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Sample records for 18o fractionation factors

  1. 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.

  2. Oxygen isotope fractionation in the ocean surface and 18O/16O of atmospheric O2

    NASA Astrophysics Data System (ADS)

    Luz, Boaz; Barkan, Eugeni

    2011-12-01

    We have recently published a new evaluation of Earth's Dole effect, which was based, in part, on measurements of δO2/Ar, δ17O and δ18O of dissolved argon and oxygen in the ocean surface. In calculations of the oxygen isotope effect due to photosynthesis and respiration (ɛup), gross O2 production (G) was an important factor. However, our estimates of G were based on an approximate equation, and in a recent publication it has been suggested that G obtained with this equation could be underestimated by about 33%. If true, such underestimation of G might lead to different ɛup values. To test this possibility, we have used a new rigorous equation with relevant information on isotopic composition of photosynthetic O2 and recalculated ɛup. Given the uncertainties, the new values do not differ from the previous ones, and therefore, the implications of the strong fractionation in the upper ocean (˜25‰) to the global Dole effect remain as in our original publication.

  3. Factors influencing the 18O/16O-ratio in meat juices.

    PubMed

    Thiem, Ines; Lüpke, Matthias; Seifert, Hermann

    2004-09-01

    With respect to the question of whether the 18O/16O-ratio of meat water could be used for meat origin analysis, factors influencing its delta18O-value have been examined. The 18O/16O-ratio of meat water differs geographically, similar to known differences in precipitation and ground water. In Great Britain higher enrichments in 18O were found in southern samples and in Germany in northern samples. However, it was not possible to distinguish between British and German beef: their 18O/16O-ratios overlapped. British bovine samples the variation range of delta18O-values was 2.8 per thousand; in porcine samples it was 2.0 per thousand. British meat liquids from beef were enriched in 18O by 1.3 +/- 0.3 per thousand compared with pork. In porcine samples of litter mates with identical breeding and age at slaughter, the range in the delta18O-values among individuals was 2.4 per thousand. Experiments revealed significant influences of the meat's storage and handling conditions on the 18O/16O-ratio. After 10 h at 21.5 or 18.5 degrees C the delta18O-value increased by 0.4 or 0.3 per thousand per h, respectively, in samples (50 g) of chopped meat. The observed magnitude of changes might compensate for the geographical and seasonal differences. A precise origin assignment of the affected specimen on the base of delta18O-values of meat water is hence bound to be impossible.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. Online Determination of 18O Fractionation Between CO2 and Soil-Water during Soil Dessication by a Novel Mid-Infrared CO2 Isotope Analyzer Coupled to an Dynamic Chamber Incubation System

    NASA Astrophysics Data System (ADS)

    Nowak, A.

    2015-12-01

    The stable oxygen isotope composition of CO2 is an important tracer for quantifying gas interactions between soils and atmosphere. Soils impact atmospheric 18O-CO2 signatures by CO2-H2O equilibration during diffusion of CO2 through the soil column. However, recent research has revealed that also catalytic reactions by carbonic anhydrase, an enzyme used by microorganisms for triggering the conversion of CO2 and water to bicarbonate and protons, is an important factor influencing the oxygen isotopic signature of CO2. In order to study the importance of biotic and abiotic factors for 18O-CO2, we used a novel mid infrared 18O/13C-CO2 analyser coupled to a dynamic chamber system, which allowed us to measure online 18O and 13C of a continuous CO2 stream percolating through soil samples while drying out from fully water saturated to air dry. Our results indicate that changes in CO2- 18O signatures peak at certain soil moistures levels, which is most probably catalysed by the activity of certain microbial groups under optimum growth conditions. More analyses with different soil types and depths, combined with molecular analyses are planned in order to understand the importance of microbial processes and dynamics for influencing soil-CO2 interactions.

  11. The mechanism of haem catabolism. A study of haem breakdown in spleen microsomal fraction and in a model system by 18O labelling and metal substitution.

    PubMed Central

    King, R F; Brown, S B

    1978-01-01

    The mechanism of bile-pigment formation from haem breakdown was studied by using 18O labelling of the molecular oxygen required for macrocyclic ring cleavage. For haem degradation by the spleen microsomal haem oxygenase system, mass spectrometry of the product bilirubin revealed that cleavage occurred by the Two-Molecule Mechanism, i.e. the terminal lactam oxygen atoms in bilirubin were derived from two different oxygen molecules. Similarly, degradation of myoglobin by coupled oxidation with ascorbate and oxygen proceeded via the Two-Molecule Mechanism. Cobalt and manganese complexes of protoporphyrin IX were not degraded by either the haem oxygenase system or the coupled oxidation system. This result suggests that the iron atom possesses unique properties in facilitating porphyrin breakdown. PMID:697745

  12. 13C, 18O, and D fractionation effects in the reactions of CH3OH isotopologues with Cl and OH radicals.

    PubMed

    Feilberg, Karen L; Gruber-Stadler, Margret; Johnson, Matthew S; Mühlhäuser, Max; Nielsen, Claus J

    2008-11-01

    A relative rate experiment is carried out for six isotopologues of methanol and their reactions with OH and Cl radicals. The reaction rates of CH2DOH, CHD2OH, CD3OH, (13)CH3OH, and CH3(18)OH with Cl and OH radicals are measured by long-path FTIR spectroscopy relative to CH3OH at 298 +/- 2 K and 1013 +/- 10 mbar. The OH source in the reaction chamber is photolysis of ozone to produce O((1)D) in the presence of a large excess of molecular hydrogen: O((1)D) + H2 --> OH + H. Cl is produced by the photolysis of Cl2. The FTIR spectra are fitted using a nonlinear least-squares spectral fitting method with measured high-resolution infrared spectra as references. The relative reaction rates defined as alpha = k(light)/k(heavy) are determined to be: k(OH + CH3OH)/k(OH + (13)CH3OH) = 1.031 +/- 0.020, k(OH + CH3OH)/k(OH + CH3(18)OH) = 1.017 +/- 0.012, k(OH + CH3OH)/k(OH + CH2DOH) = 1.119 +/- 0.045, k(OH + CH3OH)/k(OH + CHD2OH) = 1.326 +/- 0.021 and k(OH + CH3OH)/k(OH + CD3OH) = 2.566 +/- 0.042, k(Cl + CH3OH)/k(Cl + (13)CH3OH) = 1.055 +/- 0.016, k(Cl + CH3OH)/k(Cl + CH3(18)OH) = 1.025 +/- 0.022, k(Cl + CH3OH)/k(Cl + CH2DOH) = 1.162 +/- 0.022 and k(Cl + CH3OH)/k(Cl + CHD2OH) = 1.536 +/- 0.060, and k(Cl + CH3OH)/k(Cl + CD3OH) = 3.011 +/- 0.059. The errors represent 2sigma from the statistical analyses and do not include possible systematic errors. Ground-state potential energy hypersurfaces of the reactions were investigated in quantum chemistry calculations at the CCSD(T) level of theory with an extrapolated basis set. The (2)H, (13)C, and (18)O kinetic isotope effects of the OH and Cl reactions with CH3OH were further investigated using canonical variational transition state theory with small curvature tunneling and compared to experimental measurements as well as to those observed in CH4 and several other substituted methane species.

  13. Diffusivity fractionations of H2(16)O/H2(17)O and H2(16)O/H2(18)O in air and their implications for isotope hydrology.

    PubMed

    Barkan, Eugeni; Luz, Boaz

    2007-01-01

    We have determined the isotope effects of (17)O and (18)O substitution of (16)O in H(2)O on molecular diffusivities of water vapor in air by the use of evaporation experiments. The derived diffusion fractionation coefficients (17)alpha(diff) and (18)alpha(diff) are 1.0146 +/- 0.0002 and 1.0283 +/- 0.0003, respectively. We also determined, for the first time, the ratio ln((17)alpha(diff))/ln((18)alpha(diff)) as 0.5185 +/- 0.0002. This ratio, which is in excellent agreement with the theoretical value of 0.5184, is significantly smaller than the ratio in vapor-liquid equilibrium (0.529). We show how this new experimental information gives rise to (17)O excess in meteoric water, and how it can be applied in isotope hydrology.

  14. 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

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. In vivo isotope-fractionation factors and the measurement of deuterium- and oxygen-18-dilution spaces from plasma, urine, saliva, respiratory water vapor, and carbon dioxide

    SciTech Connect

    Wong, W.W.; Cochran, W.J.; Klish, W.J.; Smith, E.O.; Lee, L.S.; Klein, P.D.

    1988-01-01

    In vivo isotope-fractionation factors were determined for hydrogen and oxygen between plasma water samples and samples of urine, saliva, respiratory water vapor, and carbon dioxide in 20 normal adults. The isotope-fractionation factors ranged from 0.944 to 1.039 for /sup 2/H in breath water vapor and for /sup 18/O in breath CO/sub 2/, respectively. When corrected for isotope fractionation, the /sup 2/H- and /sup 18/O-dilution spaces determined from urine, saliva, respiratory water, and CO/sub 2/ were within -0.10 +/- 1.09 kg (mean +/- SD, n = 60) and 0.04 +/- 0.68 kg (n = 80), respectively, of the values determined from plasma. In the absence of these corrections, we observed a 6% overestimation of /sup 2/H-dilution space and a 1% overestimation of /sup 18/O-dilution space from the use of respiratory water values. A 4% underestimation of the /sup 18/O-dilution space was observed for breath CO/sub 2/ without correction for isotope fractionation.

  20. 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

  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. C18O Depletion in Starless Cores in Taurus

    NASA Astrophysics Data System (ADS)

    Ford, Amanda Brady; Shirley, Yancy L.

    2011-02-01

    We present here findings for C18O depletion in eight starless cores in Taurus: TMC-2, L1498, L1512, L1489, L1517B, L1521E, L1495A-S, and L1544. We compare observations of the C18O J = 2-1 transition taken with the ALMA prototype receiver on the Heinrich Hertz Submillimeter Telescope to results of radiative transfer modeling using RATRAN. We use temperature and density profiles calculated from dust continuum radiative transfer models to model the C18O emission. We present modeling of three cores, TMC-2, L1489, and L1495A-S, which have not been modeled before, and compare our results for the five cores with published models. We find that all of the cores but one, L1521E, are substantially depleted. We also find that varying the temperature profiles of these model cores has a discernable effect, and varying the central density has an even larger effect. We find no trends with depletion radius or depletion fraction with the density or temperature of these cores, suggesting that the physical structure alone is insufficient to fully constrain evolutionary state. We are able to place tighter constraints on the radius at which C18O is depleted than the absolute fraction of depletion. As the timeline of chemical depletion depends sensitively on the fraction of depletion, this difficulty in constraining depletion fraction makes comparison with other timescales, such as the free-fall timescale, very difficult.

  3. 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.

  4. Constraining Historical NOx Concentrations Using Variations in Atmospheric 18O18O: A Status Report

    NASA Astrophysics Data System (ADS)

    Yeung, L. Y.; Young, E. D.; Ash, J. L.; Boering, K. A.; Sowers, T. A.

    2013-12-01

    Historical concentrations of nitrogen oxides, ozone, and other short-lived tropospheric oxidants are not well known. The best observational constraints come from starch-paper measurements (i.e., via the Schönbein method) made in Europe during the late 1800s; they suggest that tropospheric ozone increased several-fold during the 20th century, but uncertainties in those measurements and other paleo-oxidant indicators have limited the accuracy of observations available for validating long-term chemistry-climate models. Isotopic bond ordering in molecular oxygen could be exploited as a new constraint on past oxidant concentrations: Rare isotopes in O2 are re-arranged through O(3P) + O2 isotope exchange reactions in the atmosphere, resulting in relative proportions of 18O18O that depend on temperature, O2 residence time, and O(3P) concentration. Increased tropospheric O(3P) concentrations, arising from increasing emissions and photolysis of nitrogen oxides, likely altered the relative proportions of 18O18O near the surface. In this sense, the isotopic bond ordering in tropospheric O2 (i.e., Δ36) records information about the concentrations of O(3P) and its principal tropospheric source, NO2. I will present recent progress towards this application, including improved constraints on the global budget from measurements of stratospheric air, biological isotopic fractionation, and an experimental photochemical calibration of Δ36. Preliminary measurements of air from the Antarctic firn indicate a decrease in Δ36 of 0.1‰ over the past century. If the tropospheric residence time of O2 has remained unchanged, the data suggest that global surface O(3P) concentrations have increased ~50% during this time period. This result may be consistent with Schönbein-method measurements if large increases in NOx emissions occurred mainly over continental regions, with limited increases over the oceans. Extending this record further into the past could test predictions about NOx

  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. Theoretical calculation of oxygen equilibrium isotope fractionation factors involving various NOy molecules, radOH, and H2O and its implications for isotope variations in atmospheric nitrate

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Michalski, Greg

    2016-10-01

    The oxygen stable isotope composition (δ18O) of nitrogen oxides [NOx = nitric oxide (NO) + nitrogen dioxide (NO2)] and their oxidation products (NOy = NOx + nitric acid (HNO3) + particulate nitrate (p-NO3-) + nitrate radical (NO3) + dinitrogen pentoxide (N2O5) + nitrous acid (HONO) + …) have been shown to be a useful tool for inferring the proportion of NOx that is oxidized by ozone (O3). However, isotopic fractionation processes may have an influence on δ18O of various NOy molecules and other atmospheric O-bearing molecules pertinent to NOx oxidation chemistry. Here we have evaluated the impacts of O isotopic exchange involving NOy molecules, the hydroxyl radical (radOH), and water (H2O) using reduced partition function ratios (xβ) calculated by hybrid density functional theory. Assuming atmospheric isotopic equilibrium is achieved between NO and NO2 during the daytime, and NO2, NO3, and N2O5 during the nighttime, δ18O-δ15N compositions were predicted for the major atmospheric nitrate formation pathways using our calculated exchange fractionation factors and isotopic mass-balance. Our equilibrium model predicts that various atmospheric nitrate formation pathways, including NO2 + radOH → HNO3, N2O5 + H2O + surface → 2HNO3, and NO3 + R → HNO3 + Rrad will yield distinctive δ18O-δ15N compositions. Our calculated δ18O-δ15N compositions match well with previous atmospheric nitrate measurements, and will potentially help better understand the role oxidation chemistry plays on the N and O isotopic composition of atmospheric nitrate.

  7. 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.

  8. The three-isotope method for equilibrium isotope fractionation factor determination: Unfounded optimism

    NASA Astrophysics Data System (ADS)

    Cao, X.; Hayles, J. A.; Bao, H.

    2015-12-01

    The equilibrium isotope fractionation factor α is a fundamental parameter in stable isotope geochemistry. Although equilibrium α can be determined by theoretical calculation or by measurement of natural samples, direct laboratory experiments are ultimately required to verify those results. The attainment of a true exchange equilibrium in experiments is often difficult, but three methods have been devised and used to ensure that an equilibrium α has been obtained in an isotope exchange experiment. These are the two-directional method, partial-exchange method, and three-isotope method. Of these, the three-isotope method is thought to be the most rigorous. Using water-water exchange as a basic unit, we have developed a set of complex exchange models to study when and why the three-isotope method may work well or not. We found that the method cannot promise to lead to an equilibrium α before the kinetic complexity of the specific exchange experiment is known. An equilibrium point in δ17O-δ18O space can be reached only when all of the isotope exchange pathways are fully reversible, i.e. there is no mass loss at any instant, and the forward and backward reactions share the same pathway. If the exchange pathways are not fully reversible, steady state may be reached, but a steady state α can be very different from the equilibrium α. Our results validated the earlier warning that the trajectory for three-isotope evolution in δ17O-δ18O space may be a distinctly curved line or contain more than one straight line due to the non-fully reversible isotope exchange reactions. The three-isotope method for equilibrium α determination is not as rigorous or as promising as it may seem. Instead, the trajectory of three-isotope evolution provides detailed insights into the kinetics of isotope exchange between compounds. If multiple components exist in the exchange system, the δ17O-δ18O evolving trajectory would be more complex.

  9. 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

  10. 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.

  11. Ratio of 18o Versus 13c As Indicator of Ecological and Physiological Adaptability In The Coral Genus Madracis

    NASA Astrophysics Data System (ADS)

    Maier, C.; Bak, R. P. M.

    Scleractinian corals hosting endosymbiotic algae (zooxanthellae) occur over a wide depth range within the photic zone of coral reefs. While some corals occur within a very narrow range others can be found over the whole reef slope. Within the genus Madracis we compared the skeletal 13C and 18O of three species that are very distinct in their distributional depth range. The species M. pharensis occurs over a wide range between 5 and > 60 m depth, while M. mirabilis and M. formosa are restricted to a narrow range growing shallow (<20 m) or deep (> 40 m), respectively. We hypothesize, that the distinct distributional depth range of the three species is due to physiological adaptation to the respective light regimes, and that this species specific adaptation must be reflected in the skeletal 18O and 13C signals. Skeletal isotope fractionation is controlled by kinetic (both 13C and 18O ) and metabolic (13C only) isotope effects. Apart from environmental factors (temperature and salinity), the calcification rate and P:R ratio control isotope fractionation. This means, that (1) the efficiency with which corals under various light regimes photosynthesize and calcify and (2) the linkage between photosynthesis and calcification become apparent when applying skeletal 13C versus 18O of the 3 Madracis species according to the model of McConnaughey (Geochim. Cosmochim. Acta, 53: 151-162, 1989). Comparing e.g. 13C vs. 18O ratios of M. pharensis (broad depth range) and M. formosa (narrow range, deep) sampled at 50 m depth, stable isotopes of M. pharensis plot on the kinetic line, while the isotopes of the deep adapted M. formosa are offset from the kinetic line. This indicates, that M. pharensis is hardly growing and is hence at its distributional depth limit, while M. formosa has even in 50 m depth a positive P:R ratio and skeletal growth. Therefore, the ratio of 13C and 18O might be useful as `proxy' in coral physiology and ecology. Vice versa an ecological approach in questions

  12. 13C18O in Earth's Atmosphere: a New Proxy for Constraining CO Budget

    NASA Astrophysics Data System (ADS)

    Guo, W.; Eiler, J. M.

    2005-12-01

    Despite its low average mixing ratio (70-100 ppbv), carbon monoxide plays an important role in atmospheric chemistry. It is the major sink of OH radicals, and thus strongly influences the oxidizing capacity of the atmosphere, and the lifetimes of many other atmospheric trace gases (e.g., methane, NHMCs and HCFCs). At present, the budget of atmospheric CO is constrained by its mixing ratio, δ13C, δ18O, δ17O values, inventory analysis and inverse modeling. However, the major sources of CO (CH4-oxidation, NMHC-oxidation, biomass burning, anthropogenic emissions and the ocean) vary in flux and isotopic composition, and some overlap one another in isotopic composition. Therefore, its atmospheric budget cannot be rigorously defined by inversion of the existing isotopic and concentration records. Here we introduce measurements of the abundance anomaly of the 13C18O isotopologue of carbon monoxide as an additional constraint on its atmospheric budget. We define the 13C18O anomaly as the deviation of its actual abundance from its expected statistical abundance,Δ13C18O=(([13C18O]actual/[12C16O]actual)/([13C18O]stati stical /[12C16O]statistical)-1)×1000. Abundances of 13C18O are measured by quantitatively oxidizing CO to CO2 over the Schutze reagent, and then measuring mass 47 (mainly 13C18O16O) in the product CO2, which is proportional to the abundance of 13C18O in the starting CO. External precision of Δ13C18O for repeated measurements of pure CO averages 0.03‰(one standard deviation). We expect Δ13C18O in atmospheric carbon monoxide to be sensitive to: mixing between CO of different isotopic compositions, thermodynamic fractionations, diffusion, and kinetic isotope effects accompanying chemical reactions. We have investigated the thermodynamic fractionation of Δ13C18O by performing measurements on carbon monoxide samples catalytically equilibrated at high temperatures (300-1000°C). Measured Δ13C18O values, ranging from ~0.08‰ to ~0.47‰, vary as a function

  13. 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

  14. Molecular and cluster structures in 18O

    NASA Astrophysics Data System (ADS)

    von Oertzen, W.; Dorsch, T.; Bohlen, H. G.; Krücken, R.; Faestermann, T.; Hertenberger, R.; Kokalova, Tz.; Mahgoub, M.; Milin, M.; Wheldon, C.; Wirth, H.-F.

    2010-01-01

    We have studied the multi-nucleon transfer reaction 12C ( 7Li ,p) at E lab = 44 MeV, populating states in the oxygen isotope 18O . The experiments were performed at the Tandem accelerator of the Maier-Leibniz Laboratory in Munich using the high-resolution Q3D magnetic spectrograph. States were populated up to an excitation energy of 21.2MeV with an overall energy resolution of 45keV, and 30 new states of 18O have been identified. The structure of the rotational bands observed is discussed in terms of cluster bands with the underlying cluster structures: 14C ⊗ α and 12C ⊗ 2 n ⊗ α . Because of the broken intrinsic reflection symmetry in these structures the corresponding rotational bands appear as parity doublets.

  15. 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

  16. 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.

  17. Theoretical prediction for several important equilibrium Ge isotope fractionation factors

    NASA Astrophysics Data System (ADS)

    Tang, M.; Li, X.; Liu, Y.

    2008-12-01

    As a newly emerging field, the stable isotope geochemistry of germanium (Ge) needs basic equilibrium fractionation factors to explore its unknown world. In this study, the Ge isotope fractionations between systems including the aqueous Ge(OH)4 and GeO(OH)3- which are the dominant Ge species in seawater, the Ge-bearing organic complexes (e.g. Ge-catechol, Ge-oxalic acid and Ge-citric acid), the quartz- (or opal- ), albite-, K-feldspar- and olivine- like mineral structures are studied. It is the first time that some geologically important equilibrium Ge isotope fractionation factors are reported. Surprisingly, up to 5 per mil large isotopic fractionations between these Ge isotope systems are found at 25 degree. These results suggest a potentially broad application for the Ge isotope geochemistry. Our theoretical calculations are based on the Urey model (or Bigeleisen-Mayer equation) and high level quantum chemistry calculations. The B3LYP/6-311+G(d,p) level quantum chemistry method and the explicit solvent model ("water droplet" method) are used. Many different conformers are also used for the aqueous complexes in order to reduce the possible errors coming from the differences of configurations in solution. The accuracy of our calculation of the Ge isotopic fractionations is estimated about 0.2 per mil. Our results show quartz-like or opal-like structure can enrich most heavy Ge isotopes. Relative to quartz (or opal), some Ge isotopic fractionations are (at 25 C): quartz-organic Ge = 4-5,quartz-Ge(OH)4 =0.9,quartz-GeO(OH)3- =1.5,quartz-albite=0.6,quartz-K-feldspar=0.4 and quartz-olivine=3.9 per mil. The large fractionations between inorganic Ge complexes and organic Ge ones could be used to distinguish the possible bio-involving processes. Our results suggest a good explanation to the experimental observations of Siebert et al. (2006) and Rouxel et al. (2006) and provide important constraints to the study of Ge cycle in ocean.

  18. Iron isotopic fractionation factor between magnetite and hydrous silicic melt

    NASA Astrophysics Data System (ADS)

    Huang, F.; Lundstrom, C. C.

    2006-12-01

    A "thermal migration" experiment was conducted in the piston cylinder to investigate the changes in composition of a wet andesitic bulk composition in a temperature gradient at 0.5 GPa. A homogeneous andesite powder (AGV-1 containing 4 wt.% H2O was sealed in a AuPd double capsule with the hot end at 950°C and the bottom end 350°C for 66 days. The charge changes from 100% melt at the top to the progressively more crystalline with the sequential appearance of apatite, magnetite, amphibole, biotite, plagioclase, quartz, and K-feldspar. We microdrilled 5 samples along the temperature gradient and analyzed these for Fe isotope ratios by double spike MC-ICP-MS at UIUC. Results show that the 100% melt area is depleted in heavy Fe isotopes relative to all more crystalline portions of the experiment (4 samples) with the offset in {δ}^{56/54}FeIRMM of about 1.7‰. This does not appear to reflect Fe loss in the experiment as the Fe content and isotopes mass balance and no detectable Fe was found in the capsule after the experiment. Instead the offset is interpreted to reflect the combination of diffusive fractionation of Fe moving by diffusion and possible equilibrium fractionations between melt and magnetite that occurs throughout the crystalline portion of the experiment. However, both the isotopic fractionation factor between magnetite and melt and the effect of diffusion on Fe isotopes remains unknown. We are currently investigating Fe isotopic fractionation factor between magnetite and melt and effects of melt diffusion on Fe isotopes. To assess diffusion, we will microdrill and analyze melt-melt diffusion couples from Lundstrom(G-Cubed, 2003). To assess magnetite-melt fractionation, we have begun piston cylinder experiments at 0.5 GPa and 800°C using a starting material synthesized based on the melt composition within the thermal migration experiment. Initial experiments produce a layer of 100% melt on top of a 2-phase mush of magnetite-melt. This will allow

  19. 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.

  20. A new mechanistic model of δ18O-N2O formation by denitrification

    NASA Astrophysics Data System (ADS)

    Snider, David M.; Venkiteswaran, Jason J.; Schiff, Sherry L.; Spoelstra, John

    2013-07-01

    Anaerobic incubations of flooded and non-flooded agricultural soils and stream sediment were conducted with 18O-labelled water to investigate the stable isotope ratios (δ15N and δ18O) of nitrous oxide (N2O) produced from denitrification. The rates of N2O production and δ15N- and δ18O-N2O values were measured. The amount of oxygen exchange (O-exchange) with water, and the nitrogen and oxygen isotope effects (ɛ) were calculated. The net 15N isotope effect (NO3- → N2O) for denitrification in this study varied from -30‰ to -9‰. The net 18O isotope effect ranged between +32‰ and +60‰ and was negatively correlated to the total fraction of O-exchange, which varied between 0.40 and 0.94. This manuscript describes a new, comprehensive set of mathematical expressions that can be used to model δ18O values of N2O formed by denitrification and calculate the magnitude of O-exchange and the net 18O isotope effect for denitrification. This mathematical approach is compared to another method of approximating O-exchange (Snider et al., 2009), and we show that this older method provides a minimum estimate of O-exchange. Using this mechanistic model, we discuss how N2O consumption, open/closed systems, and variations in the N2O:N2 ratio can influence the observed δ18O-N2O. The net 18O isotope effect for denitrification in this study was partially controlled by the fractions of O-exchange and N2O reduction, which were likely influenced by the actively denitrifying microbial community and the soil moisture. We conclude that δ18O-N2O values are, in many cases, useful tracers of N2O production because they are often higher than the majority of nitrification-derived δ18O-N2O values. The usefulness of δ18O values to apportion sources must be determined on a case-by-case basis.

  1. 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

  2. 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.

  3. 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

  4. 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...

  5. 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

  6. Cellulose (delta)18O is an index of leaf-to-air vapor pressure difference (VPD) in tropical plants.

    PubMed

    Kahmen, Ansgar; Sachse, Dirk; Arndt, Stefan K; Tu, Kevin P; Farrington, Heraldo; Vitousek, Peter M; Dawson, Todd E

    2011-02-01

    Cellulose in plants contains oxygen that derives in most cases from precipitation. Because the stable oxygen isotope composition, δ(18)O, of precipitation is associated with environmental conditions, cellulose δ(18)O should be as well. However, plant physiological models using δ(18)O suggest that cellulose δ(18)O is influenced by a complex mix of both climatic and physiological drivers. This influence complicates the interpretation of cellulose δ(18)O values in a paleo-context. Here, we combined empirical data analyses with mechanistic model simulations to i) quantify the impacts that the primary climatic drivers humidity (e(a)) and air temperature (T(air)) have on cellulose δ(18)O values in different tropical ecosystems and ii) determine which environmental signal is dominating cellulose δ(18)O values. Our results revealed that e(a) and T(air) equally influence cellulose δ(18)O values and that distinguishing which of these factors dominates the δ(18)O values of cellulose cannot be accomplished in the absence of additional environmental information. However, the individual impacts of e(a) and T(air) on the δ(18)O values of cellulose can be integrated into a single index of plant-experienced atmospheric vapor demand: the leaf-to-air vapor pressure difference (VPD). We found a robust relationship between VPD and cellulose δ(18)O values in both empirical and modeled data in all ecosystems that we investigated. Our analysis revealed therefore that δ(18)O values in plant cellulose can be used as a proxy for VPD in tropical ecosystems. As VPD is an essential variable that determines the biogeochemical dynamics of ecosystems, our study has applications in ecological-, climate-, or forensic-sciences.

  7. 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

  8. The MMCO-EOT conundrum: same benthic δ18O, different CO2

    NASA Astrophysics Data System (ADS)

    Stap, Lennert; van de Wal, Roderik; de Boer, Bas; Bintanja, Richard; Lourens, Lucas

    2016-04-01

    Knowledge on temporal variations of Earth's climate over the past 38 Myr largely stems from benthic δ18O records. These records are difficult to interpret, however, since they document combined effects of deep-sea temperature and ice volume variations. Information on CO2 is expanding, but remains highly uncertain and intermittent. Attempts to determine the long-term relations between δ18O, sea level and CO2 from proxy data suffer from paucity of data and apparent inconsistency among different records. One outstanding issue is the difference recorded in proxy CO2 data between the Eocene-Oligocene boundary (EOT) and the Middle-Miocene Climatic Optimum (MMCO), while similar levels of benthic δ18O are shown during these time periods. Here, we take a model-based approach to deconvolute the benthic δ18O signal, and reconcile knowledge on benthic δ18O, sea level, CO2 and temperature. We obtain continuous and mutually consistent 38-Myr-long simulations of these variables, by forcing a coupled ice sheet-climate model inversely with benthic δ18O observations. We investigate the factors influencing Arctic and Antarctic polar amplification, and the relation between sea level and CO2. Furthermore, we show that different CO2 between the EOT and MMCO, as indicated by proxy data, can only be obtained if we impose erosion or tectonic movement of the Antarctic continent over time.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. Evaporative enrichment and time lags between delta18O of leaf water and organic pools in a pine stand.

