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Sample records for 18o 2h 3h

  1. 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

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

    SciTech Connect

    Smith, Brian; Menchaca, Leticia

    1999-01-01

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

  3. 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.

  4. Water-Isotopes (2H, 3H, 18O) to trace the source and timing of recharge in a fractured granite aquifer in Western Kenya, Africa

    NASA Astrophysics Data System (ADS)

    Kralik, Martin; Whylidal, Stefan; Asunah, Francis; Sültenfuß, Jürgen

    2014-05-01

    The Vihiga District in West Kenya North-West of Lake Victoria is one of the most densely populated areas in Kenya with 1033 person per square kilometer. To find the most suitable location of an own well for a Primary School in this district, springs, school wells and creeks were sampled in the surroundings to get information about the hydrological cycle in the area. The Waluka Primary school (0.02134°N, 34.64311°E) is situated on the northern slope of the Maragoli Hills 20 km to the North-West of the Nyanzan provincial capital of Kisumu at the eastern shore of Lake Victoria. The hilly relief varies between 1535 - 1675m. The yearly precipitation is between 1200-1600 mm/a (23°C mean temperature) with biannual rainy seasons in which the long rains are generally from March to May as the Inter-Tropical Convergence Zone (ITCZ) moves northwards, and the short rains are typically from October to December as the ITCZ retreats southwards. A lateritic soil covers a thin alteration zone above the Precambrian Maragoli-Granite (Saggerson, 1952). Water circulates either in the thin alteration zone or in fault zones cutting through the Precambrian granite. From discharge measurements of two springs and a creek at the end of the dry season (February 2012) a minimum discharge of ca. 10-20 L/s km2 (300-600 mm) can be estimated. The water is of the alkaline sulfate-nitrate type with low mineralization (70-150 μ S/cm, 25°C) and a low pH of about 5 to 6. The delta oxygen-18 and deuterium value ranges between -2.84 to -1.98 oand -8.5 to - 3.9 o(VSMOW). The deuterium excess ranges from 11.7-14.2 oThe water of one spring and well close to the school have a tritium content of 1.42 - 1.62 TU. All groundwater has a low arsenium, fluorine and uranium content, which had only a short soil passage. The relatively elevated, but not problematic content in nitrate (10 - 16 mg/L) probaly reflects the intensive agricultural activities in this area. As the mean δ 18O values during the rainy

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

    PubMed

    Lu, Feng H

    2009-10-01

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

  7. Rotational spectroscopy of 2H,3H-perfluoropentane

    NASA Astrophysics Data System (ADS)

    Duong, Chinh H.; Obenchain, Daniel A.; Cooke, S. A.; Novick, Stewart E.

    2016-06-01

    The structure of 2H,3H-perfluoropentane, CF3CHFCHFCF2CF3, has been determine by a combination of Chirp-pulsed Fourier transform microwave (CP-FTMW) spectroscopy and cavity FTMW spectroscopy. Of the four possible stereoisomers, only the enantiomeric pair (R,R)/(S,S) were observed experimentally; there was no spectroscopic evidence for the enantiomeric pair (R,S)/(S,R). The conformeric structure of the (R,R)/(S,S) stereoisomer(s) was that of partial helices with C-C-C-C dihedral angles of 12° (helical) and 1° (staggered).

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

    NASA Astrophysics Data System (ADS)

    Awad, S.

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

  9. One dimensional 1H, 2H and 3H

    NASA Astrophysics Data System (ADS)

    Vidal, A. J.; Astrakharchik, G. E.; Vranješ Markić, L.; Boronat, J.

    2016-05-01

    The ground-state properties of one-dimensional electron-spin-polarized hydrogen 1H, deuterium 2H, and tritium 3H are obtained by means of quantum Monte Carlo methods. The equations of state of the three isotopes are calculated for a wide range of linear densities. The pair correlation function and the static structure factor are obtained and interpreted within the framework of the Luttinger liquid theory. We report the density dependence of the Luttinger parameter and use it to identify different physical regimes: Bogoliubov Bose gas, super-Tonks–Girardeau gas, and quasi-crystal regimes for bosons; repulsive, attractive Fermi gas, and quasi-crystal regimes for fermions. We find that the tritium isotope is the one with the richest behavior. Our results show unambiguously the relevant role of the isotope mass in the properties of this quantum system.

  10. Study of the $\\tau^- to 3h^- 2h^+ \

    SciTech Connect

    Aubert, Bernard; Barate, R.; Boutigny, D.; Couderc, F.; Karyotakis, Y.; Lees, J.P.; Poireau, V.; Tisserand, V.; Zghiche, A.; Grauges, E.; Palano, A.; Pappagallo, M.; Pompili, A.; Chen, J.C.; Qi, N.D.; Rong, G.; Wang, P.; Zhu, Y.S.; Eigen, G.; Ofte, I.; Stugu, B. /more authors..

    2005-05-04

    The branching fraction of the {tau}{sup -} {yields} 3h{sup -} 2h{sup +} {nu}{sub {tau}} decay (h = {pi}, K) is measured with the BABAR detector to be (8.56 {+-} 0.05 {+-} 0.42) x 10{sup -4}, where the first error is statistical and the second systematic. The observed structure of this decay is significantly different from the phase space prediction, with the {rho} resonance playing a strong role. The decay {tau}{sup -} {yields} f{sub 1}(1285){pi}{sup -}{nu}{sub {tau}}, with the f{sub 1}(1285) meson decaying to four charged pions, is observed and the branching fraction is measured to be (3.9 {+-} 0.7 {+-} 0.5) x 10{sup -4}.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  13. 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

  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. 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).

  16. 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

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  19. Seasonal variation in natural abundance of 2H and 18O in urine samples from rural Nigeria

    PubMed Central

    Dugas, Lara R.; Brieger, William; Tayo, Bamidele O.; Alabi, Tunrayo; Schoeller, Dale A.; Luke, Amy

    2015-01-01

    The doubly labeled water (DLW) method is used to measure free-living energy expenditure in humans. Inherent to this technique is the assumption that natural abundances of stable isotopes 2H and 18O in body water remain constant over the course of the measurement period and after elimination of the loading dose of DLW will return to the same predose level. To determine variability in the natural abundances of 2H and 18O in humans living in a region with seasonal shifts in rain patterns and sources of drinking water, over the course of 12 mo we collected weekly urine samples from four individuals living in southwest Nigeria as well as samples of their drinking water. From ongoing regional studies of hypertension, obesity, and energy expenditure, we estimated average water turnover rate, urine volumes, and sodium and potassium excretion. Results suggest that 2H and 18O in urine, mean concentrations of urinary sodium and potassium, urine volume, and total body turnover differed significantly from dry to rainy season. Additionally, seasonal weather variables (mean monthly maximum temperatures, total monthly rainfall, and minimum relative humidity) were all significantly associated with natural abundances in urine. No seasonal difference was observed in drinking water samples. Findings suggest that natural abundances in urine may not remain constant as assumed, and studies incorporating DLW measurements across the transition of seasons should interpret results with caution unless appropriate doses of the tracers are used. PMID:25977450

  20. Indirect Approach To The {sup 2}H(d,p){sup 3}H Reaction Study

    SciTech Connect

    Sparta, R.; Pizzone, R. G.; Spitaleri, C.; Cherubini, S.; Crucilla, V.; Gulino, M.; La Cognata, M.; Lamia, L.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Aliotta, M.; Burjan, V.; Hons, Z.; Kroha, V.; Mrazek, J.; Kiss, G.; McCleskey, M.; Trache, L.

    2010-11-24

    In order to understand primordial and stellar nucleosynthesis, we have studied {sup 2}H(d,p){sup 3}H reaction at 0.4 MeV down to astrophysical energies. Knowledge of its S-factor is interesting also to plan reactions for fusion reactors to produce energy. The {sup 2}H(d,p)H reaction has been studied through the Trojan Horse Method applied to the three-body reaction {sup 2}H(He,pt)H, at beam energy of 17 MeV. Once selection of protons and tritons detected in coincidence and the selection of quasi-free events, the obtained S-factor is compared with direct measurements. Such data are in agreement with the direct ones and a pole invariance test has been obtained comparing the present results with another {sup 2}H(d,p){sup 3}H THM measurements, where a different spectator particle was employed.

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  2. Observation of Isotope Ratios (δ2H, δ18O, 87Sr/86Sr) of Tap Water in Urban Environments

    NASA Astrophysics Data System (ADS)

    Mancuso, C. J.; Tipple, B. J.; Ehleringer, J. R.

    2014-12-01

    Urban environments are centers for rapidly growing populations. In order to meet the culinary water needs of these areas, municipal water departments use water from multiple locations and/or sources, often piped differentially to different locations within a municipality. This practice creates isotopically distinct locations within an urban area and therefore provides insight to urban water management practices. In our study we selected urban locations in the Salt Lake Valley, UT (SLV) and San Francisco Bay Area, CA (SFB) where we hypothesized geographically distinct water isotopic ratio differences existed. Within the SLV, municipal waters come from the same mountainous region, but are derived from different geologically distinct watersheds. In contrast, SFB waters are derived from regionally distinct water sources. We hypothesized that the isotope ratios of tap waters would differ based upon known municipal sources. To test this, tap water samples were collected throughout the urban regions in SLV and SFB and analyzed for δ2H, δ18O and 87Sr/86Sr isotope ratios. Seasonal collections were also made to assess if isotope ratios differed throughout the year. Within SLV and SFB, different regions were characterized by distinct paired δ18O and 87Sr/86Sr values. These different realms also agreed with known differences in municipal water supplies within the general geographic region. Waters from different cities within Marin County showed isotopic differences, consistent with water derived from different local reservoirs. Seasonal variation was observed in paired δ18O and 87Sr/86Sr values of tap water for some locations within SLV and SFB, indicating management decisions to shift from one water source to another depending on demand and available resources. Our study revealed that the δ18O and 87Sr/86Sr values of tap waters in an urban region can exhibit significant differences despite close spatial proximity if districts differ in their use of local versus

  3. 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 δ18O2H 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.

  4. 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 δ18O2H 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.

  5. Multi-tracer approach (18O, 3H/3He, CFC, SF6, 35S) to find the best emergency drinking water supply, Vorarlberg, Austria

    NASA Astrophysics Data System (ADS)

    Kralik, Martin; Vergnaud, Virginie; Uriostegui, Stephanie; Esser, Bradley

    2016-04-01

    To provide an emergency drinking water supply in case of catastrophic events (regional chemical accidents, floods, earth quakes etc.), wells and springs should be known which are fed by a large reservoir. Such reservoirs provide a good filtering capacity and long Mean Residence Times (MRTs) of the raw water. Their existence allows to use these resources for longer periods excluding the danger of contamination. This provides the water authorities the necessary time to set measures to protect the general water supply. After preselection of 16 wells and springs all over the territory of the province of Vorarlberg at the western end of Austria by the local water authority, these wells and springs were measured (water temperature, electric conductivity, pH and dissolved oxygen content) and sampled monthly for δ 18O/2H measurements over the winter half-year 2013/14. At the same time the tritium concentrations of the October and March samples were measured as well. Based on the variation of the monthly on-site measurements and the δ 18O/2H results 12 wells and springs were selected for further investigations. On these sites samples for 3H/3He, CFC-11/12/113, SF6 and sulphur-35 measurements were collected in August 2014. As expected from a humid alpine area, non of the selected springs or wells showed really long MRTs. Five out of 16 investigated sites are regarded as well suited to be used as emergency water source with a range of MRTs of 9 - 30 years. Five springs and wells are regarded of limited suitability due to the shorter MRTs of 5 - 9 years. In two springs the 3H/3He method could not be applied due to He-degassing in a karst-system and during sampling. CFC and SF6 excess at some sites with anthropogenic and geogenic sources hampered the utilisation of these gases as dating tool, but they were useful as source tracers. Sulphur-35 was detected in two wells only, indicating contribution of very young water (< 1 year). In both cases MRTs of 13 - 17 years, calculated

  6. Synthesis of (3) H, (2) H4 and (14) C-SCH 417690 (Vicriviroc).

    PubMed

    Hesk, D; Borges, S; Hendershot, S; Koharski, D; McNamara, P; Ren, S; Saluja, S; Truong, V; Voronin, K

    2016-05-15

    Vicriviroc or SCH 417690 is a potent and selective antagonist of the CCR5 receptor. CCR5 receptor antagonists have the potential for the treatment of HIV infections. Four distinct isotopically labelled forms of SCH 417690 were synthesized. Low specific activity [(3) H]SCH 417690 was prepared for a preliminary absorption, distribution, metabolism and excretion evaluation of the compound and [(14) C]SCH 417690 for more definitive absorption, distribution, metabolism and excretion work, including an absorption, metabolism and excretion study in man. In addition, high specific activity [(3) H]SCH 417690 was prepared for CCR5 receptor binding work and [(2) H4 ]SCH 417690 was prepared as an internal standard for a liquid chromatography-mass spectrometry bioanalytical method. The paper discusses the synthesis of four isotopically labelled forms of SCH 417690. PMID:26991320

  7. Characterization Results for the 2014 HTF 3H & 2H Evaporator Overhead Samples

    SciTech Connect

    Washington, A.

    2015-05-11

    This report tabulates the radiochemical analysis of the 3H and 2H evaporator overhead samples for 137Cs, 90Sr, and 129I to meet the requirements in the Effluent Treatment Project (ETP) Waste Acceptance Criteria (WAC) (rev. 6). This report identifies the sample receipt date, preparation method, and analysis performed in the accumulation of the listed values. All data was found to be within the ETP WAC (rev. 6) specification for the Waste Water Collection Tanks (WWCT).

  8. Large-scale spatial variation in plant δ2H and δ18O - altitude, longitude and tissue type effects

    NASA Astrophysics Data System (ADS)

    West, J. B.

    2012-12-01

    A critical component of the hydrologic cycle response to climatic variation and directional change at multiple scales is the role of vegetation. Plants modulate biological activities at short and long time scales in response to climate drivers like precipitation, including changing stomatal conductance and the spatial deployment of leaf and root biomass. Over longer time periods, species replacement and changes in dominant plant form (e.g., herbaceous versus woody) also have important effects on hydrologic pathways and the magnitudes of hydrologic fluxes along those pathways. The isotopic composition of plant tissues provides an important recorder of the dynamics of these interactions. While this is the case, important questions remain about the primary drivers of plant tissue hydrogen and oxygen isotope ratio variation and how to develop improved, realistic mechanistic models of plant tissue variation in δ2H and δ18O, thus limiting the inferences that can be drawn from isotopic variation in plant tissues. In particular, the relative strengths of climatic drivers versus physiologically-based variation remain the subject of significant debate. I report here on work designed to better understand how plants record this variation in plant tissues across relatively large spatial scales. A transect (approximately 1900 km long) was established from the Continental Divide in North America (at approximately 39° N latitude) to the Coast Range. Leaf, branch, and tree core samples of Pseudotsuga menziesii were collected across the transect. At each location along the transect, samples were collected from at least three elevations and on the western and eastern slopes of the target mountain range. Significant variation in δ2H and δ18O was observed and the relative effects of the drivers at multiple scales (within-site elevation and aspect and across the longitudinal transect) will be discussed in the context of current models of plant cellulose isotopic composition.

  9. 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.

  10. 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

  11. Continuous flow 2H/1H and 18O/16O analysis of water samples with dual inlet precision.

    PubMed

    Gehre, M; Geilmann, H; Richter, J; Werner, R A; Brand, W A

    2004-01-01

    A method for isotope ratio analysis of water samples is described comprising an on-line high-temperature reduction technique in a helium carrier gas. Using a gas-tight syringe, injection of 0.5 to 1 microL sample is made through a heated septum into a glassy carbon reactor at temperatures in excess of 1300 degrees C. More than 150 injections can be made per day and both isotope ratios of interest, delta2H and delta18O, can be measured with the same setup. The technique has the capability to transfer high-precision stable isotope ratio analysis of water samples from a specialized to a routine laboratory task compatible with other common techniques (automated injection for GC, LC, etc.). Experiments with an emphasis on the reactor design were made in two different laboratories using two different commercially available high-temperature elemental analyser (EA) systems. In the Jena TC/EA unit, sample-to-sample memory (single injection) has been reduced to approximately 1% and high precision of about 0.1 per thousand for delta18O and < 1 per thousand for delta2H has been achieved by a redesign of the glassy carbon reactor and by redirecting the gas flow of the commercial TC/EA unit. With the modified reactor, the contact of water vapour with surfaces other than glassy carbon is avoided completely. The carrier gas is introduced at the bottom of the reactor thereby flushing the outer tube compartment of the tube-in-tube assembly before entering the active heart of the reactor.With the Leipzig high-temperature reactor (HTP) similar precision was obtained with a minor modification (electropolishing) of the injector metal sleeve. With this system, the temperature dependence of the reaction has been studied between 1100 and 1450 degrees C. Complete yield and constant isotope ratio information has been observed only for temperatures above 1325 degrees C. For temperatures above 1300 degrees C the reactor produces an increasing amount of CO background from reaction of glass

  12. Cometary implications of recent laboratory experiments on the photochemistry of the C2H and C3H2 radicals

    NASA Technical Reports Server (NTRS)

    Jackson, William M.; Bao, Yihan; Urdahl, Randall S.; Song, Xueyu; Gosine, Jai; Lu, Chi

    1992-01-01

    Recent laboratory results on the photodissociation of the C2H and C3H2 radicals are described. These studies show that the C2 and C3 radicals are produced by the 193 nm photolysis of the C2H and C3H2 radicals, respectively. The quantum state distributions that were determined for the C2 radicals put certain constraints on the initial conditions for any models of the observed C2 cometary spectra. Experimental observations of C2 formed by the 212.8 nm photolysis of C2H are used to calculate a range of photochemical lifetimes for the C2H radical.

  13. Direct analysis of δ2H and δ18O in natural and enriched human urine using laser-based, off-axis integrated cavity output spectroscopy.

    PubMed

    Berman, Elena S F; Fortson, Susan L; Snaith, Steven P; Gupta, Manish; Baer, Douglas S; Chery, Isabelle; Blanc, Stephane; Melanson, Edward L; Thomson, Peter J; Speakman, John R

    2012-11-20

    The stable isotopes of hydrogen (δ(2)H) and oxygen (δ(18)O) in human urine are measured during studies of total energy expenditure by the doubly labeled water method, measurement of total body water, and measurement of insulin resistance by glucose disposal among other applications. An ultrasensitive laser absorption spectrometer based on off-axis integrated cavity output spectroscopy was demonstrated for simple and inexpensive measurement of stable isotopes in natural isotopic abundance and isotopically enriched human urine. Preparation of urine for analysis was simple and rapid (approximately 25 samples per hour), requiring no decolorizing or distillation steps. Analysis schemes were demonstrated to address sample-to-sample memory while still allowing analysis of 45 natural or 30 enriched urine samples per day. The instrument was linear over a wide range of water isotopes (δ(2)H = -454 to +1702 ‰ and δ(18)O = -58.3 to +265 ‰). Measurements of human urine were precise to better than 0.65 ‰ 1σ for δ(2)H and 0.09 ‰ 1σ for δ(18)O for natural urines, 1.1 ‰ 1σ for δ(2)H and 0.13 ‰ 1σ for δ(18)O for low enriched urines, and 1.0 ‰ 1σ for δ(2)H and 0.08 ‰ 1σ for δ(18)O for high enriched urines. Furthermore, the accuracy of the isotope measurements of human urines was verified to better than ±0.81 ‰ in δ(2)H and ±0.13 ‰ in δ(18)O (average deviation) against three independent isotope-ratio mass spectrometry laboratories. The ability to immediately and inexpensively measure the stable isotopes of water in human urine is expected to increase the number and variety of experiments which can be undertaken. PMID:23075099

  14. Direct analysis of δ2H and δ18O in natural and enriched human urine using laser-based, Off-Axis Integrated Cavity Output Spectroscopy

    PubMed Central

    Berman, Elena S.F.; Fortsona, Susan L.; Snaith, Steven P.; Gupta, Manish; Baer, Douglas S.; Chery, Isabelle; Blanc, Stephane; Melanson, Edward L.; Thomson, Peter J; Speakman, John R.

    2012-01-01

    The stable isotopes of hydrogen (δ2H) and oxygen (δ18O) in human urine are measured during studies of total energy expenditure by the doubly labeled water method, measurement of total body water, and measurement of insulin resistance by glucose disposal among other applications. An ultrasensitive laser absorption spectrometer based on off-axis integrated cavity output spectroscopy was demonstrated for simple and inexpensive measurement of stable isotopes in natural isotopic abundance and isotopically enriched human urine. Preparation of urine for analysis was simple and rapid (approx. 25 samples per hour), requiring no decolorizing or distillation steps. Analysis schemes were demonstrated to address sample-to-sample memory while still allowing analysis of 45 natural or 30 enriched urine samples per day. The instrument was linear over a wide range of water isotopes (δ2H = −454 to +1702 ‰ and δ18O= −58.3 to +265 ‰). Measurements of human urine were precise to better than 0.65 ‰ 1σ for δ2H and 0.09 ‰ 1σ for δ18O for natural urines, 1.1 ‰ 1σ for δ2H and 0.13 ‰ 1σ for δ18O for low enriched urines, and 1.0 ‰ 1σ for δ2H and 0.08 ‰ 1σ for δ18O for high enriched urines. Furthermore, the accuracy of the isotope measurements of human urines was verified to better than ±0.81 ‰ in δ2H and ±0.13 ‰ in δ18O (average deviation) against three independent IRMS laboratories. The ability to immediately and inexpensively measure the stable isotopes of water in human urine is expected to increase the number and variety of experiments which can be undertaken. PMID:23075099

  15. Influence of landscape features on variation of δ2H and δ18O in seasonal mountain snowpack

    NASA Astrophysics Data System (ADS)

    Kipnis, E. L.; Chapple, W.; Frank, J. M.; Traver, E.; Ewers, B. E.; Williams, D. G.

    2014-12-01

    Streamflow contributions from snowpack remain difficult to predict in snow dominated headwater catchments in the Rocky Mountains. There remains considerable uncertainty in how environmental change in mountain watersheds alter seasonal snowpack accumulation and development and how these relationships translate from gaged to ungaged catchments. Stable isotope analysis is a valuable tool for determining the contribution and changes of different source inputs to catchment water budgets. Stable isotope values in snowpack integrate source inputs and processes such as water vapor exchange, selective redistribution, and melt. For better understanding of how these physical processes vary at local and catchment scales, snowpack density, depth, snow water equivalence (SWE), δ2H and δ18O were examined at peak snowpack in spring 2013 and 2014 and at monthly time steps throughout the winter of 2013-2014. Distributed data and sample collection occurred between 2400 and 3300 m elevation across two pine beetle and spruce beetle impacted forest stands with variable canopy cover in the Libby Creek and Nash Fork Little Laramie River basins, Medicine Bow Range, Wyoming. Peak snowpack within these watersheds was 10% below historic average in 2013 and 50% above average in 2014 (NRCS Snotel data). Even with these contrasting peak snowpack patterns, elevation described less than 40% of the spatial variation of snow water equivalents (SWE) across the watersheds for both seasons. Hydrogen and oxygen isotope ratio values of snowpack sampled monthly in 2014 revealed early season separation from the local meteoric water line, suggesting some kinetic isotope effects. However, isotope ratio values at peak snowpack in 2013 reflected no such signal at any sampling location. The influence of landscape position and canopy cover will be modeled to detect and scale spatial and temporal changes in SWE and stable isotope composition of snowpack. Such an approach will provide increased understanding of

  16. Treatment methods for the determination of delta2H and delta18O of hair keratin by continuous-flow isotope-ratio mass spectrometry.

    PubMed

    Bowen, Gabriel J; Chesson, Lesley; Nielson, Kristine; Cerling, Thure E; Ehleringer, James R

    2005-01-01

    The structural proteins that comprise approximately 90% of animal hair have the potential to record environmentally and physiologically determined variation in delta2H and delta18O values of body water. Broad, systematic, geospatial variation in stable hydrogen and oxygen isotopes of environmental water and the capacity for rapid, precise measurement via methods such as high-temperature conversion elemental analyzer/isotope ratio mass spectrometry (TC/EA-IRMS) make these isotope systems particularly well suited for applications requiring the geolocation of hair samples. In order for such applications to be successful, however, methods must exist for the accurate determination of hair delta2H and delta18O values reflecting the primary products of biosynthesis. Here, we present the results of experiments designed to examine two potential inaccuracies affecting delta2H and delta18O measurements of hair: the contribution of non-biologic hydrogen and oxygen to samples in the form of sorbed molecular water, and the exchange of hydroxyl-bound hydrogen between hair keratin and ambient water vapor. We show that rapid sorption of molecular water from the atmosphere can have a substantial effect on measured delta2H and delta18O values of hair (comprising approximately 7.7% of the measured isotopic signal for H and up to approximately 10.6% for O), but that this contribution can be effectively removed through vacuum-drying of samples for 6 days. Hydrogen exchange between hair keratin and ambient vapor is also rapid (reaching equilibrium within 3-4 days), with 9-16% of the total hydrogen available for exchange at room temperature. Based on the results of these experiments, we outline a recommended sample treatment procedure for routine measurement of delta2H and delta18O in mammal hair. PMID:16047316

  17. Stable isotope (δ18O and δ2H) data for precipitation, stream water, and groundwater in Puerto Rico

    USGS Publications Warehouse

    Scholl, Martha A.; Torres-Sanchez, Angel; Rosario-Torres, Manuel

    2014-01-01

    , hurricanes, and cold fronts, although frequent low-intensity orographic showers occur throughout the year in the mountains. The stable isotope signatures of rainfall (δ2H and δ18O) are broadly correlated with the weather type that produced the rainfall (Scholl and others, 2009; Scholl and Murphy, 2014).

  18. Identification and correction of spectral contamination in 2H/1H and 18O/16O measured in leaf, stem, and soil water.

    PubMed

    Schultz, Natalie M; Griffis, Timothy J; Lee, Xuhui; Baker, John M

    2011-11-15

    Plant water extracts typically contain organic materials that may cause spectral interference when using isotope ratio infrared spectroscopy (IRIS), resulting in errors in the measured isotope ratios. Manufacturers of IRIS instruments have developed post-processing software to identify the degree of contamination in water samples, and potentially correct the isotope ratios of water with known contaminants. Here, the correction method proposed by an IRIS manufacturer, Los Gatos Research, Inc., was employed and the results were compared with those obtained from isotope ratio mass spectrometry (IRMS). Deionized water was spiked with methanol and ethanol to create correction curves for δ(18)O and δ(2)H. The contamination effects of different sample types (leaf, stem, soil) and different species from agricultural fields, grasslands, and forests were compared. The average corrections in leaf samples ranged from 0.35 to 15.73‰ for δ(2)H and 0.28 to 9.27‰ for δ(18)O. The average corrections in stem samples ranged from 1.17 to 13.70‰ for δ(2)H and 0.47 to 7.97‰ for δ(18)O. There was no contamination observed in soil water. Cleaning plant samples with activated charcoal had minimal effects on the degree of spectral contamination, reducing the corrections, by on average, 0.44‰ for δ(2)H and 0.25‰ for δ(18)O. The correction method eliminated the discrepancies between IRMS and IRIS for δ(18)O, and greatly reduced the discrepancies for δ(2)H. The mean differences in isotope ratios between IRMS and the corrected IRIS method were 0.18‰ for δ(18)O, and -3.39‰ for δ(2)H. The inability to create an ethanol correction curve for δ(2)H probably caused the larger discrepancies. We conclude that ethanol and methanol are the primary compounds causing interference in IRIS analyzers, and that each individual analyzer will probably require customized correction curves. PMID:22006400

  19. Stable Isotope Values of the Mesoamerican Monsoon: δ18O and δ2H Values Reveal Climate Controls on Summer Rainfall Amount

    NASA Astrophysics Data System (ADS)

    Bernal, J. P.; Lachniet, M. S.; Rosales Lagarde, L.; Morales Puente, P.; Cienfuegos, E.

    2014-12-01

    Paleoclimate reconstructions using δ18O as a proxy for the isotopic composition of rainfall are based upon the mostly untested assumption that either rainfall amount or equilibration temperature are the main drivers modulating the isotopic composition of pluvial precipitation. Whilst a broad correlation between geographical location and driving mechanisms has been long recognized (i.e. amount effect is pervasive in tropical areas), further tests are required to determine the effect that different sources of moisture might impose on the isotopic composition of precipitation, particularly in areas where contributions from different ocean-basins might be significant, such as south Mexico. Here, we present the δ18O and δ2H composition of summer rainfall collected throughout south, central and western Mexico, particularly from Veracruz, Puebla, Guerrero, Morelos, Mexico City, Jalisco, Michoacán and Querétaro states. The geographical and temporal extent of our sampling (2004, 2005, 2007, 2008, 2011) results in a large dataset comprising more than 600 samples and represents the base data to understand the atmospheric mechanisms modulating the isotopic composition of rainfall in Mexico. Our data span a range of 30‰ in δ18O, from high values nearest the Gulf of Mexico coast and during weak rainfall events, to lowest values in high-altitude central Mexico and during heavy rainfall events associated with tropical cyclones. Values on the Pacific Coast are intermediate, and likely reflect a contribution of both Gulf of Mexico and Pacific sources. Our data define a meteoric water line of δ2H = 7.92 × δ18O + 9.48, which indicate that most precipitation values formed close to isotopic equilibrium with water vapor. The two primary physiographic variables controlling δ18O values are distance from the Gulf of Mexico and altitude, which together explain about 70% of the variation in spatial δ18O values.

  20. 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.

  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

    Interpretations of the primary paleoceanographic information recorded in stable oxygen isotope values (δ18O) of biogenic CaCO3 can be obscured by disequilibrium effects. CaCO3 is often depleted in 18O relative to the δ18O values expected for precipitation in thermodynamic equilibrium with ambient seawater as a result of vital effects. Vital effects in δ18O have been explained in terms of the influence of fluid pH on the overall δ18O of the sum of dissolved inorganic carbon (DIC) species (often referred to as "pH model") and in terms of 18O depletion as a result of the kinetic effects associated with CO2 hydration (CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+) and CO2 hydroxylation (CO2 + OH- ↔ HCO3-) in the calcification sites (so-called "kinetic model"). This study addresses the potential role of an enzyme, carbonic anhydrase (CA), that catalyzes inter-conversion of CO2 and HCO3- in relation to the underlying mechanism of vital effects. We performed quantitative inorganic carbonate precipitation experiments in order to examine the changes in 18O equilibration rate as a function of CA concentration. Experiments were performed at pH 8.3 and 8.9. These pH values are comparable to the average surface ocean pH and elevated pH levels observed in the calcification sites of some coral and foraminiferal species, respectively. The rate of uncatalyzed 18O exchange in the CO2-H2O system is governed by the pH-dependent DIC speciation and the kinetic rate constant for CO2 hydration and hydroxylation, which can be summarized by a simple mathematical expression. The results from control experiments (no CA addition) are in agreement with this expression. The results from control experiments also suggest that the most recently published kinetic rate constant for CO2 hydroxylation has been overestimated. When CA is present, the 18O equilibration process is greatly enhanced at both pH levels due to the catalysis of CO2 hydration by the enzyme. For example, the time required for 18O

  2. Chemical destruction of CH3I, C2H5I, 1-C3H7I, and 2-C3H7I in saltwater

    NASA Astrophysics Data System (ADS)

    Jones, Charlotte E.; Carpenter, Lucy J.

    2007-07-01

    Destruction of volatile iodocarbons in the oceans can potentially play an important role in determining the predominant chemical forms of iodine emitted to the atmosphere. Here we report chlorination and hydrolysis removal rates for CH3I, C2H5I, 1-C3H7I, and 2-C3H7I relevant to oceanic conditions. We have used these rates to calculate oceanic lifetimes for each iodocarbon with respect to total chemical destruction, as a function of seawater temperature. The resulting lifetimes are compared to typical iodocarbon oceanic residence times with respect to volatilization to the MBL. The rate of destruction of 2-C3H7I is much more rapid than chemical removal of the primary alkyl iodides, potentially explaining previous observations of lower 2-C3H7I concentrations in seawater compared to 1-C3H7I. Finally, in light of these results, we briefly discuss the potential impact of rising global seawater temperatures on oceanic iodocarbon concentrations.

  3. Approaches for achieving long-term accuracy and precision of δ18O and δ2H for waters analyzed using laser absorption spectrometers.

    PubMed

    Wassenaar, Leonard I; Coplen, Tyler B; Aggarwal, Pradeep K

    2014-01-21

    The measurement of δ(2)H and δ(18)O in water samples by laser absorption spectroscopy (LAS) are adopted increasingly in hydrologic and environmental studies. Although LAS instrumentation is easy to use, its incorporation into laboratory operations is not as easy, owing to extensive offline data manipulation required for outlier detection, derivation and application of algorithms to correct for between-sample memory, correcting for linear and nonlinear instrumental drift, VSMOW-SLAP scale normalization, and in maintaining long-term QA/QC audits. Here we propose a series of standardized water-isotope LAS performance tests and routine sample analysis templates, recommended procedural guidelines, and new data processing software (LIMS for Lasers) that altogether enables new and current LAS users to achieve and sustain long-term δ(2)H and δ(18)O accuracy and precision for these important isotopic assays. PMID:24328223

  4. On the calibration of continuous, high-precision delta18O and delta2H measurements using an off-axis integrated cavity output spectrometer.

    PubMed

    Wang, Lixin; Caylor, Kelly K; Dragoni, Danilo

    2009-02-01

    The (18)O and (2)H of water vapor serve as powerful tracers of hydrological processes. The typical method for determining water vapor delta(18)O and delta(2)H involves cryogenic trapping and isotope ratio mass spectrometry. Even with recent technical advances, these methods cannot resolve vapor composition at high temporal resolutions. In recent years, a few groups have developed continuous laser absorption spectroscopy (LAS) approaches for measuring delta(18)O and delta(2)H which achieve accuracy levels similar to those of lab-based mass spectrometry methods. Unfortunately, most LAS systems need cryogenic cooling and constant calibration to a reference gas, and have substantial power requirements, making them unsuitable for long-term field deployment at remote field sites. A new method called Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS) has been developed which requires extremely low-energy consumption and neither reference gas nor cryogenic cooling. In this report, we develop a relatively simple pumping system coupled to a dew point generator to calibrate an ICOS-based instrument (Los Gatos Research Water Vapor Isotope Analyzer (WVIA) DLT-100) under various pressures using liquid water with known isotopic signatures. Results show that the WVIA can be successfully calibrated using this customized system for different pressure settings, which ensure that this instrument can be combined with other gas-sampling systems. The precisions of this instrument and the associated calibration method can reach approximately 0.08 per thousand for delta(18)O and approximately 0.4 per thousand for delta(2)H. Compared with conventional mass spectrometry and other LAS-based methods, the OA-ICOS technique provides a promising alternative tool for continuous water vapor isotopic measurements in field deployments. PMID:19142848

  5. Analysis of stable isotope ratios (δ18O and δ2H) in precipitation of the Verde River watershed, Arizona 2013 through 2014

    USGS Publications Warehouse

    Beisner, Kimberly R.; Paretti, Nicholas V.; Tucci, Rachel S.

    2016-01-01

    Stable isotope delta values (δ18O and δ2H) of precipitation can vary with elevation, and quantification of the precipitation elevation gradient can be used to predict recharge elevation within a watershed. Precipitation samples were analyzed for stable isotope delta values between 2003 and 2014 from the Verde River watershed of north-central Arizona. Results indicate a significant decrease in summer isotopic values overtime at 3,100-, 4,100-, 6,100-, 7,100-, and 8,100-feet elevation. The updated local meteoric water line for the area is δ2H = 7.11 δ18O + 3.40. Equations to predict stable isotopic values based on elevation were updated from previous publications in Blasch and others (2006), Blasch and Bryson (2007), and Bryson and others (2007). New equations were separated for samples from the Camp Verde to Flagstaff transect and the Prescott to Chino Valley transect. For the Camp Verde to Flagstaff transect, the new equations for winter precipitation are δ18O = -0.0004z − 8.87 and δ2H = -0.0029z − 59.8 (where z represents elevation in feet) and the summer precipitation equations were not statistically significant. For the Prescott to Chino Valley transect, the new equations for summer precipitation are δ18O = -0.0005z − 3.22 and δ2H = -0.0022z − 27.9; the winter precipitation equations were not statistically significant and, notably, stable isotope values were similar across all elevations. Interpretation of elevation of recharge contributing to surface and groundwaters in the Verde River watershed using the updated equations for the Camp Verde to Flagstaff transect will give lower elevation values compared with interpretations presented in the previous studies. For waters in the Prescott and Chino Valley area, more information is needed to understand local controls on stable isotope values related to elevation.

  6. In-situ unsaturated zone stable water isotope (2H and 18O) measurements in semi-arid environments using tunable off-axis integrated cavity output spectroscopy

    NASA Astrophysics Data System (ADS)

    Gaj, M.; Beyer, M.; Koeniger, P.; Wanke, H.; Hamutoko, J.; Himmelsbach, T.

    2015-06-01

    Stable isotopes (deuterium, 2H, and oxygen-18, 18O) of soil pore water were measured directly in the field using tunable off-axis integrated cavity output spectroscopy (OA-ICOS) and commercially available soil gas probes in a semi-arid region of the Cuvelai-Etosha-Basin, Namibia. High spatial and temporal resolution was achieved in the study area with reasonable accuracy and measurements were in agreement with laboratory-based cryogenic vacuum extraction and subsequent cavity ring down laser spectroscopic isotope analysis (CRDS). After drift correction of the isotope data, mean precision for over 140 measurements of two consecutive field campaigns in June and November 2014 were 1.8 and 0.46 ‰ for δ2H and 18O, respectively. Mean Accuracy using quality check standards was 5 and 0.3 ‰ for δ2H and δ18O, respectively. Results support the applicability of an in-situ measurement system for the determination of stable isotopes in soil pore water. Spatio-temporal variability could be deduced with the observed data in an extremely dry evaporation dominated environment which was sporadically affected by intermittent rainfall.

  7. USGS46 Greenland ice core water – A new isotopic reference material for δ2H and δ18O measurements of water

    USGS Publications Warehouse

    Coplen, Tyler B.; Qi, Haiping; Tarbox, Lauren V.; Lorenz, Jennifer M.; Buck, Bryan

    2015-01-01

    Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ2H) and stable oxygen (δ18O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ2H and δ18O values of this reference water were −235.8 ± 0.7‰ and −29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ2H and δ18O values of SLAP reference water are, respectively, −428 and −55.5‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.

  8. Reconstructing lake evaporation history and the isotopic composition of precipitation by a coupled δ18O2H 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 δ18O2H 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.

  9. {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reactions at sub-coulomb energies

    SciTech Connect

    Tumino, A.; Spitaleri, C.; Mukhamedzhanov, A. M.; Typel, S.; Sparta, R.; Aliotta, M.; Kroha, V.; Hons, Z.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Mrazek, J.; Pizzone, R. G.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.

    2012-11-20

    The {sup 2}H({sup 3}He,p{sup 3}H){sup 1}H and {sup 2}H({sup 3}He,n{sup 3}He){sup 1}H processes have been measured in quasi free kinematics to investigate for the first time the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reactions by means of the Trojan Horse Method. The {sup 3}He+d experiment was performed at 18 MeV, corresponding the a d-d energy range from 1.5 MeV down to 2 keV. This range overlaps with the relevant region for Standard Big Bang Nucleosynthesis as well as with the thermal energies of future fusion reactors and deuterium burning in the Pre Main Sequence phase of stellar evolution. This is the first pioneering experiment in quasi free regime where the charged spectator is detected. Both the energy dependence and the absolute value of the bare nucleus S(E) factors have been extracted for the first time. They deviate by more than 15% from available direct data with new S(0) values of 57.4{+-}1.8 MeVb for {sup 3}H+p and 60.1{+-}1.9 MeVb for {sup 3}He+n. None of the existing fitting curves is able to provide the correct slope of the new data in the full range, thus calling for a revision of the theoretical description. This has consequences in the calculation of the reaction rates with more than a 25% increase at the temperatures of future fusion reactors.

  10. Use of 2H and 18O stable isotopes to investigate water sources for different ages of Populus euphratica along the lower Heihe River

    USGS Publications Warehouse

    Shubao Liu; Yaning Chen; Yapeng Chen; Friedman, Jonathan M.; Gonghuan Fan; Hati, Jarre Heng A.

    2015-01-01

    Investigation of the water sources used by trees of different ages is essential to formulate a conservation strategy for the riparian tree, P. euphratica. This study addressed the contributions of different potential water sources to P. euphratica based on levels of stable oxygen and hydrogen isotopes (δ18O, δ2H) in the xylem of different aged P. euphratica, as well as in soil water and groundwater along the lower Heihe River. We found significant differences in δ18O values in the xylem of different aged P. euphratica. Specifically, the δ18O values of young, mature and over-mature forests were −5.368(±0.252) ‰, −6.033(± 0.185) ‰ and −6.924 (± 0.166) ‰, respectively, reflecting the reliance of older trees on deeper sources of water with a δ18O value closer to that of groundwater. Different aged P. euphratica used different water sources, with young forests rarely using groundwater (mean <15 %) and instead primarily relying on soil water from a depth of 0–50 cm (mean >45 %), and mature and over-mature forests using water from deeper than 100 cm derived primarily from groundwater.

  11. New determination of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reaction rates at astrophysical energies

    SciTech Connect

    Tumino, A.; Spartà, R.; Spitaleri, C.; Pizzone, R. G.; La Cognata, M.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Mukhamedzhanov, A. M.; Typel, S.; Tognelli, E.; Degl'Innocenti, S.; Prada Moroni, P. G.; Burjan, V.; Kroha, V.; Hons, Z.; Mrazek, J.; Piskor, S.; Lamia, L.

    2014-04-20

    The cross sections of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reactions have been measured via the Trojan Horse method applied to the quasi-free {sup 2}H({sup 3}He,p {sup 3}H){sup 1}H and {sup 2}H({sup 3}He,n {sup 3}He){sup 1}H processes at 18 MeV off the proton in {sup 3}He. For the first time, the bare nucleus S(E) factors have been determined from 1.5 MeV, across the relevant region for standard Big Bang nucleosynthesis, down to the thermal energies of deuterium burning in the pre-main-sequence (PMS) phase of stellar evolution, as well as of future fusion reactors. Both the energy dependence and the absolute value of the S(E) factors deviate by more than 15% from the available direct data and existing fitting curves, with substantial variations in the electron screening by more than 50%. As a consequence, the reaction rates for astrophysics experience relevant changes, with a maximum increase of up to 20% at the temperatures of the PMS phase. From a recent primordial abundance sensitivity study, it turns out that the {sup 2}H(d,n){sup 3}He reaction is quite influential on {sup 7}Li, and the present change in the reaction rate leads to a decrease in its abundance by up to 10%. The present reaction rates have also been included in an updated version of the FRANEC evolutionary code to analyze their influence on the central deuterium abundance in PMS stars with different masses. The largest variation of about 10%-15% pertains to young stars (≤1 Myr) with masses ≥1 M {sub ☉}.

  12. New Determination of the 2H(d,p)3H and 2H(d,n)3He Reaction Rates at Astrophysical Energies

    NASA Astrophysics Data System (ADS)

    Tumino, A.; Spartà, R.; Spitaleri, C.; Mukhamedzhanov, A. M.; Typel, S.; Pizzone, R. G.; Tognelli, E.; Degl'Innocenti, S.; Burjan, V.; Kroha, V.; Hons, Z.; La Cognata, M.; Lamia, L.; Mrazek, J.; Piskor, S.; Prada Moroni, P. G.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.

    2014-04-01

    The cross sections of the 2H(d,p)3H and 2H(d,n)3He reactions have been measured via the Trojan Horse method applied to the quasi-free 2H(3He,p 3H)1H and 2H(3He,n 3He)1H processes at 18 MeV off the proton in 3He. For the first time, the bare nucleus S(E) factors have been determined from 1.5 MeV, across the relevant region for standard Big Bang nucleosynthesis, down to the thermal energies of deuterium burning in the pre-main-sequence (PMS) phase of stellar evolution, as well as of future fusion reactors. Both the energy dependence and the absolute value of the S(E) factors deviate by more than 15% from the available direct data and existing fitting curves, with substantial variations in the electron screening by more than 50%. As a consequence, the reaction rates for astrophysics experience relevant changes, with a maximum increase of up to 20% at the temperatures of the PMS phase. From a recent primordial abundance sensitivity study, it turns out that the 2H(d,n)3He reaction is quite influential on 7Li, and the present change in the reaction rate leads to a decrease in its abundance by up to 10%. The present reaction rates have also been included in an updated version of the FRANEC evolutionary code to analyze their influence on the central deuterium abundance in PMS stars with different masses. The largest variation of about 10%-15% pertains to young stars (<=1 Myr) with masses >=1 M ⊙.

  13. Concentration effects on laser-based δ18 O and δ2 H measurements and implications for the calibration of vapour measurements with liquid standards.

