of a Brownian motion, called a tempered fractional Brownian motion, can exhibit semi-long range dependence. The increments of this process, called tempered fractional Gaussian noise, provide a useful new stochastic model for wind speed data. A tempered fractional difference forms the basis for numerical methods to solve tempered fractional diffusion equations, and it also provides a useful new correlation model in time series.

  7. High-frequency observations of δ2H and δ18O in storm rainfall

    NASA Astrophysics Data System (ADS)

    Stoecker, F.; Klaus, J.; Pangle, L. A.; Garland, C.; McDonnell, J. J.

    2012-12-01

    Stable isotopes ratios of hydrogen (2H/1H) and oxygen (18O/16O) are indispensable tools for investigation of the hydrologic cycle. Recent technological advances with laser spectroscopy now enable high-frequency measurement of key water cycle components. While the controls on rainfall isotope composition have been known generally for some time, our understanding of the effect of inter- and intra-storm processes on fine scale rainfall isotope composition is poorly understood. Here we present a new approach to observe inter- and intra-storm isotope variability in precipitation in high-frequency. We investigate the temporal development of δ2H and δ18O within and between discrete rainstorm. δ2H and δ18O in precipitation was measured from November 2011 to February 2012 in Corvallis, OR using a flow-cell combined with a Liquid Water Isotope Analyzer (LWIA-24d, Los Gatos Research, Inc.). The average sample frequency was 15 samples per hour, resulting in more than 3100 samples during the observation period. 27 separate rainstorms were identified in the dataset based on minimum inter-event time, minimum precipitation depth, and minimum number of isotope measurements. Event meteoric water lines were developed for each event. We observed short-term isotopic patterns (e.g., V-shaped trends), high-rate changes (5.3‰/h) and large absolute changes in isotopic composition (20‰) on intra-event scale. V-shaped trends appeared to be related to individual storm fronts detected by air temperature, cloud heights (NEXRAD radar echo tops) and cloud trajectories (Hybrid Single Particle Lagrangian Integrated Trajectory Model (HYSPLIT)). Despite this, we could detect no linear correlation between event-based isotopic variables (slope, δ2H-intercept, δ2H, δ18O) and the event meteoric water line. Furthermore, the composite event meteoric water line (i.e. the local meteoric water line) showed a wider spread for heavy isotopes than for light isotopes, caused presumably by different

  8. Carbonate clumped isotope constraints on Silurian ocean temperature and seawater δ18O

    NASA Astrophysics Data System (ADS)

    Cummins, Renata C.; Finnegan, Seth; Fike, David A.; Eiler, John M.; Fischer, Woodward W.

    2014-09-01

    Much of what we know about the history of Earth’s climate derives from the chemistry of carbonate minerals in the sedimentary record. The oxygen isotopic compositions (δ18O) of calcitic marine fossils and cements have been widely used as a proxy for past seawater temperatures, but application of this proxy to deep geologic time is complicated by diagenetic alteration and uncertainties in the δ18O of seawater in the past. Carbonate clumped isotope thermometry provides an independent estimate of the temperature of the water from which a calcite phase precipitated, and allows direct calculation of the δ18O of the water. The clumped isotope composition of calcites is also highly sensitive to recrystallization and can help diagnose different modes of diagenetic alteration, enabling evaluation of preservation states and identification of the most pristine materials from within a sample set-critical information for assessing the quality of paleoproxy data generated from carbonates. We measured the clumped isotope composition of a large suite of calcitic fossils (primarily brachiopods and corals), sedimentary grains, and cements from Silurian (ca. 433 Ma) stratigraphic sections on the island of Gotland, Sweden. Substantial variability in clumped isotope temperatures suggests differential preservation with alteration largely tied to rock-buffered diagenesis, complicating the generation of a stratigraphically resolved climate history through these sections. Despite the generally high preservation quality of samples from these sections, micro-scale observations of calcite fabric and trace metal composition using electron backscatter diffraction and electron microprobe analysis suggest that only a subset of relatively pristine samples retain primary clumped isotope signatures. These samples indicate that Silurian tropical oceans were likely warm (33 ± 7 °C) and similar in oxygen isotopic composition to that estimated for a “modern” ice-free world (δ18OVSMOW of -1

  9. Triple isotope (δD, δ17O, δ18O) study on precipitation, drip water and speleothem fluid inclusions for a Western Central European cave (NW Switzerland)

    NASA Astrophysics Data System (ADS)

    Affolter, Stéphane; Häuselmann, Anamaria D.; Fleitmann, Dominik; Häuselmann, Philipp; Leuenberger, Markus

    2015-11-01

    Deuterium (δD) and oxygen (δ18O) isotopes are powerful tracers of the hydrological cycle and have been extensively used for paleoclimate reconstructions as they can provide information on past precipitation, temperature and atmospheric circulation. More recently, the use of 17Oexcess derived from precise measurement of δ17O and δ18O gives new and additional insights in tracing the hydrological cycle whereas uncertainties surround this proxy. However, 17Oexcess could provide additional information on the atmospheric conditions at the moisture source as well as about fractionations associated with transport and site processes. In this paper we trace water stable isotopes (δD, δ17O and δ18O) along their path from precipitation to cave drip water and finally to speleothem fluid inclusions for Milandre cave in northwestern Switzerland. A two year-long daily resolved precipitation isotope record close to the cave site is compared to collected cave drip water (3 months average resolution) and fluid inclusions of modern and Holocene stalagmites. Amount weighted mean δD, δ18O and δ17O are -71.0‰, -9.9‰, -5.2‰ for precipitation, -60.3‰, -8.7‰, -4.6‰ for cave drip water and -61.3‰, -8.3‰, -4.7‰ for recent fluid inclusions respectively. Second order parameters have also been derived in precipitation and drip water and present similar values with 18 per meg for 17Oexcess whereas d-excess is 1.5‰ more negative in drip water. Furthermore, the atmospheric signal is shifted towards enriched values in the drip water and fluid inclusions (Δ of ˜ + 10‰ for δD). The isotopic composition of cave drip water exhibits a weak seasonal signal which is shifted by around 8-10 months (groundwater residence time) when compared to the precipitation. Moreover, we carried out the first δ17O measurement in speleothem fluid inclusions, as well as the first comparison of the δ17O behaviour from the meteoric water to the fluid inclusions entrapment in speleothems

  10. Comparing three methods of NEE-flux partitioning from the same grassland ecosystem: the 13C, 18O isotope approach and using simulated Ecosystem respiration

    NASA Astrophysics Data System (ADS)

    Siegwolf, R.; Bantelmann, E.; Saurer, M.; Eugster, W.; Buchmann, N.

    2007-12-01

    As a change in the global climate occurs with increasing temperatures, the Carbon exchange processes of terrestrial ecosystems will change as well. However, it is difficult to quantify the degree to what ecosystem respiration will change relative to the CO2 uptake by photosynthesis. To estimate the carbon sequestration potential of terrestrial vegetation cover it is essential to know both fluxes: ecosystem respiration and the carbon uptake by the vegetation cover. Therefore the net ecosystem exchange of CO2 (NEE) was measured with the eddy covariance method and separated into assimilation and respiration flux. We applied three different approaches, 1) the conventional method, applying the nighttime relationship between soil temperature and NEE for calculating the respiration flux during the day, 2) the use of stable carbon and 3) oxygen isotopes. We compared the results of the three partitioning exercises for a temperate grassland ecosystem in the pre-Alps of Switzerland for four days in June 2004. The assimilation flux derived with the conventional NEE partitioning approach, was best represented at low PAR and low temperatures, in the morning between 5 and 9 am. With increasing temperature and PAR the assimilation for the whole canopy was underestimated. For partitioning NEE via 18O approach, correlations of temperature and radiation with assimilation and respiration flux were significantly higher for the partitioning approach with 18O than for the 13C NEE partitioning. A sensitivity analysis showed the importance of an accurate determination of the equilibrium term θ between CO2 and leaf water δ18O for the NEE partitioning with 18O. For using 13C to partition NEE, the correct magnitude of the 13C fractionation and for the respiration term is essential. The analysis of the data showed that for low light and low morning temperatures the conventional method delivers reasonably good results. When the temperatures exceeded 21°C the isotope approach provided the

  11. Seasonal variations in δ13C and δ18O of atmospheric CO2 measured in the urban boundary layer over Vancouver, Canada in relation to fuel emissions.

    NASA Astrophysics Data System (ADS)

    Lee, J.; Christen, A.; Ketler, R.; Nesic, Z.; Schwendenmann, L.; Semmens, C.

    2014-12-01

    Recent advances in techniques to measure carbon dioxide (CO2) in urban plumes show potential for validating and monitoring emission inventories at regional to urban scale. A major challenge remains the attribution of elevated CO2 in urban plumes to different fuel and biogenic sources. Stable isotopes are a promising source of additional information. Here, we report a full year of measurements of CO2 mixing ratios, δ13C and δ18O in CO2 in the urban boundary layer over Vancouver, Canada. The goal of the work is to link seasonally changing isotopic composition to dominant fuel sources and put the urban enhancement into the context of regional background concentrations. Atmospheric composition in the urban atmosphere was measured continuously using a tunable diode laser absorption system (TGA 200, Campbell Scientific, Logan, UT, USA). In addition, end member signatures were determined by means of bag samples from representative fuel emission sources (gasoline, diesel, natural gas). While δ13C depends on the fuel type and origin (for Vancouver in 2013/14: δ13C gasoline 27.2‰; diesel -28.8‰; natural gas -41.6‰), δ18O is fractionated in catalytic converters (d18O gasoline vehicles -12.5‰; diesel -18.6‰; natural gas -22.7‰) and exhibits higher variability between samples. Additional signatures were determined for human, soil and plant respiration. During the study year, monthly mean mixing ratios in the urban atmosphere ranged between 410.5 (Jul) and 425.7 ppm (Dec), which was on average 18 ppm elevated above the regional background. As expected, mean monthly δ13C was lower in winter than summer with seasonally changing intercepts between -33.6‰ (JJF) and -27.7‰ (MJJ). Making the simple assumption that natural gas and gasoline are the only major fuel sources, natural gas would contribute ~45% to emissions in winter and ~3% in early summer, which is lower than the downscaled Local Emissions Inventory (57% in winter and 20% in summer). Mean δ18O showed

  12. Establishing a grassland signature in veins: 18O in the leaf water of C3 and C4 grasses

    PubMed Central

    Helliker, Brent R.; Ehleringer, James R.

    2000-01-01

    We show that 18O evaporative enrichment of bulk leaf water in grass species can be significantly more enriched than predicted by the Craig–Gordon model, with C4 grasses considerably more enriched than C3 grasses. Our results suggest that the unanticipated 18O leaf water enrichment of grasses is attributable to the progressive evaporative enrichment along parallel veins (a function of both leaf length and interveinal distance), a pattern that does not occur in Dicotyledonous species. We propose that the differential 18O enrichment of grasses will result in distinct C18O16O biospheric signals from grassland and forest ecosystems, allowing for further partitioning of terrestrial carbon fluxes. PMID:10884421

  13. Morphology-controlled synthesis of W18O49 nanostructures and their near-infrared absorption properties.

    PubMed

    Guo, Chongshen; Yin, Shu; Yan, Mei; Kobayashi, Makoto; Kakihana, Masato; Sato, Tsugio

    2012-04-16

    The morphology-controlled synthesis and near-infrared (NIR) absorption properties of W(18)O(49) were systematically investigated for the application of innovative energy-saving windows. Various morphologies of W(18)O(49), such as nanorods, nanofibers, nanograins, nanoassembles, nanoplates, and nanoparticles, with various sizes were successfully synthesized by solvothermal reactions using organic alcohols as reaction media and WCl(6), W(EtO)(6), and WO(3) solids as the tungsten source. W(18)O(49) nanorods of less than 50 nm in length showed the best optical performance as an effective solar filter, which realized high transmittance in the visible region as well as excellent shielding properties of NIR light. Meanwhile, the W(18)O(49) nanorods also exhibited strong absorption of NIR light and instantaneous conversion of the absorbed photoenergy to the local heat. PMID:22443484

  14. Microbial sulfate reduction rates and sulfur and oxygen isotope fractionations at oil and gas seeps in deepwater Gulf of Mexico

    SciTech Connect

    Aharon, P.; Fu, B.

    2000-01-01

    sulfate reduction and anaerobic methane oxidation are the dominant microbial processes occurring in hydrate-bearing sediments at bathyal depths in the Gulf of Mexico where crude oil and methane are advecting through fault conduits to the seafloor. The oil and gas seeps are typically overlain by chemosynthetic communities consisting of thiotrophic bacterial mats (Beggiatoa spp.) and methanotrophic mussels (Bathymodiolus spp.), respectively. Cores were recovered with a manned submersible from fine-grained sediments containing dispersed gas hydrates at the threshold of stability. Estimated sulfate reduction rates are variable but generally are substantially higher in crude oil seeps (up to 50 times) and methane seeps (up to 600 times) relative to a non-seep reference sediment. Sulfur and oxygen isotope fractionation factors are highest in the reference sediment but substantially lower in the seep sediments and are controlled primarily by kinetic factors related to sulfate reduction rates. Kinetic effects also control the {delta}{sup 34}S/{delta}{sup 18}O ratios such that slow microbial rates yield low ratios whereas faster rates yield progressively higher ratios. The seep data contradict previous claims that {delta}{sup 34}S/{delta}{sup 18}O ratios are diagnostic of either microbial sulfate reduction at a fixed {delta}{sup 34}S/{delta}{sup 18}O ratio of 4/1 or lower ratios caused by SO{sub 4}-H{sub 2}O equilibration at ambient temperatures. The new results offer a better understanding of methane removal via anaerobic oxidation in the sulfate reduction zone of hydrate-bearing sediments and have significant implications regarding the origin and geochemical history of sedimentary sulfate reconstructed on the basis of {delta}{sup 34}S and {delta}{sup 18}O compositions.

  15. An experimental study on isotope fractionation in a mesoporous silica-water system with implications for vadose-zone hydrology

    NASA Astrophysics Data System (ADS)

    Lin, Ying; Horita, Juske

    2016-07-01

    Soil water dynamics within a thick vadose (unsaturated) zone is a key component in the hydrologic cycle in arid regions. In isotopic studies of soil water, the isotopic composition of adsorbed/pore-condensed water within soils has been assumed to be identical to that of bulk liquid water. To test this critical assumption, we have conducted laboratory experiments on equilibrium isotope fractionation between adsorbed/condensed water in mesoporous silica (average pore diameter 15 nm) and the vapor at relative pressures p/po = 0.3-1.0 along the adsorption-desorption isotherm at 30 °C. The isotope fractionation factors between condensed water in the silica pores and the vapor, α(2H) and α(18O), are smaller than those between liquid and vapor of bulk water (1.074 and 1.0088, respectively, at 30 °C). The α(2H) and α(18O) values progressively decrease from 1.064 and 1.0083 at p/po = 1 to 1.024 and 1.0044 at p/po = 0.27 for hydrogen and oxygen isotopes, respectively, establishing trends very similar to the isotherm curves. Empirical formulas relating α(2H) and α(18O) to the proportions of filled pores (f) are developed. Our experimental results challenge the long-held assumption that the equilibrium isotope fractionation factors for the soil water-vapor are identical to those of liquid water-vapor system with potential implications for arid-zone and global water cycles, including paleoclimate proxies in arid regions.

  16. Validation of δ18O as a proxy for past monsoon rain by multi-GCM simulations

    NASA Astrophysics Data System (ADS)

    Midhun, M.; Ramesh, R.

