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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

    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.

  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

    DOEpatents

    Smith, Brian; Menchaca, Leticia

    1999-01-01

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

  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. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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).

  11. 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

  12. Isoscapes of δ18O and δ2H reveal climatic forcings on Alaska and Yukon precipitation

    NASA Astrophysics Data System (ADS)

    Lachniet, Matthew S.; Lawson, Daniel E.; Stephen, Haroon; Sloat, Alison R.; Patterson, William P.

    2016-08-01

    Spatially extensive Arctic stable isotope data are sparse, inhibiting the climatic understanding required to interpret paleoclimate proxy records. To fill this need, we constrained the climatic and physiographic controls on δ18O and δD values of stream waters across Alaska and the Yukon to derive interpolated isoscape maps. δ18O is strongly correlated to winter temperature parameters and similarity of the surface water line (δ2H = 8.0 × δ18O + 6.4) to the Global Meteoric Water Line suggests stream waters are a proxy for meteoric precipitation. We observe extreme orographic δ18O decreases and a trans-Alaskan continental gradient of -8.3‰ 1000 km-1. Continental gradients are high in coastal zones and low in the interior. Localized δ18O increases indicate inland air mass penetration via topographic lows. Using observed δ18O/temperature gradients, we show that δ18O decreases in a ˜24 ka permafrost ice wedge relative to the late Holocene indicate mean annual and coldest quarter temperature reductions of 8.9 ± 1.7°C and 17.2 ± 3.2°C, respectively.

  13. 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

  14. Infrared Predissociation Spectroscopy of the Hydrocarbon Cations C_3H^+, C_2H^+, and C_3H_2^+

    NASA Astrophysics Data System (ADS)

    Brünken, Sandra; Lipparini, Filippo; Gauss, Jürgen; Stoffels, Alexander; Redlich, Britta; van der Meer, Lex; Berden, Giel; Oomens, Jos; Schlemmer, Stephan

    2016-06-01

    Reactive hydrocarbon cations play an important role in the astrochemistry of the interstellar medium, but spectroscopic data, needed for their identification in astronomical observations, is sparse. Here we report the first gas-phase vibrational spectra of the linear C_3H^+ (^1 Σ), the radical cation C_2H^+ (^3 Π), and the linear-/cyclic-C_3H_2^+ (^2 Π /^2A_1, resp.). Broadband spectra were recorded by Ne- and He-messenger infrared-predissociation (IR-PD) action spectroscopy in a cryogenic (4-11 K) ion trap instrument (FELion) in the 250-3500 {wn} range using a free electron laser and a MIR-OPO at the FELIX (Free-Electron Laser for Infrared eXperiments) laboratory. The band positions (determined with a precision of 1-2 wn) covering the C-H and C-C stretching as well as several bending modes are compared to high-level (CCSD(T) with large basis sets) quantum-chemical calculations with an emphasis on anharmonic effects and on the influence of the rare-gas messenger atom. The experimental and theoretical data provide a solid basis for subsequent IR high-resolution studies, with the ultimate goal to predict and measure accurate rotational spectra for a radio-astronomical search of these molecular ions in space.

  15. 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

  16. 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

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

    PubMed Central

    Herskowitz, Lawrence J.; Koch, Steven J.

    2014-01-01

    We show for the first time the effects of heavy-hydrogen water (2H2O) and heavy-oxygen water (H218O) on the gliding speed of microtubules on kinesin-1 coated surfaces. Increased fractions of isotopic waters used in the motility solution decreased the gliding speed of microtubules by a maximum of 21% for heavy-hydrogen and 5% for heavy-oxygen water. We also show that gliding microtubule speed returns to its original speed after being treated with heavy-hydrogen water. We discuss possible interpretations of these results and the importance for future studies of water effects on kinesin and microtubules. We also discuss the implication for using heavy waters in biomolecular devices incorporating molecular motors. PMID:24711961