    PubMed

    Schmidt, Markus; Maseyk, Kadmiel; Lett, Céline; Biron, Philippe; Richard, Patricia; Bariac, Thierry; Seibt, Ulli

    2010-12-30

    Recently available isotope ratio infrared spectroscopy can directly measure the isotopic composition of atmospheric water vapour (δ(18) O, δ(2) H), overcoming one of the main limitations of isotope ratio mass spectrometry (IRMS) methods. Calibrating these gas-phase instruments requires the vapourisation of liquid standards since primary standards in principle are liquids. Here we test the viability of calibrating a wavelength-scanned cavity ring-down spectroscopy (CRDS) instrument with vapourised liquid standards. We also quantify the dependency of the measured isotope values on the water concentration for a range of isotopic compositions. In both liquid and vapour samples, we found an increase in δ(18) O and δ(2) H with water vapour concentration. For δ(18) O, the slope of this increase was similar for liquid and vapour, with a slight positive relationship with sample δ-value. For δ(2) H, we found diverging patterns for liquid and vapour samples, with no dependence on δ-value for vapour, but a decreasing slope for liquid samples. We also quantified tubing memory effects to step changes in isotopic composition, avoiding concurrent changes in the water vapour concentration. Dekabon tubing exhibited much stronger, concentration-dependent, memory effects for δ(2) H than stainless steel or perfluoroalkoxy (PFA) tubing. Direct vapour measurements with CRDS in a controlled experimental chamber agreed well with results obtained from vapour simultaneously collected in cold traps analysed by CRDS and IRMS. We conclude that vapour measurements can be calibrated reliably with liquid standards. We demonstrate how to take the concentration dependencies of the δ-values into account. Copyright © 2010 John Wiley & Sons, Ltd. PMID:21080508

  14. The Organocatalytic Approach to Enantiopure 2H- and 3H-Pyrroles: Inhibitors of the Hedgehog Signaling Pathway.

    PubMed

    Kötzner, Lisa; Leutzsch, Markus; Sievers, Sonja; Patil, Sumersing; Waldmann, Herbert; Zheng, Yiying; Thiel, Walter; List, Benjamin

    2016-06-27

    A divergent approach to enantioenriched 2H- and 3H-pyrroles catalyzed by a spirocyclic phosphoric acid is reported that makes use of a Fischer-type indolization and a [1,5]-alkyl shift. Catalyzed by the chiral phosphoric acid STRIP, good to excellent yields and enantioselectivities could be obtained. Remarkably, biological evaluation reveals one of these novel 2H-pyrroles to be a potent but nontoxic inhibitor of the Hedgehog signaling pathway by binding to the Smoothened protein. PMID:27239757

  15. Trojan Horse particle invariance for 2H(d,p)3H reaction: a detailed study

    NASA Astrophysics Data System (ADS)

    Pizzone, R. G.; Spitaleri, C.; Bertulani, C. A.; Mukhamedzhanov, A. M.; Blokhintsev, L.; La Cognata, M.; Lamia, L.; Rinollo, A.; Spartá, R.; Tumino, A.

    2014-03-01

    In the last decades the Trojan Horse method has played a crucial role for the measurement of several charged particle induced reactions cross sections of astrophysical interest. To better understand its cornerstones and its applications to physical cases many tests were performed to verify all its properties and the possible future perspectives. The Trojan Horse nucleus invariance for the binary d(d,p)t reaction was therefore tested using the quasi free 2H(6Li, pt)4He and 2H(3He,pt)H reactions after 6Li and 3He break-up, respectively. The astrophysical S(E)-factor for the d(d,p)t binary process was then extracted in the framework of the Plane Wave Approximation applied to the two different break-up schemes. The obtained results are compared with direct data as well as with previous indirect investigations. The very good agreement confirms the applicability of the plane wave approximation and suggests the independence of binary indirect cross section on the chosen Trojan Horse nucleus also for the present case.

  16. Validation of the doubly-labeled water (H/sup 3/H/sup 18/O) method for measuring water flux and energy metabolism in tenebrionid beetles

    SciTech Connect

    Cooper, P.D.

    1981-01-01

    Doubly-labeled water (H/sup 3/H/sup 18/O) has been used to determine water flux and energy metabolism in a variety of vertebrates. This study examines the applicability of this technique to arthropods. The theory of the technique depends upon the assumption that doubly-labeled water introduced into the animal's body water equilibrates with water and carbon dioxide by the action of carbonic anhydrase. Tritium (/sup 3/H) is lost from the animal only with water while oxygen-18 is lost with both water and carbon dioxide. The difference bwtween the rates of loss of the two isotopes is proportional to CO/sub 2/ loss rate. Validation of the use of tritiated water for measuring water flux was accomplished by comparing gravimetric measurements of water gain with flux rates determined by loss of tritiated water. At room humidity, an overestimate for influx calculated from labeled water calculations was found, averaging 12 mg H/sub 2/O (g.d)/sup -1/. Comparison of CO/sub 2/ loss rate determined isotopically with rates of CO/sub 2/ loss determined by standard metabolic rates also yielded overestimates for the isotopic technique, overestimates ranging between 20 and 30%. The relevance of this for studies using labeled water for studying water fluxes and free metabolism of free-ranging arthropods is discussed.

  17. Measurement of the 2H(d ,p ) 3H reaction at astrophysical energies via the Trojan-horse method

    NASA Astrophysics Data System (ADS)

    Li, Chengbo; Wen, Qungang; Fu, Yuanyong; Zhou, Jing; Zhou, Shuhua; Meng, Qiuying; Spitaleri, C.; Tumino, A.; Pizzone, R. G.; Lamia, L.

    2015-08-01

    The study of the 2H(d ,p ) 3H reaction is very important for the nucleosynthesis in both the standard Big Bang and stellar evolution, as well as for the future fusion reactor's planning of energy production. The 2H(d ,p ) 3H bare nucleus astrophysical S (E ) factor has been measured indirectly at energies from about 400 keV down to several keV by means of the Trojan-horse method applied to the quasifree process 2H(6Li ,p t ) 4He induced at a lithium beam energy of 9.5 MeV, which is closer to the zero-quasifree-energy point. An accurate analysis leads to the determination of the Sbare(0 ) =56.7 ±2.0 keV b and of the corresponding electron screening potential Ue=13.2 ±4.3 eV. In addition, this work gives an updated test for the Trojan-horse nucleus invariance by comparing with previous indirect investigations using the 3He=(d +p ) breakup.

  18. Application of δ18O, δD, 3H-3He and CFCs to characterize the nitrate contamination of groundwater in Eumsung, Korea

    NASA Astrophysics Data System (ADS)

    Ju, Y. J.; Kaown, D.; Hahm, D.; Kim, I.; Lee, S. S.; Koh, E. H.; Kim, M.; Yoon, Y. Y.; Lee, K. K.

    2015-12-01

    We measured the major ions, stable oxygen and hydrogen isotopes, 3H-3He and CFCs concentration in groundwater to identify the characteristics of nitrate contamination and to understand the groundwater recharge patterns. In this study, 17 groundwater samples were collected for 5days (from March 3rd to 7th, 2015) in Eumseong, Korea. In the study area, NO3- concentrations in some groundwater samples (16 of 17) ranged from 5.7 to 103.7 mg/L (avg. 43.3 mg/L), which were substantially higher than the drinking water quality standard (10 mg/L). These excess NO3- inputs in groundwater seem to be originated from the agricultural use of chemical fertilizers because major ions associated with fertilizers were significantly correlated with NO3-. It seems that major groundwater recharge event during monsoon season is highly probable from the analysis of δ18O and δD. The apparent groundwater age using 3H-3He and CFCs varies from 5 to 40 yrs although the study area is small (1 km2). For the samples showed large deficiency of 3He, the sensitivity analysis was performed using NOBLE 90 in an effort to quantify the degassed amount. Since nitrate sources are quite evenly distributed through the field site, groundwater ages from shallow aquifer is inversely correlated with the nitrate concentrations. Our result implies that the 3H-3He ratio can be a useful indicator of tracing the recharge pattern of groundwater but also the nitrate loading characteristic in a small scale agricultural area. Acknowlegments: Financial support was provided by the "R&D Project on Environmental Management of Geologic CO2 Storage" from the KEITI (Project Number: 2014001810003) and the research project of "Advanced Technology for Groundwater Development and Application in Riversides (Geowater+)" in "Water Resources Management Program (code 11 Technology Innovation C05)" of the MOLIT and the KAIA in Korea.

  19. Biscayne aquifer drinking water (USGS45): a new isotopic reference material for δ2H and δ18O measurements of water

    USGS Publications Warehouse

    Lorenz, Jennifer M.; Tarbox, Lauren V.; Buck, Bryan; Qi, Haiping; Coplen, Tyler B.

    2014-01-01

    RATIONALE As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from drinking water collected from the Biscayne aquifer in Ft. Lauderdale, Florida. METHODS This isotopic reference water was filtered, homogenized, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry. This reference material is available by the case of 144 glass ampoules containing either 4 mL or 5 mL of water in each ampoule. RESULTS The δ2H and δ18O values of this reference material are –10.3 ± 0.4 ‰ and –2.238 ± 0.011 ‰, respectively, relative to VSMOW, on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. CONCLUSIONS This isotopic reference material, designated as USGS45, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer. 

  20. Stable isotope (2H, 17O, 18O) and hydro chemical patterns of precipitation collected in weekly resolution at Hannover, Germany

    NASA Astrophysics Data System (ADS)

    Koeniger, Paul; Himmelsbach, Thomas

    2016-04-01

    Long-term observations of stable isotopes (δ18O and δ2H) in precipitation were initiated in May 2008 at the Federal Institute of Geosciences and Natural Resources (BGR) in Hannover, Germany. In 2014 all precipitation samples were re-analyzed because a purchase of a new laser spectrometer (Picarro L2140-i) now allowed measurements of δ17O and a calculation of the 17O-excess parameter. Starting in October 2015 a routine analysis of hydro chemical parameters was added whenever enough sample aliquot was available (major ions, trace elements). A discussion of the stable isotope data of the seven year series of weekly precipitation samples (n = 370) will be presented. Beneath general patterns (seasonality and trends) we also focus on importance of amount weighing procedures, corrections for minor rain amounts, aspects of sample storage and re-analyzes, as well as impacts through changes in analytical equipment (IRMS, CRD spectroscopy) which is visible from the data. For stable isotopes a Thermo Fisher delta plus IRMS (Gasbench and H-Device) was used until 2011 and from 2012 on a Picarro L2120-i water vapor analyzer with long-term accuracies for quality check samples better than 0.2‰ and 0.8‰ for δ18O and δ2H, respectively.

  1. Precipitation origin and evaporation of lakes in semi-arid Patagonia (Argentina) inferred from stable isotopes ( δ18O, δ2H)

    NASA Astrophysics Data System (ADS)

    Mayr, Christoph; Lücke, Andreas; Stichler, Willibald; Trimborn, Peter; Ercolano, Bettina; Oliva, Gabriel; Ohlendorf, Christian; Soto, Julio; Fey, Michael; Haberzettl, Torsten; Janssen, Stephanie; Schäbitz, Frank; Schleser, Gerhard H.; Wille, Michael; Zolitschka, Bernd

    2007-02-01

    Stable isotope approaches are often used for estimating water balances of lakes. Such studies require regional background information about hydrogen and oxygen isotope variability of lakes and their potential inflows. Here, a stable isotope database ( δ2H and δ18O) is presented for estimating evaporation to inflow ratios ( E/ I) of lakes in semi-arid southern Patagonia. Water samples of 23 lakes and ponds located in the Patagonian steppe at about 52°S were sampled during three subsequent austral summers. Two deep crater lakes, Laguna Azul and Laguna Potrok Aike, were studied in more detail during a two-years monitoring. Furthermore, precipitation, groundwater and atmospheric water vapor were sampled for isotope analyses. Presented data imply that the isotopic composition of rainfall in southeastern Patagonia is predominantly determined by precipitation amount and moisture source area. For the investigated area, the first meteoric water and evaporation lines in δ2H vs. δ18O space are presented. The database was further used to estimate the water balances of the two crater lakes, Laguna Azul and Laguna Potrok Aike, which are in the focus of recent paleoclimatic investigations. According to that approach about 50% and 60%, respectively, of the water entering Laguna Azul and Laguna Potrok Aike via surface and subsurface inflow evaporates. These results testify a considerable flow of lake waters into the groundwater.

  2. Ground water/surface water interactions in Lake Naivasha, Kenya, using delta 18O, delta D, and 3H/3He age-dating.

    PubMed

    Ojiambo, B S; Poreda, R J; Lyons, W B

    2001-01-01

    We have analyzed a series of ground water samples from the Lake Naivasha region, Kenya, for their helium isotopic composition. Lake Naivasha is unique among the East Africa Rift Valley lakes in that it is fresh. It has long been thought that the low salinity of this lake is due, in part, to rapid water loss from the lake into the local ground water system. Our results show that the Olkaria geothermal waters, south of the lake, are devoid of tritium and, thus, are more than 50 years old. An important implication of these results is that even if Olkaria geothermal reservoir water originated from Lake Naivasha, it has been underground for a long time, (> 50 years) and is not derived from present-day Lake Naivasha water. This flow time is of the same order of magnitude as conservative major solutes, such as chloride, as determined through residence time calculations. On the north side of Lake Naivasha, deep wells (91 m) have water approximately 20 years old. Water from these wells has stable isotopic values resembling those of nearby rivers, and high-elevation eastern Rift water. This indicates that this water recharges from rains from high eastern Rift Valley escarpments. Many of the shallow wells on the south side of the lake have 3H/3He ages between four and 17 years. The young ages and the delta 18 O-enriched signature of the water from these wells indicate that they are recharged by a mixture of water from the lake, Rift flanks, and water from deep pumping wells that is recharged during irrigation. Water mixing ratio calculations using delta 18O and delta D isotopes show that about 50% to 70% of the southern ground water system is derived from the lake, while the Olkaria geothermal reservoir water shows that 40% to 50% of this water is originally lake water. Calculated mean recharge rates range from 0.10 to 1.59 m/yr with a mean of 0.52 +/- 0.40 m/yr. Estimated horizontal velocity from 3H/3He age dating between Lake Naivasha and a well about 3 km to the south is

  3. Coupling δ2H and δ18O biomarker results yields information on relative humidity and isotopic composition of precipitation - a climate transect validation study

    NASA Astrophysics Data System (ADS)

    Tuthorn, M.; Zech, R.; Ruppenthal, M.; Oelmann, Y.; Kahmen, A.; del Valle, H. F.; Eglinton, T.; Rozanski, K.; Zech, M.

    2015-06-01

    The hydrogen isotopic composition (δ2H) of leaf waxes, especially of n-alkanes (δ2Hn-alkanes), is increasingly used for paleohydrological and paleoclimate reconstructions. However, it is challenging to disentangle past changes in the isotopic composition of precipitation and changes in evapotranspirative enrichment of leaf water, which are both recorded in leaf wax δ2H values. In order to overcome this limitation, Zech M. et al. (2013) proposed a coupled δ2Hn-alkanes-δ18Osugar biomarker approach. This coupled approach allows for calculating (i) biomarker-based "reconstructed" δ2Hδ18O values of leaf water (δ2Hδ18Oleaf water), (ii) biomarker-based reconstructed deuterium excess (d-excess) of leaf water, which mainly reflects evapotranspirative enrichment and which can be used to reconstruct relative air humidity (RH) and (iii) biomarker-based reconstructed δ2Hδ18Oprecipitation values. Here we present a climate transect validation study by coupling new results from δ2H analyses of n-alkanes and fatty acids in topsoils along a climate transect in Argentina with previously measured δ18O results obtained for plant-derived sugars. Accordingly, both the reconstructed RH and δ2Hδ18Oprecipitation values correlate highly significantly with actual RH and δ2Hδ18Oprecipitation values. We conclude that compared to single δ2Hn-alkane or δ18Osugar records, the proposed coupled δ2Hn-alkane-δ18Osugar biomarker approach will allow more robust δ2Hδ18Oprecipitation reconstructions in future paleoclimate research. Additionally, the proposed coupled δ2Hn-alkane-δ18Osugar biomarker approach allows for the establishment of a "paleohygrometer", more specifically, the reconstruction of mean summer daytime RH changes/history.

  4. Effects of land use on the distribution of stable isotopes of water (18O/2H) in a deep unconfined aquifer and its role for recharge estimates.

    NASA Astrophysics Data System (ADS)

    Müller, Sascha; Jessen, Søren; Engesgaard, Peter; Jari Leskelä, Jari

    2014-05-01

    /2H signal for the Rabis Creek aquifer is slightly displaced from the GMWL with a slope of 7.8. Slopes for each single well reveal that groundwater areas under agricultural and heath areas have lower slopes between 6 and 7 indicating stronger effects of soil evaporation on the recharged water. Groundwater derived from forest areas show slopes close to 8 and, thus seem to be less affected by soil evaporation. Recharge estimates based on the offset of 18O/2H from the GMWL differ between the land use types by 150 mm, but are generally overestimated by a factor of 1.5-2 compared to recharge values estimated for the area from earlier studies. This suggest that a) flow zonation in aquifer plays a role for the recharge estimate or b) estimates based on the offset from a local meteoric water line (LMWL) could result in more appropriate recharge values. Generally, the study shows that the δ18O in groundwater can be used to trace land use from recharging areas. However, refined recharge estimates are subject to ongoing research.

  5. In situ unsaturated zone water stable isotope (2H and 18O) measurements in semi-arid environments: a soil water balance

    NASA Astrophysics Data System (ADS)

    Gaj, Marcel; Beyer, Matthias; Koeniger, Paul; Wanke, Heike; Hamutoko, Josefina; Himmelsbach, Thomas

    2016-02-01

    Stable isotopes (deuterium, 2H, and oxygen-18, 18O) of soil water were measured in the field using a liquid water isotope analyzer (tunable off-axis integrated cavity output spectroscope, OA-ICOS, LGR) and commercially available soil gas probes (BGL-30, UMS, Munich) in the semi-arid Cuvelai-Etosha Basin (CEB), Namibia. Results support the applicability of an in situ measurement system for the determination of stable isotopes in soil pore water. High spatial and temporal resolution was achieved in the study area with reasonable accuracy and measurements were in agreement with laboratory-based cryogenic vacuum extraction and subsequent cavity ring-down laser spectroscopic isotope analysis (CRDS, L2120-i, Picarro Inc.). After drift and span correction of the in situ isotope data, precision for over 140 measurements taken during two consecutive field campaigns (June and November 2014) was 1.8 and 0.48 ‰ for δ2H and δ18O, respectively. Mean measurement trueness is determined using quality check standards and was 5 and 0.3 ‰ for δ2H and δ18O, respectively. The isotope depth profiles are used quantitatively to calculate a soil water balance. The contribution of transpiration to total evapotranspiration ranged between 72 and 92 %. Shortly after a rain event, the contribution of transpiration was much lower, at 35 to 50 %. Potential limitations of such an in situ system are related to environmental conditions which could be minimized by using a temperature-controlled chamber for the laser spectrometer. Further, the applicability of the system using previously oven-dried soil material might be limited by physicochemical soil properties (i.e., clay minerals). Uncertainty in the in situ system is suggested to be reduced by improving the calibration procedure and further studying fractionation effects influencing the isotope ratios in the soil water, especially at low water contents. Furthermore, the influence of soil-respired CO2 on isotope values within the root zone

  6. Determination of the δ2H and δ18O of soil water and water in plant matter; RSIL lab code 1700

    USGS Publications Warehouse

    Revesz, Kinga M.; Buck, Bryan; Coplen, Tyler B.

    2012-01-01

    The purpose of the Reston Stable Isotope Laboratory lab code 1700 is to determine the δ2H/1H), abbreviated as δ2H, and the δ18O/16O), abbreviated as δ18O, of soil water and water in plant matter. This method is based on the observation that water and toluene form an azeotropic mixture at 84.1 °C. This temperature is substantially lower than the boiling points of water (100 °C) and toluene (110 °C), but water and toluene are immiscible at ambient temperature. The water content of a soil or plant is determined by weighing, drying, and reweighing a small amount of sample. Sufficient sample to collect 3 to 5 milliliters of water after distillation is loaded into a distillation flask. Sufficient toluene is added so that the sample is immersed throughout the entire distillation to minimize evaporation of water, which would affect the δ2H and δ18O values. The mixture of sample and toluene is heated in a flask to its boiling point (84.1 °C) so that water from the sample and toluene can distill together into a specially designed collection funnel. The temperature of 84.1 °C is maintained until the water has been quantitatively transferred to the collection funnel, at which time the temperature is raised to the boiling point of the remaining component (toluene, 110 °C). The collection funnel is maintained at ambient temperature so that the sample water and toluene can be separated physically. After separation, the sample water is purified by addition of paraffin wax to the container with the sample water, capping the container, and heating to approximately 60 °C to melt the wax. Trace amounts of toluene will dissolve in the wax, purifying the sample water for isotopic analysis. The isotopic composition of the purified water is then determined by equilibration with gaseous hydrogen or carbon dioxide, followed by dual-inlet isotope-ratio mass spectrometry. Because laser-absorption spectrometry is sensitive to organic compounds, such as trace toluene remaining in

  7. Determination of energy expenditure during heavy exercise, normal daily activity, and sleep using the doubly-labelled-water (/sup 2/H/sub 2/ 18O) method

    SciTech Connect

    Stein, T.P.; Hoyt, R.W.; Settle, R.G.; O'Toole, M.; Hiller, W.D.

    1987-03-01

    Energy expenditure of four subjects was measured by the doubly-labelled-water (/sup 2/H/sub 2/ 18O) method to determine if energy expenditure could be determined over short periods. Three subjects were studied while they performed 8 h of heavy exercise in a laboratory environment. Urine and blood samples were taken before and after exercise. Estimated energy expended during 8 h of high-intensity exercise for three subjects was 757 +/- 118 kcal/h by the doubly-labelled-water method using urine and a two-point calculation, which compared favorably with 735 +/- 82 kcal/h obtained by respiratory gas exchange. For the fourth subject, daytime, nighttime, and daily energy expenditure was calculated by both the two-pair method and decay-curve analysis of urine and saliva samples collected in the morning and at night. Daytime and nighttime energy expenditures differed significantly (p less than 0.05).

  8. Environmental isotopes (18O, 2H, and 87Sr/86Sr) as a tool in groundwater investigations in the Keta Basin, Ghana

    NASA Astrophysics Data System (ADS)

    Jørgensen, Niels; Banoeng-Yakubo, Bruce

    2001-03-01

    Analyses of environmental isotopes (18O, 2H, and 87Sr/86Sr) are applied to groundwater studies with emphasis on saline groundwater in aquifers in the Keta Basin, Ghana. The 87Sr/86Sr ratios of groundwater and surface water of the Keta Basin primarily reflect the geology and the mineralogical composition of the formations in the catchments and recharge areas. The isotopic compositions of 18O and 2H of deep groundwater have small variations and plot close to the global meteoric water line. Shallow groundwater and surface water have considerably larger variations in isotopic compositions, which reflect evaporation and preservation of seasonal fluctuations. A significant excess of chloride in shallow groundwater in comparison to the calculated evaporation loss is the result of a combination of evaporation and marine sources. Groundwaters from deep wells and dug wells in near-coastal aquifers are characterized by relatively high chloride contents, and the significance of marine influence is evidenced by well-defined mixing lines for strontium isotopes, and hydrogen and oxygen stable isotopes, with isotopic compositions of seawater as one end member. The results derived from environmental isotopes in this study demonstrate that a multi-isotope approach is a useful tool to identify the origin and sources of saline groundwater. Résumé. L'analyse des isotopes du milieu (18O, 2H, et 87Sr/86Sr) a été mise en œuvre pour des études hydrogéologiques portant sur des eaux souterraines salées des aquifères du bassin de Keta (Ghana). Les rapports isotopiques 87Sr/86Sr de l'eau souterraine et de l'eau de surface du bassin de Keta reflètent principalement la géologie et la composition minéralogique des formations des bassins d'alimentation et des zones de recharge. Les compositions isotopiques en 18O et en 2H des eaux souterraines profondes présentent de faibles variations et se placent près de la droite des eaux météoriques mondiales. Les eaux des nappes peu profondes

  9. Environmental isotopes (18O, 2H, and 87Sr/86Sr) as a tool in groundwater investigations in the Keta Basin, Ghana

    NASA Astrophysics Data System (ADS)

    Jørgensen, Niels; Banoeng-Yakubo, Bruce

    2001-03-01

    Analyses of environmental isotopes (18O, 2H, and 87Sr/86Sr) are applied to groundwater studies with emphasis on saline groundwater in aquifers in the Keta Basin, Ghana. The 87Sr/86Sr ratios of groundwater and surface water of the Keta Basin primarily reflect the geology and the mineralogical composition of the formations in the catchments and recharge areas. The isotopic compositions of 18O and 2H of deep groundwater have small variations and plot close to the global meteoric water line. Shallow groundwater and surface water have considerably larger variations in isotopic compositions, which reflect evaporation and preservation of seasonal fluctuations. A significant excess of chloride in shallow groundwater in comparison to the calculated evaporation loss is the result of a combination of evaporation and marine sources. Groundwaters from deep wells and dug wells in near-coastal aquifers are characterized by relatively high chloride contents, and the significance of marine influence is evidenced by well-defined mixing lines for strontium isotopes, and hydrogen and oxygen stable isotopes, with isotopic compositions of seawater as one end member. The results derived from environmental isotopes in this study demonstrate that a multi-isotope approach is a useful tool to identify the origin and sources of saline groundwater. Résumé. L'analyse des isotopes du milieu (18O, 2H, et 87Sr/86Sr) a été mise en œuvre pour des études hydrogéologiques portant sur des eaux souterraines salées des aquifères du bassin de Keta (Ghana). Les rapports isotopiques 87Sr/86Sr de l'eau souterraine et de l'eau de surface du bassin de Keta reflètent principalement la géologie et la composition minéralogique des formations des bassins d'alimentation et des zones de recharge. Les compositions isotopiques en 18O et en 2H des eaux souterraines profondes présentent de faibles variations et se placent près de la droite des eaux météoriques mondiales. Les eaux des nappes peu profondes

  10. 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

  11. Homocatenation of aluminum: alkane-like structures of Li2Al2H6 and Li3Al3H8.

    PubMed

    Gish, J Tyler; Popov, Ivan A; Boldyrev, Alexander I

    2015-03-27

    A new class of aluminum homocatenated compounds (LinAlnH2n+2) is proposed based on quantum chemical calculations. In these compounds, Al abstracts an electron from Li, becoming valence isoelectronic with C, Si, and Ge, thus mimicking respective structural features of Group 14 hydrides. Using the Coalescence Kick search program coupled with density functional theory calculations, we investigated the potential energy surfaces of Li2Al2 H6 and Li3Al3H6 . Then single-point-energy coupled-cluster calculations were performed for the lowest energy structures found. Indeed, the global minima established for Li2 Al2 H6 and Li3 Al3 H6 contain the Al2 H6(2-) and Al3H6(3-) kernels, which are isostructural with ethane (C2H6), disilane (Si2H6), digermane (Ge2 H6) and propane (C3H8), trisilane (Si3H8), trigermane (Ge3H8) molecules, respectively. Structural, energetic, and electronic characteristics of the Li2 Al2 H6 and Li3 Al3 H8 compounds are presented and the viability of their synthesis is discussed. PMID:25704853

  12. Continental and local climatic influences on hydrology of eucalypt-Nothofagus ecosystems revealed by δ2H, δ13C, and δ18O of ecosystem samples

    NASA Astrophysics Data System (ADS)

    Pfautsch, Sebastian; Gessler, Arthur; Rennenberg, Heinz; Weston, Christopher J.; Adams, Mark A.

    2010-03-01

    Marrying knowledge of variation in large-scale climatic parameters such as rainfall and evaporation to physiological ecology has long been argued as a powerful approach to advancing understanding of hydrology of catchments. Widely used hydrological models for assessing water yield depend on key plant attributes such as whether or not plant water use is coupled to atmospheric and/or soil water status. We analyzed δ2H and δ18O signatures of long-term rainwater collections from coastal sites near Melbourne, Australia, and in northwest Tasmania and compared them with their counterparts in rainwater, stream water, soil water, and twig water data collected over a 2 year period from south facing Eucalyptus-Nothofagus forests in the Cement Creek catchment of Mt. Donna Buang, about 70 km east of the city of Melbourne. Within the catchment, progressive evaporative enrichment among rain, soil, and twig water accounted for observed δ2H and δ18O signatures. We observed a major shift in both δ2H and δ18O signatures of rain and stream water between 2001/2002 and 2003. The shift was likely due to changes in atmospheric conditions and especially relative contributions to rainwater from oceanic and continental sources. Our plant isotope data argue strongly that radiation, not water, is a primary limitation for Nothofagus on Mt. Donna Buang. The δ18O and δ13C signatures of foliage varied with season and with topography. For the wettest and driest years in the 1978-2000 record, strong and consistent altitudinal gradients in δ13C of tree rings had a slope of between 4‰ and 5‰ km-1 of altitude. Our data highlight the importance of background (e.g., rainfall and atmospheric CO2) isotope data to interpretation of plant isotope data. Taken together with the literature, our isotope data lead us to conclude that (1) in periods of close to average rainfall, the observed meteoric water line at Mt. Donna Buang and at other stations in southeast Australia departs strongly in slope

  13. Background considerations for the 2H(7Be,3H)6Be experimental data II: Three-body continuum

    NASA Astrophysics Data System (ADS)

    Chae, K. Y.; Guimarães, V.

    2015-11-01

    The present article reports second background considerations for the experimentally obtained 2H(7Be,3H)6Be differential cross sections. The one-neutron transfer reaction was measured in inverse kinematics by using radioactive 7Be ( t 1/2 = 53.2 days) beams at the Holifield Radioactive Ion Beam Facility of the Oak Ridge National Laboratory in 2004 in order to search for the resonances in the unbound 6Be nucleus. Resonances in this nucleus would affect the 3He(3He,2 p)4He reaction rate of the proton-proton chain occurring in stars such as our sun. The result shows, however, that the direct transfer to 6Be resonances is not particularly strong compared to other reaction channels that can produce tritons in the exit channels. The goals of the present work is to better understand the cross section data from transfer reaction measurements by adopting background considerations using the three-body continuum.

  14. The use of δ(2)H and δ(18)O isotopic analyses combined with chemometrics as a traceability tool for the geographical origin of bell peppers.

    PubMed

    de Rijke, E; Schoorl, J C; Cerli, C; Vonhof, H B; Verdegaal, S J A; Vivó-Truyols, G; Lopatka, M; Dekter, R; Bakker, D; Sjerps, M J; Ebskamp, M; de Koster, C G

    2016-08-01

    Two approaches were investigated to discriminate between bell peppers of different geographic origins. Firstly, δ(18)O fruit water and corresponding source water were analyzed and correlated to the regional GNIP (Global Network of Isotopes in Precipitation) values. The water and GNIP data showed good correlation with the pepper data, with constant isotope fractionation of about -4. Secondly, compound-specific stable hydrogen isotope data was used for classification. Using n-alkane fingerprinting data, both linear discriminant analysis (LDA) and a likelihood-based classification, using the kernel-density smoothed data, were developed to discriminate between peppers from different origins. Both methods were evaluated using the δ(2)H values and n-alkanes relative composition as variables. Misclassification rates were calculated using a Monte-Carlo 5-fold cross-validation procedure. Comparable overall classification performance was achieved, however, the two methods showed sensitivity to different samples. The combined values of δ(2)H IRMS, and complimentary information regarding the relative abundance of four main alkanes in bell pepper fruit water, has proven effective for geographic origin discrimination. Evaluation of the rarity of observing particular ranges for these characteristics could be used to make quantitative assertions regarding geographic origin of bell peppers and, therefore, have a role in verifying compliance with labeling of geographical origin. PMID:26988484

  15. FieldSpec: A field portable mass spectrometer prototype for high frequency measurements of δ (2) H and δ (18) O ratios in water

    NASA Astrophysics Data System (ADS)

    López Días, Veneranda; Quang Hoang, Hung; Martínez-Carreras, Núria; Barnich, François; Wirtz, Tom; Pfister, Laurent; McDonnell, Jeffrey

    2016-04-01

    Hydrological studies relying on stable water isotopes to better understand water sources, flowpaths and transit times are currently limited by the coarse temporal resolution of sampling and analysis protocols. At present, two kinds of lab-based instruments are used : (i) the standard isotope ratio mass spectrometers (IRMS) [1] and (ii) the laser-based instruments [2, 3]. In both cases, samples need to be collected in the field and then transferred to the laboratory for the water isotopic ratio measurements (even further complex sample preparation is required for the IRMS). Hence, past and ongoing research targets the development of field deployable instruments for measuring stable water isotopes at high temporal frequencies. While recent studies have demonstrated that laser-based instruments may be taken to the field [4, 5], their size and power consumption still restrict their use to sites equipped with mains power or generators. Here, we present progress on the development of a field portable mass spectrometer (FieldSpec) for direct high frequency measurements of δ2H and δ18O ratios in water. The FieldSpec instrument is based upon the use of a double focusing magnetic sector mass spectrometer in combination with an electron impact ion source and a membrane dual inlet system. The instrument directly collects liquid water samples in the field, which are then converted into water vapour before being injected into the mass spectrometer for the stable isotope analysis. δ2H and δ18O are derived from the measured mass spectra. All the components are arranged in a vacuum case having a suit case type dimension with portable electronics and battery. Proof-of-concept experiments have been carried out to characterize the instrument. The results show that the FieldSpec instrument has good linearity (R2 = 0.99). The reproducibility of the instrument ranges between 1 and 4 ‰ for δ2H and between 0.1 and 0.4 ‰ for δ18O isotopic ratio measurements. A measurement

  16. Hydrochemical and isotopic (2H, 18O and 37Cl) constraints on evolution of geothermal water in coastal plain of Southwestern Guangdong Province, China

    NASA Astrophysics Data System (ADS)

    Chen, Liuzhu; Ma, Teng; Du, Yao; Xiao, Cong; Chen, Xinming; Liu, Cunfu; Wang, Yanxin

    2016-05-01

    Geothermal energy is abundant in Guangdong Province of China, however, majority of it is still unexploited. To take full advantage of this energy, it is essential to know the information of geothermal system. Here, physical parameters such as pH and temperature, major ion (Na+, Ca2 +, Mg2 +, Cl-, SO42 - and HCO3-), trace elements (Br-, Sr2 +, Li+ and B3 +) and stable isotopes (2H, 18O and 37Cl) in geothermal water, non-geothermal water (river water, cold groundwater) and seawater were used to identify the origin and evolution of geothermal water in coastal plain of Southwest of Guangdong. Two separate groups of geothermal water have been identified in study area. Group A, located in inland of study area, is characterized by Na+ and HCO3-. Group B, located in coastal area, is characterized by Na+ and Cl-. The relationships of components vs. Cl for different water samples clearly suggest the hydrochemical differences caused by mixing with seawater and water-rock interactions. It's evident that water-rock interactions under high temperature make a significant contribution to hydrochemistry of geothermal water for both Group A and Group B. Besides, seawater also plays an important role during geothermal water evolution for Group B. Mixing ratios of seawater with geothermal water for Group B are calculated by Cl and Br binary diagram, the estimated results show that about < 1% to < 35% of seawater has mixed into geothermal water, and seawater might get into the geothermal system by deep faults. Molar Na/Cl ratios also support these two processes. Geothermal and non-geothermal water samples plot around GMWL in the δ2H vs. δ18O diagram, indicating that these samples have a predominant origin from meteoric water. Most of geothermal water samples display δ37Cl values between those of the non-geothermal water and seawater samples, further reveals three sources of elements supply for geothermal water, including atmospheric deposition, bedrocks and seawater, which show a

  17. Identifying residence times and streamflow generation processes using δ18O and δ2H in meso-scale catchments in the Abay/Upper Blue Nile, Ethiopia

    NASA Astrophysics Data System (ADS)

    Tekleab, S.; Wenninger, J.; Uhlenbrook, S.

    2013-08-01

    Measurements of the stable isotopes oxygen-18 (18O) and deuterium (2H) were carried out in two meso-scale catchments, Chemoga (358 km2) and Jedeb (296 km2) south of Lake Tana, Abay/Upper Blue Nile basin, Ethiopia. The region is of paramount importance for the water resources in the Nile basin. Stable isotope composition in precipitation, spring water and streamflow were analyzed (i) to characterize the spatial and temporal variations of water fluxes; (ii) to estimate the mean residence time of water using a sine wave regression approach; and (iii) to identify runoff components using classical two component hydrograph separations at a seasonal time scale. The results show that the isotopic composition of precipitation exhibit marked seasonal variations, which suggests different sources of moisture generation for the rainfall in the study area. The Atlantic-Indian ocean, Congo basin, and the Sud swamps are the likely the potential moisture source areas during the main rainy (summer) season. While, the Indian-Arabian, and Mediterranean Sea moisture source areas during little rain (spring), and dry (winter) seasons. The spatial variation of the isotopic composition is affected by the amount effect and to less extent by altitude and temperature effects. A mean altitude effect of -0.12‰ (100 m)-1 for 18O and -0.58‰ (100 m)-1 for 2H were discernable in precipitation isotope composition. The seasonal variations of the isotopic signature of the spring water exhibit a damped response as compared to the river waters, which shows that the spring water has longer residence times than the river water. Results from the hydrograph separation at a seasonal time scale indicate the dominance of event water with an average of 71% and 64% of the total runoff during the wet season in the Chemoga and Jedeb catchment, respectively. The stable isotope compositions of streamflow samples were damped compared to the input function of precipitation for both catchments and this damping was

  18. Analysis of δ18O and δ2H of fluid inclusion water in speleothems using cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Arienzo, M. M.; Swart, P. K.; Schroeder, C.; Hsiao, G.; Vonhof, H. B.

    2012-12-01

    Fluid inclusion isotope analysis is the analysis of microscopic, water filled cavities in speleothems. These cavities preserve drip water at the time of formation and fluid inclusions isotopic analysis provides information on the formation water (δ18Ow) and temperature can be calculated. The determination of δ18Ow and temperature is valuable for paleoclimate reconstructions. Recent work on speleothem fluid inclusions has utilized continuous-flow isotopic ratio mass spectrometry (IRMS) methods for determination of δ18Ow and δ2H of fluid inclusion water (Vonhof et al., Rapid. Comm. Mass Spec., 20:2553-2558, 2006; Dublyansky, and Spotl, Rapid. Comm. Mass Spec., 23: 2605-2613, 2009). Here we present a new technique utilizing cavity-ring down spectroscopy (CRDS) for δ18O and δ2H analysis of fluid inclusions and compare the data obtained to that measured on the Amsterdam Device which is a crusher system linked with an IRMS developed at the VU University Amsterdam. The extraction line at the University of Miami is an in-line system directly interfaced with the Picarro CRDS isotopic water analyzer and the design of the line is similar to the Amsterdam Device. The extraction line consists of a crusher device which is a modified valve unit, a septum port for the direct injection of water and a water trap. The CRDS technique is based on using a near infrared laser which is scanned over the H2O spectral range and by measuring the absorption spectra by ring-down, isotopic abundances are determined. This system has the potential for greater precision measurements than traditional IRMS systems. Therefore for fluid inclusion analysis, CRDS may prove to be an alternative to IRMS.

  19. Energy costs of surgery as measured by the doubly labeled water (/sup 2/H/sub 2//sup 18/O) method

    SciTech Connect

    Novick, W.M.; Nusbaum, M.; Stein, T.P.

    1988-01-01

    Energy expenditure before and after surgery was determined in seven patients by the doubly labeled water (/sup 2/H/sub 2//sup 18/O) method (DLW). The values were compared with values obtained by respiratory gas exchange by means of a metabolic measuring cart (MMC). Patients were maintained on total parenteral nutrition before and after trauma. The principal finding was an increase in the rate of CO/sub 2/ production of 11.9 +/- 5.0% after surgery. This corresponds to a 267 +/- increase in energy expenditure (p less than 0.05). No trauma-associated change in energy expenditure was found with the MMC. The correlation of preoperative values from MMC and DLW was not statistically significant (r = 0.25), nor was the correlation of MMC and the Harris-Benedict equation, but the correlation of DLW with Harris-Benedict equation was statistically significant (r = 0.73, p less than 0.05). We suggest that the discrepancy is because the DLW method measures the cumulative energy expenditure over a period, whereas the MMC gives a spot measurement.

  20. Sauna, sweat and science - quantifying the proportion of condensation water versus sweat using a stable water isotope ((2)H/(1)H and (18)O/(16)O) tracer experiment.

    PubMed

    Zech, Michael; Bösel, Stefanie; Tuthorn, Mario; Benesch, Marianne; Dubbert, Maren; Cuntz, Matthias; Glaser, Bruno

    2015-01-01

    Most visitors of a sauna appreciate the heat pulse that is perceived when water is poured on the stones of a sauna stove. However, probably only few bathers are aware that this pleasant heat pulse is caused by latent heat being released onto our skin due to condensation of water vapour. In order to quantify the proportion of condensation water versus sweat to dripping water of test persons we conducted sauna experiments using isotopically labelled (δ(18)O and δ(2)H) thrown water as tracer. This allows differentiating between 'pure sweat' and 'condensation water'. Two ways of isotope mass balance calculations were applied and yielded similar results for both water isotopes. Accordingly, condensation contributed considerably to dripping water with mean proportions of 52 ± 12 and 54 ± 7% in a sauna experiment in winter semester 2011/12 and 30 ± 13 and 33 ± 6% in a sauna experiment in winter semester 2012/13, respectively, depending on the way of calculating the isotope mass balance. It can be concluded from the results of our dual isotope labelling sauna experiment that it is not all about sweat in the sauna. PMID:26110629

  1. Global prediction of δA and δ2H18O evaporation slopes for lakes and soil water accounting for seasonality

    NASA Astrophysics Data System (ADS)

    Gibson, J. J.; Birks, S. J.; Edwards, T. W. D.

    2008-06-01

    Global trends in the δ2H18O enrichment slope of continental lakes and shallow soil water undergoing natural evaporation are predicted on the basis of a steady state isotope balance model using basic monthly climate data (i.e., temperature and humidity), isotopes in precipitation data, and a simple equilibrium liquid-vapor model to estimate isotopes in atmospheric moisture. The approach, which demonstrates the extension of well-known conceptual models in stable isotope hydrology to the global scale, is intended to serve as a baseline reference for evaluating field-based isotope measurements of vapor, surface water, and soil water and as a diagnostic tool for more complex ecosystem models, including isotope-equipped climate models. Our simulations reproduce the observed local evaporation line slopes (4-5 range for lakes and 2-3 range for soil water) for South America, Africa, Australia, and Europe. A systematic increase in slopes (5-8 range for lakes) toward the high latitudes is also predicted for lakes and soil water in northern North America, Asia, and Antarctica illustrating a latitudinal (mainly seasonality-related) control on the evaporation signals that has not been widely reported. The over-riding control on the poleward steepening of the local evaporation lines is found to be the isotopic separation between evaporation-flux-weighted atmospheric moisture and annual precipitation, and to lesser extents temperature and humidity, all of which are influenced by enhanced seasonality in cold regions.

  2. 2H,3H-Decafluoropentane-Based Nanodroplets: New Perspectives for Oxygen Delivery to Hypoxic Cutaneous Tissues

    PubMed Central

    Jose, Jithin; Khadjavi, Amina; Cavallo, Federica; Quaglino, Elena; Panariti, Alice; Rivolta, Ilaria; Benintende, Emilio; Varetto, Gianfranco; Argenziano, Monica; Troia, Adriano; Cavalli, Roberta; Guiot, Caterina

    2015-01-01

    Perfluoropentane (PFP)-based oxygen-loaded nanobubbles (OLNBs) were previously proposed as adjuvant therapeutic tools for pathologies of different etiology sharing hypoxia as a common feature, including cancer, infection, and autoimmunity. Here we introduce a new platform of oxygen nanocarriers, based on 2H,3H-decafluoropentane (DFP) as core fluorocarbon. These new nanocarriers have been named oxygen-loaded nanodroplets (OLNDs) since DFP is liquid at body temperature, unlike gaseous PFP. Dextran-shelled OLNDs, available either in liquid or gel formulations, display spherical morphology, ~600 nm diameters, anionic charge, good oxygen carrying capacity, and no toxic effects on human keratinocytes after cell internalization. In vitro OLNDs result more effective in releasing oxygen to hypoxic environments than former OLNBs, as demonstrated by analysis through oxymetry. In vivo, OLNDs effectively enhance oxy-hemoglobin levels, as emerged from investigation by photoacoustic imaging. Interestingly, ultrasound (US) treatment further improves transdermal oxygen release from OLNDs. Taken together, these data suggest that US-activated, DFP-based OLNDs might be innovative, suitable and cost-effective devices to topically treat hypoxia-associated pathologies of the cutaneous tissues. PMID:25781463

  3. 2H,3H-decafluoropentane-based nanodroplets: new perspectives for oxygen delivery to hypoxic cutaneous tissues.

    PubMed

    Prato, Mauro; Magnetto, Chiara; Jose, Jithin; Khadjavi, Amina; Cavallo, Federica; Quaglino, Elena; Panariti, Alice; Rivolta, Ilaria; Benintende, Emilio; Varetto, Gianfranco; Argenziano, Monica; Troia, Adriano; Cavalli, Roberta; Guiot, Caterina

    2015-01-01

    Perfluoropentane (PFP)-based oxygen-loaded nanobubbles (OLNBs) were previously proposed as adjuvant therapeutic tools for pathologies of different etiology sharing hypoxia as a common feature, including cancer, infection, and autoimmunity. Here we introduce a new platform of oxygen nanocarriers, based on 2H,3H-decafluoropentane (DFP) as core fluorocarbon. These new nanocarriers have been named oxygen-loaded nanodroplets (OLNDs) since DFP is liquid at body temperature, unlike gaseous PFP. Dextran-shelled OLNDs, available either in liquid or gel formulations, display spherical morphology, ~600 nm diameters, anionic charge, good oxygen carrying capacity, and no toxic effects on human keratinocytes after cell internalization. In vitro OLNDs result more effective in releasing oxygen to hypoxic environments than former OLNBs, as demonstrated by analysis through oxymetry. In vivo, OLNDs effectively enhance oxy-hemoglobin levels, as emerged from investigation by photoacoustic imaging. Interestingly, ultrasound (US) treatment further improves transdermal oxygen release from OLNDs. Taken together, these data suggest that US-activated, DFP-based OLNDs might be innovative, suitable and cost-effective devices to topically treat hypoxia-associated pathologies of the cutaneous tissues. PMID:25781463

  4. Fabrication of Indocyanine Green and 2H, 3H-perfluoropentane loaded microbubbles for fluorescence and ultrasound imaging

    NASA Astrophysics Data System (ADS)

    He, Yutong; Wu, Qiang; Ma, Rong; Chang, Shufang; Shao, Pengfei; Xu, Ronald

    2016-03-01

    As a near-infrared (NIR) fluorescence dye, Indocyanine Green (ICG) has not gained broader clinical applications, owing to its multiple limitations such as concentration-dependent aggregation, low fluorescence quantum yield, poor physicochemical stability and rapid elimination from the body. In the meanwhile, 2H,3H-perfluoropentane (H-PFP) has been widely studied in ultrasound imaging as a vehicle for targeted delivery of contrast agents and drugs. We synthesized a novel dual-modal fluorescence and ultrasound contrast agent by encapsulating ICG and H-PFP in lipid microbubbles using a liquid-driven coaxial flow focusing (LDCFF) process. Uniform microbubbles with the sizes ranging from 1-10um and great ICG loading efficiency was achieved by this method. Our benchtop experiments showed that ICG/H-PFP microbubbles exhibited less aggregation, increased fluorescence intensity and more stable photostability compared to free ICG aqueous solution. Our phantom experiments demonstrated that ICG/H-PFP microbubbles enhanced the imaging contrasts in fluorescence imaging and ultrasonography. Our animal experiments indicated that ICG/H-PFP microbubbles extended the ICG life time and facilitated dual mode fluorescence and ultrasound imaging in vivo.