    2016-03-01

    Stable oxygen isotope ratios (δ18O) of tree cellulose and speleothem carbonate are useful proxies for past monsoon rain in many tropical regions, as a decrease in rain δ18O is observed with increase in rainfall on a monthly time scale. This amount effect varies spatially; therefore a local calibration, with actual measurements of rain amount and its δ18O is required. Such observations, however, are quite limited in space and time. To circumvent this difficulty, many isotope enabled general circulation models (GCMs) are used to aid the interpretation of 18O proxies; nevertheless, all such simulations taken together are yet to be evaluated against observations over the Indian summer monsoon (ISM) region. Here we examine ten such GCM simulations archived by the stable water isotope INtercomparison Group, phase 2. The spatial patterns of simulated ISM rainfall and its δ18O are in good agreement with the limited observations available. Simulations nudged with observed wind fields show better skill in reproducing the observed spatio-temporal pattern of rainfall and its δ18O. A large discrepancy is observed in the magnitude of the simulated amount effect over the Indian subcontinent between the models and observation, probably because models simulate the spatial distribution of monsoon precipitation differently. Nudged simulations show that interannual variability of rainfall δ18O at proxy sites are controlled by either regional (rather than local) rainfall or upstream rain out. Interannual variability of rainfall δ18O over the East Asian region is well correlated with ENSO, while it is only weakly correlated over the Indian sub-continent.

  17. Seasonal variations recorded in cave monitoring results and a 10 year monthly resolved speleothem δ18O and δ13C record from the Han-sur-Lesse cave, Belgium

    NASA Astrophysics Data System (ADS)

    Van Rampelbergh, M.; Verheyden, S.; Allan, M.; Quinif, Y.; Keppens, E.; Claeys, P.

    2014-04-01

    Speleothems provide paleoclimate information on multi-millennial to decadal scales in the Holocene. However seasonal or even monthly resolved records remain scarce. They require fast growing stalagmites and a good understanding of the proxy transfer function on very short time scales. The Proserpine stalagmite from the Han-sur-Less cave (Belgium) displays seasonal layers of 0.5 to 2 mm thickness that reconstruct paleoclimates at a monthly scale. Through a regular cave monitoring, we acquired a good understanding of how δ18O and δ13C signals in modern calcite reflect climate variations on sub-seasonal scale. Cave parameters vary seasonally in response to the activity of the vegetation cover and outside air temperature. From December to June, the cave remains in "winter-mode". Outside temperatures are cold inducing low cave air and water temperatures. Bio-productivity in the soil is limited leading to low pCO2, higher δ13C composition of the CO2 in the cave air and high discharge due to the inactivity of the plant coverage. From June to December, the cave switches to "summer-mode" and the measured factors display an opposite behavior. The δ18O and δ13C signals of fresh calcite precipitated on glass slabs vary seasonally. Lowest δ18O values occur during the summer-mode when the δ13C values are high. The δ18O composition of the calcite is in equilibrium with the drip water δ18O and display seasonal variations due to changes in the cave air and water temperature. In contrast to the δ18O signal, δ13C values of the calcite precipitated on the glass slabs do not reflect equilibrium conditions. Highest δ13C values occur during summer, when discharge rates are low increasing the evaporation effect on the thin water film covering the stalagmite. This same antithetical behavior of the δ18O vs. the δ13C signals is seen in the monthly resolved speleothem record that covers the period between 1976 and 1985 AD. Dark layers are formed during summer, while light layers

  18. Modern decrease of δ18O in Mediterranean sediments over the last 150 y: anthropogenic forcing and natural variability

    NASA Astrophysics Data System (ADS)

    Alessio, S.; Taricco, C.; Vivaldo, G.; Ghil, M.

    2012-04-01

    Our previous work (Taricco et al., 2009) has documented a high-resolution record of foraminiferal δ18O isotopic ratio that covers the last two millennia. This record was obtained from a shallow-water sediment core drilled in the Central Mediterranean (Gallipoli Terrace in the Gulf of Taranto, Ionian Sea), and dated with high accuracy by tephroanalysis and radiometric measurements. The δ18O series so obtained spans the last 2200 years and shows a steep decrease during the Industrial Era. We use here pre-industrial δ18O variations to design and tune algorithms able to forecast the natural variability in the δ18O series over the last 150 y (Alessio et al., 2012). Autoregressive (AR) models and feed-forward neural networks are applied to the highly significant components revealed by Singular Spectrum Analysis (SSA). Comparison between the forecast and the actual δ18O signal during the Industrial Era shows that the natural contribution to the modern δ18O variation decreased gradually, until it reached roughly 40% as early as the end of the 1970s.

  19. 18O depletion in monsoon rain relates to large scale organized convection rather than the amount of rainfall.

    PubMed

    Lekshmy, P R; Midhun, M; Ramesh, R; Jani, R A

    2014-01-01

    Oxygen isotopic variations in rainfall proxies such as tree rings and cave calcites from South and East Asia have been used to reconstruct past monsoon variability, mainly through the amount effect: the observed (18)O depletion of rain with increasing amount, manifested as a negative correlation of the monthly amount of tropical rain with its δ(18)O, both measured at the same station. This relation exhibits a significant spatial variability, and at some sites (especially North-East and peninsular India), the rainfall proxies are not interpretable by this effect. We show here that relatively higher (18)O-depletion in monsoon rain is not related necessarily to its amount, but rather, to large scale organized convection. Presenting δ(18)O analyses of ~654 samples of daily rain collected during summer 2012 across 9 stations in Kerala, southern India, we demonstrate that although the cross correlations between the amounts of rainfall in different stations is insignificant, the δ(18)O values of rain exhibit highly coherent variations (significant at P = 0.05). Significantly more (18)O-depletion in the rain is caused by clouds only during events with a large spatial extent of clouds observable over in the south eastern Arabian Sea. PMID:25012535

  20. Adenosine triphosphate utilization rates and metabolic pool sizes in intact cells measured by transfer of 18O from water.

    PubMed Central

    Dawis, S M; Walseth, T F; Deeg, M A; Heyman, R A; Graeff, R M; Goldberg, N D

    1989-01-01

    The hydrolytic rates and metabolic pool sizes of ATP were determined in intact cells by monitoring the time courses of 18O incorporation from 18O-water into the gamma-phosphoryl of ATP and orthophosphate. To calculate the rate of ATP hydrolysis, a kinetic model is used to fit the time course of the 18O labeling. The size of the metabolic pool of ATP is calculated from the 18O distribution after isotopic equilibrium has been achieved. Metabolic pools have a binomial distribution of 18O whereas nonmetabolic pools exhibit negligible 18O labeling. The application and limitations of this approach are illustrated with data from isolated toad retinas and human platelets. At 22 degrees C, the time constant of ATP hydrolysis in the dark-adapted toad retina is about 30 s. Under these conditions, over 80% of the retinal ATP is involved in high-energy phosphate metabolism. It is calculated that when cGMP metabolic flux in the photoreceptors is maximally stimulated by light, it accounts for 10% of the ATP utilization by the entire retina. The time constant of ATP hydrolysis in human platelets at 37 degrees C is approximately 1 s, and 60% of the platelet ATP is involved in energy metabolism. PMID:2930826

  1. Comparison of ejection fraction and Goldman risk factor analysis to dipyridamole-thallium 201 studies in the evaluation of cardiac morbidity after aortic aneurysm surgery

    SciTech Connect

    McEnroe, C.S.; O'Donnell, T.F. Jr.; Yeager, A.; Konstam, M.; Mackey, W.C. )

    1990-04-01

    Associated coronary artery disease is the critical factor that influences early and late mortality after abdominal aortic aneurysm surgery. Dipyridamole-thallium 201 scintigraphy, left ventricular ejection fraction, and Goldman risk factor analysis have been suggested as preoperative noninvasive screening methods to detect significant coronary artery disease. In this series of 95 elective abdominal aortic aneurysm repairs dipyridamole-thallium 201 scintigraphy was highly predictive of the absence of perioperative cardiac morbidity (96% specificity, 44/46 normal scans, no cardiac morbidity), whereas ejection fraction (73% specificity, 31/42 normal ejection fraction, no cardiac morbidity) and Goldman risk factor analysis (84% specificity, 44/51 class I, no cardiac morbidity) were less. Furthermore, thallium redistribution on dipyridamole-thallium 201 scintigraphy leading to coronary angiography identified a significant number of patients with occult coronary artery disease who required preoperative coronary revascularization (8%, 8/95) and might have remained undetected on the basis of left ventricular ejection fraction or Goldman risk factor analysis. Finally, fixed thallium deficit, which some investigators have interpreted as a low probability finding for cardiac morbidity, was associated with a higher than expected incidence of cardiac complications. Forty-six percent (7/15) of all postoperative cardiac complications (three myocardial infarctions, three ischemic events, one death) occurred in patients with abdominal aortic aneurysms with fixed deficits. This suggests that patients with fixed deficits on dipyridamole-thallium 201 scintigraphy should be considered for later delayed (4 hours) thallium images or coronary angiography or both.

  2. Isotopic fractionation factor and hydrogenic potential in 2-hydroxy-1,1,1,5,5,5-hexafluoro-2-penten-4-one

    SciTech Connect

    Kreevoy, M.M.; Ridl, B.A.

    1981-04-02

    The title compound (enol-hexafluoroacetylacetone) has an isotopic fractionation factor of 0.6 +- 0.1. This, and much other information about this compound, can be rationalized if the enolic hydrogen bridges between the two oxygens and is governed by a double minimum potential function with a central maximum of approx. 3000 cm/sup -1/ (8 kcal/mol)(eq 10).

  3. Inferring heterogeneity in aquitards using high-resolution deltaD and delta18O profiles.

    PubMed

    Hendry, M Jim; Wassenaar, L I

    2009-01-01

    Vertical depth profiles of pore water isotopes (deltaD and delta18O) in clay-rich aquitards have been used to show that solute transport is dominated by molecular diffusion, to define the timing of geologic events, and to estimate vertical hydraulic conductivity. The interpretation of the isotopic profiles in these studies was based on pore water samples collected from piezometers installed in nests (typically 4 to 15 piezometers) over depths of 10 to 80 m. Data from piezometer nests generally have poor vertical resolution (meters), raising questions about their capacity to reveal the impact of finer scale heterogeneities such as permeable sand bodies or fractured till zones on solute transport. Here, we used high-resolution (30-cm) depth profiles of deltaD and delta18O from two continuously cored boreholes in a till aquitard to provide new insights into the effects of sand bodies on solute transport. High-resolution core-derived profiles indicate that such heterogeneities can cause major deviations from one-dimensional diffusion profiles. Further, comparison of piezometer-measured values with best-fit diffusion trends shows subtle deviations, suggesting the presence of heterogeneities that should not be ignored. High-resolution profiles also more clearly defined the contact between the highly fractured oxidized zone and the underlying unoxidized zone than the piezometers. PMID:19735307

  4. A high-resolution δ18O record and Mediterranean climate variability

    NASA Astrophysics Data System (ADS)

    Taricco, C.; Vivaldo, G.; Alessio, S.; Rubinetti, S.; Mancuso, S.

    2015-03-01

    A high-resolution, well-dated foraminiferal δ18O record from a shallow-water core drilled from the Gallipoli Terrace in the Gulf of Taranto (Ionian Sea), previously measured over the last two millennia, has been extended to cover 707 BC-AD 1979. Spectral analysis of this series, performed using singular-spectrum analysis (SSA) and other classical and advanced methods, strengthens the results obtained analysing the shorter δ18O profile, detecting the same highly significant oscillations of about 600, 380, 170, 130 and 11 years, respectively explaining about 12, 7, 5, 2 and 2% of the time series total variance, plus a millennial trend (18% of the variance). The comparison with the results of multi-channel singular-spectrum analysis (MSSA) applied to a data set of 26 Northern Hemisphere (NH) temperature-proxy records shows that NH temperature anomalies share with our local record a~long-term trend and a bicentennial (170-year period) cycle. These two variability modes, previously identified as temperature-driven, are the most powerful modes in the NH temperature data set. Both the long-term trends and the bicentennial oscillations, when reconstructed locally and hemispherically, show coherent phases. Furthermore, the corresponding local and hemispheric amplitudes are comparable if changes in the precipitation-evaporation balance of the Ionian sea, presumably associated with temperature changes, are taken into account.

  5. A high-resolution δ18O record and Mediterranean climate variability

    NASA Astrophysics Data System (ADS)

    Taricco, C.; Vivaldo, G.; Alessio, S.; Rubinetti, S.; Mancuso, S.

    2014-10-01

    A~high-resolution, well-dated foraminiferal δ18O record from a shallow-water core drilled from the Gallipoli Terrace in the Gulf of Taranto (Ionian Sea), previously measured over the last two millennia, has been extended to cover 707 BC-1979 AD. Spectral analysis of this series, performed by Singular Spectrum Analysis (SSA) and other classical and advanced methods, strengthens the results obtained analysing the shorter δ18O profile, detecting the same highly significant oscillations of about 600 yr, 380 yr, 170 yr, 130 yr, and 11 yr, respectively explaining about 12%, 7%, 5%, 2% and 2% of the time series total variance, plus a millennial trend (18% of the variance). The comparison with the results of Multi-channel Singular Spectrum Analysis (MSSA) applied to a data set of 26 Northern Hemisphere (NH) temperature-proxy records shows that NH temperature anomalies share with our local record a long-term trend and a bicentennial cycle. These two variability modes, previously identified as temperature-driven, are the most powerful modes in the NH temperature data set. Both the long-term trends and the bicentennial oscillations, when reconstructed locally and hemispherically, show coherent phases. Also the corresponding local and hemispheric amplitudes are comparable, if changes in the precipitation-evaporation balance of the Ionian sea, presumably associated with temperature changes, are taken into account.

  6. Millennial-scale features in ?18O from a stalagmite in the eastern United States

    NASA Astrophysics Data System (ADS)

    Hardt, B. F.; Doctor, D. H.; Gao, Y.; Rowe, H. D.; Cheng, H.; Edwards, R.

    2013-12-01

    The oxygen isotope record of calcite from a stalagmite collected from Grand Caverns in Virginia, USA shows evidence of millennial-scale variability that appears to be coherent with Dansgaard/Oeschger events observed in Greenland ice. Sample GC-S02 grew from 82 - 13 ka BP and ranges in δ18O composition from -8 to -4 ‰ (VPDB) with multiple instances of millennial-scale changes in excess of 1‰. As δ18O in GC-S02 is more positive during MIS 2 than MIS 3, change in mean annual temperature is not a likely explanation for the observed variability. The carbon and oxygen isotopic records of calcite are independent and show no evidence of covaration (r = -0.1). Changes in the seasonal timing of precipitation provides an alternate explanation for the data, particularly given the potential for warm- and cool-season precipitation to come from different sources (Gulf of Mexico versus the Atlantic ocean). Grand Caverns is located in the Shenandoah River watershed within the Appalachian Great Valley, suggesting a meaningful role for Atlantic moisture. The age model is based on high-precision U-Th ages, making this record a potential benchmark for the region.

  7. Impacts of Tibetan Plateau uplift on atmospheric dynamics and associated precipitation δ18O

    NASA Astrophysics Data System (ADS)

    Botsyun, Svetlana; Sepulchre, Pierre; Risi, Camille; Donnadieu, Yannick

    2016-06-01

    Palaeoelevation reconstructions of mountain belts have become a focus of modern science since surface elevation provides crucial information for understanding both geodynamic mechanisms of Earth's interior and the influence of mountain growth on climate. Stable oxygen isotopes palaeoaltimetry is one of the most popular techniques nowadays, and relies on the difference between δ18O of palaeo-precipitation reconstructed using the natural archives, and modern measured values for the point of interest. Our goal is to understand where and how complex climatic changes linked with the growth of mountains affect δ18O in precipitation. For this purpose, we develop a theoretical expression for the precipitation composition based on the Rayleigh distillation and the isotope-equipped atmospheric general circulation model LMDZ-iso outputs. Experiments with reduced height over the Tibetan Plateau and the Himalayas have been designed. Our results show that the isotopic composition of precipitation is very sensitive to climate changes related to the growth of the Himalayas and Tibetan Plateau. Specifically our simulations suggest that only 40 % of sampled sites for palaeoaltimetry depict a full topographic signal, and that uplift-related changes in relative humidity (northern region) and precipitation amount (southern region) could explain absolute deviations of up to 2.5 ‰ of the isotopic signal, thereby creating biases in palaeoelevation reconstructions.

  8. Late Holocene northeastern Morocco hydroclimate reconstruction revealed from speleothems d18O record

    NASA Astrophysics Data System (ADS)

    Sifeddine, A.; Bouchaou, L., Sr.; Cruz, F. W., Sr.; Apaéstegui, J. E.; Moquet, J. S., Jr.; Strikis, N. M.; Guyot, J. L., Sr.; Cheng, H.; Auler, A. S.; Beraaouz, E. H., Sr.