  18. Spring response to precipitation events using δ(18)O and δ(2)H in the Tanour catchment, NW Jordan.

    PubMed

    Hamdan, Ibraheem; Wiegand, Bettina; Toll, Mathias; Sauter, Martin

    2016-12-01

    The Tanour spring is one of the several karst springs located in the northern part of Jordan. Water samples from the Tanour spring and precipitation were collected in the area of Ajloun in NW Jordan for the analysis of stable oxygen and hydrogen isotopes to evaluate the spring response to precipitation events. Rainwater and snow samples were collected from different elevations during winters of 2013-2014 and 2014-2015. In addition, spring samples were collected between December 2014 and March 2015. δ(18)O values in rainwater vary from -3.26 to -17.34 ‰ (average: -7.84 ± 3.23 ‰), while δ(2)H values range between -4.4 and -110.4 ‰ (average: -35.7 ± 25.0 ‰). Deuterium excess ranges from 17.8 to 34.1 ‰ (average: 27.1 ± 4.0 ‰). The Local Meteoric Water Line for the study area was calculated to be δ(2)H = 7.66*δ(18)O + 24.43 (R(2) = 0.98). Pre-event spring discharge showed variation in δ(18)O (range -6.29 to -7.17 ‰; average -6.58 ± 0.19 ‰) and δ(2)H values (range -28.8 to -32.7 ‰; average: -30.5 ± 1.0 ‰). In contrast, δ(18)O and δ(2)H rapidly changed to more negative values during rainfall and snowmelt events and persisted for several days before returning to background values. Spring water temperature, spring discharge, and turbidity followed the trend in isotopic composition during and after the precipitation events. The rapid change in the isotopic composition, spring discharge, water temperature, and turbidity in response to recharge events is related to fast water travel times and low storage capacity in the conduit system of the karst aquifer. Based on the changes in the isotopic composition of spring water after the precipitation events, the water travel time in the aquifer is in the order of 5-11 days.

  19. 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

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

    PubMed

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

    2012-06-01

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

  1. Seawater intrusion into groundwater aquifer through a coastal lake - complex interaction characterised by water isotopes (2)H and (18)O.

    PubMed

    Gemitzi, Alexandra; Stefanopoulos, Kyriakos; Schmidt, Marie; Richnow, Hans H

    2014-01-01

    The present study investigates the complex interactions among surface waters, groundwaters and a coastal lake in northeastern Greece, using their stable isotopic composition (δ(18)O, δ(2)H) in combination with hydrogeological and hydrochemical data. Seasonal and spatial trends of water isotopes were studied and revealed that all water bodies in the study area interact. It was also shown that the aquifer's increased salinity is not due to fossil water from past geological periods, but is attributed to brackish lake water intrusion into the aquifer induced by the extensive groundwater pumping for irrigation purposes. Quantification of the contribution of the lake to the aquifer was achieved using the simple dilution formula. The isotopic signatures of the seawater and the groundwaters are considerably different, so there is a very little possibility of direct seawater intrusion into the aquifer.

  2. 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.

  3. 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).

  4. 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.

  5. 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

  6. Frequency Comb Assisted IR Measurements of H_3^+, H_2D^+ and D_2H^+ Transitions

    NASA Astrophysics Data System (ADS)