    PubMed

    Barnard, Romain L; Salmon, Yann; Kodama, Naomi; Sörgel, Karin; Holst, Jutta; Rennenberg, Heinz; Gessler, Arthur; Buchmann, Nina

    2007-05-01

    Understanding ecosystem water fluxes has gained increasing attention, as climate scenarios predict a drier environment for many parts of the world. Evaporative enrichment of (18)O (Delta(18)O) of leaf water and subsequent enrichment of plant organic matter can be used to characterize environmental and physiological factors that control evaporation, based on a recently established mechanistic model. In a Pinus sylvestris forest, we measured the dynamics of oxygen isotopic composition (delta(18)O) every 6 h for 4 d in atmospheric water vapour, xylem sap, leaf water and water-soluble organic matter in current (N) and previous year (N-1) needles, phloem sap, together with leaf gas exchange for pooled N and N-1 needles, and relevant micrometeorological variables. Leaf water delta(18)O showed strong diel periodicity, while delta(18)O in atmospheric water vapour and in xylem sap showed little variation. The Delta(18)O was consistently lower for N than for N-1 needles, possibly related to phenological stage. Modelled leaf water Delta(18)O showed good agreement with measured values when applying a non-steady state evaporative enrichment model including a Péclet effect. We determined the time lags between delta(18)O signals from leaf water to water-soluble foliar organic matter and to phloem sap at different locations down the trunk, which clearly demonstrated the relevance of considering these time-lag effects for carbon transport, source-sink and carbon flux partitioning studies. PMID:17407532

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

    PubMed

    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

    2009-07-14

    The stratospheric CO(2) oxygen isotope budget is thought to be governed primarily by the O((1)D)+CO(2) 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 CO(2) isotopologue (16)O(13)C(18)O, in concert with (18)O and (17)O 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 (16)O(13)C(18)O, observed as proportions in the polar vortex that are higher than in any naturally derived CO(2) sample to date. We show, through photochemical experiments, that lower (16)O(13)C(18)O proportions observed in the midlatitudes are determined primarily by the O((1)D)+CO(2) isotope exchange reaction, which promotes a stochastic isotopologue distribution. In contrast, higher (16)O(13)C(18)O 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((1)D)+CO(2). We believe the most plausible explanation for this meridional variation is either an unrecognized isotopic fractionation associated with the mesospheric photochemistry of CO(2) or temperature-dependent isotopic exchange on polar stratospheric clouds. Unraveling the ultimate source of stratospheric (16)O(13)C(18)O enrichments may impose additional isotopic constraints on biosphere-atmosphere carbon exchange, biosphere productivity, and their respective responses to climate change.

  15. 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

  16. 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.

  17. THz and Ft-Ir Study of 18-O Isotopologues of Sulfur Dioxide: 32S16O18O and 32S18O_2

    NASA Astrophysics Data System (ADS)

    Margulès, L.; Motiyenko, R. A.; Demaison, J.; Perrin, Agnes; Kwabia Tchana, F.; Manceron, Laurent

    2016-06-01

    Sulfur dioxide is a molecule that have a great interest in different domains: for atmospheric and planetology chemistry, it is also ubiquitous and abundant in interstellar medium. If the 16O species were extensively studied, this is not the case of the 18O isotopologues. The aim of this study is first to complete the rotational spectra of the ground state with these new measurements up to 1.5 THz, previous measurements are up to 1050 GHz for the 32S16O18O species, and 145 GHz concerning the 32S18O_2 species. The second part is making a global fit of the rotational and vibrational transitions for the excited vibrational states. For the v_2 band, we will complete the recent I.R. analysis. About the triad (v_1, 2v_2, v_3): 32S18O_2 species was studied, but not the 32S16O18O one. and 145 GHz concerning the 32S18O_2 species. The second part is making a global fit of the rotational and vibrational transitions for the excited vibrational states. For the v_2 band, we will complete the recent I.R. analysis. About the triad (v_1, 2v_2, v_3): 32S18O_2 species was studied, but not the 32S16O18O one. The FT-IR spectra were recorded on the AILES Beamline at Synchrotron SOLEIL using the Synchrotron light source, coupled to the Bruker IFS125HR Fourier transform spectrometer. The THz spectra were obtained from 150 to 1500 GHz using the Lille's solid state spectrometer. The analysis is in progress, the latest results will be presented. Support from the French Laboratoire d'Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-0005 of the Programme d'Investissements d'Avenir is acknowledged Belov, S. P.; et al., 1998, J. Mol. Spectrosc. 191, 17 Lindermayer, J.; et al., 1985, J. Mol. Spectrosc. 110, 357 Gueye, F.; et al. Mol. Phys. in press Ulenikov, O. N.; et al., 2015, JQSRT 166, 13 Brubach, J.; et al., 2010, AIP Conf. Proc. 1214, 81 Zakharenko, O.; et al., 2015, J. Mol. Spectrosc. 317, 41

  18. 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.

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

    PubMed

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

    2015-06-03

    The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 ((18)O) and carbon-13 ((13)C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of (18)O/(16)O and (13)C/(12)C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of (18)O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of (18)O in breath CO2 were manifested in individuals without the infections. In contrast, the (13)C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to (13)C-enriched glucose uptake, whereas a distinguishable change of breath (13)C/(12)C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the (18)O and (13)C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath (12)C(18)O(16)O and (13)C(16)O(16)O 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.

  20. 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.

  1. 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

  2. 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

  3. Using 16O/18O to Determine the Evolutionary History of the R Coronae Borealis Stars

    NASA Astrophysics Data System (ADS)

    Clayton, Geoffrey; Geballe, Tom; Welch, Douglas; Tisserand, Patrick

    2014-08-01

    All of the Galactic hydrogen-deficient carbon (HdC) and R Coronae Borealis (RCB) stars for which oxygen isotopic ratios can be measured, show 16O/18O < 5, values that are orders of magnitude lower than measured in other stars (the Solar value is 500). This suggests that most if not all HdC and RCB stars are highly enriched in 18O. This is an important clue to determining the evolutionary pathways of HdC and RCB stars, for which two models have been proposed: the double degenerate (white dwarf (WD) merger), and the final helium-shell flash (FF). No overproduction of 18O is expected in the FF scenario. However, some RCB stars also show characteristics, such as 13C and Lithium, seen in FF stars. Therefore, we are conducting a survey of all the RCB stars in the LMC and SMC for the characteristics of a WD merger or a FF. Most of the stars have been surveyed for 13C already, and we are also planning to survey them for Lithium. But no RCB star in the Magellanic Clouds has been observed for 18O. The Magellanic Clouds provide an unbiased, relatively complete sample of RCB stars which are at a known distance so their bolometric luminosities can be used in our stellar evolution models. This proposal is to use Gemini/Flamingos-2 to survey all of the Magellanic Cloud stars, which are cool enough to show CO bands, for the presence of 18O near 2.3 micron. This survey, combined with our stellar evolution models, will reveal the true fraction of RCB stars formed by each of the proposed scenarios.

  4. Ice export from the Laptev and East Siberian Sea derived from δ18O values

    NASA Astrophysics Data System (ADS)

    Rosén, Per-Olov; Andersson, Per S.; Alling, Vanja; Mörth, Carl-Magnus; Björk, Göran; Semiletov, Igor; Porcelli, Don

    2015-09-01

    Ice export from the vast Arctic Siberian shelf is calculated using δ18O values and salinity data for water samples collected during the International Siberian Shelf Study between August and September 2008 (ISSS-08). The samples represent a wide range of salinities and δ18O values due to river water inputs and sea ice removal. We estimate the fraction of water that has been removed as ice by interpreting observed δ18O values and salinities as a result of mixing between river water and sea water end-members as well as to fractional ice removal. This method does not assume an ice end-member of fixed composition, which is especially important when applied on samples with large differences in salinity. The results show that there is net transport of ice from both the Laptev and the Eastern Siberian Seas, and in total 3000 km3 of sea ice is exported from the shelf. The annual total export of ice from the entire region, calculated from the residence time of water on the shelf, is estimated to be 860 km3 yr-1. Thus, changes in ice production on the shelf may have great impact on sea ice export from the Arctic Ocean.

  5. High- & Low-δ18O magma: Comparative study of crustal and mantle plagiogranites from the Oman ophiolite

    NASA Astrophysics Data System (ADS)

    Alberts, R. C.; Grimes, C. B.; Koepke, J.; Erdmann, M.; Kitajima, K.; Spicuzza, M. J.; Valley, J. W.

    2015-12-01

    Plagiogranite (PLGT) from the crust and mantle sections of the Oman ophiolite preserve widely varied δ18O values that monitor different processes occurring during ophiolite construction. Mantle-like δ18O values are expected if MORB fractionation played a dominant role in PLGT genesis. Magmatic values (monitored here by zircon) shifted away from the mantle-like range indicate open system processes which include partial melting of hydrothermally-altered crust or influx of subduction-related, sediment-derived melt. Zircon (zrn) and quartz (qtz) from twenty-four new samples of PLGT from the crustal and mantle sections of the Oman ophiolite were analyzed for δ18O. Rock-averaged δ18O from the sheeted dikes (zrn: 4.3-4.5‰, qtz: 6.7-6.9‰) and dike-gabbro transition (zrn: 3.9-4.8‰, qtz: 4.7-7.7‰) are mostly below values in magmatic equilibrium with MORB (zrn = 5.2±0.5‰, qtz = 7.0-7.5‰). δ18O for PLGT in the gabbro section (zrn: 4.8-5.1‰, qtz: 7.7-8.3‰) are mostly mantle-like. Quartz is generally found to be more variable than coexisting zrn and likely experienced some sub-solidus exchange. When organized into a relative structural position, δ18Ozrn values typically increase with depth. The lowest δ18Ozrn are observed near the dike-gabbro transition and are consistent with petrogenesis involving hydrous partial melting of mafic crust previously hydrothermally-altered at high-T. The return to nominally mantle-equilibrated δ18Ozrn deeper in the gabbro section may reflect decreasing seawater-signatures of fluids penetrating to depth, lower water/rock ratios, or extreme fractional crystallization. Crustal PLGT thus predate the development of high δ18O signatures in the upper oceanic crust as it cools and experiences low temperature hydrothermal alteration. Mantle PLGT intrusions (1-3 m thick) from the Haylayn block extend to considerably higher rock-averaged δ18O values (zrn: 5.1-15.4‰, qtz: 7.0-18.5‰). Individual rocks (5 samples) were uniform in

  6. 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

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Modelling the δ 18O value of cave drip water and speleothem calcite

    NASA Astrophysics Data System (ADS)

    Wackerbarth, A.; Scholz, D.; Fohlmeister, J.; Mangini, A.

    2010-11-01

    Stable isotope signals recorded in speleothems have provided important insights about past climate variability in recent years. Quantitative reconstruction of mean annual temperature and the amount of precipitation, however, remains difficult because the stable isotope signals are influenced by various processes. Here we present a drip water model, which shows how these climate parameters affect the oxygen isotope signal of cave drip water. In the model the dependence of the δ 18O value of drip water on mean annual temperature is established by correlation to the amount of winter precipitation and winter temperature. Application of the model to two caves in western Germany reveals a strong influence of winter rainfall on the oxygen isotope composition of cave drip water in this region. Assuming equilibrium isotope fractionation between drip water and calcite, we provide a function relating the δ 18O value of speleothem calcite to mean annual surface temperature. This function shows a clear anticorrelation between temperature and the δ 18O value of speleothem calcite, which has been previously reported for several caves in central and northern Europe. By inverse application of this function, we tentatively reconstruct average temperatures for the period between 6 and 1.5 ka from the δ 18O signals of two stalagmites from Atta and Bunker Cave (western Germany). The resulting temperature curves are very sensitive to the value used for the correlation between the amount of winter precipitation and winter temperature. Since this correlation was probably not constant in the past, the reconstructed temperature curves are associated with substantial uncertainty.

  12. Using 16O/18O to Determine the Evolutionary History of the R Coronae Borealis Stars

    NASA Astrophysics Data System (ADS)

    Clayton, Geoffrey; Geballe, Tom; Welch, Douglas; Tisserand, Patrick

    2013-08-01

    Of the Galactic hydrogen-deficient carbon (HdC) and R Coronae Borealis (RCB) stars for which oxygen isotopic ratios can be measured, all of them show 16O/18O < 5, values that are orders of magnitude lower than measured in other stars (the Solar value is 500). This suggests that most if not all HdC and RCB stars are highly enriched in 18O. This is an important clue in determining the evolutionary pathways of HdC and RCB stars, for which two models have been proposed: the double degenerate (white dwarf (WD) merger), and the final helium-shell flash (FF). No overproduction of 18O is expected in the FF scenario. However, some RCB stars also show characteristics, such as 13C and Lithium, seen in FF stars. Therefore, we are conducting a survey all the RCB stars in the LMC and SMC for the characteristics of a WD merger or a FF. Most of the stars have been surveyed for 13C already and we plan to survey them for Lithium in the future. This proposal is to use Gemini/Flamingos-2 to survey all the stars, which are cool enough to show CO bands, for the presence of 18O near 2.3 micron. The Magellanic Clouds provide an unbiased, relatively complete sample of RCB stars which are at a known distance so their bolometric luminosities can be used in our stellar evolution models. This survey, combined with our models, will reveal the true fraction of RCB stars formed by each of the proposed scenarios.

  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.

  14. 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

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. 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

  20. 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.

  1. /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.

  2. 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.

  3. Possible non-equilibrium oxygen isotope effects in mantle nodules, an alternative to the Kyser-O'Neil-Carmichael18O/16O geothermometer

    NASA Astrophysics Data System (ADS)

    Gregory, Robert T.; Taylor, Hugh P.; Kyser, T. Kurtis; O'Neil, James R.; Carmichael, Ian S. E.

    1986-03-01

    Kyser, O'Neil, and Carmichael (1981, 1982) measured the δ 18O values of coexisting minerals from peridotite nodules in alkali basalts and kimberlites, interpreting the nodules as equilibrium assemblages. Using Ca-Mg-Fe element-partition geothermometric data, they proposed an empirical18O/16O geothermometer: T(°C)=1,151-173 Δ-68 Δ 2, where Δ is the per mil pyroxene-olivine fractionation. However, this geothermometer has an unusual “crossover” at 1,150 °C, and in contrast to what might be expected during closed-system equilibrium exchange, the most abundant mineral in the nodules (olivine) shows a much greater range in δ 18O (+4.4 to +7.5) than the much less abundant pyroxene (all 50 pyroxene analyses from spinel peridotites lie within the interval +5.3 to +6.5). On δ 18O-olivine vs. δ 18O-pyroxene diagrams, the mantle nodules exhibit data arrays that cut across the Δ 18O=zero line. These arrays strongly resemble the non-equilibrium quartzfeldspar and feldspar-pyroxene δ 18O arrays that we now know are diagnostic of hydrothermally altered plutonic igneous rocks. Thus, we have re-interpreted the Kyser et al. data as non-equilibrium phenomena, casting doubt on their empirical geothermometer. The peridotite nodules appear to have been open systems that underwent metasomatic exchange with an external, oxygen-bearing fluid (CO2, magma, H2O, etc.); during this event, the relatively inert pyroxenes exchanged at a much slower rate than did the coexisting olivines and spinels, in agreement with available exchange-rate and diffusion measurements on these minerals. This accounts for the correlation between Δ 18O pyroxene-olivine and the whole-rock δ 18O of the peridotites, which is a major difficulty with the equilibrium interpretation.

  4. High resolution δ 18O and δ 13C records from an annually laminated Scottish stalagmite and relationship with last millennium climate

    NASA Astrophysics Data System (ADS)

    Baker, Andy; Wilson, Rob; Fairchild, Ian J.; Franke, Joerg; Spötl, Christoph; Mattey, Dave; Trouet, Valerie; Fuller, Lisa

    2011-12-01

    High-resolution (annual to decadal) stable isotope records of oxygen and carbon are analysed from an annually laminated stalagmite from NW Scotland. The sample, which was deposited for ~ 1000 yrs until 1996 AD, has previously provided annual resolution climate reconstructions of local rainfall and regional winter North Atlantic Oscillation (wNAO) from variations in annual growth rate. For our stalagmite, for which modern cave monitoring demonstrates that equilibrium deposition is highly likely for δ 18O but not for δ 13C, stalagmite δ 13C originally derives from soil CO 2 produced predominantly by microbial respiration, modified by degassing-related kinetic fractionation, and δ 18O from the composition of infiltrating water during periods of infiltrating water. Both the presence of fluorescent laminae and modern drip-water monitoring demonstrate a drip hydrology that comprises both event and storage components. Over the instrumental period, no correlations between stalagmite or rainfall δ 18O and precipitation amount or temperature are observed, but correlations are observed between rainfall δ 18O and 500 mb height at regional IAEA monitoring stations. However, no correlations are observed between stalagmite δ 18O and instrumental and reconstructed atmospheric circulation, preventing a simple palaeoclimate interpretation of the stalagmite δ 18O proxy. Stalagmite δ 13C has a stronger temporal autocorrelation than δ 18O, indicative of soil mixing of respired CO 2 and significant variability between drips and at different times; correlations with instrumental climate data are therefore not possible. The relative timing of changes in growth rate, δ 18O and δ 13C are discussed, and interpretations compared with other regional climate records. We conclude that, over the last millennium at this mid-latitude cave site, neither δ 18O nor δ 13C cannot be interpreted as a simple paleoclimate proxy.

  5. 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 ‰.

  6. 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…

  7. 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.

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

    PubMed Central

    Wang, Guoan; Jia, Yufu; Li, Wei

    2015-01-01

    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. PMID:26056012

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

    PubMed

    Wang, Guoan; Jia, Yufu; Li, Wei

    2015-06-09

    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 (12)C to enrich in the released CO2 while (13)C 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.

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

    PubMed

    Wang, Guoan; Jia, Yufu; Li, Wei

    2015-01-01

    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 (12)C to enrich in the released CO2 while (13)C 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. PMID:26056012

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

    PubMed

    Sturchio, Neil C; Böhlke, John Karl; Beloso, Abelardo D; Streger, Sheryl H; Heraty, Linnea J; Hatzinger, Paul B

    2007-04-15

    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 degrees C and 22 degrees C with acetate as the electron donor. Perchlorate was completely reduced by both strains within 280 h at 22 degrees C and 615 h at 10 degrees C. Measured values of isotopic fractionation factors were epsilon(18)O = -36.6 to -29.0% per hundred and epsilon(37)Cl = -14.5 to -11.5% per hundred, and these showed no apparent systematic variation with either temperature or bacterial strain. An experiment using (18)O-enriched water (delta(18)O = +198% per hundred) gave results indistinguishable from those observed in the isotopically normal water (delta(18)O = -8.1% per hundred) used in the other experiments, indicating negligible isotope exchange between perchlorate and water during biodegradation. The fractionation factor ratio epsilon(18)O/epsilon(37)Cl 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 (epsilon(18)O/ epsilon(37)Cl) also has significant implications for forensic studies. PMID:17533841

  13. 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.; 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. The Accuracy of Paleoenvironmental Reconstructions Based on Spring and Wetland Gastropod 18O Values: A Field Study

    NASA Astrophysics Data System (ADS)

    Sharpe, S. E.; Forester, R. M.

    2008-12-01

    Paired live gastropods and water samples were collected monthly for over two years from two localities near Reno, Nevada: a relatively stable cold, low-flow spring and a highly-variable wetland. Shell samples from gastropods (Gyraulus, Physella, Planorbella, Stagnicola) were crushed to a homogeneous powder and analyzed for stable isotopes (n=115). Annual δ18O water values varied between -15.6 and - 14.8‰ (SMOW) and water temperature varied between 12 and 23° C at the spring locality. Shell δ18O values at the spring locality ranged from 15.5 to 19.9‰ (SMOW). The gastropod δ18O values exhibited the general pattern of seasonal variability (lower values in warm months and higher values in cold months) although they were offset from the expected equilibrium fractionation value, possibly reflecting a vital effect, calcification in a microhabitat, or error in estimating the timing (e.g., month) of calcification. The offset averaged 0.8‰ for Physella and 2.8‰ for Stagnicola. In contrast to the spring, the wetland annual δ18O water varied between -13.0 and -2.4‰, while water temperature varied between 4 and 26° C. Shell δ18O values ranged from 20.7 to 30.2‰ reflecting seasonal extremes of hydrologic input (springflow and runoff) to output (evaporation) in the wetland and possibly diurnal and monthly variability in the system and differential seasonal or diurnal shell growth. Different hydrologic systems have characteristic isotope systematics. This study shows that δ18O gastropod shell values are useful to infer seasonal changes and annual variability in hydrologic settings. Settings with limited seasonal variability host mollusks with relatively limited shell δ18O variability and vice versa. Life strategies (e.g., mobility, behavior, reproduction, and longevity) and possibly physiology (e.g., gills, lungs, or pseudobranch) of different genera, however, can affect isotopic values in the same setting and therefore, may be of critical importance when

  19. 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.

  20. Targeting erythrocyte carbonic anhydrase and 18O-isotope of breath CO2 for sorting out type 1 and type 2 diabetes

    PubMed Central

    Ghosh, Chiranjit; Mandal, Santanu; Banik, Gourab D.; Maity, Abhijit; Mukhopadhyay, Prabuddha; Ghosh, Shibendu; Pradhan, Manik

    2016-01-01

    The inability to envisage the acute onset and progression of type 1 diabetes (T1D) has been a major clinical stumbling block and an important area of biomedical research over the last few decades. Therefore there is a pressing need to develop a new and an effective strategy for early detection of T1D and to precisely distinguish T1D from type 2 diabetes (T2D). Here we describe the precise role of the enzymatic activity of carbonic anhydrase (CA) in erythrocytes in the pathogenesis of T1D and T2D. We show that CA activities are markedly altered during metabolism of T1D and T2D and this facilitates to the oxygen-18 (18O) isotopic fractionations of breath CO2. In our observations, T1D exhibited considerable depletions of 18O-isotopes of CO2, whereas T2D manifested isotopic enrichments of 18O in breath CO2, thus unveiling a missing link of breath18O-isotopic fractionations in T1D and T2D. Our findings suggest that the alterations in erythrocytes CA activities may be the initial step of altered metabolism of T1D and T2D, and breath 18O-isotope regulated by the CA activity is a potential diagnostic biomarker that can selectively and precisely distinguish T1D from T2D and thus may open a potential unifying strategy for treating these diseases. PMID:27767104

  1. Effect of (2)H and (18)O water isotopes in kinesin-1 gliding assay.

    PubMed

    Maloney, Andy; Herskowitz, Lawrence J; Koch, Steven J

    2014-01-01

    We show for the first time the effects of heavy-hydrogen water ((2)H2O) and heavy-oxygen water (H2 (18)O) on the gliding speed of microtubules on kinesin-1 coated surfaces. Increased fractions of isotopic waters used in the motility solution decreased the gliding speed of microtubules by a maximum of 21% for heavy-hydrogen and 5% for heavy-oxygen water. We also show that gliding microtubule speed returns to its original speed after being treated with heavy-hydrogen water. We discuss possible interpretations of these results and the importance for future studies of water effects on kinesin and microtubules. We also discuss the implication for using heavy waters in biomolecular devices incorporating molecular motors. PMID:24711961

  2. Terahertz spectroscopy of ground state HD18O

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Pearson, John C.; Drouin, Brian J.; Miller, Charles E.; Kobayashi, Kaori; Matsushima, Fusakazu

    2016-10-01

    Terahertz absorption spectroscopy was employed to measure the ground state pure rotational transitions of the water isotopologue HD18O . A total of 105 pure rotational transitions were observed in the 0.5-5.0 THz region with ∼ 100 kHz accuracy for the first time. The observed positions were fit to experimental accuracy using the Euler series expansion of the asymmetric-top Hamiltonian together with the literature Microwave, Far-IR and IR data in the ground state and ν2 . The new measurements and predictions reported here support the analysis of astronomical observations by high-resolution spectroscopic telescopes such as SOFIA and ALMA where laboratory rest frequencies with uncertainties of 1 MHz or less are required for proper analysis of velocity resolved astrophysical data.

  3. 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

  4. δ2H and δ18O of human body water: a GIS model to distinguish residents from non-residents in the contiguous USA.

    PubMed

    Podlesak, David W; Bowen, Gabriel J; O'Grady, Shannon; Cerling, Thure E; Ehleringer, James R

    2012-06-01

    An understanding of the factors influencing the isotopic composition of body water is important to determine the isotopic composition of tissues that are used to reconstruct movement patterns of humans. The δ(2)H and δ(18)O values of body water (δ(2)H(bw) and δ(18)O(bw)) are related to the δ(2)H and δ(18)O values of drinking water (δ(2)H(dw) and δ(18)O(dw)), but clearly distinct because of other factors including the composition of food. Here, we develop a mechanistic geographical information system (GIS) model to produce spatial projections of δ(2)H(bw) and δ(18)O(bw) values for the USA. We investigate the influence of gender, food, and drinking water on the predicted values by comparing them with the published values. The strongest influence on the predicted values was related to the source of δ(2)H(dw) and δ(18)O(dw) values. We combine the model with equations that describe the rate of turnover to produce estimates for the time required for a non-resident to reach an isotopic equilibrium with a resident population.

  5. 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

  6. 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

  7. 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).

  8. 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.

  9. Using the Difference in 18O-enrichment in Pedogenic Carbonates and Freshwater Mollusk Shells as a Paleoaridity Proxy

    NASA Astrophysics Data System (ADS)

    Snell, K. E.; Koch, P. L.

    2008-12-01

    Aridity is an important climatic attribute, yet few proxies exist to reconstruct this parameter in the past. Here we present initial results from a study using the difference in oxygen isotope value between pedogenic carbonate and freshwater mollusk shells as a proxy for aridity. These carbonates record the oxygen isotope value of the soil water and surface water from which they precipitate, respectively, as well as temperature- dependent isotopic fractionation. Evaporation causes 18O-enrichment of water that may influence the isotopic composition of both reservoirs. Soil water is more susceptible to evaporative enrichment, however, whereas surface waters more closely track the oxygen isotope value of precipitation. If both carbonates are collected from the same region, and if we assume they form at essentially the same temperature, the 18O-enrichment of soil carbonate (soil water) relative to bivalve carbonate (surface water) may reflect aridity. Alternatively, it is possible to determine the temperature of formation of each carbonate independently using the carbonate clumped isotope thermometer (Ghosh, et al., 2006), and then to solve for the oxygen isotope value of soil and surface water. To test the premise that the extent of 18O-enrichment in pedogenic vs. bivalve carbonate will reflect aridity, we collected pedogenic carbonate, freshwater mollusk shells, and stream water samples across an aridity gradient in the midwestern United States (MN, IA, NE, SD). We discovered that while pedogenic carbonates apparently formed from soil waters that are 18O-enriched relative to meteoric water, samples from drier regions are not more strongly 18O-enriched than those from wetter regions. We will extend the study to include samples from even drier regions, such as those in the southwestern US, as 18O enrichment may only become highly pronounced under very arid conditions. While our results have not yet established this approach as a viable tool for reconstructing aridity

  10. The correlation between 18O/ 16O ratios of meteoric water and surface temperature: its use in investigating terrestrial climate change over geologic time

    NASA Astrophysics Data System (ADS)

    Fricke, Henry C.; O'Neil, James R.

    1999-07-01

    Correlations between mean annual temperature (MAT) and the weighted average oxygen isotope composition of yearly precipitation (δ 18O pt) are well-known, but the utility of modern relations to make reliable estimates of temperature change over geological time is uncertain. This question has been addressed by using seasonal subsets of the global data base of temperature and isotopic measurements to represent two different climate modes. A comparison of middle- to high-latitude δ 18O pt/temperature relations for each climate mode reveals (1) a significant offset between them, and (2) a difference in the strength of their correlations. The offset in relations is due to differences in temperature and water vapor budget in the tropics, and can lead to serious underestimates of temperature change. Differences in the strength of correlations arise from the influence of climate mode-specific, non-temperature factors on δ 18O pt. The overall result is that no single relation can be used in all cases to make unambiguous temperature estimates using a temporal record of δ 18O pt values. One way to overcome these problems is to reconstruct δ 18O pt/temperature relations for the time periods being investigated. If an appropriate proxy for δ 18O pt is available, it may also be possible to estimate temperature without relying on δ 18O pt/temperature relations. A promising alternative to these options is to use records of δ 18O pt to test predictions of global climate models, an approach that may allow a reliable and more complete reconstruction to be made of climate change over geologic time.

  11. Effects of environmental parameters, leaf physiological properties and leaf water relations on leaf water delta18O enrichment in different Eucalyptus species.

    PubMed

    Kahmen, Ansgar; Simonin, Kevin; Tu, Kevin P; Merchant, Andrew; Callister, Andrew; Siegwolf, Rolf; Dawson, Todd E; Arndt, Stefan K

    2008-06-01

    Stable oxygen isotope ratios (delta18O) have become a valuable tool in the plant and ecosystem sciences. The interpretation of delta18O values in plant material is, however, still complicated owing to the complex interactions among factors that influence leaf water enrichment. This study investigated the interplay among environmental parameters, leaf physiological properties and leaf water relations as drivers of the isotopic enrichment of leaf water across 17 Eucalyptus species growing in a common garden. We observed large differences in maximum daily leaf water delta18O across the 17 species. By fitting different leaf water models to these empirical data, we determined that differences in leaf water delta18O across species are largely explained by variation in the Péclet effect across species. Our analyses also revealed that species-specific differences in transpiration do not explain the observed differences in delta18O while the unconstrained fitting parameter 'effective path length' (L) was highly correlated with delta18O. None of the leaf morphological or leaf water related parameters we quantified in this study correlated with the L values we determined even though L was typically interpreted as a leaf morphological/anatomical property. A sensitivity analysis supported the importance of L for explaining the variability in leaf water delta18O across different species. Our investigation highlighted the importance of future studies to quantify the leaf properties that influence L. Obtaining such information will significantly improve our understanding of what ultimately determines the delta18O values of leaf water across different plant species. PMID:18208514

  12. Population attributable fraction of modifiable risk factors for Alzheimer disease: A systematic review of systematic reviews

    PubMed Central

    Hazar, Narjes; Seddigh, Leila; Rampisheh, Zahra; Nojomi, Marzieh

    2016-01-01

    Background: Alzheimer’s disease (AD) is the most common type of dementia. Demonstrating the modifiable risk factors of AD can help to plan for prevention of this disease. The aim of the current review was to characterize modifiable cardiovascular risk factors of AD using existing data and determine their contribution in AD development in Iran and the world. Methods: The systematic search was done in Medline, Scopus, and Cochrane databases from inception to May 2014 to find systematic reviews or meta-analyses about association between AD and cardiovascular modifiable risk factors included diabetes, hypertension (HTN), physical inactivity, smoking, hypercholesterolemia, and overweight and obesity. The population attributable fraction (PAF) was calculated for these risk factors in Iran and the world. Results: Of 2651 articles, 11 were eligible for data extraction after assessing relevancy and quality. Diabetes mellitus (DM) type 2, smoking, physical inactivity, overweight and obesity were significantly associated with increased risk of AD. Physical inactivity with 22.0% and smoking with 15.7% had the highest PAF for AD in Iran and the world, respectively. Conclusion: Our findings demonstrated that modifiable cardiovascular risk factors could increase the risk of AD. Moreover, about one-third of AD cases were attributed to five modifiable risk factors. PMID:27648178

  13. Population attributable fraction of modifiable risk factors for Alzheimer disease: A systematic review of systematic reviews

    PubMed Central

    Hazar, Narjes; Seddigh, Leila; Rampisheh, Zahra; Nojomi, Marzieh

    2016-01-01

    Background: Alzheimer’s disease (AD) is the most common type of dementia. Demonstrating the modifiable risk factors of AD can help to plan for prevention of this disease. The aim of the current review was to characterize modifiable cardiovascular risk factors of AD using existing data and determine their contribution in AD development in Iran and the world. Methods: The systematic search was done in Medline, Scopus, and Cochrane databases from inception to May 2014 to find systematic reviews or meta-analyses about association between AD and cardiovascular modifiable risk factors included diabetes, hypertension (HTN), physical inactivity, smoking, hypercholesterolemia, and overweight and obesity. The population attributable fraction (PAF) was calculated for these risk factors in Iran and the world. Results: Of 2651 articles, 11 were eligible for data extraction after assessing relevancy and quality. Diabetes mellitus (DM) type 2, smoking, physical inactivity, overweight and obesity were significantly associated with increased risk of AD. Physical inactivity with 22.0% and smoking with 15.7% had the highest PAF for AD in Iran and the world, respectively. Conclusion: Our findings demonstrated that modifiable cardiovascular risk factors could increase the risk of AD. Moreover, about one-third of AD cases were attributed to five modifiable risk factors.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. Theoretical calculation of nitrogen isotope equilibrium exchange fractionation factors for various NOy molecules

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Michalski, Greg

    2015-09-01

    The nitrogen stable isotope ratio (15N/14N) of nitrogen oxides (NOx = NO + NO2) and its oxidation products (NOy = NOx + PAN (peroxyacetyl nitrate = C2H3NO5) + HNO3 + NO3 + HONO + N2O5 + ⋯ + particulate nitrates) has been suggested as a tool for partitioning NOx sources; however, the impact of nitrogen (N) equilibrium isotopic fractionation on 15N/14N ratios during the conversion of NOx to NOy must also be considered, but few fractionation factors for these processes have been determined. To address this limitation, computational quantum chemistry calculations of harmonic frequencies, reduced partition function ratios (15β), and N equilibrium isotope exchange fractionation factors (αA/B) were performed for various gaseous and aqueous NOy molecules in the rigid rotor and harmonic oscillator approximations using the B3LYP and EDF2 density functional methods for the mono-substitution of 15N. The calculated harmonic frequencies, 15β, and αA/B are in good agreement with available experimental measurements, suggesting the potential to use computational methods to calculate αA/B values for N isotope exchange processes that are difficult to measure experimentally. Additionally, the effects of solvation (water) on 15β and αA/B were evaluated using the IEF-PCM model, and resulted in lower 15β and αA/B values likely due to the stabilization of the NOy molecules from dispersion interactions with water. Overall, our calculated 15β and αA/B values are accurate in the rigid rotor and harmonic oscillator approximations and will allow for the estimation of αA/B involving various NOy molecules. These calculated αA/B values may help to explain the trends observed in the N stable isotope ratio of NOy molecules in the atmosphere.