    2014-12-01

    Two well dated oxygen isotope (d18O) records of speleothems collected in Chaara cave located in the Northeastern Morocco are used to investigate variations in hydroclimate conditions during the last 2000 years. The results shown in this work confirm the previous works of the North Atlantic Oscillation (NAO) reconstruction during the last millennium and bring new implications concerning its evolution extending the MCA. Our (d18O) results characterized by positive values during the Medieval Warm Period (MWP) and more negative ones during the Little Ice Ages (LIA) are in agreement with those published by Trouet et al., 2009 and Wassenburg et al., 2013. They confirm that the both periods were dominated by persistent NAO+ and NAO-conditions respectively. In addition; they highlight new evidence of the NAO evolution to beyond the last 1000 years. NAO+ conditions recorded during the MCA persist until 500 AD and NAO- conditions dominate the Dark cold Period (DACP) as recorded during the LIA. Finally, the Current Warm Period (CWP) was marked by a clear change in isotope variations linked to decreased precipitation controlled by intensification in NAO + conditions.

  9. ENSO flavors in a tree-ring δ18O record from Indonesia

    NASA Astrophysics Data System (ADS)

    Schollaen, Karina; Karamperidou, Christina; Helle, Gerhard

    2014-05-01

    The existence of so-called ENSO flavors (Cold Tongue and Warm Pool El Nino), their underlying mechanisms and potential changes in their frequency of occurrence is an active field of research in the climate science community. Previous work has shown the distinct teleconnection patterns of ENSO flavors and SST, precipitation and salinity in the tropics, which should be taken into account when interpreting palaeo-climate proxies. At the same time, proxies from key locations with distinct ENSO-flavors signals can provide long continuous records, essential for identifying possible trends and (multi)decadal variability of ENSO flavor occurrence. Here, we show that one such key region is Java (Indonesia), where the ENSO influence on precipitation is significant for Warm Pool ENSO, and non-significant for Cold Tongue ENSO. We do so by investigating the ENSO signal in a 108-year long (1900-2007) tree-ring δ18O record of teak (Tectona grandis) trees growing in a lowland rain forest in Central Java. Climate response analysis with regional monthly rainfall data reveals that the tree-ring δ18O record is significantly correlated to rainfall, and is sensitive to the occurrence of Warm Pool ENSO events, as well as La Nina events. The results presented here demonstrate the ability of tree-ring stable isotope records to provide palaeo-climate records able to distinguish between the two ENSO flavors, with broad applicability to studies on past ENSO variability.

  10. Validating methods for measuring delta18O and delta13C in otoliths from freshwater fish.

    PubMed

    Guiguer, K R R A; Drimmie, R; Power, M

    2003-01-01

    The ability of the phosphoric acid digestion technique to extract carbon dioxide from biogenic carbonates and reliably reproduce delta(18)O and delta(13)C signatures from standard reference materials (NBS-18, NBS-19) was tested and shown to produce accurate, unbiased measurements of non-biologic materials. The effects of roasting preparation methods commonly reported when analyzing biogenic carbonates were also tested in a series of experiments using reference standards and otoliths obtained from aquacultured Arctic charr and rainbow trout. Roasting had no effect on the isotope measurement of reference standards. No significant differences between mean oxygen isotope signatures from paired experiments with roasted and non-roasted fish otoliths were found. However, otolith oxygen isotope measurements were significantly enriched in comparison to rearing water-based measurements for both species. Agreement between expected isotopic equilibrium and measured otolith delta(18)O values varied as a function of roasting temperature and between species. Criteria for the selection of appropriate roasting temperatures are suggested and favour 350 degrees C in freshwater fish where unbiased estimates of average rearing water temperatures and known differences in rearing temperatures were obtained. Carbon isotopic disequilibria were observed for both species. A mixing model analysis established differences in the percentage of metabolically derived carbon in studied otoliths, with Arctic charr deriving a greater proportion of otolith delta(13)C from metabolism as a result of higher metabolic rates. PMID:12590395

  11. Contribution of 19F resonances on 18O( p, α)15N reaction rate

    NASA Astrophysics Data System (ADS)

    Benmeslem, Meriem; Chafa, Azzedine; Barhoumi, Slimane; Tribeche, Mouloud

    2014-08-01

    The 18O( p, α)15N reaction influences the isotopes production such as 19F, 18O, and 15N which can be used to test the models of stellar evolution. 19F is synthesized in both asymptotic giant branch (AGB) and metal-rich Wolf-Rayet (WR) stars. Using R-matrix theory we allow new values of resonances parameters in 19F. We show that the most important contribution to the differential and total cross section at low energies, comes from the levels in 19F situated at resonances energies E R =151, 680 and 840 keV with spin and parity 1/2+. The total width of the 680 keV resonance is badly known. So, we have focused on this broad resonance corresponding to the 8.65 MeV level in 19F. We delimit the temperature range in which each resonance contribution to the total reaction rate occurs by analyzing the ratio ( N A < σν> i / N A < σν>). This allowed us to show that the 680 and 840 keV broad resonances strongly dominate the reaction rate over the stellar temperature range T 9=0.02-0.06 and T 9=0.5-5. Finally, these results were compared to NACRE and Iliadis astrophysical compilations.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  14. Evidence of the chemical reaction of (18)O-labelled nitrite with CO2 in aqueous buffer of neutral pH and the formation of (18)OCO by isotope ratio mass spectrometry.

    PubMed

    Tsikas, Dimitrios; Böhmer, Anke; Gros, Gerolf; Endeward, Volker

    2016-05-01

    Inorganic nitrite (NO2(-), ON-O(-) ←→ (-)O-NO) is the autoxidation product of nitric oxide (NO). Nitrite can also be formed from inorganic nitrate (ONO2(-)), the major oxidation product of NO in erythrocytes, by the catalytic action of bacterial nitrate reductase in gut and oral microflora. Nitrite can be reduced to NO by certain cellular proteins and enzymes, as well as in the gastric juice under acidic conditions. Hemoglobin, xanthine oxidoreductase and carbonic anhydrase (CA) have been reported to convert nitrite to NO. Renal CA isoforms are involved in the reabsorption of nitrite and may, therefore, play an important role in NO homeostasis. Yet, the mechanisms underlying the action of CA on nitrite are incompletely understood. The nitrate/nitrite system is regarded as a reservoir of NO. We have recently shown that nitrite reacts chemically with carbon dioxide (CO2), the regular substrate of CA. The present communication reports a stable isotope ratio mass spectrometry (IRMS) study on the reaction of NO2(-) and CO2 performed in 50 mM HEPES buffer of pH 7.4 at 37 °C. By using (18)O-labelled nitrite ((18)ON-O(-)/(-18)O-NO) and CO2 we observed formation of (18)O-labelled CO2. This finding is an unequivocal evidence of the chemical reaction of (18)ON-O(-)/(-18)O-NO with CO2. The reaction is rapid and involves nucleophilic attack of the negatively charged nitrite via one of its oxygen atoms on the partially positively charged CO2 molecule to form the putative intermediate (18)ON-O-CO2(-)/(-)O2C-(18)O-NO. The by far largest fraction of this intermediate decomposes back to (18)ON-O(-)/(-18)O-NO and CO2. A very small fraction of the intermediate, however, rearranges and finally decomposes to form (18)OCO and nitrite. This reaction is slower in the presence of an isolated erythrocytic CA isoform II. In summary, NO2(-), CO2 and CA are ubiquitous. The chemical reaction of NO2(-) with CO2 and its modulation by CA isoforms may play important roles in the transport of

  15. TEMPERED FRACTIONAL CALCULUS

    PubMed Central

    MEERSCHAERT, MARK M.; SABZIKAR, FARZAD; CHEN, JINGHUA

    2014-01-01

    Fractional derivatives and integrals are convolutions with a power law. Multiplying by an exponential factor leads to tempered fractional derivatives and integrals. Tempered fractional diffusion equations, where the usual second derivative in space is replaced by a tempered fractional derivative, govern the limits of random walk models with an exponentially tempered power law jump distribution. The limiting tempered stable probability densities exhibit semi-heavy tails, which are commonly observed in finance. Tempered power law waiting times lead to tempered fractional time derivatives, which have proven useful in geophysics. The tempered fractional derivative or integral of a Brownian motion, called a tempered fractional Brownian motion, can exhibit semi-long range dependence. The increments of this process, called tempered fractional Gaussian noise, provide a useful new stochastic model for wind speed data. A tempered difference forms the basis for numerical methods to solve tempered fractional diffusion equations, and it also provides a useful new correlation model in time series. PMID:26085690

  16. Assessing the relationship between the δ18O signatures of siliceous sponge spicules and water in a~tropical lacustrine environment (Minas Gerais, Brazil)

    NASA Astrophysics Data System (ADS)

    Matteuzzo, M. C.; Alexandre, A.; Varajão, A. F. D. C.; Volkmer-Ribeiro, C.; Almeida, A. C. S.; Varajão, C. A. C.; Vallet-Coulomb, C.; Sonzogni, C.; Miche, H.

    2013-08-01

    Siliceous sponge spicules constitute an important siliceous component of lacustrine sediments, together with widespread diatom frustules. In contrast to diatom frustules, siliceous spicules are formed in sponges in an enzymatic way. Previous attempts to use their oxygen isotopic signature (δ18Osilica) as a paleoenvironmental proxy have led to contradictory conclusions. These attempts demonstrated the need to further assess whether sponges form their silica in oxygen isotopic equilibrium with water. For this reason, we measured the δ18O signature of sponge spicules from a single freshwater species (Metania spinata) grown on natural and artificial supports over nine months in a small Brazilian pond (Lagoa Verde, northwestern Minas Gerais). The δ18Osilica values were obtained using the infrared (IR) laser-heating fluorination technique following a controlled isotopic exchange (CIE). The δ18O values (δ18Owater) and temperature of the pond water were periodically measured and reconstructed over the course of the sponge growth. Assuming that silica may form continuously in the spicules, temperature and δ18Owater values over the months of growth were weighted using a sponge growth coefficient previously established for Metania spinata. The δ18Osilica values of sponges grown simultaneously and on similar substrates were scattered. No relationships were observed between the Δ18Osilica-water and water temperature when the reconstructed values were considered. Conversely, a positive correlation was obtained, with a coefficient of 0.3‰ °C-1 (R2 = 0.63), when δ18Owater values and water temperature at the time of sample collection were considered. Such a positive temperature coefficient clearly indicates that the freshwater sponge Metania spinata does not form its siliceous spicules in oxygen isotopic equilibrium with the pond water. Instead, one or several biologically controlled kinetic fractionation mechanisms may be in play during the various steps of silica

  17. Possible isotopic fractionation effects in sputtered minerals

    NASA Technical Reports Server (NTRS)

    Haff, P. K.; Watson, C. C.; Tombrello, T. A.

    1980-01-01

    A model which makes definite predictions for the fractionation of isotopes in sputtered material is discussed. The fractionation patterns are nonlinear, and the pattern for a particular set of isotopes depends on the chemical matrix within which those isotopes are contained. Calculations are presented for all nonmonoisotopic elements contained in the minerals perovskite, anorthite, ackermanite, enstatite, and troilite. All isotopes are fractionated at the level of approximately 4-6 deg/o per atomic mass unit. Oxygen is always positively fractionated (heavier isotopes sputtered preferentially), and heavier elements are generally negatively fractioned (light isotopes sputtered preferentially). The value of Delta (O-18:O-16) is always less by about 1.8 deg/o than a linear extrapolation based upon the calculated delta (O-17:O-16) value would suggest. The phenomenon of both negative and positive fractionation patterns from a single target mineral are used to make an experimental test of the proposed model.

  18. Hydrochemistry and 18O/16O and 2H/1H Ratios of Ugandan Waters

    NASA Astrophysics Data System (ADS)

    Gebremichael, M. G.; Jasechko, S.

    2013-12-01

    Today, 70% of the 35 million people living in Uganda have access to an improved water source, ranking Uganda 148 out of 179 nations reporting in 2010 (Millennium Development Goals Indicators). 80% of Ugandans rely on groundwater as their primary drinking water source, collecting at springs or from shallow wells. Similarly, 80% of Ugandans rely upon agriculture - usually rain fed - as their primary income source. Despite lack of access to protected water sources faced by 10 million Ugandans, and the importance of the blue economy to Uganda's continued development, a country-wide investigation of the chemistry and the stable oxygen and hydrogen isotope compositions of waters has yet to be completed. Here we present 250 analyses of 18O/16O, 2H/1H and dissolved ion concentrations of Ugandan lakes, rivers, groundwaters and springs collected during July, 2013. We use the new data to characterize regional scale groundwater recharge sources, advection pathways and interactions with surface waters. Large lakes - Albert, Edward and Victoria - show increases in 18O/16O and 2H/1H ratios consistent with open water evaporation, and are shown to be distinct from nearby groundwaters, suggesting minimal recharge from large lakes to the subsurface. Salinities of eastern Ugandan groundwaters are elevated relative to samples collected from the central and western regions, suggesting that longer groundwater residence times and enhanced water-rock interactions characterize these waters. Springs from western Uganda show a shift in 18O/16O to higher values as a result of hydrothermal water-rock exchanges. Dissolved ion and noble gas concentrations show potential for use in assessing geothermal energy resources, perhaps aiding the Ugandan Ministry for Energy, Minerals and Development to meet their goal of increasing renewable energy from 4% (current) to 61% of total use by 2017 (Nyakabwa-Atwoki, 2013). Millennium Development Goals Indicators. mdgs.un.org/unsd/mdg/data.aspx Nyakabwa

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

    PubMed Central

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

    2011-01-01

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

  20. Late Quaternary Climate and Precipitation δ18o Variations over the Tibetan Plateau from Paleoclimate Modeling

    NASA Astrophysics Data System (ADS)

    Ehlers, T. A.; Li, J.; Werner, M.; Mutz, S.; Steger, C.; Paeth, H.; Poulsen, C. J.; Feng, R.

    2014-12-01

    The Himalaya-Tibet orogen hosts some of the largest modern climate gradients on Earth. Quaternary climate change between glacial and interglacial cycles is an important driver for landscape and ecological change in the region. A common observational approach for documenting climate change is the measurement of modern precipitation, and terrestrial archives of, δ18O. In this study, we investigate variations in Mid Holocene (MH) and Last Glacial Maximum (LGM) climate and precipitation δ18O (δ18Op). Paleoclimate model results for 3 time slices are considered including: Pre-industrial, MH and LGM conditions. These experiments bridge spatial and temporal timescales of environmental change over the plateau and provide a means for interpreting observational data sets. Climate and precipitation δ18O (δ18Op) variations over the Plateau are investigated using an atmospheric general circulation model equipped with isotope tracking capabilities (ECHAM5-wiso). Simulations are conducted at a resolution of 1.1°´1.1°, with 31 vertical levels (T106 L31). Pre-industrial boundary conditions come from AMIP2. MH and LGM boundary conditions come from a coupled atmosphere-ocean model ECHO-G, with vegetation cover from PMIP (http://pmip2.lsce.ipsl.fr). Results are presented in comparison to pre-industrial conditions. More specifically, during the MH surface temperatures were ~0.5 C higher on the central and western plateau and ~0.5 C cooler across the Himalaya. Mean annual MH precipitation was <100 mm/yr higher on the plateau and 300-500 mm/yr higher across the Himalaya. MH δ18Op is 1 per mil depleted on the plateau and 1 per mil enriched across the Himalaya. In contrast, during the LGM surface temperatures were ~2-4 C lower across the Himalaya and Tibet. Mean annual LGM precipitation was 200-600 mm/yr lower over the same region, and δ18Op was 2-4 per mil enriched relative to pre-industrial predictions. The causes for the previous δ18Op changes are discussed in the context of

  1. 1300 micron continuum and C18O line mapping of giant molecular cloud cores. II. W3, NGC 2264, NGC 6334I, RHO Ophiuchi and S140.