  5. The {sup 2}H(d,p){sup 3}H Reaction At Astrophysical Energies Studied Via The Trojan Horse Method And Pole Approximation Validity Test

    SciTech Connect

    Sparta, R.; Pizzone, R. G.; Spitaleri, C.; Cherubini, S.; Crucilla, V.; Gulino, M.; La Cognata, M.; Lamia, L.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Aliotta, M.; Burjan, V.; Hons, Z.; Kroha, V.; Mrazek, J.; Kiss, G.; McCleskey, M.; Trache, L.

    2010-03-01

    In order to understand primordial and stellar nucleosynthesis, we have studied {sup 2}H(d,p){sup 3}H reaction at 0, 4 MeV down to astrophysical energies. Knowledge of this S-factor is interesting also to plan reactions for fusion reactors to produce energy. {sup 2}H(d,p){sup 3}H has been studied through the Trojan Horse Method applied to the three-body reaction {sup 2}H({sup 3}He,pt)H, at a beam energy of 17 MeV. Once protons and tritons are detected in coincidence and the quasi-free events are selected, the obtained S-factor has been compared with direct reactions results. Such data are in agreement with the direct ones, and a pole invariance test has been obtained comparing the present result with another {sup 2}H(d,p){sup 3}H THM one, performed with a different spectator particle (see fig. 1).

  6. Effects of recharge and discharge on delta2H and delta18O composition and chloride concentration of high arsenic/fluoride groundwater from the Datong Basin, northern China.

    PubMed

    Xie, Xianjun; Wang, Yanxin; Su, Chunli; Duan, Mengyu

    2013-02-01

    To better understand the effects of recharge and discharge on the hydrogeochemistry of high levels of arsenic (As) and fluoride (F) in groundwater, environmental isotopic composition (delta2H and delta18O) and chloride (Cl) concentrations were analyzed in 29 groundwater samples collected from the Datong Basin. High arsenic groundwater samples (As > 50 micog/L) were found to be enriched in lighter isotopic composition that ranged from -92 to -78 per thousand for deuterium (delta2H) and from -12.5 to -9.9 per thousand for oxygen-18 (delta18O). High F-containing groundwater (F > 1 mg/L) was relatively enriched in heavier isotopic composition and varied from -90 to -57 per thousand and from -12.2 to -6.7 per thousand for delta2H and delta18O, respectively. High chloride concentrations and delta18O values were primarily measured in groundwater samples from the northern and southwestern portions of the study area, indicating the effect of evaporation on groundwater. The observation of relatively homogenized and low delta18O values and chloride concentrations in groundwater samples from central part of the Datong Basin might be a result of fast recharge by irrigation returns, which suggests that irrigation using arsenic-contaminated groundwater affected the occurrence of high arsenic-containing groundwater in the basin. PMID:23472327

  7. Measuring variations of δ18O and δ2H in atmospheric water vapour using laser spectroscopy: an instrument characterisation study

    NASA Astrophysics Data System (ADS)

    Aemisegger, F.; Sturm, P.; Graf, P.; Sodemann, H.; Pfahl, S.; Knohl, A.; Wernli, H.

    2012-02-01

    Variations of stable water isotopes in water vapour have become measurable at a measurement frequency of about 1 Hz in recent years using novel laser spectroscopic techniques. This enables us to perform continuous measurements for process-based investigations of the atmospheric water cycle at the time scales relevant for synoptic meteorology. An important prerequisite for the interpretation of data from automated field measurements lasting for several weeks or months is a detailed knowledge about instrument properties and the sources of measurement uncertainty. We present here a comprehensive characterisation and comparison study of two commercial laser spectroscopic systems based on cavity ring-down spectroscopy (Picarro) and off-axis integrated cavity output spectroscopy (Los Gatos Research). The uncertainty components of the measurements were first assessed in laboratory experiments, focussing on the effects of (i) water vapour mixing ratio, (ii) measurement stability, (iii) uncertainties due to calibration and (iv) response times of the isotope measurements due to adsorption-desorption processes on the tubing and measurement cavity walls. Based on the experience from our laboratory experiments we set up a one-week field campaign for comparing measurements of the ambient isotope signals of the two laser spectroscopic systems. The optimal calibration strategy determined for both instruments was applied as well as the correction functions for water vapour mixing ratio effects. The root mean square difference between the isotope signals from the two instruments during the field deployment was 2.3‰ for δ2H, 0.5‰ for δ18O and 3.1‰ for deuterium excess. These uncertainty estimates from field measurements compare well to those found in the laboratory experiments. The present quality of measurements from laser spectroscopic instruments combined with a calibration system opens new possibilities for investigating the atmospheric water cycle and the land

  8. Measuring variations of δ18O and δ2H in atmospheric water vapour using two commercial laser-based spectrometers: an instrument characterisation study

    NASA Astrophysics Data System (ADS)

    Aemisegger, F.; Sturm, P.; Graf, P.; Sodemann, H.; Pfahl, S.; Knohl, A.; Wernli, H.

    2012-07-01

    Variations of stable water isotopes in water vapour have become measurable at a measurement frequency of about 1 Hz in recent years using novel laser spectroscopic techniques. This enables us to perform continuous measurements for process-based investigations of the atmospheric water cycle at the time scales relevant for synoptic and mesoscale meteorology. An important prerequisite for the interpretation of data from automated field measurements lasting for several weeks or months is a detailed knowledge about instrument properties and the sources of measurement uncertainty. We present here a comprehensive characterisation and comparison study of two commercial laser spectroscopic systems based on cavity ring-down spectroscopy (Picarro) and off-axis integrated cavity output spectroscopy (Los Gatos Research). The uncertainty components of the measurements were first assessed in laboratory experiments, focussing on the effects of (i) water vapour mixing ratio, (ii) measurement stability, (iii) uncertainties due to calibration and (iv) response times of the isotope measurements due to adsorption-desorption processes on the tubing and measurement cavity walls. Based on the experience from our laboratory experiments, we set up a one-week field campaign for comparing measurements of the ambient isotope signals from the two laser spectroscopic systems. The optimal calibration strategy determined for both instruments was applied as well as the correction functions for water vapour mixing ratio effects. The root mean square difference between the isotope signals from the two instruments during the field deployment was 2.3‰ for δ2H, 0.5‰ for δ18O and 3.1‰ for deuterium excess. These uncertainty estimates from field measurements compare well to those found in the laboratory experiments. The present quality of measurements from laser spectroscopic instruments combined with a calibration system opens new possibilities for investigating the atmospheric water cycle and

  9. Coupling 2H and 18O biomarker results provides new insight into palaeohumidity changes in East Africa during the last glacial

    NASA Astrophysics Data System (ADS)

    Hepp, Johannes; Zech, Roland; Tuthorn, Mario; Glaser, Bruno; Rozanski, Kazimierz; Zech, Wolfgang; Zech, Michael

    2015-04-01

    We couple compound-specific δ2H results of leaf wax-derived n-alkanes with compound-specific δ18O results of hemicellulose-derived sugars extracted from the loess-paleosol-sequence Maundi (3° 10'27.5'S, 37° 31'05.8'E) located on the south-eastern slopes of Mt. Kilimanjaro at ~ 2780 m above sea level. This coupled biomarker approach allows inter alia establishing a ca. 100 ka record of the isotopic composition of leaf water. Accordingly, the deuterium-excess of leaf water may serve as a proxy for palaeohumidity. Furthermore, the coupled biomarker approach allows reconstructing the isotopic composition of palaeoprecipitation (by using the slope the local evaporation line derived from a simple Craig-Gordon model). Our results suggest that sedimentary δ2Hleaf-wax records should not be interpreted directly in terms of reflecting δ2Hprec because variable leaf water evaporative enrichment can strongly overprint the δ2Hprec signal. The Maundi δ2Hn-alkane record can be compared with δ2Hwax records from Lake Challa, Lake Tanganyika and Lake Malawi. Accordingly, the Maundi δ2Hn-alkane record is generally in good agreement with the Lake Challa and the Lake Tanganyika δ2Hwax records. However, a clear altitude effect can be seen in the δ2H records (Maundi: 2780 m a.s.l.; Lake Challa: 880 m a.s.l.; Lake Tanganyika: 773 m a.s.l.; Lake Malawi: 474 m a.s.l.). Moreover, the Maundi δ2Hn-alkane record reveals a clear smaller range compared to the other δ2Hwax records. Finally, especially the Lake Malawi δ2Hwax record reveals also clearly different features than the other available δ2Hwax records. These differences resulted in different interpretations of the δ2Hwax records (amount effect vs. source effect). Our coupled δ18Osugar and δ2Hn-alkane approach sheds new light into this discussion. In brief, reconstructed low deuterium-excessleaf-water values during the African Humid Period (AHP) indicate humid climatic conditions. By contrast, higher deuterium

  10. Conversion of erythro-D-sphinganine to its (1-/sup 2/H/sub 1/) and (1-/sup 3/H/sub 1/) derivatives

    SciTech Connect

    Crossman, M.W.; Hirschberg, C.B.

    1984-07-01

    A convenient chemical synthesis of erythro-D-(1-2H1) sphinganine and erythro-D-(1-3H1)sphinganine is described. The approach utilizes a stereospecific starting material (natural sphinganine prepared from bovine brain sphingomyelin) and applies a sequence of selective protection of functional groups yielding 2-acetamido-3-O-benzoyloctadecan-1-ol. Oxidation of the primary alcohol to an aldehyde followed by NaB2H4 or NaB3H4 reduction and hydrolysis of the protective groups yields erythro-D-(1-2H1)sphinganine or erythro-D-(1-3H1)sphinganine. The synthetic intermediates and isotopically labeled sphinganines are characterized by infrared analysis, 1H-nuclear magnetic resonance, optical rotation, and gas-liquid radiochromatographic and mass spectral fragmentation analyses. The (1-2H1) and (1-3H1) derivatives were obtained with overall yields (and isotope enrichments) of 11% (min. 84 mol% 2H1) and 8% (60 mCi/mmol), respectively.

  11. Rhodium-catalyzed cascade oxidative annulation leading to substituted naphtho[1,8-bc]pyrans by sequential cleavage of C(sp2)-H/C(sp3)-H and C(sp2)-H/O-H bonds.

    PubMed

    Tan, Xing; Liu, Bingxian; Li, Xiangyu; Li, Bin; Xu, Shansheng; Song, Haibin; Wang, Baiquan

    2012-10-01

    The cascade oxidative annulation reactions of benzoylacetonitrile with internal alkynes proceed efficiently in the presence of a rhodium catalyst and a copper oxidant to give substituted naphtho[1,8-bc]pyrans by sequential cleavage of C(sp(2))-H/C(sp(3))-H and C(sp(2))-H/O-H bonds. These cascade reactions are highly regioselective with unsymmetrical alkynes. Experiments reveal that the first-step reaction proceeds by sequential cleavage of C(sp(2))-H/C(sp(3))-H bonds and annulation with alkynes, leading to 1-naphthols as the intermediate products. Subsequently, 1-naphthols react with alkynes by cleavage of C(sp(2))-H/O-H bonds, affording the 1:2 coupling products. Moreover, some of the naphtho[1,8-bc]pyran products exhibit intense fluorescence in the solid state. PMID:22989331

  12. Assessment of the amount of body water in the Red Knot (Calidris canutus): an evaluation of the principle of isotope dilution with 2H, (17)O, and (18)O as measured with laser spectrometry and isotope ratio mass spectrometry.

    PubMed

    Kerstel, Erik R T; Piersma, Theunis; Piersma, Theunis A J; Gessaman, James A; Gessaman, G Jim; Dekinga, Anne; Meijer, Harro A J; Visser, G Henk

    2006-03-01

    We have used the isotope dilution technique to study changes in the body composition of a migratory shorebird species (Red Knot, Calidris canutus) through an assessment of the amount of body water in it. Birds were quantitatively injected with a dose of water with elevated concentrations of 2H, (17)O, and (18)O. Thereafter, blood samples were taken and distilled. The resulting water samples were analysed using an isotope ratio mass spectrometry (for 2H and (18)O only) and a stable isotope ratio infrared laser spectrometry (2H, (17)O, and (18)O) to yield estimates of the amount of body water in the birds, which in turn could be correlated to the amount of body fat. Here, we validate laser spectrometry against mass spectrometry and show that all three isotopes may be used for body water determinations. This opens the way to the extension of the doubly labelled water method, used for the determination of energy expenditure, to a triply labelled water method, incorporating an evaporative water loss correction on a subject-by-subject basis or, alternatively, the reduction of the analytical errors by statistically combining the (17)O and (18)O measurements. PMID:16500750

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  14. Heats of formation and thermodynamic functions for C2H, C3H, and C4H from 300 K to 6000 K

    NASA Technical Reports Server (NTRS)

    Saturno, A. F.

    1982-01-01

    A review of the energy level and heat of formation data for the species C2H, C3H, and C4H is given. The procedure for computing thermochemical data from partition function is also reviewed. Working expressions for approximate partition functions, free-energy function, enthalpy function, and heat capacity for a linear polyatomic species are presented.

  15. Measurement of Whole-Body CO2 Production in Birds Using Real-Time Laser-Derived Measurements of Hydrogen (δ(2)H) and Oxygen (δ(18)O) Isotope Concentrations in Water Vapor from Breath.

    PubMed

    Mitchell, G W; Guglielmo, C G; Hobson, K A

    2015-01-01

    The doubly labeled water (DLW) method is commonly used to measure energy expenditure in free-living wildlife and humans. However, DLW studies involving animals typically require three blood samples, which can affect behavior and well-being. Moreover, measurement of H (δ(2)H) and O (δ(18)O) isotope concentrations in H2O derived from blood using conventional isotope ratio mass spectrometry is technically demanding, time-consuming, and often expensive. A novel technique that would avoid these constraints is the real-time measurement of δ(2)H and δ(18)O in the H2O vapor of exhaled breath using cavity ring-down (CRD) spectrometry, provided that δ(2)H and δ(18)O from body H2O and breath were well correlated. Here, we conducted a validation study with CRD spectrometry involving five zebra finches (Taeniopygia guttata), five brown-headed cowbirds (Molothrus ater), and five European starlings (Sturnus vulgaris), where we compared δ(2)H, δ(18)O, and rCO2 (rate of CO2 production) estimates from breath with those from blood. Isotope concentrations from blood were validated by comparing dilution-space estimates with measurements of total body water (TBW) obtained from quantitative magnetic resonance. Isotope dilution-space estimates from δ(2)H and δ(18)O values in the blood were similar to and strongly correlated with TBW measurements (R(2) = 0.99). The (2)H and (18)O (ppm) in breath and blood were also highly correlated (R(2) = 0.99 and 0.98, respectively); however, isotope concentrations in breath were always less enriched than those in blood and slightly higher than expected, given assumed fractionation values between blood and breath. Overall, rCO2 measurements from breath were strongly correlated with those from the blood (R(2) = 0.90). We suggest that this technique will find wide application in studies of animal and human energetics in the field and laboratory. We also provide suggestions for ways this technique could be further improved. PMID:26658408

  16. Updated evidence of the Trojan horse particle invariance for the 2H(d,p)3H reaction

    NASA Astrophysics Data System (ADS)

    Pizzone, R. G.; Spitaleri, C.; Bertulani, C. A.; Mukhamedzhanov, A. M.; Blokhintsev, L.; La Cognata, M.; Lamia, L.; Rinollo, A.; Spartá, R.; Tumino, A.

    2013-02-01

    The Trojan horse nucleus invariance for the binary d(d,p)t reaction was tested by means of an experiment using the quasifree 2H(6Li,pt)4He and 2H(3He,pt)H reactions after 6Li and 3He breakup, respectively. The astrophysical S(E) factor for the d(d,p)t binary process was extracted from the present data in the framework of the plane wave approximation applied to the two different breakup schemes. The obtained results are compared with direct data as well as with previous indirect investigations. The very good agreement confirms the applicability of the plane wave approximation and suggests the independence of the binary indirect cross section on the chosen Trojan horse nucleus also for the present case.

  17. Synthesis and Application of Tetrahydro-2H-fluorenes by a Pd(0)-Catalyzed Benzylic C(sp(3) )-H Functionalization.

    PubMed

    Suetsugu, Satoshi; Muto, Nobusuke; Horinouchi, Misa; Tsukano, Chihiro; Takemoto, Yoshiji

    2016-06-01

    A new method has been developed for the synthesis of tetrahydro-2H-fluorenes based on a Pd(0)-catalyzed benzylic C(sp(3) )-H functionalization. Importantly, the success of the cyclization step was dependent on there being substituents at the two positions ortho to the benzylic group to avoid an undesired C(sp(2) )-H functionalization. This method was subsequently used to prepare the right-hand fragment of the hexacyclic triterpenoid benzohopanes, and therefore represents a powerful tool for the construction of the related compounds. PMID:27124498

  18. Anthranil: An Aminating Reagent Leading to Bifunctionality for Both C(sp(3) )-H and C(sp(2) )-H under Rhodium(III) Catalysis.

    PubMed

    Yu, Songjie; Tang, Guodong; Li, Yingzi; Zhou, Xukai; Lan, Yu; Li, Xingwei

    2016-07-18

    Previous direct C-H nitrogenation suffered from simple amidation/amination with limited atom-economy and is mostly limited to C(sp(2) )-H substrates. In this work, anthranil was designed as a novel bifunctional aminating reagent for both C(sp(2) )-H and C(sp(3) )-H bonds under rhodium(III) catalysis, thus affording a nucleophilic aniline tethered to an electrophilic carbonyl. A tridendate rhodium(III) complex has been isolated as the resting state of the catalyst, and DFT studies established the intermediacy of a nitrene species. PMID:27121133

  19. Steric course of the rhodium-catalyzed decarbonylation of chiral 4-methyl-[1-3H,2-2H1]pentanal.

    PubMed

    Otsuka, H; Floss, H G

    1987-04-01

    (R)- and (S)-4-methyl-[1-3H,2-2H1]pentanal were prepared from L- and D-leucine via leucic acid and (S)- and (R)-4-methyl-[2-2H1]pentanoic acid. Decarbonylation of these samples with tris-(triphenylphosphine)rhodium chloride followed by Kuhn-Roth oxidation of the resulting 2-methylbutane gave chiral acetic acid of 35% e.e. S and 31% e.e. R configuration, respectively. The decarbonylation reaction thus proceeds with net retention of configuration, possibly accompanied by some racemization. PMID:2955591

  20. Synthesis of 2H-1,3-benzoxazin-4(3H)-one derivatives containing indole moiety: their in vitro evaluation against PDE4B.

    PubMed

    Rao, Raja Mohan; Luther, Bethala Jawahar; Rani, Chekuri Sharmila; Suresh, Namburi; Kapavarapu, Ravikumar; Parsa, Kishore V L; Rao, Mandava V Basaveswara; Pal, Manojit

    2014-02-15

    A number of 2H-1,3-benzoxazin-4(3H)-one derivatives containing indole or benzofuran moieties were synthesized by using Pd/C-Cu mediated coupling-cyclization strategy as a key step. The o-iodoanilides or o-iodophenol were coupled with 3-{2-(prop-2-ynyloxy)ethyl}-2H-benzo[e][1,3]oxazin-4(3H)-one using 10%Pd/C-CuI-PPh3 as a catalyst system and Et3N as a base to give the target compounds. All the synthesized compounds were tested for their PDE4B inhibitory potential in vitro using a cell based cAMP reporter assay. Some of them showed fold increase of the cAMP level when tested at 30 μM. A representative compound showed encouraging PDE4B inhibitory properties that were supported by its docking results. PMID:24440301

  1. Rh(III)-Catalyzed Oxidative Annulation Leading to Substituted Indolizines by Cleavage of C(sp(2))-H/C(sp(3))-H Bonds.

    PubMed

    Shen, Bingxue; Li, Bin; Wang, Baiquan

    2016-06-17

    Rhodium(III)-catalyzed oxidative annulation reactions of pyridinium trifluoromethanesulfonate salts with alkynes leading to substituted indolizines by cleavage of C(sp(2))-H/C(sp(3))-H bonds are developed. The starting materials are readily available, and the reactions have a broad substrate scope. This reaction overcomes some drawbacks of the previous indolizine synthetic methods and provides a new efficient route to indolizine derivatives. PMID:27267054

  2. Astrophysical S factors of radiative {sup 3}He{sup 4}He, {sup 3}H{sup 4}He, and {sup 2}H{sup 4}He capture

    SciTech Connect

    Dubovichenko, S. B.

    2010-09-15

    The possibility of describing the astrophysical S factors for radiative {sup 3}He{sup 4}He capture at energies of up to 15 keV and radiative {sup 3}H{sup 4}He and {sup 2}H{sup 4}He capture at energies of up 5 keV is considered on the basis of the potential cluster model involving forbidden states.

  3. Ab initio chemical kinetics for SiH2 + Si2H6 and SiH3 + Si2H5 reactions and the related unimolecular decomposition of Si3H8 under a-Si/H CVD conditions.

    PubMed

    Raghunath, P; Lin, M C

    2013-10-24

    The kinetics and mechanisms for SiH2 + Si2H6 and SiH3 + Si2H5 reactions and the related unimolecular decomposition of Si3H8 have been investigated by ab initio molecular orbital theory based on the QCISD(T)/CBS//QCISD/6-311++G(d,p) method in conjunction with quantum statistical variational Rice-Ramsperger-Kassel-Marcus (RRKM) calculations. For the barrierless radical association processes, their variational transition states have been characterized by the CASPT2//CASSCF method. The species involved in the study are known to coexist under CVD conditions. The results show that the association reaction of SiH2 and Si2H6 producing Si3H8 occurs by insertion via its lowest-energy path forming a loose hydrogen-bonding molecular complex with 8.3 kcal/mol binding energy; the reaction is exothermic by 55.0 kcal/mol. The chemically activated Si3H8 adduct can fragment by several paths, producing SiH4 + SiH3SiH (-0.7 kcal/mol), Si(SiH3)2 + H2 (-1.4 kcal/mol), and SiH3SiH2SiH + H2 (-1.4 kcal/mol). The predicted enthalpy changes as given agree well with available thermochemical data. Three other decomposition channels of Si3H8 occurring by Si-H or Si-Si breaking were found to be highly endothermic, and the reactions take place without a well-defined barrier. The heats of formation of Si3H8, SiH2SiH, Si2H4, i-Si3H7, n-Si3H7, Si(SiH3)2, and SiH3SiH2SiH have been predicted and found to be in close agreement with those available data in the literature. The product branching rate constants for SiH2 + Si2H6 and SiH3 + Si2H5 reactions and the thermal unimolecular decomposition of Si3H8 for all low-energy paths have been calculated with multichannel variational RRKM theory covering varying P,T conditions typically employed in PECVD and Cat-CVD processes for hydrogenated amorphous silicon (a-Si/H) film growth. The results were also found to be in good agreement with available kinetic data. Our kinetic results may be employed to model and control very large-area a-Si/H film growth for a

  4. Tracer (18O, 3H, 3H/3He, CFC and SF6) and hydrochemistry to elucidate processes and mean residence times in porous aquifers in the South-East of Austria (Grazer and Leibnitzer Feld)

    NASA Astrophysics Data System (ADS)

    Kralik, M.; Humer, F.; Darling, G.; Sültenfuß, J.; Wyhlidal, S.

    2012-04-01

    The European Water Framework Directive requires the surface and groundwater bodies in the EU to be back to good quality conditions by 2015. To elucidate the mean residence time (MRT), the recharge area and the potential source of contaminations in particular monitoring wells a combination of several tracers has to be applied at least over one year to answer these questions with confidence. For the implementation of this goal it is necessary that any measures to improve groundwater quality show an impact depending on the MRT. The two groundwater bodies "Grazer Feld" and "Leibnitzer Feld" in the southern part of Styria, Austria stretch out along the river Mur in the N - S direction and covers an area of 166 and 103 km2. The porous aquifer of 10 - 20 m (Grazer Feld) of 6 - 10 m (Leibnitzer Feld) thickness consists of sandy gravel and boulders. In both groundwater bodies are about 2/3 of the aquifer is covered by loam of variable thickness. The depth to water varies between 2 - 20 and 2 - 8 m, respectively. The mean precipitation rate is 900 mm/a. The groundwater runs more or less along the river Mur with a small gradient. The northern part of the Grazer Feld groundwater body is dominated by the urban structure of the city of Graz. The southern part and the groundwater body Leibnitzer Feld is impacted intensively by agricultural use. Due to the extensive agricultural use it contains high concentrations of nitrate and pesticides and shows other hydrochemical changes caused by urbanisation and industrial use. In 33 monitoring wells delta oxygen-18 was analysed four times during one year within the framework of the Austrian hydrochemical groundwater monitoring system. During one campaign 3H, 3H/3He, CFCs and SF6 was analysed in all wells. In addition, the same methods were applied on depth-resolved groundwater samples at selected wells (Kralik et al. 2011). The results of the 3H-input and 3H/3He-models support in both groundwater bodies the rapid water circulation (<5

  5. Sub-Doppler Jet-Cooled Infrared Spectroscopy of ND2H2+ and ND3H+ in the NH Stretch Fundamental Modes

    NASA Astrophysics Data System (ADS)

    Chang, Chih-Hsuan; Nesbitt, David

    2014-06-01

    Sub-Doppler jet-cooled rovibrational spectra of ND3H+, ND2H2+, and NDH3+ ions in various fundamental NH modes were observed and analyzed using difference frequency generation infrared spectroscopy. The ions were generated in the concentration-modulation slit-jet expansion via a H3+ proton transfer mechanism in a discharge mixture of ND3/H2O and H2 gases. NH mode excitation in ND3H+ ion yielded a prominent Q branch feature and parallel band rotational structure. Rotational transitions were confirmed unambiguously by four-line ground state combination differences within frequency measurement accuracy (10 MHz). The band origin was determined to be 3316.8413(9) cm-1. Perturbation in the upper state was observed from analysis of residuals. In the case of ND2H2+, both NH symmetric (b-type) and anti-symmetric (c-type) modes were observed and assigned for the first time, yielding band origins of 3297.5440(1) and 3337.9050(1) cm-1, respectively. The intensity for the two fundamental bands was interpreted with simple context of a bond-dipole model. The present study provided high precision ground state rotational constants (A"=4.85675(4), B"=3.96829(4), C"=3.44667(6) cm-1), which should facilitate microwave searches for isotope-substituted ammonium ions in the regions of interstellar medium, such as dense molecular clouds or younger stellar objects.

  6. Effects of groundwater residence time and recharge rate on nitrate contamination deduced from δ18O, δD, 3H/ 3He and CFCs in a small agricultural area in Chuncheon, Korea

    NASA Astrophysics Data System (ADS)

    Kaown, Dugin; Koh, Dong-Chan; Lee, Kang-Kun

    2009-03-01

    SummaryStable isotopes of water, chlorofluorocarbon (CFCs), and 3H/ 3He were applied in combination with hydrogeochemical data to analyze recharge patterns and nitrate contamination of shallow groundwater systems in a small agricultural area, Yupori, Chuncheon (Korea), where the eastern part is on hill slopes and the western part is low lands. The values of δ18O and δD indicated that groundwater is derived mainly from summer precipitation, which is more pronounced in the western part than in the eastern part. The apparent groundwater ages using CFC-113 and 3H/ 3He ranged from 13 to 31 yr, and are younger in the western part than in the eastern part. Dispersion models fit concentrations of 3H and CFC-113 for most wells of the eastern part with intermediate dispersion parameters. Nitrate concentrations were higher in the western part than the eastern part due to the land use pattern and topography. Stable isotopes of water and groundwater ages indicated that higher recharge rate affected by multiple sources of contamination is dominant in the western part whereas limited recharge with weak nitrate sources is considerable in the eastern part. This groundwater flow pattern corresponds to the different nitrate concentrations in the western and the eastern part. Groundwater residence time and recharge rate play an important role in the spatial distribution of NO 3 concentration in the study area as well as land use pattern.

  7. Multi-isotope labelling of organic matter by diffusion of 2H/18O-H2O vapour and 13C-CO2 into the leaves and its distribution within the plant

    NASA Astrophysics Data System (ADS)

    Studer, M. S.; Siegwolf, R. T. W.; Leuenberger, M.; Abiven, S.

    2015-03-01

    Isotope labelling is a powerful tool to study elemental cycling within terrestrial ecosystems. Here we describe a new multi-isotope technique to label organic matter (OM). We exposed poplars (Populus deltoides × nigra) for 14 days to an atmosphere enriched in 13CO2 and depleted in 2H218O. After 1 week, the water-soluble leaf OM (δ13C = 1346 ± 162‰) and the leaf water were strongly labelled (δ18O = -63 ± 8, δ2H = -156 ± 15‰). The leaf water isotopic composition was between the atmospheric and stem water, indicating a considerable back-diffusion of vapour into the leaves (58-69%) in the opposite direction to the net transpiration flow. The atomic ratios of the labels recovered (18O/13C, 2H/13C) were 2-4 times higher in leaves than in the stems and roots. This could be an indication of the synthesis of more condensed compounds in roots and stems (e.g. lignin vs. cellulose) or might be the result of O and H exchange and fractionation processes during phloem transport and biosynthesis. We demonstrate that the three major OM elements (C, O, H) can be labelled and traced simultaneously within the plant. This approach could be of interdisciplinary interest in the fields of plant physiology, palaeoclimatic reconstruction or soil science.

  8. The {sup 3}He(e,e'p){sup 2}H and {sup 4}He(e,e'p){sup 3}H reactions at high momentum transfer

    SciTech Connect

    Ford, William P.; Schiavilla, Rocco; Van Orden, J. W.

    2014-03-01

    We present updated calculations for observables in the processes {sup 3}He(e,e'p){sup 2}H, {sup 4}He(e,e'p){sup 3}H and {sup 4}He(e-vector, e'p-vector){sup 3}H. This update entails the implementation of improved nucleon-nucleon (NN) amplitudes to describe final state interactions (FSI) within a Glauber approximation and includes full spin-isospin dependence in the profile operator. In addition, an optical potential, which has also been updated since previous work, is utilized to treat FSI for the {sup 4}He(e,e'p){sup 3}H and {sup 4}He(e-vector, e'p-vector){sup 3}H reactions. The calculations are compared with experimental data and show good agreement between theory and experiment. Comparisons are made between the various approximations in the Glauber treatment, including model dependence due to the NN scattering amplitudes, rescattering contributions, and spin dependence. We also analyze the validity of the Glauber approximation at the kinematics the data is available, by comparing to the results obtained with the optical potential.

  9. Hydration of DNA by tritiated water and isotope distribution: a study by /sup 1/H, /sup 2/H, and /sup 3/H NMR spectroscopy

    SciTech Connect

    Mathur-De Vre, R.; Grimee-Declerck, R.; Lejeune, P.; Bertinchamps, A.J.

    1982-06-01

    The hydration layer of DNA (0.75%) in tritiated water represents 3.5% of solvent /sup 3/HHO. The combined effects of temperature (-6 to -40/sup 0/C) and H/sub 2/O//sup 2/H/sub 2/O solvent composition on the spin-lattice relaxation times of water protons and deuterons suggest selective distribution of isotopes in the hydration layer. The ''hydration isotope'' effect and the localization of tritiated water molecules in the hydration layer of DNA have important implications in describing the radiobiological effects of tritiated water because the initial molecular damage caused by /sup 3/HHO (internal radiation source) localizes close to /sup 3/H due to the short range and low energy of /sup 3/H ..beta.. rays.

  10. Stable Isotopes (δ18O and δ2H) Help to Delineate Flow Paths and the Importance of Different Climate Patterns in Watersheds of the Luquillo Mountains, Puerto Rico

    NASA Astrophysics Data System (ADS)

    Scholl, M. A.; Shanley, J. B.; Scatena, F. N.

    2009-12-01

    Precipitation isotopic signatures can help determine the relative importance of different rainfall regimes in the interactions between water, soils, and ecosystems in watersheds. The tropical forest in the Luquillo Mountains of Puerto Rico can receive over 5000 mm of precipitation per year. Recent modeling studies indicate that global climate change or local land use changes may lead to a decline in precipitation amounts. Weather analysis showed that 29% of rain input to the Luquillo Mountains was trade-wind orographic rainfall, and 30% of rainfall could be attributed to easterly waves and low pressure systems, with the remainder from fronts, troughs, and isolated thunderstorms. Trade-wind orographic precipitation usually occurs as frequent, low-intensity and low-volume rain events, whereas easterly waves and low-pressure systems have higher volume and more intense rainfall. To help determine the importance of different precipitation types in the forest water cycle, monthly precipitation samples from a network of rain and cloud water collectors and stream samples from two watersheds were collected and analyzed for δ18O and δ2H. Weekly throughfall and rain samples were also collected at one site during five periods of different rainfall intensity to determine whether isotopic fractionation occurs when rain falls through the forest canopy. Seasonal rainfall sources have distinct isotopic signatures, partly due to differences in cloud height associated with the seasonal climate patterns. Monthly precipitation samples during the dry season had average isotopic values of -1.5‰ δ18O and +2.3‰ δ2H, associated with the weather pattern of trade-wind showers and fronts. Rainy season precipitation, from easterly waves and low pressure systems, had average monthly values of -3.7‰ δ18O and -16‰ δ2H. Precipitation during months with significant low pressure systems had average values of -5.9‰ δ18O and -36‰ δ2H. Isotopic composition of stream water at higher

  11. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1212, LB5136_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 Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1212, LB5136_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  12. Heat of Mixing and Solution of Ethanol C2H6O + C3H6O3 Dimethyl carbonate (HMSD1121, LB4328_H)

    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 'heat of Mixing and Solution of Ethanol C2H6O + C3H6O3 Dimethyl carbonate (HMSD1121, LB4328_H)' providing data from direct calorimetric measurement of molar excess enthalpy at variable mole fraction and constant pressure and temperature.

  13. Heat of Mixing and Solution of Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (HMSD1111, LB4314_H)

    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 'heat of Mixing and Solution of Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (HMSD1111, LB4314_H)' providing data from direct low-pressure calorimetric measurement of molar excess enthalpy at variable mole fraction and constant temperature.

  14. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1111, LB5133_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 Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1111, LB5133_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  15. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1111, LB4256_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1111, LB4256_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  16. Vapor-Liquid Equilibrium in the Mixture 1,2-Dichloroethane C2H4Cl2 + C3H3N Propenenitrile (EVLM1211, LB5647_E)

    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 'vapor-Liquid Equilibrium in the Mixture 1,2-Dichloroethane C2H4Cl2 + C3H3N Propenenitrile (EVLM1211, LB5647_E)' providing data from direct measurement of temperature at variable mole fraction in liquid phase and constant pressure.

  17. Volumetric Properties of the Mixture Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1111, LB4250_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1111, LB4250_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  18. Volumetric Properties of the Mixture Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1412, LB4277_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1412, LB4277_V)' providing data by calculation of isentropic compressibility from low-pressure density and thermodynamic speed of sound data at variable mole fraction and constant temperature, in the single-phase region(s).

  19. Volumetric Properties of the Mixture Ethanol C2H6O + C3H3N Propenenitrile (VMSD1511, LB4925_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Ethanol C2H6O + C3H3N Propenenitrile (VMSD1511, LB4925_V)' providing data from direct measurement of low-pressure thermodynamic speed of sound at variable mole fraction and constant temperature, in the single-phase region(s).

  20. Volumetric Properties of the Mixture Ethanol C2H6O + C3H3N Propenenitrile (VMSD1212, LB4917_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Ethanol C2H6O + C3H3N Propenenitrile (VMSD1212, LB4917_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  1. Volumetric Properties of the Mixture Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1511, LB4264_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1511, LB4264_V)' providing data from direct measurement of low-pressure thermodynamic speed of sound at variable mole fraction and constant temperature, in the single-phase region(s).

  2. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1212, LB4258_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1212, LB4258_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  3. Volumetric Properties of the Mixture Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1212, LB4257_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1212, LB4257_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  4. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1412, LB4276_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1412, LB4276_V)' providing data by calculation of isentropic compressibility from low-pressure density and thermodynamic speed of sound data at variable mole fraction and constant temperature, in the single-phase region(s).

  5. Volumetric Properties of the Mixture Ethanol C2H6O + C3H3N Propenenitrile (VMSD1111, LB4908_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Ethanol C2H6O + C3H3N Propenenitrile (VMSD1111, LB4908_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  6. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1511, LB4270_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' 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 Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1511, LB4270_V)' providing data from direct measurement of low-pressure thermodynamic speed of sound at variable mole fraction and constant temperature, in the single-phase region(s).

  7. Study of the reactions /sup 2/H(d, p)/sup 3/H and /sup 2/H(d,n)/sup 3/He with a polarized deuteron beam. Extrapolation of the cross sections to the low-energy region

    SciTech Connect

    Ad'yasevich, B.P.; Antonenko, V.G.; Bragin, V.N.

    1981-05-01

    On the basis of analysis of experimental data on the vector analyzing power of the nuclear reactions /sup 2/H(d,p)/sup 3/H and /sup 2/H(d,n)/sup 3/He and data on the total cross sections for these reactions at energies from 13 to 485 keV we have separated the total cross sections into partial cross sections for s and p waves and have calculated the total cross sections for very low energies down to 0.3 keV. For these same reactions we have calculated the intensities of production of energetic products in a heated deuterium plasma. A formula for practical calculations of this intensity is obtained.

  8. Study of the reactions /sup 2/H(d,p)/sup 3/H and /sup 2/H(d,n)/sup 3/He with a polarized deuteron beam. Measurement of the analyzing power

    SciTech Connect

    Ad'yasevich, B.P.; Antonenko, V.G.; Fomenko, D.E.

    1981-03-01

    The angular distributions of all charged particles produced in the mirror reactions /sup 2/H(d,p)/sup 3/H and /sup 2/H(d,n)/sup 3/He in a gaseous deuterium target approx.10 keV thick have been measured for polarized-deuteron energies from 60 to 485 keV for various orientations of the beam axis. The angular distributions of the analyzing powers A/sub y/(theta), A/sub z/z(theta), A/sub x/z(theta), and A/sub x/x-yy(theta) have been measured for 12 values of the energy for each reaction at angles from 20/sup 0/ to 150/sup 0/ (in the laboratory frame). The results are shown as contour diagrams and compared with the results of similar experiments. The differences found are attributed to the effect of the target thickness and the energy calibration.

  9. High resolution pore water delta2H and delta18O measurements by H2O(liquid)-H2O(vapor) equilibration laser spectroscopy.

    PubMed

    Wassenaar, L I; Hendry, M J; Chostner, V L; Lis, G P

    2008-12-15

    A new H2O(liquid)-H2O(vapor) pore water equilibration and laser spectroscopy method provides a fast way to obtain accurate high resolution deltaD and delta18O profiles from single core samples from saturated and unsaturated geologic media. The precision and accuracy of the H2O(liquid)-H2O(vapor) equilibration method was comparable to or better than conventional IRMS-based methods, and it can be conducted on geologic cores that contain volumetric water contents as low as 5%. Significant advantages of the H2O(liquid)-H2O(vapor) pore water equilibration method and laser isotopic analysis method include dual hydrogen- and oxygen-isotope assays on single small core samples, low consumable and instrumentation costs, and the potential for field-based hydrogeologic profiling. A single core is sufficient to obtain detailed vertical isotopic depth profiles in geologic, soil, and lacustrine pore water, dramatically reducing the cost of obtaining pore water by conventional wells or physical water extraction methods. In addition, other inherent problems like contamination of wells by leakage and drilling fluids can be eliminated. PMID:19174902

  10. Phenyl Substituted 4-Hydroxypyridazin-3(2H)-ones and 5-Hydroxypyrimidin-4(3H)-ones: Inhibitors of Influenza A Endonuclease

    PubMed Central

    2015-01-01

    Seasonal and pandemic influenza outbreaks remain a major human health problem. Inhibition of the endonuclease activity of influenza RNA-dependent RNA polymerase is attractive for the development of new agents for the treatment of influenza infection. Our earlier studies identified a series of 5- and 6-phenyl substituted 3-hydroxypyridin-2(1H)-ones that were effective inhibitors of influenza endonuclease. These agents identified as bimetal chelating ligands binding to the active site of the enzyme. In the present study, several aza analogues of these phenyl substituted 3-hydroxypyridin-2(1H)-one compounds were synthesized and evaluated for their ability to inhibit the endonuclease activity. In contrast to the 4-aza analogue of 6-(4-fluorophenyl)-3-hydroxypyridin-2(1H)-one, the 5-aza analogue (5-hydroxy-2-(4-fluorophenyl)pyrimidin-4(3H)-one) did exhibit significant activity as an endonuclease inhibitor. The 6-aza analogue of 5-(4-fluorophenyl)-3-hydroxypyridin-2(1H)-one (6-(4-fluorophenyl)-4-hydroxypyridazin-3(2H)-one) also retained modest activity as an inhibitor. Several varied 6-phenyl-4-hydroxypyridazin-3(2H)-ones and 2-phenyl-5-hydroxypyrimidin-4(3H)-ones were synthesized and evaluated as endonuclease inhibitors. The SAR observed for these aza analogues are consistent with those previously observed with various phenyl substituted 3-hydroxypyridin-2(1H)-ones. PMID:25225968

  11. Influence of different organic fertilizers on quality parameters and the delta(15)N, delta(13)C, delta(2)H, delta(34)S, and delta(18)O values of orange fruit (Citrus sinensis L. Osbeck).

    PubMed

    Rapisarda, Paolo; Camin, Federica; Fabroni, Simona; Perini, Matteo; Torrisi, Biagio; Intrigliolo, Francesco

    2010-03-24

    To investigate the influence of different types of fertilizers on quality parameters, N-containing compounds, and the delta(15)N, delta(13)C, delta(2)H, delta (34)S, and delta(18)O values of citrus fruit, a study was performed on the orange fruit cv. 'Valencia late' (Citrus sinensis L. Osbeck), which was harvested in four plots (three organic and one conventional) located on the same farm. The results demonstrated that different types of organic fertilizers containing the same amount of nitrogen did not effect important changes in orange fruit quality parameters. The levels of total N and N-containing compounds such as synephrine in fruit juice were not statistically different among the different treatments. The delta(15)N values of orange fruit grown under fertilizer derived from animal origin as well as from vegetable compost were statistically higher than those grown with mineral fertilizer. Therefore, delta(15)N values can be used as an indicator of citrus fertilization management (organic or conventional), because even when applied organic fertilizers are of different origins, the natural abundance of (15)N in organic citrus fruit remains higher than in conventional ones. These treatments also did not effect differences in the delta(13)C, delta(2)H, delta(34)S, and delta(18)O values of fruit. PMID:20184327

  12. DETECTIONS OF C{sub 2}H, CYCLIC-C{sub 3}H{sub 2}, AND H{sup 13}CN IN NGC 1068

    SciTech Connect

    Nakajima, T.; Takano, S.; Kohno, K.; Inoue, H.

    2011-02-20

    We used the Nobeyama 45 m telescope to conduct a spectral line survey in the 3 mm band (85.1-98.4 GHz) toward one of the nearest galaxies with an active galactic nucleus (AGN), NGC 1068, and the prototypical starburst galaxy NGC 253. The beam size of this telescope is {approx} 18'', which was sufficient to spatially separate the nuclear molecular emission from the emission of the circumnuclear starburst region in NGC 1068. We detected rotational transitions of C{sub 2}H, cyclic-C{sub 3}H{sub 2}, and H{sup 13}CN in NGC 1068. These are detections of carbon-chain and carbon-ring molecules in NGC 1068. In addition, the C{sub 2}H N = 1-0 lines were detected in NGC 253. The column densities of C{sub 2}H were determined to be 3.4 x 10{sup 15} cm{sup -2} in NGC 1068 and 1.8 x 10{sup 15} cm{sup -2} in NGC 253. The column densities of cyclic-C{sub 3}H{sub 2} were determined to be 1.7 x 10{sup 13} cm{sup -2} in NGC 1068 and 4.4 x 10{sup 13} cm{sup -2} in NGC 253. We calculated the abundances of these molecules relative to CS for both NGC 1068 and NGC 253, and found that there were no significant differences in the abundances between the two galaxies. This result suggests that the basic carbon-containing molecules are either insusceptible to AGN or are tracing cold (T{sub rot} {approx} 10 K) molecular gas rather than X-ray irradiated hot gas.

  13. Using Halogens (Cl, Br, F, I) and Stable Isotopes of Water (δ18O, δ2H) to Trace Hydrological and Biogeochemical Processes in Prairie Wetlands

    NASA Astrophysics Data System (ADS)

    Levy, Z. F.; Lu, Z.; Mills, C. T.; Goldhaber, M. B.; Rosenberry, D. O.; Mushet, D.; Siegel, D. I.; Fiorentino, A. J., II; Gade, M.; Spradlin, J.