  19. Contribution of soil respiration in tropical, temperate, and boreal forests to the 18O enrichment of atmospheric O2

    NASA Astrophysics Data System (ADS)

    Angert, Alon; Barkan, Eugeni; Barnett, Bruce; Brugnoli, Enrico; Davidson, Eric A.; Fessenden, Julianna; Maneepong, Somsak; Panapitukkul, Nipa; Randerson, James T.; Savage, Kathleen; Yakir, Dan; Luz, Boaz

    2003-09-01

    The 18O content of atmospheric O2 is an important tracer for past changes in the biosphere. Its quantitative use depends on knowledge of the discrimination against 18O associated with the various O2 consumption processes. Here we evaluated, for the first time, the in situ 18O discrimination associated with soil respiration in natural ecosystems. The discrimination was estimated from the measured [O2] and δ18O of O2 in the soil-air. The discriminations that were found are 10.1 ± 1.5‰, 17.8 ± 1.0‰, and 22.5 ± 3.6‰, for tropical, temperate, and boreal forests, respectively, 17.9 ± 2.5‰ for Mediterranean woodland, and 15.4 ± 1.6‰ for tropical shrub land. Current understanding of the isotopic composition of atmospheric O2 is based on the assumption that the magnitude of the fractionation in soil respiration is identical to that of dark respiration through the cytochrome pathway alone (˜18‰). The discrimination we found in the tropical sites is significantly lower, and is explained by slow diffusion in soil aggregates and root tissues that limits the O2 concentration in the consumption sites. The high discrimination in the boreal sites may be the result of high engagement of the alternative oxidase pathway (AOX), which has high discrimination associated with it (˜27‰). The intermediate discrimination (˜18‰) in the temperate and Mediterranean sites can be explained by the opposing effects of AOX and diffusion limitation that cancel out. Since soil respiration is a major component of the global oxygen uptake, the contribution of large variations in the discrimination, observed here, to the global Dole Effect should be considered in global scale studies.

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    before chemical purification. Initial results provide an equilibrium 98Mo/95Mo isotope fractionation factor between metal and silicate liquids of -0.18±0.10% (2σ) at 1400°C and 1 GPa. Although the relative mass difference of these Mo isotopes is smaller than for Fe isotopes, this result implies that metal-silicate segregation may have led to mass-dependent stable Mo isotope fractionation, as opposed to Fe isotopes. A possible explanation is that the bonding environment of Mo may counterbalance its relatively small mass separation. At reducing conditions, Mo occurs in 4+ valence state in silicates [4] and thus its bond strength difference between metal and silicate may be more similar to that of Si than Fe. Stable Mo isotopes may thus become an important tool for constraining the conditions of core formation in asteroids and terrestrial planets. [1] Rubie et al. (2011) EPSL 301, 31-42. [2] Shahar et al. (2009) EPSL 288, 228-234. [3] Poitrasson et al. (2009) EPSL 278, 376-385. [4] Farges et al. (2006) Can. Min. 44, 731-753.

  1. 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

  2. What drives the millennial and orbital variations of δ18O atm?

    NASA Astrophysics Data System (ADS)

    Landais, A.; Dreyfus, G.; Capron, E.; Masson-Delmotte, V.; Sanchez-Goñi, M. F.; Desprat, S.; Hoffmann, G.; Jouzel, J.; Leuenberger, M.; Johnsen, S.

    2010-01-01

    The isotopic composition of atmospheric oxygen ( δ18O atm) is a complex marker that integrates changes in global sea-level, water cycle, and biosphere productivity. A strong signature of orbital precession has been identified leading to the use of low-resolution measurements of δ18O atm to date ice core records. However, the drivers of these δ18O atm variations are still poorly known. Here, we combine records of millennial and orbital scale variations on the NorthGRIP, Vostok, and EPICA Dome C (EDC) ice cores to explore the origin of δ18O atm variations. We show that, superimposed on the dominant precession signal, millennial δ18O atm variations record systematic decreases during warm phases of the Dansgaard-Oeschger events and systematic increases during the cold phases. We show that at both timescales δ18O atm is strongly related to the monsoon activity itself influenced by precessional and millennial shifts in InterTropical Convergence Zone (ITCZ). Then, we show that despite its simplicity, the Dole effect defined as the difference between δ18O atm and δ18O of global sea-level enables one to remove the obliquity signal within the δ18O atm record and is a good indicator of hydrological cycle and biosphere productivity. Finally, we compare the δ18O atm records to past changes in atmospheric composition recorded in ice cores and conclude that δ18O atm responds much more than CH 4 to precession signal, in contrast with earlier views. Similarities observed at orbital timescales between CO 2 and δ18O atm reveal a stronger coupling than previously thought between the carbon and the oxygen cycles.

  3. 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.

  4. 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.

  5. 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.

  6. Predictable components in global speleothem δ18O

    NASA Astrophysics Data System (ADS)

    Fischer, Matt J.

    2016-01-01

    The earth's ice-ocean-atmosphere system is made up of subsystems which have different dynamics and which evolve at different timescales. Examples include the slow dynamics of ice sheet growth and melting, the tropical response to precessional cycles (˜21,000 years), and the fast dynamics of Dansgaard-Oeschger cycles (˜1500 years). Since dynamical systems evolve along characteristic trajectories, they are, to some extent, predictable. Further, it should be possible to decompose any dynamical system that is made up of subsystems with discrete dynamics and characteristic timescales, into time series which capture those discrete components. This study reviews five methods which can potentially achieve this, including: Optimal Persistence Analysis (OPA), Slow Feature Analysis (SFA), Principal Trend Analysis (PTA), Average Predictability Time Decomposition (APTD) and Forecastable Components Analysis (ForeCA). These methods produce sets of components that are in some way predictable, such that each component is more predictable than the next component, but each method uses a different measure of predictability. The five methods are applied to a global dataset of speleothem δ18O spanning the period 22-0 ka BP. The two leading predictable components are a monotonic trend, and a low-frequency oscillation with a periodicity of ˜21,000 years. The methods ForeCA and PTA cleanly separate these two components from higher-frequency signals. The third predictable component consists predominantly of a peak which ramps up during Heinrich Stadial 1, and falls thereafter. Furthermore, predictable components analysis can be used not only to investigate the predictability within a field, but can be extended to exploring the predictability between fields, such as between the northern hemisphere field and the southern hemisphere field. Predictable components analysis allows a better insight into the dynamical components of climate fields, and hence should be a useful tool for improving

  7. 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

  8. 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.

  9. 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.

  10. The environmental signals that CAN and CANNOT be inferred from δ18O signals in plant cellulose

    NASA Astrophysics Data System (ADS)

    Kahmen, A.; Sachse, D.; Arndt, S. K.; Tu, K. P.; Vitousek, P.; Dawson, T. E.

    2009-12-01

    Cellulose is one of the most abundant plant compounds on Earth, and contains oxygen that ultimately has its origin from water. The stable oxygen isotope composition, δ18O, of water is strongly associated with environmental conditions. It follows therefore that the δ18O of leaf (δ18OLC) and stem (δ18OSC) cellulose is regarded as a powerful indicator of environmental conditions. Interpretations of what determines the δ18OLC and δ18OSC are, however, complicated by the fact that δ18OLC and δ18OSC are controlled by both air temperature (Tair) that is known to influence the isotopic composition of the plant’s source water and relative humidity (RH) that drives isotope enrichment of H218O in a leaf. Here, we show the results of an investigation where we combined empirical data with model simulations to specifically test 1) the magnitude of the impacts that RH and Tair have on δ18OLC and δ18OSC and 2) determine which environmental signal is ultimately reflected in δ18OLC and δ18OSC. Our analyses revealed that δ18OLC and δ18OSC values are equally sensitive to RH and Tair and that distinguishing which of these factors best explains the underlying variation in δ18OLC and δ18OSC cannot be accomplished in the absence of other biological and environmental data. RH and Tair effects on δ18O values of plant cellulose can, however, be integrated into a single index of aridity - the leaf to air vapor pressure deficit (VPD). We show that there is a near universal relationship between VPD and the δ18O values of plant cellulose that is robust across all the climate zones that we investigated in this study. Despite the fact that several parameters can affect the δ18O values of plant cellulose our analysis shows that δ18O values of plant cellulose is a powerful indicator of aridity and therefore provides a pivotal tool for applications in ecological- climate- or forensic sciences.

  11. 18O isotopic separation of stream nitrate sources in mid-Appalachian forested watersheds

    NASA Astrophysics Data System (ADS)

    Williard, Karl W. J.; DeWalle, David R.; Edwards, Pamela J.; Sharpe, William E.

    2001-10-01

    The δ18O values of atmospheric nitrate deposition, microbe-produced nitrate, and stream nitrate were measured to determine the dominant source of stream nitrate in 27 mid-Appalachian headwater forested watersheds (12-771 ha) with varying bedrock geologies, land disturbance histories, and stand ages. The 12 monthly composite nitrate δ18O values of wet deposition and throughfall exhibited similar pronounced seasonal trends, with relatively depleted δ18O values during the summer. Wet deposition and throughfall nitrate δ18O values were not significantly different between northern (Leading Ridge, PA) and southern (Fernow, WV) regional sampling sites, indicating that δ18O values were spatially similar across the study area. Atmospheric nitrate δ18O values were significantly greater than microbe-produced nitrate δ18O values, allowing the two sources of stream nitrate to be separated. During four baseflow and three stormflow sampling periods, microbe-produced nitrate was the dominant (>70%) source of nitrate in the study streams. This result does not mean atmospheric nitrogen deposition should be discounted as a source of forested stream nitrate, because atmospheric deposition is the primary external contributor to the long-term soil nitrogen pool that ultimately drives soil nitrate production rates. Stream nitrate δ18O values were greater during stormflow periods compared to baseflow periods, indicating greater contributions of atmospheric nitrate during storm events. Neither microbe-produced nitrate δ18O values from incubated forest soil samples nor stream nitrate δ18O values showed strong relationships with land disturbance history or stand age. However, watersheds dominated by Pottsville/Allegheny bedrock and associated extremely acid soils had greater summer stream nitrate δ18O values than watersheds containing predominantly Catskill/Chemung/Pocono and Mauch Chunk/Greenbrier bedrock. Inhibited microbial nitrate production by low soil pH could account for

  12. Modification of the δ18O value of meteoric water to cave drip water and speleothem calcite

    NASA Astrophysics Data System (ADS)

    Wackerbarth, Anne; Scholz, Denis; Fohlmeister, Jens; Mangini, Augusto

    2010-05-01

    Stable isotope signals of speleothems have proved to be valuable archives for past climate variability in recent years. They provide the possibility of precise dating using the Th/U-method and allow high resolution isotope analyses. The stable isotope signal of stalagmites strongly depends on the isotopic composition of the drip water which is affected by climate parameters, vegetation parameters and the residence time in the soil and epikarst layer. To understand how the δ18O value of drip water and stalagmite calcite is influenced by climate parameters, we developed the Drip Water Model, where the input parameters are: temperature, amount of cave infiltration, air humidity, the type of vegetation and the CO2 content of soil air. The δ18O value of precipitation is determined in dependency on temperature by a linear data fit. Evapotranspiration modifies both, the isotopic composition and the amount of drip water, since evaporation is accompanied by kinetic fractionation while transpiration is not. Hence, depending on the ratio of evaporation to transpiration the soil water is enriched in heavy oxygen. Evapotranspiration is higher in the warmer months, leading to a larger contribution of winter precipitation to drip water. The model establishes a weighting function for the δ18O value of a monthly water parcel and determines its contribution to the annual mean composition of speleothem calcite. The Ca2+ content decides how much calcite is able to precipitate from the water parcel. The model shows that despite that the CO2 content of soil air being higher in summer than in winter, the Ca2+ content of drip water is lower in summer than in winter when the residence time of the water in the soil and epikarst is in only in the range of few months. This results in even stronger weight of cooler months on the isotopic composition of stalagmites from Atta Cave, Bunker Cave and B7 Cave in Central Europe. The reversed model enables us to tentatively reconstruct average

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. Analysis of the climate signal contained within δ 18O and growth rate parameters in two Ethiopian stalagmites

    NASA Astrophysics Data System (ADS)

    Baker, Andy; Asrat, Asfawossen; Fairchild, Ian J.; Leng, Melanie J.; Wynn, Peter M.; Bryant, Charlotte; Genty, Dominique; Umer, Mohammed

    2007-06-01

    We combine surface and cave climate monitoring with multiple stalagmite parameters to help understand and calibrate the climate records contained within stalagmites from a region with strong rainfall seasonality. Two actively growing stalagmites from Ethiopia were analysed in order to investigate the climate signal contained within δ 18O and growth rate parameters. The δ 18O and growth rate of the two stalagmites give different responses to surface climate due to variations in the climate signal transfer. Both stalagmites (Merc-1 and Asfa-3) have a climate response that is seasonal; however this signal is subsequently smoothed by the mixing of event and storage water within the aquifer. Merc-1 responds more to high frequency ('event') climate, due to a greater ratio of event to storage water in this sample, whereas Asfa-3 responds more to low frequency ('storage') climate. In addition, different parameters respond to different seasons. For example, stalagmite Asfa-3, from greater depth from the surface and with a slow drip rate, has a growth rate that responds to the amount of summer rain. In contrast, Merc-1, closer to the surface and with a faster drip rate, exhibits no clear response to surface climate, probably due to a more complex climate signal transfer. δ 18O response varies with stalagmite due to the interplay between rainfall forcing factors (amount, seasonality) and disequilibrium kinetics, with opposing correlations between seasonal rainfall and δ 18O between the samples. Our results demonstrate that analysis of seasonal climate forcing, and transfer functions reflecting the mixing of event and storage water, may be the most appropriate approach to develop of transfer functions appropriate for high-resolution, stalagmite climate reconstruction.

  20. 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

  1. 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.

  2. 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.

  3. 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

  4. Freshwater budget of the Canada Basin, Arctic Ocean, from salinity, δ18O, and nutrients

    NASA Astrophysics Data System (ADS)

    Yamamoto-Kawai, M.; McLaughlin, F. A.; Carmack, E. C.; Nishino, S.; Shimada, K.

    2008-01-01

    The contribution of freshwater components (e.g., meteoric, sea ice, and Pacific water) in the Canada Basin is quantified using salinity, δ18O, and nutrient data collected in 2003 and 2004. The penetration depth of sea ice meltwater is limited to the upper 30 m, and brine, rejected during sea ice formation, is observed from 30 to 250 m depth. The fraction of meteoric water is high in the upper 50 m and decreases with depth. Pacific water entering via Bering Strait is the main source of freshwater below 50 m depth. Bering Strait throughflow, which transports Pacific water with salinity 32.5 together with meteoric water supplied upstream of the Bering Strait, contributes up to 75% of freshwater input (>3200 km3 a-1) to the Canada Basin. The mean residence time of Pacific water in the Canada Basin is estimated to be 11 years. Precipitation and river runoff from both North American and Eurasian continents add >800 km3 a-1 and sea ice formation removes <900 km3 a-1 (<0.6 m a-1) of fresh water. The export of ice and liquid fresh water from the Canada Basin contributes ˜40% of the freshwater flux from the Arctic Ocean to the North Atlantic Ocean.

  5. 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

  6. 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

  7. [Correlation of delta18O in precipitation and moisture sources at Yunfu, Western Guangdong Province, China].

    PubMed

    Zheng, Yan-Ming; Zhong, Wei; Peng, Xiao-Ying; Xue, Ji-Bin; Zhao, Yin-Juan; Ma, Qiao-Hong; Cai, Ying

    2009-03-15

    Fifty-nine samples of atmospheric precipitation were collected at Yunfu, Western Guangdong province during the period of April 5, 2005 to April 1, 2006 and their oxygen isotopic compositions were analyzed. Results show that delta18O values range from -12.47 per thousand to -0.18 per thousand with an average of -4.91 per thousand; the delta18O values of summer and autumn (from May to September) are relatively lower, ranging from -10.00 per thousand to -5.00 per thousand with an average of -6.30 per thousand; the delta18O values of winter and spring (from October to next April) are relatively higher, ranging from - 3.00 per thousand to - 1.00 per thousand with an average of - 2.20 per thousand. These delta18O values have relatively marked negative correlation with the corresponding temperatures and water vapour pressure and their coefficients are both -0.60; but they have had negative correlation with the precipitation amount, the coefficient is -0.33. Comparing with the monthly delta18O value of Guangzhou atmospheric precipitation, those of Yunfu City is relatively lower, maybe the reason is that Yunfu City is influenced by stronger South-West Asian Monsoon. The results of HYSPLIT back trajectory analysis indicated that the differences of delta18O values are determined by different water vapour sources during the pre-rainy season (from April to June), post-rainy season (from July to September) and non-rainy season (from October to next April), so the delta18O values can be considered as an indicator of denoting their water vapour sources, relatively higher delta18O values denote the water vapour sources are denaturalized tropical hot air mass located in the subtropical sea areas (including the South China Sea), western Pacific Ocean; relatively lower delta18O values indicate denaturalized tropical hot air mass from the India Ocean and Bengal Gulf.

  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. 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.

  10. Optimization of the Safety Factor Profile for High Noninductive Current Fraction Discharges in DIII-D

    SciTech Connect

    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.; Murakami, Masanori; Petrie, T W; Petty, C C.; Rhodes, T. L.; Zeng, L.

    2011-01-01

    In order to assess the optimum q profile for discharges in DIII-D with 100% of the current driven noninductively (f(NI) = 1), the self-consistent response of the plasma profiles to changes in the q profile was studied in high f(NI), high beta(N) discharges through a scan of q(min) and q(95) at two values of beta(N). As expected, both the bootstrap current fraction, f(BS), and f(NI) increased with q(95). The temperature and density profiles were found to broaden as either q(min) or beta(N) is increased. A consequence is that f(BS) does not continue to increase at the highest values of q(min). A scaling function that depends on q(min), q(95), and the peaking factor for the thermal pressure was found to represent well the f(BS)/beta(N) inferred from the experimental profiles. The changes in the shapes of the density and temperature profiles as beta(N) is increased modify the bootstrap current density (J(BS)) 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 J(BS) in order to match the profiles of the noninductive current density (J(NI)) 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 f(BS). The profiles of J(NI) and J were most similar at q(min) approximate to 1.35-1.65, q(95) approximate to 6.8, where f(BS) is also maximum, establishing this q profile as the optimal choice for f(NI) = 1 operation in DIII-D with the existing set of external current drive sources.

  11. Isotopic (δ18O, δD and deuterium excess) records from the TALDICE ice core (East Antarctica) (Invited)

    NASA Astrophysics Data System (ADS)

    Stenni, B.; Buiron, D.; Masson-Delmotte, V.; Bonazza, M.; Braida, M.; Chappellaz, J.; Frezzotti, M.; Falourd, S.; Minster, B.; Selmo, E.

    2010-12-01

    Paleotemperature reconstructions from Antarctic ice cores rely mainly on δD and δ18O records and the main key factors controlling the observed distribution of δD and δ18O in Antarctic surface snow are mainly related to the condensation temperature of the precipitation and the origin of moisture. The deuterium excess, d = δD - 8*δ18O, contains information about climate conditions prevailing in the source regions of precipitation and can be used as an integrated tracer of past hydrological cycle changes. In the framework of the TALos Dome Ice CorE (TALDICE) project, a deep ice core (1620 m) has been drilled at Talos Dome, a peripheral dome of East Antarctica facing the Ross Sea, about 550 km north of Taylor Dome and 1100 km East from the EPICA Dome C drilling site. The TALDICE coring site (159°11'E 72°49'S; 2315 m; T -41°C; www.taldice.org) is located near the dome summit and is characterised by an annual snow accumulation rate of 80 mm water equivalent. Backtrajectory analyses suggest that Talos Dome is mainly influenced by air masses arriving both from the Pacific (Ross Sea) and Indian Ocean sectors. A preliminary dating based on an ice flow model and an inverse method suggests for the upper 1580 m an age of about 300,000 years BP. The full TALDICE δ18O record obtained from the bag samples as well as δD and deuterium excess data are presented here. The δ18O and δD measurements were carried out in Italy and France on a continuous basis of 1 m. These new records will be compared to the ones obtained from the EDC ice core as well as with other East Antarctic ice core records. In particular, we will focus on the whole isotopic profiles, in good agreement with other inland deep ice cores, and on the last deglaciation, showing climatic changes at Talos Dome in phase with the Antarctic plateau and suggesting that the bipolar see saw with Greenland temperature is also valid for this new coastal site facing the Ross Sea sector.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. Holocene Climate History of North Central Minnesota, Interpreted From δ D and δ \\18O of Lake Sediments

    NASA Astrophysics Data System (ADS)

    Zabielski, V.; Ito, E.; Wright, H.; Huang, Y.; van Leeuwen, J.; Stefanova, I.; Wenger, D.; Williams, J. W.; Person, M.

    2004-12-01

    Stable isotopes of authigenic carbonates in lake sediments are routinely used to reconstruct past climate. When carbonates are absent, other stable isotope records such as cellulose oxygen and δ D of specific organic compounds such as palmitic acid (PA) are being used to infer water temperature. Here we show that δ D of PA can be used to reconstruct aridity in appropriate climatic settings. Cored sediment from Moody Lake, located near the base of the Crow Wing River watershed, was analyzed for lithological variations indicative of lake-level, total organic and inorganic carbon, pollen, O and C isotopes of authigenic calcite and H isotopes of PA. Modern sediments in Moody Lake contain no authigenic carbonates, but lower sections contain 5 ˜10% total inorganic carbon. Total organic carbon varies between 10 ˜35% in the deep-water core. The δ \\18O values varies from -8‰ at about 11ka \\14C increasing to -2‰ at ca. 4ka \\14C. The δ D values are approximately -210‰ at 11ka \\14C and -180‰ at the top, with a peak of -170‰ in the mid-section. The δ D values of PA can be converted to that of water using a published equation. If we assume that authigenic carbonate is formed only during warm summer months, say at 25° C, the small temperature dependence of carbonate oxygen isotope fractionation allows us to estimate the δ \\18O of water without introducing a large error, given the range of 6‰ in δ \\18O values. When the two calculated isotope values are compared to the Global Meteoric Water Line and to local (Minneapolis) precipitation, they fall on an evaporation line of slope ˜5, a typical slope observed for the region. Mid-Holocene values are farthest from the local meteoric precipitation indicating greater aridity, and early Holocene values closer to the meteoric precipitation. The overall pattern is interpreted as reflecting cooler and wetter conditions in the early Holocene, gradually increasing temperatures toward the mid-Holocene, much higher

  18. 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...

  19. 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

  20. Co-occurring species differ in tree-ring delta(18)O trends.

    PubMed

    Marshall, John D; Monserud, Robert A

    2006-08-01

    The stable oxygen isotope ratio (delta(18)O) of tree-ring cellulose is jointly determined by the delta(18)O of xylem water, the delta(18)O of atmospheric water vapor, the humidity of the atmosphere and perhaps by species-specific differences in leaf structure and function. Atmospheric humidity and the delta(18)O of water vapor vary seasonally and annually, but if the canopy atmosphere is well mixed, atmospheric characteristics should be uniform among co-occurring trees. In contrast, xylem water delta(18)O is determined by the delta(18)O of water being drawn from the soil, which varies with depth. If co-occurring trees draw water from different soil depths, this soil-water delta(18)O signal would be manifest as differences in delta(18)O among the trees. We examined the variation in tree ring delta(18)O, over eight decades during the 20th Century, among three species co-occurring in natural forest stands of the northern Rocky Mountains in the USA. We sampled 10 Douglas-firs (Pseudotsuga menziesii (Mirb.) Franco var. glauca), 10 ponderosa pines (Pinus ponderosa Laws.) and seven western white pines (Pinus monticola Dougl.). As expected, variation in atmospheric conditions was recorded in the delta(18)O of the cellulose produced in a given year, but observed climatic correlations with delta(18)O were weak. Significant correlations with June climate data included: daily maximum temperature (r = 0.29), daily minimum temperature (r = -0.25), mean temperature (r = 0.20), mean daily precipitation (r = -0.54), vapor pressure deficit (r = 0.32) and solar radiation (r = 0.44). Lagged effects were observed in Douglas-fir and western white pine. In these species, the delta(18)O of a given annual ring was correlated with the delta(18)O of the previous ring. Ponderosa pine showed no significant autocorrelation. Although the species means were correlated among years (r = 0.67 to 0.76), ponderosa pine was consistently enriched in delta(18)O relative to the other species; differences

  1. /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.

  2. 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

  3. Exploring factors affecting measurements of the static coefficient of friction: An application of fractional factorial experiment design

    NASA Astrophysics Data System (ADS)

    Folkerts, Timothy J.

    2004-10-01

    The common undergraduate experiment for determining the static coefficient of friction between a wooden block and a horizontal tabletop often produces inconsistent results. We show how several factors influence the measured magnitude and consistency of the coefficient of friction. We utilize a fractional factorial experimental design, which is a method that has been specifically developed to effectively and efficiently uncover key factors that most strongly influence experimental results.

  4. 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

  5. Pulmonary NO and C18O2 uptake during pressure-induced lung expansion in rabbits.

    PubMed

    Heller, Hartmut; Schuster, Klaus-Dieter

    2007-01-01

    In artificially ventilated animals we investigated the dependence of the pulmonary diffusing capacities of nitric oxide (NO) and doubly 18O-labeled carbon dioxide (DLNO, DLC18O2) on lung expansion with respect to ventilator-driven increases in intrapulmonary pressure. For this purpose we applied computerized single-breath experiments to 11 anesthetized paralyzed rabbits (weight 2.8-3.8 kg) at various alveolar volumes (45-72 ml) by studying the almost entire inspiratory limb of the respective pressure/volume curves (intrapulmonary pressure: 6-27 cmH2O). The animals were ventilated with room air, employing a computerized ventilatory servo-system that we designed to maintain mechanical ventilation and to execute the particular lung function tests automatically. Each single-breath maneuver was started from residual volume (13.5+/-2 ml, mean+/-SD) by inflating the rabbit lungs with 35-55 ml indicator gas mixture containing 0.05% NO in N2 or 0.9% C18O2 in N2. Alveolar partial pressures of NO and C18O2 were measured by respiratory mass spectrometry. Values of DLNO and DLC18O2 ranged between 1.55 and 2.49 ml/(mmHg min) and 11.7 and 16.6 ml/(mmHg min), respectively. Linear regression analyses yielded a significant increase in DLNO with simultaneous increase in alveolar volume (P<0.005) and intrapulmonary pressure (P<0.023) whereas DLC18O2 was not improved. Our results suggest that the ventilator-driven lung expansion impaired the C18O2 blood uptake conductance, finally compensating for the beneficial effect of the increase in alveolar volume on DLC18O2 values.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. Greenland ice core δ18O records - from Camp Century to NEEM

    NASA Astrophysics Data System (ADS)

    Vinther, B. M.

    2012-04-01

    During the past five decades deep ice cores have been drilled at six locations on the Greenland Ice Sheet, all cores yielding records of δ18O from the past. Hence δ18O records from southern, central and north-western Greenland locations can now be interpreted. Furthermore several δ18O records from ice cores drilled on small ice caps in the vicinity of the Greenland Ice Sheet are available. An inter-comparison of the Holocene sections of the ice cores has suggested that both climate change and ice sheet elevation change played major parts in determining the millennial scale evolution of the δ18O signals seen in the records [Vinther et al. 2009]. While all glacial δ18O records show very prominent abrupt climate change in the form of Dansgaard-Oeschger cycles it is interesting to note that long term trends in glacial δ18O differ between the records. A significant part of these differences are likely to be a consequence of different elevation histories in the different areas of the Greenland Ice Sheet during the glacial period. Reference: Vinther, B.M, Buchardt, S.L., Clausen, H.B., Dahl-Jensen, D., Johnsen, S.J., Fisher, D.A., Koerner, R.M., Raynaud, D., Lipenkov, V., Andersen, K.K, Blunier, T., Rasmussen, S.O., Steffensen, J.P., Svensson, A.M., Holocene thinning of the Greenland ice sheet, Nature, 461, 385-388, 2009.