    Jusko, Pavol; Asvany, Oskar; Schlemmer, Stephan

    2016-06-01

    We present recent measurements of the fundamental transitions of H_3^+, H_2D^+ and D_2H^+ in a 4 K 22-pole trap by action spectroscopic techniques. Either Laser Induced Inhibition of Cluster Growth (He attachment at T≈4 K), endothermic reaction of H_3^+ with O_2, or deuterium exchange has been used as measurement scheme. We used a 3 μm optical parametric oscillator coupled to a frequency comb in order to achieve accuracy generally below 1 MHz. Five transitions of H_3^+, eleven of H_2D^+ and ten of D_2H^+ were recorder in our spectral range. We compare our H_3^+ results with two previous frequency comb assisted works. Moreover, accurate determination of the frequency allows us to predict pure rotational transitions for H_2D^+ and D_2H^+ in the THz range. P. Jusko, C. Konietzko, S. Schlemmer, O. Asvany, J. Mol. Spec. 319 (2016) 55 O. Asvany, S. Brünken, L. Kluge, S. Schlemmer, Appl. Phys. B 114 (2014) 203 O. Asvany, J. Krieg, S. Schlemmer, Rev. Sci. Instr. 83 (2012) 093110 J.N. Hodges, A.J. Perry, P.A. Jenkins, B.M. Siller, B.J. McCall, J. Chem. Phys. 139 (2013) 164201 H.-C. Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, J.-T. Shy, Phys. Rev. Lett. 109 (2012) 263002

  7. a Rotational Study of 2H-3H-PERFLUOROPENTANE and its Isotopologues

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

    The chirped pulse Fourier transform microwave spectrum of 2H-3H-perfluoropentane has been observed and assigned. Given a racemic mixture sample of the four available structural isomers, only the (S,S) structure was observed in the broadband spectrum. Attempts at observing the 13C isotopologues on a Balle-Flygare cavity type spectrometer and their assignments will be discussed, along with an examination of the theoretical predictions for the structure and rotational constants of the molecule against their experimental values. Structural results of the monomer will also be compared with those of the helical structure of C2 perfluoropentane. Joseph A. Fournier, Robert K. Bohn, John A. Montgomery Jr., Masao Onda. J. Phys. Chem. 114 (1118), 2010.

  8. Leaf water (18) O and (2) H enrichment along vertical canopy profiles in a broadleaved and a conifer forest tree.

    PubMed

    Bögelein, Rebekka; Thomas, Frank M; Kahmen, Ansgar

    2017-01-01

    Distinguishing meteorological and plant-mediated drivers of leaf water isotopic enrichment is prerequisite for ecological interpretations of stable hydrogen and oxygen isotopes in plant tissue. We measured input and leaf water δ(2) H and δ(18) O as well as micrometeorological and leaf morpho-physiological variables along a vertical gradient in a mature angiosperm (European beech) and gymnosperm (Douglas fir) tree. We used these variables and different enrichment models to quantify the influence of Péclet and non-steady state effects and of the biophysical drivers on leaf water enrichment. The two-pool model accurately described the diurnal variation of leaf water enrichment. The estimated unenriched water fraction was linked to leaf dry matter content across the canopy heights. Non-steady state effects and reduced stomatal conductance caused a higher enrichment of Douglas fir compared to beech leaf water. A dynamic effect analyses revealed that the light-induced vertical gradients of stomatal conductance and leaf temperature outbalanced each other in their effects on evaporative enrichment. We conclude that neither vertical canopy gradients nor the Péclet effect is important for estimates and interpretation of isotopic leaf water enrichment in hypostomatous trees. Contrarily, species-specific non-steady state effects and leaf temperatures as well as the water vapour isotope composition need careful consideration.

  9. 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

  10. Nqrs Data for C3H12INO7 [C3H7NO2·HIO3·2(H2O)] (Subst. No. 0646)

    NASA Astrophysics Data System (ADS)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C3H12INO7 [C3H7NO2·HIO3·2(H2O)] (Subst. No. 0646)

  11. 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.

  12. 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.

  13. 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).

  14. 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.

  15. 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.

  16. 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.

    2016-04-25

    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.

  17. 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.

  18. Ab initio study of {sup 2}H(d,{gamma}){sup 4}He, {sup 2}H(d,p){sup 3}H, and {sup 2}H(d,n){sup 4}He reactions and the tensor force

    SciTech Connect

    Arai, K.; Aoyama, S.; Suzuki, Y.; Descouvemont, P.; Baye, D.