    2014-12-01

    Prairie pothole wetlands are ubiquitous features of the Great Plains of North America, and important habitat for amphibians and migratory birds. The salinity of proximal wetlands varies highly due to groundwater-glacial till interactions, which influence wetland biota and associated ecosystem functions. Here we use halogens and stable isotopes of water to fingerprint hydrological and biogeochemical controls on salt cycling in a prairie wetland complex. We surveyed surface, well, and pore waters from a groundwater recharge wetland (T8) and more saline closed (P1) and open (P8) basin discharge wetlands in the Cottonwood Lake Study Area (ND) in August/October 2013 and May 2014. Halogen concentrations varied over a broad range throughout the study area (Cl = 2.2 to 170 mg/L, Br = 13 to 2000 μg/L, F = < 30 (MDL) to 740 μg/L, I = 1 to 538 μg/L). The Cl/Br molar ratios were higher (171 to 574) at the recharge wetland, indicating meteoric sources, and had a tighter and lower range (33 to 320) at the down-gradient sites. The Cl/I molar ratios of waters throughout the site had a wide range (32 to 26,000). Lowest values occurred at the upgradient shore of P1 (32 to 43) due to low Cl concentrations and the center of P1 (196 to 213) where pore water of weathered till underlying 1.2 m of organic-rich sediment and silty clay soil is enriched in I to ~500 µg/L. Stable isotopes of water showed that evaporation-enriched pond water (δ18O = -9.5 to -2.71 ‰) mixes with shallow groundwater in the top 0.6 m of fringing wetland soils and 1.2 m of the substrate in the center of P1. Our results suggest endogenous sources for Br and I within the prairie landscape that may be controlled by biological mechanisms or weathering of shale from glacial till.

  14. Theoretical study of the radiative capture reactions {sup 2}H(n,{gamma}){sup 3}H and {sup 2}H(p,{gamma}){sup 3}He at low energies

    SciTech Connect

    M. Viviani; R. Schiavilla; A. Kievsky

    1996-02-01

    Correlated Hyperspherical Harmonics wave functions with {Delta}-isobar admixtures obtained from realistic interactions are used to study the thermal neutron radiative capture on deuterium, and the {sup 2}H({rvec p},{gamma}){sup 3}He and p({rvec d},{gamma}){sup 3}He reactions in the center of mass energy range 0-100 keV. The nuclear electromagnetic current includes one and two-body components. Results for the {sup 2}H({rvec d},{gamma}){sup 3}H cross section and photon polarization parameter, as well as for the energy dependence of the astrophysical factor and angular distributions of the differential cross section, vector and tensor analyzing powers, and photon linear polarization coefficient of the {sup 2}H({rvec p},{gamma}){sup 3}He and p({rvec d},{gamma}){sup 3}He reactions are reported. Large effects due to two-body currents, in particular the long-range ones associated with the tensor component of the nucleon-nucleon interaction, are observed in the photon polarization parameter and vector analyzing power. Good, quantitative agreement between theory and experiment is found for all observables, with the exception of the vector analyzing power for which the calculated values underestimate the data by about 30%.

  15. Reconstruction of late Quaternary relative humidity changes on the southern slopes of Mt. Kilimanjaro, East Africa, using a coupled δ2H18O biomarker paleohygrometer

    NASA Astrophysics Data System (ADS)

    Hepp, Johannes; Zech, Roland; Rozanski, Kazimierz; Tuthorn, Mario; Glaser, Bruno; Greule, Markus; Keppler, Frank; Huang, Yongsong; Zech, Wolfgang; Zech, Michael

    2016-04-01

    Our understanding of African paleoclimate/-hydrological history is decisively based on lake level and lake sediment studies. It furthermore improved remarkably during the last decade thanks to emerging stable isotope techniques such as compound-specific deuterium analysis of sedimentary leaf wax biomarkers (δ2Hleaf wax). Here we present results from a multi-proxy biomarker study carried out on a ~100 ka paleosol sequence developed in the Maundi crater at ~2780 m a.s.l. on the southeastern slopes of Mt. Kilimanjaro in equatorial East Africa. The Maundi stable isotope records established for hemicellulose-derived sugars, lignin- and pectin-derived methoxyl groups and leaf wax-derived fatty acid and n-alkane biomarkers (δ18Osugars, δ2Hmethoxyl groups, δ2Hfatty acids and δ2Hn‑alkanes) reveal differences but also similar patterns. Maxima characterize the period from 70 to 60 ka, the last glacial maximum (LGM) and the Younger Dryas (YD), whereas minima occur during the Holocene. The application of a 'coupled δ2Hn‑alkane-δ18Osugar paleohygrometer' allows the reconstruction of the Late Quaternary relative humidity (RH) history of the Maundi study site. Accordingly, the reconstructed RH changes are well in agreement with the Maundi pollen results. Apart from the overall regional moisture availability, the intensification versus weakening of the trade wind inversion, which affects the diurnal montane atmospheric circulation on the slopes of Mt. Kilimanjaro, is suggested as local second important factor controlling the RH history at Maundi. Furthermore, the Maundi results of the coupled δ2Hn‑alkane-δ18Osugar approach caution against interpreting δ2Hleaf wax (as well as δ18Osugar) records straight forwards in terms of reflecting δ2Hprec, because variably and primarily RH-dependent isotopic evapotranspirative enrichment of leaf water can mask δ2Hprec changes. Concerning the biomarker-based reconstructed Maundi δ2H/δ18Oprec record, the comparison with the

  16. LIMS for Lasers 2015 for achieving long-term accuracy and precision of δ2H, δ17O, and δ18O of waters using laser absorption spectrometry

    USGS Publications Warehouse

    Coplen, Tyler B.; Wassenaar, Leonard I

    2015-01-01

    Although laser absorption spectrometry (LAS) instrumentation is easy to use, its incorporation into laboratory operations is not easy, owing to extensive offline manipulation of comma-separated-values files for outlier detection, between-sample memory correction, nonlinearity (δ-variation with water amount) correction, drift correction, normalization to VSMOW-SLAP scales, and difficulty in performing long-term QA/QC audits. METHODS: A Microsoft Access relational-database application, LIMS (Laboratory Information Management System) for Lasers 2015, was developed. It automates LAS data corrections and manages clients, projects, samples, instrument-sample lists, and triple-isotope (δ(17) O, δ(18) O, and δ(2) H values) instrumental data for liquid-water samples. It enables users to (1) graphically evaluate sample injections for variable water yields and high isotope-delta variance; (2) correct for between-sample carryover, instrumental drift, and δ nonlinearity; and (3) normalize final results to VSMOW-SLAP scales. RESULTS: Cost-free LIMS for Lasers 2015 enables users to obtain improved δ(17) O, δ(18) O, and δ(2) H values with liquid-water LAS instruments, even those with under-performing syringes. For example, LAS δ(2) HVSMOW measurements of USGS50 Lake Kyoga (Uganda) water using an under-performing syringe having ±10 % variation in water concentration gave +31.7 ± 1.6 ‰ (2-σ standard deviation), compared with the reference value of +32.8 ± 0.4 ‰, after correction for variation in δ value with water concentration, between-sample memory, and normalization to the VSMOW-SLAP scale. CONCLUSIONS: LIMS for Lasers 2015 enables users to create systematic, well-founded instrument templates, import δ(2) H, δ(17) O, and δ(18) O results, evaluate performance with automatic graphical plots, correct for δ nonlinearity due to variable water concentration, correct for between-sample memory, adjust for drift, perform VSMOW-SLAP normalization, and

  17. Synthesis and X-ray diffraction study of [UO{sub 2}(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}] {center_dot} 2C{sub 12}H{sub 18}O

    SciTech Connect

    Serezhkina, L. B.; Vologzhanina, A. V.; Klynin, E. S.; Korlyukov, A. A.; Moiseev, I. K.; Serezhkin, V. N.

    2012-03-15

    The compound [UO{sub 2}(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}] {center_dot} 2C{sub 12}H{sub 18}O was synthesized and studied by IR spectroscopy and X-ray diffraction. The structure consists of the neutral island groups [UO{sub 2}(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}], which belong to the crystal-chemical group AB{sup 01}{sub 2}M{sup 1}{sub 2} (A = UO{sub 2}{sup 2+}, B{sup 01} = NO{sub 3}{sup -}, M{sup 1} = H{sub 2}O) of uranyl complexes, and 1-adamantyl methyl ketone molecules. The characteristic features of the association of the complexes [UO{sub 2}(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}] and 1-adamantyl methyl ketone molecules in the crystal structure via hydrogen bonds are considered with the use of Voronoi-Dirichlet polyhedra.

  18. Isotopic monitoring (2H, 18O) of the St. Lawrence and Ottawa rivers between 1997 and 2003- Links with interannual climatic variability and hydrological processes in their catchment basins

    NASA Astrophysics Data System (ADS)

    Myre, A.; Hillaire-Marcel, C.

    2004-05-01

    This study based on a water isotope (18O and 2H) monitoring of the St. Lawrence and Ottawa rivers (Canada) is a contribution to the international IAEA project: Isotopes tracing of hydrologic processes in large river basins [Gibson et al., 2002. EOS 83: 613 et p.]. Sampling of the St. Lawrence and Ottawa river waters started in 1997, on a biweekly to weekly basis. Monitoring stations are located at Montreal (i.e., at the outlet of the Great Lakes), Quebec City (the estuary of the St. Lawrence) and at the Carillon hydroelectric dam, near the outlet of a major tributary, the Ottawa River into the St. Lawrence itself. The goal of the study was to examine the seasonal and interannual variability of isotopic signatures of the St. Lawrence and Ottawa rivers, in relation notably with interannual climatic variations, and seasonal hydrologic processes in the watershed (summer evaporation, snowmelt, transit time of precipitation signals into runoff). Waters sampled at the three stations depict distinct isotopic compositions. At Montreal, relatively stable isotopic composition are observed with a mean weighted annual value of -54 % for 2H and -7.1 % for 18O. The Ottawa River water at Carillon also displays stable isotopic compositions but much lighter values (weighted mean annual values: -80 % for 2H and -10.8 % for 18O). Finally, isotopic compositions at Quebec City are intermediate between those of Montreal and Carillon, but show a much larger variability. They reflect mixing between the heavy isotope enriched Great Lakes water, the lighter water from the Ottawa River, and highly variable inputs from smaller tributaries (from the Laurentides and Appalachian mountains). The mean weighted isotopic compositions at Quebec City are -65 % and -8.6 %, respectively for 2H and 18O). Evaporative enrichment, in particular during low water level episodes, seem to be more important in the Ottawa River catchment than in the Great Lakes basin, based on a comparison of isotopic clusters at

  19. Microwave Plasma-Activated Chemical Vapor Deposition of Nitrogen-Doped Diamond. I. N2/H2 and NH3/H2 Plasmas.

    PubMed

    Truscott, Benjamin S; Kelly, Mark W; Potter, Katie J; Johnson, Mack; Ashfold, Michael N R; Mankelevich, Yuri A

    2015-12-31

    We report a combined experimental/modeling study of microwave activated dilute N2/H2 and NH3/H2 plasmas as a precursor to diagnosis of the CH4/N2/H2 plasmas used for the chemical vapor deposition (CVD) of N-doped diamond. Absolute column densities of H(n = 2) atoms and NH(X(3)Σ(-), v = 0) radicals have been determined by cavity ring down spectroscopy, as a function of height (z) above a molybdenum substrate and of the plasma process conditions, i.e., total gas pressure p, input power P, and the nitrogen/hydrogen atom ratio in the source gas. Optical emission spectroscopy has been used to investigate variations in the relative number densities of H(n = 3) atoms, NH(A(3)Π) radicals, and N2(C(3)Πu) molecules as functions of the same process conditions. These experimental data are complemented by 2-D (r, z) coupled kinetic and transport modeling for the same process conditions, which consider variations in both the overall chemistry and plasma parameters, including the electron (Te) and gas (T) temperatures, the electron density (ne), and the plasma power density (Q). Comparisons between experiment and theory allow refinement of prior understanding of N/H plasma-chemical reactivity, and its variation with process conditions and with location within the CVD reactor, and serve to highlight the essential role of metastable N2(A(3)Σ(+)u) molecules (formed by electron impact excitation) and their hitherto underappreciated reactivity with H atoms, in converting N2 process gas into reactive NHx (x = 0-3) radical species. PMID:26593853

  20. Solvation effects on reactive intermediates: The benzyl radical and its clusters with Ar, N2, CH4, C2H6, and C3H8

    NASA Astrophysics Data System (ADS)

    Disselkamp, R.; Bernstein, E. R.

    1993-03-01

    Mass resolved excitation spectra are presented for the benzyl radical and its clusters with Ar, N2, CH4, C2H6, and C3H8. The cluster spectra exhibit small redshifts (≤50 cm-1) relative to the unclustered benzyl radical for the D1(1 2A2)←D0(1 2B2) and D2(2 2B2)←D0(1 2B2) electronic transition regions. A unique set of low energy van der Waals modes is observed for these clusters for each excited electronic state investigated. The cluster spectra also reveal significant vibronic coupling between the two excited electronic states of the benzyl radical, as evidenced by a single vibrational predissociation threshold for each cluster. Ab initio calculations are performed on the benzyl radical to examine excited electronic state structure, predict transition energies, estimate ionization energy, and determine partial atomic charges in the electronic states of interest. The resulting partial charges are used in empirical atom-atom potential energy calculations to aid in the understanding of cluster spectroscopic shifts, binding energies, and van der Waals modes.

  1. Results from Boiling Temperature Measurements for Saturated Solutions in the Systems NaCl + Ca(NO3)2 + H2O, NaNO3 + KNO3 + H2O, and NaCl + KNO3 + H2O, and Dry Out Temperatures for NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O

    SciTech Connect

    Rard, J A

    2005-11-29

    Boiling temperature measurements have been made for saturated ternary solutions of NaCl + KNO{sub 3} + H{sub 2}O and NaNO{sub 3} + KNO{sub 3} + H{sub 2}O at three selected salt ratios and for NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O over the full composition range. The maximum boiling temperature found for the NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O system is 164.7 {+-} 0.6 C, and the composition is estimated to occur at x(Ca(NO{sub 3}){sub 2}) {approx} 0.25. Experiments were also performed for the five component NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O mixtures with the molar ratio of NaCl:NaNO{sub 3}:KNO{sub 3} held essentially constant at 1:0.9780:1.1468 as the solute mole fraction of Ca(NO{sub 3}){sub 2}, x(Ca(NO{sub 3}){sub 2}), was varied between 0 and 0.25. The NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O system forms low melting mixtures and thus boiling temperatures for saturated were not determined. Instead, the temperatures corresponding to the cessation of boiling (i.e., dry out temperatures) of these liquid mixtures were determined. These dry out temperatures range from {approx} 300 C when x(Ca(NO{sub 3}){sub 2}) = 0 to {ge} 400 C when x(Ca(NO{sub 3}){sub 2}) = 0.20 and 0.25. The investigated mixture compositions correspond to some of the major mineral assemblages that are predicted to control the deliquescence relative humidity of salts formed by leaching dust samples from the proposed nuclear repository at Yucca Mountain, Nevada.

  2. Palladium-catalyzed bisarylation of 3-alkylbenzofurans to 3-arylalkyl-2-arylbenzofurans on water: tandem C(sp(3))-H and C(sp(2))-H activation reactions of 3-alkylbenzofurans.

    PubMed

    Cho, Beom Shin; Chung, Young Keun

    2015-10-01

    A protocol involving facile sequential C(sp(3))-H and C(sp(2))-H activation reactions of 3-alkylbenzofurans catalyzed by Pd(OAc)2 in the presence of pivalic acid, silver salt, and tricyclohexylphosphine 'on water' was developed. Aryl iodides were used as substrates in a tandem bisarylation reaction to generate 3-arylalkyl-2-arylbenzofurans in moderate to high yields at room temperature. The reaction revealed in this study is a rare example of consecutive C(sp(3))-H and C(sp(2))-H bond activation under mild reaction conditions. PMID:26287028

  3. Investigation of spatio-temporal variability of water uptake in a groundwater-dependent ecosystem using a stable isotope approach (δ18O, δ2H): Pfyn Forest, Switzerland

    NASA Astrophysics Data System (ADS)

    Bertrand, G.; Masini, J.; Goldscheider, N.; Gobat, J. M.; Hunkeler, D.

    2012-04-01

    This work consists of an eco-hydrogeological study of the Pfyn Forest (46o17'35''N; 7o31'59''E, z = 550 m) which is a 6 km long alluvial zone in the upper Rhône valley, near Sierre (Wallis, Switzerland). From a hydrological point of view, the Rhône has a glacio-nival regime type in this area. Between low-flow and high-flow periods, groundwater levels strongly vary (about 8 m) near the main river-aquifer interaction zone in the most upgradient part of the site. In contrast, the downstream part of Pfyn is characterized by a low groundwater level fluctuation of about 1 or 2 m. From an ecological point of view, the riverine fringe at Pfyn presents a broadly recognized natural value but faces many threats due to human activities (derivation channel located upstream, gravel pits). Phytocoenosis vary from dry environments associations (with Scots pines, feather grass) upstream to active floodplain associations (with poplars, alders, willows) and likely dependent on groundwater, downstream. Between these two end-members, a transition mixed forest occurs. In the context of a potential hydrologic alteration due to global climatic change in a close future, this ecosystem should face modifications of the various water source (rainwater, groundwater) proportion and availability. In order to constrain the meteorological, hydrological, pedological and ecological factors governing water uptakes by trees, isotopic characterizations (δ18O, δ2H) of each water compartment (precipitations, groundwater, river, soil, xylem) coupled with the evaluation of the water balance, has been carried out. The investigation focused on 3 different sites located along a transect through the alluvial valley between April 2010 and February 2011, with a twice-monthly resolution. The data permit to obtain three major findings: - At first, an overview of both δ18O and δ2H data shows that rainwater, groundwater, soil water and plant water are usually located on the regional meteoric water line. For

  4. Coupling of continuous in situ ecosystem water vapor, precipitation, plant and soil water isotope (δ2H, δ18O and d-excess) measurements in Arctic Alaska to understand a changing water cycle

    NASA Astrophysics Data System (ADS)

    Welker, J. M.; Klein, E. S.; Leffler, J.; Cherry, J. E.; Young, J. M.

    2013-12-01

    A changing Arctic water cycle is focusing our efforts on the patterns and processes governing the exchange of water between the land surface and the atmosphere. We initiated a NSF EAGER study of the changing Arctic water cycle with a cross-scale water isotope (ecosystem-landscape and region) study employing tower, aircraft and satellite measurements in N Alaska. At the land surface, we measured in situ, continuous ecosystem δ2H and δ18O in water vapor isotopes along a vertical profile (0.1 to 3 m) in late winter, spring, and summer of 2013 at the Toolik Lake Field Station in Arctic Alaska. The continuous water vapor measurements are being combined with soil, plant and precipitation water isotope measurements, and species-level transpiration rates. Diurnal patterns of δ2H values in water vapor vary systematically from the soil surface, through the plant canopy and in the near boundary layer ranging between -200 ‰ at the surface to -240 ‰ at 3 m. These vertical patterns were also observed in d-excess ranging from 5 ‰ near the soil surface to -15 ‰ at 3 m. These patterns disappeared at night indicating their link with evapotranspiration. These data will serve as the foundation for a Bayesian model to articulate the sources, species, and processes governing the exchange of H2O with the lower boundary layer; and will also help to calibrate ecosystem, landscape (aircraft) and regional (satellite) measurements of the water vapor isotopes above different vegetation types (tussock tundra, riparian tundra, and recently burned tundra) and regions (Northern Foothills of the Brooks Range and the Arctic Coastal Plain). Continuous water vapor isotope traits in Arctic Tundra from the soil surface (0.02 m) to 3 m above the tundra for a window of time during the 2013 growing season. The diurnal patterns depict the evidence for transpiration and evaporation as the values above the soil (0.02 m) and in the canopy (0.2m) are enriched during the day and become depleted during

  5. Synthesis, resolution and anticonvulsant activity of chiral N-1'-ethyl,N-3'-(1-phenylethyl)-(R,S)-2'H,3H,5'H-spiro-(2-benzofuran-1,4'-imidazolidine)-2',3,5'-trione diastereomers.

    PubMed

    Sadarangani, Ishwar R; Bhatia, Souful; Amarante, Daniel; Lengyel, Istvan; Stephani, Ralph A

    2012-04-01

    Four new N-1',N-3'-disubstituted-2'H,3H,5'H-spiro-(2-benzofuran-1,4'-imidazolidine)-2',3,5'-triones bearing a chiral N-3' substituent were synthesized, resolved and their anticonvulsant activity was obtained and determined that the activity was not stereoselective. PMID:22401865

  6. 21 CFR 73.3123 - 6-Ethoxy-2-(6-ethoxy-3-oxobenzo[b]thien-2(3H)-ylidene) benzo[b]thiophen-3 (2H)-one.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ..., DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3123 6-Ethoxy-2-(6-ethoxy-3-oxobenzo thien-2(3H)-ylidene) benzo thiophen-3 (2H)-one....

  7. 21 CFR 73.3123 - 6-Ethoxy-2-(6-ethoxy-3-oxobenzo[b]thien-2(3H)-ylidene) benzo[b]thiophen-3 (2H)-one.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ..., DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3123 6-Ethoxy-2-(6-ethoxy-3-oxobenzo thien-2(3H)-ylidene) benzo thiophen-3 (2H)-one....

  8. Measurements of the Differential Cross Sections for the Elastic n-{sup 3}H and n-{sup 2}H Scattering at 14.1 MeV by Using an Inertial Confinement Fusion Facility

    SciTech Connect

    Frenje, J. A.; Li, C. K.; Seguin, F. H.; Casey, D. T.; Petrasso, R. D.; McNabb, D. P.; Navratil, P.; Quaglioni, S.; Sangster, T. C.; Glebov, V. Yu; Meyerhofer, D. D.

    2011-09-16

    For the first time the differential cross section for the elastic neutron-triton (n-{sup 3}H) and neutron-deuteron (n-{sup 2}H) scattering at 14.1 MeV has been measured by using an inertial confinement fusion facility. In these experiments, which were carried out by simultaneously measuring elastically scattered {sup 3}H and {sup 2}H ions from a deuterium-tritium gas-filled inertial confinement fusion capsule implosion, the differential cross section for the elastic n-{sup 3}H scattering was obtained with significantly higher accuracy than achieved in previous accelerator experiments. The results compare well with calculations that combine the resonating-group method with an ab initio no-core shell model, which demonstrate that recent advances in ab initio theory can provide an accurate description of light-ion reactions.

  9. Effects of distortion of the intercluster motion in {sup 2}H, {sup 3}He, {sup 3}H, {sup 6}Li, and {sup 9}Be on Trojan horse applications

    SciTech Connect

    Pizzone, R. G.; Spitaleri, C.; La Cognata, M.; Lamia, L.; Romano, S.; Mukhamedzhanov, A. M.; Blokhintsev, L. D.; Bertulani, C. A.; Irgaziev, B. F.

    2009-08-15

    Deuteron induced quasifree scattering and reactions have been extensively investigated in the past few decades as well as {sup 6}Li, {sup 3}H, {sup 3}He, and {sup 9}Be induced reactions. This was done not only for the investigation of nuclear structure and reaction mechanisms but also for important astrophysical applications (Trojan horse method). In particular the widths of the spectator momentum distributions in several nuclei, which have been used as Trojan horses, have been obtained as a function of the transferred momentum. Applications of Trojan horse method will also be discussed because the momentum distribution of the spectator particle inside the nucleus is a important input for this method. This gives hints on distortion effects at low energies important for nuclear astrophysics.

  10. MOLECULAR SURVIVAL IN EVOLVED PLANETARY NEBULAE: DETECTION OF H{sub 2}CO, c-C{sub 3}H{sub 2}, AND C{sub 2}H IN THE HELIX

    SciTech Connect

    Tenenbaum, E. D.; Woolf, N. J.; Ziurys, L. M.; Milam, S. N. E-mail: nwoolf@as.arizona.ed E-mail: Stefanie.N.Milam@nasa.go

    2009-10-20

    H{sub 2}CO, c-C{sub 3}H{sub 2}, and C{sub 2}H have been identified in the neutral envelope of the highly evolved planetary nebula (PN), the Helix (also know as NGC 7293). Emission from these species were detected toward a peak position in CO, 372'' east of the central star, using the facilities of the Arizona Radio Observatory (ARO). C{sub 2}H and c-C{sub 3}H{sub 2} were identified on the basis of their 3 mm transitions, measured with the ARO 12 m, while five lines of H{sub 2}CO were observed using the 12 m at 2 and 3 mm and the ARO Submillimeter Telescope at 1 mm. From a radiative transfer analysis of the formaldehyde emission, the molecular material was determined to have a density of n(H{sub 2}) approx3 x 10{sup 5} cm{sup -3}, with a kinetic temperature of T {sub kin} approx20 K. Column densities for C{sub 2}H, H{sub 2}CO, and c-C{sub 3}H{sub 2} of N {sub tot} approx1.4 x 10{sup 13} cm{sup -2}, 1.1 x 10{sup 12} cm{sup -2}, and 3 x 10{sup 11} cm{sup -2}, respectively, were derived, corresponding to fractional abundances relative to H{sub 2} of f (H{sub 2}CO) = 1 x 10{sup -7}, f (c-C{sub 3}H{sub 2}) = 3 x 10{sup -8}, and f (C{sub 2}H) = 1 x 10{sup -6} {sub .} The physical conditions found support the notion that molecules in evolved PNe survive in dense clumps in pressure equilibrium, shielded from photodissociation. The presence of H{sub 2}CO, c-C{sub 3}H{sub 2}, and C{sub 2}H, along with the previously observed species CN, HNC, HCN, and HCO{sup +}, indicates that a relatively complex chemistry can occur in the late stages of PN evolution, despite potentially destructive ultraviolet radiation. These molecules have also been observed in diffuse clouds, suggesting a possible connection between molecular material in evolved PNe and the diffuse ISM.

  11. Gas-phase reactions of the bare Th2+ and U2+ ions with small alkanes, CH4, C2H6, and C3H8: experimental and theoretical study of elementary organoactinide chemistry.

    PubMed

    Di Santo, Emanuela; Santos, Marta; Michelini, Maria C; Marçalo, Joaquim; Russo, Nino; Gibson, John K

    2011-02-16

    The gas-phase reactions of two dipositive actinide ions, Th(2+) and U(2+), with CH(4), C(2)H(6), and C(3)H(8) were studied by both experiment and theory. Fourier transform ion cyclotron resonance mass spectrometry was employed to study the bimolecular ion-molecule reactions; the potential energy profiles (PEPs) for the reactions, both observed and nonobserved, were computed by density functional theory (DFT). The experiments revealed that Th(2+) reacts with all three alkanes, including CH(4) to produce ThCH(2)(2+), whereas U(2+) reacts with C(2)H(6) and C(3)H(8), with different product distributions than for Th(2+). The comparative reactivities of Th(2+) and U(2+) toward CH(4) are well explained by the computed PEPs. The PEPs for the reactions with C(2)H(6) effectively rationalize the observed reaction products, ThC(2)H(2)(2+) and UC(2)H(4)(2+). For C(3)H(8) several reaction products were experimentally observed; these and additional potential reaction pathways were computed. The DFT results for the reactions with C(3)H(8) are consistent with the observed reactions and the different products observed for Th(2+) and U(2+); however, several exothermic products which emerge from energetically favorable PEPs were not experimentally observed. The comparison between experiment and theory reveals that DFT can effectively exclude unfavorable reaction pathways, due to energetic barriers and/or endothermic products, and can predict energetic differences in similar reaction pathways for different ions. However, and not surprisingly, a simple evaluation of the PEP features is insufficient to reliably exclude energetically favorable pathways. The computed PEPs, which all proceed by insertion, were used to evaluate the relationship between the energetics of the bare Th(2+) and U(2+) ions and the energies for C-H and C-C activation. It was found that the computed energetics for insertion are entirely consistent with the empirical model which relates insertion efficiency to the

  12. Vapor-Liquid Equilibrium in the Mixture 1,1,2,2-Tetrachloroethane C2H2Cl4 + C3H3N Propenenitrile (EVLM1211, LB5648_E)

    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 'vapor-Liquid Equilibrium in the Mixture 1,1,2,2-Tetrachloroethane C2H2Cl4 + C3H3N Propenenitrile (EVLM1211, LB5648_E)' providing data from direct measurement of temperature at variable mole fraction in liquid phase and constant pressure.

  13. Energy transport in photoexcited crystals of K3[Tb(C2O4)3(H2O)].2H2O: Transfer from Tb3+ to Nd3+ and Eu3+

    NASA Astrophysics Data System (ADS)

    Kahwa, Ishenkumba A.; Parkes, Charmaine C.; McPherson, Gary L.

    1995-10-01

    The luminescence decay dynamics of Tb3+(5D4) and Eu(5D0) in triclinic (P1¯) crystalline K3[Ln(C2O4)3(H2O)].2H2O solids was studied between 10 and 298 K in order to establish the energy-transport characteristics. The luminescence decay rate of Tb3+ (740 s-1 for Ln=Tb3+) is temperature independent for the pure terbium complex; with introduction of Ln3+ dopants (e.g., Ln=Nd, Eu) faster decay rates which are temperature dependent are obtained. For the Eu3+ dopant, excitation buildup on the Eu3+(5D0) decay curve upon Tb3+(5D4) excitation confirms that energy transfer from Tb3+(5D4) to Ln3+ is active. The temperature dependence of the energy-transfer process in the K3[Eu0.83Tb0.17(C2O4)3(H2O)].2H2O mixed complex is well described by a relatively simple empirical expression based on Boltzmann's statistical dynamics of Eu3+ electronic energy among the 7FJ (J=0,1,2) terms. The limiting Eu3+-Tb3+ transfer rates are ~5.4×103 and 5.3×104 s-1 at 77 and 298 K, respectively. Energy migration on the terbium sublattice was confirmed by comparing Huber's [Phys. Rev. B 20, 2707 (1979)] trapping functions for K3[Eu0.4Tb0.6(C2O4)3(H2O)].2H2O and K3[Eu0.4Tb0.1Gd0.5(C2O4)3(H2O)].2H2O (Gd3+ serving as a scatterer for Tb3+ excitation). Although the structure of the complexes features a one-dimensional zigzag array of Ln3+ ions, energy transport is diffusive and not one dimensional.

  14. Pd-Catalyzed sequential β-C(sp(3))-H arylation and intramolecular amination of δ-C(sp(2))-H bonds for synthesis of quinolinones via an N,O-bidentate directing group.

    PubMed

    Guan, Mingyu; Pang, Yubo; Zhang, Jingyu; Zhao, Yingsheng

    2016-05-19

    The pharmacological importance of 2-quinolinone derivatives is well known. Herein, we developed an effective protocol for the synthesis of 2-quinolinone derivatives by palladium-catalyzed sequential β-C(sp(3))-H arylation and selective intramolecular C(sp(2))-H/N-H amination starting with aryl iodides and carboxylic acids. A novel directing group, glycine dimethylamide, was used in the synthesis. We synthesized various quinolinone derivatives, including 5-substituted quinolinones, which are difficult to obtain using the traditional pathway. The directing group could be easily removed and could be readily transformed into other useful functional groups. PMID:27161570

  15. Monitoring dehydration of the organic-inorganic [(C3H7)4N][SnCl5(H2O)]·2H2O compound using simultaneous thermal and Raman studies

    NASA Astrophysics Data System (ADS)

    Hajlaoui, S.; Chaabane, I.; Guidara, K.; Bulou, A.

    2016-07-01

    In this work we report the experimental studies of the structural phase transition in the [(C3H7)4N]SnCl5(H2O)]·2H2O compound by differential scanning calorimetric (DSC) and Raman spectroscopic. The X-ray powder diffraction study of the [(C3H7)4N][SnCl5(H2O)]·2H2O sample at room temperature showed that this compound is monoclinic and has P121/c1 space group. Differential scanning calorimetric disclosed two types of phase transitions in the temperature range 356-376 (T1) K and at 393 K (T2) characterized, by a loss of water molecules and probably a reconstruction of new anionic parts after T2 transition. The Raman scattering spectra recorded at various temperatures in the wavenumber range from 100 to 3800 cm- 1 covering the domains of existence of changes in the vicinity of the two phase transitions detected by DSC measurement. A detailed study of the spectral parameters (wave number, reduced intensity and the full width at half maximum) as a function of temperature of a chosen band, associated with (νs(Snsbnd O) + νs(Snsbnd Cl)), based on an order-disorder model allowed us to obtain information relative to the activation energy and correlation length.

  16. Study of the tau- ---> pi- pi- pi+ pi0 pi0 nu/tau and tau- --> 3h- 2h+ nu/tau Decays Using the BaBar Detector

    SciTech Connect

    Sobie, R.; /Victoria U.

    2005-06-21

    The {tau}{sup -} {yields} {pi}{sup -}{pi}{sup -}{pi}{sup +}{pi}{sup 0}{pi}{sup 0}{nu}{sub {tau}} and {tau}{sup -} {yields} 3h{sup -} 2h{sup +} {nu}{sub {tau}} decays have been studied using the BABAR experiment at the PEP-II e{sup +}e{sup -} storage ring. Preliminary branching fractions are given for the {tau}{sup -} {yields} {pi}{sup -}{pi}{sup -}{pi}{sup +}{pi}{sup 0}{pi}{sup 0}{nu}{sub {tau}} and to the sub-channels {tau}{sup -} {yields} {eta}{pi}{sup -} {pi}{sup 0}{nu}{sub {tau}} and {tau}{sup -} {yields} {omega}(782){pi}{sup -}{pi}{sup 0}{nu}{sub {tau}}. A preliminary upper limit is given on the branching fraction for the {phi}(1020){pi}{sup -}{pi}{sup 0}{nu}{sub {tau}} mode. In addition a preliminary measurement of the branching fraction of the {tau}{sup -} {yields} 3h{sup -}2h{sup +} {nu}{sub {tau}} decay (h = {pi}, K) is presented.

  17. Monitoring dehydration of the organic-inorganic [(C3H7)4N][SnCl5(H2O)]·2H2O compound using simultaneous thermal and Raman studies.

    PubMed

    Hajlaoui, S; Chaabane, I; Guidara, K; Bulou, A

    2016-07-01

    In this work we report the experimental studies of the structural phase transition in the [(C3H7)4N]SnCl5(H2O)]·2H2O compound by differential scanning calorimetric (DSC) and Raman spectroscopic. The X-ray powder diffraction study of the [(C3H7)4N][SnCl5(H2O)]·2H2O sample at room temperature showed that this compound is monoclinic and has P121/c1 space group. Differential scanning calorimetric disclosed two types of phase transitions in the temperature range 356-376 (T1) K and at 393K (T2) characterized, by a loss of water molecules and probably a reconstruction of new anionic parts after T2 transition. The Raman scattering spectra recorded at various temperatures in the wavenumber range from 100 to 3800cm(-1) covering the domains of existence of changes in the vicinity of the two phase transitions detected by DSC measurement. A detailed study of the spectral parameters (wave number, reduced intensity and the full width at half maximum) as a function of temperature of a chosen band, associated with (νs(SnO)+νs(SnCl)), based on an order-disorder model allowed us to obtain information relative to the activation energy and correlation length. PMID:27070530

  18. On the Formation and Isomer Specific Detection of Propenal (C2H3CHO) and Cyclopropanone (c-C3H4O) in Interstellar Model Ices - A Combined FTIR and Reflectron Time-of-Flight Mass Spectroscopic Study

    NASA Astrophysics Data System (ADS)

    Abplanalp, Matthew J.; Borsuk, Aleca; Jones, Brant M.; Kaiser, Ralf I.

    2015-11-01

    The formation routes of two structural isomers—propenal (C2H3CHO) and cyclopropanone (c-C3H4O)—were investigated experimentally by exposing ices of astrophysical interest to energetic electrons at 5.5 K thus mimicking the interaction of ionizing radiation with interstellar ices in cold molecular clouds. The radiation-induced processing of these ices was monitored online and in situ via Fourier Transform Infrared spectroscopy and via temperature programmed desorption exploiting highly sensitive reflectron time-of-flight mass spectrometry coupled with single photon ionization in the post irradiation phase. To selectively probe which isomer(s) is/are formed, the photoionization experiments were conducted with 10.49 and 9.60 eV photons. Our studies provided compelling evidence on the formation of both isomers—propenal (C2H3CHO) and cyclopropanone (c-C3H4O)—in ethylene (C2H4)—carbon monoxide (CO) ices forming propenal and cyclopropanone at a ratio of (4.5 ± 0.9):1. Based on the extracted reaction pathways, the cyclopropanone molecule can be classified as a tracer of a low temperature non-equilibrium chemistry within interstellar ices involving most likely excited triplet states, whereas propenal can be formed at ultralow temperatures, but also during the annealing phase via non-equilibrium as well as thermal chemistry (radical recombination). Since propenal has been detected in the interstellar medium and our laboratory experiments demonstrate that both isomers originated from identical precursor molecules our study predicts that the hitherto elusive second isomer—cyclopropanone—should also be observable toward those astronomical sources such as Sgr B2(N) in which propenal has been detected.

  19. Comparison between IRMS and CRDS methods in the determination of isotopic ratios {sup 2}H/{sup 1}H and {sup 18}O/{sup 16}O in water

    SciTech Connect

    Santos, T. H. R.; Zucchi, M. R.; Lemaire, T.; Azevedo, A. E. G.

    2013-05-06

    Traditionally, the method used for measuring the isotope ratios is the Isotope Ratio Mass Spectrometers (IRMS). A new method has been used to determine the isotopic abundances, the Cavity Ring-Down Spectroscopy (CRDS). It consists of a technique of direct absorption, of high sensitivity, which is based on measuring the absorption ratio, as a function of time, of the light confined in a high finesse optical cavity, instead of the magnitude of light beam absorption. The values of {sup 18}O/{sup 16}O and D/H ratios are determined with respect to international standards VSMOW, GISP and SLAP from the International Atomic Energy Agency (IAEA). In this work, the IRMS and CRDS techniques are compared, verifying that the CRDS technique is promising and has some advantages compared to IRMS. It uses a smaller amount of sample, the isotope measurements are made simultaneously from the steam, reducing the analysis time. It also shows good reproducibility and accuracy, and it does not require a preliminary sample preparation.

  20. Ab initio studies on cyanoacetylenes of astrochemical interest: [Y(Ctbnd C)CN, Y dbnd C2H5, C3H7, C4H9, F, Cl, Br and CN

    NASA Astrophysics Data System (ADS)

    Kodi Ramanah, D.; Surajbali, P.; Rhyman, L.; Alswaidan, I. A.; Fun, H.-K.; Somanah, R.; Ramasami, P.

    2016-01-01

    Theoretical studies were performed on seven potential interstellar and circumstellar substituted cyanoacetylenes, Y(Ctbnd C)CN [Y = C2H5, C3H7, C4H9, F, Cl, Br and CN]. Geometry optimizations were carried out using the DFT/B3LYP, the CCSD and CCSD(T) levels of theory. The cc-pVTZ basis set was used for all atoms. Frequency computations were also carried out at the same level of theory as for the optimization to check the nature of the stationary points. The molecular and spectroscopic parameters of the cyanoacetylenes were computed. An analysis of these parameters is in line with the satisfactory performance of the B3LYP/cc-pVTZ level compared to the golden standard, the CCSD(T) level. The theoretical data reported in this work should facilitate future identifications of these cyanoacetylenes in extraterrestrial locations. Plausible mechanisms for the formation of these molecules have been proposed.

  1. ACE-FTS observation of a young biomass burning plume: first reported measurements of C2H4, C3H6O, H2CO and PAN by infrared occultation from space

    NASA Astrophysics Data System (ADS)

    Coheur, P.-F.; Herbin, H.; Clerbaux, C.; Hurtmans, D.; Wespes, C.; Carleer, M.; Turquety, S.; Rinsland, C. P.; Remedios, J.; Hauglustaine, D.; Boone, C. D.; Bernath, P. F.

    2007-10-01

    In the course of our study of the upper tropospheric composition with the infrared Atmospheric Chemistry Experiment - Fourier Transform Spectrometer (ACE-FTS), we found an occultation sequence that on 8 October 2005, sampled a remarkable plume near the east coast of Tanzania. Model simulations of the CO distribution in the Southern hemisphere are performed for this period and they suggest that the emissions for this event likely originated from a nearby forest fire, after which the plume was transported from the source region to the upper troposphere. Taking advantage of the very high signal-to-noise ratio of the ACE-FTS spectra over a wide wavenumber range (750-4400 cm-1), we present in-depth analyses of the chemical composition of this plume in the middle and upper troposphere, focusing on the measurements of weakly absorbing pollutants. For this specific biomass burning event, we report simultaneous observations of an unprecedented number of organic species. Measurements of C2H4 (ethene), C3H4 (propyne), H2CO (formaldehyde), C3H6O (acetone) and CH3COO2NO2 (peroxyacetylnitrate, abbreviated as PAN) are the first reported detections using infrared occultation spectroscopy from satellites. Based on the lifetime of the emitted species, we discuss the photochemical age of the plume and also report, whenever possible, the enhancement ratios relative to CO.

  2. ACE-FTS observation of a young biomass burning plume: first reported measurements of C2H4, C3H6O, H2CO and PAN by infrared occultation from space

    NASA Astrophysics Data System (ADS)

    Coheur, P.-F.; Herbin, H.; Clerbaux, C.; Hurtmans, D.; Wespes, C.; Carleer, M.; Turquety, S.; Rinsland, C. P.; Remedios, J.; Hauglustaine, D.; Boone, C. D.; Bernath, P. F.

    2007-06-01

    In the course of our study of the upper tropospheric composition with the infrared Atmospheric Chemistry Experiment - Fourier Transform Spectrometer (ACE-FTS), we found an occultation sequence that on 8 October 2005, sampled a remarkable plume near the east coast of Tanzania. Model simulations of the CO distribution in the Southern hemisphere are performed for this period and they demonstrate that the emissions for this event originated from a nearby forest fire, after which the plume was transported from the source region to the upper troposphere. Taking advantage of the very high signal-to-noise ratio of the ACE-FTS spectra over a wide wavenumber range (750-4400 cm-1), we present in-depth analyses of the chemical composition of this plume in the middle and upper troposphere, focusing on the measurements of weakly absorbing pollutants. For this specific biomass burning event, we report simultaneous observations of an unprecedented number of organic species. Measurements of C2H4 (ethene), C3H4 (propyne), H2CO (formaldehyde), C3H6O (acetone) and CH3COO2NO2 (peroxyacetylnitrate, abbreviated as PAN) are the first reported detections using infrared occultation spectroscopy from satellites. Based on the lifetime of the emitted species, we discuss the photochemical age of the plume and also report, whenever possible, the enhancement ratios relative to CO.

  3. ACE-FTS Observation of a Young Biomass Burning Plume: First Reported Measurements of C2H4, C3H6O, H2CO and PAN by Infrared Occultation from Space

    NASA Technical Reports Server (NTRS)

    Coheur, Pierre-Francois; Herbin, Herve; Clerbaux, Cathy; Hurtmans, Daniel; Wespes, Catherine; Carleer, Michel; Turquety, Solene; Rinsland, Curtis P.; Remedios, John; Hauglustaine, Didier; Boone, Chris D.; Bernath, Peter F.

    2007-01-01

    In the course of our study of the upper tropospheric composition with the infrared 35 Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE FTS), we 36 found an occultation sequence that on 8 October 2005, sampled a remarkable plume near the 37 east coast of Tanzania. Model simulations of the CO distribution in the Southern hemisphere 38 are performed for this period and they demonstrate that the emissions for this event originated 39 from a nearby forest fire, after which the plume was transported from the source region to the 40 upper troposphere. Taking advantage of the very high signal-to-noise ratio of the ACE FTS 41 spectra over a wide wavenumber range (750-4400 cm(exp -1), we present in-depth analyses of the 42 chemical composition of this plume in the middle and upper troposphere, focusing on the 43 measurements of weakly absorbing pollutants. For this specific biomass burning event, we 44 report simultaneous observations of an unprecedented number of organic species. 45 Measurements of C2H4 (ethene), C3H4 (propyne), H2CO (formaldehyde), C3H6O (acetone) 46 and CH3COO2NO2 (perxoxyacetylnitrate, abbreviated as PAN) are the first reported 47 detections using infrared occultation spectroscopy from satellites. Based on the lifetime of the 48 emitted species, we discuss the photochemical age of the plume and also report, whenever 49 possible, the enhancement ratios relative to CO.

  4. Metal-containing ligands for mixed-metal polymers: novel Cu(II)-Ag(I) mixed-metal coordination polymers generated from [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O and silver(I) salts.

    PubMed

    Dong, Y B; Smith, M D; zur Loye, H C

    2000-05-01

    One Cu(II)-containing ligand and two Cu(II)-Ag(I) mixed-metal coordination polymers have been synthesized. [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O (1) was obtained as a molecular complex with two uncoordinated nitrogen donors by the reaction of 2-methylpyrazine-5-carboxylate sodium with CuCl(2).2H2O in water. Compound 1 crystallized in the triclinic space group P1, with a = 10.498(2) A, b = 11.000(2) A, c = 8.1424(16) A, alpha = 98.33(3) degrees, beta = 101.83(3) degrees, gamma = 66.68(3) degrees, and Z = 2. Reactions of 1 with silver(I) salts have been studied. Two Cu(II)-Ag(I) mixed-metal coordination polymers, namely, Ag[Cu(2-methylpyrazine-5-carboxylate)2.(H2O)2](BF4) (2) and Ag[Cu(2-methylpyrazine-5-carboxylate)2.(H2O)2](NO3) (3), have been generated by treating 1 with AgBF4 and AgNO3, respectively. Compound 2 crystallized in the monoclinic space group C2/c, with a = 25.827(5) A, b = 9.6430(19) A, c = 7.4525(15) A, beta = 94.74(3) degrees, and Z = 4. Compound 3 also crystallized in the monoclinic space group C2/c, with a = 25.855(5) A, b = 9.782(2) A, c = 7.1201(14) A, beta = 96.90(3) degrees, and Z = 4. The main structural feature in both 2 and 3 is a zigzag Cu(II)-Ag(I) mixed-metal chain, in which the alternating Cu(II) and Ag(I) centers are linked by 2-methylpyrazine-5-carboxylate spacers. The effect of the nitrate counterion was illustrated by compound 3, in which a novel [Ag+...NO3-] coordination chain has been found which acts as the connector to cross-link the one-dimensional zigzag chains into a three-dimensional network. In addition, an identical interchain O-H...O hydrogen bonding system has been found in both 2 and 3 and has been shown to play a significant role in directing the alignment of the one-dimensional mixed-metal polymer chains in the crystalline state. The magnetic susceptibilities of 2 and 3 were measured and found to follow the Curie law (mu eff = 1.85 for 2 and 1.83 for 3). PMID:11428114

  5. Identification of ligand efficient, fragment-like hits from an HTS library: structure-based virtual screening and docking investigations of 2H- and 3H-pyrazolo tautomers for Aurora kinase A selectivity.