  12. Late-Pleistocene precipitation δ18O interpolated across the global landmass

    NASA Astrophysics Data System (ADS)

    Jasechko, Scott

    2016-08-01

    Global water cycles, ecosystem assemblages, and weathering rates were impacted by the ˜4°C of global warming that took place over the course of the last glacial termination. Fossil groundwaters can be useful indicators of late-Pleistocene precipitation isotope compositions, which, in turn, can help to test hypotheses about the drivers and impacts of glacial-interglacial climate changes. Here, a global catalog of 126 fossil groundwater records is used to interpolate late-Pleistocene precipitation δ18O across the global landmass. The interpolated data show that extratropical late-Pleistocene terrestrial precipitation was near uniformly depleted in 18O relative to the late Holocene. By contrast, tropical δ18O responses to deglacial warming diverged; late-Pleistocene δ18O was higher-than-modern across India and South China but lower-than-modern throughout much of northern and southern Africa. Groundwaters that recharged beneath large northern hemisphere ice sheets have different Holocene-Pleistocene δ18O relationships than paleowaters that recharged subaerially, potentially aiding reconstructions of englacial transport in paleo ice sheets. Global terrestrial late-Pleistocene precipitation δ18O maps may help to determine 3-D groundwater age distributions, constrain Pleistocene mammal movements, and better understand glacial climate dynamics.

  13. 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.

  14. Statistical Model to Analyze Quantitative Proteomics Data Obtained by 18O/16O Labeling and Linear Ion Trap Mass Spectrometry

    PubMed Central

    Jorge, Inmaculada; Navarro, Pedro; Martínez-Acedo, Pablo; Núñez, Estefanía; Serrano, Horacio; Alfranca, Arántzazu; Redondo, Juan Miguel; Vázquez, Jesús

    2009-01-01

    Statistical models for the analysis of protein expression changes by stable isotope labeling are still poorly developed, particularly for data obtained by 16O/18O labeling. Besides large scale test experiments to validate the null hypothesis are lacking. Although the study of mechanisms underlying biological actions promoted by vascular endothelial growth factor (VEGF) on endothelial cells is of considerable interest, quantitative proteomics studies on this subject are scarce and have been performed after exposing cells to the factor for long periods of time. In this work we present the largest quantitative proteomics study to date on the short term effects of VEGF on human umbilical vein endothelial cells by 18O/16O labeling. Current statistical models based on normality and variance homogeneity were found unsuitable to describe the null hypothesis in a large scale test experiment performed on these cells, producing false expression changes. A random effects model was developed including four different sources of variance at the spectrum-fitting, scan, peptide, and protein levels. With the new model the number of outliers at scan and peptide levels was negligible in three large scale experiments, and only one false protein expression change was observed in the test experiment among more than 1000 proteins. The new model allowed the detection of significant protein expression changes upon VEGF stimulation for 4 and 8 h. The consistency of the changes observed at 4 h was confirmed by a replica at a smaller scale and further validated by Western blot analysis of some proteins. Most of the observed changes have not been described previously and are consistent with a pattern of protein expression that dynamically changes over time following the evolution of the angiogenic response. With this statistical model the 18O labeling approach emerges as a very promising and robust alternative to perform quantitative proteomics studies at a depth of several thousand proteins

  15. 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

  16. 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

  17. 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

  18. Towards a Better Understanding of the Oxygen Isotope Signature of Atmospheric CO2: Determining the 18O-Exchange Between CO2 and H2O in Leaves and Soil On-line with Laser-Based Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gangi, L.; Rothfuss, Y.; Vereecken, H.; Brueggemann, N.

    2013-12-01

    The oxygen isotope signature of carbon dioxide (δ18O-CO2) is a powerful tool to disentangle CO2 fluxes in terrestrial ecosystems, as CO2 attains a contrasting 18O signature by the interaction with isotopically different soil and leaf water pools during soil respiration and photosynthesis, respectively. However, using the δ18O-CO2 signal to quantify plant-soil-atmosphere CO2 fluxes is still challenging due to a lack of knowledge concerning the magnitude and effect of individual fractionation processes during CO2 and H2O diffusion and during CO2-H2O isotopic exchange in soils and leaves, especially related to short-term changes in environmental conditions (non-steady state). This study addresses this research gap by combined on-line monitoring of the oxygen isotopic signature of CO2 and water vapor during gas exchange in soil and plant leaves with laser-based spectroscopy, using soil columns and plant chambers. In both experimental setups, the measured δ18O of water vapor was used to infer the δ18O of liquid water, and, together with the δ18O-CO2, the degree of oxygen isotopic equilibrium between the two species (θ). Gas exchange experiments with different functional plant types (C3 coniferous, C3 monocotyledonous, C3 dicotyledonous, C4) revealed that θ and the influence of the plant on the ambient δ18O-CO2 (CO18O-isoforcing) not only varied on a diurnal timescale but also when plants were exposed to limited water availability, elevated air temperature, and abrupt changes in light intensity (sunflecks). Maximum θ before treatments ranged between 0.7 and 0.8 for the C3 dicotyledonous (poplar) and C3 monocotyledonous (wheat) plants, and between 0.5 and 0.6 for the conifer (spruce) and C4 plant (maize) while maximum CO18O-isoforcing was highest in wheat (0.03 m s-1 ‰), similar in poplar and maize (0.02 m s-1 ‰), and lowest in spruce (0.01 m s-1 ‰). Multiple regression analysis showed that up to 97 % of temporal dynamics in CO18O-isoforcing could be

  19. Oxygen isotope fractionation between analcime and water: An experimental study

    SciTech Connect

    Karlsson, H.R.; Clayton, R.N. )

    1990-05-01

    The fractionation of oxygen isotopes between natural analcime ({approximately}100 {mu}m) and water has been determined at 300, 350, and 400{degree}C at fluid pressures ranging from 1.5 to 5.0 kbar. Isotope ratios were obtained for the analcime framework, the channel water, and bulk water. Analcimes from Surtsey (145{degree}C), DSDP Hole 417A (30 to 55{degree}C), and Guam (25{degree}C) were used to constrain the fractionation factors below 300{degree}C. Analcime channel water exchanged completely with external water in all runs. Although some retrograde exchange may have occurred during quenching, the results indicate that the channel water is depleted in {sup 18}O relative to bulk water by a constant value of {approximately}5{per thousand}, nearly independent of temperature. Analcime is the first hydrated mineral found to have water of hydration depleted in {sup 18}O. Analcime framework oxygen exchanged 80, 90, and 96% at 300{degree}C for 412 h, 350{degree}C for 178 h, and 400{degree}C for 120 h, respectively. Equilibrium {Delta}{sup 18}O ({per thousand}) are as follows: 2.9 (400{degree}C), 4.5 (350{degree}C), and 5.8 (300{degree}C) for the experimental runs and 12.2 (145{degree}C) and 24.2 to 28.2 (30-55{degree}C) for the empirical data. The analcime-water fractionation curve is within experimental error of that of calcite-water. The exchange had little effect on grain morphology and does not involve recrystallization. This is the fastest exchange observed for a silicate. The rapid exchange rates indicate that zeolites in active high-temperature geothermal areas are in oxygen isotopic equilibrium with ambient fluids. Once calibrated, zeolites may be among the best low-temperature oxygen isotope geothermometers.

  20. Interpreting δD and δ18O isotopic signals of ambient water vapor in PNW coniferous forest using a high frequency CRDS analyzer

    NASA Astrophysics Data System (ADS)

    Allen, S. T.; Bond, B. J.; McDonnell, J. J.; Brooks, J. R.; Thomas, C. K.

    2010-12-01

    Wavelength-Scanned Cavity Ring-Down Spectroscopy provides real-time simultaneous measurement of stable isotopologues of water vapor in natural environments. Continuous, high-frequency sampling provides a new and exciting look at water cycle processes and creates many new possibilities for studying the vapor phase of the hydrologic cycle. However, as with any new tool, the first challenge is to understand the sources of variability in the signal. This includes disentangling potential instrument variability from environmental variability as well as the identification and quantification of environmental end members. We deployed a Picarro L-1102 Liquid / Vapor analyzer at the mouth of a small watershed in the H.J. Andrews Experimental Forest located in the West-Central Oregon Cascades range in November, 2009. The steeply-sloped watershed is covered by a closed-canopied, young-mature Douglas fir forest; it has been used for many previous ecological, hydrological, and meteorological studies. The data reveal very high diel variability in δD in and δ18O as well as δD to δ18O ratios and a strong deviation from the global meteoric water line. A hysteresis effect differs dramatically from one day to the next and confounds apparent trends. To interpret these results, we are conducting controlled tests of instrument performance and we propose a plan to partition individual vapor source contributions. Application of this vapor signature to ecological or hydrological studies requires knowledge of individual end-member contributions to the isotope measurements. We hypothesize that by determining end-member fluxes and in-situ fractionation factors paired with micrometeorological data, we can better understand processes driving these patterns. Combined with meteorological tower data, high frequency data allows the possibility of scaling up from continuous point measurements to ecosystem-scale processes. Previous studies in this watershed have demonstrated the ability to estimate

  1. Coherency of late Holocene European speleothem δ18O records linked to North Atlantic Ocean circulation

    NASA Astrophysics Data System (ADS)

    Deininger, Michael; McDermott, Frank; Mudelsee, Manfred; Werner, Martin; Frank, Norbert; Mangini, Augusto

    2016-09-01

    Speleothem δ18O records provide valuable information about past continental environmental and climatic conditions, although their interpretation is often not straightforward. Here we evaluate a compilation of late Holocene speleothem δ18O records using a Monte Carlo based Principal Component Analysis (MC-PCA) method that accounts for uncertainties in individual speleothem age models and for the variable temporal resolution of each δ18O record. The MC-PCA approach permits not only the identification of temporally coherent changes in speleothem δ18O; it also facilitates their graphical depiction and evaluation of their spatial coherency. The MC-PCA method was applied to 11 Holocene speleothem δ18O records that span most of the European continent (apart from the circum-Mediterranean region). We observe a common (shared) mode of speleothem δ18O variability that suggests millennial-scale coherency and cyclicity during the last 4.5 ka. These changes are likely caused by variability in atmospheric circulation akin to that associated with the North Atlantic Oscillation, reflecting meridionally shifted westerlies. We argue that these common large-scale variations in European speleothem δ18O records are in phase with changes in the North Atlantic Ocean circulation indicated by the vigour of the Iceland Scotland Overflow Water (ISOW), the strength of the subpolar gyre (SPG) and an ocean stacked North Atlantic ice rafted debris (IRD) index. Based on a recent modelling study, we conclude that these changes in the North Atlantic circulation history may be caused by wind stress on the ocean surface driven by shifted westerlies. However, the mechanisms that ultimately force the westerlies remain unclear.

  2. The MMCO-EOT conundrum: Same benthic δ18O, different CO2

    NASA Astrophysics Data System (ADS)

    Stap, Lennert B.; Wal, Roderik S. W.; De Boer, Bas; Bintanja, Richard; Lourens, Lucas J.

    2016-09-01

    Knowledge on climate change during the Cenozoic largely stems from benthic δ18O records, which document combined effects of deep-sea temperature and ice volume. Information on CO2 is expanding but remains uncertain and intermittent. Attempts to reconcile δ18O, sea level, and CO2 by studying proxy data suffer from paucity of data and apparent inconsistencies among different records. One outstanding issue is the difference suggested by proxy CO2 data between the Eocene-Oligocene boundary (EOT) and the Middle-Miocene Climatic Optimum (MMCO), while similar levels of δ18O are shown during these times. This conundrum implies changing relations between δ18O, CO2, and temperature over time. Here we use a coupled climate-ice sheet model, forced by two different benthic δ18O records, to obtain continuous and mutually consistent records of δ18O, CO2, temperature, and sea level over the period 38 to 10 Myr ago. We show that the different CO2 levels between the EOT and MMCO can be explained neither by the standard configuration of our model nor by altering the uncertain ablation parametrization on the East Antarctic Ice Sheet. However, we offer an explanation for the MMCO-EOT conundrum by considering erosion and/or tectonic movement of Antarctica, letting the topography evolve over time. A decreasing height of the Antarctic continent leads to higher surface temperatures, reducing the CO2 needed to maintain the same ice volume. This also leads to an increasing contribution of ice volume to the δ18O signal. This result is, however, dependent on how the topographic changes are implemented in our ice sheet model.

  3. 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.

  4. 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.

  5. 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.

  6. Organic matter as a potential complementary tool for delta(18)O data interpretation in heterogeneous aquifers.

    PubMed

    Blondel, Thibaut; Travi, Yves; Emblanch, Christophe; Dudal, Yves

    2010-03-01

    Evaluating transit time by using delta(18)O seasonal variation is often difficult in a Mediterranean context due to the erratic rainfall signature added to the complexity of flow mixing. The present study aims to show that using organic matter can improve interpretations of the delta(18)O signal. The natural fluorescence of organic compounds and dissolved organic carbon (DOC) data were recorded in the underground low-noise laboratory, located within the catchment area of the Fontaine de Vaucluse karstic system, over a four-year period. By combining both total fluorescence and DOC, a systematic seasonal variation is observed only due to soil-water interaction. Therefore, when the recharge rate is enough at the time of the season concerned, a new specific seasonal tracer, independent of rainfall signature, is available. Besides, the DOC concentration is a tracer of rapid infiltration with short transit time associated with high DOC concentration, while long transit time waters are characterised by a low DOC concentration. Then this can also shed light on such a mixing, recent/old waters. A more sensitive interpretation of delta(18)O variations is then possible: if the rainfall amount and delta(18)O follow a seasonal trend, both tracers may be used in the same way; if the recharge is discontinuous due to discontinuous rainfall regime, delta(18)O tracing alone is usable; in case of erratic or smooth rainfall signature during the homogeneous rainy period, fluorescent organic matter tracing alone is then usable.

  7. Uranium isotopic fractionation factors during U(VI) reduction by bacterial isolates

    NASA Astrophysics Data System (ADS)

    Basu, Anirban; Sanford, Robert A.; Johnson, Thomas M.; Lundstrom, Craig C.; Löffler, Frank E.

    2014-07-01

    We experimentally determined the magnitude of uranium isotopic fractionation induced by U(VI) reduction by metal reducing bacterial isolates. Our results indicate that microbial U(VI) reduction induces isotopic fractionation; heavier isotopes (i.e., 238U) partition into the solid U(IV) products. The magnitudes of isotopic fractionation (expressed as ε = 1000‰ * (α-1)) for 238U/235U were 0.68‰ ± 0.05‰ and 0.99‰ ± 0.12‰ for Geobacter sulfurreducens strain PCA and strain IFRC-N, respectively. The ε values for Anaeromyxobacter dehalogenans strain FRC-W, strain FRC-R5, a novel Shewanella isolate, and Desulfitobacterium sp. strain Viet1 were 0.72‰ ± 0.15‰, 0.99‰ ± 0.12‰, 0.96‰ ± 0.16‰ and 0.86‰ ± 0.06‰, respectively. Our results show that the maximum ε values of ∼1.0‰ were obtained with low biomass (∼107 cells/mL) and low electron donor concentrations (∼500 μM). These results provide an initial assessment of 238U/235U shifts induced by microbially-mediated U(VI) reduction, which is needed as 238U/235U data are increasingly applied as redox indicators in various geochemical settings.

  8. 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.

    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

  9. 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.

  10. 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

  11. Conodont apatite δ18O signatures indicate climatic cooling as a trigger of the Late Devonian mass extinction

    NASA Astrophysics Data System (ADS)

    Joachimski, Michael M.; Buggisch, Werner

    2002-08-01

    The oxygen isotopic composition of conodont apatite from two Frasnian-Famennian boundary sections was measured in order to reconstruct variations in marine paleotemperatures during the late Frasnian mass-extinction event. The measured conodont apatite δ18O values reveal two positive excursions with maximum amplitudes of +1‰ to +1.5‰ that parallel positive excursions in the carbonate carbon isotopic composition. The +3‰ excursions in carbonate δ13C have been interpreted as consequences of enhanced organic carbon burial rate resulting in a decrease in atmospheric CO2 concentration. Climatic cooling as a potential consequence of lower atmospheric CO2 concentration is confirmed by the conodont apatite δ18O records, which translate into cooling of low-latitude surface waters by 5 7 °C. Repeated cooling of the low latitudes during the late Frasnian had a severe impact on the tropical shallow-water faunas that were probably adapted to warm surface-water temperatures and severely affected during the late Frasnian crisis. These prominent variations in ocean-water temperature were stressful to the tropical shallow-water fauna and potentially culminated in low origination rates of new species, one of the major factors of the decline in diversity during the latest Frasnian.

  12. Sources of ground water salinity on islands using 18O, 2H, and 34S.

    PubMed

    Allen, D M

    2004-01-01

    Stable isotopes of 18O and 2H in water, and 34S and 18O in dissolved SO4, are used to verify the interpretation of the chemical evolution and proposed sources of salinity for two islands that have undergone postglacial rebound. Results for delta18O and delta34S in dissolved SO4 on the Gulf Islands, southwest British Columbia, Canada, suggest a three-component mixing between (1) atmospheric SO4 derived largely from recharge of meteoric origin, (2) modern marine SO4 associated with either modern-day salt water intrusion or Pleistocene age sea water, and (3) terrestrial SO4. The age of the marine SO4 is uncertain based on the geochemistry and SO4 isotopes alone. Two options for mixing of saline ground waters are proposed--either between current-day marine SO4 and atmospheric SO4, or between older (Pleistocene age) marine SO4 and atmospheric SO4, delta18O and delta2H compositions are relatively consistent between both islands, with a few samples showing evidence of mixing with water that is a hybrid mixture of Fraser River water and ocean water. The isotopic composition of this hybrid water is approximately delta18O = 10 per thousand. delta18O and delta2H values for many saline ground waters plot close to the global meteoric water line, which is distinctly different from the local meteoric water line. This suggests a meteoric origin for ground waters that is different from the current isotopic composition of meteoric waters. It is proposed these waters may be late Pleistocene in age and were recharged when the island was submerged below sea level and prior to rebound at the end of the last glaciation. PMID:14763614

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. Determination of hexavalent chromium reduction using Cr stable isotopes: isotopic fractionation factors for permeable reactive barrier materials.

    PubMed

    Basu, Anirban; Johnson, Thomas M

    2012-05-15

    Cr stable isotope measurements can provide improved estimates of the extent of Cr(VI) reduction to less toxic Cr(III). The relationship between observed (53)Cr/(52)Cr ratio shifts and the extent of reduction can be calibrated by determining the isotopic fractionation factor for relevant reactions. Permeable reactive barriers (PRB) made of Fe(0) and in situ redox manipulation (ISRM) zones effectively remediate Cr-contaminated aquifers. Here, we determine the isotopic fractionations for dominant reductants in reactive barriers and reduced sediments obtained from an ISRM zone at the US DOE's Hanford site. In all cases, significant isotopic fractionation was observed; fractionation (expressed as ε) was -3.91‰ for Fe(II)-doped goethite, -2.11‰ for FeS, -2.65‰ for green rust, -2.67‰ for FeCO(3), and -3.18‰ for ISRM zone sediments. These results provide a better calibration of the relationship between Cr isotope ratios and the extent of Cr(VI) reduction and aid in interpretation of Cr isotope data from systems with reactive barriers. PMID:22424120

  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. 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

    DOEpatents

    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.

  20. 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

  1. ({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.

  2. Using (18)O/(16)O exchange to probe an equilibrium space-charge layer at the surface of a crystalline oxide: method and application.

    PubMed

    De Souza, Roger A; Martin, Manfred

    2008-05-01

    The use of an (18)O/(16)O exchange experiment as a means for probing surface space-charge layers in oxides is examined theoretically and experimentally. On the basis of a theoretical treatment, isotope penetration profiles are calculated for (18)O/(16)O exchange across a gas-solid interface and subsequent diffusion of the labelled isotope through an equilibrium space-charge layer depleted of mobile oxygen vacancies and into a homogeneous bulk phase. Profiles calculated for a range of conditions all have a characteristic shape: a sharp drop in isotope fraction close to the surface followed by a normal bulk diffusion profile. Experimental (18)O profiles in an exchanged (001) oriented single crystal of Fe-doped SrTiO(3) were measured by time-of-flight secondary ion mass spectrometry (ToF-SIMS). By extracting the space-charge potential from such profiles, we demonstrate that this method allows the spatially resolved characterization of space-charge layers at the surfaces of crystalline oxides under thermodynamically well-defined conditions.

  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. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. 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

  11. 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

  12. Dynamic phosphometabolomic profiling of human tissues and transgenic models by 18O-assisted 31P NMR and mass spectrometry

    PubMed Central

    Nemutlu, Emirhan; Zhang, Song; Gupta, Anu; Juranic, Nenad O.; Macura, Slobodan I.; Terzic, Andre; Jahangir, Arshad

    2012-01-01

    Next-generation screening of disease-related metabolomic phenotypes requires monitoring of both metabolite levels and turnover rates. Stable isotope 18O-assisted 31P nuclear magnetic resonance (NMR) and mass spectrometry uniquely allows simultaneous measurement of phosphometabolite levels and turnover rates in tissue and blood samples. The 18O labeling procedure is based on the incorporation of one 18O into Pi from [18O]H2O with each act of ATP hydrolysis and the distribution of 18O-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 18O-labeling procedures has revealed significant differences in the dynamics of G-6-P[18O] (glycolysis), G-3-P[18O] (substrate shuttle), and G-1-P[18O] (glycogenolysis) between human and rat atrial myocardium. In human atria, the turnover of G-3-P[18O], 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[18O] and decreased G-1-P[18O] metabolic dynamics. The metabolomic profile of creatine kinase M-CK/ScCKmit−/−-deficient hearts is characterized by a higher G-6-[18O]P turnover rate, G-6-P levels, glycolytic capacity, γ/β-phosphoryl of GTP[18O] turnover, as well as β-[18O]ATP and β-[18O]ADP turnover, indicating altered glycolytic, guanine nucleotide, and adenylate kinase metabolic flux. Thus, 18O-assisted gas chromatography-mass spectrometry and 31P NMR provide a suitable

  13. Mg and 18O Variations in the Shell of the Chilean Gastropod Concholepas concholepas Reflect SST and Growth Rate variations

    NASA Astrophysics Data System (ADS)

    Guzman, N.; Lazareth, C. E.; Poitrasson, F.; Cuif, J.; Ortlieb, L.

    2004-12-01

    To validate the use of fossil mollusc shells as recorders of environmental conditions, a primary calibration study was carried out on modern shells of the Chilean gastropod Concholepas concholepas, the so-called southern hemisphere abalone which is particularly abundant in Holocene archaeological sites. Organisms were maintained in culture tanks and feed with live mytilids. The sea water temperature in the tank was recorded every half-an-hour by an automatic device. The experiment lasted several months. Periodical marking with calcein provided a precise chronological control of the shell growth. Thus, well-dated high resolution chemical profiles could be directly compared with temperatures during shell formation. Geochemical analyses of the calcite layers include Mg, Sr and 16O/18O composition. Trace elements were analysed using Laser Ablation ICP-MS and Electron Microprobe while stable isotopes were measured on a Secondary Ion Mass spectrometry (SIMS). The shell growth rate during two months of formation varied between 30 and 140 µm/day which allows us to reach a temporal resolution for chemical profiles between a few hours and three days. The growth rate variations do not seem to be related to temperature fluctuations. Only Mg content was analytically reproducible and showed significant variations across the shells. The Mg high-resolution profiles display a grossly sinusoidal shape. Shells from different sites along the coasts of Chile showed mean Mg contents of 300 ppm and 500 ppm for mean temperatures of 17 and 20° C, respectively. This suggests a gross correlation between Mg and temperature. However, high resolution Mg results do not show an exact fitting neither with temperature nor with growth rates. Other parameters, like shell ageing as suggested by an amplitude increase observed near the edge of one of the shells, or other complex biological factors, may influence Mg incorporation into the shell. \\delta 18O values of the calcite vary between -1,5 and 2

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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

  2. Solar 18O/17O and the Setting for Solar Birth

    NASA Astrophysics Data System (ADS)

    Clayton, D. D.

    2004-03-01

    The burst of star formation during the gaeous merger of the Milky Way with a low-metallicity dwarf galaxy created not only the Si-isotope correlation in mainstream SiC grains but also the anomalously large ^18O/^17O ratio in the sun.

  3. 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.

  4. 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...

  5. ISOTOPIC RATIOS OF {sup 18}O/{sup 17}O IN THE GALACTIC CENTRAL REGION

    SciTech Connect

    Zhang, J. S.; Sun, L. L.; Riquelme, D.; Henkel, C.; Lu, D. R.; Zhang, Y.; Wang, J. Z.; Li, J.; Wang, M.

    2015-08-15

    The {sup 18}O/{sup 17}O isotopic ratio of oxygen is a crucial measure of the secular enrichment of the interstellar medium by ejecta from high-mass versus intermediate-mass stars. So far, however, there is a lack of data, particularly from the Galactic center (GC) region. Therefore, we have mapped typical molecular clouds in this region in the J = 1–0 lines of C{sup 18}O and C{sup 17}O with the Delingha 13.7 m telescope (DLH). Complementary pointed observations toward selected positions throughout the GC region were obtained with the IRAM 30 m and Mopra 22 m telescopes. C{sup 18}O/C{sup 17}O abundance ratios reflecting the {sup 18}O/{sup 17}O isotope ratios were obtained from integrated intensity ratios of C{sup 18}O and C{sup 17}O. For the first time, C{sup 18}O/C{sup 17}O abundance ratios are determined for Sgr C (V ∼ −58 km s{sup −1}), Sgr D (V ∼ 80 km s{sup −1}), and the 1.°3 complex (V ∼ 80 km s{sup −1}). Through our mapping observations, abundance ratios are also obtained for Sgr A (∼0 and ∼50 km s{sup −1} component) and Sgr B2 (∼60 km s{sup −1}), which are consistent with the results from previous single-point observations. Our frequency-corrected abundance ratios of the GC clouds range from 2.58 ± 0.07 (Sgr D, V ∼ 80 km s{sup −1}, DLH) to 3.54 ± 0.12 (Sgr A, ∼50 km s{sup −1}). In addition, strong narrow components (line width less than 5 km s{sup −1}) from the foreground clouds are detected toward Sgr D (−18 km s{sup −1}), the 1.°3 complex (−18 km s{sup −1}), and M+5.3−0.3 (22 km s{sup −1}), with a larger abundance ratio around 4.0. Our results show a clear trend of lower C{sup 18}O/C{sup 17}O abundance ratios toward the GC region relative to molecular clouds in the Galactic disk. Furthermore, even inside the GC region, ratios appear not to be uniform. The low GC values are consistent with an inside-out formation scenario for our Galaxy.

  6. 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

  7. 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.

  8. Holocene record of precipitation seasonality from lake calcite δ18O in the central Rocky Mountains, United States

    USGS Publications Warehouse

    Anderson, Lesleigh

    2011-01-01

    A context for recent hydroclimatic extremes and variability is provided by a ~10 k.y. sediment carbonate oxygen isotope (??18O) record at 5-100 yr resolution from Bison Lake, 3255 m above sea level, in northwestern Colorado (United States). Winter precipitation is the primary water source for the alpine headwater lake in the Upper Colorado River Basin and lake water ??18O measurements reflect seasonal variations in precipitation ??18O. Holocene lake water ??18O variations are inferred from endogenic sedimentary calcite ??18O based on comparisons with historic watershed discharge records and tree-ring reconstructions. Drought periods (i.e., drier winters and/or a more rain-dominated seasonal precipitation balance) generally correspond with higher calcite ??18O values, and vice-versa. Early to middle Holocene ??18O values are higher, implying a rain-dominated seasonal precipitation balance. Lower, more variable ??18O values after ca. 3500 yr ago indicate a snow-dominated but more seasonally variable precipitation balance. The middle to late Holocene ??18O record corresponds with records of El Ni??o Southern Oscillation intensification that supports a teleconnection between Rocky Mountain climate and North Pacific sea-surface temperatures at decade to century time scales. ?? 2011 Geological Society of America.

  9. 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.

  10. 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.

  11. 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

  12. Temperature dependence of oxygen isotope fractionation in coccolith calcite: A culture and core top calibration of the genus Calcidiscus

    NASA Astrophysics Data System (ADS)

    Candelier, Yaël; Minoletti, Fabrice; Probert, Ian; Hermoso, Michaël

    2013-01-01

    species of this genus. This also indicates that our culture calibration may be applied to all Calcidiscus coccoliths found in the sediment. We compared the culture calibration to δ18O measured from near-monogeneric Calcidiscus fractions separated out from core top sediments. We found concordant 18O fractionation factors for the core top calibration with a good linear coefficient (r = 0.94). The near-monogeneric Calcidiscus assemblages seem, however, to record slightly heaviest δ18O values compared to the data of culture study. This discrepancy may be due to a possible seasonality effect on the production of Calcidiscus coccoliths. The uncertainty of the calibration is of similar magnitude to those of other proxies used for SST reconstruction, such as foraminiferal δ18O or the alkenone undersaturation index. This confirms that coccoliths can be used as a complementary or alternative substrate to foraminiferal shells for isotopic analyses. Comparing δ18O of coccoliths to these other SST proxies, or developing an interspecific comparison of coccolith geochemistry may give insights into the carbonate chemistry of seawater through key periods of the geological record.

  13. 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

  14. 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

  15. 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

  16. 18O/16O studies of fossil fissure fumaroles from the Valley of Ten Thousand Smokes, Alaska

    NASA Astrophysics Data System (ADS)

    Warner Holt, Elizabeth; Taylor, Hugh

    2001-03-01

    At three sample sites where there are good exposures of the upper 15 m of the 1912 ash-flow sheet in the Valley of Ten Thousand Smokes (VTTS), Alaska, 18O/16O studies indicate that fumarolic activity produced a very wide range of δ18O values (-0.1 to +12.6; n=32) in the groundmass adjacent to fossil fissure fumaroles. This contrasts sharply with the uniformity of δ18O in the groundmass away from fumarolic conduits (δ18O=+5.9 to +7.1; n=7) and in all of the feldspar phenocrysts (δ18O=+6.11 to +7.51 for 11 samples from this study and Hildreth 1987), independent of whether these were collected from fossil fumaroles or from unaltered tuff. Only one sample contained feldspars that were even slightly 18O-enriched relative to the others (cloudy plagioclase δ18O=+8.45), and this sample also contained the most 18O-enriched groundmass of any of those analyzed (δ18O=+12.6). This preservation of primary magmatic δ18O values in the VTTS feldspar phenocrysts is clearly a consequence of the extremely short time span (i.e., 1912 to 1923) of vigorous, high-temperature, fumarolic activity in the 1912 ash-flow sheet. These 18O/16O systematics are strikingly similar to those discovered in the 2.8-Ma intracaldera Chegem Tuff (Gazis et al. 1996) and in the fossil fumaroles in the outflow sheet of the 0.76 Ma Bishop Tuff (Holt and Taylor 1998), thus confirming that a similar type of fumarolic meteoric-hydrothermal activity occurred above the zone of intense welding in all three of these ash-flow tuffs. This is particularly important, because it provides a direct linkage between the older tuffs and the actual observations at the VTTS of steam chemistry, water/rock interaction, circulation geometry, flow velocities, and fumarolic temperatures (up to 645°C). The 18O/16O effects in the VTTS can all be explained in terms of a two-stage history: (a) an early, 10- to 15-year-long, high-temperature (>450°C), fumarolic 18O-depletion event (groundmass δ18O=-0.1 to +4.8); and (b) a

  17. 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

  18. 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

  19. 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.