    PubMed

    Schwartz, P R; Snell, R L; Schloerb, F P

    1989-01-01

    In this paper we present nearly simultaneous 1300 microns continuum and J = 2-1 C18O maps of the cores of five molecular clouds, W3, NGC 2264, NGC 6334I, rho Oph, and S140. The purpose of this experiment was to compare these two column density tracers. We find that dust continuum and C18O emission are equally effective tracers of column density in molecular cloud cores and give a good indication of cloud structure. When the maps are analyzed in terms of the quantity q = Q/[a rho RX(C18O)], we find that q does not vary by much more than an order of magnitude either within objects or from object to object, implying that nominal dust parameters of absorption efficiency, radius, and gas-to-dust ratio and CO abundance are on average correct in a variety of sources. We did detect source-to-source variations in q. This variation could be either in the dust-to-CO number density ratio or in grain parameters. These variations are not well correlated with total source luminosity, average or typical temperature, or total column density. The best example of this variation appears to be rho Oph where q is about a factor of 7 lower than is typically found. Our approach is analogous to the study of the A nu to CO ratio and is probably equivalent to extending this study to large A nu if the same grains are responsible for both optical opacity and far-infrared to millimeter-wave emission. There is no fundamental reason to expect A nu/NCO or q to be constant and, in fact, we have found that it is not constant in even a small source sample. PMID:11538349

  2. Mg/Ca, Sr/Ca, δ18O and δ13C chemistry of Quaternary lacustrine ostracode shells from the North American continental interior

    NASA Astrophysics Data System (ADS)

    Ito, Emi

    The application of fossil ostracode shell chemistry to the reconstruction of past continental climate must take into consideration both short-term and long-term changes in the hydrologic budget of the lakes. This is particularly true when working in areas of strong seasonality in temperature and precipitation and negative effective moisture where many lakes owe their existence to inflow from groundwater. Moreover the chemistry (especially Mg/Ca and Sr/Ca) and δ18O of lake water may respond differently to hydrologic changes depending on whether they are caused by climate or other factors. These complications make clear how important it is to have information on ostracode ecology, to conduct a time-series monitoring study of the modern system, and to employ other proxy records. Examples of such studies are available from many semi-arid and arid regions of the world. Here I use Rice and Coldwater Lakes, North Dakota, as examples from the northern Great Plains of North America to illustrate these points. Decadally resolved Mg/Ca ratio variations for Rice Lake for the last 2000 years show excellent correlation with the GISP2 ice core δ18O record sampled at the same temporal resolution. Mg/Ca data for Rice and Coldwater Lakes also show good agreement with each other and with diatom-inferred salinity records for Coldwater as well as for Moon Lake located 100 km NNE of Coldwater Lake. However, δ18O records for neither lake are correlated with Mg/Ca records and highlight the importance of knowing the hydrology of each system.

  3. 18O-Labeled Proteome Reference as Global Internal Standards for Targeted Quantification by Selected Reaction Monitoring-Mass Spectrometry

    SciTech Connect

    Kim, Jong Seo; Fillmore, Thomas L.; Liu, Tao; Robinson, Errol W.; Hossain, Mahmud; Champion, Boyd L.; Moore, Ronald J.; Camp, David G.; Smith, Richard D.; Qian, Weijun

    2011-10-11

    Selected reaction monitoring-mass spectrometry (SRM-MS) is an emerging technology for high throughput targeted protein quantification and verification in biological and biomarker discovery studies; however, the cost associated with the use of stable isotope labeled synthetic peptides as internal standards is prohibitive for quantitatively screening large numbers of candidate proteins as often required in the pre-verification phase of biomarker discovery. Herein we present the proof-of-concept experiments of using an 18O-labeled 'universal' reference as comprehensive internal standards for quantitative SRM-MS analysis. With an 18O-labeled whole proteome sample as reference, every peptide of interest will have its own corresponding heavy isotope labeled internal standard, thus providing an ideal approach for quantitative screening of a large number of candidates using SRM-MS. Our results showed that the 18O incorporation efficiency using a recently improved protocol was >99.5% for most peptides investigated, a level comparable to 13C/15N labeled synthetic peptides in terms of heavy isotope incorporation. The accuracy, reproducibility, and linear dynamic range of quantification were further assessed based on known ratios of standard proteins spiked into mouse plasma with an 18O-labeled mouse plasma reference. A dynamic range of four orders of magnitude in relative concentration was obtained with high reproducibility (i.e., coefficient of variance <10%) based on the 16O/18O peak area ratios. Absolute and relative quantification of C-reactive protein and prostate-specific antigen were demonstrated by coupling an 18O-labeled reference with standard additions of protein standards. Collectively, our results demonstrated that the use of 18O-labeled reference provides a convenient and effective strategy for quantitative SRM screening of large number of candidate proteins.

  4. Cold air incursions, δ18O variability, and monsoon dynamics associated with snow days at Quelccaya Ice Cap, Peru

    NASA Astrophysics Data System (ADS)

    Hurley, John V.; Vuille, Mathias; Hardy, Douglas R.; Burns, Stephen J.; Thompson, Lonnie G.

    2015-08-01

    Quelccaya Ice Cap in the Andes of Peru contains an annually resolved δ18O record covering the past 1800 years; yet atmospheric dynamics associated with snow deposition and δ18O variability at this site are poorly understood. Here we make use of 10 years of snow pit and short core δ18O data and hourly snow-height measurements obtained by an automated weather station deployed at the ice cap's summit to analyze linkages between snowfall, δ18O, and the South American summer monsoon (SASM). Snow accumulation peaks in December and is negative May-September. Snow δ18O values decrease gradually through austral summer from about -17 to -24‰. Surface snow δ18O is altered after deposition during austral winter from about -24 to -15‰. More than 70% of the total snow accumulation is tied to convection along the leading edge of cold air incursions of midlatitude air advected equatorward from southern South America. Snowfall amplitude at Quelccaya Ice Cap varies systematically with regional precipitation, atmospheric dynamics, midtroposphere humidity, and water vapor δD. Strongest snowfall gains correspond with positive precipitation anomalies over the western Amazon Basin, increased humidity, and lowered water vapor δD values, consistent with the "amount effect." We discuss ventilation of the monsoon, modulated by midlatitude cold air advection, as potentially diagnostic of the relationship between SASM dynamics and Quelccaya snowfall. Results will serve as a basis for development of a comprehensive isotopic forward model to reconstruct past monsoon dynamics using the ice core δ18O record.

  5. Influence of Interstellar FUV Radiation on the Abundance Ratio of 13CO to C18O in L 1551

    NASA Astrophysics Data System (ADS)

    Lin, Sheng-Jun; Shimajiri, Yoshito; Hara, Chihomi; Lai, Shih-Ping; Nakamura, Fumitaka; Sugitani, Koji; Kawabe, Ryohei; Kitamura, Yoshimi; Yoshida, Atsushi; Tatei, Hidefumi; Akashi, Toshiya; Tsukagushi, Takashi

    2015-08-01

    To investigate the relationship between the far-ultraviolet (FUV) radiation and the abundance ratios between 13CO and C18O, we observed L 1551 in 12CO (J=1-0), 13CO (J=1-0) and C18O (J=1-0) using the Nobeyama Radio Observatory 45 m telescope with an angular resolution of ~22" (corresponding to 0.017 pc at a distance of 160 pc). L 1551 is chosen because it is relatively isolated in Taurus-Auriga complex, providing an ideal environment for studying the variation of abundance ratio due to the penetration of the FUV photons. L 1551 is a young star-forming region containing at least 6 young protostars between Class I and Class III stages and a quiescent elongated starless core. The distribution of 12CO emission shows the outflows coming from 2 youngest protostars IRS5 and NE. The 13CO and C18O are detected throughout the whole region with enhancement around the outflows and depletion in the outflow cavities. To avoid the influence of outflows, we exclude the outflow regions for X(13CO)/X(C18O) abundance ratio calculation. X(13CO)/X(C18O) is found in the range of 3.2 -- 36.2 with a mean value of 7.6. Comparing to the extinction map derived from Herschel observations, we found that the abundance ratio reaches its maximum at low AV and decreases to typical solar system value of 5.5 within the starless core. The high X(13CO)/X(C18O) value at the low AV value in L 1551 is most likely due to the selective FUV photodissociation of C18O. This is in contrast with Orion-A region where its internal OB stars keep the abundance ratio at a high level greater than ~10.

  6. Controlling factors of Ca isotope fractionation in scleractinian corals evaluated by temperature, pH and light controlled culture experiments

    NASA Astrophysics Data System (ADS)

    Inoue, Mayuri; Gussone, Nikolaus; Koga, Yasuko; Iwase, Akihiro; Suzuki, Atsushi; Sakai, Kazuhiko; Kawahata, Hodaka

    2015-10-01

    In this study, the 44Ca/40Ca ratios of Porites australiensis grown under three different culture experiments composed of temperature, pH and light controlled culture experiments are measured. The temperature dependent isotope fractionation of 0.02‰/°C deduced from this study is similar to inorganic aragonite, but the degree of isotope fractionation is about +0.4‰ offset in corals. These observations agree with earlier results on different coral species, suggesting Ca isotope fractionation during Ca transmembrane transport in corals. While in cultured corals a significant temperature dependence of δ44Ca is observed, the relationships between calcium isotope fractionation and pH as well as light intensity are negligible. Therefore variation of δ44Ca in Porites corals is mainly controlled by temperature. A combination of δ44Ca and Sr/Ca of corals in temperature controlled experiments cannot be explained by Rayleigh type fractionation directly from a fluid, which is seawater-like in terms of δ44Ca and Sr/Ca. Through coral-specific biomineralization processes, overall mean δ44Ca of scleractinian corals including previous studies are different from biogenic aragonites secreted by sclerosponges and pteropods, but are comparable with those of bivalves as well as calcitic coccolithophores and foraminifers. These findings are important for better understanding biomineralization in corals and in order to constrain the Ca isotopic composition of oceanic Ca sinks in response to climate changes and associated with shifts of calcite and aragonite seas.

  7. LED-based Fourier transform spectroscopy of 16O12C18O and 12C18O2 in the 11,260-11,430 cm-1 range

    NASA Astrophysics Data System (ADS)

    Serdyukov, V. I.; Sinitsa, L. N.; Lugovskoi, A. A.; Borkov, Yu. G.; Tashkun, S. A.; Perevalov, V. I.

    2016-07-01

    The absorption spectrum of the 16O12C18O and 12C18O2 carbon dioxide isotopologues has been recorded in the 11,260- 11,430 cm-1 spectral range using Bruker IFS 125 HR Fourier transform spectrometer with resolution 0.05 cm-1 at temperature 297 K and path length 24 m. The 18O enriched sample of carbon dioxide at total pressure 96.5 mbar was used for these purposes. The spectrometer used LED emitter as a light source. This gave possibility to reach the minimal detectable absorption coefficient αmin~1.4×10-7 cm-1 using 23,328 scans. In the recorded spectrum we have assigned the 00051-00001 band for both 16O12C18O and 12C18O2 isotopologues using the predictions performed within the framework of the method of effective operators. The line positions and intensities of the observed bands are found. The comparison of the observed and predicted line positions and intensities is performed confirming good accuracy of the predictions. The spectroscopic parameters for the observed bands are determined.

  8. Two-neutron stripping in ({sup 18}O, {sup 16}O) and (t,p) reactions

    SciTech Connect

    Cavallaro, M.; Agodi, A.; Carbone, D.; Cunsolo, A.; Bondì, M.; Cappuzzello, F.; Nicolosi, D.; Tropea, S.; Borello-Lewin, T.; Rodrigues, M. R. D.; De Napoli, M.; Garcia, V. N.

    2014-11-11

    The {sup 12}C({sup 18}O,{sup 16}O){sup 14}C reactions has been investigated at 84 MeV incident energy. The charged ejectiles produced in the reaction have been momentum analyzed and identified by the MAGNEX magnetic spectrometer. Q-value spectra have been extracted with an energy resolution of 160 keV (Full Width at Half Maximum) and several known bound and resonant states of {sup 14}C have been identified up to 15 MeV. In particular, excited states with dominant 2p - 4h configuration are the most populated. The absolute values of the cross sections have been extracted showing a striking similarity with those measured for the same transitions by (t,p) reactions. This indicates that the effect of the {sup 16}O core is negligible in the reaction mechanism.

  9. States of {sup 15}C via the ({sup 18}O,{sup 16}O) reaction

    SciTech Connect

    Cappuzzello, F.; Carbone, D.; Cavallaro, M.; Cunsolo, A.; Orrigo, S. E. A.; Foti, A.; Rodrigues, M. R. D.

    2010-04-30

    A study of the {sup 15}C states was pursued in 2008 at the Catania INFN-LNS laboratory by the {sup 13}C({sup 18}O,{sup 16}O){sup 15}C reaction at 84 MeV incident energy. The {sup 16}O ejectiles were detected at forward angles by the MAGNEX magnetic spectrometer. The spectra show several known low lying states up to about 7 MeV excitation energy as well as two unknown resonant structures at about 11.4 and 13.5 MeV. The strong excitation of these latter together with the measured width of about 2 MeV FWHM could indicate the presence of collective modes of excitation connected to the transfer of a correlated neutron pair.

  10. Optimised conditions for the synthesis of (17)O and (18)O labelled cholesterol.

    PubMed

    de la Calle Arregui, Celia; Purdie, Jonathan A; Haslam, Catherine A; Law, Robert V; Sanderson, John M

    2016-02-01

    Conditions are described for the preparation of cholesterol with (17)O and (18)O labels from i-cholesteryl methyl ether using minimal amounts of isotopically enriched water. Optimum yields employed trifluoromethanesulfonic acid as catalyst in 1,4-dioxane at room temperature with 5 equivalents of water. An isotopic enrichment >90% of that of the water used for the reaction could be attained. Tetrafluoroboric acid could also be used as catalyst, at the expense of a lower overall reaction yield. Byproducts from the reaction included dicholesteryl ether, methyl cholesteryl ether, compounds formed by ether hydrolysis, and olefins arising from elimination reactions. Reactions in tetrahydrofuran yielded significant amounts of cholesteryl ethers formed by reaction with alcohols arising from hydrolysis of the solvent. PMID:26724708

  11. Biochemical assessment of growth factors and circulation of blood components contained in the different fractions obtained by centrifugation of venous blood.

    PubMed

    Corigiano, M; Ciobanu, G; Baldoni, E; Pompa, G

    2014-01-01

    The aim of this study was to evaluate a biochemical marker with different elements of a normal blood serum and centrifuged blood serum after a different rotation system. For this technique, we used five fractions of a blood Concentrated Growth Factors system (bCGF) and a particular device for the different rotation program. Blood samples were collected from 10 volunteers aged between 35 and 55 in the Operative Unit of the “Sapienza” University of Rome with only a fraction of different biochemical elements. Through an individual blood phase separator tube of venous blood, active factions of serum and 4 fractions of red buffy coat were taken. The biochemical markers with 14 elements were examined at times: P1-11 minutes, P2-12minutes, P3-15 minutes. Exclusively biological materials which are normally applied in the regeneration techniques for different defects and lesions were used with this technique. After specific rotation programs, a different result was obtained for each cycle: P1, P2, P3. In test tubes obtained by separated blood, we observed a higher concentration of proteins, ions, and other antigens compared to normal blood plasma. Examining the biochemical results of different elements, we observed an increase (P≤0,01). Since each person’s DNA is different, we could not have the same results in 5 fractions of blood concentration, we did, however, find a good increase in only a fraction of proteins, immunoglobulin and different ions. We obtained five fractions after centrifugation, and we had an increase in different biochemical elements compared to normal blood (P≤0,01) which is significant at different times. These biochemical elements were stimulated by different growth factors, which are used by the immune system, and they induced the formation of hard and soft tissues and good regeneration. PMID:25001662

  12. Equilibrium Iron Isotope Fractionation Factors of Minerals: Reevaluation from the Data of Nuclear Inelastic Resonant X-ray Scattering and Mossbauer Spectroscopy

    SciTech Connect

    Polyakov, Dr. V. B.; Clayton, R. N.; Horita, Juske; Mineev, S. D.