    PubMed

    Sarvagalla, Sailu; Singh, Vivek Kumar; Ke, Yi-Yu; Shiao, Hui-Yi; Lin, Wen-Hsing; Hsieh, Hsing-Pang; Hsu, John T A; Coumar, Mohane Selvaraj

    2015-01-01

    Furanopyrimidine 1 (IC50 = 273 nM, LE = 0.36, LELP = 10.28) was recently identified by high-throughput screening (HTS) of an in-house library (125,000 compounds) as an Aurora kinase inhibitor. Structure-based hit optimization resulted in lead molecules with in vivo efficacy in a mouse tumour xenograft model, but no oral bioavailability. This is attributed to "molecular obesity", a common problem during hit to lead evolution during which degradation of important molecular properties such as molecular weight (MW) and lipophilicity occurs. This could be effectively tackled by the right choice of hit compounds for optimization. In this regard, ligand efficiency (LE) and ligand efficiency dependent lipophilicity (LELP) indices are more often used to choose fragment-like hits for optimization. To identify hits with appropriate LE, we used a MW cut-off <250, and pyrazole structure to filter HTS library. Next, structure-based virtual screening using software (Libdock and Glide) in the Aurora A crystal structure (PDB ID: 3E5A) was carried out, and the top scoring 18 compounds tested for Aurora A enzyme inhibition. This resulted in the identification of a novel tetrahydro-pyrazolo-isoquinoline hit 7 (IC50 = 852 nM, LE = 0.44, LELP = 8.36) with fragment-like properties suitable for further hit optimization. Moreover, hit 7 was found to be selective for Aurora A (Aurora B IC50 = 35,150 nM) and the possible reasons for selectivity investigated by docking two tautomeric forms (2H- and 3H-pyrazole) of 7 in Auroras A and B (PDB ID: 4AF3) crystal structures. This docking study shows that the major 3H-pyrazole tautomer of 7 binds in Aurora A stronger than in Aurora B. PMID:25344840

  6. The influence of temperature (20-1000 °C) on binary mixtures of solid solutions of CH 3COOLi·2H 2O-MgHPO 4·3H 2O

    NASA Astrophysics Data System (ADS)

    Umbreit, Michał H.; Paukszta, Dominik

    2009-11-01

    Thermally induced phase transitions (20-1000 °C) in the substrates and binary mixtures of CH 3COOLi·2H 2O(1)-MgHPO 4·3H 2O(11) have been analysed. Changes taking place on dehydration and thermal dissociation of binary mixtures prepared with percent molar ratios of 90-10% were studied by differential thermal analysis (TG, DTG, DTA), IR-spectroscopy and WAXS. The above-mentioned substrates changed their structure when heated for 1 h at 500 or 1000 °C. CH 3COOLi·2H 2O(1) (ID: 23-1171) changed the structure at 500 °C to that of Li 2CO 3 (ID: 22-1141), while at 1000 °C the structure was impossible to analyse as the compound reacted both with porcelain and with platinum (crucible materials). MgHPO 4·3H 2O(11) (Newberyite, ID: 35-780, 19-762) changed its structure at 500 °C to amorphous phase and at 1000 °C to Mg 2P 2O 7 (ID: 32-626). The following compounds were assayed in the respective binary mixtures heated at 500 °C for 1 h: 70% (1)-30%(11): LiMgPO 4 (ID: 18-735), MgO (ID: 4-829); 50%(1)-50%(11): LiMgPO 4 (ID: 18-735), Li 3PO 4 (ID: 25-1030); 30%(1)-70%(11): LiMgPO 4 (ID: 32-574); binary mixtures heated at 1000 °C contained the following compounds: 70%(1)-30%(11): LiMgPO 4 (ID: 32-574,18-735), Li 3PO 4 (ID: 15-760,25-1030), MgO (ID: 4-829); 50%(1)-50%(11): LiMgPO 4 (ID: 32-574, 18-735), MgO (ID: 4-829); 30%(1)-70%(11): LiMgPO 4 (ID: 18-735, 32-574), Mg 2P 2O 7 (ID: 22-1152, 8-38), Li 4SiO 4 (37-1472).

  7. Iridium complexes containing mesoionic C donors: selective C(sp3)-H versus C(sp2)-H bond activation, reactivity towards acids and bases, and catalytic oxidation of silanes and water.

    PubMed

    Petronilho, Ana; Woods, James A; Mueller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

    2014-11-24

    Metalation of a C2-methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp(3))-H bond activation of the C2-bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp(2))-H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp(2))-H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D(+) and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir-C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6,000 h(-1) with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol-4-ylidene ligands and is more than three times faster than with the triazolylidene analogue. PMID:25302630

  8. Repetitively pulsed atmospheric pressure discharge treatment of rough polymer surfaces: II. Treatment of micro-beads in He/NH3/H2O and He/O2/H2O mixtures

    NASA Astrophysics Data System (ADS)

    Bhoj, Ananth N.; Kushner, Mark J.

    2008-08-01

    Plasmas are increasingly being used to functionalize the surface of polymers having complex shapes for biomedical applications such as tissue scaffolds and drug delivering micro-beads. The functionalization often requires affixation of amine (NH2) or O-containing groups. In this paper, results are discussed from a two-dimensional computational investigation of the atmospheric pressure plasma functionalization of non-planar and porous surfaces of polypropylene with NHx and O-containing groups. For the former, the discharge is sustained in He/NH3/H2O mixtures in a dielectric barrier-corona configuration. Significant microscopic non-uniformities arise due to competing pathways for reactive gas phase radicals such as OH and NH2, and on the surface by the availability of OH to initiate amine attachment. The treatment of inside surfaces of porous polymer micro-beads placed on an electrode is particularly sensitive to view angles to the discharge and pore size, and is ultimately controlled by the relative rates of radical transport and surface reactions deep into the pores. The functionalization of micro-beads suspended in He/O2/H2O discharges is rapid with comparable treatment of the outer and interior surfaces, but varies with the location of the micro-bead in the discharge volume.

  9. N-Oxide as an Intramolecular Oxidant in the Baeyer-Villiger Oxidation: Synthesis of 2-Alkyl-2H-indazol-3-yl Benzoates and 2-Alkyl-1,2-dihydro-3H-indazol-3-ones.

    PubMed

    Schütznerová, Eva; Krchňák, Viktor

    2016-05-01

    In this study, we describe the intramolecular Baeyer-Villiger oxidation of ketones to esters using N-oxide. 2-Nitro-N-alkyl-N-(2-oxo-2-phenylethyl)benzenesulfonamide compounds are known to undergo base-mediated C-arylation followed by N-N bond formation, producing unstable five-membered ring intermediates that spontaneously dehydrate to indazole oxides. We identified the reaction conditions under which the cyclic intermediate undergoes acid-mediated intramolecular Baeyer-Villiger oxidation of the ketone in which N-oxide serves as the intramolecular oxidizing agent. The solid-phase synthesis plays a critical role in the successful transformation, allowing rapid access to the unstable but Baeyer-Villiger oxidation-prone intermediate. This synthetic route provides practical access to 2-alkyl-2H-indazol-3-yl benzoates and 2-alkyl-1,2-dihydro-3H-indazol-3-ones, which are known privileged structures possessing remarkable diverse pharmacologically relevant activities. PMID:27035416

  10. Characterization, molecular modeling and antimicrobial activity of metal complexes of tridentate Schiff base derived from 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione and 2-aminophenol

    NASA Astrophysics Data System (ADS)

    Adly, Omima M. I.

    Metal complexes of Ni(II), Co(II), Cd(II), VO(IV) and UO2(VI) as well as several Cu(II) salts, including Cl,NO3-,AcO,ClO4- and SO4-2 with a tridentate O2N donor Schiff base ligand (H2L), synthesized by condensation of 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione with 2-aminophenol, were prepared and characterized on the basis of elemental analyses, spectral, magnetic, molar conductance and thermal gravimetric analysis. Square planar, tetrahedral and octahedral geometries have been assigned to the prepared complexes. Molecular parameters of the ligand and its metal complexes have been calculated and correlated with the experimental data, and the changes of bond lengths are linearly correlated with IR data. The antimicrobial activities of the synthesized compounds were tested in vitro against the sensitive organisms Staphylococcus aureus as Gram positive bacteria, Proteus vulgaris as Gram negative bacteria and Candida albicans as fungus strain, and the results are discussed.

  11. Effects of oxygen tension and dextran-shelled/2H,3H-decafluoropentane-cored oxygen-loaded nanodroplets on secretion of gelatinases and their inhibitors in term human placenta.

    PubMed

    Prato, Mauro; Khadjavi, Amina; Magnetto, Chiara; Gulino, Giulia Rossana; Rolfo, Alessandro; Todros, Tullia; Cavalli, Roberta; Guiot, Caterina

    2016-01-01

    Matrix metalloproteinases (MMPs) and their endogenous inhibitors (TIMPs) need to be finely modulated in physiological processes. However, oxygen tension influences MMP/TIMP balances, potentially leading to pathology. Intriguingly, new 2H,3H-decafluoropentane-based oxygen-loaded nanodroplets (OLNDs) have proven effective in abrogating hypoxia-dependent dysregulation of MMP and TIMP secretion by single cell populations. This work explored the effects of different oxygen tensions and dextran-shelled OLNDs on MMP/TIMP production in an organized and multicellular tissue (term human placenta). Chorionic villous explants from normal third-trimester pregnancies were incubated with/without OLNDs in 3 or 20% O2. Explants cultured at higher oxygen tension released constitutive proMMP-2, proMMP-9, TIMP-1, and TIMP-2. Hypoxia significantly altered MMP-2/TIMP-2 and MMP-9/TIMP-1 ratios enhancing TIMP-2 and reducing proMMP-2, proMMP-9, and TIMP-1 levels. Intriguingly, OLNDs effectively counteracted the effects of low oxygen tension. Collectively, these data support OLND potential as innovative, nonconventional, and cost-effective tools to counteract hypoxia-dependent dysregulation of MMP/TIMP balances in human tissues. PMID:26523859

  12. Spectroscopic and structural studies of new mononucleating tetradentate Schiff base metal chelates derived from 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione and 1,3-diaminopropane

    NASA Astrophysics Data System (ADS)

    Adly, Omima M. I.; Taha, Ali; Fahmy, Shery A.

    2015-08-01

    Metal complexes with the general formula Some newly transition metal complexes, [ML(H2O)x(NO3)y], x = 1-2 and y = 0-1, [M = Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Ce(III), Cd(II), Zn(II) or UO2(VI)], L= of the Schiff base (H2L) derived from the reaction of 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione with 1,3-diaminopropane have been prepared and characterized by physical, spectral and analytical data. The structure of the Schiff - base acts as dibasic tetradentate N2O2 for the complexation reaction with Cr(III), Fe(III), Co(II), Cu(II), Ni(II), Ce(III), Cd(II), and UO2(II) ions via phenolates oxygen and nitrogen of azomethine groups. Based on spectral data and magnetic moments, an octahedral geometry may be proposed for the synthesized complexes except cerium(III) complex which has pentagonal bipyramidal arrangement. The low values of the molar conductance indicate non-electrolyte nature of complexes, while 1:1 electrolyte for cerium(III)- and chromium(III)-complexes. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. All the synthesized compounds were tested for in vitro antibacterial activity against some Gram-positive and Gram-negative bacteria, yeast and fungus. Molecular structure of the Schiff base ligand and its complexes were optimized for the proposed structures on the basis of semiempirical PM3 method.

  13. Synthesis, molecular modeling, thermal and spectral studies of metal complexes of hydrazone derived from 5-acetyl-4-hydroxy-2 H-1,3-thiazine-2,6(3 H)-dione and thiosemicarbazide

    NASA Astrophysics Data System (ADS)

    Adly, Omima M. I.

    2011-09-01

    Metal complexes with the general formula [ML(H 2O)(CH 3OH) x]· nH 2O·(CH 3OH) y(NO 3) z [M = Cu(II), Ni(II), Co(II), VO(IV), Cr(III), Cd(II), Zn(II) or UO 2(VI); x = 0-2; y = 0,1; z = 0,1; n = 0-2, 6 and L = hydrazone (H 2L) derived from condensation of thiosemicarbazide with 5-acetyl-4-hydroxy-2 H-1,3-thiazine-2,6(3 H)-dione. The synthesized ligand and its metal complexes have been characterized on the basis of elemental analyses, spectral and magnetic studies as well as thermal gravimetric analysis (TGA). The deprotonated ligand acts as a dibasic tridentate (ONS) via phenolate oxygen, azomethine (C dbnd N), and thiolate (C-S) groups. Copper(II) complex exhibits square planar geometry. Nickel(II), chromium(III) and dioxouranium(VI) complexes exhibit octahedral geometry. Cobalt(II), cadmium(II) and zinc(II) complexes showed tetrahedral geometry, whereas oxovanadium(IV) reveals square pyramidal geometry. Thermal analysis are investigated and showed either three or four thermal decomposition steps. Kinetic parameters ( Ea, A, Δ H, Δ S and Δ G) of the thermal decomposition stages have been evaluated using Coats-Redfern equations. The molecular parameters of the ligand and its metal complexes have been calculated and correlated with the experimental data such as IR and TGA results.

  14. Dynamics of H abstraction from alcohols (CH3OH, C2H5OH and 2-C3H7OH) using velocity map imaging in crossed molecular beams

    SciTech Connect

    Ahmed, M.; Peterka, D.S.; Suits, A.G.

    1999-09-01

    The crossed beam reactions of ground state Cl ({sup 2}P{sub 3/2}) atoms with alcohols (CH{sub 3}OH, C{sub 2}H{sub 5}OH and 2-C{sub 3}H{sub 7}OH) have been studied using the technique of velocity map imaging (VELMI). The corresponding hydroxyalkyl radical was detected via single photon ionization using 157 nm laser light. The double differential cross sections were obtained at collision energies of 8.7 kcal/mol for methanol, 6.0 and 9.7 kcal/mol for ethanol, and 11.9 kcal/mol for 2-propanol. In all cases, the scattering was predominantly in the backward-sideways direction suggesting direct rebound dynamics, with varying amounts of sideways-scattering. In the case of methanol, the angular distributions were predominantly in the sideways-backward direction with respect to the incoming alcohol beam. Scattering was into the backward hemisphere at the lower collision energy for ethanol, with enhancement of sideways scattering with an increase in collision energy. Isoropanol gave scattering predominantly in the backward direction. Coupling between the translational energy and angular distributions was particularly significant for ethanol at the lower collision energy. All of the translational energy distributions peaked at about 6 kcal/mol and on average 30-40% of the available energy was deposited into product translation for all the alcohols studied. These results are contrasted with previous H abstraction studies performed on Cl-hydrocarbon systems. A case is made for the technique of vacuum ultraviolet one-photon ionization in conjunction with VELMI being useful in studying the reaction dynamics for many polyatomic systems.

  15. Layered hybrid organic-inorganic Co(II) alkylphosphonates. Synthesis, crystal structure and magnetism of the first two members of the series: Co[(CH{sub 3}PO{sub 3})(H{sub 2}O)] and Co[(C{sub 2}H{sub 5}PO{sub 3})(H{sub 2}O)

    SciTech Connect

    Bauer, Elvira M.; Bellitto, Carlo . E-mail: carlo.bellitto@ism.cnr.it; Colapietro, Marcello . E-mail: m.colapietro@caspur.it; Ibrahim, Said A.; Mahmoud, Mohamed R.; Portalone, Gustavo; Righini, Guido

    2006-02-15

    Co[(CH{sub 3}PO{sub 3})(H{sub 2}O)] (1) and Co[(C{sub 2}H{sub 5}PO{sub 3})(H{sub 2}O)] (2) were prepared by the hydrothermal method and isolated as blue-violet platelet crystals. They were characterized by X-ray diffraction, FT-IR, TGA-DSC techniques and their magnetic properties studied by a dc-SQUID magnetometer. Compound (1) shows an hybrid layered structure, made of alternating inorganic and organic layers along the a-direction of the unit cell. The inorganic layers contain Co(II) ions six-coordinated by five phosphonate oxygen atoms and one from the water molecule. These layers are separated by bi-layers of methyl groups and van der Waals contacts are established between them. In compound (2), the layered hybrid structure is rather similar to that described for compound (1), but the alternation of the inorganic and organic layers is along the b-direction of the unit cell. The magnetic behavior of (1) and (2) as function of temperature and magnetic field was studied. The compounds obey the Curie-Weiss law at temperatures above 100K, the Curie C, and Weiss {theta} constants for the methyl derivative being C=3.36cm{sup 3}Kmol{sup -1} and {theta}=-53K and for the ethyl derivative C=3.62cm{sup 3}Kmol{sup -1} and {theta}=-75K, respectively. The observed magnetic moments for Co atom at room temperature (i.e. {mu}{sub eff}=5.18 and 5.38 BM, respectively) are higher than those expected for a spin-only value for high spin Co(II) (S=3/2), revealing a substantial orbital contribution to the magnetic moment. The negative values of {theta} are an indication of the presence of antiferromagnetic exchange couplings between the near-neighbors Co(II) ions, within the layers. [Co(C{sub n}H{sub 2n+1}PO{sub 3})(H{sub 2}O)] (n=1,2) are 2D Ising antiferromagnets at low temperatures.

  16. A Carbonylation Approach Toward Activation of Csp2-H and Csp3-H Bonds: Cu-Catalyzed Regioselective Cross Coupling of Imidazo[1,2-a]pyridines with Methyl Hetarenes.

    PubMed

    Lei, Sai; Mai, Yingying; Yan, Caijuan; Mao, Jianwen; Cao, Hua

    2016-08-01

    An efficient copper-catalyzed selective cross coupling of imidazo[1,2-a]pyridines with methyl hetarenes has been reported. This transformation opened a new route to synthesize the C-3 carbonyl imidazo[1,2-a]pyridine derivative, which is a common structural motif in natural products and pharmaceuticals. (18)O-labeling experiments indicated that the oxygen source of products originated from O2. PMID:27388919

  17. Contributions of excited {sup 6}Li and {sup 7}Li nuclei to the production of {sup 4}He+{sup 2}H and {sup 4}He+{sup 3}H systems in {sup 16}O{sub p} collisions at a momentum of 3.25 GeV/c per nucleon

    SciTech Connect

    Olimov, K.; Glagolev, V. V.; Gulamov, K. G.; Lutpullaev, S. L.; Kurbanov, A. R.; Olimov, A. K.; Petrov, V. I.; Yuldashev, A. A.

    2013-07-15

    New experimental data on the cross sections for the yield of excited {sup 6}Li* and {sup 7}Li* nuclei and on their contributions to the production of {sup 4}He + {sup 2}H and {sup 4}He+{sup 3}H light dinuclear systems in {sup 16}O{sub p} collisions at a momentumof 3.25 A GeV/c per nucleon are presented.

  18. U(IV)/Ln(III) mixed site in polymetallic oxalato complexes. Part III: Structure of Na[Yb(C 2O 4) 2(H 2O)]·3H 2O and the derived quadratic series (NH 4+) 1-x[ Ln1-xU x (C 2O 4) 2(H 2O)]·(3+ x) H 2O, Ln=Y, Pr-Sm, Gd, Tb

    NASA Astrophysics Data System (ADS)

    Chapelet-Arab, B.; Duvieubourg, L.; Nowogrocki, G.; Abraham, F.; Grandjean, S.

    2006-12-01

    Single crystals of a new sodium ytterbium oxalate Na[Yb(C 2O 4) 2(H 2O)]·3H 2O ( 1) and six mixed lanthanide (III)-uranium (IV) oxalates (NH 4+) 1-x[ Ln1-xU x (C 2O 4) 2(H 2O)]·(3+ x) H 2O, Ln=Y, x=0.47 ( 2), Ln=Pr, x=0.42 ( 3), Ln=Nd, x=0.60 ( 4), Ln=Sm, x=0.55 ( 5), Ln=Gd, x=0.25 ( 6) and Ln=Tb, x=0.52 ( 7) have been grown using slow diffusion through silica gels. The crystal structures of all the compounds have been determined by single-crystal X-ray diffraction. For compound 1 the symmetry is monoclinic, space group Pc, cell dimensions a=8.559(2) Å, b=8.564(2) Å, c=14.938(3) Å, β=103.062(3), Z=4. The structure of 1 is isotypic with Na[Y(C 2O 4) 2(H 2O)]·3H 2O and consists of layers formed by four-membered rings of Yb connected through oxalate ions. The ytterbium atom is nine-coordinated by oxygen from four bis-bidentate oxalate ligands and one water molecule which alternate up and down the layer. Na + ions and supplementary water molecules are located between the layers. The six mixed lanthanide (III)-uranium (IV) oxalates, 2- 7, are isotypic, the symmetry is tetragonal, space group P4/ n, the unit cell parameters are in the range 8.7239(12)-8.9116(6) and 7.854(2)-7.9487(9) Å for a and c, respectively, Z=2. The structure of the six compounds is built from the same two-dimensional arrangement of alternating metallic and oxalate ions forming four-membered rings. The layers are similar to that observed in 1 and the mixed Ln(III)/U(IV) oxalate layers are obtained by partial substitution of Ln(III) by U(IV) in a nine-coordinated site, the charge surplus being compensated by removal of monovalent cations in the interlayer space. The ammonium ions and the water molecules are disordered in the same crystallographic site. Thus these compounds form the third series of mixed lanthanide (III)-uranium (IV) oxalates, the tetragonal one, that completes the two others previously reported, the hexagonal and the triclinic series.

  19. 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

  20. Synthesis, structural elucidation and spectroscopic analysis of 3a,8b-dihydroxy-4-oxo-1H,2H,3H,3aH,4H,8bH-indeno[1,2-d]imidazolidin-2-iminium chloride

    NASA Astrophysics Data System (ADS)

    Uma Devi, T.; Priya, S.; Selvanayagam, S.; Ravikumar, K.; Anitha, K.

    2012-11-01

    Ninhydrin guanidinium chloride (3a,8b-dihydroxy-4-oxo-1H,2H,3H,3aH,4H,8bH-indeno [1,2-d]imidazolidin-2-iminium chloride) a semiorganic crystal was synthesized. The structure was determined using X-ray single crystal technique. Comparisons between the FT-IR spectrum of ninhydrin guanidinium chloride with ninhydrin were made. Melting point was found using thermal measurements. The molecular geometry, vibrational frequencies and Mulliken charges of the compound in the ground state have been calculated by the density functional theory (DFT) method with 3-21G(d,p) basis set and theoretical frequencies were compared with the experimental FT-IR spectrum. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis, natural bond orbitals (NBO) and thermodynamic properties at various temperatures of the compound were investigated by theoretical calculations.

  1. Metal-ligand interaction of lanthanides with coumarin derivatives. Part I. Complexation of 3-(1-aminoethylidene)-2H-chromene-2,4(3H)-dione with La(III), Ce(III), Nd(III) and Ho(III).

    PubMed

    Swiatek, Mirosława; Kufelnicki, Aleksander

    2012-01-01

    Solutions of lanthanum(III), cerium(III), neodymium(III) and holmium(III) nitrates with 3-(1-aminoethylidene)-2H-chromene-2,4(3H)-dione (1) in 10% v/v dioxane-water medium were used. Coordination modes of 1 with the selected lanthanides have been examined. Hydroxo-complexes with deprotonated water molecules from the inner coordination sphere have been stated in basic medium. Stability constants of the forming complex species were determined by potentiometric titrations using Superquad and Hyperquad2003 programs. The most stable complexes are formed with La(III). The UV-Vis spectra of the Nd(III)-1 system confirmed the L:M = 1:1 stoichiometry evaluated potentiometrically. PMID:23285658

  2. Synthesis, characterization and magnetic property of a new 3D iron phosphite: |C{sub 4}N{sub 3}H{sub 14}|[Fe{sub 3}(HPO{sub 3}){sub 4}F{sub 2}(H{sub 2}O){sub 2}] with intersecting channels

    SciTech Connect

    Qiao Jian; Zhang Lirong; Yu Yang; Li Guanghua; Jiang Tianchan; Huo Qisheng; Liu Yunling

    2009-07-15

    A new open-framework iron (III) phosphite |C{sub 4}N{sub 3}H{sub 14}|[Fe{sub 3}(HPO{sub 3}){sub 4}F{sub 2}(H{sub 2}O){sub 2}] has been solvothermally synthesized by using diethylenetriamine (DETA) as the structure-directing agent. Single-crystal X-ray diffraction analysis reveals that the compound crystallizes in the monoclinic space group C2/c having unit cell parameters a=12.877(3) A, b=12.170(2) A, c=12.159(2) A, beta=93.99(3){sup o}, V=1900.9(7) A{sup 3}, and Z=4 with R{sub 1}=0.0447, wR{sub 2}=0.0958. The complex structure consists of HPO{sub 3} pseudo-tetrahedra and {l_brace}Fe{sub 3}O{sub 14}F{sub 2}{r_brace} trimer building units. The assembly of these building units generates 3D inorganic framework with intersecting 6-, 8-, and 10-ring channels. The DETA cations are located in the 10-ring channels linked by hydrogen bonds. The Moessbauer spectrum shows that there exhibit two crystallographically independent iron (III) atoms. And the magnetic investigation shows the presence of antiferromagnetic interactions. Further characterization of the title compound was performed using X-ray powder diffraction (XRD), infrared (IR) spectra, thermal gravimetric analyses (TGA), inductively coupled plasma (ICP) and elemental analyses. - Graphical abstract: A new three-dimensional iron phosphite with intersecting 6-, 8-, 10-ring channels has been solvothermally synthesized by using diethylenetriamine (DETA) as the structure-directing agent.

  3. 2H and 18O depletion of water close to organic surfaces

    NASA Astrophysics Data System (ADS)

    Chen, Guo; Auerswald, Karl; Schnyder, Hans

    2016-06-01

    Hydrophilic surfaces influence the structure of water close to them and may thus affect the isotope composition of water. Such an effect should be relevant and detectable for materials with large surface areas and low water contents. The relationship between the volumetric solid : water ratio and the isotopic fractionation between adsorbed water and unconfined water was investigated for the materials silage, hay, organic soil (litter), filter paper, cotton, casein and flour. Each of these materials was equilibrated via the gas phase with unconfined water of known isotopic composition to quantify the isotopic difference between adsorbed water and unconfined water. Across all materials, isotopic fractionation was significant (p<0.05) and negative (on average -0.91 ± 0.22 ‰ for 18/16O and -20.6 ± 2.4 ‰ for 2/1H at an average solid : water ratio of 0.9). The observed isotopic fractionation was not caused by solutes, volatiles or old water because the fractionation did not disappear for washed or oven-dried silage, the isotopic fractionation was also found in filter paper and cotton, and the fractionation was independent of the isotopic composition of the unconfined water. Isotopic fractionation became linearly more negative with increasing volumetric solid : water ratio and even exceeded -4 ‰ for 18/16O and -44 ‰ for 2/1H. This fractionation behaviour could be modelled by assuming two water layers: a thin layer that is in direct contact and influenced by the surface of the solid and a second layer of varying thickness depending on the total moisture content that is in equilibrium with the surrounding vapour. When we applied the model to soil water under grassland, the soil water extracted from 7 and 20 cm depth was significantly closer to local meteoric water than without correction for the surface effect. This study has major implications for the interpretation of the isotopic composition of water extracted from organic matter, especially when the volumetric solid : water ratio is larger than 0.5 or for processes occurring at the solid-water interface.

  4. Distinguishing sources of ground water recharge by using δ2H and δ18O

    USGS Publications Warehouse

    Blasch, Kyle W.; Bryson, Jeannie R.

    2007-01-01

    Stable isotope values of hydrogen and oxygen from precipitation and ground water samples were compared by using a volumetrically based mixing equation and stable isotope gradient to estimate the season and location of recharge in four basins. Stable isotopes were sampled at 11 precipitation sites of differing elevation during a 2-year period to quantify seasonal stable isotope contributions as a function of elevation. Supplemental stable isotope data collected by the International Atomic Energy Association during a 14-year period were used to reduce annual variability of the mean seasonal stable isotope data. The stable isotope elevation relationships and local precipitation elevation relationships were combined by using a digital elevation model to calculate the total volumetric contribution of water and stable isotope values as a function of elevation within the basins. The results of these precipitation calculations were compared to measured ground water stable isotope values at the major discharge points near the terminus of the basins. Volumetric precipitation contributions to recharge were adjusted to isolate contributing elevations. This procedure provides an improved representation of recharge contributions within the basins over conventional stable isotope methods. Stable isotope values from wells and springs at the terminus of each basin were used to infer the elevations of precipitation important for recharge of the regional ground water flow system. Ancillary climatic, geologic, and stable isotope values were used to further constrain the location where precipitation is entering the ground water flow system.

  5. Protonation of metal hydrides by strong acids. Formation of an equilibrium mixture of dihydride and dihydrogen complexes from protonation of Cp{sup *}Os(CO){sub 2}H. Structural characterization of [CpW(CO){sub 2}(PMe{sub 3})(H){sub 2}]{sup +}OTf{sup -}

    SciTech Connect

    Bullock, R.M.; Song, J.S.; Szalda, D.J.

    1996-05-14

    Cp{sup *}Os(CO){sub 2}H is protonated by triflic acid (HOTf) in CD{sub 2} Cl{sub 2} solution to give an equilibrium mixture (87:13) of the dihydride [Cp{sup *}Os(CO){sub 2}(H){sub 2}]{sup +}OTf{sup -} and the dihydrogen complex [Cp{sup *}Os(CO){sub 2}({eta}{sup 2}-H{sub 2})]{sup +}OTf{sup -}. The acidity of these protonated species is roughly comparable to HOTf, since only partial protonation was observed. In the absence of acid, the T{sub 1} of the hydride ligand of Cp{sup *}Os(CO){sub 2}H is 5.9 s at -80{degree}C. When all of the Cp{sup *}Os(CO){sub 2}H is protonated by excess HOTf,the T{sub l} (-80{degree}C) of the terminal hydride ligands of [Cp{sup *}Os(CO){sub 2}(H){sub 2}]{sup +}OTf{sup -} is 2.8 s, while the T{sub l} of the dihydrogen ligand of [Cp{sup *}Os(CO){sub 2}({eta}{sup 2}-H{sub 2})]{sup +} OTf{sup -} is 19 ms, (-80{degree}C). The observed T{sub l} values of the Os-H resonance of Cp{sup *}Os(CO){sub 2}H decreased significantly under conditions of partial protonation, indicating intermolecular proton transfer among [Cp{sup *}Os(CO){sub 2}({eta}{sup 2}H{sub 2})]{sup +}OTf{sup -}, [Cp{sup *}Os(CO){sub 2}(H){sub 2}]{sup +}OTf{sup -}, Cp{sup *}Os(CO){sub 2}H, and HOTf. IR spectra indicate that the two CO ligands of [Cp{sup *}Os(CO){sub 2}(H){sub 2}]{sup +} (and hence the hydrides as well) are trans to each other in the four-legged piano stool geometry. 62 refs., 6 figs., 8 tabs.

  6. Using 14C and 3H to understand groundwater flow and recharge in an aquifer window

    NASA Astrophysics Data System (ADS)

    Atkinson, A. P.; Cartwright, I.; Gilfedder, B. S.; Cendón, D. I.; Unland, N. P.; Hofmann, H.

    2014-12-01

    Knowledge of groundwater residence times and recharge locations is vital to the sustainable management of groundwater resources. Here we investigate groundwater residence times and patterns of recharge in the Gellibrand Valley, southeast Australia, where outcropping aquifer sediments of the Eastern View Formation form an "aquifer window" that may receive diffuse recharge from rainfall and recharge from the Gellibrand River. To determine recharge patterns and groundwater flow paths, environmental isotopes (3H, 14C, δ13C, δ18O, δ2H) are used in conjunction with groundwater geochemistry and continuous monitoring of groundwater elevation and electrical conductivity. The water table fluctuates by 0.9 to 3.7 m annually, implying recharge rates of 90 and 372 mm yr-1. However, residence times of shallow (11 to 29 m) groundwater determined by 14C are between 100 and 10 000 years, 3H activities are negligible in most of the groundwater, and groundwater electrical conductivity remains constant over the period of study. Deeper groundwater with older 14C ages has lower δ18O values than younger, shallower groundwater, which is consistent with it being derived from greater altitudes. The combined geochemistry data indicate that local recharge from precipitation within the valley occurs through the aquifer window, however much of the groundwater in the Gellibrand Valley predominantly originates from the regional recharge zone, the Barongarook High. The Gellibrand Valley is a regional discharge zone with upward head gradients that limits local recharge to the upper 10 m of the aquifer. Additionally, the groundwater head gradients adjacent to the Gellibrand River are generally upwards, implying that it does not recharge the surrounding groundwater and has limited bank storage. 14C ages and Cl concentrations are well correlated and Cl concentrations may be used to provide a first-order estimate of groundwater residence times. Progressively lower chloride concentrations from 10

  7. 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.

  8. Metal ion interactions with nucleobases in the tetradentate 1,4,7,10-tetraazacyclododecane (cyclen)-ligand system: Crystal structures of [Cu(cyclen)(adeninato)]·ClO 4·2H 2O, [{Cu(cyclen)} 2(hypoxanthinato)]·(ClO 4) 3, [Cu(cyclen)(theophyllinato)] 3·(ClO 4) 3·2H 2O, and [Cu(cyclen)(xanthinato)]·(0.7ClO 4)·(0.3ClO 4)·3H 2O·(0.5H 2O) 3

    NASA Astrophysics Data System (ADS)

    Rahman, Md. Shahidur; Yuan, Hou Qun; Kikuchi, Takanori; Fujisawa, Ikuhide; Aoki, Katsuyuki

    2010-03-01

    Reaction of 1,4,7,10-tetraazacyclododecane (cyclen) and Cu(ClO 4) 2·6H 2O with nucleobases (adenine, hypoxanthine, xanthine, theophylline, cytosine, or uracil) under alkaline conditions gave four ternary cyclen-metal-nucleobase complexes, [Cu(cyclen)(adeninato)]·ClO 4·2H 2O ( 1), [{Cu(cyclen)} 2(hypoxanthinato)]·(ClO 4) 3 ( 2), [Cu(cyclen)(theophyllinato)] 3·(ClO 4) 3·2H 2O ( 3), and [Cu(cyclen)(xanthinato)]·(0.7ClO 4)·(0.3ClO 4)·3H 2O·(0.5H 2O) 3 ( 4), whose crystal structures were determined by X-ray diffraction. In the adenine complex 1, a cyclen-capped square-pyramidal Cu 2+ ion binds to an adeninato ligand through N(9) with the formation of an intramolecular interligand hydrogen bond between the secondary amino nitrogen of cyclen and N(3) of the base. In the hypoxanthine complex 2, two cyclen-capped Cu 2+ ions bind to a hypoxanthinato ligand, one through N(7) with the formation of an intramolecular N(cyclen)-H···O(6) hydrogen bond and the other through N(9) to form an intramolecular N(cyclen)-H···N(3) hydrogen bond. Similarly, in both the theophylline complex 3 and the xanthine complex 4, each cyclen-capped Cu 2+ ion binds to a theophyllinato or xanthinato ligand through N(7) with the formation of an intramolecular N(cyclen)-H···O(6) hydrogen bond. However, unlike in 2, steric constraints between amino group(s) of cyclen and the methyl group at N(3) of theophylline in 3 or the proton attached to N(9) of xanthine in 4 preclude the metal bonding to N(9) in 3 or N(3) in 4. The significance of intramolecular interligand interaction as a factor that affects metal-binding site(s) on nucleobases is emphasized.

  9. 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.

  10. Synthesis, structure, and physical properties of [Sm(C{sub 6}NO{sub 2}H{sub 5}){sub 3}(H{sub 2}O){sub 2}]{sub 2n}.(H{sub 5}O{sub 2}){sub n}(ZnCl{sub 5}){sub n}(ZnCl{sub 4}){sub 2n}.(H{sub 2}O){sub 2n} with unprecedented ZnCl{sub 5}{sup 3-} species

    SciTech Connect

    Xie Yiming Chen Wentong; Wu Jihuai

    2008-08-15

    A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex [Sm(C{sub 6}NO{sub 2}H{sub 5}){sub 3}(H{sub 2}O){sub 2}]{sub 2n}.(H{sub 5}O{sub 2}){sub n}(ZnCl{sub 5}){sub n}(ZnCl{sub 4}){sub 2n}.(H{sub 2}O){sub 2n} (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characteristic of a one-dimensional polycationic chain-like structure and unprecedented ZnCl{sub 5}{sup 3-} species. Photoluminescent investigation reveals that the title complex displays interesting emissions in a wide region. Optical absorption spectra of 1 reveal the presence of an optical gap of 3.59 eV. - Graphical abstract: A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex was synthesized. It is characteristic of a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions in a wide region. Optical absorption spectra of 1 reveal the presence of a wide optical bandgap.

  11. 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.

  12. Viscosity, Second pVT-Virial Coefficient, and Diffusion of Pure and Mixed Small Alkanes CH4, C2H6, C3H8, n-C4H10, i-C4H10, n-C5H12, i-C5H12, and C(CH3)4 Calculated by Means of an Isotropic Temperature-Dependent Potential. I. Pure Alkanes

    NASA Astrophysics Data System (ADS)

    Zarkova, L.; Hohm, U.; Damyanova, M.

    2006-09-01

    Reference tables of second pVT-virial coefficients B(T ), viscosity η(T ), and self-diffusion ρD(T ) are given for all neat alkanes CnH2n+2, n <6, for temperatures T ⩽1200K starting at 100K for CH4, 150K for C2H6, and 180K for C3H8, n-C4H10, i-C4H10, n-C5H12, i-C5H12, and C(CH3)4. Restricting ourselves to low densities the thermophysical properties are calculated by means of an isotropic (n-6) Lennard-Jones temperature dependent potential (LJTDP). In this model the potential well depth ɛeff(T ) and the separation at minimum energy Rm(eff)(T) are explicitly temperature dependent, whereas the repulsive term n >12 is independent of T. The LJTDP has been used before in order to construct reference tables of thermophysical properties of neat gases [Zarkova and Hohm, J. Phys. Chem. Ref. Data 31, 183 (2002)] and binary mixtures [Zarkova, Hohm, and Damyanova, J. Phys. Chem. Ref. Data 32, 1591 (2003)]. However, those studies were restricted to atoms and globularly shaped nondipolar molecules. Here the approach is extended to elongated, not necessarily spherically symmetric, and in part slightly dipolar molecules. As in previous works the potential parameters ɛ(eff)(T), Rm(eff)(T), and n are determined by minimizing the root-mean-square deviation between calculated and experimentally obtained thermophysical properties B(T ), η(T ), ρD(T ), and the second acoustic virial coefficient β(T ) normalized to their experimental error. In extension of our previous efforts we present a thorough statistical analysis of the experimental input data which gives us the possibility to select primary data which could be used to build up a database.

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

    PubMed

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

    2013-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  15. W18O49 Nanowires as Ultraviolet Photodetector

    PubMed Central

    2010-01-01

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

  16. Using 14C and 3H to understand groundwater flow and recharge in an aquifer window

    NASA Astrophysics Data System (ADS)

    Atkinson, A. P.; Cartwright, I.; Gilfedder, B. S.; Cendón, D. I.; Unland, N. P.; Hofmann, H.

    2014-06-01

    Knowledge of groundwater residence times and recharge locations are vital to the sustainable management of groundwater resources. Here we investigate groundwater residence times and patterns of recharge in the Gellibrand Valley, southeast Australia, where outcropping aquifer sediments of the Eastern View Formation form an "aquifer window" that may receive diffuse recharge and recharge from the Gellibrand River. To determine recharge patterns and groundwater flowpaths, environmental isotopes (3H, 14C, δ13C, δ18O, δ2H) are used in conjunction with groundwater geochemistry and continuous monitoring of groundwater elevation and electrical conductivity. Despite the water table fluctuating by 0.9-3.7 m annually producing estimated recharge rates of 90 and 372 mm yr-1, residence times of shallow (11-29 m) groundwater determined by 14C ages are between 100 and 10 000 years. 3H activities are negligible in most of the groundwater and groundwater electrical conductivity in individual areas remains constant over the period of study. Although diffuse local recharge is evident, the depth to which it penetrates is limited to the upper 10 m of the aquifer. Rather, groundwater in the Gellibrand Valley predominantly originates from the regional recharge zone, the Barongarook High, and acts as a regional discharge zone where upward head gradients are maintained annually, limiting local recharge. Additionally, the Gellibrand River does not recharge the surrounding groundwater and has limited bank storage. 14C ages and Cl concentrations are well correlated and Cl concentrations may be used to provide a first-order estimate of groundwater residence times. Progressively lower chloride concentrations from 10 000 years BP to the present day are interpreted to indicate an increase in recharge rates on the Barongarook High.

  17. 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

  18. 3H-Penciclovir (3H-PCV) Uptake Assay

    PubMed Central

    Sekar, Thillai V; Paulmurugan, Ramasamy

    2016-01-01

    Thymidine Kinase from human Herpes simplex virus type 1 (HSV1-TK) in combination with specific substrate prodrug nucleotide analogue ganciclovir (GCV) has been widely used as suicidal therapeutic gene for cancer gene therapy. HSV1, and its mutant (HSV1-sr39TK) with improved substrate specificity, were used as reporter genes for PET-imaging of various biological functions in small animals, by combining with radiolabeled substrates such as 18F-FHBG and 124I-FIAU. 3H-Penciclovir (PCV) uptake assay is a method of choice used to determine the expression level of HSV1-TK in mammalian cells and tissues. HSV1-TK phosphorylate PCV and result in the formation of penciclovir monophosphate, and its subsequent phopsphorylation by cellular TK lead to the formation of penciclovir triphosphate, which is trapped selectively in cells expressing HSV-TK. 3H-Penciclovir enables the detection of penciclovir uptake of mammalian cells and tissues by radioactive procedures such as scintillation counting. Here we describe the protocol to carry out 3H-Penciclovir uptakes in mammalian cells.

  19. 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.

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

    PubMed Central

    Tommasi, Immacolata; Fusco, Caterina

    2013-01-01

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

  1. Seasonal and elevational variation of δ18O and δ2H in the Willamette River basin

    EPA Science Inventory

    Climate change is expected to dramatically alter the timing and quantity of water within the nation’s river systems. These changes are driven by variation in the form, location and amount of precipitation that will affect the temporal and spatial distribution of river source wat...

  2. Using δ2H and δ18O in assessing water quality condition of the nation’s water

    EPA Science Inventory

    The Clean Water Act mandates reporting on the condition of the nation’s waters. The Environmental Protection Agency implemented National Aquatic Resource Surveys (NARS) to address this mandate, including the National Lakes Assessment conducted in 2007. This study focuses on whe...

  3. Rapid preparation of pyrogen-free 2H2(18)O for human-nutrition studies

    SciTech Connect

    Wong, W.W.; Leggitt, J.L.; Clarke, L.L.; Klein, P.D. )

    1991-03-01

    We describe a compact ultrafiltration system for the removal of pyrogens and bacteria from water labeled with the stable isotopes of deuterium and oxygen-18. The ultrafiltration system is constructed from readily available commercial components and can achieve complete removal of pyrogens and bacteria from 1L contaminated water within 30 min. By use of our procedure, loss of the isotopically labeled water by retention in the filtration system was minimal. The purified water is suitable for both oral and intravenous administration to healthy human subjects participating in nutrition studies.

  4. 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

  5. EFFECT OF RAPID SHALLOW BREATHING ON THE DISTRIBUTION OF 18-O-LABELED OZONE REACTION PRODUCT IN THE RESPIRATORY TRACT OF THE RAT

    EPA Science Inventory

    We examined the effect of breathing pattern on ozone reaction product content within the respiratory tract. Thirty-four anesthetized, maleWistar rats were exposed to oxygen-18 (18O)-labeled ozone at 1.0 ppm for 2 h using a dual-chamber, negative-pressure ventilation system. Fre...

  6. Ion-neutral reaction of the C2H2N+ cation with C2H2: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Fathi, P.; Geppert, W. D.; Kaiser, A.; Ascenzi, D.

    2016-03-01

    The ion-neutral reactions of the C2H2N+ cation with C2H2 have been investigated using a Guided Ion Beam Mass Spectrometer (GIB-MS). The following ionic products were observed: CH3+, C2H2+, C2H3+, HNC+ /HCN+ , HCNH+, C3H+ , C2N+ , C3H3+, HCCN+ and C4H2N+ . Theoretical calculations have been carried out to propose reaction pathways leading to the observed products. These processes are of relevance for the generation of long chain nitrogen-containing species and they may be of interest for the chemistry of Titan's ionosphere or circumstellar envelopes.

  7. Microautoradiographic localisation of [3H]sucrose and [3H]mannitol in Robinia pseudoacacia pulvinar tissues during phytochrome-mediated nyctinastic closure.