  20. 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

  1. Paleoclimatic reconstruction using the correlation in δ18O of hackberry carbonate and environmental water, North America

    USGS Publications Warehouse

    Jahren, A. Hope; Amundson, Ronald; Kendall, Carol; Wigand, Peter

    2001-01-01

    Celtis sp. (commonly known as “hackberry”) fruits were collected from 101 North American sites located in 13 states and one Canadian province between the years of 1979–1994. The biomineralized carbonate endocarp of the hackberry, which is a common botanical fossil found throughout the Quaternary sediments of the Great Plains, was analyzed for its δ18O value and plotted against the δ18O value of site environmental water to demonstrate the potential of the hackberry as a paleoclimate indicator. This correlation was reinforced by intensive studies on extracted tissue-water δ18O value and hackberry endocarp carbonate δ18O value from three trees in Sterling, Colorado. The observed correlation in the large data set between hackberry endocarp carbonate δ18O value and environmental water is [endocarp δ18O=38.56+0.69×environmental water δ18O] (R=0.88; R2=0.78; p value<0.0001). The relation of the hackberry carbonate to temperature in the Great Plains was the following: (average daily-maximum growing season temperature [°C])=6.33+0.67 (δ18O of endocarp carbonate) (R=0.73; R2=0.54; pvalue=0.0133). The δ18O value of early Holocene fossil hackberry carbonate in the Pintwater Cave, southern Nevada, suggested precipitation δ18O values more positive than today (∼−4‰ early Holocene vs ∼−9 to −10‰ today). This shift, combined with paleobotanical data, suggests an influx of summer monsoonal moisture to this region in the early Holocene. Alternatively, the more positive δ18O values could be viewed as suggestive of warmer temperatures, although the direct use of Great Plains hackberry/temperature relationships to the Great Basin is of debatable value.

  2. 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

  3. 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

  4. 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

  5. 18O/16O studies of fossil fissure fumaroles from the Valley of Ten Thousand Smokes, Alaska

    NASA Astrophysics Data System (ADS)

    Holt, Elizabeth Warner; Taylor, Hugh P.

    2001-06-01

    At three sample sites where there are good exposures of the upper 15 m of the 1912 ash-flow sheet in the Valley of Ten Thousand Smokes (VTTS), Alaska, 18O/16O studies indicate that fumarolic activity produced a very wide range of δ18O values (-0.1 to +12.6; n=32) in the groundmass adjacent to fossil fissure fumaroles. This contrasts sharply with the uniformity of δ18O in the groundmass away from fumarolic conduits (δ18O=+5.9 to +7.1; n=7) and in all of the feldspar phenocrysts (δ18O=+6.11 to +7.5 1 for 11 samples from this study and Hildreth 1987), independent of whether these were collected from fossil fumaroles or from unaltered tuff. Only one sample contained feldspars that were even slightly 18O-enriched relative to the others (cloudy plagioclase δ18O=+8.45). and this sample also contained the most 180-enriched groundmass of any of those analyzed (δ18O=+12.6). This preservation of primary magmatic δ18O values in the VTTS feldspar phenocrysts is clearly a consequence of the extremely short time span (i.e., 1912 to ≈1923) of vigorous, high-temperature, fumarolic activity in the 1912 ash-flow sheet. These 18O/l6O systematica are strikingly similar to those discovered in the 2.8-Ma intracaldera Chegem Tuff (Gazis et al. 1996) and in the fossil fumaroles in the outflow sheet of the 0.76 Ma Bishop Tuff (Holt and Taylor 1998), thus confirming that a similar type of fumarolic meteoric-hydro-thermal activity occurred above the zone of intense welding in all three of these ash-flow tuffs. This is particularly important, because it provides a direct linkage between the older tuffs and the actual observations at the VTTS of steam chemistry, water/rock interaction, circulation geometry, flow velocities, and fumarolic temperatures (up to 645°C). The 18O/l6O effects in the VTTS can all be explained in terms of a two-stage history: (a) an early, 10- to 15-year-long, high-temperature (τ;450°C), fumarolic 18O-depletion event (groundmass δ18O=-0.1 to +4.8); and (b) a

  6. 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

  7. Value of epidermal growth factor receptor status compared with growth fraction and other factors for prognosis in early breast cancer.

    PubMed Central

    Gasparini, G.; Bevilacqua, P.; Pozza, F.; Meli, S.; Boracchi, P.; Marubini, E.; Sainsbury, J. R.

    1992-01-01

    The epidermal growth factor receptor (EGFR) is a transmembrane glycoprotein whose expression is important in the regulation of breast cancer cell growth. The relationship between EGFR status (determined by an immunocytochemical assay) and various prognostic factors was investigated in 164 primary breast cancers. Overall 56% of tumours were EGFR-positive and the expression of EGFR was unrelated to axillary node status, tumour size and histological grade; and it was poorly associated with the tumour proliferative activity measured by Ki-67 immuno-cytochemistry. The relapse-free survival (RFS) probability at 3-years was significantly worse for patients with EGFR positive tumours (P = 0.003) and for those whose Ki-67 score was > 7.5% (P = 0.0027), as well as in patients with axillary node involvement (P = 0.01) and with poorly differentiated tumours (P = 0.04). Immunocytochemical determination of EGFR and cell kinetics gave superimposable prognostic information for predicting RFS with odds ratios of 3.51, when evaluated singly. In our series of patients EGFR, Ki-67 and node status retain their prognostic value concerning RFS in multivariate analysis. The 3-year probability of overall survival (OS) was significantly better in node-negative patients (P = 0.04) and was similar in EGFR-positive and negative patients. In conclusion, EGFR status appears to be a significant and independent indicator of recurrence in human breast cancer and the concomitant measurement of the tumour proliferative activity seems to improve the selection of patients with different risks of recurrence. PMID:1419645

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. 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+

  13. Pre-treatment Effects on Coral Skeletal δ 13C and δ 18O

    NASA Astrophysics Data System (ADS)

    Grottoli, A. G.; Gibb, O.; Wellington, G. M.

    2003-12-01

    Pre-treatment protocols for coral skeletal stable carbon (δ 13C) and oxygen (δ 18O) isotope analyses include no treatment, bleach (NaOH), hydrogen peroxide (H2O2), or vacuum roasting prior to analysis. Such pre-treatments are used to remove organic material prior to isotopic analyses. Researchers that do not pre-treat samples argue that such treatments result in non-linear shifts in coral skeletal δ 13C and δ 18O thus increasing the analytical error in the δ 13C and δ 18O values. Vacuum roasting does cause isotopic shifts and is no longer practiced. However, both no pre-treatment and pre-treatment (with either NaOH or H2O2) coral δ 13C and δ 18O values continue to be published in the literature. In all previous studies of the effects of NaOH and H2O2 pre-treatments on coral δ 13C and δ 18O, the samples sizes were typically small and the exact time interval being sampled and compared was not specifically controlled. Here, we evaluated the effects of NaOH and H2O2 pre-treatments on coral skeletal δ 13C and δ 18O in Pavona clavus and Pavona gigantea from Panama, and Porites compressa from Hawaii. In Panama, at least five coral fragments from five different colonies of each species were stained on November 1978 and April 1979 then collected in November 1979. In Hawaii, at least five coral fragments from five different colonies at 1.7 and 7 m depths were stained on 1 September and 21 November 1996 then collected 2 March 1997. For each fragment, a bulk skeletal sample was extracted representing the entire growth interval between the two stain lines yielding at least 24 mg of material. Sampling between the stain lines ensured that all of the fragments from a given site and species were sampled over the same time interval and avoided any potential contamination from the tissue layer. Eight milligram subsamples from each fragment were subjected to 24 hours of the following treatments: NaOH, H2O2, Milli-Q filtered water (control), or no pre-treatment (control

  14. Assessing the Contribution of Sea Surface Temperature and Salinity to Coral δ18O using a Weighted Forward Model

    NASA Astrophysics Data System (ADS)

    Horlick, K. A.; Thompson, D. M.; Anderson, D. M.

    2015-12-01

    The isotopic ratio of 16O/18O18O) in coral carbonate skeletons is a robust, high-resolution proxy for sea surface temperature (SST) and sea surface salinity (SSS) variability predating the instrumental record. Although SST and δ18O-water (correlated to SSS) variability both contribute to the δ18O signal in the coral carbonate archive, the paucity and limited temporal span of SST and SSS instrumental observations limit the ability to differentiate respective SST and SSS contribution to each δ18O record. From instrumental datasets such as HadISST v.3, ERSST, SODA, and Delcroix (2011), we forward model the δ18O ("pseudoproxy") signal using the linear bivariate forward model from Thompson 2011 ("pseudoproxy"= a1(SST)+a2(SSS)). By iteratively weighting (between 0 and 1 by 0.005) the relative contribution of SST and SSS terms to the δ18O "pseudoproxy" following Gorman et al. 2012 method, we derive the percent contributions of SST and SSS to δ18O at each site based on the weights that produce the optimal correlation to the observed coral δ18O signal. A Monte Carlo analysis of error propagation in the weighted and unweighted pseudoproxy time series was used to determine how well the weighted and unweighted forward models captured observed δ18O variance. Across the south-western Pacific (40 sites) we found that SST contributes from less than 8 to more than 78% of the variance. This work builds upon this simple forward model of coral δ18O and improves our understanding of potential sources of differences in the observed and forward modeled δ18O variability. These results may also improve SST and SSS reconstructions from corals by highlighting the reef areas whose coral δ18O signal is most heavily influenced by SST and SSS respectively. Using an inverse approach, creating a transfer function, local SST and SSS could also be reconstructed based on the site-specific weights and observed coral δ18O time series.

  15. 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.

  16. 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.

  17. 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.

  18. A Method to Determine 18O Kinetic Isotope Effects in the Hydrolysis of Nucleotide Triphosphates

    PubMed Central

    Du, Xinlin; Ferguson, Kurt; Sprang, Stephen R.

    2007-01-01

    A method to determine 18O kinetic isotope effects (KIE) in the hydrolysis of GTP is described that is generally applicable to reactions involving other nucleotide triphosphates. Internal competition, wherein the substrate of the reaction is a mixture of 18O-labeled and unlabeled nucleotides, is employed and the change in relative abundance of the two species in the course of the reaction is used to calculate KIE. The nucleotide labeled with 18O at sites of mechanistic interest also contains 13C at all carbon positions, while the 16O-nucleotide is depleted of 13C. The relative abundance of the labeled and unlabeled substrates or products is reflected in the carbon isotope ratio (13C/12C) in GTP or GDP, which is determined by use of a liquid chromatography-coupled isotope ratio mass spectrometer (LC-coupled IRMS). The LC is coupled to the IRMS by an Isolink™ interface (ThermoFinnigan). Carbon isotope ratios can be determined with accuracy and precision greater than 0.04%, and are consistent over an order of magnitude in sample amount. KIE values for Ras/NF1333-catalyzed hydrolysis of [β18O3,13C]GTP were determined by change in the isotope ratio of GTP or GDP or the ratio of the isotope ratio of GDP to that of GTP. KIE values computed in the three ways agree within 0.1%, although the method using the ratio of isotope ratios of GDP and GTP gives superior precision (< 0.1%). A single KIE measurement can be conducted in 25 minutes with less than 5 μg nucleotide reaction product. PMID:17963711

  19. 13C-18O isotope signatures and ‘clumped isotope’ thermometry in foraminifera and coccoliths

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

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

  20. Southern Hemisphere forcing of Pliocene δ18O and the evolution of Indo-Asian monsoons

    NASA Astrophysics Data System (ADS)

    Clemens, Steven C.; Prell, Warren L.; Sun, Youbin; Liu, Zhengyu; Chen, Guangshan

    2008-12-01

    The Milankovitch paradigm links the timing (phase) of ice volume minima to summer insolation maxima in the hemisphere where ice volume dominates; consistent application of this paradigm dictates that Pliocene ice volume minima should lag Southern Hemisphere summer insolation maxima. We infer the magnitude of this lag on the basis of the phase relationship between equatorial sea surface temperature and benthic δ18O. We infer that Pliocene δ18O minima should lag obliquity maxima by 19° (2.2 ka), broadly consistent with the current global marine δ18O chronology, and precession maxima by 32° (2 ka), a difference of 160° (10.2 ka) relative to the current global marine δ18O chronology. Only in the context of this revision are Pliocene summer and winter monsoon phase relationships consistent with direct orbital forcing across the entire Indo-Asian region, including marine and terrestrial proxies from the Chinese Loess Plateau, the South China Sea, and the Arabian Sea. Strong Pliocene summer and winter monsoons were in phase with one another, strengthened at obliquity minima and precession minima; the summer monsoon was also strengthened at precession maxima, yielding a semiprecession spectral signal. Strong Pliocene monsoons at orbital extremes indicate a direct response to fast physics processes including sensible heating and cooling of the Asian landmass and, for the summer monsoon, the export of latent heat from the southern Indian Ocean. As Northern Hemisphere ice volume grew into the Pleistocene, the timing of strong winter and summer monsoons drifted apart becoming influenced by the combined effects of fast physics and slow physics (ice volume) variables. The phase of strong winter monsoons shifted toward ice maxima, and the phase of strong summer monsoons shifted toward ice minima.

  1. The mechanism of haem catabolism. Bilirubin formation in living rats by [18O]oxygen labelling.

    PubMed Central

    Brown, S B; King, R F

    1978-01-01

    1. The pathway of haem breakdown in living rats was studied by using 18O in the oxygen that the animals consumed. By cannulation of the common bile duct and collection of bile, labelled bilirubin was isolated and its mass spectrum determined. One set of results was obtained for a rat to which haemoglobin had been intravenously administered and another set obtained for a rat that was not given exogenous haem. Isomerization of bilirubin IXalpha to the XIIIalpha and IIIalpha isomers did not occur to any significant extent. The 18O-labelling pattern obtained in the bilirubin was consistent with a Two-Molecule Mechanism, whereby the terminal lactam oxygen atoms of bilirubin are derived from different oxygen molecules. The consequences of this mechanism are discussed in terms of the possible intermediates of the catabolic pathway. 2. 18O-labelled bilirubin appeared in the bile in less than 10 min after exposure of the animals to labelled oxygen. This result suggests that all of the chemical transformations involving production of biliverdin, reduction to bilirubin and conjugation of the bilirubin are fast processes. 3. The quantitative recovery of label obtained in the experiments suggests that there is little or no exchange of newly synthesized bilirubin with existing bilirubin pools in the animal. PMID:637844

  2. 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

  3. Pleistocene seasonal temperature variations recorded in the δ18O of Bison priscus teeth

    NASA Astrophysics Data System (ADS)

    Bernard, Aurélien; Daux, Valérie; Lécuyer, Christophe; Brugal, Jean-Philip; Genty, Dominique; Wainer, Karine; Gardien, Véronique; Fourel, François; Jaubert, Jacques

    2009-06-01

    Oxygen isotope analysis of phosphate in tooth enamel of mammals ( δ18O p) constitutes a valuable method to reconstruct past air temperatures in continental environments. The method is based on interdependent relationships between the δ18O of apatite phosphate, body fluids, environmental waters and air temperatures. Continuous tooth growth and absence of enamel remodelling in bovid teeth ensures a reliable record of the intra-annual variability of air temperature through an incremental δ18O analysis from apex to cervix. This method has been applied to Bison priscus dental remains of the late Middle Pleistocene from the fossiliferous layer of a cave at Coudoulous I in South-Western France (Layer 4). The stacked oxygen isotope signal obtained by combining 9 bison teeth shows sinusoidal variations (15.0‰ to 19.1‰ V-SMOW) of seasonal origin over 2.5 yr. The corresponding computed MAT of 9 ± 3 °C is about 4 °C lower than at present. Seasons appear more contrasted in Coudoulous I during Layer 4 deposition with summers as warm as present ones (19 ± 3 °C) and significantly colder winters about 0 ± 3 °C compared to 6 ± 1 °C at present.

  4. 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.

  5. 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.

  6. Separating soil and leaf water 18O isotopic signals in plant stem cellulose

    NASA Astrophysics Data System (ADS)

    Sternberg, Leonel da Silveira Lobo; Anderson, William T.; Morrison, Kanema

    2003-07-01

    The oxygen-18 signal of soil and leaf water are both recorded in heterotrophically synthesized plant stem cellulose. Presently, these signals can only be teased apart with modeling and assumptions on the nature of the isotopic enrichment of leaf water. A method by which these two signals are chemically separated and analyzed is tested here. Heterotrophically synthesized cellulose from germinating seeds having a mixture of isotopic signals from the reserve carbohydrate (starch) and that of the water during cellulose synthesis was hydrolyzed and the resulting glucose converted to glucose phenylosazone. The analysis of the 18O/ 16O ratios of cellulose and of glucose phenylosazone were used to calculate the oxygen isotope ratio of the oxygen attached to the second carbon of the glucose moieties of the cellulose molecule. The calculated δ 18O value of this oxygen was highly correlated with that of the water available for cellulose synthesis showing a nearly one-to-one relationship (slope = 1.027) and leading to the conclusion that it completely exchanges with water during heterotrophic cellulose synthesis. Once this method is refined so as to increase precision, it will be possible to derive the δ 18O values of soil water available to plants from the oxygen isotope analysis of stem cellulose and its derivative.

  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. 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

  9. If you are interested in submitting a paper to this journal visit: Isotopic fractionation and the quantification of ^1^7O anomalies in the oxygen three-isotope system - an appraisal and geochemical significance

    NASA Astrophysics Data System (ADS)

    Miller, Martin F.

    2002-06-01

    The oxygen three-isotope plot provides valuable insights to geochemical and cosmochemical processes in which the relationship of 17O/ 16O relative to 18O/ 16O is of interest. It is generally recognised, however, that the usual format of this diagram, illustrating the variation of δ 17O with δ 18O, is based on the approximation of a power law function to linear format. In contrast, the relationship between δ 17O and δ 18O for entity a measured with respect to reference b is accurately represented by the linear function: 1000 ln1+ δ 17O/1000=λ1000 ln1+ δ 18O/1000+1000 ln[1+k a,b] where k a,b is a measure of the offset (if any) of a from the mass-dependent fractionation line, of slope λ, on which b lies. The respective ordinate and abscissa scales are essentially unchanged from those of the corresponding δ 17O versus δ 18O plot yet, unlike the latter, the slope of the fractionation line is invariant to both the magnitude of the δ values and to the isotopic composition of the reference. Application to high precision measurements which encompass a wide range of δ values reveals that slope differences (or indeed similarities) between comparable data sets may be disguised by the limitations of the δ 17O versus δ 18O diagram, with adverse consequences for the accurate quantification of Δ 17O values. This may be addressed by re-defining Δ 17O, the offset from a reference fractionation line, as 1000 k a,b. In turn, this is very closely approximated by 1000ln[1+ k a,b], the intercept on the ordinate axis of a 1000ln[1+(δ 17O/1000)] versus 1000ln[1+(δ 18O/1000)] plot, for values of 1000 k a,b not exceeding ˜5. The same analysis shows that the fractionation factor α 17/16 for a given system is related to the corresponding α 18/16 value by: α 17/16=[1+k a,b](α 18/16) λ These findings are equally applicable to the reporting of data from other three-isotope systems, such as magnesium.

  10. 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

  11. 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

  12. 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

  13. Patient factors influencing the concentration of stromal vascular fraction (SVF) for adipose-derived stromal cell (ASC) therapy in dogs.

    PubMed

    Astor, Donniel E; Hoelzler, Michael G; Harman, Robert; Bastian, Richard P

    2013-07-01

    The objective of this study was to determine whether patient factors influence the concentration of the stromal vascular fraction (SVF) in fat for adipose-derived stromal cell (ASC) therapy in dogs. A total of 1265 dogs underwent adipose collection surgeries by veterinarians for processing by the Vet-Stem laboratory and data on cell counts and patient factors were collected. Body condition score (BCS) and breed size did not significantly affect the viable cells per gram (VCPG) of adipose tissue that represents the viable SVF. Age significantly affected the VCPG, with dogs in age quartile 1 having a significantly higher VCPG than those in quartile 2 (P = 0.003) and quartile 4 (P = 0.002). Adipose tissue collected at the falciform location had significantly fewer VCPG than tissue collected at the thoracic wall and inguinal locations (P < 0.001). When the interaction of gender and location was evaluated, there were significantly fewer VCPG in tissue collected at the falciform location than at the thoracic wall and inguinal locations in female spayed dogs (P < 0.001) and male neutered dogs (P < 0.001), but not in female intact dogs (P = 0.743) or male intact dogs (P = 0.208). It was concluded that specific patient factors should be taken into consideration in order to obtain the maximal yield of VCPG from an adipose collection procedure.

  14. 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

  15. 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.

  16. Association of Modifiable Risk Factors and Left Ventricular Ejection Fraction among Hospitalized Native Hawaiians and Pacific Islanders with Heart Failure

    PubMed Central

    Seto, Todd B; Kaholokula, Joseph K; Howard, Barbara; Ratner, Robert E

    2014-01-01

    Background: Heart Failure (HF) disproportionately affects Native Hawaiians and Other Pacific Islanders (NHOPIs). This study examines risk factors associated with left ventricular ejection fraction (LVEF) among 151 hospitalized NHOPI HF patients enrolled at a single tertiary care hospital between June 2006 and April 2010. Methods: Enrollment criteria: (1) NHOPI by self-identification. (2) Age ≥ 21 yrs. (3) Diagnosis of HF defined: (a) left ventricular ejection fraction (LVEF) ≤ 40% or LVEF ≤ 60% with abnormal diastolic function and (b) classic HF signs/symptoms. LVEF was measured by echocardiography within 6 weeks of hospitalization. Clinical measures, medical history, and questionnaires were assessed using standardized protocols. Linear regression modeling was used to examine the association of significant correlates of LVEF, which were then included en bloc into the final model. A P-value < .05 was considered statistically significant. Results: Of 151 participants, 69% were men, mean age 54.3 ± 13.5 years, blood pressure 112 ± 20/69 ± 15 mmHg, and body mass index (BMI) 36.9 ± 9 kg/m2. Twenty-five percent of participants were smokers, 45% used alcohol and 23% reported a history of methamphetamine use. Clinically, 72% had hypertension, 49% were diabetic and 37% had a prior myocardial infarction. Nearly 60% had moderate to severe LVEF (< 35%). Higher LVEF was independently associated with female sex and greater BMI (P < .04) while pacemaker/defibrillator and methamphetamine use was independently associated with lower LVEF (P < .05). Conclusions: Methamphetamine use and BMI may be important modifiable risk factors associated with LVEF and may be important targets for improving HF morbidity and mortality. PMID:25535596

  17. 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.

  18. 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.

  19. Influence of clouds and diffuse radiation on ecosystem-atmosphere CO2 and CO18O exchanges

    NASA Astrophysics Data System (ADS)

    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.

    2009-03-01

    This study evaluates the potential impact of clouds on ecosystem CO2 and CO2 isotope fluxes ("isofluxes") in two contrasting ecosystems (a broadleaf deciduous forest and a C4 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 CO2 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 C4 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 δ18O of CO2 may be driven by large-scale changes in clouds and aerosols and their impacts on diffuse radiation, photosynthesis, and relative humidity.

  20. 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.

  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, 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.

  2. New Benthic δ18o Stacks and Age Models for the Last Glacial Cycle (0-150 kyr ago)

    NASA Astrophysics Data System (ADS)

    Lisiecki, L. E.; Stern, J. V.

    2014-12-01

    The δ18O of formainiferal calcite is a common paleoceanographic proxy, which measures ice volume and deep water temperature change. Foraminiferal δ18O is also often used to create marine sediment core age models by aligning down-core variations in δ18O to a global stack, or average. However, the most commonly used stack, known as "LR04," has an outdated age model, assumes global benthic δ18O synchrony, and is biased to the Atlantic [Lisiecki and Raymo, 2005]. Here we present six regional benthic δ18O stacks of the last glacial cycle (0-150 kyr) that are combined to form a volume-weighted global stack with data from 263 sites. We develop new benthic δ18O age models using regional radiocarbon dates from 0-40 ka and correlations to the GICC05 layer-counted Greenland age model from 40-56 ka [Svensson et al., 2008] and U-Th-dated Chinese speleothems from 56-150 kyr [Wang et al., 2001; Cheng et al., 2009; Barker et al, 2011]. Additional features of the new stacks are diachronous benthic δ18O changes during the last two glacial terminations and explicit age uncertainty estimates throughout. Our new global stack indicates that some portions of the LR04 stack are up to 4 kyr too young. We estimate corrections to the LR04 age model throughout the Pleistocene that imply faster climate responses to orbital forcing than previously estimated.

  3. 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

    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).

  4. 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).

  5. 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

  6. 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.

  7. Continental-scale patterns in modern wood cellulose δ18O: Implications for interpreting paleo-wood cellulose δ18O

    NASA Astrophysics Data System (ADS)

    Richter, S. L.; Johnson, A. H.; Dranoff, M. M.; Taylor, K. D.

    2008-06-01

    The isotopic composition of ancient wood may be a useful archive of some climatic or geochemical conditions of the past, but presently there are many uncertainties that constrain such interpretations. We sampled naturally growing, predominantly native trees in forested regions of North America and the Caribbean to evaluate the strength of the relationships among cellulose δ18O (δ18Ocel), relative humidity (RH), precipitation δ18O (δ18Oppt), and mean annual temperature (MAT) at the continental scale, and the general range of variability in δ18Ocel associated with site hydrologic conditions and species differences. We found up to 4‰ differences among different species growing at the same site, that conifer cellulose at a site is more enriched than angiosperm cellulose by 1.5‰ (p < 0.001), and that differences in landscape position, reflecting differing access to the water table, produced differences of <1‰ in δ18Ocel. At the continental scale, δ18Ocel was strongly influenced by modeled δ18Oppt (R2 = 0.80, p < 0.001). Average summer minimum RH (RHmin) combined with δ18Oppt explained more of the variability (R2 = 0.93, p < 0.001) in δ18Ocel across North American and Caribbean forests. MAT and δ18Ocel were also strongly correlated across North America (R = 0.91 and 0.95, p < 0.001, for angiosperms and conifers, respectively). The difference between δ18Oppt and δ18Ocel is not constant (varying from 35-44‰) and is inversely correlated with δ18Oppt. The relationships among δ18Oppt, RHmin, δ18Ocel, and MAT established for North America and the Caribbean applied reasonably well when δ18Ocel was used to estimate MAT and δ18Oppt in Asia, Europe, and South America, but there were important exceptions. The most accurate predictions of MAT and δ18Oppt from δ18Ocel require RHmin. Predictions of δ18Oppt and MAT made from δ18Ocel alone produced errors of up to 8‰ and 16 °C, respectively.

  8. 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.

  9. 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

  10. Factors affecting recall rate and false positive fraction in breast cancer screening with breast tomosynthesis - A statistical approach.

    PubMed

    Rosso, Aldana; Lång, Kristina; Petersson, Ingemar F; Zackrisson, Sophia

    2015-10-01

    In this study, we investigate which factors affect the false positive fraction (FPF) for digital breast tomosynthesis (DBT) compared to digital mammography (DM) in a screening population by using classification and regression trees (C&RT) and binary marginal generalized linear models. The data was obtained from the Malmö Breast Tomosynthesis Screening Trial, which aimed to compare the performance of DBT to DM in breast cancer screening. By using data from the first half of the study population (7500 women), a tree with the recall probability for different groups was calculated. The effect of age and breast density on the FPF was estimated using a binary marginal generalized linear model. Our results show that breast density and breast cancer were the main factors influencing recall. The FPF is mainly affected by breast density and increases with breast density for DBT and DM. In conclusion, the results obtained with C&RT are easy to interpret and similar to those obtained using binary marginal generalized linear models. The FPF is approximately 40% higher for DBT compared to DM for all breast density categories.

  11. 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

  12. 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.

  13. 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

  14. 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.

  15. Response of meteoric δ18O to surface uplift — Implications for Cenozoic Andean Plateau growth

    NASA Astrophysics Data System (ADS)

    Insel, Nadja; Poulsen, Christopher J.; Ehlers, Todd A.; Sturm, Christophe

    2012-02-01

    The timing and magnitude of surface uplift provide important constraints on geodynamic models of orogen formation. Oxygen isotope (δ18O) and mass-47 isotopolog (Δ47) compositions from terrestrial carbonate sediments have been used with modern isotope and temperature lapse rates to infer past surface elevations of the Andes. However, these paleoaltimetry interpretations are contentious because variations in the oxygen isotope composition in meteoric water (δ18Op) are caused by changes in elevation (orographic) and regional climate. Here, we use a limited-domain isotope-tracking general circulation model to simulate changes in δ18Op and isotopic lapse rates in response to Andean surface uplift, and to re-evaluate δ18O and Δ47 changes in late Miocene carbonates previously associated with rapid Andean growth. Results indicate that Andean surface uplift leads to changes in low-level atmospheric circulation and an increase in precipitation along the eastern Andean flank which influences isotopic source and amount effects. Simulated changes in Andean δ18Op are not systematic with an increase in surface elevation, but are instead a function of orographic thresholds that abruptly change regional climate. A δ18Op decrease of > 5‰ over the central Andes and an increase in isotopic lapse rates (up to 0.8‰ km- 1) coincide with Andean surface uplift from 75 to 100% of modern elevation. These changes in the isotopic signature could account for the entire 3-4‰ δ18O depletion in late Miocene carbonate nodules, and suggest an Andean paleoelevation of ~ 3000 m (75% of modern elevations) before 10 Ma.

  16. 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.

  17. Reconstruction of drip-water δ18O based on calcite oxygen and clumped isotopes of speleothems from Bunker Cave (Germany)

    NASA Astrophysics Data System (ADS)

    Kluge, T.; Affek, H. P.; Marx, T.; Aeschbach-Hertig, W.; Riechelmann, D. F. C.; Scholz, D.; Riechelmann, S.; Immenhauser, A.; Richter, D. K.; Fohlmeister, J.; Wackerbarth, A.; Mangini, A.; Spötl, C.

    2012-07-01

    The geochemical signature of many speleothems used for reconstruction of past continental climates is affected by kinetic isotope fractionation. This limits quantitative paleoclimate reconstruction and, in cases where the kinetic fractionation varies with time, also affects relative paleoclimate interpretations. In carbonate archive research, clumped isotope thermometry is typically used as proxy for absolute temperatures. In the case of speleothems, however, clumped isotopes provide a sensitive indicator for disequilibrium effects. The extent of kinetic fractionation co-varies in Δ47 and δ18O so that it can be used to account for disequilibrium in δ18O and to extract the past drip-water composition. Here we apply this approach to stalagmites from Bunker Cave (Germany) and calculate drip-water δ18Ow values for the Eemian, Marine Isotope Stage (MIS) 3, and the Holocene, relying on independent temperature estimates and accounting for disequilibrium. Applying the co-variation method to modern calcite precipitates yields drip-water δ18Ow values in agreement with modern cave drip-water δ18Ow of -7.9 ± 0.3‰, despite large and variable disequilibrium effects in both calcite δ18Oc and Δ47. Reconstructed paleo-drip-water δ18Ow values are lower during colder periods (e.g., MIS 3: -8.5 ± 0.4‰ and the early Holocene at 11 kyr: -9.3 ± 0.1‰) and show higher values during warmer climatic periods (e.g., the Eemian: -7.5 ± 0.2‰ and the Holocene Climatic Optimum: -7.2 ± 0.3‰). This new approach offers a unique possibility for quantitative climate reconstruction including the assessment of past hydrological conditions while accounting for disequilibrium effects.