    2012-11-12

    The {sup 2}H(d,p){sup 3}H, {sup 2}H(d,n){sup 3}He, and {sup 2}H(d,{gamma}){sup 4}He reactions at low energies are studied with realistic nucleon-nucleon interactions in an ab initio approach. The obtained astrophysical S-factors are all in very good agreement with experiment. The most important channels for both transfer and radiative capture are all found to dominate thanks to the tensor force.

  19. USGS48 Puerto Rico precipitation - A new isotopic reference material for δ2H and δ18O measurements of water

    USGS Publications Warehouse

    Qi, Haiping; Coplen, Tyler B.; Tarbox, Lauren V.; Lorenz, Jennifer M.; Scholl, Martha A.

    2014-01-01

    A new secondary isotopic reference material has been prepared from Puerto Rico precipitation, which was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material, designated as USGS48, is intended to be one of two 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 δ2H and δ18O values of this reference water are−2.0±0.4 and−2.224±0.012 ‰, respectively, relative to Vienna Standard Mean Ocean Water on scales normalised such that the δ2H and δ18O values of Standard Light Antarctic Precipitation reference water are−428 and−55.5 ‰, respectively. 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. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule.

  20. 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.

  1. Ligand-promoted alkylation of C(sp3)-H and C(sp2)-H bonds.

    PubMed

    Zhu, Ru-Yi; He, Jian; Wang, Xiao-Chen; Yu, Jin-Quan

    2014-09-24

    9-Methylacridine was identified as a generally effective ligand to promote a Pd(II)-catalyzed C(sp(3))-H and C(sp(2))-H alkylation of simple amides with various alkyl iodides. This alkylation reaction was applied to the preparation of unnatural amino acids and geometrically controlled tri- and tetrasubstituted acrylic acids.

  2. Photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 in the VUV region

    NASA Technical Reports Server (NTRS)

    Xia, T. J.; Chien, T. S.; Wu, C. Y. Robert; Judge, D. L.

    1991-01-01

    Using synchrotron radiation as a continuum light source, the photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 have been measured from their respective ionization thresholds to 1060 A. The vibrational constants associated with the nu(2) totally symmetric, out-of-plane bending vibration of the ground electronic state of PH3(+) have been obtained. The cross sections and quantum yields for producing neutral products through photoexcitation of these molecules in the given spectral regions have also been determined. In the present work, autoionization processes were found to be less important than dissociation and predissociation processes in NH3, PH3, and C2H4. Several experimental techniques have been employed in order to examine the various possible systematic errors critically.

  3. 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.

  4. 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.

  5. Simultaneous analysis of 17O/16O, 18O/16O and 2H/1H of gypsum hydration water by cavity ring‐down laser spectroscopy

    PubMed Central

    Mather, Ian; Rolfe, James; Evans, Nicholas P.; Herwartz, Daniel; Staubwasser, Michael; Hodell, David A.

    2015-01-01

    Rationale The recent development of cavity ring‐down laser spectroscopy (CRDS) instruments capable of measuring 17O‐excess in water has created new opportunities for studying the hydrologic cycle. Here we apply this new method to studying the triple oxygen (17O/16O, 18O/16O) and hydrogen (2H/1H) isotope ratios of gypsum hydration water (GHW), which can provide information about the conditions under which the mineral formed and subsequent post‐depositional interaction with other fluids. Methods We developed a semi‐automated procedure for extracting GHW by slowly heating the sample to 400°C in vacuo and cryogenically trapping the evolved water. The isotopic composition (δ17O, δ18O and δ2H values) of the GHW is subsequently measured by CRDS. The extraction apparatus allows the dehydration of five samples and one standard simultaneously, thereby increasing the long‐term precision and sample throughput compared with previous methods. The apparatus is also useful for distilling brines prior to isotopic analysis. A direct comparison is made between results of 17O‐excess in GHW obtained by CRDS and fluorination followed by isotope ratio mass spectrometry (IRMS) of O2. Results The long‐term analytical precision of our method of extraction and isotopic analysis of GHW by CRDS is ±0.07‰ for δ17O values, ±0.13‰ for δ18O values and ±0.49‰ for δ2H values (all ±1SD), and ±1.1‰ and ±8 per meg for the deuterium‐excess and 17O‐excess, respectively. Accurate measurement of the 17O‐excess values of GHW, of both synthetic and natural samples, requires the use of a micro‐combustion module (MCM). This accessory removes contaminants (VOCs, H2S, etc.) from the water vapour stream that interfere with the wavelengths used for spectroscopic measurement of water isotopologues. CRDS/MCM and IRMS methods yield similar isotopic results for the analysis of both synthetic and natural gypsum samples within analytical error of the two methods. Conclusions We