    2007-01-01

    We have critically reevaluated equilibrium iron isotope fractionation factors for oxide and sulfide minerals using recently acquired data obtained by Moessbauer spectroscopy and inelastic nuclear resonant X-ray scattering (INRXS) synchrotron radiation. Good agreement was observed in the iron {beta}-factors of metallic iron ({alpha}-Fe) and hematite calculated using both Moessbauer- and INRXS-derived data, which supports the validity and reliability of the calculations. Based on this excellent agreement, we suggest the use of the present data on the iron {beta}-factors of hematite as a reference. The previous Moessbauer-derived iron {beta}-factor for magnetite has been modified significantly based on the Fe-sublattice density of states obtained from the INRXS experiments. This resolves the disagreement between naturally observed iron isotope fractionation factors for mineral pairs involving magnetite and those obtained from the calculated {beta}-factors. The correctness of iron {beta}-factor for pyrite has been corroborated by the good agreement with experimental data of sulfur isotope geothermometers of pyrite-galena and pyrite-sphalerite. A good correlation between the potential energy of the cation site, the oxidation state of iron and the iron {beta}-factor value has been established. Specifically, ferric compounds, which have a higher potential energy of iron than ferrous compounds, have higher {beta}-factors. A similar dependence of b-factors on the oxidation state and potential energy could be extended to other transition metals. Extremely low values of INRXS-derived iron {beta}-factors for troilite and Fe{sub 3}S significantly widen the range of iron b-factors for covalently bonded compounds.

  13. Effects of land use on the distribution of stable isotopes of water (18O/2H) in a deep unconfined aquifer and its role for recharge estimates.

    NASA Astrophysics Data System (ADS)

    Müller, Sascha; Jessen, Søren; Engesgaard, Peter; Jari Leskelä, Jari

    2014-05-01

    /2H signal for the Rabis Creek aquifer is slightly displaced from the GMWL with a slope of 7.8. Slopes for each single well reveal that groundwater areas under agricultural and heath areas have lower slopes between 6 and 7 indicating stronger effects of soil evaporation on the recharged water. Groundwater derived from forest areas show slopes close to 8 and, thus seem to be less affected by soil evaporation. Recharge estimates based on the offset of 18O/2H from the GMWL differ between the land use types by 150 mm, but are generally overestimated by a factor of 1.5-2 compared to recharge values estimated for the area from earlier studies. This suggest that a) flow zonation in aquifer plays a role for the recharge estimate or b) estimates based on the offset from a local meteoric water line (LMWL) could result in more appropriate recharge values. Generally, the study shows that the δ18O in groundwater can be used to trace land use from recharging areas. However, refined recharge estimates are subject to ongoing research.

  14. Body temperatures of modern and extinct vertebrates from 13C-18O bond abundances in bioapatite

    PubMed Central

    Eagle, Robert A.; Schauble, Edwin A.; Tripati, Aradhna K.; Tütken, Thomas; Hulbert, Richard C.; Eiler, John M.

    2010-01-01

    The stable isotope compositions of biologically precipitated apatite in bone, teeth, and scales are widely used to obtain information on the diet, behavior, and physiology of extinct organisms and to reconstruct past climate. Here we report the application of a new type of geochemical measurement to bioapatite, a “clumped-isotope” paleothermometer, based on the thermodynamically driven preference for 13C and 18O to bond with each other within carbonate ions in the bioapatite crystal lattice. This effect is dependent on temperature but, unlike conventional stable isotope paleothermometers, is independent from the isotopic composition of water from which the mineral formed. We show that the abundance of 13C-18O bonds in the carbonate component of tooth bioapatite from modern specimens decreases with increasing body temperature of the animal, following a relationship between isotope “clumping” and temperature that is statistically indistinguishable from inorganic calcite. This result is in agreement with a theoretical model of isotopic ordering in carbonate ion groups in apatite and calcite. This thermometer constrains body temperatures of bioapatite-producing organisms with an accuracy of 1–2 °C. Analyses of fossilized tooth enamel of both Pleistocene and Miocene age yielded temperatures within error of those derived from similar modern taxa. Clumped-isotope analysis of bioapatite represents a new approach in the study of the thermophysiology of extinct species, allowing the first direct measurement of their body temperatures. It will also open new avenues in the study of paleoclimate, as the measurement of clumped isotopes in phosphorites and fossils has the potential to reconstruct environmental temperatures. PMID:20498092

  15. Insolation Gradient Reconciling Early Warming Relative to d18O Terminations

    NASA Astrophysics Data System (ADS)

    Liu, Z.; Herbert, T. D.

    2002-12-01

    Milankovitch theory ‘ that ice-volume is controlled by the insolation at critical latitudes and seasons (65*N) ‘ has been favored for its ability to account for some key features of Pleistocene glaciations. However, one of perplexing mysteries unresolved by this theory is that, about 3 to 1 million years ago, ice sheets varied at almost metronomic 41-ka obliquity cycles, while the 21-ka precessional period is dominant in insolation. Another related problem but not addressed by this theory is that some of climatic proxies suggest an early transition relative to the insolation, resulting in a `causality problem' if insolation is claimed as the external forcing. For example, U-Th dating of some coral reefs, d18O of calcite vein, and sea surface temperature (SST) records have shown that the penultimate transition occurred as early as 135-142 ka ago, whereas the June insolation was below the average before ~133 ka ago. These two puzzles (41-ka variability and timing of transitions) can be resolved if one uses insolation gradients between high and low latitudes, in addition to 65*N insolation alone, as the external driving force of ice ages. The insolation gradient has a strikingly similar distribution of frequency variances to paleoclimatic records (SST and d18O) before the late Pleistocene. One of the insolation gradient minimum, occurring at ~149 ka ago, 10 ka earlier than the insolation minimum, could well explain the early penultimate transition (e.g. SSTs and sea levels). We argue that Pleistocene glaciations are controlled by insolation gradients. Interglacials correspond to stronger insolation gradients, caused by either increasing high-latitude insolation, as Milankovitch theory states, or a reduction in low-latitude insolation which provides less northward atmospheric heat (moisture) transport, as some climate models suggest.

  16. Historical droughts in northern Vietnam captured by variability in speleothem δ18O

    NASA Astrophysics Data System (ADS)

    Hardt, B. F.; McGee, D.; Burns, S. J.; Hieu, N.; Hieu, D. T.

    2015-12-01

    Speleothem records overlapping with the historical period offer valuable comparisons of documentary evidence with speleothem proxy data. These records provide opportunities to 'ground-truth' the paleo-record, fill in gaps in the historical record, and more confidently extent the paleo-record into deeper time. Here we present isotopic results from a stalagmite collected in northern Vietnam spanning 1200 to 1950 CE, a period with a rich historical record in Vietnam. This sample adds significantly to the relatively sparse paleoclimate record from Southeast Asia. The record includes several multi-decadal positive excursions of ≥1 per mille in calcite δ18O. A preliminary age model, based on six U/Th ages, suggests possible correspondence to noted droughts from the historical record, including the Angkor Droughts, the Ming Dynasty Drought, the Strange Parallels Drought, and the Victorian Holocaust Drought. As modeling studies indicate a strong correlation between rainfall δ18O and both the intensity of summer monsoon winds and summer rainfall over northern Vietnam (e.g., Liu et al., 2014), these excursions are consistent with a decrease in regional precipitation. The Vietnam record shows an overall negative trend during the Little Ice Age. The study site is located well south of the westerly wind belt, ruling out a shift between monsoonal and mid-latitude circulation systems as a likely explanation for the northern Vietnam record. We explore the correspondence between our record and other proxy data from Southeast Asia and suggest possible implications of the differences between Vietnamese and Chinese speleothem records during the Little Ice Age. References cited: Liu Z., Wen X., Brady E. C., Otto-Bliesner B., Yu G., Lu H., Cheng H., Wang Y., Zheng W., Ding Y., Edwards R. L., Cheng J., Liu W. and Yang H. (2014) Chinese cave records and the East Asia Summer Monsoon. Quaternary Science Reviews 83, 115-128.

  17. An explanation for the 18O excess in Noelaerhabdaceae coccolith calcite

    NASA Astrophysics Data System (ADS)

    Hermoso, M.; Minoletti, F.; Aloisi, G.; Bonifacie, M.; McClelland, H. L. O.; Labourdette, N.; Renforth, P.; Chaduteau, C.; Rickaby, R. E. M.

    2016-09-01

    Coccoliths have dominated the sedimentary archive in the pelagic environment since the Jurassic. The biominerals produced by the coccolithophores are ideally placed to infer sea surface temperatures from their oxygen isotopic composition, as calcification in this photosynthetic algal group only occurs in the sunlit surface waters. In the present study, we dissect the isotopic mechanisms contributing to the "vital effect", which overprints the oceanic temperatures recorded in coccolith calcite. Applying the passive diffusion model of carbon acquisition by the marine phytoplankton widely used in biogeochemical and palaeoceanographic studies, our results suggest that the oxygen isotope offsets from inorganic calcite in fast dividing species Emiliania huxleyi and Gephyrocapsa oceanica originates from the legacy of assimilated 18O-rich CO2 that induces transient isotopic disequilibrium to the internal dissolved inorganic carbon (DIC) pool. The extent to which this intracellular isotopic disequilibrium is recorded in coccolith calcite (1.5 to +3‰ over a 10 to 25 °C temperature range) is set by the degree of isotopic re-equilibration between CO2 and water molecules before intracellular mineralisation. We show that the extent of re-equilibration is, in turn, set by temperature through both physiological (dynamics of the utilisation of the DIC pool) and thermodynamic (completeness of the re-equilibration of the relative 18O-rich CO2 influx) processes. At the highest temperature, less ambient aqueous CO2 is present for algal growth, and the consequence of carbon limitation is exacerbation of the oxygen isotope vital effect, obliterating the temperature signal. This culture dataset further demonstrates that the vital effect is variable for a given species/morphotype, and depends on the intricate relationship between the environment and the physiology of biomineralising algae.

  18. The First Detailed 2H and 18O Isoscapes of Freshwater in Scotland

    NASA Astrophysics Data System (ADS)

    Meier-Augenstein, W.; Hoogewerff, J.; Kemp, H. F.; Frew, D.

    2012-04-01

    Scotland's freshwater lochs and reservoirs provide a vital resource for sustaining biodiversity, agriculture, food production as well as for human consumption. Regular monitoring of freshwater quality by the Scottish Environmental Protection Agency (SEPA) fulfils the legislative requirements but new scientific methods involving stable isotope analysis present an opportunity for delivering on current and nascent government policies [1] and gaining a greater understanding of Scottish waters and their importance in the context of climate change, environmental sustainability and the aforementioned functions. In brief, 2H and 18O isoscapes of Scottish freshwater could be used to support fundamental and applied research in: • Climate change - These first ever isoscapes will provide a baseline against which future environmental impact can be assessed due to changes in the characteristic isotope composition of freshwater lochs and reservoirs. • Scottish branding - Location specific stable isotope signatures of Scottish freshwater have the potential to be used as a tool for provenancing and thus protecting premium Scottish produce such as Scottish beef, Scottish berries and Scottish Whisky. During 2011, freshwater samples were collected with the support of SEPA from more than 80 freshwater lochs and reservoirs across Scotland. Here we present the result of the 2H and 18O stable isotope analyses of these water samples together with the first isoscapes generated based on these data. [1] Adaptation Framework - Adapting Our Ways: Managing Scotland's Climate Risk (2009): Scotland's Biodiversity: It's in Your Hands - A strategy for the conservation and enhancement of biodiversity in Scotland (2005); Recipe For Success - Scotland's National Food and Drink Policy (2009); Scottish Planning Policy Environmental Report (2009); Scottish Planning Policy (SPP) 15 Planning for Rural Development (2005); National Planning Policy Guideline (NPPG) 14: Natural Heritage (1999).

  19. Towards A Modern Calibration Of The 238U/235U Paleoredox Proxy: Apparent Uranium Isotope Fractionation Factor During U(VI)-U(IV) Reduction In The Black Sea

    NASA Astrophysics Data System (ADS)

    Rolison, J. M.; Stirling, C. H.; Middag, R.; Rijkenberg, M. J. A.; De Baar, H. J. W.

    2015-12-01

    The isotopic compositions of redox-sensitive metals, including uranium (U), in marine sediments have recently emerged as powerful diagnostic tracers of the redox state of the ancient ocean-atmosphere system. Interpretation of sedimentary isotopic information requires a thorough understating of the environmental controls on isotopic fractionation in modern anoxic environments before being applied to the paleo-record. In this study, the relationship between ocean anoxia and the isotopic fractionation of U was investigated in the water column and sediments of the Black Sea. The Black Sea is the world's largest anoxic basin and significant removal of U from the water column and high U accumulation rates in modern underlying sediments have been documented. Removal of U from the water column occurs during the redox transition of soluble U(VI) to relatively insoluble U(IV). The primary results of this study are two-fold. First, significant 238U/235U fractionation was observed in the water column of the Black Sea, suggesting the reduction of U induces 238U/235U fractionation with the preferential removal of 238U from the aqueous phase. Second, the 238U/235U of underlying sediments is related to the water column through the isotope fractionation factor of the reduction reaction but is influenced by mass transport processes. These results provide important constraints on the use of 238U/235U as a proxy of the redox state of ancient oceans.

  20. Oxygen and carbon isotope fractionation in the system dolomite-water-CO2 to elevated temperatures

    NASA Astrophysics Data System (ADS)

    Horita, Juske

    2014-03-01

    An experimental study was conducted to determine oxygen and carbon isotope fractionation factors in the system dolomite-water-CO2 at 80-350 and 100-250 °C, respectively, by means of direct precipitation (80 °C) and dolomitization of CaCO3 (100-350 °C). The products are protodolomite with slight Ca-excess (80-100 °C) and well-ordered stoichiometric dolomite (150-350 °C). Several experimental artifacts (inheritance, premature reactions, and kinetic effects) were tested, although attainment of isotope equilibrium cannot be proven. 18O/16O fractionation factors of (proto)dolomite-water at 80-350 °C can be readily expressed with 1σ error: 103lnα=3.140(±0.022)·{106}/{T2}-3.14(±0.11). Our experimental study, which is generally consistent with a majority of experimental and theoretical studies in the literature, provides for the first time an accurate equation over a wide range of temperature. In combination of the calcite-water equation (O’Neil et al., 1969; Friedman and O’Neil, 1977), 18O/16O fractionation factors of (proto)dolomite-calcite at 80-350 °C can also be expressed with 1σ error: 103lnα=0.351(±0.028)·{106}/{T2}-0.25(±0.13). Dolomite is slightly (0.7-2.6‰) enriched in 18O relative to calcite in this temperature range. Given the very good linearity with a 1/T2 term, the above two equations may be extrapolated beyond the temperature range. Our experimental results of 13C/12C fractionation between CO2 and dolomite at 100-250 °C also show a linear function with a 1/T2 term with a cross-over temperature of 200 °C, which differs from results of theoretical calculations.

  1. A high-resolution peak fractionation approach for streamlined screening of nuclear-factor-E2-related factor-2 activators in Salvia miltiorrhiza.

    PubMed

    Zhang, Hui; Luo, Li-Ping; Song, Hui-Peng; Hao, Hai-Ping; Zhou, Ping; Qi, Lian-Wen; Li, Ping; Chen, Jun

    2014-01-24

    Generation of a high-purity fraction library for efficiently screening active compounds from natural products is challenging because of their chemical diversity and complex matrices. In this work, a strategy combining high-resolution peak fractionation (HRPF) with a cell-based assay was proposed for target screening of bioactive constituents from natural products. In this approach, peak fractionation was conducted under chromatographic conditions optimized for high-resolution separation of the natural product extract. The HRPF approach was automatically performed according to the predefinition of certain peaks based on their retention times from a reference chromatographic profile. The corresponding HRPF database was collected with a parallel mass spectrometer to ensure purity and characterize the structures of compounds in the various fractions. Using this approach, a set of 75 peak fractions on the microgram scale was generated from 4mg of the extract of Salvia miltiorrhiza. After screening by an ARE-luciferase reporter gene assay, 20 diterpene quinones were selected and identified, and 16 of these compounds were reported to possess novel Nrf2 activation activity. Compared with conventional fixed-time interval fractionation, the HRPF approach could significantly improve the efficiency of bioactive compound discovery and facilitate the uncovering of minor active components. PMID:24406141

  2. Estimation of EEC, unattached fraction and equilibrium factor for the assessment of radiological dose using pin-hole cup dosimeters and deposition based progeny sensors.