  18. Reconstruction of drip-water δ18O based on calcite oxygen and clumped isotopes of speleothems from Bunker Cave (Germany)

    NASA Astrophysics Data System (ADS)

    Kluge, T.; Affek, H. P.; Marx, T.; Aeschbach-Hertig, W.; Riechelmann, D. F. C.; Scholz, D.; Riechelmann, S.; Immenhauser, A.; Richter, D. K.; Fohlmeister, J.; Wackerbarth, A.; Mangini, A.; Spötl, C.

    2013-02-01

    The geochemical signature of many speleothems used for reconstruction of past continental climates is affected by kinetic isotope fractionation. This limits quantitative paleoclimate reconstruction and, in cases where the kinetic fractionation varies with time, also affects relative paleoclimate interpretations. In carbonate archive research, clumped isotope thermometry is typically used as proxy for absolute temperatures. In the case of speleothems, however, clumped isotopes provide a sensitive indicator for disequilibrium effects. The extent of kinetic fractionation co-varies in Δ47 and δ18O so that it can be used to account for disequilibrium in δ18O and to extract the past drip-water composition. Here we apply this approach to stalagmites from Bunker Cave (Germany) and calculate drip-water δ18Ow values for the Eemian, MIS3, and the Holocene, relying on independent temperature estimates and accounting for disequilibrium. Applying the co-variation method to modern calcite precipitates yields drip-water δ18Ow values in agreement with modern cave drip-water δ18Ow of -7.9 ± 0.3‰, despite large and variable disequilibrium effects in both calcite δ18Oc and Δ47. Reconstructed paleo-drip-water δ18Ow values are lower during colder periods (e.g., MIS3: -8.6 ± 0.4‰ and the early Holocene at 11 ka: -9.7 ± 0.2‰) and show higher values during warmer climatic periods (e.g., the Eemian: -7.6 ± 0.2‰ and the Holocene Climatic Optimum: -7.2 ± 0.3‰). This new approach offers a unique possibility for quantitative climate reconstruction including the assessment of past hydrological conditions while accounting for disequilibrium effects.

  19. 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

  20. 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

  1. 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.

  2. 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

  3. 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

  4. 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

  5. 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

  6. 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

  7. Mechanism of bile-pigment synthesis in algae. 18O incorporation into phycocyanobilin in the unicellular rhodophyte, Cyanidium caldarium.

    PubMed Central

    Brown, S B; Holroyd, A J; Troxler, R F

    1980-01-01

    The origin of the lactam oxygen atoms of phycocyanobilin from Cyanidium caldarium was studied using 18O labelling. By inhibiting photosynthesis, a high 18O enrichment was maintained in the gas phase and the resulting incorporation of label showed that the lactam oxygen atoms were derived from two oxygen molecules. Slow exchange of these oxygen atoms with water was demonstrated directly by using H218O. PMID:7470059

  8. The potential origins and palaeoenvironmental implications of high temporal resolution δ 18O heterogeneity in coral skeletons

    NASA Astrophysics Data System (ADS)

    Allison, Nicola; Finch, Adrian A.; EIMF

    2010-10-01

    δ 18O was determined at high spatial resolution (beam diameter ˜30 μm) by secondary ion mass spectrometry (SIMS) across 1-2 year sections of 2 modern Porites lobata coral skeletons from Hawaii. We observe large (>2‰) cyclical δ 18O variations that typically cover skeletal distances equivalent to periods of ˜20-30 days. These variations do not reflect seawater temperature or composition and we conclude that skeletal δ 18O is principally controlled by other processes. Calcification site pH in one coral record was estimated from previous SIMS measurements of skeletal δ 11B. We model predicted skeletal δ 18O as a function of calcification site pH, DIC residence time at the site and DIC source (reflecting the inputs of seawater and molecular CO 2 to the site). We assume that oxygen isotopic equilibration proceeds at the rates observed in seawater and that only the aqueous carbonate ion is incorporated into the precipitating aragonite. We reproduce successfully the observed skeletal δ 18O range by assuming that DIC is rapidly utilised at the calcification site (within 1 h) and that ˜80% of the skeletal carbonate is derived from seawater. If carbonic anhydrase catalyses the reversible hydration of CO 2 at the calcification site, then oxygen isotopic equilibration times may be substantially reduced and a larger proportion of the skeletal carbonate could be derived from molecular CO 2. Seasonal skeletal δ 18O variations are most pronounced in the skeleton deposited from late autumn to winter (and coincide with the high density skeletal bands) and are dampened in skeleton deposited from spring to summer. We observed no annual pattern in sea surface temperature or photosynthetically active radiation variability which could potentially correlate with the coral δ 18O. At present we are unable to resolve an environmental cue to drive seasonal patterns of short term skeletal δ 18O heterogeneity.

  9. 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.

  10. 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.

  11. Probability distribution functions of δ15N and δ18O in groundwater nitrate to probabilistically solve complex mixing scenarios

    NASA Astrophysics Data System (ADS)

    Chrystal, A.; Heikoop, J. M.; Davis, P.; Syme, J.; Hagerty, S.; Perkins, G.; Larson, T. E.; Longmire, P.; Fessenden, J. E.

    2010-12-01

    Elevated nitrate (NO3-) concentrations in drinking water pose a health risk to the public. The dual stable isotopic signatures of δ15N and δ18O in NO3- in surface- and groundwater are often used to identify and distinguish among sources of NO3- (e.g., sewage, fertilizer, atmospheric deposition). In oxic groundwaters where no denitrification is occurring, direct calculations of mixing fractions using a mass balance approach can be performed if three or fewer sources of NO3- are present, and if the stable isotope ratios of the source terms are defined. There are several limitations to this approach. First, direct calculations of mixing fractions are not possible when four or more NO3- sources may be present. Simple mixing calculations also rely upon treating source isotopic compositions as a single value; however these sources themselves exhibit ranges in stable isotope ratios. More information can be gained by using a probabilistic approach to account for the range and distribution of stable isotope ratios in each source. Fitting probability density functions (PDFs) to the isotopic compositions for each source term reveals that some values within a given isotopic range are more likely to occur than others. We compiled a data set of dual isotopes in NO3- sources by combining our measurements with data collected through extensive literature review. We fit each source term with a PDF, and show a new method to probabilistically solve multiple component mixing scenarios with source isotopic composition uncertainty. This method is based on a modified use of a tri-linear diagram. First, source term PDFs are sampled numerous times using a variation of stratified random sampling, Latin Hypercube Sampling. For each set of sampled source isotopic compositions, a reference point is generated close to the measured groundwater sample isotopic composition. This point is used as a vertex to form all possible triangles between all pairs of sampled source isotopic compositions

  12. Spatial variability of δ18O-PO4 in soils.

    NASA Astrophysics Data System (ADS)

    Granger, Steve; Blackwell, Martin; Tamburini, Federica; Guo, Rongrong; Peukert, Sabine; McGrath, Steve

    2014-05-01

    There is growing interest in the potential for using the δ18OPO4 values of different phosphate sources in the environment to enable identification of sources of phosphate in surface waters. The basis of the study is the belief that different sources of PO4 may have different δ18O values. One of the primary sources of PO4 in runoff from agricultural land is the soil itself. Therefore, in order to account for the PO4 derived from soils in surface waters, it is vital that the degree of spatial variability of its δ18O isotopic values are known, in order that suitable soil sampling approaches can be taken when assessing the soil as a source in future studies. A spatial study of the variability of the δ18OPO4 variability of soils collected from a grazed pasture on the North Wyke Farm Platform was carried out incorporating grid-sampling at a range of spatial scales. Results show that variability across a range of scales is minimal, meaning that, in this case, a relatively small number of samples would be required in order to identify accurately the mean δ18OPO4 value of the soil. This study represents an important contribution towards the methodological development studies required in this field of research in order that the full potential of the δ18OPO4 technique for biological and environmental research can be achieved.

  13. 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.

  14. Novel /sup 18/O kinetic isotope effect in an. cap alpha. -chymotrypsin catalyzed transesterification

    SciTech Connect

    Wang, C.L.A.; Trout, C.M.; Calvo, K.C.; Klapper, M.H.; Wong, L.K.

    1980-01-30

    Reactions were started by injecting the nitrophenyl ester into a stoppered vial immersed in a constant-temperature bath (4/sup 0/C) containing a mixture of /sup 16/O plus /sup 18/O-ethanol, ..cap alpha..-chymotrypsin, and buffer. As the reaction proceeded, samples were withdrawn and injected into a gas chromatograph connected to a quadrupole mass spectrometer controlled by a data acquisition and processing system. The intensities from individual ions were displayed as a function of time to yield chromatographic peaks. Relative /sup 18/O enrichments were computed from the ratios of the peak areas, and the apparent KIE was then calculated from the ratio of enrichments in alcohol and ester. The values of the plateau KIE were less than or equal to 0.90 for all experiments. The apparent first-order rate constant can also be calculated from the magnitude of the initial burst and the slope of the zero-order absorbence increase. This apparent rate constant varies linearly with the ethanol concentration permitting calculation of the second-order rate associated with the formation of the ethyl ester product. 2 figures, 1 table.

  15. 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.

  16. Stable isotope ( 18O) investigations on the processes controlling fluoride contamination of groundwater

    NASA Astrophysics Data System (ADS)

    Datta, P. S.; Deb, D. L.; Tyagi, S. K.

    1996-10-01

    Groundwater is being used extensively in the Delhi area for both irrigation and raw water requirement. Fluoride contamination in groundwater is therefore a matter of concern for the planners and managers of water resources. Stable isotope ( 18O) and fluoride signatures in groundwater have been discussed, in this context, to characterise the sources and controlling processes of fluoride contamination. The study indicates that almost 50% of the area is affected by fluoride contamination beyond the maximum permissible limit. The wide range (0.10-16.5 ppm) in fluoride concentration suggests contributions from both point and non-point sources. Very high fluoride levels in groundwater are mostly found in the vicinity of brick kilns. Significant quantities of evaporated (isotopically enriched) rainfall, irrigation water and surface runoff water from surrounding farmland also percolate along with fluoride salts from the soils to the groundwater system. The process of adsorption and dispersion of fluoride species in the soil as well as lateral mixing of groundwater along specific flow-paths control the groundwater fluoride and 18O composition. The groundwater system has more than two isotopically distinct non-point source origins, causing spatial and temporal variations in fluoride concentration. Issues related to harmful effects of excessive use of high-fluoride groundwater and management options have also been discussed.

  17. 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.

  18. 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

    2014-07-11

    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.

  19. [Characteristics of delta18O in precipitation and water vapor sources in Lanzhou City and its surrounding area].

    PubMed

    Chen, Fen-Li; Zhang, Ming-Jun; Ma, Qian; Li, Xiao-Fei; Wang, Sheng-Jie; Li, Fei

    2013-10-01

    Based on the 243 daily precipitation samples and meteorological statistics at the four stations at Lanzhou city and its surrounding area (Yongdeng, Gaolan and Yuzhong) from April 2011 to March 2012, the characteristics of stable isotopes in precipitation, as well as the correlation between stable isotopes and meteorological records, were analyzed. The precipitation equation of Lanzhou city and its surrounding area were calculated through the regression analysis, and the water vapor source of the four sites was tracked by the HYSPLIT 4. 9 model, and water vapor transmission regime was established. Results showed that the precipitation equation of deltaD =7.48 delta18O + 8.13 indicated intense evaporation; delta18O value was low in winter but high in summer; The variations of observed d-excess was stable all over the year, but there was variation in different time periods; The spatial distribution showed that the weighted delta18O value decreased from the west to the east; The linear relationships between delta18O and temperature was positive correlation, but the linear relationships between delta18O and precipitation was negative correlation; The seasonal variations of delta18O indicated that westerly water vapor, local moisture and summer monsoon all had influence on this region in a large scale, but the westerly water vapor played a dominant role. However, the impact of monsoon moisture had a seasonal limitation, mainly during the period from June to early August.

  20. 18O depletion in monsoon rain relates to large scale organized convection rather than the amount of rainfall

    PubMed Central

    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 18O depletion of rain with increasing amount, manifested as a negative correlation of the monthly amount of tropical rain with its δ18O, 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 18O-depletion in monsoon rain is not related necessarily to its amount, but rather, to large scale organized convection. Presenting δ18O 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 δ18O values of rain exhibit highly coherent variations (significant at P = 0.05). Significantly more 18O-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

  1. 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

  2. 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

  3. Correlated δ18O and [Ti] in lunar zircons: a terrestrial perspective for magma temperatures and water content on the Moon

    NASA Astrophysics Data System (ADS)

    Valley, John W.; Spicuzza, Michael J.; Ushikubo, Takayuki

    2014-01-01

    Zircon grains were separated from lunar regolith and rocks returned from four Apollo landing sites, and analyzed in situ by secondary ion mass spectrometry. Many regolith zircons preserve magmatic δ18O and trace element compositions and, although out of petrologic context, represent a relatively unexplored resource for study of the Moon and possibly other bodies in the solar system. The combination of oxygen isotope ratios and [Ti] provides a unique geochemical signature that identifies zircons from the Moon. The oxygen isotope ratios of lunar zircons are remarkably constant and unexpectedly higher in δ18O (5.61 ± 0.07 ‰ VSMOW) than zircons from Earth’s oceanic crust (5.20 ± 0.03 ‰) even though mare basalt whole-rock samples are nearly the same in δ18O as oceanic basalts on Earth (~5.6 ‰). Thus, the average fractionation of oxygen isotopes between primitive basalt and zircon is smaller on the Moon [Δ18O(WR-Zrc) = 0.08 ± 0.09 ‰] than on Earth (0.37 ± 0.04 ‰). The smaller fractionations on the Moon suggest higher temperatures of zircon crystallization in lunar magmas and are consistent with higher [Ti] in lunar zircons. Phase equilibria estimates also indicate high temperatures for lunar magmas, but not specifically for evolved zircon-forming melts. If the solidus temperature of a given magma is a function of its water content, then so is the crystallization temperature of any zircon forming in that melt. The systematic nature of O and Ti data for lunar zircons suggests a model based on the following observations. Many of the analyzed lunar zircons are likely from K, rare earth elements, P (KREEP)-Zr-rich magmas. Zircon does not saturate in normal mafic magmas; igneous zircons in mafic rocks are typically late and formed in the last most evolved portion of melts. Even if initial bulk water content is moderately low, the late zircon-forming melt can concentrate water locally. In general, water lowers crystallization temperatures, in which case late

  4. 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.

  5. Plasma proteome response to severe burn injury revealed by 18O-labeled "universal" reference-based quantitative proteomics.

    PubMed

    Qian, Wei-Jun; Petritis, Brianne O; Kaushal, Amit; Finnerty, Celeste C; Jeschke, Marc G; Monroe, Matthew E; Moore, Ronald J; Schepmoes, Athena A; Xiao, Wenzhong; Moldawer, Lyle L; Davis, Ronald W; Tompkins, Ronald G; Herndon, David N; Camp, David G; Smith, Richard D

    2010-09-01

    A burn injury represents one of the most severe forms of human trauma and is responsible for significant mortality worldwide. Here, we present the first quantitative proteomics investigation of the blood plasma proteome response to severe burn injury by comparing the plasma protein concentrations of 10 healthy control subjects with those of 15 severe burn patients at two time-points following the injury. The overall analytical strategy for this work integrated immunoaffinity depletion of the 12 most abundant plasma proteins with cysteinyl-peptide enrichment-based fractionation prior to LC-MS analyses of individual patient samples. Incorporation of an 18O-labeled "universal" reference among the sample sets enabled precise relative quantification across samples. In total, 313 plasma proteins confidently identified with two or more unique peptides were quantified. Following statistical analysis, 110 proteins exhibited significant abundance changes in response to the burn injury. The observed changes in protein concentrations suggest significant inflammatory and hypermetabolic response to the injury, which is supported by the fact that many of the identified proteins are associated with acute phase response signaling, the complement system, and coagulation system pathways. The regulation of approximately 35 proteins observed in this study is in agreement with previous results reported for inflammatory or burn response, but approximately 50 potentially novel proteins previously not known to be associated with burn response or inflammation are also found. Elucidating proteins involved in the response to severe burn injury may reveal novel targets for therapeutic interventions as well as potential predictive biomarkers for patient outcomes such as multiple organ failure.

  6. Determination of the Fe(II)aq-magnetite equilibrium iron isotope fractionation factor using the three-isotope method and a multi-direction approach to equilibrium

    NASA Astrophysics Data System (ADS)

    Frierdich, Andrew J.; Beard, Brian L.; Scherer, Michelle M.; Johnson, Clark M.

    2014-04-01

    Magnetite is ubiquitous in the Earth's crust and its presence in modern marine sediments has been taken as an indicator of biogeochemical Fe cycling. Magnetite is also the most abundant Fe oxide in banded iron formations (BIFs) that have not been subjected to ore-forming alteration. Magnetite is therefore an important target of stable Fe isotope studies, and yet interpretations are currently difficult because of large uncertainties in the equilibrium stable Fe isotope fractionation factors for magnetite relative to fluids and other minerals. In this study, we utilized the three-isotope method (57Fe-56Fe-54Fe) to explore isotopic exchange via an enriched-57Fe tracer, and natural mass-dependent fractionation using 56Fe/54Fe variations, during reaction of aqueous Fe(II) (Fe(II)aq) with magnetite. Importantly, we employed a multi-direction approach to equilibrium by reacting four 57Fe-enriched Fe(II) solutions that had distinct 56Fe/54Fe ratios, which identifies changes in the instantaneous Fe isotope fractionation factor and hence identifies kinetic isotope effects. We find that isotopic exchange can be described by two 56Fe/54Fe fractionations, where an initial rapid exchange (∼66% isotopic mixing within 1 day) involved a relatively small Fe(II)aq-magnetite 56Fe/54Fe fractionation, followed by slower exchange (∼25% isotopic mixing over 50 days) that was associated with a larger Fe(II)aq-magnetite 56Fe/54Fe fractionation; this later fractionation is interpreted to approach isotopic equilibrium between Fe(II)aq and the total magnetite. All four Fe(II) solutions extrapolate to the same final equilibrium 56Fe/54Fe fractionation for Fe(II)aq-magnetite of -1.56±0.20‰ (2σ) at 22 °C. Additional experiments that synthesized magnetite via conversion of ferrihydrite by reaction with aqueous Fe(II) yield final 56Fe/54Fe fractionations that are identical to those of the exchange experiments. Our experimental results agree well with calculated fractionation factors using

  7. 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

  8. 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

  9. 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

  10. 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

  11. 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

  12. 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

  13. 18O-labeled proteome reference as global internal standards for targeted quantification by selected reaction monitoring-mass spectrometry.

    PubMed

    Kim, Jong-Seo; Fillmore, Thomas L; Liu, Tao; Robinson, Errol; Hossain, Mahmud; Champion, Boyd L; Moore, Ronald J; Camp, David G; Smith, Richard D; Qian, Wei-Jun

    2011-12-01

    Selected reaction monitoring (SRM)-MS is an emerging technology for high throughput targeted protein quantification and verification in biomarker discovery studies; however, the cost associated with the application of stable isotope-labeled synthetic peptides as internal standards can be prohibitive for screening a large number of candidate proteins as often required in the preverification phase of discovery studies. Herein we present a proof of concept study using an (18)O-labeled proteome reference as global internal standards (GIS) for SRM-based relative quantification. The (18)O-labeled proteome reference (or GIS) can be readily prepared and contains a heavy isotope ((18)O)-labeled internal standard for every possible tryptic peptide. Our results showed that the percentage of heavy isotope ((18)O) incorporation applying an improved protocol was >99.5% for most peptides investigated. The accuracy, reproducibility, and linear dynamic range of quantification were further assessed based on known ratios of standard proteins spiked into the labeled mouse plasma reference. Reliable quantification was observed with high reproducibility (i.e. coefficient of variance <10%) for analyte concentrations that were set at 100-fold higher or lower than those of the GIS based on the light ((16)O)/heavy ((18)O) peak area ratios. The utility of (18)O-labeled GIS was further illustrated by accurate relative quantification of 45 major human plasma proteins. Moreover, quantification of the concentrations of C-reactive protein and prostate-specific antigen was illustrated by coupling the GIS with standard additions of purified protein standards. Collectively, our results demonstrated that the use of (18)O-labeled proteome reference as GIS provides a convenient, low cost, and effective strategy for relative quantification of a large number of candidate proteins in biological or clinical samples using SRM.

  14. 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.

  15. 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.

  16. Tumor necrosis factor-α suppresses the protein fractional synthesis rate of the small intestine stimulated by glutamine in rats

    PubMed Central

    ZHOU, JIHONG; FAN, SHENGXIAN; CAO, YACHENG; ZHU, MINGFANG; HAN, YONG; CAO, XUEYING; LI, YOUSHENG

    2015-01-01

    The objective of this study was to examine whether and how TNF-α affects glutamine-enhanced protein synthesis and the expression of the amino acid transporter ASCT2 in the small intestine at the mRNA and protein levels. A total of 30 male Sprague-Dawley rats were randomly assigned into three groups, namely the total parenteral nutrition (TPN; control), glutamine-treated (Gln), and glutamine- and tumor necrosis factor-α (TNF-α)-treated (TNF-α) groups. At 30 min prior to examination, all rats were mainlined with [L-15N]leucine. The concentration of TNF-α in plasma and of glutamine in plasma and the small intestine was measured. The fractional synthesis rate (FSR) of protein and the mRNA and protein expression levels of ASCT2 in the small intestine were assessed. The level of TNF-α was highest in the TNF-α group and the glutamine concentration was elevated to a greater extent in the TNF-α group than in the other two groups. However, the FSR of protein in the small intestine was significantly higher in the Gln group compared with that in the TNF-α group. The mRNA and protein expression levels of ASCT2 in the experimental groups were significantly higher that those in the control group, but did not differ significantly between the Gln and TNF-α groups. These results indicate that TNF-α may attenuate glutamine-stimulated protein synthesis in the small intestine in the early stage of sepsis in rats. The mechanism may be that TNF-α inhibits the function of the glutamine transporter in the uptake the glutamine into target cells for protein synthesis. This inhibition may occur at or following protein translation. PMID:25574232

  17. 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.

  18. Rapid uplift of the Altiplano revealed through 13C-18O bonds in paleosol carbonates.

    PubMed

    Ghosh, Prosenjit; Garzione, Carmala N; Eiler, John M

    2006-01-27

    The elevation of Earth's surface is among the most difficult environmental variables to reconstruct from the geological record. Here we describe an approach to paleoaltimetry based on independent and simultaneous determinations of soil temperatures and the oxygen isotope compositions of soil waters, constrained by measurements of abundances of 13C-18O bonds in soil carbonates. We use this approach to show that the Altiplano plateau in the Bolivian Andes rose at an average rate of 1.03 +/- 0.12 millimeters per year between approximately 10.3 and approximately 6.7 million years ago. This rate is consistent with the removal of dense lower crust and/or lithospheric mantle as the cause of elevation gain.

  19. 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.

  20. 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).

  1. 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.

  2. 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

  3. Metal-catalyzed phosphodiester cleavage: secondary 18O isotope effects as an indicator of mechanism.

    PubMed

    Rawlings, Jill; Cleland, W Wallace; Hengge, Alvan C

    2006-12-27

    Information about the transition states of metal-catalyzed hydrolysis reactions of model phosphate compounds has been obtained through determination of isotope effects (IEs) on the hydrolysis reactions. Metal complexation has been found to significantly alter the transition state of the reaction from the alkaline hydrolysis reaction, and the transition state is quite dependent on the particular metal ion used. For the diester, ethyl p-nitrophenyl phosphate, the nonbridge 18O effect for the hydrolysis reactions catalyzed by Co(III) 1,5,9-triazacyclononane and Eu(III) were 1.0006 and 1.0016, respectively, indicative of a slightly associative transition state and little net change in bonding to the nonbridge oxygen. The reaction catalyzed by Zn(II) 1,4,7,10-tetraazacyclododecane had an 18O nonbridge IE of 1.0108, showing the reaction differs significantly from the reaction of the noncomplexed diester and resembles the reactions of triesters. Reaction with Co(III) 1,4,7,10-tetraazacyclododecane showed an inverse effect of 0.9948 reflecting the effects of bonding of the diester to the Co(III). Lanthanide-catalyzed hydrolysis has been observed to have unusually large 15N effects. To further investigate this effect, the 15N effect on the reaction catalyzed by Ce(IV) bis-Tris propane solutions at pH 8 was determined to be 1.0012. The 15N effects were also measured for the reaction of the monoester p-nitrophenyl phosphate by Ce(IV) bis-Tris propane (1.0014) and Eu(III) bis-Tris propane (1.0012). These smaller effects at pH 8 indicate that a smaller negative charge develops on the nitrogen during the hydrolysis reaction.

  4. Robust MS quantification method for phospho-peptides using 18O/16O labeling

    PubMed Central

    Andersen, Claus A; Gotta, Stefano; Magnoni, Letizia; Raggiaschi, Roberto; Kremer, Andreas; Terstappen, Georg C

    2009-01-01

    Background Quantitative measurements of specific protein phosphorylation sites, as presented here, can be used to investigate signal transduction pathways, which is an important aspect of cell dynamics. The presented method quantitatively compares peptide abundances from experiments using 18O/16O labeling starting from elaborated MS spectra. It was originally developed to study signaling cascades activated by amyloid-β treatment of neurons used as a cellular model system with relevance to Alzheimer's disease, but is generally applicable. Results The presented method assesses, in complete cell lysates, the degree of phosphorylation of specific peptide residues from MS spectra using 18O/16O labeling. The abundance of each observed phospho-peptide from two cell states was estimated from three overlapping isotope contours. The influence of peptide-specific labeling efficiency was removed by performing a label swapped experiment and assuming that the labeling efficiency was unchanged upon label swapping. Different degrees of phosphorylation were reported using the fold change measure which was extended with a confidence interval found to reflect the quality of the underlying spectra. Furthermore a new way of method assessment using simulated data is presented. Using simulated data generated in a manner mimicking real data it was possible to show the method's robustness both with increasing noise levels and with decreasing labeling efficiency. Conclusion The fold change error assessable on simulated data was on average 0.16 (median 0.10) with an error-to-signal ratio and labeling efficiency distributions similar to the ones found in the experimentally observed spectra. Applied to experimentally observed spectra a very good match was found to the model (<10% error for 85% of spectra) with a high degree of robustness, as assessed by data removal. This new method can thus be used for quantitative signal cascade analysis of total cell extracts in a high throughput mode

  5. 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.

  6. 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.

  7. Evaluation of Speleothem Oxygen Isotope Fractionation from a Tropical Cave on the Island of Guam

    NASA Astrophysics Data System (ADS)

    Moore, M. W.; Hardt, B. F.; Banner, J. L.; Jenson, J. W.

    2013-12-01

    values from the substrate calcite are strongly correlated with the Mg-Ca ratios of dripwater. Oxygen isotope values and the Mg-Ca ratio in drip waters are also well correlated, which may be due to coherence between the seasonal cycle of dripwater δ18O and the drier conditions that would cause prior calcite precipitation. The δ13C and Mg-Ca correlation is consistent with prior calcite precipitation affecting δ13C. Ongoing research is examining the relationship between calcite growth rate and the departure from equilibrium. When evaluated in the context of similar studies, the data from Guam show reasonable agreement with the fractionation factor of Tremaine et al., 2011, which was constructed from results for cave environments.

  8. 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).

  9. Climatic effects on the δ18O and δ13C of cellulose in the desert tree Tamarix jordanis

    NASA Astrophysics Data System (ADS)

    Lipp, J.; Trimborn, P.; Edwards, T.; Waisel, Y.; Yakir, D.

    1996-09-01

    The {13C}/{12C} and {18O}/{16O} ratios of stem cellulose of Tamarix jordanis (a tree common in wadis of rid regions) increased with decreasing relative humidity (RH) in individual trees growing along a climatic gradient in Israel. The response to RH observed in the δ18O of the wood cellulose was strongly similar to that observed in leaf water over a diurnal cycle. Most of the data for δ13C and all of the data for δ18O could be fitted to two independent linear equations that, combined, allowed the reconstruction of RH and the δ18O of source water from the isotopic composition of ancient T. jordanis wood previously reported from the ancient fortress of Masada. Since the Roman period, RH at Masada decreased by about 17%, while the δ18O value of local groundwater remained similar to present-day values, suggesting that changing atmospheric circulation has played a role in climate change in the Middle East over the past two millennia.

  10. 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.

  11. Role of tropical cyclones in determining the fate of Bay of Bengal vapor contributed rain δ18O values

    NASA Astrophysics Data System (ADS)

    Sanyal, Prasanta; Basu, Sayak

    2016-04-01

    The evaluation of robust future climate prediction is well dependent on the cognition of past and present hydrological systems which could be traced through the oxygen isotopic composition (δ18O) of rain. Compared to Peninsular and Southern India, explanation for the variability in δ18O values of monsoonal rain is sparse for the Eastern India. Analysis (and published records) of Indian summer monsoon (ISM) rain at the entry point of Bay of Bengal (BoB) vapor into the continent showed the gradual depletion of 18O in the ISM rain is determined by the surface run-off and location of cyclone generation in BoB. The timing and density of cyclones control the maxima in amount and minima in δ18O value of ISM rain and possibly also responsible for the long-term (last 10 years) decrease in rain δ18O values (and amount). Large spatial variation and temporally robustness of weak and insignificant amount effect suggested reconsideration of reconstructed past climate records along the track of BoB vapor. The memory effect of atmospheric vapor is found to lower the amount effect.

  12. The interstellar C18O/C17O ratio in the solar neighbourhood: The ρ Ophiuchus cloud

    NASA Astrophysics Data System (ADS)

    Wouterloot, J. G. A.; Brand, J.; Henkel, C.

    2005-02-01

    Observations of up to ten carbon monoxide (CO and isotopomers) transitions are presented to study the interstellar C18O/C17O ratio towards 21 positions in the nearby (d˜140 pc) low-mass star forming cloud ρ Oph. A map of the C18O J=1-0 distribution of parts of the cloud is also shown. An average 12C18O/12C17O isotopomeric ratio of 4.11 ± 0.14, reflecting the 18O/17O isotope ratio, is derived from Large Velocity Gradient (LVG) calculations. From LTE column densities we derive a ratio of 4.17±0.26. These calculations also show that the kinetic temperature decreases from about 30 K in the cloud envelope to about 10 K in the cloud cores. This decrease is accompanied by an increase of the average molecular hydrogen density from 104 cm-3 to ⪆105 cm-3. Towards some lines of sight C18O optical depths reach values of order unity. Based on observations collected with the Swedish/ESO Submillimeter Telescope (SEST) at the European Southern Observatory, Chile (ESO 62.I-0752). All spectra (some of which are shown in Fig. \\ref{spectra}) are available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/430/549

  13. 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

  14. 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.