    PubMed

    Moysset, L; Llambrich, E; López-Iglesias, C; Simón, E

    2006-11-01

    We have analysed the incorporation of [(3)H]sucrose and [(3)H]mannitol in pulvinar motor cells of Robinia pseudoacacia L. during phytochrome-mediated nyctinastic closure. Pairs of leaflets, excised 2 h after the beginning of the photoperiod, were fed with 50 mM [(3)H]sucrose or [(3)H]mannitol, irradiated with red (15 min) or far-red (5 min) light and placed in the dark for 2-3 h. Label uptake was measured in whole pulvini by liquid scintillation counting. The distribution of labelling in pulvinar sections was assessed by both light and electron microautoradiography. [(3)H]Sucrose uptake was twice that of [(3)H]mannitol incorporation in both red- and far-red-irradiated pulvini. In the autoradiographs, [(3)H]sucrose and [(3)H]mannitol labelling was localised in the area from the vascular bundle to the epidermis, mainly in vacuoles, cytoplasm, and cell walls. Extensor and flexor protoplasts displayed a different distribution of [(3)H]sucrose after red and far-red irradiation. Far-red light drastically reduced the [(3)H]sucrose incorporation in extensor protoplasts and caused a slight increase in internal flexor protoplasts. After red light treatment, no differences in [(3)H]sucrose labelling were found between extensor and flexor protoplasts. Our results indicate a phytochrome control of sucrose distribution in cortical motor cells and seem to rule out the possibility of sucrose acting as an osmoticum. PMID:17102931

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

    PubMed

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

    2016-04-18

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  10. On the use of stable oxygen isotope (δ18O) measurements for tracking avian movements in North America

    PubMed Central

    Hobson, Keith A; Koehler, Geoff

    2015-01-01

    Tracking migratory animals has benefitted using measurements of naturally occurring stable isotopes of hydrogen (δ2H) in keratinous tissues such as hair and feathers to link animal origins to continental patterns or isoscapes of δ2H in precipitation. However, for most taxa, much less information exists on the use of stable oxygen isotope ratios (δ18O) despite the fact that δ2H and δ18O are strongly linked in environmental waters through the meteoric relationship and the possibility of using both isotopes to infer greater information on origins and climatic conditions where tissues are grown. A fundamental requirement of using stable isotopes to assign individuals and populations to origins is the development of a rescaling function linking environmental food web signals to the tissue of interest and for birds, this has not been carried out. Here, we derived the relationship between H and O isotopes in known source feathers of 104 individuals representing 11 species of insectivorous passerines sampled across the strong precipitation isoscape of North America. We determined again a strong expected relationship between feather δ2H (δ2Hf) and long-term amount-weighted precipitation δ2H (δ2Hp; r2 = 0.77), but the corresponding relationship between δ18Of and δ18Op was poor (r2 = 0.32) for the same samples. This suggests that δ2H measurements are currently more useful for assignment of insectivorous songbirds to precipitation isoscapes but does not preclude other uses of the δ18Of data. Currently, mechanisms responsible for the decoupling of H and O isotopes in food webs is poorly known, and we advocate a much broader sampling of both isotopes in the same keratinous tissues across precipitation isotope gradients and across taxa to resolve this issue and to increase the power of using water isotopes to track migratory animals. PMID:25691999

  11. /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.

  12. Contributions of evaporation, isotopic non-steady state transpiration and atmospheric mixing on the delta18O of water vapour in Pacific Northwest coniferous forests.

    PubMed

    Lai, Chun-Ta; Ehleringer, James R; Bond, Barbara J; Paw U, Kyaw Tha

    2006-01-01

    Changes in the 2H and 18O of atmospheric water vapour provide information for integrating aspects of gas exchange within forest canopies. In this study, we show that diurnal fluctuations in the oxygen isotope ratio (delta 18O) as high as 4% per hundred were observed for water vapour (delta (18)Ovp) above and within an old-growth coniferous forest in the Pacific Northwest region of the United States. Values of delta 18Ovp decreased in the morning, reached a minimum at midday, and recovered to early-morning values in the late afternoon, creating a nearly symmetrical diurnal pattern for two consecutive summer days. A mass balance budget was derived and assessed for the 18O of canopy water vapour over a 2-d period by considering the 18O-isoflux of canopy transpiration, soil evaporation and the air entering the canopy column. The budget was used to address two questions: (1) do delta 18O values of canopy water vapour reflect the biospheric influence, or are such signals swamped by atmospheric mixing? and (2) what mechanisms drive temporal variations of delta 18Ovp? Model calculations show that the entry of air into the canopy column resulted in an isotopically depleted 18O-isoflux in the morning of day 1, causing values of delta 18Ovp, to decrease. An isotopically enriched 18O-isoflux resulting from transpiration then offset this decreased delta 18Ovp later during the day. Contributions of 18O-isoflux from soil evaporation were relatively small on day 1 but were more significant on day 2, despite the small H2(16)O fluxes. From measurements of leaf water volume and sapflux, we determined the turnover time of leaf water in the needles of Douglas-fir trees as approximately 11 h at midday. Such an extended turnover time suggests that transpiration may not have occurred at the commonly assumed isotopic steady state. We tested a non-steady state model for predicting delta 18O of leaf water. Our model calculations show that assuming isotopic steady state increased isoflux of

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  14. First continuous measurements of δ18O-CO2 in air with a Fourier transform infrared spectrometer

    NASA Astrophysics Data System (ADS)

    Vardag, S. N.; Hammer, S.; Sabasch, M.; Griffith, D. W. T.; Levin, I.

    2015-02-01

    The continuous in situ measurement of δ18O in atmospheric CO2 opens a new door to differentiating between CO2 source and sink components with high temporal resolution. Continuous 13C-CO2 measurement systems have already been commercially available for some time, but until now, only few instruments have been able to provide a continuous measurement of the oxygen isotope ratio in CO2. Besides precise 13C/12C observations, the Fourier transform infrared (FTIR) spectrometer is also able to measure the 18O / 16O ratio in CO2, but the precision and accuracy of the measurements have not yet been evaluated. Here we present a first analysis of δ18O-CO2 (and δ13C-CO2) measurements with the FTIR analyser in Heidelberg. We used Allan deviation to determine the repeatability of δ18O-CO2 measurements and found that it decreases from 0.25‰ for 10 min averages to about 0.1‰ after 2 h and remains at that value up to 24 h. We evaluated the measurement precision over a 10-month period (intermediate measurement precision) using daily working gas measurements and found that our spectrometer measured δ18O-CO2 to better than 0.3‰ at a temporal resolution of less than 10 min. The compatibility of our FTIR-spectrometric measurements to isotope-ratio mass-spectrometric (IRMS) measurements was determined by comparing FTIR measurements of cylinder gases and ambient air with IRMS measurements of flask samples, filled with gases of the same cylinders or collected from the same ambient air intake. Two-sample t tests revealed that, at the 0.01 significance level, the FTIR and the IRMS measurements do not differ significantly from each other and are thus compatible. We describe two weekly episodes of ambient air measurements, one in winter and one in summer, and discuss what potential insights and new challenges combined highly resolved CO2, δ13C-CO2 and δ18O-CO2 records may provide in terms of better understanding regional scale continental carbon exchange processes.

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

    SciTech Connect

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

    2006-03-13

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

  16. Comparisons of observed and modelled lake δ18O variability

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  19. Astronomical identification of the C3H radical

    NASA Astrophysics Data System (ADS)

    Thaddeus, P.; Gottlieb, C. A.; Hjalmarson, A.; Johansson, L. E. B.; Irvine, W. M.; Friberg, P.; Linke, R. A.

    1985-07-01

    The C3H radical has been identified in the millimeter-wave spectra of IRC +10216 and TMC-1. In IRC +10216, four rotational transitions have been observed, three in the lower fine-structure ladder (2Pi1/2) and one in the upper (2Pi3/2), each a resolved or partially resolved lambda-doublet. In TMC-1, both lambda components of the lowest lying 3/2-1/2 transition of the 2Pi1/2 ladder have been observed, each with well-resolved hfs. In IRC +10216, the excitation of C3H is similar to that of SiCC: the rotational temperature Trot within the 2Pi1/2 ladder is low (8.5 K), because of rapid radiative decay, while Trot across the ladders is high (about 52 K), because interconnecting far-IR radiative transitions are only weakly permitted. The column density of C3H in IRC +10216 averaged over the estimated source diameter of 84 arcsec is 2.8 x 10 to the 13th/sq cm, an order of magnitude less than that of C2H and C4H.

  20. 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.

  1. Understanding the C3H2 cyclic-to-linear ratio in L1544

    NASA Astrophysics Data System (ADS)

    Sipilä, O.; Spezzano, S.; Caselli, P.

    2016-06-01

    Aims: We aim to understand the high cyclic-to-linear C3H2 ratio (32 ± 4) that has been observed toward L1544. Methods: We combined a gas-grain chemical model with a physical model for L1544 to simulate the column densities of cyclic and linear C3H2 observed toward L1544. The most important reactions for the formation and destruction of both forms of C3H2 were identified, and their relative rate coefficients were varied to find the best match to the observations. Results: We find that the ratio of the rate coefficients of C3H3+ + e- ➝ C3H2 + H for cyclic and linear C3H2 must be ~ 20 to reproduce the observations, depending on the branching ratios assumed for the C3H3+ + e- ➝ C3H + H2 reaction. In current astrochemical networks it is assumed that cyclic and linear C3H2 are formed in a 1:1 ratio in the aforementioned reactions. Laboratory studies and/or theoretical calculations are needed to confirm the results of our chemical modeling, which is based on observational constraints.

  2. Seasonal variations in soil carbonic anhydrase activity in a pine forest ecosystem as inferred from soil CO18O flux measurements

    NASA Astrophysics Data System (ADS)

    Ogee, Jerome; Wingate, Lisa; Bosc, Alexandre; Burlett, Régis

    2015-04-01

    Quantifying terrestrial carbon storage and predicting the sensitivity of ecosystems to climate change relies on our ability to obtain observational constraints on photosynthesis and respiration at large scales (ecosystem, regional and global). Photosynthesis (GPP), the largest CO2 flux from the land surface, is currently estimated with considerable uncertainty (1-3). Robust estimates of global GPP can be obtained from an atmospheric budget of the oxygen isotopic composition (δ18O) of atmospheric CO2, provided that we have a good knowledge of the δ18O signatures of the terrestrial CO2 fluxes (1,4). The latter reflect the δ18O of leaf and soil water pools because CO2 exchanges 'isotopically' with water [CO2+H218O⇔H2O+CO18O]. This exchange can be accelerated by the enzyme carbonic anhydrase (CA). In leaves, where CA is present and abundant, this isotopic equilibrium is reached almost instantaneously. As a consequence, and because soil and leaf water pools have different δ18O signatures, CO2 fluxes from leaves and soils carry very distinct δ18O signals and can thus be tracked from the fluctuations in the δ18O of atmospheric CO2 (δa). There is growing evidence that the accelerated isotopic exchange between CO2 and water due to CA activity is a widespread phenomenon in soils as well (4). At the global scale, accounting for soil CA activity dramatically shifts the influence of soil and leaf fluxes on δa, thus changing the estimates of terrestrial gross CO2 fluxes (1,4). In this talk we will briefly present the current state of understanding of the environmental and ecological causes behind the variability in CA activity observed in soils and illustrate, using field data from a temperate pine forest, how soil CA activity varies over a single growing season and how it responds to soil surface environmental variables. References 1. L. R. Welp et al., Interannual variability in the oxygen isotopes of atmospheric CO2 driven by El Niño, Nature 477, 579-582 (2011

  3. $sup 18$O enrichment process in UO$sub 2$F$sub 2$ utilizing laser light

    DOEpatents

    DePoorter, G.L.; Rofer-DePoorter, C.K.

    1975-12-01

    Photochemical reaction induced by laser light is employed to separate oxygen isotopes. A solution containing UO$sub 2$F$sub 2$, HF, H$sub 2$O and a large excess of CH$sub 3$OH is irradiated with laser light of appropriate wavelength to differentially excite the UO$sub 2$$sup 2+$ ions containing $sup 16$O atoms and cause a reaction to proceed in accordance with the reaction 2 UO$sub 2$F$sub 2$ + CH$sub 3$OH + 4 HF $Yields$ 2 UF$sub 4$ down arrow + HCOOH + 3 H$sub 2$O. Irradiation is discontinued when about 10 percent of the UO$sub 2$F$sub 2$ has reacted, the UF$sub 4$ is filtered from the reaction mixture and the residual CH$sub 3$OH and HF plus the product HCOOH and H$sub 2$O are distilled away from the UO$sub 2$F$sub 2$ which is thereby enriched in the $sup 18$O isotope, or the solution containing the UO$sub 2$F$sub 2$ may be photochemically processed again to provide further enrichment in the $sup 18$O isotope.

  4. 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.

  5. 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.

  6. 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.

  7. A conceptual model of flow to the Waikoropupu Springs, NW Nelson, New Zealand, based on hydrometric and tracer (18O, Cl,3H and CFC) evidence

    NASA Astrophysics Data System (ADS)

    Stewart, M. K.; Thomas, J. T.

    2008-01-01

    The Waikoropupu Springs, a large karst resurgence 4 km from the coast, are supplied by the Arthur Marble Aquifer (AMA) underlying the Takaka Valley, South Island, New Zealand. New evidence on the recharge sources in the catchment, combined with previous results, is used to establish a new recharge model for the AMA. Combined with the oxygen-18 mass balance, this yields a quantitative description of the inputs and outputs to the aquifer. It shows that the Main Spring is sourced mainly from the karst uplands (74%), with smaller contributions from the Upper Takaka River (18%) and valley rainfall (8%), while Fish Creek Spring contains mostly Upper Takaka River water (50%). In addition, much of the Upper Takaka River contribution to the aquifer (58%) bypasses the springs and is discharged offshore via submarine springs. The chemical concentrations of the Main Spring show input of 0.5% of sea water on average, which varies with flow and derives from the deep aquifer. Tritium measurements spanning 40 yr, and CFC-11 measurements, give a mean residence time of 8 yr for the Main Spring water using the preferred two-component model. Our conceptual flow model, based on the flow, chloride, oxygen-18 and age measurements, invokes two different flow systems with different recharge sources to explain the flow within the AMA. One system contains deeply penetrating old water with mean age 10.2 yr and water volume 3 km3, recharged from the karst uplands. The other, at shallow levels below the valley floor, has much younger water with mean age 1.2 yr and water volume 0.4 km3, recharged by Upper Takaka River and valley rainfall. The flow systems contribute in different proportions to the Main Spring, Fish Creek Springs and offshore springs. Their very different behaviours, despite being in the same aquifer, are attributed to the presence of a diorite intrusion below the surface of the lower valley, which diverts the deep flow towards the Waikoropupu Springs and allows much of the shallow flow to pass over the intrusive and escape via submarine springs.

  8. A conceptual model of flow to the Waikoropupu Springs, NW Nelson, New Zealand, based on hydrometric and tracer (18O, Cl,3H and CFC) evidence

    NASA Astrophysics Data System (ADS)

    Stewart, M. K.; Thomas, J. T.

    2007-05-01

    The Waikoropupu Springs, a large karst resurgence 4 km from the coast, are supplied by the Arthur Marble Aquifer (AMA) underlying the Takaka Valley, South Island, New Zealand. New evidence on the recharge sources in the catchment, combined with previous results, is used to establish a new recharge model for the AMA. Combined with the oxygen-18 mass balance, this yields a quantitative description of the inputs and outputs to the aquifer. It shows that the Main Spring is sourced mainly from the karst uplands (74%), with smaller contributions from the Upper Takaka River (18%) and valley rainfall (8%), while Fish Creek Spring contains mostly Upper Takaka River water (50%). In addition, much of the Upper Takaka River contribution to the aquifer (58%) bypasses the springs and is discharged offshore via submarine springs. The chemical concentrations of the Main Spring show input of 0.5% of sea water on average, which varies with flow and derives from the deep aquifer. Tritium measurements spanning 40 years, and CFC-11 measurements, give a mean residence time of 8 years for the Main Spring water using the preferred two-component model. Our conceptual flow model, based on the flow, chloride, oxygen-18 and age measurements, invokes two different flow systems with different recharge sources to explain the flow within the AMA. One system contains deeply penetrating old water with mean age 10.2 years and water volume 3 km3, recharged from the karst uplands. The other, at shallow levels below the valley floor, has much younger water, with mean age 1.2 years and water volume 0.4 km3, recharged by Upper Takaka River and valley rainfall. The flow systems contribute in different proportions to the Main Spring, Fish Creek Springs and offshore springs. Their very different behaviours, despite being in the same aquifer, are attributed to the presence of a diorite intrusive below the surface of the lower valley, which diverts the deep flow towards the Waikoropupu Springs and allows much of the shallow flow to pass over the intrusive and escape via submarine springs.

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  10. K4[Pt2(H2P2O5)4Cl]•3H2O

    NASA Astrophysics Data System (ADS)

    Villars, P.; Cenzual, K.; Gladyshevskii, R.; Shcherban, O.; Dubenskyy, V.; Kuprysyuk, V.; Savysyuk, I.; Zaremba, R.

    This document is part of Subvolume A11 'Structure Types. Part 11: Space Groups (135) P42/mbc - (123) P4/mmm' of Volume 43 'Crystal Structures of Inorganic Compounds' of Landolt-Börnstein - Group III 'Condensed Matter'.

  11. K4[Pt2(H2P2O5)4Br]•3H2O

    NASA Astrophysics Data System (ADS)

    Villars, P.; Cenzual, K.; Gladyshevskii, R.; Shcherban, O.; Dubenskyy, V.; Kuprysyuk, V.; Savysyuk, I.; Zaremba, R.

    This document is part of Subvolume A11 'Structure Types. Part 11: Space Groups (135) P42/mbc - (123) P4/mmm' of Volume 43 'Crystal Structures of Inorganic Compounds' of Landolt-Börnstein - Group III 'Condensed Matter'.

  12. Redetermination of [Gd(NO3)3(H2O)4]·2H2O

    PubMed Central

    Taha, Ziyad A.; Ajlouni, Abdulaziz; Hijazi, Ahmed K.; Kühn, Fritz E.; Herdtweck, Eberhardt

    2012-01-01

    The crystal structure of the title compound, tetra­aqua­tris­(nitrato-κ2 O,O′)gadolinium(III) dihydrate, was redetermined from single-crystal X-ray data. In comparison with the first determination [Ma et al. (1991 ▶). Wuji Huaxue Xuebao, 7, 351–353], all H atoms could be located, accompanied with higher accuracy and precision. The GdIII atom shows a ten-coordination with three nitrate ligands behaving in a bidentate manner and the other positions being occupied by four water mol­ecules, forming a distorted bicapped square anti­prism. Two nitrate ions coordinate to the metal atom with similar bond lengths while the third shows a more asymmetric bonding behaviour. An intricate network of O—H⋯O hydrogen bonds, including the lattice water mol­ecules, stabilizes the crystal packing. PMID:22807698

  13. Frequency comb assisted measurement of fundamental transitions of cold H3+, H2D+ and D2H+

    NASA Astrophysics Data System (ADS)

    Jusko, Pavol; Konietzko, Christoph; Schlemmer, Stephan; Asvany, Oskar

    2016-01-01

    H3+ and two of its deuterated variants have been trapped and cooled in a 4 K trap machine, and their fundamental vibrational transitions probed with the laser induced reactions method. With the help of a frequency comb system the line centers are determined with high accuracy and precision, typically well below 1 MHz. For the deuterated variants, ground state combination differences allow for comparison with existing rotational THz data, and the accurate prediction thereof.

  14. The Photon Polarization Parameter of 2H(n, γ)3H reaction with Inclusion of the Electric Quadrupole Contribution

    NASA Astrophysics Data System (ADS)

    Sadeghi, H.; Mosavi-Khansari, M.

    2014-09-01

    We use effective field theory (EFT) for the calculation of neutron—deuteron radiative capture at very low energies. We present here the use of EFT to calculate a low-energy photo-nuclear observable in three-body systems, the photon polarization parameter and fore—aft asymmetry at thermal neutron energies up to next-to-next to leading order (N2LO), with inclusion of the electric quadrupole contribution. The photon polarization parameter in total is found to be Rc = -0.421 ± 0.003 and is in good agreement with the other modern theoretical calculations based on modern nucleon—nucleon potentials. In comparison with our previous work, a satisfactory agreement with the available experimental data is found by inclusion of the electric quadrupole contribution.

  15. Redetermination of [Pr(NO3)3(H2O)4]·2H2O

    PubMed Central

    Decadt, Roel; Van Der Voort, Pascal; Van Driessche, Isabel; Van Deun, Rik; Van Hecke, Kristof

    2012-01-01

    The structure of the title compound, tetra­aqua­tris­(nitrato-κ2 O,O′)praseodymium(III) dihydrate, was redetermined. The structure models derived from the previous determinations [Rumanova et al. (1964 ▶). Kristallografiya, 9, 642–654; Fuller & Jacobson (1976 ▶). Cryst. Struct. Commun. 5, 349–352] were confirmed, but now with all H atoms unambiguously located, revealing a complex O—H⋯O hydrogen-bonding network, extending throughout the whole structure. In the title compound, the coordination environment of the PrIII atom can best be described as a distorted bicapped square anti­prism defined by three bidentate nitrate anions and four water mol­ecules. Additionally, two lattice water mol­ecules are observed in the crystal packing. The title compound is isotypic with several other lanthanide-containing nitrate analogues. PMID:22807700

  16. Excimer-laser-induced oxidation of diborane: Formation and isolation of HBO, HB 18O AND H 3B 3O 3 in argon matrices

    NASA Astrophysics Data System (ADS)

    Ault, Bruce S.

    1989-05-01

    An excimer laser operating at 193 nm has been employed in conjunction with the matrix isolation technique to study the reaction of B 2H 6 with oxygen atoms. N 2O and O 2 were used as photolytic oxygen atom sources, and a number of oxidation products were detected. Absorptions near 750 and 1813 cm -1 were assigned to H 11BO; experiments with 18O led to production of HB 18O for the first time, and the identification of two of the fundamentals of this species. Also, H 3B 3O 3 was detected near 910, 1380 and 2610 cm -1. In addition, the most intense fundamental of BH 3 was tentatively identified at 1138 cm -1. These observations support the most recently postulated mechanism for the oxidation of diborane, and the suggested intermediacy of HBO in the process.

  17. 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.

  18. 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

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

    PubMed

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

    2014-01-01

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

  20. Comprehensive inter-laboratory calibration of reference materials for δ18O versus VSMOW using various on-line high-temperature conversion techniques

    USGS Publications Warehouse

    Brand, Willi A.; Coplen, Tyler B.; Aerts-Bijma, Anita T.; Böhlke, J.K.; Gehre, Matthias; Geilmann, Heike; Groning, Manfred; Jansen, Henk G.; Meijer, Harro A. J.; Mroczkowski, Stanley J.; Qi, Haiping; Soergel, Karin; Stuart-Williams, Hilary; Weise, Stephan M.; Werner, Roland A.

    2009-01-01

    −55.5‰ The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for δ18O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios (δ18O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ18O values of two or more internationally distributed nitrates (USGS34, IAEA-NO-3, and USGS35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the δ18O values at a later time should it become necessary. The high-temperature reduction technique for analyzing δ18O and δ2H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible. 

  1. 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

  2. Fabrication and tests of 3He and 2H targets for beam polarization measurement

    PubMed

    Naqvi; Aksoy; Nagadi; Al-Ohali; Kidwai; Fageeha

    2000-09-01

    3He and 2H targets were fabricated through implantation of 3He and 2H ions in 0.2-0.3 mm thick tantalum and titanium foils. The energy of 3He and 2H ions was 45-100 and 78 keV, respectively. Ions beams with typical current of 90-300 microA were used for implantation. Stability tests of 3He and 2H targets were carried out by monitoring the yield of 3He(d, p)4He and 2H(d, p)3H reactions. For the 3He target, the reaction yield was stable for both tantalum and titanium foils but the most stabilized maximum yield was observed for the 100 keV tantalum target. In the case of 2H targets, the yield increased with increasing total dose implanted on the target. PMID:10972150

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

    NASA Astrophysics Data System (ADS)

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

    2011-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  5. Electron paramagnetic resonance spectra and structures of Cu(C sub 2 H sub 4 ), Cu(C sub 2 H sub 4 ) sub 2 , and Cu(C sub 2 H sub 4 ) sub 3 in hydrocarbon matrices

    SciTech Connect

    Howard, J.A.; Joly, H.A.; Mile, B. )

    1990-02-22

    Two mononuclear {pi}-complexes, Cu(C{sub 2}H{sub 4}) and Cu(C{sub 2}H{sub 4}){sub 2}, have been positively identified by EPR spectroscopy from reaction of Cu atoms and ethylene at 77 K in inert hydrocarbon matrices on a rotating cryostat. The spectra of these copper(O) complexes are consistent with dative bonding for both species and with a C{sub 2v} structure for Cu(C{sub 2}H{sub 4}) and a D{sub 2h} structure for Cu(C{sub 2}H{sub 4}){sub 2}. Spectra of Cu({sup 13}CH{sub 2}CH{sub 2}) and Cu({sup 13}CH{sub 2}CH{sub 2}){sub 2} are consistent with these assignments. A third complex is formed in both adamantane and cyclohexane that could be Cu(C{sub 2}H{sub 4}){sub 2} with a structure other than D{sub 2h} but is more likely to be the mononuclear trisligand complex Cu(C{sub 2}H{sub 4}){sub 3} with a D{sub 3h} structure. In the absence of a well-resolved isotropic spectrum of Cu({sup 13}CH{sub 2}CH{sub 2}){sub 3}, this assignment must however be taken as tentative.

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

    NASA Astrophysics Data System (ADS)

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

    2004-12-01

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

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  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. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  12. Thermodynamic Modeling of the SRS Evaporators: Part II. The 3H System

    SciTech Connect

    Jantzen, C.M.

    2001-10-02

    Accumulations of two solid phases have formed scale deposits in the Savannah River Site 2H Evaporator system since late 1996. The aluminosilicate scale deposits caused the evaporator pot to become inoperable in October 1999. Accumulations of the diuranate phase have caused criticality concerns in the SRS 2H Evaporator. In order to ensure that similar deposits are not and will not form in the SRS 3H Evaporator, thermodynamically derived activity diagrams specific to the feeds processed from Tanks 30 and 32 are evaluated in this report.

  13. Survey of groundwater isotopic composition (δ2H and δ18O) from the southwestern Edwards Aquifer and regionally associated aquifers

    NASA Astrophysics Data System (ADS)

    West, J. B.; Shallock, J. R.; Cooper, R.

    2009-12-01

    Aquifers are an important source of water for growing human populations, while they also support numerous critical ecosystem functions, including supplying water to springs and rivers necessary for terrestrial and aquatic ecosystems and the sometimes endangered species that are part of them. As human populations increase and the climate changes, demands on aquifer resources will continue to increase. To support these growing populations, urban areas in particular seek to develop additional water resources with, in some cases, not well-understood impacts on interconnected aquifers as well as the terrestrial and aquatic ecosystems that depend on spring-fed surface water. In addition, large-scale changes to terrestrial systems (e.g., removal of woody vegetation) can be motivated by a desire to enhance aquifer recharge, but an understanding of the effect of those efforts on the regional water cycle is hampered, in part, by a lack of detailed understanding of the interactions of various features below ground. It is critical therefore to understand the relationships between waters found in different formations, as well as among surface and ground waters to improve our understanding of the consequences of increasing human demands and the impacts of climate change. We have conducted a survey of wells in south central Texas that access major and minor aquifers, including the karst-type Edwards (BFZ) aquifer and several regional minor aquifers. The primary objective of this survey was to establish baseline information from which to develop further targeted research using event-based sampling and a range of additional data on precipitation, geology, and other spatially explicit information. We sampled multiple wells in an area west of San Antonio, TX that access the primary major and minor aquifers in the region. The isotopic compositions of water taken from these wells at various locations and depths were similar, suggesting that these aquifers experience significant mixing, and are not strongly isolated from each other. Our results are consistent with recent reports based on elemental composition of waters sampled from wells also in the region. Future work will expand to include connections with surface waters and address precipitation event-based dynamics.

  14. Identification and correction of spectral contamination in 2H/1H and 18O/16O measured in leaf, stem, and soil water

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Plant water extracts typically contain organic materials that may cause spectral interference using isotope ratio infrared spectroscopy (IRIS), resulting in errors in the measured isotope ratios. IRIS manufacturers have developed post-processing software to identify the degree of contamination in wa...

  15. WILLAMETTE BASIN SURFACE WATER ISOSCAPE (18O AND 2H) FOR INTERPRETING TEMPORAL CHANGES OF SOURCE WATER WITHIN THE RIVER.

    EPA Science Inventory

    Understanding how water sources for rivers are shifting spatially over time will greatly aid our ability to understand climate impacts on rivers. Because stable isotopes of precipitation vary geographically, variation in the stable isotopes of river water can indicate source wat...

  16. Willamette Basin Surface Water Isoscape (18O and 2H): Interpreting Temporal Changes of Source Water within the River

    EPA Science Inventory

    Determining how water sources for rivers vary over time can greatly enhance our understanding and management of land use and climate change impacts on rivers. Because the stable isotope composition of precipitation can vary geographically, variation in the stable isotope composi...

  17. Using 2H and 18O in assessing evaporation and water residence time of lakes in EPA’s National Lakes Assessment.

    EPA Science Inventory

    Stable isotopes of water and organic material can be very useful in monitoring programs because stable isotopes integrate information about ecological processes and record this information. Most ecological processes of interest for water quality (i.e. denitrification) require si...

  18. Combined /sup 2/H and /sup 18/O isotope effects in support of a concerted, synchronous elimination of acetaldehyde from a bis(benzyl ethyl ether) radical cation

    SciTech Connect

    Allison, C.E.; Stringer, M.B.; Bowie, J.H.; Derrick, P.J.

    1988-09-14

    No evidence has been found of hydrogen scrambling accompanying decomposition of the benzyl ether molecular ion at times approaching 100 ..mu..s. Isotope effects upon produce ion abundances have been measured for elimination of acetaldehyde from the molecular ions of multiply labeled diethoxyxylenes and compared with the results of calculations of kinetic isotope effects using the quasi-equilibrium theory. It is concluded that this rearrangement involving a 6-membered cyclic transition state can be described as a concerted, synchronous process. 31 references, 7 figures, 1 table.

  19. /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.

  20. 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...

  1. Triangular D3h Symmetry in the Rotation-Vibration Spectrum of 12C

    NASA Astrophysics Data System (ADS)

    Gai, Moshe

    2015-02-01

    Our recent measurements of new states in 12C including the second 2+ at 10 MeV and the high spin 5- state at 22.4 MeV allow us to study the Rotation-Vibration spectrum of 12C from which evidence for a new (D3h) geometrical symmetry emerges. The data fit very well to the predicted (ground state) rotational band of an oblate equilateral triangular spinning top with a D3h symmetry characterized by the sequence of states: 0+, 2+, 3-, 4+/-, 5- with almost degenerate 4+ and 4- (parity doublet) states. Such a D3h symmetry was observed in triatomic molecules, and it is observed in 12C for the first time in nuclear physics. The triatomic like structure in nuclei is reminiscent of the discovery of diatomic α+14C structure in 18O. We discuss a classification of other rotation-vibration bands in 12C such as the (0+) Hoyle band and the (1-) bending mode band and suggest measurements in search of the predicted ("missing") states that may shed new light on clustering in 12C and light nuclei. In particular, the observation (or non observation) of the predicted ("missing") states in the Hoyle band will allow us to conclude the geometrical arrangement of the three alpha particles composing the Hoyle state at 7.654 MeV in 12C.

  2. Microbial H2 cycling does not affect δ2H values of ground water

    USGS Publications Warehouse

    Landmeyer, J.E.; Chapelle, F.H.; Bradley, P.M.

    2000-01-01

    Stable hydrogen-isotope values of ground water (δ2H) and dissolved hydrogen concentrations (H(2(aq)) were quantified in a petroleum-hydrocarbon contaminated aquifer to determine whether the production/consumption of H2 by subsurface microorganisms affects ground water &delta2H values. The range of &delta2H observed in monitoring wells sampled (-27.8 ‰c to -15.5 ‰c) was best explained, however, by seasonal differences in recharge temperature as indicated using ground water δ18O values, rather than isotopic exchange reactions involving the microbial cycling of H2 during anaerobic petroleum-hydrocarbon biodegradation. The absence of a measurable hydrogen-isotope exchange between microbially cycled H2 and ground water reflects the fact that the amount of H2 available from the anaerobic decomposition of petroleum hydrocarbons is small relative to the amount of hydrogen present in water, even though milligram per liter concentrations of readily biodegradable contaminants are present at the study site. Additionally, isotopic fractionation calculations indicate that in order for H2 cycling processes to affect δ2H values of ground water, relatively high concentrations of H2 (>0.080 M) would have to be maintained, considerably higher than the 0.2 to 26 nM present at this site and characteristic of anaerobic conditions in general. These observations suggest that the conventional approach of using δ2H and δ18O values to determine recharge history is appropriate even for those ground water systems characterized by anaerobic conditions and extensive microbial H2 cycling.

  3. The Trojan Horse Method as a tool to investigate low-energy resonances: the {sup 18}O(p, {alpha}){sup 15}N and {sup 17}O(p, {alpha}){sup 14}N cases

    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.

    2010-08-12

    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.

  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. Predicting animal δ18O: Accounting for diet and physiological adaptation

    NASA Astrophysics Data System (ADS)

    Kohn, Matthew J.

    1996-12-01

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

  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. 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.

  8. 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.

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

    SciTech Connect

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

    1986-05-01

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

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

    PubMed

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-09-01

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

  13. Theoretical microwave spectral constants for C3H/+/ and C4H/+/

    NASA Technical Reports Server (NTRS)

    Wilson, S.; Green, S.

    1980-01-01

    A number of linear conjugated carbon chain molecules have been observed in the interstellar gas. It has been suggested that ion molecule chemistry schemes may explain the formation of these compounds. In the present paper, theoretical bond lengths and rotation constants are obtained for C3H(+) and C4H(+). Calculations for C3 are used to assess the accuracy of the former. Recent results for C2H(+) are examined.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  15. Accurate experimental determination of the isotope effects on the triple point temperature of water. II. Combined dependence on the 18O and 17O abundances

    NASA Astrophysics Data System (ADS)

    Faghihi, V.; Kozicki, M.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; Peruzzi, A.; Meijer, H. A. J.

    2015-12-01

    This paper is the second of two articles on the quantification of isotope effects on the triple point temperature of water. In this second article, we address the combined effects of 18O and 17O isotopes. We manufactured five triple point cells with waters with 18O and 17O abundances exceeding widely the natural abundance range while maintaining their natural 18O/17O relationship. The 2H isotopic abundance was kept close to that of VSMOW (Vienna Standard Mean Ocean Water). These cells realized triple point temperatures ranging between  -220 μK to 1420 μK with respect to the temperature realized by a triple point cell filled with VSMOW. Our experiment allowed us to determine an accurate and reliable value for the newly defined combined 18, 17O correction parameter of AO  =  630 μK with a combined uncertainty of 10 μK. To apply this correction, only the 18O abundance of the TPW needs to be known (and the water needs to be of natural origin). Using the results of our two articles, we recommend a correction equation along with the coefficient values for isotopic compositions differing from that of VSMOW and compare the effect of this new equation on a number of triple point cells from the literature and from our own institute. Using our correction equation, the uncertainty in the isotope correction for triple point cell waters used around the world will be  <1 μK.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  17. 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

  18. 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

  19. Photodisintegration of /sup 3/H and /sup 3/He. [Threshold to 25 MeV

    SciTech Connect

    Faul, D.D.

    1980-09-01

    The photoneutron cross sections for /sup 3/H and /sup 3/He have been measured from threshold to approx. 25 MeV with monoenergetic photons from the annihilation in flight of fast positrons at the LLL Electron-Positron Linear Accelerator facility. These reactions include the two-body breakup of /sup 3/H and the three-body breakup of both /sup 3/H and /sup 3/He; these measurements for /sup 3/H are the first to span the energy region across the peaks of the cross sections. An efficient BF/sub 3/-tube-and-paraffin neutron detector and high-pressure gaseous samples of several moles each (the activity of the /sup 3/H sample was approx. 200,000 Ci) were employed in these measurements. Measurements on /sup 16/O and /sup 2/H also were performed to verify the absolute cross-section scale. The results, when compared with each other and with results for the two-body breakup cross section for /sup 3/He from the literature, show that the two-body breakup cross sections for /sup 3/H and /sup 3/He have nearly the same shape, but the one for /sup 3/He lies lower in magnitude; the three-body breakup cross section for /sup 3/He lies higher in magnitude and is broader in the peak region and also rises less sharply from threshold than that for /sup 3/H; and these measured differences between the cross sections for the breakup modes largely compensate in their sum, so that the total photon absorption cross sections for /sup 3/H and /sup 3/He are nearly the same in both size and shape at energies near and above their peaks. Theoretical results from the literature disagree with the experimental results to a certain extent over the entire photon-energy region for which the photoneutron cross sections were measured. 50 figures, 7 tables.

  20. Synthetic studies towards putative yuremamine using an iterative C(sp(3))-H arylation strategy.

    PubMed

    Calvert, Matthew B; Sperry, Jonathan

    2016-06-28

    An overview of an iterative, 8-aminoquinoline (AQ)-directed C(sp(3))-H arylation strategy towards the pyrroloindole structure initially assigned to the alkaloid yuremamine is described. During initial efforts using a model indane system, it was discovered that the iodoresorcinol unit was not a viable C(sp(3))-H arylation partner when masked as its dimethyl ether but upon switching to a MOM group, the ether oxygen served to stabilise the high valent Pd intermediate during the reaction, thus promoting reductive elimination and leading to acceptable yields of the C(sp(3))-H arylation product. The second C(sp(3))-H arylation with an iodopyrogallol gave a 1,3-diarylated model yuremamine system possessing the desired 1,3-cis relationship. When the successful model studies were applied to a pyrroloindole system in pursuit of yuremamine, it became apparent that C9 underwent competing C(sp(2))-H arylation if left vacant, but installing a tryptamine side chain at this site prevented the desired C(sp(3))-H arylation from occurring altogether. However, a C9-methyl pyrroloindole underwent iterative C(sp(3))-H arylation at C1 with an iodoresorcinol followed by C3 with an iodopyrogallol to give a diarylated product with the aryl groups in the undesired 1,3-trans-relationship, arising from epimerisation at C1 during the second C(sp(3))-H arylation event. Although the synthesis of putative yuremamine was not accomplished, several findings are disclosed that will serve as useful additions to the burgeoning field of directed C(sp(3))-H arylations and related C-H functionalization reactions. PMID:26891188

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

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

  3. Differential binding of /sup 3/H-imipramine and /sup 3/H-mianserin in rat cerebral cortex

    SciTech Connect

    Dumbrille-Ross, A.; Tang, S.W.; Coscina, D.V.

    1981-11-16

    Drug competition profiles, effect of raphe lesion, and sodium dependency of the binding of two antidepressant drugs /sup 3/H-imipramine and /sup 3/H-mianserin to rat cerebral cortex homogenate were compared to examine whether the drugs bound to a common ''antidepressant receptor.'' Of the neurotransmitters tested, only serotonin displaced binding of both /sup 3/H-imipramine and /sup 3/H-mianserin. /sup 3/H-Mianserin binding was potently displaced by serotonin S/sub 2/ antagonists and exhibited a profile similar to that of /sup 3/H-spiperone binding. In the presence of the serotonin S/sub 2/ antagonist spiperone, antihistamines (H/sub 1/) potently displaced /sup 3/H-mianserin binding. /sup 3/H-Imipramine binding was displaced potently by serotonin uptake inhibitors. The order of potency of serotonergic drugs in displacing /sup 3/H-imipramine binding was not similar to their order in displacing /sup 3/H-spiperone or -3H-serotonin binding. Prior midbrain raphe lesions greatly decreased the binding of /sup 3/H-imipramine but did not alter binding of /sup 3/H-mianserin. Binding of /sup 3/H-imipramine but not /sup 3/H-mianserin was sodium dependent. These results show that /sup 3/H-imipramine and /sup 3/H-mianserin bind to different receptors. /sup 3/H-Imipramine binds to a presynaptic serotonin receptor which is probably related to a serotonin uptake recognition site, the binding of which is sodium dependent. /sup 3/H-Mianserin binds to postsynaptic receptors, possibly both serotonin S/sub 2/ and histamine H/sub 1/ receptors, the binding of which is sodium independent.

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

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2002-12-01

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

  7. 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.

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

    USGS Publications Warehouse

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

    2004-01-01

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

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

    SciTech Connect

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

    1991-04-16

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

  10. δ18O and δ13C values of modern brachiopod shells

    NASA Astrophysics Data System (ADS)

    Carpenter, Scott J.; Lohmann, Kyger C.

    1995-09-01

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

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

    PubMed

    Hagopian, William M; Jahren, A Hope

    2010-09-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-01-01

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

  13. 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

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

    PubMed Central

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

    2009-01-01

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

  15. 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.

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

    PubMed

    Perini, Matteo; Camin, Federica

    2013-06-01

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

  17. 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.

  18. Comprehensive inter-laboratory calibration of reference materials for d18O versus VSMOW using various on-line high-temperature conversion techniques

    USGS Publications Warehouse

    Coplen, Tyler B.; Bohlke, Johnkarl F.; Mroczkowski, Stanley J.; Qi, Haiping; Brand, Willi A.; Aerts-Bijma, Anita T.; Gehre, Matthias; Geilmann, Heike; Groning, Manfred

    2009-01-01

    IAEA-602 benzoic acid +71.28?±?0.36‰ USGS35 sodium nitrate +56.81?±?0.31‰ IAEA-NO-3 potassium nitrate +25.32?±?0.29‰ IAEA-601 benzoic acid +23.14?±?0.19‰ IAEA-SO-5 barium sulfate +12.13?±?0.33‰ NBS 127 barium sulfate +8.59?±?0.26‰ VSMOW2 water 0‰ IAEA-600 caffeine -3.48?±?0.53‰ IAEA-SO-6 barium sulfate -11.35?±?0.31‰ USGS34 potassium nitrate -27.78?±?0.37‰ SLAP water -55.5‰ The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for d18O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios (d18O) of nitrates, sulfates, or organic material should explicitly state in their reports the d18O values of two or more internationally distributed nitrates (USGS34, IAEA-NO-3, and USGS35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the d18O values at a later time should it become necessary. The high-temperature reduction technique for analyzing d18O and d2H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible."

  19. Pressure Effects on Product Channels of the Allyl Radical Reactions; C3H5+C3H5 and C3H5+CH3

    NASA Astrophysics Data System (ADS)

    Halpern, J. B.; N'Doumi, M.; Fahr, A.

    2011-12-01

    Relatively large hydrocarbon molecules (C4, C6 and larger) have been detected in several planetary environments. The mechanism for the formation of such large molecular species and detailed mechanism for their potential destruction are not well understood and are of considerable current interest. Previously we have studied the kinetics and product channels of small unsaturated hydrocarbon radical (C2 and C3s) reactions relevant to planetary atmospheric modeling. Reactions of C2 radicals (such as vinyl, H2CCH and ethynyl C2H) and C3 radicals (such as propargyl, HCCCH2) can affect the abundances of a large number of stable observable C3, C4, C5, C6 and larger molecules, including linear, aromatic and even poly aromatic molecules. Pressure-dependent product yields have been determined experimentally for the self- and cross-radical reactions performed at 298 K and at pressures between ~4 Torr (0.5 kPa) and 760 Torr (101 kPa). Final reaction products were quantitatively determined using a gas chromatograph with mass spectrometry/flame ionization detection (GC/MS/FID). In some cases complementary computational studies extended the pressure and temperature range of the experiments and provided valuable information on the complex reaction mechanisms. Theses studies provide a systematic framework so that important energetic and structural parameters for radical-radical reactions can be assessed. Here we report recent results for the allyl radical reactions H2CCCH3+ H2CCCH3 and H2CCCH3+CH3. For the allyl radical self-reaction, at high pressures the "head -to-head", combination channel forming 1,5-hexadiene is dominant with a combination/disproportionation = 1,5-hexadiene/propyne ratio of about 24 at 500 Torr (67 kPa, T=298K). At low pressures the ratio is substantially reduced to about 1.2 (at 0.3 kPa) and other major products are observed including allene, propene, 1-butene and propyne.

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

    SciTech Connect

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

    2006-04-15

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

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

    SciTech Connect

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

    2009-02-02

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

  2. ({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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  4. 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

  5. Comparison of (/sup 3/H)nicotine and (/sup 3/H)acetylcholine binding in mouse brain: regional distribution

    SciTech Connect

    Sershen, H.; Reith, M.E.; Hashim, A.; Lajtha, A.

    1985-06-01

    In a continuing study of nicotine binding sites, the authors determined the relative amount of nicotine binding and acetylcholine binding in various brain regions of C57/BL and of DBA mice. Although midbrain showed the highest and cerebellum the lowest binding for both (/sup 3/H)nicotine and (/sup 3/H)acetylcholine, the ratio of nicotine to acetylcholine binding showed a three-fold regional variation. Acetylcholine inhibition of (/sup 3/H)nicotine binding indicated that a portion of nicotine binding was not inhibited by acetylcholine. These results indicate important differences between the binding of (+/-)-(/sup 3/H)nicotine and that of (/sup 3/H)acetylcholine.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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...

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2005-11-01

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

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

    NASA Astrophysics Data System (ADS)

    Tabor, Neil J.

    2007-01-01

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

  17. 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

  18. 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

  19. 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.

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  4. Anionic ordering and thermal properties of FeF3·3H2O.

    PubMed

    Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; Wattiaux, Alain; Demourgues, Alain; Salanne, Mathieu; Groult, Henri; Dambournet, Damien

    2015-10-01

    Iron fluoride trihydrate can be used to prepare iron hydroxyfluoride with the hexagonal-tungsten-bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of β-FeF3·3H2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF6]n and [FeF2(H2O)4]n. The decomposition of FeF3·3H2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF3-x(OH)x with the HTB structure. The release of H2O and HF was monitored by thermal analysis and physical characterizations during the decomposition of FeF3·3H2O. An average distribution of FeF4(OH)2 distorted octahedra in HTB-FeF3-x(OH)x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F(-) and H2O. This study provides a clear understanding of the structure and thermal properties of FeF3·3H2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes. PMID:26378743

  5. Anionic ordering and thermal properties of FeF3·3H2O

    DOE PAGESBeta

    Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; Wattiaux, Alain; Demourgues, Alain; Salanne, Mathieu; Groult, Henri; Dambournet, Damien

    2015-09-17

    In this study, iron fluoride tri-hydrate can be used to prepare iron hydroxyfluoride with the Hexagonal-Tungsten-Bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of β-FeF3·3H2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF6]n and [FeF2(H2O)4]n. The decomposition of FeF3·3H2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF3-x(OH)x with the HTB structure. The release of H2O and HF was monitored by thermal analysis andmore » physical characterizations during the decomposition of FeF3·3H2O. An average distribution of FeF4(OH)2 distorted octahedra in HTB-FeF3-x(OH)x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F- and H2O. This study provides a clear understanding of the structure and thermal properties of FeF3·3H2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes.« less

  6. Near infrared diode laser spectroscopy of C2H2, H2O, CO2 and their isotopologues and the application to TDLAS, a tunable diode laser spectrometer for the martian PHOBOS-GRUNT space mission

    NASA Astrophysics Data System (ADS)

    Durry, G.; Li, J. S.; Vinogradov, I.; Titov, A.; Joly, L.; Cousin, J.; Decarpenterie, T.; Amarouche, N.; Liu, X.; Parvitte, B.; Korablev, O.; Gerasimov, M.; Zéninari, V.