    PubMed

    Bangotra, Pargin; Mehra, Rohit; Kaur, Kirandeep; Kanse, Sandeep; Mishra, Rosaline; Sahoo, B K

    2015-10-01

    High concentration of radon ((222)Rn), thoron ((220)Rn) and their decay products in environment may increase the risk of radiological exposure to the mankind. The (222)Rn, (220)Rn concentration and their separate attached and unattached progeny concentration in units of EEC have been measured in the dwellings of Muktsar and Mansa districts of Punjab (India), using Pin-hole cup dosimeters and deposition based progeny sensors (DTPS/DRPS). The indoor (222)Rn and (220)Rn concentration was found to vary from 21 Bqm(-3) to 94 Bqm(-3) and 17 Bqm(-3) to 125 Bqm(-3). The average EEC (attached + unattached) of (222)Rn and (220)Rn was 25 Bqm(-3) and 1.8 Bqm(-3). The equilibrium factor for (222)Rn and (220)Rn in studied area was 0.47 ± 0.13 and 0.05 ± 0.03. The equilibrium factor and unattached fraction of (222)Rn and (220)Rn has been calculated separately. Dose conversion factors (DCFs) of different models have been calculated from unattached fraction for the estimation of annual effective dose in the studied area. From the experimental data a correlation relationship has been observed between unattached fraction (f(p)(Rn)) and equilibrium factor (F(Rn)). The present work also aims to evaluate an accurate expression among available expression in literature for the estimation of f(p)(Rn). PMID:26117280

  3. Intra-shell d18O in Cultured Benthic Foraminiferan Amphistegina lobifera and the Influence of Seawater Carbonate Chemistry and Temperature on this Isotopic Composition

    NASA Astrophysics Data System (ADS)

    Rollion-Bard, C.; Erez, J.; Zilberman, T.; Segev, E.

    2006-12-01

    Using secondary ion mass spectrometry (SIMS) we looked at the natural variability in the oxygen isotope ratio of the shallow water, symbionts bearing foraminiferan A. lobifera. Live foraminifera were collected in June 2005 in the Gulf of Eilat, Israel. Vertical section exposing the knob area of this species represents the growth history of this species from December 2004 to June 2005. SIMS profile at a resolution of ~ 2 weeks yielded δ^1^8O changes of ~ 1.5 ‰, (from -0.1 ‰ to 1.45 ‰) that are compatible with the known temperature changes for the Gulf of Eilat for this period (20 to 25° C). Natural variability between primary and secondary calcite at the knob area were obtained on horizontal section of the upper knob area. The primary calcite is on average 2 ‰ more negative then the secondary calcite that represents the bulk of the skeleton (more then 95 % by weight). The δ^1^8O in the margin keel area of A. lobifera is also lower compared to the bulk secondary calcite. Specimens that were cultured in the laboratory at a constant temperature and inorganic carbon but at different pH have increased their CaCO3 weight by roughly a factor of 8. Single specimen from each pH (ranging between 7.9 and 8.5) was investigated with the SIMS at the knob area. While there is some variability within each specimen (perhaps related to the primary calcite), the general trend was a decrease in δ^1^8O with increasing pH (or CO32^- concentration), in agreement with previous studies on planktonic foraminifera. Specimens cultured in laboratory at a constant pH, but different temperature were also analysed in the knob area. The temperature range is between 21 and 33° C (experiments at 21, 24, 27 and 33° C). While there is also some variability within each specimen, the trend was a decrease in δ^1^8O with increasing temperature. The decrease measured is 2.7 ± 0.7 ‰ for the entire temperature range, which is completely in agreement with the theoretical value (-0.2 ‰ per

  4. Electrochemical zinc insertion into W{sub 18}O{sub 49}: Synthesis and characterization of new bronzes

    SciTech Connect

    Martinez-de la Cruz, A.; Amador, U.; Rodriguez-Carvajal, J.; Garcia-Alvarado, F. . E-mail: flaga@ceu.es

    2005-10-15

    Divalent zinc ions have been electrochemically inserted into W{sub 18}O{sub 49}, producing zinc bronzes. Under our experimental conditions, W{sub 18}O{sub 49} accepts zinc reversibly as a guest up to 0.9 ions per formula. The reaction seems to proceed through the formation of a solid solution in which the W-O framework of the parent oxide is maintained. The location of the Zn{sup 2+} ions in the framework of W{sub 18}O{sub 49} has been determined by neutron diffraction on a chemically prepared sample having the composition Zn{sub 0.34}W{sub 18}O{sub 49}. As a main result, we found that Zn prefers to insert in one of the four types of quadrangular tunnels. More precisely, it is displaced from the center to occupy a low coordination site. This result indicates that a significant covalent character exists in the Zn-O bond. - Graphical Abstract: The structure of Zn{sub 0.36}W{sub 18}O{sub 49} projected along the b-axis.

  5. Sources of nitrate in the Arno River waters: Constraints from d15N and d18O

    USGS Publications Warehouse

    Nisi, Barbara; Vaselli, Orlando; Buccianti, Antonella; Silva, Steven R.

    2005-01-01

    Running waters in anthropogenically affected areas are susceptible to nitrate contamination. Source identification is a fundamental step for the development of effective remediation. Previous studies pointed to pollution by nitrogen-bearing contaminants in the Arno Basin. In this paper, eleven surface water samples have been analysed for main and trace components and 15N/14N and 18O/16O ratios, with the aim of identifying for the first time the origin of nitrate in the Arno River Basin so that further investigations can appropriately be designed. d18O(NO3)and d15N(NO3) values have allowed to hypothesise the main sources of nitrate, as follows: i) mineralized fertilizer, ii) soil-organic nitrogen, iii) manure and septic waste. The anomalously high d15N and d18O values in the Chiana (d15N=24.9‰ and d18O=15.5‰) and Usciana tributaries (d15N=30.1‰ and d18O=7.2‰) show a low probability of belonging to the same population as that of the other samples and can be related to denitrification process of nitrate from animal waste/sewage and/or an industrial process (e.g. tanneries).

  6. Intra-seasonal dynamics in metabolic processes of 13C/12C and 18O/16O in components of Scots pine twigs from southern Siberia interpreted with a conceptual framework based on the Carbon Metabolism Oscillatory Model

    PubMed Central

    2012-01-01

    Background Carbon isotope data from conifer trees play an important role in research on the boreal forest carbon reservoir in the global carbon cycle. Carbon isotopes are routinely used to study interactions between the environment and tree growth. Moreover, carbon isotopes became an essential tool for the evaluation of carbon assimilation and transport from needles into reserve pools, as well as the allocation of stored assimilates within a tree. The successful application and interpretation of carbon isotopes rely on the coherence of isotopic fractionation modeling. This study employs a new Carbon Metabolism Oscillatory Model (CMOM) to interpret the experimental data sets on metabolic seasonal dynamics of 13C/12 C and 18O/16O ratios measured in twig components of Scots pine growing in southern Siberia (Russia). Results The dynamics of carbon isotopic variables were studied in components of Pinus sylvestris L. in light and in dark chambers during the vegetation period from 14 June to 28 July 2006. At the beginning of this period water-soluble organic matter, mostly labile sugars (including sucrose as the main component) and newly formed bulk needle material, displayed relatively “light” δ13C values (depletion in 13 C). Then, 13 C content increased again with noticeable “depletion” events in the middle of the growth period. A gradual 13 C accumulation took place in the second half of the vegetation period. Similar effects were observed both in the light and in the dark with some temporal shifts. Environmental factors did not influence the δ13C values. A gradual 12C-depletion effect was noticed in needles of the previous year. The δ13C values of sucrose and proteins from needle biomass altered independently from each other in the light chamber. A distinct negative correlation between δ13C and δ18O values was revealed for all studied variables. Conclusions The abrupt 13C depletion recorded by all tested trees for the period from June to July

  7. Growth Rates, Stable Oxygen Isotopes (18O), and Strontium (Sr/Ca) Composition in Two Species of Pacific Sclerosponges (Acanthocheatetes wellsi and Astrosclera willeyana) with 18O Calibration and Application to Paleoceanography

    SciTech Connect

    Grottoli, A.; Adkins, J; Panero, W; Reaman, D; Moots, K

    2010-01-01

    The isotopic and elemental composition of sclerosponge skeletons is used to reconstruct paleoceanographic records. Yet few studies have systematically examined the natural variability in sclerosponge skeletal {delta}{sup 18}O, growth, and Sr/Ca, and how that may influence the interpretation of sclerosponge proxy records. Here, we analyzed short records in seven specimens of Acanthocheatetes wellsi (high-Mg calcite, 21 mol% Mg) from Palau, four A. wellsi (high-Mg calcite, 21 mol% Mg) from Saipan, and three Astrosclera willeyana (aragonite) sclerosponges from Saipan, as well as one long record in an A. wellsi specimen from Palau spanning 1945-2001.5. In Saipan, species-specific and mineralogical effects appear to have a negligible effect on sclerosponge {delta}{sup 18}O, facilitating the direct comparison of {delta}{sup 18}O records between species at a given location. At both sites, A. wellsi {delta}{sup 18}O and growth rates were sensitive to environmental conditions, but Sr/Ca was not sensitive to the same conditions. High-resolution {delta}{sup 18}O analyses confirmed this finding as both A. wellsi and A. willeyana deposited their skeleton in accordance with the trends in isotopic equilibrium with seawater, though with a 0.27{per_thousand} offset in the case of A. willeyana. In the high-Mg-calcite species A. wellsi, Mg may be interfering with Sr incorporation into the skeleton. On multidecadal timescales, A. wellsi sclerosponge {delta}{sup 18}O in Palau tracked the Southern Oscillation Index variability post-1977, but not pre-1977, coincident with the switch in the Pacific Decadal Oscillation (PDO) at {approx}1976. This suggests that water mass circulation in the region is influenced by El Nino-Southern Oscillation variability during positive PDO phases, but not during negative ones.

  8. The iron isotope composition of enstatite meteorites: Implications for their origin and the metal/sulfide Fe isotopic fractionation factor

    NASA Astrophysics Data System (ADS)

    Wang, Kun; Savage, Paul S.; Moynier, Frédéric

    2014-10-01

    due to intensive impact-induced shearing stress, or the ultimate destruction of the Shallowater parent body. Analysis of separated enstatite meteorite mineral phases show that the magnetic phase (Fe metal) is systematically enriched in the heavier Fe isotopes when compared to non-magnetic phases (Fe hosted in troilite), which agrees with previous experimental observations and theoretical calculations. The difference between magnetic and non-magnetic phases from enstatite achondrites provides an equilibrium metal-sulfide Fe isotopic fractionation factor of Δ56Femetal-troilite = δ56Femetal - δ56Fetroilite of 0.129 ± 0.060‰ (2 SE) at 1060 ± 80 K, which confirms the predictions of previous theoretical calculations.

  9. Experimental calibration of silicon and oxygen isotope fractionations between quartz and water at 250°C by in situ microanalysis of experimental products and application to zoned low δ30Si quartz overgrowths

    DOE PAGESBeta

    Pollington, Anthony D.; Kozdon, Reinhard; Anovitz, Lawrence M.; Georg, R. Bastian; Spicuzza, Michael J.; Valley, John W.

    2015-12-01

    The interpretation of silicon isotope data for quartz is hampered by the lack of experimentally determined fractionation factors between quartz and fluid. Further, there is a large spread in published oxygen isotope fractionation factors at low temperatures, primarily due to extrapolation from experimental calibrations at high temperature. We report the first measurements of silicon isotope ratios from experimentally precipitated quartz and estimate the equilibrium fractionation vs. dissolved silica using a novel in situ analysis technique applying secondary ion mass spectrometry to directly analyze experimental products. These experiments also yield a new value for oxygen isotope fractionation. Quartz overgrowths up tomore » 235 μm thick were precipitated in silica–H2O–NaOH–NaCl fluids, at pH 12–13 and 250 °C. At this temperature, 1000lnα30Si(Qtz–fluid) = 0.55 ± 0.10‰ and 1000lnα18O(Qtz–fluid) = 10.62 ± 0.13‰, yielding the relations 1000lnα30Si(Qtz–fluid) = (0.15 ± 0.03) * 106/T2 and 1000lnα18O(Qtz–fluid) = (2.91 ± 0.04) * 106/T2 when extended to zero fractionation at infinite temperature. Values of δ30Si(Qtz) from diagenetic cement in sandstones from the basal Cambrian Mt. Simon Formation in central North America range from 0 to ₋5.4‰. Paired δ18O and δ30Si values from individual overgrowths preserve a record of Precambrian weathering and fluid transport. In conclusion, the application of the experimental quartz growth results to observations from natural sandstone samples suggests that precipitation of quartz at low temperatures in nature is dominated by kinetic, rather than equilibrium, processes.« less

  10. Measurement of Whole-Body CO2 Production in Birds Using Real-Time Laser-Derived Measurements of Hydrogen (δ(2)H) and Oxygen (δ(18)O) Isotope Concentrations in Water Vapor from Breath.

    PubMed

    Mitchell, G W; Guglielmo, C G; Hobson, K A

    2015-01-01

    The doubly labeled water (DLW) method is commonly used to measure energy expenditure in free-living wildlife and humans. However, DLW studies involving animals typically require three blood samples, which can affect behavior and well-being. Moreover, measurement of H (δ(2)H) and O (δ(18)O) isotope concentrations in H2O derived from blood using conventional isotope ratio mass spectrometry is technically demanding, time-consuming, and often expensive. A novel technique that would avoid these constraints is the real-time measurement of δ(2)H and δ(18)O in the H2O vapor of exhaled breath using cavity ring-down (CRD) spectrometry, provided that δ(2)H and δ(18)O from body H2O and breath were well correlated. Here, we conducted a validation study with CRD spectrometry involving five zebra finches (Taeniopygia guttata), five brown-headed cowbirds (Molothrus ater), and five European starlings (Sturnus vulgaris), where we compared δ(2)H, δ(18)O, and rCO2 (rate of CO2 production) estimates from breath with those from blood. Isotope concentrations from blood were validated by comparing dilution-space estimates with measurements of total body water (TBW) obtained from quantitative magnetic resonance. Isotope dilution-space estimates from δ(2)H and δ(18)O values in the blood were similar to and strongly correlated with TBW measurements (R(2) = 0.99). The (2)H and (18)O (ppm) in breath and blood were also highly correlated (R(2) = 0.99 and 0.98, respectively); however, isotope concentrations in breath were always less enriched than those in blood and slightly higher than expected, given assumed fractionation values between blood and breath. Overall, rCO2 measurements from breath were strongly correlated with those from the blood (R(2) = 0.90). We suggest that this technique will find wide application in studies of animal and human energetics in the field and laboratory. We also provide suggestions for ways this technique could be further improved. PMID:26658408

  11. A Novel Method for Relative Quantitation of N-Glycans by Isotopic Labeling Using 18O-Water

    PubMed Central

    Tao, Shujuan; Orlando, Ron

    2014-01-01

    Quantitation is an essential aspect of comprehensive glycomics study. Here, a novel isotopic-labeling method is described for N-glycan quantitation using 18O-water. The incorporation of the 18O-labeling into the reducing end of N-glycans is simply and efficiently achieved during peptide-N4-(N-acetyl-β-glucosaminyl) asparagine amidase F release. This process provides a 2-Da mass difference compared with the N-glycans released in 16O-water. A mathematical calculation method was also developed to determine the 18O/16O ratios from isotopic peaks. Application of this method to several standard glycoprotein mixtures and human serum demonstrated that this method can facilitate the relative quantitation of N-glycans over a linear dynamic range of two orders, with high accuracy and reproducibility. PMID:25365792

  12. Holocene East Asian summer monsoon records in northern China and their inconsistency with Chinese stalagmite δ18O records

    NASA Astrophysics Data System (ADS)