  6. 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.

  7. 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.

  8. 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. 

  9. 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.

  10. 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

  11. Abstraction and addition kinetics of C2H radicals with CH4, C2H6, C3H8, C2H4, and C3H6: CVT/SCT/ISPE and hybrid meta-DFT methods.

    PubMed

    Dash, Manas Ranjan; Rajakumar, B

    2015-02-07

    Rate coefficients for the reactions of C2H radicals with methane (k1), ethane (k2), propane (k3), ethylene (k4), and propylene (k5) were computed using canonical variational transition state theory (CVT) coupled with hybrid-meta density functional theory (DFT) over a wide range of temperatures from 150 to 5000 K. The quantum chemical tunneling effect was corrected by the small curvature tunneling (SCT) method. The dynamic calculations are performed using the variational transition state theory (VTST) with the interpolated single-point energies (ISPE) method at the CCSD(T)/cc-pVTZ//M06-2X/6-31+G(d,p) level of theory. Intrinsic reaction coordinate (IRC) calculations were performed to verify that the transition states are connected to the reactants and products. The rate coefficients obtained over the studied temperature range yield the following Arrhenius expressions (cm(3) molecule(-1) s(-1)): k1 = 4.69 × 10(-19)T(2.44) exp[331/T], k2 = 4.29 × 10(-17)T(2.11) exp[432/T], k3 = 4.81 × 10(-17)T(1.98) exp[697/T], k4 = 7.54 × 10(-21)T(2.96) exp[1942/T], and k5 = 8.04 × 10(-23)T(3.44) exp[3011/T] cm(3) molecule(-1) s(-1). Branching ratio calculation for the reactions of C2H radicals with ethylene and propylene shows that the abstraction reactions are not important at lower temperatures. However, as the temperature increases, abstraction reactions become more important.

  12. 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

  13. 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).

  14. Autonomous Instrumentation for Fast, Continuous and Accurate Isotopic Measurements of Water Vapor (δ18O, δ 2H, H2O) in the Field

    NASA Astrophysics Data System (ADS)

    Liem, J. S.; Dong, F.; Owano, T. G.; Baer, D. S.

    2010-12-01

    Stable isotopes of water vapor are powerful tracers to investigate the hydrological cycle and ecological processes. Therefore, continuous, in-situ and accurate measurements of δ18O and δ2H are critical to advance the understanding of water-cycle dynamics worldwide. Furthermore, the combination of meteorological techniques and high-frequency isotopic water measurements can provide detailed time-resolved information on the eco-physiological performance of plants and enable improved understanding of water fluxes at ecosystem scales. In this work, we present recent development and field deployment of a novel Water Vapor Isotope Measurement System (WVIMS) capable of simultaneous in situ measurements of δ18O and δ2H and water mixing ratio (H2O) with high precision, accuracy and speed (up to 10 Hz measurement rate). The WVIMS consists of an Analyzer (Water Vapor Isotope Analyzer), based on cavity enhanced laser absorption spectroscopy, and a Standard Source (Water Vapor Isotope Standard Source), based on quantitative evaporation of a liquid water standard (with known isotopic content), and operates in a dual-inlet configuration. The WVIMS automatically controls the entire sample and data collection, data analysis and calibration process to allow for continuous, autonomous unattended long-term operation. The WVIMS has been demonstrated for accurate (i.e. fully calibrated) measurements ranging from 500 ppmv (typical of arctic environments) to over 30,000 ppmv (typical of tropical environments) in air. Dual-inlet operation, which involves regular calibration with isotopic water vapor reference standards, essentially eliminates measurement drift, ensures data reliability, and allows operation over an extremely wide ambient temperature range (5-45C). This presentation will include recent measurements recorded using the WVIMS in plant growth chambers and in arctic environments. The availability of this new instrumentation provides new opportunities for detailed continuous