  15. Modification of the volumetric growth responses and steady-state hypoxic fractions of xenografted DLD-2 human colon carcinomas by administration of basic fibroblast growth factor or suramin.

    PubMed Central

    Leith, J. T.; Papa, G.; Quaranto, L.; Michelson, S.

    1992-01-01

    We studied the growth characteristics and hypoxic fractions of DLD-2 human colon tumours xenografted into male nude mice either in the unperturbed state or after i.p. injection (q.i.d. x 7) of basic fibroblast growth factor (0.25 mg kg-1) or suramin (50 mg kg-1). Hypoxic fractions were measured by clonogenic excision assay 1 day after administration b FGF or suramin was stopped. As compared to controls, the growth of tumours in b FGF treated mice was increased by a factor of 1.5 as indicated by the relative volumes of tumours on the day of excision. Similarly, suramin decreased the growth of DLD-2 tumours by a factor of 1.6. The percentage of hypoxic cells in control neoplasms was 42.9% (95% confidence limits 34.2-52.1%). In mice that received basic fibroblast growth factor injections, hypoxic fractions decreased to 19.1% (95% confidence limits 13.5-26.9%). In contrast, in mice treated with suramin, the percentage of hypoxic cells increased to 74.0% (95% confidence limits 65.3-83.9%). These data indicate that the biology of solid tumours can be significantly modified by alteration of growth factor status. PMID:1503909

  16. 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.

  17. Liquid-vapor fractionation of oxygen and hydrogen isotopes of water from the freezing to the critical temperature

    NASA Astrophysics Data System (ADS)

    Horita, Juske; Wesolowski, David J.

    1994-08-01

    The equilibrium fractionation factors of oxygen and hydrogen isotopes between liquid water and water vapor have been precisely determined from 25 to 350°C on the VSMOW-SLAP scale, using three different types of apparatus with static or dynamic techniques for the sampling of water vapor. Our results for both oxygen and hydrogen isotope fractionation factors between 25 and 100°C are in excellent agreement with the literature (e.g., MAJOUBE, 1971). Our results for the hydrogen isotope fractionation factor above 100°C also agree quantitatively with the literature values of MERLIVAT et al. (1963) and BOTTINGA (1968). The results for the hydrogen isotope fractionation factor obtained in this study and from most of the literature were regressed to the equation, 10 3Inα 1-v(D) = 1158.8( T 3/10 9) -1620.1 ( T 2/10 6) + 794.84( T/10 3) -161.04 + 2.9992( 10 9/T 3), from 0°C to the critical temperature of water (374.1°C) within ± 1.2(1σ) ( n = 157); T( K). The cross- over temperature is 229 ± 13° C (1σ). Our values for the oxygen isotope fractionation factor between liquid water and water vapor are, however, at notable variance with the only dataset available above 100°C in the literature ( BOTTINGA, 1968), which is systematically higher (av. + 0.15 in 10 3 In α 1-v( 18O)) with large errors (± 0.23 in 1σ). Our results and most of the literature data below 100°C were regressed to the equation, 10 3 In α 1-v( 18O) = -7.685 + 6.7123( 10 3/T) - 1.6664( 10 6/T 2) + 0.35041 ( 10 9/T 3), from 0 to 374.1°C within ± 0.11 (1σ)( n = 112); T( K). A third water-steam isotope geothermometer, using the ratio of ΔδD/Δδ 18O given by water and steam samples, is readily obtained from the above equations. This geothermometer is less affected by incomplete separation of water and steam, and partial condensation of steam than those employing the oxygen and hydrogen isotopic compositions alone.

  18. 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

  19. Stable oxygen isotopes (delta18(O)) in Austrocedrus chilensis tree rings reflect climate variability in northwestern Patagonia, Argentina.

    PubMed

    Roig, F A; Siegwolf, R; Boninsegna, J A

    2006-11-01

    The stable oxygen isotope (delta (18)O) composition of Austrocedrus chilensis (D. Don) Endl. (Cupressaceae) tree rings potentially provide retrospective views of changes in environment and climate in the semi-arid lands of Patagonia. We report the development of the first annually resolved delta (18)O tree-ring chronology obtained from natural forests of the foothills of the northwestern Patagonian Andes. The isotope record spans between 1890 and 1994 AD. We explore the probable links between this record and the climate of the region. Air temperatures during summer conditions are significantly, but not strongly, inversely correlated with annual delta (18)O values from Austrocedrus tree rings. The strongest correlations are between the southern oscillation index (SOI) and the tree rings. The existence of millennial-age Austrocedrus trees in northern Patagonia provides interesting possibilities for examining these climate-related isotopic signals over most of the last 1,000 years.

  20. 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

  1. A novel methodological approach for δ(18)O analysis of sugars using gas chromatography-pyrolysis-isotope ratio mass spectrometry.

    PubMed

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

    2013-01-01

    Although the instrumental coupling of gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) for compound-specific δ(18)O analysis has been commercially available for more than a decade, this method has been hardly applied so far. Here we present the first GC-Py-IRMS δ(18)O results for trimethylsilyl-derivatives of plant sap-relevant sugars and a polyalcohol (glucose, fructose, sucrose, raffinose and pinitol). Particularly, we focus on sucrose, which is assimilated in leaves and which is the most important transport sugar in plants and hence of utmost relevance in plant physiology and paleoclimate studies. Replication measurements of sucrose standards and concentration series indicate that the GC-Py-IRMS δ(18)O measurements are not stable over time and that they are amount (area) dependent. We, therefore, suggest running sample batch replication measurements in alternation with standard concentration series of reference material. This allows for carrying out (i) a drift correction, (ii) a calibration against reference material and (iii) an amount (area) correction. Tests with (18)O-enriched water do not provide any evidence for oxygen isotope exchange reactions affecting sucrose and raffinose. We present the first application of GC-Py-IRMS δ(18)O analysis for sucrose from needle extract (soluble carbohydrate) samples. The obtained δ(18)Osucrose/ Vienna Standard Mean Ocean Water (VSMOW) values are more positive and vary in a wider range (32.1-40.1 ‰) than the δ(18)Obulk/ VSMOW values (24.6-27.2 ‰). Furthermore, they are shown to depend on the climate parameters maximum day temperature, relative air humidity and cloud cover. These findings suggest that δ(18)Osucrose of the investigated needles very sensitively reflects the climatically controlled evaporative (18)O enrichment of leaf water and thus highlights the great potential of GC-Py-IRMS δ(18)Osucrose analysis for plant physiology and paleoclimate studies. PMID:24313371

  2. 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.

  3. 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.

  4. 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.

  5. The 18O/16O Ratio of 2-Billion-Year-Old Seawater Inferred from Ancient Oceanic Crust.

    PubMed

    Holmden, C; Muehlenbachs, K

    1993-03-19

    An oxygen isotope profile of the 2-billion-year-old Purtuniq ophiolite overlaps with similar profiles of younger ophiolites and the modern oceanic crust. This overlap implies (i) that there was a similar style of seawater-ocean crust interaction during the past 2 billion years; (ii) that the oxygen isotope composition of early Proterozoic seawater was similar to the modern value; (iii) that early Proterozoic sea-floor spreading rates were similar to, or greater than, average modern rates; and (iv) that early Proterozoic carbonate rocks and cherts with low (18)O/(16)O ratios do not reflect global-scale (18)O depletion of early Proterozoic oceans. PMID:17816892

  6. 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

  7. 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

  8. 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 PAGES

    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

  9. Fractionation of oxygen isotopes by root respiration: Implications for the isotopic composition of atmospheric O 2

    NASA Astrophysics Data System (ADS)

    Angert, Alon; Luz, Boaz

    2001-06-01

    The ratio of 18O/ 16O in atmospheric oxygen depends on the isotopic composition of the substrate water used in photosynthesis and on discrimination against 18O in respiratory consumption. The current understanding of the composition of air O 2 attributes the magnitude of the respiratory fractionation to biochemical mechanisms alone. Thus the discrimination against 18O is assumed as 18‰ in normal dark respiration and 25‰ to 30‰ in cyanide resistant respiration. Here we report new results on the fractionation of O 2 isotopes in root respiration. The isotopic fractionation was determined from the change in δ 18O of air due to partial uptake by roots in closed containers. The discrimination in these experiments was in the range of 11.9‰ to 20.0‰ with an average of 14.5‰. This average is significantly less than the known discrimination in dark respiration. A simple diffusion-respiration model was used to explain the isotopic discrimination in roots. Available data show that O 2 concentration inside roots is low due to slow diffusion. As a result, due to diffusion and biological uptake at the consumption site inside the root, the overall discrimination is small. Root respiration is an important component of the global oxygen uptake. Our new result that the discrimination against 18O is less than generally thought indicates that the mechanisms affecting δ 18O of atmospheric oxygen should be re-evaluated.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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

  15. Oxygen determination in materials by 18O(p,αγ)15N nuclear reaction

    NASA Astrophysics Data System (ADS)

    Kumar, Sanjiv; Sunitha, Y.; Reddy, G. L. N.; Sukumar, A. A.; Ramana, J. V.; Sarkar, A.; Verma, Rakesh

    2016-07-01

    The paper presents a proton induced γ-ray emission method based on 18O(p,αγ)15N nuclear reaction to determine bulk oxygen in materials. The determination involves the measurement of 5.27 MeV γ-rays emitted following the de-excitation of 15N nuclei. A description of the energetics of the reaction is given to provide an insight into the origin of 5.27 MeV γ-rays. In addition, thick target γ-ray yields and the limits of detection are measured to ascertain the analytical potential of the reaction. The thick-target γ-ray yields are measured with a high purity germanium detector and a bismuth germanate detector at 0° as well as 90° angles in 3.0-4.2 MeV proton energy region. The best limit of detection of about 1.3 at.% is achieved at 4.2 MeV proton energy for measurements at 0° as well 90° angles with the bismuth germanate detector while the uncertainty in quantitative analysis is <8%. The reaction has a probing depth of several tens of microns. Interferences can arise from fluorine due to the occurrence of 19F(p,αγ)16O reaction that emits 6-7 MeV γ-rays. The analytical potential of the methodology is demonstrated by determining oxygen in several oxide as well as non-oxide materials.

  16. 18O-assisted dynamic metabolomics for individualized diagnostics and treatment of human diseases.

    PubMed

    Nemutlu, Emirhan; Zhang, Song; Juranic, Nenad O; Terzic, Andre; Macura, Slobodan; Dzeja, Petras

    2012-12-01

    Technological innovations and translation of basic discoveries to clinical practice drive advances in medicine. Today's innovative technologies enable comprehensive screening of the genome, transcriptome, proteome, and metabolome. The detailed knowledge, converged in the integrated "omics" (genomics, transcriptomics, proteomics, and metabolomics), holds an immense potential for understanding mechanism of diseases, facilitating their early diagnostics, selecting personalized therapeutic strategies, and assessing their effectiveness. Metabolomics is the newest "omics" approach aimed to analyze large metabolite pools. The next generation of metabolomic screening requires technologies for high throughput and robust monitoring of metabolite levels and their fluxes. In this regard, stable isotope 18O-based metabolite tagging technology expands quantitative measurements of metabolite levels and turnover rates to all metabolites that include water as a reactant, most notably phosphometabolites. The obtained profiles and turnover rates are sensitive indicators of energy and metabolic imbalances like the ones created by genetic deficiencies, myocardial ischemia, heart failure, neurodegenerative disorders, etc. Here we describe and discuss briefly the potential use of dynamic phosphometabolomic platform for disease diagnostics currently under development at Mayo Clinic.

  17. Analysis of microdissected neurons by 18O mass spectrometry reveals altered protein expression in Alzheimer's disease

    PubMed Central

    Hashimoto, Masakazu; Bogdanovic, Nenad; Nakagawa, Hiroyuki; Volkmann, Inga; Aoki, Mikio; Winblad, Bengt; Sakai, Jun; Tjernberg, Lars O

    2012-01-01

    Abstract It is evident that the symptoms of Alzheimer's disease (AD) are derived from severe neuronal damage, and especially pyramidal neurons in the hippocampus are affected pathologically. Here, we analysed the proteome of hippocampal neurons, isolated from post-mortem brains by laser capture microdissection. By using 18O labelling and mass spectrometry, the relative expression levels of 150 proteins in AD and controls were estimated. Many of the identified proteins are involved in transcription and nucleotide binding, glycolysis, heat-shock response, microtubule stabilization, axonal transport or inflammation. The proteins showing the most altered expression in AD were selected for immunohistochemical analysis. These analyses confirmed the altered expression levels, and showed in many AD cases a pathological pattern. For comparison, we also analysed hippocampal sections by Western blot. The expression levels found by this method showed poor correlation with the neuron-specific analysis. Hence, we conclude that cell-specific proteome analysis reveals differences in the proteome that cannot be detected by bulk analysis. PMID:21883897

  18. The ({sup 18}O, {sup 16}O) reaction as a probe for nuclear spectroscopy

    SciTech Connect

    Cappuzzello, F.; Bondì, M.; Nicolosi, D.; Tropea, S.; Agodi, A.; Carbone, D.; Cavallaro, M.; Cunsolo, A.; Borello-Lewin, T.; Rodrigues, M. R. D.; De Napoli, M.; Linares, R.

    2014-11-11

    The response of nuclei to the ({sup 18}O, {sup 16}O) two-neutron transfer reaction at 84 MeV incident energy has been systematically studied at the Catania INFN-LNS laboratory. The experiments were performed using several solid targets from light ({sup 9}Be, {sup 11}B, {sup 12,13}C, {sup 16}O, {sup 28}Si) to heavy ones ({sup 58,64}Ni, {sup 120}Sn, {sup 208}Pb). The {sup 16}O ejectiles were detected at forward angles by the MAGNEX magnetic spectrometer. Exploiting the large momentum acceptance (−10%, +14%) and solid angle (50 msr) of the spectrometer, energy spectra were obtained with a relevant yield up to about 20 MeV excitation energy. The application of the powerful trajectory reconstruction technique did allow to get energy spectra with energy resolution of about 150 keV and angular distributions with angular resolution better than 0.3°. A common feature observed with light nuclei is the appearance of unknown resonant structures at high excitation energy. The strong population of these latter together with the measured width can reveal the excitation of a collective mode connected with the transfer of a pair.

  19. 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.

  20. Improved online δ18O measurements of nitrogen- and sulfur-bearing organic materials and a proposed analytical protocol

    USGS Publications Warehouse

    Qi, H.; Coplen, T.B.; Wassenaar, L.I.

    2011-01-01

    It is well known that N2 in the ion source of a mass spectrometer interferes with the CO background during the δ18O measurement of carbon monoxide. A similar problem arises with the high-temperature conversion (HTC) analysis of nitrogenous O-bearing samples (e.g. nitrates and keratins) to CO for δ18O measurement, where the sample introduces a significant N2 peak before the CO peak, making determination of accurate oxygen isotope ratios difficult. Although using a gas chromatography (GC) column longer than that commonly provided by manufacturers (0.6 m) can improve the efficiency of separation of CO and N2 and using a valve to divert nitrogen and prevent it from entering the ion source of a mass spectrometer improved measurement results, biased δ18O values could still be obtained. A careful evaluation of the performance of the GC separation column was carried out. With optimal GC columns, the δ18O reproducibility of human hair keratins and other keratin materials was better than ±0.15 ‰ (n = 5; for the internal analytical reproducibility), and better than ±0.10 ‰ (n = 4; for the external analytical reproducibility).

  1. Stable isotopic studies on chitin. III. The D/H and 18O/ 16O ratios in arthropod chitin

    NASA Astrophysics Data System (ADS)

    Schimmelmann, Arndt; DeNiro, Michael J.

    1986-07-01

    Stable hydrogen and oxygen isotope ratios are presented for carbon-bound hydrogen and for oxygen in chitin-derived substrates from 57 arthropod species collected in 50 different locations or grown under controlled conditions in the laboratory. No systematic isotopic differences were found among Insecta, Crustacea, and Merostomata. The determination of infra- and interindividual isotopic variabilities in a lobster and among individuals of crustacean populations yielded small variances of about ±3 per mil for δD values and ±0.3 per mil for δ 18O values. Molting stage and sex of crustaceans showed no systematic effects on isotopic composition. The δD and δ 18O values of ambient water showed only weak correlations with the respective δ values of chitin-derived substrates. Positive correlation was observed between δD values and trophic level. No temperature effects on δ 18O and δD values from marine crustaceans were found that exceed the natural isotopic noise level. Taken together, these observations indicate that reconstruction of water isotopic composition from arthropod chitin δD and δ 18O values will require specific information about the habits and habitats of the species involved in the analysis.

  2. Influence of Changing Atmospheric Circulation on Precipitation δ 18O-Temperature Relations in Canada during the Holocene

    NASA Astrophysics Data System (ADS)

    Edwards, Thomas W. D.; Wolfe, Brent B.; Macdonald, Glen M.

    1996-11-01

    Postglacial precipitation δ 18O history has been reconstructed for two regions of Canada. Long-term shifts in the oxygen-isotope composition of annual precipitation (δ 18O p) in southern Ontario appear to have occurred with a consistent isotope-temperature relation throughout the past 11,500 14C yr. The modern isotope-temperature relation in central Canada near present boreal treeline evidently became established between 5000 and 4000 years ago, although the relation during the last glacial maximum and deglaciation may also have been similar to present. In the early Holocene, however, unusually high δ 18O papparently persisted, in spite of low temperature locally, probably associated with high zonal index. A rudimentary sensitivity analysis suggests that a small reduction in distillation of moisture in Pacific air masses traversing the western Cordillera, perhaps accompanied by a higher summer:winter precipitation ratio, could have been responsible for the observed effect. Equivalent isotope-temperature "anomalies" apparently occurred elsewhere in western North America in response to changing early-Holocene atmospheric circulation patterns, suggesting that a time-slice map of δ 18O pfor North America during this period might provide a useful target for testing and validation of atmospheric general circulation model simulations using isotopic water tracers.

  3. Pathways for nitrate release from an alpine watershed: determination using d15N and d18O

    USGS Publications Warehouse

    Campbell, Donald H.; Kendall, Carol; Chang, Cecily C.Y.; Silva, Steven R.; Tonnessen, Kathy A.

    2002-01-01

    [1] Snowpack, snowmelt, precipitation, surface water, and groundwater samples from the Loch Vale watershed in Colorado were analyzed for ??15N and ??18O of nitrate to determine the processes controlling the release of atmospherically deposited nitrogen from alpine and subalpine ecosystems. Although overlap was found between the ??15N(NO3) values for all water types (-4 to +6???), the ??18O(NO3) values for surface water and groundwater (+10 to +30???) were usually distinct from snowpack, snowmelt, and rainfall values (+40 to +70???). During snowmelt, ??18O(NO3) indicated that about half of the nitrate in stream water was the product of microbial nitrification; at other times that amount was greater than half. Springs emerging from talus deposits had high nitrate concentrations and a seasonal pattern in ??18O(NO3) that was similar to the pattern in the streams, indicating that shallow groundwater in talus deposits is a likely source of stream water nitrate. Only a few samples of surface water and groundwater collected during early snowmelt and large summer rain events had isotopic compositions that indicated most of the nitrate came directly from atmospheric deposition with no biological assimilation and release. This study demonstrates the value of the nitrate double-isotope technique for determining nitrogen-cycling processes and sources of nitrate in small, undisturbed watersheds that are enriched with inorganic nitrogen.

  4. A model of the 4000-year paleohydrology (δ18O) record from Lake Salpetén, Guatemala

    NASA Astrophysics Data System (ADS)

    Rosenmeier, Michael F.; Brenner, Mark; Hodell, David A.; Martin, Jonathan B.; Curtis, Jason H.; Binford, Michael W.

    2016-03-01

    A simple mass-balance model provides insights into the influence of catchment vegetation changes and climate variability on the hydrologic and stable oxygen isotope (δ18O) evolution of Lake Salpetén, in the Maya Lowlands of northern Guatemala. Model simulations for the last 4000 years incorporate pollen-inferred changes in vegetation cover and account for 75% of the variance observed in the biogenic carbonate δ18O record from a long lake sediment core. Vegetation-driven hydrologic changes, however, failed to capture the full range of late Holocene sediment core δ18O variability. The model requires incorporation of additional shifts in catchment vegetation cover, inclusion of regional precipitation changes, or likely both, to explain the fluctuations observed in the lake core oxygen isotope record. Climatic interpretation of the model results suggests that there was relatively greater moisture availability between about 2400 and 1800 years ago, but increased δ18O values centered at ~ 3300, 2900, 500, and 200 calendar years before present (cal yr BP) indicate abrupt precipitation decreases. There is evidence for protracted aridity between 1500 and 800 cal yr BP.

  5. A coral δ18O record of ENSO driven sea surface salinity variability in Fiji (south -western tropical Pacific)

    NASA Astrophysics Data System (ADS)

    Le Bec, Nolwenn; Julliet-Leclerc, Anne; Corrège, Thierry; Blamart, Dominique; Delcroix, Thierry

    2000-12-01

    The role of salinity in the dynamics and thermodynamics of El Niño - Southern Oscillation (ENSO) events is increasingly being investigated. However, instrumental records of salinity are scarce and short in the tropical Pacific, and there is a clear need for a reliable salinity proxy to extend our knowledge of ENSO through time. Here, we present 40 years of δ18O data from a Fiji coral (16°48‧S-177°27‧E). The coral δ18O signal integrates both sea surface temperature (SST) and sea surface salinity (SSS) variations. On a seasonal timescale, δ18O is mainly driven by SST changes whereas on an interannual ENSO timescale, it is almost exclusively affected by SSS variability. Since interannual fluctuations of SSS are rather well correlated to the Southern Oscillation Index in Fiji, coral δ18O can be used to reconstruct paleo-salinity data with some level of confidence. This may help for tracking ENSO influences back in time.

  6. First Experimental Measurement of the {sup 18}O(p,{alpha}){sup 15}N Reaction at Astrophysical Energies

    SciTech Connect

    La Cognata, M.; Sergi, M. L.; Spitaleri, C.; Cherubini, S.; Gulino, M.; Kiss, G.; Lamia, L.; Pizzone, R. G.; Romano, S.; Mukhamedzhanov, A.; Goldberg, V.; Tribble, R.; Coc, A.; Hammache, F.; Sereville, N. de; Tumino, A.

    2010-11-24

    The {sup 18}O(p,{alpha}){sup 15}N and {sup 17}O(p,{alpha}){sup 14}N reactions are of primary importance in several as-trophysical scenarios, including nucleosynthesis inside Asymptotic Giant Branch stars and oxygen and nitrogen isotopic ratios in meteorite grains. They are also key reactions to understand exotic systems such as R-Coronae Borealis stars and novae. Thus, the measurement of their cross sections in the low energy region can be crucial to reduce the nuclear uncertainty on theoretical predictions, because the resonance parameters are poorly determined. The Trojan Horse Method, in its newly developed form particularly suited to investigate low-energy resonances, has been applied to the {sup 2}H({sup 18}O,{alpha}{sup 15}N)n and {sup 2}H({sup 17}O,{alpha}{sup 14}N)n reactions to deduce the {sup 18}O(p,{alpha}){sup 15}N and {sup 17}O(p,{alpha}){sup 14}N cross sections at low energies. Resonances in the {sup 18}O(p,{alpha}){sup 15}N and {sup 17}O(p,{alpha}){sup 14}N excitation functions have been studied and the resonance parameters deduced.

  7. The evolution of Phanerozoic seawater - Isotope paleothermometry finds consensus on Early Paleozoic warmth and constant seawater δ18O

    NASA Astrophysics Data System (ADS)

    Grossman, E. L.; Henkes, G. A.; Passey, B. H.; Shenton, B.; Yancey, T. E.; Perez-Huerta, A.

    2015-12-01

    Evolution of metazoan life is closely linked to the Phanerozoic evolution of ocean temperatures and chemistry. Oxygen isotopic evidence for early Phanerozoic paleotemperatures has been equivocal, with decreasing δ18O values with age being interpreted as warmer early oceans, decreasing seawater δ18O with age, or increasing diagenetic alteration in older samples. Here we compare an updated compilation of oxygen isotope data for carbonate and phosphate fossils and microfossils (Grossman, 2012, Geol. Time Scale, Elsevier, 195-220) with a compilation of new and existing clumped isotope data. Importantly, these data are curated based on sample preservation with special consideration given to screening techniques, and tectonic and burial history. Burial history is critical in the preservation of carbonate clumped isotope temperatures in particular, which can undergo reordering in the solid state. We use a model derived for reordering kinetics (Henkes et al., 2014, Geochim. Cosmochim. Acta 139:362-382) to screen clumped isotope data for the effects of solid-state burial alteration. With minor but significant exceptions (Late Cretaceous, Early Triassic), average δ18O values (4 m.y. window, 2 m.y. steps) for post-Devonian brachiopods, belemnites, and foraminifera, representing tropical-subtropical surface ocean conditions, yield average isotopic temperatures below 30°C (assuming a seawater δ18O value [ -1‰ VSMOW] of an "ice-free" world). In contrast, Ordovician to Devonian data show sustained temperatures of 35-40°C. Likewise, isotopic paleotemperatures from conodont apatite, known to be resistant to isotopic exchange, follow the same pattern. Clumped isotope data derived from Paleozoic brachiopod shells that experienced minimal burial (< 100 °C) and <1% reordering according to the taxon-specific clumped isotope reordering model yield typical temperatures of 25-30°C for the Carboniferous, and 35-40°C for the Ordovician-Silurian. Inserting clumped temperatures and

  8. Fractional randomness

    NASA Astrophysics Data System (ADS)

    Tapiero, Charles S.; Vallois, Pierre

    2016-11-01

    The premise of this paper is that a fractional probability distribution is based on fractional operators and the fractional (Hurst) index used that alters the classical setting of random variables. For example, a random variable defined by its density function might not have a fractional density function defined in its conventional sense. Practically, it implies that a distribution's granularity defined by a fractional kernel may have properties that differ due to the fractional index used and the fractional calculus applied to define it. The purpose of this paper is to consider an application of fractional calculus to define the fractional density function of a random variable. In addition, we provide and prove a number of results, defining the functional forms of these distributions as well as their existence. In particular, we define fractional probability distributions for increasing and decreasing functions that are right continuous. Examples are used to motivate the usefulness of a statistical approach to fractional calculus and its application to economic and financial problems. In conclusion, this paper is a preliminary attempt to construct statistical fractional models. Due to the breadth and the extent of such problems, this paper may be considered as an initial attempt to do so.

  9. Coupled silicon-oxygen isotope fractionation traces Archaean silicification

    NASA Astrophysics Data System (ADS)

    Abraham, K.; Hofmann, A.; Foley, S. F.; Cardinal, D.; Harris, C.; Barth, M. G.; André, L.

    2011-01-01

    Silica alteration zones and cherts are a conspicuous feature of Archaean greenstone belts worldwide and provide evidence of extensive mobilisation of silica in the marine environment of the early Earth. In order to understand the process(es) of silicification we measured the silicon and oxygen isotope composition of sections of variably silicified basalts and overlying bedded cherts from the Theespruit, Hooggenoeg and Kromberg Formations of the Barberton Greenstone Belt, South Africa. The δ30Si and δ18O values of bulk rock increase with increasing amount of silicification from unsilicified basalts (-0.64‰ < δ30Si < -0.01‰ and + 8.6‰ < δ18O < + 11.9‰) to silicified basalts (δ30Si and δ18O values as high as + 0.81‰ and + 15.6‰, respectively). Cherts generally have positive isotope ratios (+ 0.21‰ < δ30Si < + 1.05‰ and + 10.9 < δ18O < + 17.1), except two cherts, which have negative δ30Si values, but high δ18O (up to + 19.5‰). The pronounced positive correlations between δ30Si, δ18O and SiO2 imply that the isotope variation is driven by the silicification process which coevally introduced both 18O and 30Si into the basalts. The oxygen isotope variation in the basalts from about 8.6‰ to 15.6‰ is likely to represent temperature-dependent isotope fractionation during alteration. Our proposed model for the observed silicon isotope variation relies on a temperature-controlled basalt dissolution vs. silica deposition process.

  10. Clumped Isotope Verification of δ18O-Based Freshwater Mussel Shell Growth Chronology for a High-Resolution Climate and River Discharge Record

    NASA Astrophysics Data System (ADS)

    VanPlantinga, A.; Grossman, E. L.; Passey, B. H.; Randklev, C.

    2015-12-01

    Isotope profiles in freshwater mussel shells can be used to reconstruct climate, water source, and river discharge, but problems arise from variable water temperature and δ18O. To resolve this complexity and expand the application of isotope sclerochronology to the study of past river systems, we measured δ18O and Δ47 in two common freshwater mussel species from the Brazos River in Texas. To compare the environmental record with the shell record and develop a sclerochronology, weekly water temperature and δ18O data were collected from the Brazos River near College Station from January 2012 to August 2013. The river data reveal complex, irregular patterns for predicted aragonite δ18O. Comparing δ18O profiles from micromilled transects (70-200 µm increments) of coeval shell growth within and between shells yielded consistent patterns. Shell δ18O can be accurately matched to predicted δ18O, providing a chronology of shell growth. However, without a water temperature and δ18O record, interpreting a sclerochronology would be impossible. Shell Δ47 can potentially provide a seasonal chronology to verify the δ18O sclerochronology, which would be invaluable for the use of δ18O sclerochronology in historical and ancient shells. For Δ47 analyses, samples were taken at 0.5 mm resolution in presumed seasonal dark and light growth bands. Clumped temperatures range between 21 and 35 ± 4˚C (Henkes et al., 2013) and track the river temperature record, supporting the interpreted shell δ18O chronology. Shell Δ47-calculated water δ18O values range from -1.2 to 1.5 ± 0.9‰ and match river δ18O. High-resolution shell δ18O profiles combined with Δ47 temperatures can reconstruct a weekly history of water δ18O, and with the observed river discharge vs. water δ18O relation, produce a qualitative record of river discharge. These analytical techniques applied to a historical Brazos River mussel shell collected prior to dam construction reveal weekly records of

  11. A new derivatization method for δ18O analysis of individual carbohydrates with GC-Pyrolysis-IRMS

    NASA Astrophysics Data System (ADS)

    Lehmann, M. M.; Siegwolf, R. T.; Saurer, M.; Blees, J.; Fischer, M.; Zech, M.