    Liu, Jianbao; Chen, Jianhui; Zhang, Xiaojian; Chen, Fahu

    2016-04-01

    Monsoon precipitation over China exhibits large spatial differences. It has been found that a significantly enhanced East Asian summer monsoon (EASM) is characterized by increased rainfall in northern China and by reduced rainfall in southern China, and this relationship occurs on different time scales during the Holocene. This study presents results from a diverse range of proxy paleoclimatic records from northern China where precipitation variability is traditionally considered as an EASM proxy. Our aim is to evaluate the evolution of the EASM during the Holocene and to compare it with all of the published stalagmite δ18O records from the Asian Monsoon region in order to explore the potential mechanism(s) controlling the Chinese stalagmite δ18O. We found that the intensity of the EASM during the Holocene recorded by the traditional EASM proxy of moisture (or precipitation) records from northern China are significantly different from the Chinese stalagmite δ18O records. The EASM maximum occurred during the mid-Holocene, challenging the prevailing view of an early Holocene EASM maximum mainly inferred from stalagmite δ18O records in eastern China. In addition, all of the well-dated Holocene stalagmite δ18O records, covering a broad geographical region, exhibit a remarkably similar trend of variation and are statistically well-correlated on different time scales, thus indicating a common signal. However, in contrast with the clear consistency in the δ18O values in all of the cave records, both instrumental and paleoclimatic records exhibit significant spatial variations in rainfall on decadal-to- centennial time scales over eastern China. In addition, both paleoclimatic records and modeling results suggest that Holocene East Asian summer monsoon precipitation reached a maximum at different periods in different regions of China. Thus the stalagmite δ18O records from the EASM region should not be regarded as a reliable indicator of the strength of the East

  13. Complex dielectric modulus and relaxation response at low microwave frequency region of dielectric ceramic Ba6-3xNd8+2xTi18O54

    NASA Astrophysics Data System (ADS)

    Lee, Chian Heng; Hassan, Jumiah; Hashim, Mansor; Aziz, Raba'ah Syahidah; Saiden, Norlaily Mohd

    2014-12-01

    The desirable characteristics of Ba6-3xNd8+2xTi18O54 include high dielectric constant, low loss tangent, and high quality factor developed a new field for electronic applications. The microwave dielectric properties of Ba6-3xNd8+2xTi18O54, with x = 0.15 ceramics at different sintering temperatures (600-1300°C) were investigated. The phenomenon of polarization produced by the applied electric field was studied. The dielectric properties with respect to frequency from 1 MHz to 1.5 GHz were measured using Impedance Analyzer, and the results were compared and analyzed. The highest dielectric permittivity and lowest loss factor were defined among the samples. The complex dielectric modulus was evaluated from the measured parameters of dielectric measurement in the same frequency range, and used to differentiate the contribution of grain and grain boundary.

  14. Variability of the Indo-Pacific warm pool convection since 1867 AD in a tree cellulose δ18O record

    NASA Astrophysics Data System (ADS)

    Zhu, M.; Stott, L. D.; Buckley, B. M.

    2011-12-01

    The Indo-Pacific Warm Pool (IPWP) is a major heat and moisture source for atmospheric circulation and is influential for global climate. Various methods, e.g. satellite observations, paleoclimate reconstructions using corals, marine sediments, and speleothems, as well as climate models, have been employed to study the hydrological variability of the IPWP and its relation to global climate. In this study, we provide an alternative way to investigate this problem by analyzing the stable isotopic composition (δ18O) of tree ring cellulose, sampled subannually from Pinus merkusii that grow in Kirirom National Park of southern Cambodia. Our cellulose δ18O record, which spans the period 1867-2006, reveals regular seasonal cycles with an average amplitude of ~4 %, mainly reflecting the seasonal difference in the isotopic composition of soil moisture. The δ18O minimum value in each annual cycle is believed to represent the most isotopically- depleted precipitation of each year, which derives from the oceanic moisture from IPWP in September-October. An isotope amount effect is manifested in the cellulose δ18O minimum values, as they correlate strongly with the amount of rainout over the IPWP before the moisture is transported towards Cambodia. They correlate strongly with the outgoing long wave radiation over the IPWP as well, suggesting that the cellulose δ18O from southern Cambodia could be used to reconstruct the convection intensity over the IPWP. Spectral analysis of the cellulose δ18O reveals significant peaks that are accordant with the ENSO periodicity, 2-7 years, as well as a decadal periodicity of 13.5 years. The variability of our cellulose δ18O record on ENSO band are similar to central Pacific coral δ18O records, with reduced amplitude of variability in the1920sthrough the 1950s, a period of weak ENSO activity. The decadal variability in our cellulose record is also common in coral records, such as the 1976-77 shift, and this might be related to internal

  15. Discovery of heteroatom-"embedded" Te {W18O54} nanofunctional polyoxometalates by use of cryospray mass spectrometry.

    PubMed

    Yan, Jun; Long, De-Liang; Wilson, Elizabeth F; Cronin, Leroy

    2009-01-01

    The cryo game: Heteroatom-embedded nanofunctional clusters are described that incorporate a [Te(VI)O(6)](6-) species contained within a {W(18)O(54)} cage. Not only does the tellurium-based species activate the {W(18)O(54)} cluster surface for assembly of larger nanoscale structures, such as [H(10)Te(VI) (2)W(58)O(198)](26-), it also undergoes a redox transformation inside the cluster from [Te(VI)O(6)](6-) to [Te(IV)O(3)](2-). PMID:19434635

  16. Fluctuations in Tree Ring Cellulose d18O during the Little Ice Age Correlate with Solar Activity

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Y. T.; Yokoyama, Y.; Miyahara, H.; Nakatsuka, T.

    2008-12-01

    The Maunder Minimum (AD1645-1715), when sunspots became exceedingly rare, is known to coincide with the coldest period during the Little Ice Age. This is a useful period to investigate possible linkage between solar activity and climate because variation in solar activity was different from that of today. The solar cycle length was longer (14 and 28 years) than that of today (11 and 22 years) hence any climate archives that have similar periodic changes could be separated from other internal climate forcing. We have reported that Greenland temperature variations coincided with decadal-scale variability in solar activity during the Maunder Minimum (Miyahara et al. 2008). Here we report interannual and intra-annual relative humidity (RH) variations in central Japan during that period, using tree ring cellulose d18O in a 382-year-old Japanese cedar tree (Cryptomeria japonica). The isotopic composition of tree rings can be a powerful tool to study the relationship between solar activity and climate, because we can directly compare solar activity (D14C) and climate (d18O) with little dating error. The climate proxy obtained using tree ring cellulose d18O is correlated both negatively and positively with RH and d18O in precipitation, respectively. Since d18O in precipitation is negatively correlated with the amount of precipitation in the monsoon area, tree ring cellulose d18O can be a reliable proxy for past RH and/or amount of precipitation in the area of the interest. Tree ring cellulose d18O of the cedar tree during AD1938-1998 in fact correlates significantly with the mean RH in June in central Japan. Tree ring d18O inferred RH variability during the Maunder Minimum shows distinct high RH spikes with an approximate 14-year quasiperiodicity. All nine solar minima during AD1640-1756 deduced from tree ring D14C coincided with high RH spikes, and seven of which coincided within 1-year. Interannual RH variations also coincided with Greenland temperature during this

  17. 2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: international collaborative study report.

    PubMed

    Thomas, Freddy; Jamin, Eric

    2009-09-01

    An international collaborative study of isotopic methods applied to control the authenticity of vinegar was organized in order to support the recognition of these procedures as official methods. The determination of the 2H/1H ratio of the methyl site of acetic acid by SNIF-NMR (site-specific natural isotopic fractionation-nuclear magnetic resonance) and the determination of the 13C/12C ratio, by IRMS (isotope ratio mass spectrometry) provide complementary information to characterize the botanical origin of acetic acid and to detect adulterations of vinegar using synthetic acetic acid. Both methods use the same initial steps to recover pure acetic acid from vinegar. In the case of wine vinegar, the determination of the 18O/16O ratio of water by IRMS allows to differentiate wine vinegar from vinegars made from dried grapes. The same set of vinegar samples was used to validate these three determinations. The precision parameters of the method for measuring delta13C (carbon isotopic deviation) were found to be similar to the values previously obtained for similar methods applied to wine ethanol or sugars extracted from fruit juices: the average repeatability (r) was 0.45 per thousand, and the average reproducibility (R) was 0.91 per thousand. As expected from previous in-house study of the uncertainties, the precision parameters of the method for measuring the 2H/1H ratio of the methyl site were found to be slightly higher than the values previously obtained for similar methods applied to wine ethanol or fermentation ethanol in fruit juices: the average repeatability was 1.34 ppm, and the average reproducibility was 1.62 ppm. This precision is still significantly smaller than the differences between various acetic acid sources (delta13C and delta18O) and allows a satisfactory discrimination of vinegar types. The precision parameters of the method for measuring delta18O were found to be similar to the values previously obtained for other methods applied to wine and

  18. In situ unsaturated zone water stable isotope (2H and 18O) measurements in semi-arid environments: a soil water balance

    NASA Astrophysics Data System (ADS)

    Gaj, Marcel; Beyer, Matthias; Koeniger, Paul; Wanke, Heike; Hamutoko, Josefina; Himmelsbach, Thomas

    2016-02-01

    Stable isotopes (deuterium, 2H, and oxygen-18, 18O) of soil water were measured in the field using a liquid water isotope analyzer (tunable off-axis integrated cavity output spectroscope, OA-ICOS, LGR) and commercially available soil gas probes (BGL-30, UMS, Munich) in the semi-arid Cuvelai-Etosha Basin (CEB), Namibia. Results support the applicability of an in situ measurement system for the determination of stable isotopes in soil pore water. High spatial and temporal resolution was achieved in the study area with reasonable accuracy and measurements were in agreement with laboratory-based cryogenic vacuum extraction and subsequent cavity ring-down laser spectroscopic isotope analysis (CRDS, L2120-i, Picarro Inc.). After drift and span correction of the in situ isotope data, precision for over 140 measurements taken during two consecutive field campaigns (June and November 2014) was 1.8 and 0.48 ‰ for δ2H and δ18O, respectively. Mean measurement trueness is determined using quality check standards and was 5 and 0.3 ‰ for δ2H and δ18O, respectively. The isotope depth profiles are used quantitatively to calculate a soil water balance. The contribution of transpiration to total evapotranspiration ranged between 72 and 92 %. Shortly after a rain event, the contribution of transpiration was much lower, at 35 to 50 %. Potential limitations of such an in situ system are related to environmental conditions which could be minimized by using a temperature-controlled chamber for the laser spectrometer. Further, the applicability of the system using previously oven-dried soil material might be limited by physicochemical soil properties (i.e., clay minerals). Uncertainty in the in situ system is suggested to be reduced by improving the calibration procedure and further studying fractionation effects influencing the isotope ratios in the soil water, especially at low water contents. Furthermore, the influence of soil-respired CO2 on isotope values within the root zone

  19. Fluid participation in deep fault zones: Evidence from geological, geochemical, and 18O/16O relations

    NASA Astrophysics Data System (ADS)

    Kerrich, R.; La Tour, T. E.; Willmore, L.

    1984-06-01

    Fluid incursion into fault zones and their deeper level counterparts, brittle-ductile shear zones, is examined in a number of different crustal environments. At the Grenville front, translation was accommodated along two mylonite zones and an associated boundary fault. The high- (MZ II) and low-temperature (MZ I) mylonite zones formed at 580 to 640°C and 430 to 490°C, respectively, in the presence of fluids of metamorphic orgin indigenous to the immediate rocks. A population of posttectonic quartz veins occupying brittle fractures were precipitated from fluids with extremely negative δ18O at 200 to 300°C. The water may have been derived from downwards penetration into fault zones of low-18O precipitation on a mountain range induced by continental collision with, uplift accommodated at deep levels by the mylonite zones coupled with rebound on the boundary faults. At Lagoa Real, Brazil, Archaean gneisses overlie Proterozoic sediments along thrust surfaces and contain brittle-ductile shear zones locally occupied by uranium deposits. Following deformation at 500 to 540°C, in the presence of metamorphic fluids and under conditions of low water to rock ratio, shear zones underwent local intense oxidation and desilicification. All minerals undergo a shift of -10‰, indicating discharge of meteoric water recharged formation brines in the underlying Proterozoic sediments up through the Archaean gneisses during overthrusting: about 1000 km3 of solutions passed through these structures. At Yellow-knife, a series of large-scale shear zones developed by brittle-ductile mechanisms, involving volume dilation with migration of ˜5 wt % volatiles into the shear zone from surrounding metabasalts. This early deformation involved no departures in redox state or whole rock δ18O from background states of Fe2+/ΣFe = 0.72 and 7 to 7.5‰, respectively, attesting to conditions of low water/rock. Shear zones subsequently acted as high-permeability conduits for pulsed discharge of >9

  20. Fluid motion associated with Tertiary mylonitization and detachment faulting: 18O/16O evidence from the Picacho metamorphic core complex, Arizona

    NASA Astrophysics Data System (ADS)

    Kerrich, R.; Rehrig, W.

    1987-01-01

    Major crustal detachment faults of Tertiary age in the Picacho metamorphic core complex of southern Arizona demark three tectonic plates in a structural section characterized by the transition from undeformed granitic basement through a mylonitic carapace to brecciated and hydrothermally altered counterparts. A lower detachment fault defines the top of the lower plate and is coplanar with the overprinting of mylonites to chloritic breccias. Variably altered and fractured granite of an overlying middle plate is bounded by an upper detachment fault on which allochthonous Miocene volcanics have been superposed; the volcanics display intense oxidative potassic alteration. This overall transition is accompanied by a 10‰ increase in δ18O and a 400 °C decrease of temperature. Undeformed Oracle Granite of the lower plate (δ18O ≈7.8) retains near-magmatic mineral fractionations, but these are disturbed in mylonitic equivalents, where ambient temperatures were ˜520 °C, δ18OH2O ≈4‰, and conditions of low water/rock ratios prevailed. Chloritic breccias record a whole-rock shift to +8.5‰, accompanied by diminished temperatures of 300 °C, and the infiltration of fluids where δ18OH2O = 3‰ ± 1‰ under conditions of high water/rock ratios. A pronounced isotopic discontinuity occurs at the upper detachment fault where intensely oxidized and K-metasomatized volcanics of the upper plate are shifted to 18‰ at temperatures that diminished to ˜ 150 °C. Two distinct fluid reservoirs were involved in alteration of the lower two plates and the upper plate, respectively, the tectonic section recording an upward transition from high to low temperature, low to elevated water/rock ratios, ductile creep to brittle fracturing, and an interface of deep “exchanged” fluids with a shallow oxidized surface aqueous reservoir.

  1. Method for selective recovery of PET-usable quantities of [{sup 18}F] fluoride and [{sup 13}N] nitrate/nitrite from a single irradiation of low-enriched [{sup 18}O] water

    DOEpatents

    Ferrieri, R.A.; Schlyer, D.J.; Shea, C.

    1995-06-13

    A process for simultaneously producing PET-usable quantities of [{sup 13}N]NH{sub 3} and [{sup 18}F]F{sup {minus}} for radiotracer synthesis is disclosed. The process includes producing [{sup 13}N]NO{sub 2}{sup {minus}}/NO{sub 3}{sup {minus}}and [{sup 18}F]F{sup {minus}} simultaneously by exposing a low-enriched (20%-30%) [{sup 18}O]H{sub 2}O target to proton irradiation, sequentially isolating the [{sup 13}N]NO{sub 2}{sup {minus}}/NO{sub 3}{sup {minus}} and [{sup 18}F]F{sup {minus}} from the [{sup 18}O]H{sub 2}O target, and reducing the [{sup 13}N]NO{sub 2}{sup {minus}}/NO{sub 3}{sup {minus}} to [{sup 13}N]NH{sub 3}. The [{sup 13}N]NH{sub 3} and [{sup 18}F]F{sup {minus}} products are then conveyed to a laboratory for radiotracer applications. The process employs an anion exchange resin for isolation of the isotopes from the [{sup 18}O]H{sub 2}O, and sequential elution of [{sup 13}N]NO{sub 2}{sup {minus}}/NO{sub 3}{sup {minus}} and [{sup 18}F]F{sup {minus}} fractions. Also the apparatus is disclosed for simultaneously producing PET-usable quantities of [{sup 13}N]NH{sub 3} and [{sup 18}F]F{sup {minus}} from a single irradiation of a single low-enriched [{sup 18}O]H{sub 2}O target. 2 figs.