    2010-04-01

    A near-infrared tunable diode laser spectrometer called TDLAS has been developed that combines telecommunication-type as well as new-generation antimonide laser diodes to measure C2H2, H2O, CO2 and their isotopologues in the near infrared. This sensor is devoted to the in situ analysis of the soil of the Martian satellite PHOBOS, within the framework of the Russian space mission PHOBOS-GRUNT. In the first part of the paper, we report accurate spectroscopic measurements of C2H2 and 13C12CH2 near 1.533 μm, of H2O and CO2 at 2.682 μm and of the isotopologues 13C16O2 and 16O12C18O near 2.041 μm and H2 17O, H2 18O and HDO near 2.642 μm. The achieved line strengths are thoroughly compared to data from molecular databases or from former experimental determinations. In the second part of the paper, we describe the TDLAS spectrometer for the PHOBOS-GRUNT mission.

  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. 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

  9. Synthesis and characterization of 3H-labelled tetrahydrobiopterin.

    PubMed Central

    Werner, E R; Schmid, M; Werner-Felmayer, G; Mayer, B; Wachter, H

    1994-01-01

    We synthesized [3'-3H]-5,6,7,8-tetrahydrobiopterin from [8,5'-3H]guanosine 5'-triphosphate ([8,5'-3H]GTP) using GTP cyclohydrolase (EC 3.5.4.16), 6-pyruvoyltetrahydropterin synthase and sepiapterin reductase (EC 1.1.1.153). After purification by cation-exchange h.p.l.c. a solution of radiochemically pure (> 95%) [3'-3H]-5,6,7,8-tetrahydrobiopterin with a specific activity of 9.2 Ci/mmol was obtained. The product proved well suited for studying the binding of tetrahydrobiopterin to nitric-oxide synthase. PMID:7528005

  10. (3)H activity comparison between FTMC, VNIIM and LNE-LNHB.

    PubMed

    Cassette, Philippe; Butkus, Paulius; Gudelis, Arunas; Shilnikova, Tatiana

    2016-03-01

    An activity comparison of tritiated water was organized in 2013 between 3 laboratories: FTMC (Lithuania), LNE-LNHB (France) and VNIIM (Russia). The solution was prepared by LNHB and ampoules were sent to the others laboratories. This solution was standardized in terms of activity per unit mass by participant laboratories using the Triple to Double Coincidence Ratio (TDCR) method in liquid scintillation counting (LSC). The tritiated water solution is traceable to the solution prepared by LNHB for the CCRI(II)-K2.H-3 2009 (3)H international comparison. PMID:26651170

  11. Dissociative recombination of N2H+

    NASA Astrophysics Data System (ADS)

    dos Santos, S. Fonseca; Ngassam, V.; Orel, A. E.; Larson, Å.

    2016-08-01

    The direct and indirect mechanisms of dissociative recombination of N2H+ are theoretically studied. At low energies, the electron capture is found to be driven by recombination into bound Rydberg states, while at collision energies above 0.1 eV, the direct capture and dissociation along electronic resonant states becomes important. Electron-scattering calculations using the complex Kohn variational method are performed to obtain the scattering matrix as well as energy positions and autoionization widths of resonant states. Potential-energy surfaces of electronic bound states of N2H and N2H+ are computed using structure calculations with the multireference configuration interaction method. The cross section for the indirect mechanism is calculated using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Here vibrational excitations of the ionic core from v =0 to v =1 and v =2 for all three normal modes are considered and autoionization is neglected. The cross section for the direct dissociation along electronic resonant states is computed with wave-packet calculations using the multiconfiguration time-dependent Hartree method, where all three internal degrees of freedom are considered. The calculated cross sections are compared to measurements.

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

    NASA Astrophysics Data System (ADS)

    Johnston, E.; Osborne, M. C.

    2010-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  14. 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

  15. 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

  16. Partial chemical characterization of cyclopyrrolones ((/sup 3/H) suriclone) and benzodiazepines ((/sup 3/H)flunitrazepam) binding site: Differences

    SciTech Connect

    Zundel, J.L.; Blanchard, J.C.; Julou, L.

    1985-06-10

    Rat hippocampus membranes were treated with several protein modifying reagents (iodoacetamide, N-ethylmaleimide, tetranitromethane and N-acetylimidazole). The effects of these treatments on the binding sites of cyclopyrrolones ((/sup 3/H) suriclone), a new chemical family of minor tranquilizers, and benzodiazepines ((/sup 3/H) flunitrazepam) were investigated. Here the authors show that both ligands are similarly sensitive to cysteine alkylation: (/sup 3/H) suriclone and (/sup 3/H) flunitrazepam binding are reduced by iodoacetamide and slightly increased by N-ethylmaleimide. On the contrary they are clearly differentiated by tyrosine modification: (/sup 3/H) suriclone binding is not changed whereas (/sup 3/H) flunitrazepam binding is increased by tetranitromethane and decreased by N-acetylimidazole. The present findings and published evidence suggest cyclopyrrolones and benzodiazepines bind to distinct sites or to different allosteric forms of the benzodiazepine receptor. 28 references, 6 figures.

  17. Group theoretical analysis of the H3+ +H2 ↔ H5+ reaction

    NASA Astrophysics Data System (ADS)

    Lin, Zhou

    2016-06-01

    The H3+ +H2 →H2 + H3+ proton transfer reaction is complicated due to the proton scrambling from the large amplitude motions in the H5+ intermediate. In order to understand this reaction, high-resolution spectroscopic studies are necessary for the reactants/products and the intermediate, and the group theoretical analysis is an essential aspect in the prediction and interpretation of these spectra. With five indistinguishable protons, H5+ is characterized using the G240 complete nuclear permutation-inversion (CNPI) group. For most of the configurations sampled by the reaction path, the feasible permutations depend on the distance between the H3+ and H2 fragments. Subgroups of G240 can be used to describe these feasible permutations. Specifically, we consider two limits of the molecular configurations. The equilibrium structure of H5+ , i.e., [H2 -H -H2 ]+, can be described using the G16 molecular symmetry group, while the dissociation products, i.e., H3+ ⋯H2 , require the G24 molecular symmetry group. In the present study, a group theoretical analysis is performed for both limits, providing the symmetries for the nuclear spins and rovibrational wave functions. Also, spectroscopic properties for [H2 -H -H2 ]+, particularly rovibrational couplings and electric dipole selection rules, as well as correlations of energy levels between [H2 -H -H2 ]+ and H3+ ⋯H2 , are obtained.

  18. 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.

  19. Parkinson's disease: decreased density of /sup 3/H-imipramine and /sup 3/H-paroxetine binding sites in putamen

    SciTech Connect

    Raisman, R.; Cash, R.; Agid, Y.

    1986-04-01

    The density of high-affinity /sup 3/H-imipramine and /sup 3/H-paroxetine binding sites (two serotonin-uptake blockers) was decreased in the putamen of parkinsonian patients. The correlation between serotonin levels and the number of /sup 3/H-imipramine and /sup 3/H-paroxetine binding sites suggests that they are located on serotoninergic nerve terminals and could be used to study serotoninergic innervation in the human brain. Since imipramine and paroxetine are powerful antidepressants, these results furthermore suggest that decreased serotoninergic transmission may be implicated in the pathophysiology of depression in Parkinson's disease.

  20. Measurement of δ18O, δ17O, and 17O-excess in water by off-axis integrated cavity output spectroscopy and isotope ratio mass spectrometry.

    PubMed

    Berman, Elena S F; Levin, Naomi E; Landais, Amaelle; Li, Shuning; Owano, Thomas

    2013-11-01

    Stable isotopes of water have long been used to improve understanding of the hydrological cycle, catchment hydrology, and polar climate. Recently, there has been increasing interest in measurement and use of the less-abundant (17)O isotope in addition to (2)H and (18)O. Off-axis integrated cavity output spectroscopy (OA-ICOS) is demonstrated for accurate and precise measurements δ(18)O, δ(17)O, and (17)O-excess in liquid water. OA-ICOS involves no sample conversion and has a small footprint, allowing measurements to be made by researchers collecting the samples. Repeated (514) high-throughput measurements of the international isotopic reference water standard Greenland Ice Sheet Precipitation (GISP) demonstrate the precision and accuracy of OA-ICOS: δ(18)OVSMOW-SLAP = -24.74 ± 0.07‰ (1σ) and δ(17)OVSMOW-SLAP = -13.12 ± 0.05‰ (1σ). For comparison, the International Atomic Energy Agency (IAEA) value for δ(18)OVSMOW-SLAP is -24.76 ± 0.09‰ (1σ) and an average of previously reported values for δ(17)OVSMOW-SLAP is -13.12 ± 0.06‰ (1σ). Multiple (26) high-precision measurements of GISP provide a (17)O-excessVSMOW-SLAP of 23 ± 10 per meg (1σ); an average of previously reported values for (17)O-excessVSMOW-SLAP is 22 ± 11 per meg (1σ). For all these OA-ICOS measurements, precision can be further enhanced by additional averaging. OA-ICOS measurements were compared with two independent isotope ratio mass spectrometry (IRMS) laboratories and shown to have comparable accuracy and precision as the current fluorination-IRMS techniques in δ(18)O, δ(17)O, and (17)O-excess. The ability to measure accurately δ(18)O, δ(17)O, and (17)O-excess in liquid water inexpensively and without sample conversion is expected to increase vastly the application of δ(17)O and (17)O-excess measurements for scientific understanding of the water cycle, atmospheric convection, and climate modeling among others. PMID:24032448

  1. /sup 18/O isotope effect in /sup 13/C nuclear magnetic resonance spectroscopy. Part 9. Hydrolysis of benzyl phosphate by phosphatase enzymes and in acidic aqueous solutions

    SciTech Connect

    Parente, J.E.; Risley, J.M.; Van Etten, R.L.

    1984-12-26

    The /sup 18/O isotope-induced shifts in /sup 13/C and /sup 31/P nuclear magnetic resonance (NMR) spectroscopy were used to establish the position of bond cleavage in the phosphatase-catalyzed and acid-catalyzed hydrolysis reactions of benzyl phosphate. The application of the /sup 18/O-isotope effect in NMR spectroscopy affords a continuous, nondestructive assay method for following the kinetics and position of bond cleavage in the hydrolytic process. The technique provides advantages over most discontinuous methods in which the reaction components must be isolated and converted to volatile derivatives prior to analysis. In the present study, (..cap alpha..-/sup 13/C,ester-/sup 18/O)benzyl phosphate and (ester-/sup 18/O)benzyl phosphate were synthesized for use in enzymatic and nonenzymatic studies. Hydrolysis reactions catalyzed by the alkaline phosphatase from E. coli and by the acid phosphatases isolated from human prostate and human liver were all accompanied by cleavage of the substrate phosphorus-oxygen bond consistent with previously postulated mechanisms involving covalent phosphoenzyme intermediates. An extensive study of the acid-catalyzed hydrolysis of benzyl phosphate at 75/sup 0/C revealed that the site of bond cleavage is dependent on pH. At pH less than or equal to 1.3, the hydrolysis proceeds with C-O bond cleavage; at 1.3 < pH < 2.0, there is a mixture of C-O and P-O bond scission, the latter progressively predominating as the pH is raised; at pH greater than or equal to 2.0, the hydrolysis proceeds with exclusive P-O bond scission. (S)-(+)-(..cap alpha..-/sup 2/H)Benzyl phosphate was also synthesized. Hydrolysis of this chiral benzyl derivative demonstrated that the acid-catalyzed C-O bond scission of benzyl phosphate proceeds by an A-1 (S/sub N/1) mechanism with 70% racemization and 30% inversion at carbon. 37 references, 4 figures, 2 tables.

  2. High resolution, low temperature photoabsorption cross-section of C2H2 with application to Saturn's atmosphere

    NASA Technical Reports Server (NTRS)

    Caldwell, John; Wu, C. Y. R.; Xia, T. J.; Judge, D. L.; Wagener, R.

    1990-01-01

    New laboratory observations of the VUV absorption cross-section of C2H2, obtained under physical conditions approximating stratospheres of the giant planets, were combined with IUE observations of the albedo of Saturn, for which improved data reduction techniques have been used, to produce new models for that atmosphere. When the effects of C2H2 absorption are accounted for, additional absorption by other molecules is required. The best-fitting model also includes absorption by PH3, H2O, C2H6 and CH4. A small residual disagreement near 1600 A suggests that an additional trace species may be required to complete the model.

  3. Comparison of ( sup 3 H)Phencyclidine (( sup 3 H)PCP) and ( sup 3 H) N-(1-(2-thienyl) cyclohexyl)piperidine (( sup 3 H)TCP) binding properties to rat and human brain membranes

    SciTech Connect

    Vignon, J.; Chaudieu, I.; Allaoua, H.; Journod, L.; Javoy-Agid, F.; Agid, Y.; Chicheportiche, R.

    1989-01-01

    The investigation of ({sup 3}H)PCP and ({sup 3}H)TCP binding properties to rat cerebrum and cerebellum resulted in the demonstration of multiple binding sites for the two drugs. In the two tissue preparations PCP had a lower affinity than TCP. In membranes from the cerebrum an equal number of high affinity binding sites were present for ({sup 3}H)PCP and ({sup 3}H)TCP. However, low affinity binding sites were two times more numerous for ({sup 3}H)PCP than for ({sup 3}H)TCP. In the cerebellum, the number of high and low affinity sites labeled by the two radioligands was identical, but the number of high affinity sites was about 7 fold lower than in cerebrum. In human cerebral cortex samples ({sup 3}H)TCP also bound to two different sites. The number of high and low affinity sites were 12 and 3 times, respectively, less abundant than in the rat cerebrum. Low affinity sites were of higher affinity than corresponding sites in the rat brain. In the human cerebellum ({sup 3}H)TCP binding parameters were identical to those measured in the same region in the rat.

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

    PubMed

    Gillon, J; Yakir, D

    2001-03-30

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

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1997-07-01

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

  9. 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.

  10. Synthesis Of [2h, 13c] And [2h3, 13c]Methyl Aryl Sulfides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-03-30

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2,.sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [.sup.2 H.sub.1, .sup.13 C]methyl iodide and [.sup.2 H.sub.2, .sup.13 C]methyl iodide.

  11. 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.

  12. Reducing uncertainty in the climatic interpretations of speleothem δ18O

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

  13. 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.

  14. 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.

  15. 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

  16. The oxygen isotope composition of Karoo and Etendeka picrites: High δ18O mantle or crustal contamination?

    NASA Astrophysics Data System (ADS)

    Harris, Chris; le Roux, Petrus; Cochrane, Ryan; Martin, Laure; Duncan, Andrew R.; Marsh, Julian S.; le Roex, Anton P.; Class, Cornelia

    2015-07-01

    Oxygen isotope compositions of Karoo and Etendeka large igneous province (LIP) picrites and picrite basalts are presented to constrain the effects of crustal contamination versus mantle source variation. Olivine and orthopyroxene phenocrysts from lavas and dykes (Mg# 64-80) from the Tuli and Mwenezi (Nuanetsi) regions of the ca 180 Ma Karoo LIP have δ18O values that range from 6.0 to 6.7 ‰. They appear to have crystallized from magmas having δ18O values about 1-1.5 ‰ higher than expected in an entirely mantle-derived magma. Olivines from picrite and picrite basalt dykes from the ca 135 Ma Etendeka LIP of Namibia and Karoo-age picrite dykes from Dronning Maud Land, Antarctica, do not have such elevated δ18O values. A range of δ18O values from 4.9 to 6.0 ‰, and good correlations between δ18O value and Sr, Nd and Pb isotope ratios for the Etendeka picrites are consistent with previously proposed models of crustal contamination. Explanations for the high δ18O values in Tuli/Mwenezi picrites are limited to (1) alteration, (2) crustal contamination, and (3) derivation from mantle with an abnormally high δ18O. Previously, a variety of models that range from crustal contamination to derivation from the `enriched' mantle lithosphere have been suggested to explain high concentrations of incompatible elements such as K, and average ɛNd and ɛSr values of -8 and +16 in Mwenezi (Nuanetsi) picrites. However, the primitive character of the magmas (Mg# 73), combined with the lack of correlation between δ18O values and radiogenic isotopic compositions, MgO content, or Mg# is inconsistent with crustal contamination. Thus, an 18O-enriched mantle source having high incompatible trace element concentration and enriched radiogenic isotope composition is indicated. High δ18O values are accompanied by negative Nb and Ta anomalies, consistent with the involvement of the mantle lithosphere, whereas the high δ18O themselves are consistent with an eclogitic source. Magma δ18

  17. A method for calculating 16O/18O peptide ion ratios for the relative quantification of proteomes.

    PubMed

    Johnson, Kenneth L; Muddiman, David C

    2004-04-01

    A method is described for the identification and relative quantification of proteomes using accurate mass tags (AMT) generated by nLC-dual ESI-FT-ICR-MS on a 7T instrument in conjunction with stable isotope labeling using 16O/18O ratios. AMTs were used for putative peptide identification, followed by confirmation of peptide identity by tandem mass spectrometry. For a combined set of 58 tryptic peptides from bovine serum albumin (BSA) and human transferrin, a mean mass measurement accuracy of 1.9 ppm +/-0.94 ppm (CIM99%) was obtained. This subset of tryptic peptides was used to measure 16O/18O ratios of 0.36 +/- 0.09 (CIM99%) for BSA (micro = 0.33) and 1.48 +/- 0.47 (CIM99%) for transferrin (micro = 1.0) using a method for calculating 16O/18O ratios from overlapping isotopic multiplets arising from mixtures of 16O, 18O1, and 18O2 labeled C-termini. The model amino acid averagine was used to calculate a representative molecular formula for estimating and subtracting the contributions of naturally occurring isotopes solely as a function of peptide molecular weight. The method was tested against simulated composite 16O/18O spectra where peptide molecular weight, 16O/18O ratio, 18O1/18O2 ratios, and number of sulfur atoms were varied. Relative errors of 20% or less were incurred when the 16O/18O ratios were less than three, even for peptides where the number of sulfur atoms was over- or under-estimated. These data demonstrate that for biomarker discovery, it is advantageous to label the proteome representing the disease state with 18O; and the method is not sensitive to variations in 18O1/18O2 ratio. This approach allows a comprehensive differentiation of expression levels and tentative identification via AMTs, followed by targeted analysis of over- and under-expressed peptides using tandem mass spectrometry, for applications such as the discovery of disease biomarkers. PMID:15047049

  18. Analysis of Biogenic Silica and Quartz δ18O Utilizing TC/EA CF-IRMS

    NASA Astrophysics Data System (ADS)

    Menicucci, A. J.; Spero, H. J.; Matthews, J.

    2012-12-01

    Oxygen isotope ratio analyses of inorganic and biogenic silicates, and in particular δ18O values from diatoms, remain underutilized as a tool for paleoenvironmental reconstructions and mineralogical investigations. Measuring the δ18O in silicates is difficult and hazardous in comparison to measurements of carbonate minerals because fluorine reagents are typically utilized to break the covalent Si-O bonds. Necessary equipment to safely manipulate such materials is expensive and not readily available in most laboratories. This difficulty creates a practical limitation on paleoclimate investigations for many researchers to areas where more easily analyzed fossil material (i.e. carbonate fossils) is prevalent. This has resulted in a paucity of paleoclimate data in limnetic environments, continental interiors, and high latitude marine localities where carbonate fossils are sparse or non-existent. Measurements of δ18O from diatoms in areas where significant diatom populations exist are therefore highly desirable. Here we present a new technique to measure δ18O in silicates which is applicable to both biogenic silica and inorganic quartz samples. This new method utilizes polytetrafluoroethylene (PTFE) Teflon (C2F4) powder as a fluorine source. Over 100 inorganic quartz samples, including NBS-28, and 75 biogenic silica samples, both diatomite and fossil grass phytoliths, have been processed. These silicates span an approximate 30‰ range. Cleaned and purified samples are first dehydrated/dehydroxylated by heating to 1050oC under hard vacuum, and then loaded into silver foil sample boats. PTFE Teflon powder and graphite are added, and the samples are analyzed with a TC/EA furnace linked via continuous flow to an isotope ratio mass spectrometer (CF-IRMS). Samples are analyzed at 1450C. Mean sample yield is 92% (±8.6% at 1σ standard deviation). Teflon blanks combusted between silicates indicate no detectable silica remaining in the reaction column in between sample

  19. Reducing uncertainty in the climatic interpretations of speleothem ?18O (Invited)

    NASA Astrophysics Data System (ADS)

    Jex, C.; Phipps, S. J.; Baker, A.; Bradley, C.; Treble, P. C.

    2013-12-01

    Speleothem δ18O (δ18Ospel) is an excellent proxy for terrestrial palaeoclimate reconstruction. The δ18O of cave drip water from which a speleothem forms, records the isotopic composition of the water that infiltrates into the deep soil layers and the karst aquifer. Interpretations of δ18Ospel therefore depend upon adequate constraints on: i. the atmospheric controls on precipitation δ18O (δ18Op), and ii. the 'non-climatic' controls that dictate the nature and duration of transmission of this meteoric input through the karst aquifer and into the cave as drip water. Monitoring of cave systems and analysis of local and regional controls on modern day climate parameters and δ18Op are commonplace to aid interpretations of δ18Ospel, and to establish transfer functions between climatic parameters and δ18Ospel over instrumental time periods. However, subsequent climate reconstructions still depend upon two key assumptions: i. potential non-stationarity in the relationships between local climate and the larger-scale atmospheric circulation; and ii. routing of water through the karst aquifer. These are arguably the dominant sources of uncertainty in the climatic interpretations of δ18Ospel. We explore these two areas of uncertainty, using a δ18Ospel record from Turkey, the CSIRO Mk3L climate system model and the KarstFOR karst hydrology model. We confirm the stationarity of relationships between cool season precipitation and regional circulation dynamics associated with the North Sea - Caspian Pattern over the last 1000 years. Stalagmite δ18O is predicted for the last 500 years, using simulated precipitation and temperature from the CSIRO Mk3L model and synthetic precipitation δ18O as inputs to the KarstFOR model. Interannual variability in the δ18Ospel record is captured by KarstFOR, but we cannot reproduce the isotopically lighter conditions of the 16th to 17th Centuries. We argue that forward models of paleoclimate proxies (such as KarstFOR) embedded within

  20. Photorespiratory Rates in Wheat and Maize as Determined by 18O-Labeling 1

    PubMed Central

    de Veau, Edward J.; Burris, John E.

    1989-01-01

    A method was devised to quantify short-term photorespiratory rates in terrestrial plants using 18O-intermediates of the glycolate pathway, specifically glycolate, glycine, and serine. The pathway intermediates were isolated and analyzed on a GC/MS to determine molecular percent 18O-enrichment. Rates of glycolate synthesis were determined from 18O-labeling kinetics of the intermediates, derived rate equations, and nonlinear regression techniques. Glycolate synthesis in wheat (Triticum aestivum L.), a C3 plant, and maize (Zea mays L.), a C4 plant, was stimulated by high O2 concentrations and inhibited by high CO2 concentrations. The synthesis rates were 7.3, 2.1, and 0.7 micromoles per square decimeter per minute under a 21% O2 and 0.035% CO2 atmosphere for leaf tissue of wheat, maize seedlings, and 3-month-old maize, respectively. Photorespiratory CO2 evolution rates were estimated to be 27, 6, and 2%, respectively, of net photosynthesis for the three groups of plants under the above atmosphere. The results from maize tissue support the hypothesis that C4 plants photorespire, albeit at a reduced rate in comparison to C3 plants, and that the CO2/O2 ratio in the bundle sheath of maize is higher in mature tissue than in seedling tissue. The pool size of the three photorespiratory intermediates remained constant and were unaffected by changes in either CO2 or O2 concentrations throughout the 10-minute labeling period. This suggests that photorespiratory metabolism is regulated by other mechanism besides phosphoglycolate synthesis by ribulose-1,5-bisphosphate carboxylase/oxygenase, at least under short-term conditions. Other mechanisms could be alternate modes of synthesis of the intermediates, regulation of some of the enzymes of the photorespiratory pathway, or regulation of carbon flow between organelles involved in photorespiration. The glycolate pool became nearly 100% 18O-labeled under an atmosphere of 40% O2. This pool failed to become 100% 18O-enriched under

  1. Fallout /sup 3/H ingestion in Akita, Japan

    SciTech Connect

    Hisamatsu, S.; Takizawa, Y.; Abe, T.; Katsumata, T.

    1987-09-01

    To study fallout /sup 3/H ingestion in Japan, 16 separate food group samples were collected from Akita during 1985. The /sup 3/H concentration in free water and that in a tissue-bound form were determined separately. The average /sup 3/H concentration in the tissue-bound form was 2.2 Bq L-1, 1.7 times higher than in the free water of the food. The ingestions of /sup 3/H in the tissue-bound form and as free water in the diet were 0.60 Bq d-1 and 1.0 Bq d-1, respectively. Cereals represented the food group that contributed the most to the ingestion of tissue-bound /sup 3/H. Total /sup 3/H ingestion was estimated to be 4.1 Bq d-1. The contribution of the tissue-bound form to the total ingestion was 15%, considerably lower than reported for Italian diets. The ratio of /sup 3/H ingestion in the tissue-bound form to the free water form in the diet was similar to the ratio reported for New York City.

  2. 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.

  3. A tree-ring cellulose δ18O-based July-October precipitation reconstruction since AD 1828, northwest Thailand

    NASA Astrophysics Data System (ADS)

    Xu, Chenxi; Pumijumnong, Nathsuda; Nakatsuka, Takeshi; Sano, Masaki; Li, Zhen

    2015-10-01

    A tree-ring δ18O chronology for the period 1828-2000 was developed from four Pinus merkusii trees, to find a reliable proxy for reconstructing precipitation in northwest Thailand. Inter-tree δ18O correlations were high during the entire period (r = 0.57-0.79). The tree-ring δ18O chronology shows significant negative correlations with regional July-October precipitation during the period 1901-2000 (r = -0.62) and with July-October river flow (r = -0.54), and is in good agreement with a shorter tree-ring δ18O chronology from living Pinus kesiya in northwest Thailand. The spatial correlation analysis between tree-ring δ18O and regional July-October precipitation also support that the tree-ring δ18O of P. merkusii is a promising proxy to reconstruct precipitation in northwest Thailand. The tree-ring δ18O-based July-October reconstruction, which accounts for 37.6% of the precipitation variance, shows a close relationship with El Niño-Southern Oscillation (ENSO) during the period 1871-2000, with the exception of during the past two decades; the exception may be related to the southeastward shift of the descending limb of Walker circulation and increased frequency of central Pacific ENSO.

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

    NASA Astrophysics Data System (ADS)

    Mengel, K.; Hoefs, J.

    1990-11-01

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

  5. Photochemical Modeling of the Distribution of C3H8 in the Atmosphere of Saturn

    NASA Astrophysics Data System (ADS)

    Edgington, S. G.; Simon-Miller, A.; Jennings, D.; Bjoraker, G.; Romani, P.; Achterberg, R.; Orton, G.; Flasar, M.; Cassini CIRS Team

    2005-08-01

    Cassini's Composite Infrared Spectrometer (CIRS) has measured the abundance of C2H2 and C3H8 (Propane) at several latitudes in the Southern hemisphere. An increase of radiance with latitude towards the pole has been observed, possibly implying a corresponding increase of C3H8. In an effort explain the observed distribution of both species, it is important to model the creation, destruction, and transport of these chemical species. Furthermore, since both molecules have overlapping absorption features in the same spectral region near 748 cm-1, such modeling will aid in refining derived abundances and separating temperature effects. The photochemistry model used in Edgington et al. (1998, 1999, 2000) to model simultaneously hydrocarbons, ammonia, and phosphine is updated and expanded to include paths relevant to the creation of C3H8. Destruction occurs through photolysis, while transport would tend to spread C3H8 from its source regions. With a series of exercises in 1- and 2- dimensions, we explore the extent to which photolysis, vertical, and/or meridional transport impacts the distribution of C2H2 and C3H8 with latitude. Thermal profiles derived from CIRS observations versus latitude are used as they have an impact on numerous reaction rates. We then compare these results with abundances derived from observations taken with the CIRS instrument. Edgington, S.G., West, R.A., Friedson, A.J., Atreya, S.K., 2000. A 2-D photochemical model with meridional circulation. Bull. American. Astron. Soc., 32, 1013. Edgington, S.G., S.K. Atreya, L.M. Trafton, J.J. Caldwell, R.F. Beebe, A.A. Simon, and R.A. West, 1999. Ammonia and eddy mixing variations in the southern hemisphere of Jupiter from HST Faint Object Spectrograph Observations. Icarus, 142, 342-357. Edgington, S.G., S.K. Atreya, L.M. Trafton, J.J. Caldwell, R.F. Beebe, A.A. Simon, R.A. West, and C. Barnet, 1998. On the latitude variation of ammonia, acetylene, and phosphine altitude profiles on Jupiter from HST Faint

  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. Fallout sup 3 H in human tissue at Akita, Japan

    SciTech Connect

    Hisamatsu, S.; Takizawa, Y.; Itoh, M.; Ueno, K.; Katsumata, T.; Sakanoue, M. )

    1989-10-01

    The {sup 3}H concentration in Japanese human tissue samples is reported in this paper. Four brain, 10 liver, and nine lung samples from 11 cases were collected from Akita Prefecture in northern Japan from January to July 1986. The median of free-water {sup 3}H concentration was similar in these tissues and agreed well with the concentrations in the diet, including tap water. The median specific activity ratio of tissue-bound {sup 3}H to free-water {sup 3}H was 1.1 and was slightly lower than that in the diet. The specific activity ratio was also lower than that reported in the United States and significantly lower than in Italy.

  8. Past break-monsoon conditions detectable by high resolution intra-annual δ18O analysis of teak rings

    NASA Astrophysics Data System (ADS)

    Managave, S. R.; Sheshshayee, M. S.; Borgaonkar, H. P.; Ramesh, R.

    2010-03-01

    Intra-annual variations in the cellulose oxygen isotopic composition (δ18O) of several annual growth rings of three teak (Tectona grandis L.F.) trees from central India show a clear seasonal cycle with higher values in the early and late growing seasons and lower values in the middle. This cycle is useful to identify growth occurring during different phases of the growing season. Relative humidity (RH) appears to control the intra-annual δ18O variations rather than rainfall, and therefore past break-monsoon conditions associated with lower RH, could be detected by high resolution sub-sampling of annual rings for δ18O analysis.

  9. Stereospecific binding of 3H-phencyclidine in brain membranes.

    PubMed

    Hampton, R Y; Medzihradsky, F; Woods, J H; Dahlstrom, P J

    1982-06-21

    Phencyclidine (PCP) displaceable binding of 3H-PCP to glass-fiber filters was eliminated and total binding markedly reduced by initial treatment of the discs with 0.05% polyethyleneimine. Assessed with treated filters, unlabeled PCP displaced 3H-PCP in both rat and pigeon brain membranes with an EC50 of 1 microM. Of similar high inhibitory potency were dextrorphan, levorphanol, SKF 10047 and ketamine, while morphine, naloxone and etorphine had EC50 values higher then 1 mM. Using the dissociative anesthetic dexoxadrol and its inactive isomer levoxadrol as displacing agents, stereospecific binding of 3H-PCP was obtained in rat and pigeon brain membranes. The markedly higher potency of dexoxadrol, relative to levoxadrol, in displacing bound 3H-PCP is compatible with behavioral data for these enantiomers. However, they were equipotent in displacing 3H-PCP bound to glass-fiber filters in the absence of tissue. Heat denaturation, but not freezing, abolished stereospecific binding of 3H-PCP, which was also absent in rat liver membranes. The stereospecific binding component in brain displayed biphasic saturability at 60-70 nM and 300-400 nM, respectively. PMID:7109842

  10. (/sup 3/H)-beta-endorphin binding in rat brain

    SciTech Connect

    Houghten, R.A.; Johnson, N.; Pasternak, G.W.

    1984-10-01

    The binding of (/sup 3/H)-beta-endorphin to rat brain homogenates is complex. Although Scatchard analysis of saturation studies yields a straight line, detailed competition studies are multiphasic, suggesting that even at low concentrations of the compound, the /sup 3/H-ligand is binding to more than one class of site. A portion of (/sup 3/H)-beta-endorphin binding is sensitive to low concentrations of morphine or D-Ala2-Leu5-enkephalin (less than 5 nM). The inhibition observed with each compound alone (5 nM) is the same as that seen with both together (each at 5 nM). Thus, the binding remaining in the presence of both morphine and the enkephalin does not correspond to either mu or delta sites. The portion of (/sup 3/H)-beta-endorphin binding that is inhibited under these conditions appears to be equally sensitive to both morphine and the enkephalin and may correspond to mu1 sites. Treating membrane homogenates with naloxonazine, a mu1 selective antagonist, lowers (/sup 3/H)-beta-endorphin binding to the same degree as morphine and D-Ala2-Leu5-enkephalin alone or together. This possible binding of (/sup 3/H)-beta-endorphin to mu1 sites is consistent with the role of mu1 sites in beta-endorphin analgesia and catalepsy in vivo.

  11. Probabilistic sequence alignment of Late Pleistocene benthic δ18O data

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  12. 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

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  15. Establishing a grassland signature in veins: 18O in the leaf water of C3 and C4 grasses

    PubMed Central

    Helliker, Brent R.; Ehleringer, James R.

    2000-01-01

    We show that 18O evaporative enrichment of bulk leaf water in grass species can be significantly more enriched than predicted by the Craig–Gordon model, with C4 grasses considerably more enriched than C3 grasses. Our results suggest that the unanticipated 18O leaf water enrichment of grasses is attributable to the progressive evaporative enrichment along parallel veins (a function of both leaf length and interveinal distance), a pattern that does not occur in Dicotyledonous species. We propose that the differential 18O enrichment of grasses will result in distinct C18O16O biospheric signals from grassland and forest ecosystems, allowing for further partitioning of terrestrial carbon fluxes. PMID:10884421

  16. Morphology-controlled synthesis of W18O49 nanostructures and their near-infrared absorption properties.

    PubMed

    Guo, Chongshen; Yin, Shu; Yan, Mei; Kobayashi, Makoto; Kakihana, Masato; Sato, Tsugio

    2012-04-16

    The morphology-controlled synthesis and near-infrared (NIR) absorption properties of W(18)O(49) were systematically investigated for the application of innovative energy-saving windows. Various morphologies of W(18)O(49), such as nanorods, nanofibers, nanograins, nanoassembles, nanoplates, and nanoparticles, with various sizes were successfully synthesized by solvothermal reactions using organic alcohols as reaction media and WCl(6), W(EtO)(6), and WO(3) solids as the tungsten source. W(18)O(49) nanorods of less than 50 nm in length showed the best optical performance as an effective solar filter, which realized high transmittance in the visible region as well as excellent shielding properties of NIR light. Meanwhile, the W(18)O(49) nanorods also exhibited strong absorption of NIR light and instantaneous conversion of the absorbed photoenergy to the local heat. PMID:22443484

  17. Calculational and Experimental Investigations of the Pressure Effects on Radical - Radical Cross Combinations Reactions: C2H5 + C2H3

    NASA Technical Reports Server (NTRS)

    Fahr, Askar; Halpern, Joshua B.; Tardy, Dwight C.

    2007-01-01

    Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance

  18. Uptake of /sup 3/H-choline and synthesis of /sup 3/H-acetylcholine by human penile corpus cavernosum

    SciTech Connect

    Blanco, R.; Saenz de Tejada, I.; Azadzoi, K.; Goldstein, I.; Krane, R.J.; Wotiz, H.H.; Cohen, R.A.

    1986-03-05

    The neuroeffectors which relax penile smooth muscle and lead to erection are unknown; physiological studies of human corpus cavernosum, in vitro, have suggested a significant role of cholinergic neurotransmission. To further characterize the importance of cholinergic nerves, biopsies of human corpus cavernosum were obtained at the time of penile prosthesis implantation. Tissues were incubated in /sup 3/H-choline (10/sup -5/M, 80 Ci/mmol) in oxygenated physiological salt solution at 37/sup 0/C, pH 7.4 for 1 hour. Radiolabelled compounds were extracted with perchloric acid (0.4 M) and acetylcholine and choline were separated by HPLC; /sup 14/C-acetylcholine was used as internal standard. /sup 3/H-choline was accumulated by the tissues (20 +/- 1.9 fmol/mg), and /sup 3/H-acetylcholine was synthesized (4.0 +/- 1.1 fmol/mg). In control experiments, heating of the tissue blocked synthesis of /sup 3/H-acetylcholine. Inhibition of high affinity choline transport by hemicholinium-3 (10/sup -5/M) diminished tissue accumulation of /sup 3/H-choline and significantly reduced the synthesis of /sup 3/H-acetylcholine (0.5 +/ 0.2 fmol/mg, p < 0.05). These results provide direct evidence of neuronal accumulation of choline and enzymatic conversion to acetylcholine in human corpus cavernosum. Taken together with the physiological studies, it can be concluded that cholinergic neurotransmission in human corpus cavernosum plays a role in penile erection.

  19. Spatially Resolved L-C3H+ Emission in the Horsehead Photodissociation Region: Further Evidence for a Top-Down Hydrocarbon Chemistry

    NASA Astrophysics Data System (ADS)

    Guzmán, V. V.; Pety, J.; Goicoechea, J. R.; Gerin, M.; Roueff, E.; Gratier, P.; Öberg, K. I.

    2015-02-01

    Small hydrocarbons, such as C2H, C3H, and C3H2 are more abundant in photo-dissociation regions (PDRs) than expected based on gas-phase chemical models. To explore the hydrocarbon chemistry further, we observed a key intermediate species, the hydrocarbon ion l-C3H+, in the Horsehead PDR with the Plateau de Bure Interferometer at high-angular resolution (6″). We compare with previous observations of C2H and c-C3H2 at similar angular resolution and new gas-phase chemical model predictions to constrain the dominant formation mechanisms of small hydrocarbons in low-UV flux PDRs. We find that at the peak of the HCO emission (PDR position), the measured l-C3H+, C2H, and c-C3H2 abundances are consistent with current gas-phase model predictions. However, in the first PDR layers, at the 7.7 μm polycyclic aromatic hydrocarbon band emission peak, which are more exposed to the radiation field and where the density is lower, the C2H and c-C3H2 abundances are underestimated by an order of magnitude. At this position, the l-C3H+ abundance is also underpredicted by the model but only by a factor of a few. In addition, contrary to the model predictions, l-C3H+ peaks further out in the PDR than the other hydrocarbons, C2H and c-C3H2. This cannot be explained by an excitation effect. Current gas-phase photochemical models thus cannot explain the observed abundances of hydrocarbons, in particular, in the first PDR layers. Our observations are consistent with a top-down hydrocarbon chemistry, in which large polyatomic molecules or small carbonaceous grains are photo-destroyed into smaller hydrocarbon molecules/precursors. Based on observations obtained with the IRAM Plateau de Bure interferometer and 30 m telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain).

  20. Validation of δ18O as a proxy for past monsoon rain by multi-GCM simulations

    NASA Astrophysics Data System (ADS)

    Midhun, M.; Ramesh, R.

    2016-03-01

    Stable oxygen isotope ratios (δ18O) of tree cellulose and speleothem carbonate are useful proxies for past monsoon rain in many tropical regions, as a decrease in rain δ18O is observed with increase in rainfall on a monthly time scale. This amount effect varies spatially; therefore a local calibration, with actual measurements of rain amount and its δ18O is required. Such observations, however, are quite limited in space and time. To circumvent this difficulty, many isotope enabled general circulation models (GCMs) are used to aid the interpretation of 18O proxies; nevertheless, all such simulations taken together are yet to be evaluated against observations over the Indian summer monsoon (ISM) region. Here we examine ten such GCM simulations archived by the stable water isotope INtercomparison Group, phase 2. The spatial patterns of simulated ISM rainfall and its δ18O are in good agreement with the limited observations available. Simulations nudged with observed wind fields show better skill in reproducing the observed spatio-temporal pattern of rainfall and its δ18O. A large discrepancy is observed in the magnitude of the simulated amount effect over the Indian subcontinent between the models and observation, probably because models simulate the spatial distribution of monsoon precipitation differently. Nudged simulations show that interannual variability of rainfall δ18O at proxy sites are controlled by either regional (rather than local) rainfall or upstream rain out. Interannual variability of rainfall δ18O over the East Asian region is well correlated with ENSO, while it is only weakly correlated over the Indian sub-continent.

  1. 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

  2. Modern decrease of δ18O in Mediterranean sediments over the last 150 y: anthropogenic forcing and natural variability

    NASA Astrophysics Data System (ADS)

    Alessio, S.; Taricco, C.; Vivaldo, G.; Ghil, M.

    2012-04-01

    Our previous work (Taricco et al., 2009) has documented a high-resolution record of foraminiferal δ18O isotopic ratio that covers the last two millennia. This record was obtained from a shallow-water sediment core drilled in the Central Mediterranean (Gallipoli Terrace in the Gulf of Taranto, Ionian Sea), and dated with high accuracy by tephroanalysis and radiometric measurements. The δ18O series so obtained spans the last 2200 years and shows a steep decrease during the Industrial Era. We use here pre-industrial δ18O variations to design and tune algorithms able to forecast the natural variability in the δ18O series over the last 150 y (Alessio et al., 2012). Autoregressive (AR) models and feed-forward neural networks are applied to the highly significant components revealed by Singular Spectrum Analysis (SSA). Comparison between the forecast and the actual δ18O signal during the Industrial Era shows that the natural contribution to the modern δ18O variation decreased gradually, until it reached roughly 40% as early as the end of the 1970s.

  3. 18O depletion in monsoon rain relates to large scale organized convection rather than the amount of rainfall.

    PubMed

    Lekshmy, P R; Midhun, M; Ramesh, R; Jani, R A

    2014-01-01

    Oxygen isotopic variations in rainfall proxies such as tree rings and cave calcites from South and East Asia have been used to reconstruct past monsoon variability, mainly through the amount effect: the observed (18)O depletion of rain with increasing amount, manifested as a negative correlation of the monthly amount of tropical rain with its δ(18)O, both measured at the same station. This relation exhibits a significant spatial variability, and at some sites (especially North-East and peninsular India), the rainfall proxies are not interpretable by this effect. We show here that relatively higher (18)O-depletion in monsoon rain is not related necessarily to its amount, but rather, to large scale organized convection. Presenting δ(18)O analyses of ~654 samples of daily rain collected during summer 2012 across 9 stations in Kerala, southern India, we demonstrate that although the cross correlations between the amounts of rainfall in different stations is insignificant, the δ(18)O values of rain exhibit highly coherent variations (significant at P = 0.05). Significantly more (18)O-depletion in the rain is caused by clouds only during events with a large spatial extent of clouds observable over in the south eastern Arabian Sea. PMID:25012535

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

    NASA Astrophysics Data System (ADS)

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

    1994-08-01

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

  5. Adenosine triphosphate utilization rates and metabolic pool sizes in intact cells measured by transfer of 18O from water.

    PubMed Central

    Dawis, S M; Walseth, T F; Deeg, M A; Heyman, R A; Graeff, R M; Goldberg, N D

    1989-01-01

    The hydrolytic rates and metabolic pool sizes of ATP were determined in intact cells by monitoring the time courses of 18O incorporation from 18O-water into the gamma-phosphoryl of ATP and orthophosphate. To calculate the rate of ATP hydrolysis, a kinetic model is used to fit the time course of the 18O labeling. The size of the metabolic pool of ATP is calculated from the 18O distribution after isotopic equilibrium has been achieved. Metabolic pools have a binomial distribution of 18O whereas nonmetabolic pools exhibit negligible 18O labeling. The application and limitations of this approach are illustrated with data from isolated toad retinas and human platelets. At 22 degrees C, the time constant of ATP hydrolysis in the dark-adapted toad retina is about 30 s. Under these conditions, over 80% of the retinal ATP is involved in high-energy phosphate metabolism. It is calculated that when cGMP metabolic flux in the photoreceptors is maximally stimulated by light, it accounts for 10% of the ATP utilization by the entire retina. The time constant of ATP hydrolysis in human platelets at 37 degrees C is approximately 1 s, and 60% of the platelet ATP is involved in energy metabolism. PMID:2930826

  6. Pharmacological studies on quaternized 4(3H)-quinazolinones.

    PubMed

    Buyuktimkin, S; Ekinci, A C; Buyuktimkin, N; Otuk, G

    1992-11-01

    Locomotor activity-inhibiting, anticonvulsant, muscle relaxant, analgesic, and antimicrobial properties of 2-methyl-3-pyridinium-acetylamino-4(3H)-quinazolinone chloride (1), 2-methyl-3-(4-methylpyridinium)acetylamino-4(3H)-quinazolinone chloride (2), 2-methyl-3-(4-ethylpyridinium)acetylamino-4(3H)-quinazolinone chloride (3), 2-methyl-3-(3-carboxamidopyridinium)acetylamino-4(3H)-quinazolinon e chloride (4), and 2-methyl-3-(4-carboxamidopyridinium)-acetylamino-4(3H)- quinazolinone chloride (5) were investigated. The locomotor activity-inhibiting properties and anticonvulsant activity of 2 were almost equal to those of methaqualone. The analgesic activities of 2 and 3 in the hot-plate test were equal to that of aspirin, whereas in the Koster test, the analgesic activity of 2 was higher. The compounds did not exhibit antimicrobial or muscle relaxant properties. Most active compounds had higher lipophilicity values than those of inactive compounds. PMID:1447711

  7. A calibration of the triple oxygen isotope fractionation in the SiO2-H2O system and applications to natural samples

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Gibbons, J. A.; Maltsev, O.; Atudorei, V.; Pack, A.; Sengupta, S.; Shock, E. L.; Knauth, L. P.