    2015-12-01

    Compound specific isotope analysis (CSIA) with gas chromatography coupled to an isotope ratio mass spectrometer (GC-Pyr-IRMS) is nowadays a powerful tool that is widely used by a broad spectrum of research fields to investigate the isotopic signature of diverse metabolites. While many CSIA methods for carbon, hydrogen, and nitrogen isotopes are known, CSIA methods for the analysis of oxygen isotopes (δ18O) are still not widely established. Especially, reliable and precise methods for the δ18O analyses of individual carbohydrates are scarce, which is caused by the highly sensitive nature of the sugars. However, carbohydrates are important components of living organisms, source for many biochemical reactions, and can be found in all organisms, in soils, sediments, and in air. Thus, a method, allowing the investigation of the 18O/16O ratio in carbohydrates will enhance the scope of research using isotopes. We developed a new and easy to handle derivatization method to determine δ18O in carbohydrates with GC-Pyr-IRMS that consists of a catalyzed one-pot reaction in acetonitrile, resulting in complete methylation of all sugar hydroxyl groups within 24 hours, with silver oxide as the proton acceptor and methyl iodide as the methyl group carrier. Results derived from standard material show unrivalled δ18O precision ranging from about 0.2 to 1.1 ‰ for different individual carbohydrates of different classes and a generally very good accuracy, with a narrow range of 0.2 ‰ around the reference value, despite of high area variations. We applied this method on real samples, demonstrating that the method can commonly be used for analyzing honey samples, and for the analyses of more complex carbohydrate mixtures from plant leaves, including glucose, fructose, pinitol, and sucrose. Our new method may be used for food, beverage, and medical applications, as well as for biogeochemical and paleoclimatic sciences.

  12. How yield relates to ash content, Δ13C and Δ18O in maize grown under different water regimes

    PubMed Central

    Cabrera-Bosquet, Llorenç; Sánchez, Ciro; Araus, José Luis

    2009-01-01

    Background and Aims Stable isotopes have proved a valuable phenotyping tool when breeding for yield potential and drought adaptation; however, the cost and technical skills involved in isotope analysis limit its large-scale application in breeding programmes. This is particularly so for Δ18O despite the potential relevance of this trait in C4 crops. The accumulation of minerals (measured as ash content) has been proposed as an inexpensive way to evaluate drought adaptation and yield in C3 cereals, but little is known of the usefulness of this measure in C4 cereals such as maize (Zea mays). The present study investigates how yield relates to ash content, Δ13C and Δ18O, and evaluates the use of ash content as an alternative or complementary criterion to stable isotopes in assessing yield potential and drought resistance in maize. Methods A set of tropical maize hybrids developed by CIMMYT were subjected to different water availabilities, in order to induce water stress during the reproductive stages under field conditions. Ash content and Δ13C were determined in leaves and kernels. In addition, Δ18O was measured in kernels. Key Results Water regime significantly affected yield, ash content and stable isotopes. The results revealed a close relationship between ash content in leaves and the traits informing about plant water status. Ash content in kernels appeared to reflect differences in sink–source balance. Genotypic variation in grain yield was mainly explained by the combination of ash content and Δ18O, whilst Δ13C did not explain a significant percentage of such variation. Conclusions Ash content in leaves and kernels proved a useful alternative or complementary criterion to Δ18O in kernels for assessing yield performance in maize grown under drought conditions. PMID:19773272

  13. Isotopic Water Analyzer for Highly Precise Measurements of δ2H, δ18O, and δ17O

    NASA Astrophysics Data System (ADS)

    Berman, E. S.; Fortson, S.; Snaith, S.; Gupta, M.

    2012-12-01

    Measurements of the stable isotope ratios (δ2H, δ18O and δ17O) of both liquid water and water vapor are widely used in hydrology, atmospheric sciences, and biogeochemistry to determine the migration of water through an ecosystem. Previously, discrete samples were collected (or condensed) and transported to an isotope ratio mass spectrometer for characterization. Due to the expense and labor associated with such sampling, isotope studies were generally limited in scope and in temporal resolution. We report on the continued development of a field-portable Isotopic Water Analyzer that exploits cavity-enhanced absorption spectrometry (e.g. Off-Axis ICOS) to accurately and rapidly quantify δ2H, δ18O and δ17O of both liquid water and water vapor. The instrument is thermally-controlled to better than ±8 mK and is capable of measuring over 90 liquid samples/day with δ2H, δ18O and δ17O precisions exceeding ±0.2 ‰, ±0.05 ‰, and ±0.06 ‰ respectively. Subsequent averaging yields δ2H, δ18O and δ17O precisions exceeding ±0.077 ‰, ±0.023 ‰, and ±0.03 ‰ respectively with over 22 samples/day. The accuracy of the liquid analyzer was confirmed over a very wide dynamic range (δ2H = -455 to +671 ‰ with comparable δ18O and δ17O values) by direct comparison to isotope ratio mass spectrometry. Moreover, the ability to directly measure 17O-excess, vapor samples, and unnatural waters (e.g. plant water, soil water, urine, blood, saliva…) will also be presented.

  14. Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

    USGS Publications Warehouse

    Ufnar, David F.; Gonzalez, Luis A.; Ludvigson, Greg A.; Brenner, Richard L.; Witzkes, Brian J.

    2004-01-01

    Meteoric sphaerosiderite lines (MSLs), defined by invariant ??18O and variable ??13C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre-scale FeCO3 nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well-preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO3) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca2+, Mg2+ and Mn2+ for Fe2+. Examples of diagenetically altered Cretaceous sphaerosiderite-bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic ??18O and ??13C values are preserved. All three units contain poikilotopic calcite cements with significantly different ??18O and ??13C values from the co-occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant ??18O vs. ??13C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric ??18O and ??13C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end-member compositions. Modelled hyperbolic fluid mixing curves for the

  15. Probabilistic Stack of 180 Plio-Pleistocene Benthic δ18O Records Constructed Using Profile Hidden Markov Models

    NASA Astrophysics Data System (ADS)

    Lisiecki, L. E.; Ahn, S.; Khider, D.; Lawrence, C.

    2015-12-01

    Stratigraphic alignment is the primary way in which long marine climate records are placed on a common age model. We previously presented a probabilistic pairwise alignment algorithm, HMM-Match, which uses hidden Markov models to estimate alignment uncertainty and apply it to the alignment of benthic δ18O records to the "LR04" global benthic stack of Lisiecki and Raymo (2005) (Lin et al., 2014). However, since the LR04 stack is deterministic, the algorithm does not account for uncertainty in the stack. Here we address this limitation by developing a probabilistic stack, HMM-Stack. In this model the stack is a probabilistic inhomogeneous hidden Markov model, a.k.a. profile HMM. The HMM-stack is represented by a probabilistic model that "emits" each of the input records (Durbin et al., 1998). The unknown parameters of this model are learned from a set of input records using the expectation maximization (EM) algorithm. Because the multiple alignment of these records is unknown and uncertain, the expected contribution of each input point to each point in the stack is determined probabilistically. For each time step in the HMM-stack, δ18O values are described by a Gaussian probability distribution. Available δ18O records (N=180) are employed to estimate the mean and variance of δ18O at each time point. The mean of HMM-Stack follows the predicted pattern of glacial cycles with increased amplitude after the Pliocene-Pleistocene boundary and also larger and longer cycles after the mid-Pleistocene transition. Furthermore, the δ18O variance increases with age, producing a substantial loss in the signal-to-noise ratio. Not surprisingly, uncertainty in alignment and thus estimated age also increase substantially in the older portion of the stack.

  16. Stable isotope time-series in mammalian teeth: In situ δ18O from the innermost enamel layer

    NASA Astrophysics Data System (ADS)

    Blumenthal, Scott A.; Cerling, Thure E.; Chritz, Kendra L.; Bromage, Timothy G.; Kozdon, Reinhard; Valley, John W.

    2014-01-01

    Stable carbon and oxygen isotope ratios in mammalian tooth enamel are commonly used to understand the diets and environments of modern and fossil animals. Isotope variation during the period of enamel formation can be recovered by intra-tooth microsampling along the direction of growth. However, conventional sampling of the enamel surface provides highly time-averaged records in part due to amelogenesis. We use backscattered electron imaging in the scanning electron microscope (BSE-SEM) to evaluate enamel mineralization in developing teeth from one rodent and two ungulates. Gray levels from BSE-SEM images suggest that the innermost enamel layer, <20 μm from the enamel-dentine junction, is highly mineralized early in enamel maturation and therefore may record a less attenuated isotopic signal than other layers. We sampled the right maxillary incisor from a woodrat subjected to an experimentally induced water-switch during the period of tooth development, and demonstrate that secondary ion mass spectrometry (SIMS) can be used to obtain δ18O values with 4-5-μm spots from mammalian tooth enamel. We also demonstrate that SIMS can be used to discretely sample the innermost enamel layer, which is too narrow for conventional microdrilling or laser ablation. An abrupt δ18O switch of 16.0‰ was captured in breath CO2, a proxy for body water, while a laser ablation enamel surface intra-tooth profile of the left incisor captured a δ18O range of 12.1‰. The innermost enamel profile captured a δ18O range of 15.7‰, which approaches the full magnitude of δ18O variation in the input signal. This approach will likely be most beneficial in taxa such as large mammalian herbivores, whose teeth are characterized by less rapid mineralization and therefore greater attenuation of the enamel isotope signal.

  17. Mass-independent fractionation of oxygen isotopes during thermal decomposition of carbonates

    PubMed Central

    Miller, Martin F.; Franchi, Ian A.; Thiemens, Mark H.; Jackson, Teresa L.; Brack, André; Kurat, Gero; Pillinger, Colin T.

    2002-01-01

    Nearly all chemical processes fractionate 17O and 18O in a mass-dependent way relative to 16O, a major exception being the formation of ozone from diatomic oxygen in the presence of UV radiation or electrical discharge. Investigation of oxygen three-isotope behavior during thermal decomposition of naturally occurring carbonates of calcium and magnesium in vacuo has revealed that, surprisingly, anomalous isotopic compositions are also generated during this process. High-precision measurements of the attendant three-isotope fractionation line, and consequently the magnitude of the isotopic anomaly (Δ17O), demonstrate that the slope of the line is independent of the nature of the carbonate but is controlled by empirical factors relating to the decomposition procedure. For a slope identical to that describing terrestrial silicates and waters (0.5247 ± 0.0007 at the 95% confidence level), solid oxides formed during carbonate pyrolysis fit a parallel line offset by −0.241 ± 0.042‰. The corresponding CO2 is characterized by a positive offset of half this magnitude, confirming the mass-independent nature of the fractionation. Slow, protracted thermolysis produces a fractionation line of shallower slope (0.5198 ± 0.0007). These findings of a 17O anomaly being generated from a solid, and solely by thermal means, provide a further challenge to current understanding of the nature of mass-independent isotopic fractionation. PMID:12167677

  18. (18)O spatial patterns of vein xylem water, leaf water, and dry matter in cotton leaves.

    PubMed

    Gan, Kim Suan; Wong, Suan Chin; Yong, Jean Wan Hong; Farquhar, Graham Douglas

    2002-10-01

    Three leaf water models (two-pool model, Péclet effect, and string-of-lakes) were assessed for their robustness in predicting leaf water enrichment and its spatial heterogeneity. This was achieved by studying the (18)O spatial patterns of vein xylem water, leaf water, and dry matter in cotton (Gossypium hirsutum) leaves grown at different humidities using new experimental approaches. Vein xylem water was collected from intact transpiring cotton leaves by pressurizing the roots in a pressure chamber, whereas the isotopic content of leaf water was determined without extracting it from fresh leaves with the aid of a purpose-designed leaf punch. Our results indicate that veins have a significant degree of lateral exchange with highly enriched leaf water. Vein xylem water is thus slightly, but progressively enriched in the direction of water flow. Leaf water enrichment is dependent on the relative distances from major veins, with water from the marginal and intercostal regions more enriched and that next to veins and near the leaf base more depleted than the Craig-Gordon modeled enrichment of water at the sites of evaporation. The spatial pattern of leaf water enrichment varies with humidity, as expected from the string-of-lakes model. This pattern is also reflected in leaf dry matter. All three models are realistic, but none could fully account for all of the facets of leaf water enrichment. Our findings acknowledge the presence of capacitance in the ground tissues of vein ribs and highlight the essential need to incorporate Péclet effects into the string-of-lakes model when applying it to leaves. PMID:12376664

  19. Dilution space ratio of 2H and 18O of doubly labeled water method in humans.

    PubMed

    Sagayama, Hiroyuki; Yamada, Yosuke; Racine, Natalie M; Shriver, Timothy C; Schoeller, Dale A

    2016-06-01

    Variation of the dilution space ratio (Nd/No) between deuterium ((2)H) and oxygen-18 ((18)O) impacts the calculation of total energy expenditure (TEE) by doubly labeled water (DLW). Our aim was to examine the physiological and methodological sources of variation of Nd/No in humans. We analyzed data from 2,297 humans (0.25-89 yr old). This included the variables Nd/No, total body water, TEE, body mass index (BMI), and percent body fat (%fat). To differentiate between physiologic and methodologic sources of variation, the urine samples from 54 subjects were divided and blinded and analyzed separately, and repeated DLW dosing was performed in an additional 55 participants after 6 mo. Sex, BMI, and %fat did not significantly affect Nd/No, for which the interindividual SD was 0.017. The measurement error from the duplicate urine sample sets was 0.010, and intraindividual SD of Nd/No in repeats experiments was 0.013. An additional SD of 0.008 was contributed by calibration of the DLW dose water. The variation of measured Nd/No in humans was distributed within a small range and measurement error accounted for 68% of this variation. There was no evidence that Nd/No differed with respect to sex, BMI, and age between 1 and 80 yr, and thus use of a constant value is suggested to minimize the effect of stable isotope analysis error on calculation of TEE in the DLW studies in humans. Based on a review of 103 publications, the average dilution space ratio is 1.036 for individuals between 1 and 80 yr of age. PMID:26989221

  20. Experimental Energy Levels of HD18O and D_218O

    NASA Astrophysics Data System (ADS)

    Mikhailenko, S. N.; Naumenko, O. V.; Tashkun, S. A.; Liu, A.-W.; Hu, S.-M.

    2010-06-01

    Extended sets of experimental energy levels of HD18O and D_218O have been obtained as the result of the analysis of recent high-resolution spectra and previously reported data. Spectra of the enriched by deuterium and oxygen-18 water samples were recorded with a Bruker IFS 120HR spectrometer at room temperature in the 1000 - 9200 cm-1 range a,b for this purpose. The RITZ code h was used for analysis of the rotation-vibration transitions and the energy levels determination. New energy levels as well as comparison with previous experimental and theoretical studies will be presented. This work was supported by Grant nos. 06-03-39014 and 10-05-91176 of RFBR (Russia) and by Grant nos. 20903085 and 10574124 of NSFC (China). Work of SNM and SAT was also partly supported by CRDF (USA) Grant RUG1-2954-TO-09 and by RFBR. Grant 09-05-92508. A.-W. Liu et al., J. Mol. Spectrosc. 237, 149-162 (2006). H.-Y. Ni et al., Mol. Phys. 106, 1793-1801 (2008). J. Bellet et al., J. Mol. Spectrosc. 47, 388-402 (1973). J.W.C. Johns, J. Opt. Soc. Am. B2, 1340-1354 (1985). R.A. Toth, J. Mol. Spectrosc. 162, 41-54 (1993). W.F. Wang et al., J. Mol. Spectrosc. 176, 226-228 (1996). R.A. Toth, J. Mol. Structure, 742, 49-68 (2005). S.N. Mikhailenko et al., JQSRT, 110, 597-608 (2009). A. Liu et al., JQSRT, 110, 1781-1800 (2009). O.V. Naumenko et al., JQSRT, 111, 36-44 (2010).

  1. An Appetite for Fractions

    ERIC Educational Resources Information Center

    Wilkerson, Trena L.; Bryan, Tommy; Curry, Jane

    2012-01-01

    This article describes how using candy bars as models gives sixth-grade students a taste for learning to represent fractions whose denominators are factors of twelve. Using paper models of the candy bars, students explored and compared fractions. They noticed fewer different representations for one-third than for one-half. The authors conclude…

  2. Stable isotopes (δ 18O and δ 13C), trace and minor element compositions of Recent scleractinians and Last Glacial bivalves at the Santa Maria di Leuca deep-water coral province, Ionian Sea

    NASA Astrophysics Data System (ADS)

    Correa, Matthias López; Montagna, Paolo; Vendrell-Simón, Begoña; McCulloch, Malcolm; Taviani, Marco

    2010-03-01

    ' vital effect. The intercept of the δ 13C/δ 18O correlation line with the δ 13C DIC-composition permits recognition of δ 18O equilibrium values of aragonite and thus reconstruction of water temperatures despite strong disequilibrium precipitation. Since the environmental parameters ( T, S and δ 18O sw) are stable, the entire isotopic signal of the coral must be driven by biological fractionation and might reflect growth speed variations, potentially related to pH variations and changes in the saturation state of the calcifying fluid or seasonally varying nutrient availability. Laser ablation tracks show a trace element composition dependent to microstructural zones (fibrous aragonite vs. centres of calcification). The parabolic relation of the classical temperature proxies Mg/Ca and U/Ca point to trace element vital effects, rendering them unreliable in L. pertusa. The P/Ca ratio shows similar values as Desmophyllum dianthus, for which a linear dependence with seawater phosphate (DIP) has been previously demonstrated. Consequently L. pertusa might be an additional nutrient recorder at bathyal depths. From the same site we also analysed the stable isotopic composition of the Last Glacial pectinid bivalve Pseudamussium peslutrae, which has been radiocarbon-dated (AMS- 14C) at 26.3 ka 14C yr BP. The isotope values of the shell calcite document a strongly differing glacial temperature-salinity regime preceding the Holocene coral growth above a prominent hiatus.

  3. Tracking photosynthetic sulfide oxidation in a meromictic lake using sulfate δ34S and δ18O

    NASA Astrophysics Data System (ADS)

    Gilhooly, W. P.; Reinhard, C.; Lyons, T. W.; Glass, J. B.

    2012-12-01

    Phototrophic sulfur bacteria oxidize sulfide and fix carbon dioxide in the presence of sunlight without producing oxygen. Environmental conditions in the Paleo- and Mesoproterozoic, when atmospheric oxygen concentrations were at low levels and portions of the oceans were anoxic and sulfidic (euxinic), were conducive to widespread carbon fixation by anoxygenic photosynthesis. This pathway may have helped sustain euxinic conditions in the Proterozoic water column. With limited organic biomarker and geochemical evidence for widespread production of anoxygenic phototrophs, however, additional proxies are needed to fingerprint paleoecological and biogeochemical signals associated with photic zone euxinia. Paired δ34S and δ18O from ancient sulfates (gypsum, barite, or CAS) may offer an added constraint on the history and ecological dominance of photosynthetic S-oxidation. Sulfate-oxygen can fractionate during sulfate reduction, but the extent of isotopic enrichment is controlled either by kinetic isotope effects imparted during intracellular enzymatic steps or equilibrium oxygen exchange with ambient water. An improved understanding of these processes can be gained from modern natural environments. Mahoney Lake is a density-stratified lake located within the White Lake Basin of British Columbia. The euxinic water column supports a dense plate of purple sulfur bacteria (Amoebobacter purpureus) that thrives where free sulfide intercepts the photic zone at ~7 m water depth. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within this meromictic lake. Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S >50‰) are consistent with sulfate reduction in both the sediments and the anoxic

  4. 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

  5. HIGH-PRECISION C{sup 17}O, C{sup 18}O, AND C{sup 16}O MEASUREMENTS IN YOUNG STELLAR OBJECTS: ANALOGUES FOR CO SELF-SHIELDING IN THE EARLY SOLAR SYSTEM

    SciTech Connect

    Smith, Rachel L.; Young, Edward D.; Pontoppidan, Klaus M.; Morris, Mark R.; Van Dishoeck, Ewine F. E-mail: pontoppi@gps.caltech.edu E-mail: morris@astro.ucla.edu

    2009-08-10

    Using very high resolution ({lambda}/{delta}{lambda} {approx} 95 000) 4.7 {mu}m fundamental and 2.3 {mu}m overtone rovibrational CO absorption spectra obtained with the Cryogenic Infrared Echelle Spectrograph infrared spectrometer on the Very Large Telescope (VLT), we report detections of four CO isotopologues-C{sup 16}O, {sup 13}CO, C{sup 18}O, and the rare species, C{sup 17}O-in the circumstellar environment of two young protostars: VV CrA, a binary T Tauri star in the Corona Australis molecular cloud, and Reipurth 50, an intermediate-mass FU Ori star in the Orion Molecular Cloud. We argue that the observed CO absorption lines probe a protoplanetary disk in VV CrA, and a protostellar envelope in Reipurth 50. All CO line profiles are spectrally resolved, with intrinsic line widths of {approx}3-4 km s{sup -1} (FWHM), permitting direct calculation of CO oxygen isotopologue ratios with 5%-10% accuracy. The rovibrational level populations for all species can be reproduced by assuming that CO absorption arises in two temperature regimes. In the higher temperature regime, in which the column densities are best determined, the derived oxygen isotope ratios in VV CrA are: [C{sup 16}O]/[C{sup 18}O] =690 {+-} 30; [C{sup 16}O]/[C{sup 17}O] =2800 {+-} 300, and [C{sup 18}O]/[C{sup 17}O]=4.1 {+-} 0.4. For Reipurth 50, we find [C{sup 16}O]/[C{sup 18}O] =490 {+-} 30; [C{sup 16}O]/[C{sup 17}O] =2200 {+-} 150, [C{sup 18}O]/[C{sup 17}O] = 4.4 {+-} 0.2. For both objects, {sup 12}C/{sup 13}C are on the order of 100, nearly twice the expected interstellar medium (ISM) ratio. The derived oxygen abundance ratios for the VV CrA disk show a significant mass-independent deficit of C{sup 17}O and C{sup 18}O relative to C{sup 16}O compared to ISM baseline abundances. The Reipurth 50 envelope shows no clear differences in oxygen CO isotopologue ratios compared with the local ISM. A mass-independent fractionation can be interpreted as being due to selective photodissociation of CO in the disk

  6. Gallotannin-rich Caesalpinia spinosa fraction decreases the primary tumor and factors associated with poor prognosis in a murine breast cancer model

    PubMed Central

    2013-01-01

    Background Several treatment alternatives are available for primary breast cancer, although those for metastatic disease or inflammation associated with tumor progression are ineffective. Therefore, there is a great need for new therapeutic alternatives capable of generating an immune response against residual tumor cells, thus contributing to eradication of micrometastases and cancer stem cells. The use of complex natural products is an excellent therapeutic alternative widely used by Chinese, Hindu, Egyptian, and ancestral Latin-American Indian populations. Methods The present study evaluated cytotoxic, antitumor, and tumor progression activities of a gallotannin-rich fraction derived from Caesalpinia spinosa (P2Et). The parameters evaluated in vitro were mitochondrial membrane depolarization, phosphatidylserine externalization, caspase 3 activation, DNA fragmentation, and clonogenic activity. The parameters evaluated in vivo were tumor growth, leukocyte number, metastatic cell number, and cytokine production by flow cytometry. Results The in vitro results showed that the P2Et fraction induced apoptosis with mitochondrial membrane potential loss, phosphatidylserine externalization, caspase 3 activation, DNA fragmentation, and decreased clonogenic capacity of 4T1 cells. In vivo, the P2Et fraction induced primary tumor reduction in terms of diameter and weight in BALB/c mice transplanted with 4T1 cells and decreased numbers of metastatic cells, mainly in the spleen. Furthermore, decreases in the number of peripheral blood leukocytes (leukemoid reaction) and interleukin 6 (IL-6) serum levels were found, which are events associated with a poor prognosis. The P2Et fraction exerts its activity on the primary tumor, reduces cell migration to distant organs, and decreases IL-6 serum levels, implying tumor microenvironment mechanisms. Conclusions Overall, the P2Et fraction lessens risk factors associated with tumor progression and diminishes primary tumor size, showing

  7. Listening in on the past: what can otolith δ18O values really tell us about the environmental history of fishes?

    PubMed

    Darnaude, Audrey M; Sturrock, Anna; Trueman, Clive N; Mouillot, David; Campana, Steven E; Hunter, Ewan

    2014-01-01

    Oxygen isotope ratios from fish otoliths are used to discriminate marine stocks and reconstruct past climate, assuming that variations in otolith δ18O values closely reflect differences in temperature history of fish when accounting for salinity induced variability in water δ18O. To investigate this, we exploited the environmental and migratory data gathered from a decade using archival tags to study the behaviour of adult plaice (Pleuronectes platessa L.) in the North Sea. Based on the tag-derived monthly distributions of the fish and corresponding temperature and salinity estimates modelled across three consecutive years, we first predicted annual otolith δ18O values for three geographically discrete offshore sub-stocks, using three alternative plausible scenarios for otolith growth. Comparison of predicted vs. measured annual δ18O values demonstrated >96% correct prediction of sub-stock membership, irrespective of the otolith growth scenario. Pronounced inter-stock differences in δ18O values, notably in summer, provide a robust marker for reconstructing broad-scale plaice distribution in the North Sea. However, although largely congruent, measured and predicted annual δ18O values did not fully match [ corrected]. Small, but consistent, offsets were also observed between individual high-resolution otolith δ18O values measured during tag recording time and corresponding δ18O predictions using concomitant tag-recorded temperatures and location-specific salinity estimates. The nature of the shifts differed among sub-stocks, suggesting specific vital effects linked to variation in physiological response to temperature. Therefore, although otolith δ18O in free-ranging fish largely reflects environmental temperature and salinity, we counsel prudence when interpreting otolith δ18O data for stock discrimination or temperature reconstruction until the mechanisms underpinning otolith δ18O signature acquisition, and associated variation, are clarified. PMID

  8. Listening In on the Past: What Can Otolith δ18O Values Really Tell Us about the Environmental History of Fishes?

    PubMed Central

    Darnaude, Audrey M.; Sturrock, Anna; Trueman, Clive N.; Mouillot, David; EIMF; Campana, Steven E.; Hunter, Ewan

    2014-01-01

    Oxygen isotope ratios from fish otoliths are used to discriminate marine stocks and reconstruct past climate, assuming that variations in otolith δ18O values closely reflect differences in temperature history of fish when accounting for salinity induced variability in water δ18O. To investigate this, we exploited the environmental and migratory data gathered from a decade using archival tags to study the behaviour of adult plaice (Pleuronectes platessa L.) in the North Sea. Based on the tag-derived monthly distributions of the fish and corresponding temperature and salinity estimates modelled across three consecutive years, we first predicted annual otolith δ18O values for three geographically discrete offshore sub-stocks, using three alternative plausible scenarios for otolith growth. Comparison of predicted vs. measured annual δ18O values demonstrated >96% correct prediction of sub-stock membership, irrespective of the otolith growth scenario. Pronounced inter-stock differences in δ18O values, notably in summer, provide a robust marker for reconstructing broad-scale plaice distribution in the North Sea. However, although largely congruent, measured and predicted annual δ18O values of did not fully match. Small, but consistent, offsets were also observed between individual high-resolution otolith δ18O values measured during tag recording time and corresponding δ18O predictions using concomitant tag-recorded temperatures and location-specific salinity estimates. The nature of the shifts differed among sub-stocks, suggesting specific vital effects linked to variation in physiological response to temperature. Therefore, although otolith δ18O in free-ranging fish largely reflects environmental temperature and salinity, we counsel prudence when interpreting otolith δ18O data for stock discrimination or temperature reconstruction until the mechanisms underpinning otolith δ18O signature acquisition, and associated variation, are clarified. PMID:25279667

  9. Listening in on the past: what can otolith δ18O values really tell us about the environmental history of fishes?

    PubMed

    Darnaude, Audrey M; Sturrock, Anna; Trueman, Clive N; Mouillot, David; Campana, Steven E; Hunter, Ewan

    2014-01-01

    Oxygen isotope ratios from fish otoliths are used to discriminate marine stocks and reconstruct past climate, assuming that variations in otolith δ18O values closely reflect differences in temperature history of fish when accounting for salinity induced variability in water δ18O. To investigate this, we exploited the environmental and migratory data gathered from a decade using archival tags to study the behaviour of adult plaice (Pleuronectes platessa L.) in the North Sea. Based on the tag-derived monthly distributions of the fish and corresponding temperature and salinity estimates modelled across three consecutive years, we first predicted annual otolith δ18O values for three geographically discrete offshore sub-stocks, using three alternative plausible scenarios for otolith growth. Comparison of predicted vs. measured annual δ18O values demonstrated >96% correct prediction of sub-stock membership, irrespective of the otolith growth scenario. Pronounced inter-stock differences in δ18O values, notably in summer, provide a robust marker for reconstructing broad-scale plaice distribution in the North Sea. However, although largely congruent, measured and predicted annual δ18O values did not fully match [ corrected]. Small, but consistent, offsets were also observed between individual high-resolution otolith δ18O values measured during tag recording time and corresponding δ18O predictions using concomitant tag-recorded temperatures and location-specific salinity estimates. The nature of the shifts differed among sub-stocks, suggesting specific vital effects linked to variation in physiological response to temperature. Therefore, although otolith δ18O in free-ranging fish largely reflects environmental temperature and salinity, we counsel prudence when interpreting otolith δ18O data for stock discrimination or temperature reconstruction until the mechanisms underpinning otolith δ18O signature acquisition, and associated variation, are clarified.

  10. Specific coupling between the 13-keto carbonyl and chlorin skeletal vibrational modes of synthetic 13 1- 18O-(un)labelled metallochlorophyll derivatives

    NASA Astrophysics Data System (ADS)

    Morishita, Hidetada; Tamiaki, Hitoshi

    2009-03-01

    Metal complexes of methyl 13 1- 18O-labelled pyropheophorbide- a1-M- 18O (M = Zn, Cu and Ni) were prepared by metallation of the 18O-labelled free base ( 1- 18O) and 18O-labelling of unlabelled nickel complex ( 1-Ni). The FT-IR spectra of 1-Zn and 1-Zn- 18O in CH 2Cl 2 showed that the 13-keto carbonyl stretching vibration mode moved to about a 30-cm -1 lower wavenumber by 18O-labelling of the 13 1-oxo moiety. In 1-Cu- 18O and 1-Ni- 18O, the 13-C dbnd 18O stretching modes were close to the highest-energy wavenumber mode of chlorin skeletal C-C/C-N vibrations at around 1650 cm -1 and they were coupled in CH 2Cl 2 to give two split IR bands (Fermi resonance). A similar coupling was observed in the resonance Raman scattering of 1-Ni- 18O in the solid state. The hydrogen-bonded 13-C dbnd 16O vibration mode of 1-Ni similarly coupled with the skeletal C-C/C-N mode in CCl 4 containing 1% (v/v) 1,1,1,3,3,3-hexafluoro-2-propanol, while such a coupling was not observed in a neat CCl 4 solution of 1-Ni possessing the 13-C dbnd 16O free from any interaction. The skeletal C-C/C-N band selectively coupled with the 13-C dbnd O, not with the 3-C dbnd O, when the difference in their peak maxima was less than 20 cm -1.

  11. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681-5337 cm-1 region