  2. Complete Measurement of Stable Isotopes in N2O (δ15N, δ15Nα, δ15Nβ, δ18O, δ17O) Using Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS)

    NASA Astrophysics Data System (ADS)

    Leen, J. B.; Gupta, M.

    2014-12-01

    Nitrate contamination in water is a worldwide environmental problem and source apportionment is critical to managing nitrate pollution. Fractionation caused by physical, chemical and biological processes alters the isotope ratios of nitrates (15N/14N, 18O/16O and 17O/16O) and biochemical nitrification and denitrification impart different intramolecular site preference (15N14NO vs. 14N15NO). Additionally, atmospheric nitrate is anomalously enriched in 17O compared to other nitrate sources. The anomaly (Δ17O) is conserved during fractionation processes, providing a tracer of atmospheric nitrate. All of these effects can be used to apportion nitrate in soil. Current technology for measuring nitrate isotopes is complicated and costly - it involves conversion of nitrate to nitrous oxide (N2O), purification, preconcentration and measurement by isotope ratio mass spectrometer (IRMS). Site specific measurements require a custom IRMS. There is a pressing need to make this measurement simpler and more accessible. Los Gatos Research has developed a next generation mid-infrared Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS) analyzer to quantify all stable isotope ratios of N2O (δ15N, δ15Nα, δ15Nβ, δ18O, δ17O). We present the latest performance data demonstrating the precision and accuracy of the OA-ICOS based measurement. At an N2O concentration of 322 ppb, the analyzer quantifies [N2O], δ15N, δ15Na, δ15Nb, and δ18O with a precision of ±0.05 ppb, ±0.4 ‰, ±0.45 ‰, and ±0.6 ‰, and ±0.8 ‰ respectively (1σ, 100s; 1σ, 1000s for δ18O). Measurements of gas standards demonstrate accuracy better than ±1 ‰ for isotope ratios over a wide dynamic range (200 - 100,000 ppb). The measurement of δ17O requires a higher concentration (1 - 50 ppm), easily obtainable through conversion of nitrates in water. For 10 ppm of N2O, the instrument achieves a δ17O precision of ±0.05 ‰ (1σ, 1000s). This performance is sufficient to quantify atmospheric

  3. Landscape hydrology and scaling of nitrate 15N and 18O isotope composition in a semi-arid agroecosystem

    NASA Astrophysics Data System (ADS)

    Kelley, C. J.; Martin, R. A.; Keller, C. K.; Orr, C. H.; Huggins, D. R.; Evans, R. D.

    2014-12-01

    Understanding how pore- to hillslope-scale processes combine to control nutrient export at larger scales is a fundamental challenge in today's agroecosystems as the carbon and contamination footprints of production agriculture come under increasing scrutiny. At the Cook Agronomy Farm (CAF) Long-Term Agricultural Research (LTAR) station near Pullman, WA we are using in-field observations to track how local-scale hydrological routing and biogeochemical processing interact to control landscape-scale water and nutrient exports. Previous research at the CAF has shown that conservative tracers and reactive nutrient quantities (NO3-,and DOC concentrations, DOM quality) in landscape-scale drainage can be explained by straightforward mixing of waters from variably contributing areas. Nitrate stable isotope composition in subsurface drain effluent indicate that most leached nitrate originates from reduced nitrogen fertilizer applied to the CAF in the autumn, which undergoes nitrification and subsequent leaching. This occurs over a timespan of weeks to months. However, water samples from contributing areas exhibit nitrate d15N and d18O significantly greater than subsurface drain effluent at all locations, and time-series consistent with the occurrence of denitrification at some locations. Possible explanations include pore-scale processing of nitrogen that does not affect the other tracers (like EC, DOM quality, and DOC concentration), and landscape-scale transport pathways that bypass our field instruments. Through this work we are contributing to a broader understand of how global change and local factors and management practices interact to affect the fate of fertilizer N, which is a cross-cutting research theme of the national LTAR network.

  4. Neotropical eocene coastal floras and [sup 18]O/[sup 16]O-estimated warmer vs. cooler equatorial waters

    SciTech Connect

    Graham, A. )

    1994-03-01

    The history of the earth's sea-surface temperature (SST) in equatorial regions during the Tertiary is unsettled because of uncertainty as to the presence and extent of glaciers during the Paleogene. The [sup 16]O trapped in glaciers and subsequently released back to the ocean basins as meltwater during interglacials affects the [sup 18]O/[sup 16]O ratio of sea water, one of the variables that must be known for oxygen isotope paleotemperature analysis of calcareous fossils. Estimates of SST range from [approximately]18 to 20 C, assuming an ice-free earth, to [approximately]28 C assuming glaciers were present in the Paleogene. Low latitude SST presently averages 28C, so the former estimate gives a value 8 to 10 C cooler than present, while the latter gives a value as warm or slightly warmer than present. The figures are important for interpreting terrestrial vegetational history because the temperature differential between low and high latitudes is a major factor in determining global climates through the control of poleward transfer of heat. The middle( ) to late Eocene Gatuncillo Formation palynoflora of Panama was deposited at the ocean-continental interface at [approximately]9[degrees]N latitude. The individual components and paleocommunities are distinctly tropical and similar to the present vegetation along the Atlantic coast of southern Central America. This is consistent with data emerging from other recently studied tropical coastal biotas and represents a contribution from paleobiology toward eventually resolving the problem of Eocene equatorial marine environments. Collectively, the evidence is beginning to favor a model of Eocene SST near present values. 50 refs., 1 fig., 2 tabs.

  5. Dynamic phosphometabolomic profiling of human tissues and transgenic models by 18O-assisted ³¹P NMR and mass spectrometry.

    PubMed

    Nemutlu, Emirhan; Zhang, Song; Gupta, Anu; Juranic, Nenad O; Macura, Slobodan I; Terzic, Andre; Jahangir, Arshad; Dzeja, Petras

    2012-04-01

    Next-generation screening of disease-related metabolomic phenotypes requires monitoring of both metabolite levels and turnover rates. Stable isotope (18)O-assisted (31)P nuclear magnetic resonance (NMR) and mass spectrometry uniquely allows simultaneous measurement of phosphometabolite levels and turnover rates in tissue and blood samples. The (18)O labeling procedure is based on the incorporation of one (18)O into P(i) from [(18)O]H(2)O with each act of ATP hydrolysis and the distribution of (18)O-labeled phosphoryls among phosphate-carrying molecules. This enables simultaneous recording of ATP synthesis and utilization, phosphotransfer fluxes through adenylate kinase, creatine kinase, and glycolytic pathways, as well as mitochondrial substrate shuttle, urea and Krebs cycle activity, glycogen turnover, and intracellular energetic communication. Application of expanded (18)O-labeling procedures has revealed significant differences in the dynamics of G-6-P[(18)O] (glycolysis), G-3-P[(18)O] (substrate shuttle), and G-1-P[(18)O] (glycogenolysis) between human and rat atrial myocardium. In human atria, the turnover of G-3-P[(18)O], which defects are associated with the sudden death syndrome, was significantly higher indicating a greater importance of substrate shuttling to mitochondria. Phosphometabolomic profiling of transgenic hearts deficient in adenylate kinase (AK1-/-), which altered levels and mutations are associated to human diseases, revealed a stress-induced shift in metabolomic profile with increased CrP[(18)O] and decreased G-1-P[(18)O] metabolic dynamics. The metabolomic profile of creatine kinase M-CK/ScCKmit-/--deficient hearts is characterized by a higher G-6-[(18)O]P turnover rate, G-6-P levels, glycolytic capacity, γ/β-phosphoryl of GTP[(18)O] turnover, as well as β-[(18)O]ATP and β-[(18)O]ADP turnover, indicating altered glycolytic, guanine nucleotide, and adenylate kinase metabolic flux. Thus, (18)O-assisted gas chromatography-mass spectrometry

  6. Altered Retinoic Acid Metabolism in Diabetic Mouse Kidney Identified by 18O Isotopic Labeling and 2D Mass Spectrometry

    PubMed Central

    Starkey, Jonathan M.; Zhao, Yingxin; Sadygov, Rovshan G.; Haidacher, Sigmund J.; LeJeune, Wanda S.; Dey, Nilay; Luxon, Bruce A.; Kane, Maureen A.; Napoli, Joseph L.; Denner, Larry; Tilton, Ronald G.

    2010-01-01

    Background Numerous metabolic pathways have been implicated in diabetes-induced renal injury, yet few studies have utilized unbiased systems biology approaches for mapping the interconnectivity of diabetes-dysregulated proteins that are involved. We utilized a global, quantitative, differential proteomic approach to identify a novel retinoic acid hub in renal cortical protein networks dysregulated by type 2 diabetes. Methodology/Principal Findings Total proteins were extracted from renal cortex of control and db/db mice at 20 weeks of age (after 12 weeks of hyperglycemia in the diabetic mice). Following trypsinization, 18O- and 16O-labeled control and diabetic peptides, respectively, were pooled and separated by two dimensional liquid chromatography (strong cation exchange creating 60 fractions further separated by nano-HPLC), followed by peptide identification and quantification using mass spectrometry. Proteomic analysis identified 53 proteins with fold change ≥1.5 and p≤0.05 after Benjamini-Hochberg adjustment (out of 1,806 proteins identified), including alcohol dehydrogenase (ADH) and retinaldehyde dehydrogenase (RALDH1/ALDH1A1). Ingenuity Pathway Analysis identified altered retinoic acid as a key signaling hub that was altered in the diabetic renal cortical proteome. Western blotting and real-time PCR confirmed diabetes-induced upregulation of RALDH1, which was localized by immunofluorescence predominantly to the proximal tubule in the diabetic renal cortex, while PCR confirmed the downregulation of ADH identified with mass spectrometry. Despite increased renal cortical tissue levels of retinol and RALDH1 in db/db versus control mice, all-trans-retinoic acid was significantly decreased in association with a significant decrease in PPARβ/δ mRNA. Conclusions/Significance Our results indicate that retinoic acid metabolism is significantly dysregulated in diabetic kidneys, and suggest that a shift in all-trans-retinoic acid metabolism is a novel feature in

  7. Storage stability of keratinocyte growth factor-2 in lyophilized formulations: effects of formulation physical properties and protein fraction at the solid-air interface.

    PubMed

    Devineni, Dilip; Gonschorek, Christoph; Cicerone, Marcus T; Xu, Yemin; Carpenter, John F; Randolph, Theodore W

    2014-10-01

    Lyophilized formulations of keratinocyte growth factor-2 (KGF-2) were prepared with a range of disaccharide (sucrose or trehalose) and hydroxyethyl starch (HES) mass ratios. Protein degradation was assessed as a function of time of storage of the dried formulations at 40, 50 and 60°C. Lyophilized and stored samples were rehydrated, and protein degradation was quantified by measuring loss of monomeric protein with size exclusion chromatography and by determining chemical degradation in the soluble fraction with reverse-phase chromatography. The secondary structure of the protein in the lyophilized formulations was studied with infrared spectroscopy. The magnitudes of degradation were compared the key physical properties of the formulations including retention of protein native secondary structure, glass transition temperature (Tg), inverse mean square displacements 〈u(2)〉(-1) for hydrogen atoms (fast β relaxation), and the relaxation time τ(β), which correlates with relaxation due to fast Johari-Goldstein motions in the glass (Xu et al., 2013) [1]. In addition, specific surface areas of the lyophilized formulations were determined by Brunauer-Emmet-Teller analysis of krypton adsorption isotherms and used to estimate the fraction of the KGF-2 molecules residing at the solid-air interface. KGF-2 degradation rates were highest in formulations wherein the protein's structure was most perturbed, and wherein β relaxations were fastest, but the dominant factor governing KGF-2 degradation in freeze-dried formulations was the fraction of the protein found at the glass solid-air interface. PMID:24859390

  8. Storage Stability of Keratinocyte Growth Factor-2 in Lyophilized Formulations: Effects of Formulation Physical Properties and Protein Fraction at the Solid-Air Interface

    PubMed Central

    Devineni, Dilip; Gonschorek, Christoph; Cicerone, Marcus T; Xu, Yemin; Carpenter, John F.; Randolph, Theodore W.

    2014-01-01

    Lyophilized formulations of keratinocyte growth factor-2 (KGF-2) were prepared with a range of disaccharide (sucrose or trehalose) and hydroxyethyl starch (HES) mass ratios. Protein degradation was assessed as a function of time of storage of the dried formulations at 40, 50 and 60 °C. Lyophilized and stored samples were rehydrated, and protein degradation was quantified by measuring loss of monomeric protein with size exclusion chromatography and by determining chemical degradation in the soluble fraction with reverse-phase chromatography. The secondary structure of the protein in the lyophilized formulations was studied with infrared spectroscopy. The magnitudes of degradation were compared the key physical properties of the formulations including retention of protein native secondary structure, glass transition temperature (Tg), inverse mean square displacements −1 for hydrogen atoms (fast β relaxation), and the relaxation time τβ, which correlates with relaxation due to fast Johari-Goldstein motions in the glass[1]. In addition, specific surface areas of the lyophilized formulations were determined by Brunauer-Emmet-Teller analysis of krypton adsorption isotherms and used to estimate the fraction of the KGF-2 molecules residing at the solid-air interface. KGF-2 degradation rates were highest in formulations wherein the protein’s structure was most perturbed, and wherein β relaxations were fastest, but the dominant factor governing KGF-2 degradation in freeze-dried formulations was the fraction of the protein found at the glass solid-air interface. PMID:24859390

  9. 18O Labeling over a Coffee Break: A Rapid Strategy for Quantitative Proteomics

    PubMed Central

    Mirza, Shama P.; Greene, Andrew S.; Olivier, Michael

    2009-01-01

    Proteomics-based quantification methods for differential protein expression measurements are among the most important and challenging techniques in the field of mass spectrometry. Though numerous quantification methods have been established, no method meets all the demands for measuring accurate protein expression levels. Of the various relative quantification methods by isotopic labeling, 18O labeling method has been shown to be simple, specific, cost-effective and applicable to a wide range of analyses. However, some researchers refrain from using the method due to long incubation periods required during the labeling process. To address this problem, we demonstrate a method by which the labeling procedure can be completed in 15 min. We digested and labeled samples using immobilized trypsin on micro-spin columns to speed up the enzyme-mediated oxygen substitution, thereby completing the labeling process within 15 min with high labeling efficiency. We demonstrate the efficiency and accuracy of the method using a four protein mixture and whole cell lysate from rat vascular endothelial cells. PMID:18510357

  10. Crystal structure and charge carrier concentration of W 18O 49

    NASA Astrophysics Data System (ADS)

    Viswanathan, K.; Brandt, K.; Salje, E.

    1981-01-01

    The electrical resistivity of the tungsten oxide, W 18O 49, is 1.75 · 10 -3 Ω cm along the needle axis. The charge carrier density, as determined by reflectivity measurements, is 1.87 · 10 22 cm -3, thereby indicating that most of the charge carriers are delocalized. Hence the smaller conductivity along the needle axis than that expected for such charge carrier concentrations must be found in the structure, which has been refined using the data collected with an automatic diffractometer. The structure consists of WO 6 and WO 7 polyhedra which are linked along edges and/or corners. However, as the linkage parallel to b takes place only by sharing corners, an anisotropy in the electrical conductivity may be expected. Another explanation for the smaller conductivity may be found in the occurrence of defects such as tunnels in the structure, which may scatter the electrons. The refinement shows that the tungsten positions, determined by Magneli ( Arkiv Kemi1, 223 (1950)), are essentially correct; but the positions of the oxygens, especially two of them, differ considerably. This results in one of the tungsten atoms getting an additional coordinating oxygen, the coordination number thereby becoming seven.

  11. The ({sup 18}O, {sup 16}O) reaction as a probe for nuclear spectroscopy

    SciTech Connect

    Cappuzz