  15. Groundwater discharge and hydrologic partition of the lakes in desert environment: Insights from stable 18O/2H and radium isotopes

    NASA Astrophysics Data System (ADS)

    Luo, Xin; Jiao, Jiu Jimmy; Wang, Xu-sheng; Liu, Kun; Lian, Ergang; Yang, Shouye

    2017-03-01

    Studies of isotope characteristics of lake water in a desert can provide important information on groundwater discharge and hydrologic partition of the lakes in the desert. This paper presents the investigation of 18O and 2H stable isotopes and radiogenic radium of different water endmembers in three representative lakes of Badain-E, Badain-W and Sumujilin-S in the Badain Jaran Desert (BJD), the fourth largest desert in the world. A stable 18O and 2H isotopic buildup model is constructed to classify the hydrologic conditions of the desert lakes by estimating the ratio between groundwater discharge rate (Fin) and lake surface evaporation (E). Then the radium mass balance models are developed to quantify Fin. Based on the obtained Fin/E and Fin, Badain-E, Badain-W and Sumujilin-S are classified as flowing through, terminal and desiccating lakes, respectively, and their hydrologic partition is obtained. The groundwater discharge rate of Badain-E, Badain-W and Sumujilin-S, is estimated to be 8-10 mm d-1, 4-5 mm d-1, and 7-8 mm d-1, respectively. The total groundwater discharge to the lake areas in the BJD is about 1.68 × 105 m3 d-1. The flow-through condition explains the existence of the fresh lakes, while the terminal and desiccating conditions lead to the lake salinization over time. This study represents the first attempt to couple both stable and radium isotopic approaches to investigate the groundwater discharge and hydrologic partition of desert lakes in the BJD and is instructional to lake studies in other deserts in the world.

  16. Tensor Force Manifestations in Ab Initio Study of the {sup 2}H(d,{gamma}){sup 4}He, {sup 2}H(d,p){sup 3}H, and {sup 2}H(d,n){sup 3}He Reactions

    SciTech Connect

    Arai, K.; Aoyama, S.; Suzuki, Y.; Descouvemont, P.; Baye, D.

    2011-09-23

    The {sup 2}H(d,p){sup 3}H, {sup 2}H(d,n){sup 3}He, and {sup 2}H(d,{gamma}){sup 4}He reactions are studied at low energies in a multichannel ab initio model that takes into account the distortions of the nuclei. The internal wave functions of these nuclei are given by the stochastic variational method with the AV8{sup '} realistic interaction and a phenomenological three-body force included to reproduce the two-body thresholds. The obtained astrophysical S factors are all in very good agreement with the experiment. The most important channels for both transfer and radiative capture are identified by comparing to calculations with an effective central force. They are all found to dominate thanks to the tensor force.

  17. 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

  18. Syntheses of (3) H-labeled, (14) C-labeled, and (2) H4 -labeled SCH 444877, phosphodiesterase type 5 inhibitors.

    PubMed

    Ren, Sumei; Hesk, David; McNamara, Paul; Koharski, David; Hendershot, Sharon

    2013-01-01

    The syntheses of [(3) H]SCH 444877, [(2) H4 ]SCH 444877, and [(14) C]SCH 444877 are described. [(3) H]SCH 444877 was prepared in three steps from tritium gas. [(2) H4 ]SCH 444877 was synthesized from [(2) H4 ]ethanolamine in four steps with an overall yield of 40%. [(14) C]SCH 444877 was prepared from barium [(14) C]cyanamide in 10 steps with an overall yield of 8.1%.