    2016-08-01

    It is now recognized that variations in the Δ17O of terrestrial materials resulting from purely mass dependent fractionations, though small, have geological significance. In this study, the δ18O and δ17O values of selected low temperature quartz and silica samples were measured in order to derive the quartz-water fractionation-temperature relationship for the three oxygen isotope system. A 18O/16O quartz-water fractionation equation valid for all temperatures was generated from published high temperature exchange experiments and low temperature empirical estimates and is given by 1000ln αqz-H2O18O /16O = 4.20 (0.11) ×106/T2 - 3.3 (0.2) × 1000/T (T in Kelvins). The equilibrium δ17O-δ18O relationship is given by the equation lnα17O/16O = θlnα18O/16O . The variation of θ with temperature for the quartz-water system was determined empirically using low temperature marine diatoms, microcrystalline quartz and a modern sinter sample. A best fit to the data give the equation θSiO2 - H2O = -(1.85 ± 0.04)/T + 0.5305 , indistinguishable from an earlier theoretical estimate. Application of the quartz-water triple isotope system to low temperature samples provides constraints on both temperature and composition of the water with which the silica last equilibrated. Authigenic quartz crystallization temperatures cluster around 50 °C, which are lower than many previous estimates. The combined δ18O and δ17O values of samples considered to be in equilibrium with ocean or meteoric waters can be used to estimate both formation temperatures and the δ18O value of the meteoric water. Unlike other multiple isotopes systems, such as combined H and O isotopes in cherts, the oxygen source and diagenetic potential for both 17O/16O and 18O/16O ratios are identical, simplifying interpretations from ancient samples.

  8. A calibration of the triple oxygen isotope fractionation in the SiO2-H2O system and applications to natural samples

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Gibbons, J. A.; Maltsev, O.; Atudorei, V.; Pack, A.; Sengupta, S.; Shock, E. L.; Knauth, L. P.

    2016-08-01

    It is now recognized that variations in the Δ17O of terrestrial materials resulting from purely mass dependent fractionations, though small, have geological significance. In this study, the δ18O and δ17O values of selected low temperature quartz and silica samples were measured in order to derive the quartz-water fractionation-temperature relationship for the three oxygen isotope system. A 18O/16O quartz-water fractionation equation valid for all temperatures was generated from published high temperature exchange experiments and low temperature empirical estimates and is given by 1000ln αqz-H2O 18O /16O =4.20 (0.11) ×106/T2 - 3.3 (0.2) × 1000/T (T in Kelvins). The equilibrium δ17O-δ18O relationship is given by the equation lnα17O/16O = θlnα18O/16O . The variation of θ with temperature for the quartz-water system was determined empirically using low temperature marine diatoms, microcrystalline quartz and a modern sinter sample. A best fit to the data give the equation θSiO2-H2O = -(1.85 ± 0.04)/T + 0.5305 , indistinguishable from an earlier theoretical estimate. Application of the quartz-water triple isotope system to low temperature samples provides constraints on both temperature and composition of the water with which the silica last equilibrated. Authigenic quartz crystallization temperatures cluster around 50 °C, which are lower than many previous estimates. The combined δ18O and δ17O values of samples considered to be in equilibrium with ocean or meteoric waters can be used to estimate both formation temperatures and the δ18O value of the meteoric water. Unlike other multiple isotopes systems, such as combined H and O isotopes in cherts, the oxygen source and diagenetic potential for both 17O/16O and 18O/16O ratios are identical, simplifying interpretations from ancient samples.

  9. Inferring heterogeneity in aquitards using high-resolution deltaD and delta18O profiles.

    PubMed

    Hendry, M Jim; Wassenaar, L I

    2009-01-01

    Vertical depth profiles of pore water isotopes (deltaD and delta18O) in clay-rich aquitards have been used to show that solute transport is dominated by molecular diffusion, to define the timing of geologic events, and to estimate vertical hydraulic conductivity. The interpretation of the isotopic profiles in these studies was based on pore water samples collected from piezometers installed in nests (typically 4 to 15 piezometers) over depths of 10 to 80 m. Data from piezometer nests generally have poor vertical resolution (meters), raising questions about their capacity to reveal the impact of finer scale heterogeneities such as permeable sand bodies or fractured till zones on solute transport. Here, we used high-resolution (30-cm) depth profiles of deltaD and delta18O from two continuously cored boreholes in a till aquitard to provide new insights into the effects of sand bodies on solute transport. High-resolution core-derived profiles indicate that such heterogeneities can cause major deviations from one-dimensional diffusion profiles. Further, comparison of piezometer-measured values with best-fit diffusion trends shows subtle deviations, suggesting the presence of heterogeneities that should not be ignored. High-resolution profiles also more clearly defined the contact between the highly fractured oxidized zone and the underlying unoxidized zone than the piezometers. PMID:19735307

  10. 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.

  11. A high-resolution δ18O record and Mediterranean climate variability

    NASA Astrophysics Data System (ADS)

    Taricco, C.; Vivaldo, G.; Alessio, S.; Rubinetti, S.; Mancuso, S.

    2015-03-01

    A high-resolution, well-dated foraminiferal δ18O record from a shallow-water core drilled from the Gallipoli Terrace in the Gulf of Taranto (Ionian Sea), previously measured over the last two millennia, has been extended to cover 707 BC-AD 1979. Spectral analysis of this series, performed using singular-spectrum analysis (SSA) and other classical and advanced methods, strengthens the results obtained analysing the shorter δ18O profile, detecting the same highly significant oscillations of about 600, 380, 170, 130 and 11 years, respectively explaining about 12, 7, 5, 2 and 2% of the time series total variance, plus a millennial trend (18% of the variance). The comparison with the results of multi-channel singular-spectrum analysis (MSSA) applied to a data set of 26 Northern Hemisphere (NH) temperature-proxy records shows that NH temperature anomalies share with our local record a~long-term trend and a bicentennial (170-year period) cycle. These two variability modes, previously identified as temperature-driven, are the most powerful modes in the NH temperature data set. Both the long-term trends and the bicentennial oscillations, when reconstructed locally and hemispherically, show coherent phases. Furthermore, the corresponding local and hemispheric amplitudes are comparable if changes in the precipitation-evaporation balance of the Ionian sea, presumably associated with temperature changes, are taken into account.

  12. A high-resolution δ18O record and Mediterranean climate variability

    NASA Astrophysics Data System (ADS)

    Taricco, C.; Vivaldo, G.; Alessio, S.; Rubinetti, S.; Mancuso, S.

    2014-10-01

    A~high-resolution, well-dated foraminiferal δ18O record from a shallow-water core drilled from the Gallipoli Terrace in the Gulf of Taranto (Ionian Sea), previously measured over the last two millennia, has been extended to cover 707 BC-1979 AD. Spectral analysis of this series, performed by Singular Spectrum Analysis (SSA) and other classical and advanced methods, strengthens the results obtained analysing the shorter δ18O profile, detecting the same highly significant oscillations of about 600 yr, 380 yr, 170 yr, 130 yr, and 11 yr, respectively explaining about 12%, 7%, 5%, 2% and 2% of the time series total variance, plus a millennial trend (18% of the variance). The comparison with the results of Multi-channel Singular Spectrum Analysis (MSSA) applied to a data set of 26 Northern Hemisphere (NH) temperature-proxy records shows that NH temperature anomalies share with our local record a long-term trend and a bicentennial cycle. These two variability modes, previously identified as temperature-driven, are the most powerful modes in the NH temperature data set. Both the long-term trends and the bicentennial oscillations, when reconstructed locally and hemispherically, show coherent phases. Also the corresponding local and hemispheric amplitudes are comparable, if changes in the precipitation-evaporation balance of the Ionian sea, presumably associated with temperature changes, are taken into account.

  13. 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.

  14. 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.

  15. Late Holocene northeastern Morocco hydroclimate reconstruction revealed from speleothems d18O record

    NASA Astrophysics Data System (ADS)

    Sifeddine, A.; Bouchaou, L., Sr.; Cruz, F. W., Sr.; Apaéstegui, J. E.; Moquet, J. S., Jr.; Strikis, N. M.; Guyot, J. L., Sr.; Cheng, H.; Auler, A. S.; Beraaouz, E. H., Sr.

    2014-12-01

    Two well dated oxygen isotope (d18O) records of speleothems collected in Chaara cave located in the Northeastern Morocco are used to investigate variations in hydroclimate conditions during the last 2000 years. The results shown in this work confirm the previous works of the North Atlantic Oscillation (NAO) reconstruction during the last millennium and bring new implications concerning its evolution extending the MCA. Our (d18O) results characterized by positive values during the Medieval Warm Period (MWP) and more negative ones during the Little Ice Ages (LIA) are in agreement with those published by Trouet et al., 2009 and Wassenburg et al., 2013. They confirm that the both periods were dominated by persistent NAO+ and NAO-conditions respectively. In addition; they highlight new evidence of the NAO evolution to beyond the last 1000 years. NAO+ conditions recorded during the MCA persist until 500 AD and NAO- conditions dominate the Dark cold Period (DACP) as recorded during the LIA. Finally, the Current Warm Period (CWP) was marked by a clear change in isotope variations linked to decreased precipitation controlled by intensification in NAO + conditions.

  16. ENSO flavors in a tree-ring δ18O record from Indonesia

    NASA Astrophysics Data System (ADS)

    Schollaen, Karina; Karamperidou, Christina; Helle, Gerhard

    2014-05-01

    The existence of so-called ENSO flavors (Cold Tongue and Warm Pool El Nino), their underlying mechanisms and potential changes in their frequency of occurrence is an active field of research in the climate science community. Previous work has shown the distinct teleconnection patterns of ENSO flavors and SST, precipitation and salinity in the tropics, which should be taken into account when interpreting palaeo-climate proxies. At the same time, proxies from key locations with distinct ENSO-flavors signals can provide long continuous records, essential for identifying possible trends and (multi)decadal variability of ENSO flavor occurrence. Here, we show that one such key region is Java (Indonesia), where the ENSO influence on precipitation is significant for Warm Pool ENSO, and non-significant for Cold Tongue ENSO. We do so by investigating the ENSO signal in a 108-year long (1900-2007) tree-ring δ18O record of teak (Tectona grandis) trees growing in a lowland rain forest in Central Java. Climate response analysis with regional monthly rainfall data reveals that the tree-ring δ18O record is significantly correlated to rainfall, and is sensitive to the occurrence of Warm Pool ENSO events, as well as La Nina events. The results presented here demonstrate the ability of tree-ring stable isotope records to provide palaeo-climate records able to distinguish between the two ENSO flavors, with broad applicability to studies on past ENSO variability.

  17. Validating methods for measuring delta18O and delta13C in otoliths from freshwater fish.

    PubMed

    Guiguer, K R R A; Drimmie, R; Power, M

    2003-01-01

    The ability of the phosphoric acid digestion technique to extract carbon dioxide from biogenic carbonates and reliably reproduce delta(18)O and delta(13)C signatures from standard reference materials (NBS-18, NBS-19) was tested and shown to produce accurate, unbiased measurements of non-biologic materials. The effects of roasting preparation methods commonly reported when analyzing biogenic carbonates were also tested in a series of experiments using reference standards and otoliths obtained from aquacultured Arctic charr and rainbow trout. Roasting had no effect on the isotope measurement of reference standards. No significant differences between mean oxygen isotope signatures from paired experiments with roasted and non-roasted fish otoliths were found. However, otolith oxygen isotope measurements were significantly enriched in comparison to rearing water-based measurements for both species. Agreement between expected isotopic equilibrium and measured otolith delta(18)O values varied as a function of roasting temperature and between species. Criteria for the selection of appropriate roasting temperatures are suggested and favour 350 degrees C in freshwater fish where unbiased estimates of average rearing water temperatures and known differences in rearing temperatures were obtained. Carbon isotopic disequilibria were observed for both species. A mixing model analysis established differences in the percentage of metabolically derived carbon in studied otoliths, with Arctic charr deriving a greater proportion of otolith delta(13)C from metabolism as a result of higher metabolic rates. PMID:12590395

  18. 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.

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

    PubMed

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

    2007-01-01

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

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

    PubMed

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

    2013-01-01

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

  1. 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...

  2. 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

    Although the instrumental coupling of gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) for compound-specific δ18O analyses is commercially available for more than 10 years, this method is hardly applied by isotope researchers so far. Using GC-Py-IRMS, Zech and Glaser (2009) and Zech et al. (2013; 2012) developed and applied a method, which allows determining δ18O of hemicellulose-derived sugar biomarkers extracted from soils and sediments. However, the used methylboronic acid (MBA) derivatization is suitable only for pentoses and deoxyhexoses, not for hexoses. Here we present first GC-Py-IRMS results for TMS-(trimethylsilyl)-derivatives of plant sap-relevant sugars (glucose, fucose, sucrose, raffinose) and a polyalkohol (pinitol) produced using BSTFA (N,O-Bis(trimethylsilyl)trifluoroacetamide) as the derivatization reagent. Particularly, we focus on sucrose, which is the most important transport sugar in plants and hence of utmost relevance in plant physiology and in tree-ring studies. Replicate analyses of sucrose standards with known δ18O values suggest that the δ18O measurements are not stable over several days. A calibration (including a drift correction) against an external sucrose standard is hence essential when measuring sample batches. Furthermore, we observed a large dependence of the δ18O values on the analyte amount (area), which needs to be considered by a respective correction procedure. Tests with 18O-enriched water do not provide any evidence for oxygen exchange reactions between water and sucrose, glucose and raffinose. Finally we present the first application of compound-specific δ18O analyses from natural samples, namely from seven needle extracts (soluble carbohydrates) from a Siberian study area. Both the δ18O amplitude and values of sucrose are considerably higher (32.1‰ to 40.1‰) compared to the δ18O amplitude and values of bulk needle extract (24.6‰ to 27.2‰). We found positive correlation (although

  3. Thermal Dehydrogenation of Base-Stabilized B2H5(+) Complexes and Its Role in C-H Borylation.

    PubMed

    Prokofjevs, Aleksandrs

    2015-11-01

    Thermally induced dehydrogenation of the H-bridged cation L2B2H5(+) (L=Lewis base) is proposed to be the key step in the intramolecular C-H borylation of tertiary amine boranes activated with catalytic amounts of strong "hydridophiles". Loss of H2 from L2B2H5(+) generates the highly reactive cation L2B2H3(+), which in its sp(2)-sp(3) diborane(4) form then undergoes either an intramolecular C-H insertion with B-B bond cleavage, or captures BH3 to produce L2B3H6(+). The effect of the counterion stability on the outcome of the reaction is illustrated by formation of LBH2C6F5 complexes through disproportionation of L2B2H5(+) HB(C6F5)3(-) . PMID:26377358

  4. The composition of Saturn's atmosphere at northern temperate latitudes from Voyager IRIS spectra - NH3, PH3, C2H2, C2H6, CH3D, CH4, and the Saturnian D/H isotopic ratio

    NASA Technical Reports Server (NTRS)

    Courtin, R.; Gautier, D.; Marten, A.; Bezard, B.; Hanel, R.

    1984-01-01

    The vertical distributions and mixing ratios of minor constituents in the northern hemisphere of Saturn are investigated. Results are obtained for NH3, PH3, C2H2, C2H6, CH3D, and CH4; the D/H ratio is obtained from the CH4 and CH3D abundances. The NH3 mixing ratio in the upper atmosphere is found to be compatible with the saturated partial pressure. The inferred PH3/H2 ratio of 1.4 + or - 0.8 x 10 to the -6th is higher than the value derived from the solar P/H ratio. The stratospheric C2H2/H2 and C2H6/H2 ratios are, respectively, 2.1 + or - 1.4 x 10 to the -7th and 3.0 + or - 1.1 x 10 to the -6th; the latter decreases sharply below the 20-50 mbar level. The results for CH3D/H2 and CH4/H2 imply an enrichment of Saturn's upper atmosphere in carbon by a factor of at least three over the solar abundance. The interpretation of two NH3 lines in the five-micron window suggests a NH3/H2 ratio at the two bar level below the solar value.

  5. Homocatenation of aluminum: alkane-like structures of Li2Al2 H6 and Li3Al3H8.

    PubMed

    Gish, J Tyler; Popov, Ivan A; Boldyrev, Alexander I

    2015-03-27

    Invited for the cover of this issue is Alexander I. Boldyrev and co-workers at Utah State University. The image depicts the magician who symbolizes a chemist synthesizing molecules of "aluminum homocatenated ethane and propane" based on the idea of electronic transmutation. Read the full text of the article at 10.1002/chem.201500298. PMID:25736330

  6. Oxidative coupling between C(sp(2))-H and C(sp(3))-H bonds of indoles and cyclic ethers/cycloalkanes.

    PubMed

    Yang, Qingjing; Choy, Pui Ying; Wu, Yinuo; Fan, Baomin; Kwong, Fuk Yee

    2016-02-24

    Cross-dehydrogenative-coupling (CDC) between C-H/C-H bonds of indoles and cyclic ethers/cycloalkanes is made viable through a simple transition-metal-free pathway. With the aid of only di-tert-butyl peroxide, a number of inactive cyclic ethers and cycloalkanes can be directly coupled with indole derivatives in satisfactory yields. PMID:26842403

  7. Cross-dehydrogenative coupling of α-C(sp(3))-H of ethers/alkanes with C(sp(2))-H of heteroarenes under metal-free conditions.

    PubMed

    Ambala, Srinivas; Thatikonda, Thanusha; Sharma, Shweta; Munagala, Gurunadham; Yempalla, Kushalava Reddy; Vishwakarma, Ram A; Singh, Parvinder Pal

    2015-12-14

    Here we have developed an effective metal-free dehydrogenative coupling method wherein α-oxyalkyl and alkyl radicals were generated from various ethers and alkanes to undergo coupling with a variety of electron-deficient heteroarenes such as un/substituted iso-quinolones, quinolines, pyridines, pyrazines and pyrimidines. The persulfate-acetone-water system was optimized for the dehydrogenative coupling with cyclic ethers which gave moderate to excellent yields of α-oxyalkyl containing heteroarenes. We have also optimized the conditions for coupling with cyclic alkanes and alicyclic ethers and demonstrated by conducting the reactions with a variety of electron-deficient heteroarenes. Further, the present method is also applicable to electron deficient arenes like naphthoquinones and moreover, it didn't require any external acid. PMID:26419479

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

    NASA Astrophysics Data System (ADS)

    Seguin, A.; Norman, A. L.

    2009-12-01

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

  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. Late Quaternary Climate and Precipitation δ18o Variations over the Tibetan Plateau from Paleoclimate Modeling

    NASA Astrophysics Data System (ADS)

    Ehlers, T. A.; Li, J.; Werner, M.; Mutz, S.; Steger, C.; Paeth, H.; Poulsen, C. J.; Feng, R.

    2014-12-01

    The Himalaya-Tibet orogen hosts some of the largest modern climate gradients on Earth. Quaternary climate change between glacial and interglacial cycles is an important driver for landscape and ecological change in the region. A common observational approach for documenting climate change is the measurement of modern precipitation, and terrestrial archives of, δ18O. In this study, we investigate variations in Mid Holocene (MH) and Last Glacial Maximum (LGM) climate and precipitation δ18O (δ18Op). Paleoclimate model results for 3 time slices are considered including: Pre-industrial, MH and LGM conditions. These experiments bridge spatial and temporal timescales of environmental change over the plateau and provide a means for interpreting observational data sets. Climate and precipitation δ18O (δ18Op) variations over the Plateau are investigated using an atmospheric general circulation model equipped with isotope tracking capabilities (ECHAM5-wiso). Simulations are conducted at a resolution of 1.1°´1.1°, with 31 vertical levels (T106 L31). Pre-industrial boundary conditions come from AMIP2. MH and LGM boundary conditions come from a coupled atmosphere-ocean model ECHO-G, with vegetation cover from PMIP (http://pmip2.lsce.ipsl.fr). Results are presented in comparison to pre-industrial conditions. More specifically, during the MH surface temperatures were ~0.5 C higher on the central and western plateau and ~0.5 C cooler across the Himalaya. Mean annual MH precipitation was <100 mm/yr higher on the plateau and 300-500 mm/yr higher across the Himalaya. MH δ18Op is 1 per mil depleted on the plateau and 1 per mil enriched across the Himalaya. In contrast, during the LGM surface temperatures were ~2-4 C lower across the Himalaya and Tibet. Mean annual LGM precipitation was 200-600 mm/yr lower over the same region, and δ18Op was 2-4 per mil enriched relative to pre-industrial predictions. The causes for the previous δ18Op changes are discussed in the context of

  11. R-matrix description of particle energy spectra produced by low-energy 3H + 3H reactions

    DOE PAGESBeta

    Brune, C. R.; Caggiano, J. A.; Sayre, D. B.; Bacher, A. D.; Hale, G. M.; Paris, M. W.

    2015-07-20

    An R-matrix model for three-body final states is presented and applied to a recent measurement of the neutron energy spectrum from the 3H + 3H→ 2n + α reaction. The calculation includes the n alpha and n n interactions in the final state, angular momentum conservation, antisymmetrization, and the interference between different channels. A good fit to the measured spectrum is obtained, where clear evidence for the 5He ground state is observed. The model is also used to predict the alpha-particle spectrum from 3H + 3H as well as particle spectra from 3He + 3He. The R-matrix approach presented heremore » is very general, and can be adapted to a wide variety of problems with three-body final states.« less

  12. 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.

  13. Cold air incursions, δ18O variability, and monsoon dynamics associated with snow days at Quelccaya Ice Cap, Peru

    NASA Astrophysics Data System (ADS)

    Hurley, John V.; Vuille, Mathias; Hardy, Douglas R.; Burns, Stephen J.; Thompson, Lonnie G.

    2015-08-01

    Quelccaya Ice Cap in the Andes of Peru contains an annually resolved δ18O record covering the past 1800 years; yet atmospheric dynamics associated with snow deposition and δ18O variability at this site are poorly understood. Here we make use of 10 years of snow pit and short core δ18O data and hourly snow-height measurements obtained by an automated weather station deployed at the ice cap's summit to analyze linkages between snowfall, δ18O, and the South American summer monsoon (SASM). Snow accumulation peaks in December and is negative May-September. Snow δ18O values decrease gradually through austral summer from about -17 to -24‰. Surface snow δ18O is altered after deposition during austral winter from about -24 to -15‰. More than 70% of the total snow accumulation is tied to convection along the leading edge of cold air incursions of midlatitude air advected equatorward from southern South America. Snowfall amplitude at Quelccaya Ice Cap varies systematically with regional precipitation, atmospheric dynamics, midtroposphere humidity, and water vapor δD. Strongest snowfall gains correspond with positive precipitation anomalies over the western Amazon Basin, increased humidity, and lowered water vapor δD values, consistent with the "amount effect." We discuss ventilation of the monsoon, modulated by midlatitude cold air advection, as potentially diagnostic of the relationship between SASM dynamics and Quelccaya snowfall. Results will serve as a basis for development of a comprehensive isotopic forward model to reconstruct past monsoon dynamics using the ice core δ18O record.

  14. Influence of Interstellar FUV Radiation on the Abundance Ratio of 13CO to C18O in L 1551

    NASA Astrophysics Data System (ADS)

    Lin, Sheng-Jun; Shimajiri, Yoshito; Hara, Chihomi; Lai, Shih-Ping; Nakamura, Fumitaka; Sugitani, Koji; Kawabe, Ryohei; Kitamura, Yoshimi; Yoshida, Atsushi; Tatei, Hidefumi; Akashi, Toshiya; Tsukagushi, Takashi

    2015-08-01

    To investigate the relationship between the far-ultraviolet (FUV) radiation and the abundance ratios between 13CO and C18O, we observed L 1551 in 12CO (J=1-0), 13CO (J=1-0) and C18O (J=1-0) using the Nobeyama Radio Observatory 45 m telescope with an angular resolution of ~22" (corresponding to 0.017 pc at a distance of 160 pc). L 1551 is chosen because it is relatively isolated in Taurus-Auriga complex, providing an ideal environment for studying the variation of abundance ratio due to the penetration of the FUV photons. L 1551 is a young star-forming region containing at least 6 young protostars between Class I and Class III stages and a quiescent elongated starless core. The distribution of 12CO emission shows the outflows coming from 2 youngest protostars IRS5 and NE. The 13CO and C18O are detected throughout the whole region with enhancement around the outflows and depletion in the outflow cavities. To avoid the influence of outflows, we exclude the outflow regions for X(13CO)/X(C18O) abundance ratio calculation. X(13CO)/X(C18O) is found in the range of 3.2 -- 36.2 with a mean value of 7.6. Comparing to the extinction map derived from Herschel observations, we found that the abundance ratio reaches its maximum at low AV and decreases to typical solar system value of 5.5 within the starless core. The high X(13CO)/X(C18O) value at the low AV value in L 1551 is most likely due to the selective FUV photodissociation of C18O. This is in contrast with Orion-A region where its internal OB stars keep the abundance ratio at a high level greater than ~10.

  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. Partial phase diagram for the system NH3-H2O - The water-rich region

    NASA Technical Reports Server (NTRS)

    Johnson, M. L.; Schwake, A.; Nicol, M.

    1984-01-01

    Phase boundaries of the H2O-NH3 system for (NH3)/x/(H2O)/1-x/ have been determined with diamond-anvil cells for mixtures in two composition ranges: (1) for x in the range from 0 to 0.3, at pressures up to 4 GPa at 21 C, and (2) for x in the range from 0.46 to 0.50, at pressures up to 5 GPa from 150 to 400 K. Phases were identified visually with a microscope and polarized optics. The NH3.2(H2O) phase is strongly anisotropic with a much smaller refractive index than that of ice VII and cracks in two nonperpendicular networks. NH3.H2O has a refractive index closer to that of Ice VII and does not appear to form cracks. Both phases are colorless. Phase boundaries were determined on both increasing and decreasing pressures, and compositions of the ammonia ices were determined by estimating relative amounts of water and ammonia ices at known overall compositions. For low-ammonia compositions (x equal to or less than 0.15), the following assemblages succedd one another as pressure increases: liquid; liquid and Ice VI (at 1.0 + GPa); liquid and Ice VII (at 2.1 GPa); Ice VII and NH3.H2O (at 3.5 GPa). For x in the range from 0.15 to 0.30, the water ice and liquid fields are replaced by the NH3.2(H2O) and liquid field at pressures down to 1.0 GPa and lower.

  17. 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.

  18. States of {sup 15}C via the ({sup 18}O,{sup 16}O) reaction

    SciTech Connect

    Cappuzzello, F.; Carbone, D.; Cavallaro, M.; Cunsolo, A.; Orrigo, S. E. A.; Foti, A.; Rodrigues, M. R. D.

    2010-04-30

    A study of the {sup 15}C states was pursued in 2008 at the Catania INFN-LNS laboratory by the {sup 13}C({sup 18}O,{sup 16}O){sup 15}C reaction at 84 MeV incident energy. The {sup 16}O ejectiles were detected at forward angles by the MAGNEX magnetic spectrometer. The spectra show several known low lying states up to about 7 MeV excitation energy as well as two unknown resonant structures at about 11.4 and 13.5 MeV. The strong excitation of these latter together with the measured width of about 2 MeV FWHM could indicate the presence of collective modes of excitation connected to the transfer of a correlated neutron pair.

  19. Optimised conditions for the synthesis of (17)O and (18)O labelled cholesterol.

    PubMed

    de la Calle Arregui, Celia; Purdie, Jonathan A; Haslam, Catherine A; Law, Robert V; Sanderson, John M

    2016-02-01

    Conditions are described for the preparation of cholesterol with (17)O and (18)O labels from i-cholesteryl methyl ether using minimal amounts of isotopically enriched water. Optimum yields employed trifluoromethanesulfonic acid as catalyst in 1,4-dioxane at room temperature with 5 equivalents of water. An isotopic enrichment >90% of that of the water used for the reaction could be attained. Tetrafluoroboric acid could also be used as catalyst, at the expense of a lower overall reaction yield. Byproducts from the reaction included dicholesteryl ether, methyl cholesteryl ether, compounds formed by ether hydrolysis, and olefins arising from elimination reactions. Reactions in tetrahydrofuran yielded significant amounts of cholesteryl ethers formed by reaction with alcohols arising from hydrolysis of the solvent. PMID:26724708

  20. 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.

  1. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  3. Insolation Gradient Reconciling Early Warming Relative to d18O Terminations

    NASA Astrophysics Data System (ADS)

    Liu, Z.; Herbert, T. D.

    2002-12-01

    Milankovitch theory ‘ that ice-volume is controlled by the insolation at critical latitudes and seasons (65*N) ‘ has been favored for its ability to account for some key features of Pleistocene glaciations. However, one of perplexing mysteries unresolved by this theory is that, about 3 to 1 million years ago, ice sheets varied at almost metronomic 41-ka obliquity cycles, while the 21-ka precessional period is dominant in insolation. Another related problem but not addressed by this theory is that some of climatic proxies suggest an early transition relative to the insolation, resulting in a `causality problem' if insolation is claimed as the external forcing. For example, U-Th dating of some coral reefs, d18O of calcite vein, and sea surface temperature (SST) records have shown that the penultimate transition occurred as early as 135-142 ka ago, whereas the June insolation was below the average before ~133 ka ago. These two puzzles (41-ka variability and timing of transitions) can be resolved if one uses insolation gradients between high and low latitudes, in addition to 65*N insolation alone, as the external driving force of ice ages. The insolation gradient has a strikingly similar distribution of frequency variances to paleoclimatic records (SST and d18O) before the late Pleistocene. One of the insolation gradient minimum, occurring at ~149 ka ago, 10 ka earlier than the insolation minimum, could well explain the early penultimate transition (e.g. SSTs and sea levels). We argue that Pleistocene glaciations are controlled by insolation gradients. Interglacials correspond to stronger insolation gradients, caused by either increasing high-latitude insolation, as Milankovitch theory states, or a reduction in low-latitude insolation which provides less northward atmospheric heat (moisture) transport, as some climate models suggest.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2001-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

    Equilibrium constants for internal isotopic exchange reactions of the type: Ca12C18O16O2+Ca13C16O3↔Ca13C18O16O2+Ca12C16O3 for individual CO 32- groups in the carbonate minerals calcite (CaCO 3), aragonite (CaCO 3), dolomite (CaMg(CO 3) 2), magnesite (MgCO 3), witherite (BaCO 3), and nahcolite (NaHCO 3) are calculated using first-principles lattice dynamics. Calculations rely on density functional perturbation theory (DFPT) with norm-conserving planewave pseudopotentials to determine the vibrational frequencies of isotopically substituted crystals. Our results predict an ˜0.4‰ excess of 13C18O16O22- groups in all studied carbonate minerals at room-temperature equilibrium, relative to what would be expected in a stochastic mixture of carbonate isotopologues with the same bulk 13C/ 12C, 18O/ 16O, and 17O/ 16O ratios. The amount of excess 13C18O16O22- decreases with increasing temperature of equilibration, from 0.5‰ at 0 °C to <0.1‰ at 300 °C, suggesting that measurements of multiply substituted isotopologues of carbonate could be used to infer temperatures of ancient carbonate mineral precipitation and alteration events, even where the δ 18O of coexisting fluids is uncertain. The predicted temperature sensitivity of the equilibrium constant is ˜0.003‰/°C at 25 °C. Estimated equilibrium constants for the formation of 13C18O16O22- are remarkably uniform for the variety of minerals studied, suggesting that temperature calibrations will also be applicable to carbonate minerals not studied here without greatly compromising accuracy. A related equilibrium constant for the reaction: Ca12C18O16O2+Ca12C17O16O2↔Ca12C18O17O16O+Ca12C16O3 in calcite indicates formation of 0.1‰ excess 12C 18O 17O 16O 2- at 25 °C. In a conventional phosphoric acid reaction of carbonate to form CO 2 for mass-spectrometric analysis, molecules derived from 13C18O16O22- dominate (˜96%) the mass 47 signal, and 12C 18O 17O 16O 2- contributes most of the remainder (3%). This suggests

  8. 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

  9. Synthesis and β-glucuronidase inhibitory activity of 2-arylquinazolin-4(3H)-ones.

    PubMed

    Khan, Khalid Mohammed; Saad, Syed Muhammad; Shaikh, Nimra Naveed; Hussain, Shafqat; Fakhri, Muhammad Imran; Perveen, Shahnaz; Taha, Muhammad; Choudhary, Muhammad Iqbal

    2014-07-01

    2-Arylquinazolin-4(3H)-ones 1-25 were synthesized by reacting anthranilamide with various benzaldehydes using CuCl2·2H2O as a catalyst in ethanol under reflux. Synthetic 2-arylquinazolin-4(3H)-ones 1-25 were evaluated for their β-glucuronidase inhibitory potential. A trend of inhibition IC50 against the enzyme in the range of 0.6-198.2μM, was observed and compared with the standard d-saccharic acid 1,4-lactone (IC50=45.75±2.16μM). Compounds 13, 19, 4, 12, 14, 22, 23, 25, 15, 8, 17, 11, 21, 1, 3, 18, 9, 2, and 24 with the IC50 values within the range of 0.6-44.0μM, indicated that the compounds have superior activity than the standard. The compounds showed no cytotoxic effects against PC-3 cells. A structure-activity relationship is established. PMID:24844756

  10. H3(+) + H2 isotopic system at low temperatures: microcanonical model and experimental study.

    PubMed

    Hugo, Edouard; Asvany, Oskar; Schlemmer, Stephan

    2009-04-28

    State-to-state thermal rate coefficients for reactions of all H(3)(+) + H(2) isotopic variants are derived and compared to new experimental data. The theoretical data are also sought for astrochemical modeling of cold environments (<50 K). The rates are calculated on the basis of a microcanonical approach using the Langevin model and the conservation laws of mass, energy, angular momentum, and nuclear spin. Full scrambling of all five nuclei during the collision is assumed for the calculations and alternatively partial dynamical restrictions are considered. The ergodic principle of the collision is employed in two limiting cases, neglecting (weak ergodic limit) or accounting for explicit degeneracies of the reaction mechanisms (strong ergodic limit). The resulting sets of rate coefficients are shown to be consistent with the detailed balance and thermodynamical equilibrium constants. Rate coefficients, k(T), for the deuteration chain of H(3)(+) with HD as well as H(2)D(+)/H(3)(+) equilibrium ratios have been measured in a variable temperature 22-pole ion trap. In particular, the D(2)H(+) + HD --> D(3)(+) + H(2) rate coefficient indicates a change in reaction mechanism when going to higher temperatures. The good overall agreement between experiment and theory encourages the use of the theoretical predictions for astrophysical modeling. PMID:19405574

  11. 2H Stable Isotope Analysis of Tooth Enamel: A Pilot Study

    NASA Astrophysics Data System (ADS)

    Holobinko, Anastasia; Kemp, Helen; Meier-Augenstein, Wolfram; Prowse, Tracy; Ford, Susan

    2010-05-01

    Stable isotope analysis of biogenic tissues such as tooth enamel and bone mineral has become a well recognized and increasingly important method for determining provenance of human remains, and has been used successfully in bioarchaeological studies as well as forensic investigations (Lee-Thorp, 2008; Meier-Augenstein and Fraser, 2008). Particularly, 18O and 2H stable isotopes are well established proxies as environmental indicators of climate (temperature) and source water and are therefore considered as indicators of geographic life trajectories of animals and humans (Hobson et al., 2004; Schwarcz and Walker, 2006). While methodology for 2H analysis of human hair, fingernails, and bone collagen is currently used to determine geographic origin and identify possible migration patterns, studies involving the analysis of 2H in tooth enamel appear to be nonexistent in the scientific literature. The apparent lack of research in this area is believed to have two main reasons. (1) Compared to the mineral calcium hydroxylapatite Ca10(PO4)6(OH)2, in tooth enamel forming bio-apatite carbonate ions replace some of the hydroxyl ions at a rate of one CO32 replacing two OH, yet published figures for the degree of substitution vary (Wopenka and Pasteris, 2005). (2) Most probably due to the aforementioned no published protocols exist for sample preparation and analytical method to obtain δ2H-values from the hydroxyl fraction of tooth enamel. This dilemma has been addressed through a pilot study to establish feasibility of 2H stable isotope analysis of ground tooth enamel by continuous-flow isotope ratio mass spectrometry (IRMS) coupled on-line to a high-temperature conversion elemental analyzer (TC/EA). An array of archaeological and modern teeth has been analyzed under different experimental conditions, and results from this pilot study are being presented. References: Lee-Thorp, J.A. (2008) Archaeometry, 50, 925-950 Meier-Augenstein, W. and Fraser, I. (2008) Science & Justice

  12. 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.

  13. 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).

  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. Laeve-[1-3H]Methadone disposition in tolerant dogs.

    PubMed

    Misra, A L; Bloch, R; Vadlamani, N L; Mulé, S J

    1975-04-01

    1. Following a subcutaneous dose (4mg/kg) of [3H]methadone, peak levels of drug occurred in plasma, tissues and selected areas of the central nervous system (CNS) 2h after injection in both non-tolerant and tolerant dogs. Highest concentrations of methadone were attained in bile and lung compared to other tissues. 2. Levels of methadone in plasma, tissue and CNS of tolerant and non-tolerant animals were not markedly different up to 8h after injection, but a much faster rate of egression of free drug (lower t1/2) was observed subsequently in tolerant dogs. 3. Peak levels of methadone in various areas of the CNS ranged between 2-7 (spinal cord) to 3-6 (thalamus) mug/g in non-tolerant and 3-0 -rebellum) to 4-1 (thalamus) mug/g in tolerant dogs 2h after injection. No marked accumulation of methadone occurred in selected areas of the CNS in spite of the persistence of drug in these areas. 4. The plasma protein electrophoretic profiles did not differ between control, non-tolerant and tolerant dogs. 5. Similar qualitative patterns of metabolites were observed in non-tolerant and tolerant dogs and the development of tolerance did not appear to modify the metabolic pathways of methadone. PMID:1154803

  16. Gas-phase CO depletion and N2H+ abundances in starless cores

    NASA Astrophysics Data System (ADS)

    Lippok, N.; Launhardt, R.; Semenov, D.; Stutz, A. M.; Balog, Z.; Henning, Th.; Krause, O.; Linz, H.; Nielbock, M.; Pavlyuchenkov, Ya. N.; Schmalzl, M.; Schmiedeke, A.; Bieging, J. H.

    2013-12-01

    Context. In the dense and cold interiors of starless molecular cloud cores, a number of chemical processes allow for the formation of complex molecules and the deposition of ice layers on dust grains. Dust density and temperature maps of starless cores derived from Herschel continuum observations constrain the physical structure of the cloud cores better than ever before. We use these to model the temporal chemical evolution of starless cores. Aims: We derive molecular abundance profiles for a sample of starless cores. We then analyze these using chemical modeling based on dust temperature and hydrogen density maps derived from Herschel continuum observations. Methods: We observed the 12CO (2-1), 13CO (2-1), C18O (2-1) and N2H+ (1-0) transitions towards seven isolated, nearby low-mass starless molecular cloud cores. Using far infrared (FIR) and submillimeter (submm) dust emission maps from the Herschel key program Earliest Phases of Star formation (EPoS) and by applying a ray-tracing technique, we derived the physical structure (density, dust temperature) of these cores. Based on these results we applied time-dependent chemical modeling of the molecular abundances. We modeled the molecular emission profiles with a line-radiative transfer code and compared them to the observed emission profiles. Results: CO is frozen onto the grains in the center of all cores in our sample. The level of CO depletion increases with hydrogen density and ranges from 46% up to more than 95% in the core centers of the three cores with the highest hydrogen density. The average hydrogen density at which 50% of CO is frozen onto the grains is 1.1 ± 0.4 × 105 cm-3. At about this density, the cores typically have the highest relative abundance of N2H+. The cores with higher central densities show depletion of N2H+ at levels of 13% to 55%. The chemical ages for the individual species are on average (2 ± 1) × 105 yr for 13CO, (6 ± 3) × 104 yr for C18O, and (9 ± 2) × 104 yr for N2H

  17. Rate Coefficients of C2H with C2H4, C2H6, and H2 from 150 to 359 K

    NASA Technical Reports Server (NTRS)

    Opansky, Brian J.; Leone, Stephen R.

    1996-01-01

    Rate coefficients for the reactions C2H with C2H4, C2H6, and H2 are measured over the temperature range 150-359 K using transient infrared laser absorption spectroscopy. The ethynyl radical is formed by photolysis of C2H2 with a pulsed excimer laser at 193 nm, and its transient absorption is monitored with a color center laser on the Q(sub 11)(9) line of the A(sup 2) Pi-Chi(sup 2) Sigma transition at 3593.68 cm(exp -1). Over the experimental temperature range 150-359 K the rate constants of C2H with C2H4, C2H6, and H2 can be fitted to the Arrhenius expressions k(sub C2H4) = (7.8 +/- 0.6) x 10(exp -11) exp[(134 +/- 44)/T], k(sub C2H6) = (3.5 +/- 0.3) x 10(exp -11) exp[(2.9 +/- 16)/T], and k(sub H2) = (1.2 +/- 0.3) x 10(exp -11) exp[(-998 +/- 57)]/T cm(exp 3) molecule(exp -1) sec(exp -1). The data for C2H with C2H4 and C2H6 indicate a negligible activation energy to product formation shown by the mild negative temperature dependence of both reactions. When the H2 data are plotted together with the most recent high-temperature results from 295 to 854 K, a slight curvature is observed. The H2 data can be fit to the non-Arrhenius form k(sub H2) = 9.2 x 10(exp -18) T(sup 2.17 +/- 0.50) exp[(-478 +/- 165)/T] cm(exp 3) molecules(exp -1) sec(exp -1). The curvature in the Arrhenius plot is discussed in terms of both quantum mechanical tunneling of the H atom from H2 to the C2H radical and bending mode contributions to the partition function.

  18. 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.

  19. 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

  20. 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

  1. Quantitation of methadone enantiomers in humans using stable isotope-labeled (2H3)-, (2H5)-, and (2H8)Methadone

    SciTech Connect

    Nakamura, K.; Hachey, D.L.; Kreek, M.J.; Irving, C.S.; Klein, P.D.

    1982-01-01

    A new technique for simultaneous stereoselective kinetic studies of methadone enantiomers was developed using three deuterium-labeled forms of methadone and GLC-chemical-ionization mass spectrometry. A racemic mixture (1:1) of (R)-(-)-(2H5)methadone (l-form) and (S)-(R)-(2H3)methadone (d-form) was administered orally in place of a single daily dose of unlabeled (+/-)-(2H0)methadone in long-term maintenance patients. Racemic (+/-)-(2H8)methadone was used as an internal standard for the simultaneous quantitation of (2H0)-, (2H3)-, and (2H5)methadone in plasma and urine. A newly developed extraction procedure, using a short, disposable C18 reversed-phase cartridge and improved chemical-ionization procedures employing ammonia gas, resulted in significant reduction of the background impurities contributing to the ions used for isotopic abundance measurements. These improvements enabled the measurement of labeled plasma methadone levels for 120 hr following a single dose. This methodology was applied to the study of methadone kinetics in two patients; in both patients, the analgesically active l-enantiomer of the drug had a longer plasma elimination half-life and a smaller area under the plasma disappearance curve than did the inactive d-form.

  2. Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298K

    NASA Technical Reports Server (NTRS)

    Thorn, R. Peyton, Jr.; Payne, Walter A., Jr.; Chillier, Xavier D. F.; Stief, Louis J.; Nesbitt, Fred L.; Tardy, D. C.

    2000-01-01

    The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 < |CH3|(sub 0)/|C2H3|(sub 0) < 21. The overall rate coefficient was determined to be k1(298 K) = (1.02 +/- 0.53)x10(exp -10) cubic cm/molecule/s with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100-300 Torr He) and to a very recent study at low pressure (0.9-3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.

  3. Adiabatic hyperspherical study of weakly bound He(2)H(-), He(2)H, and HeH(2) systems.

    PubMed

    Suno, Hiroya

    2010-06-14

    The He(2)H(-), He(2)H, and HeH(2) triatomic systems are studied using the adiabatic hyperspherical representation. By adopting the best empirical interaction potentials, we search for weakly bound states of (4)He(2) H(-), (4)He(2) H, and (4)HeH(2). We consider not only zero total nuclear orbital angular momentum, J=0, states but also J>0 states. We find no bound state for the (4)He(2) H systems, while the (4)He(2) H(-) and (4)HeH(2) systems are shown to possess three and one bound states, respectively, for J(Pi)=0(+). Interestingly, one bound state has been found each for the J(Pi)=1(-) and 2(+) symmetries of the (4)He(2) H(-) anion. We shall calculate the bound state energies and analyze the molecular structure of these species in detail. PMID:20550401

  4. Direct measurements of rate constants for the reactions of CH3 radicals with C2H6, C2H4, and C2H2 at high temperatures.

    PubMed

    Peukert, S L; Labbe, N J; Sivaramakrishnan, R; Michael, J V

    2013-10-10

    The shock tube technique has been used to study the reactions CH3 + C2H6 → C2H4 + CH4 + H (1), CH3 + C2H4 → Products + H (2), and CH3 + C2H2 → Products + H (3). Biacetyl, (CH3CO)2, was used as a clean high temperature thermal source for CH3-radicals for all the three reactions studied in this work. For reaction 1, the experiments span a T-range of 1153 K ≤ T ≤ 1297 K, at P ~ 0.4 bar. The experiments on reaction 2 cover a T-range of 1176 K ≤ T ≤ 1366 K, at P ~ 1.0 bar, and those on reaction 3 a T-range of 1127 K ≤ T ≤ 1346 K, at P ~ 1.0 bar. Reflected shock tube experiments performed on reactions 1-3, monitored the formation of H-atoms with H-atom Atomic Resonance Absorption Spectrometric (ARAS). Fits to the H-atom temporal profiles using an assembled kinetics model were used to make determinations for k1, k2, and k3. In the case of C2H6, the measurements of [H]-atoms were used to derive direct high-temperature rate constants, k1, that can be represented by the Arrhenius equation k1(T) = 5.41 × 10(-12) exp(-6043 K/T) cm(3) molecules(-1) s(-1) (1153 K ≤ T ≤ 1297 K) for the only bimolecular process that occurs, H-atom abstraction. TST calculations based on ab initio properties calculated at the CCSD(T)/CBS//M06-2X/cc-pVTZ level of theory show excellent agreement, within ±20%, of the measured rate c