  19. Long-Term Precipitation Isotope Ratios (δ18O, δ2H, d-excess) in the Northeast US Reflect Atlantic Ocean Warming and Shifts in Moisture Sources

    NASA Astrophysics Data System (ADS)

    Puntsag, T.; Welker, J. M.; Mitchell, M. J.; Klein, E. S.; Campbell, J. L.; Likens, G.

    2014-12-01

    The global water cycle is exhibiting dramatic changes as global temperatures increase resulting in increases in: drought extremes, flooding, alterations in storm track patterns with protracted winter storms, and greater precipitation variability. The mechanisms driving these changes can be difficult to assess, but the spatial and temporal patterns of precipitation water isotopes (δ18O, δ2H, d-excess) provide a means to help understand these water cycle changes. However, extended temporal records of isotope ratios in precipitation are infrequent, especially in the US. In our study we analyzed precipitation isotope ratio data from the Hubbard Brook Experimental Forest in New Hampshire that has the longest US precipitation isotope record, to determine: 1) the monthly composited averages and trends from 1967 to 2012 (45 years); ; 2) the relationships between abiotic properties such as local temperatures, precipitation type, storm tracks and isotope ratio changes; and 3) the influence of regional shifts in moisture sources and/or changes in N Atlantic Ocean water conditions on isotope values. The seasonal variability of Hubbard Brook precipitation isotope ratios is consistent with other studies, as average δ18O values are ~ -15‰ in January and ~ -5 ‰ in July. However, over the 45 year record there is a depletion trend in the δ 18O values (becoming isotopically lighter with a greater proportion of 16O), which coupled with less change in δ 2H leads to increases in d-excess values from ~ -10‰ around 1970 to greater than 10‰ in 2009. These changes occurred during a period of warming as opposed to cooling local temperatures indicating other processes besides temperature are controlling long-term water isotope traits in this region. We have evidence that these changes in precipitation isotope traits are controlled in large part by an increases in moisture being sourced from a warming N Atlantic Ocean that is providing evaporated, isotopically

  20. 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

  1. Observation of enhanced rate coefficients in the H2 + + H 2 → H3 + + H reaction at low collision energies

    NASA Astrophysics Data System (ADS)

    Allmendinger, Pitt; Deiglmayr, Johannes; Höveler, Katharina; Schullian, Otto; Merkt, Frédéric

    2016-12-01

    The energy dependence of the rate coefficient of the H2 + + H 2 → H3 + + H reaction has been measured in the range of collision energies between k B ṡ 10 K and k B ṡ 300 mK . A clear deviation of the rate coefficient from the value expected on the basis of the classical Langevin-capture behavior has been observed at collision energies below k B ṡ 1 K , which is attributed to the joint effects of the ion-quadrupole and Coriolis interactions in collisions involving ortho-H2 molecules in the j = 1 rotational level, which make up 75% of the population of the neutral H2 molecules in the experiments. The experimental results are compared to very recent predictions by Dashevskaya et al. [J. Chem. Phys. 145, 244315 (2016)], with which they are in agreement.

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. Synthesis of 3H, 13C,2H3,15N and 14C-labelled SCH 466036, a histamine 3 receptor antagonist.

    PubMed

    Hesk, D; Borges, S; Dumpit, R; Hendershot, S; Koharski, D; Lavey, C; McNamara, P; Voronin, K

    2015-02-01

    The synthesis of [(3)H]SCH 466036, [Me-(3)H3]SCH 466036, [(13)C,(2)H3,(15)N]SCH 466036 and [(14)C]SCH 466036 is described. [(3)H]SCH 466036 was prepared in two steps via Raney Ni-catalysed exchange with tritiated water. [Me-(3)H3]SCH 466036 was prepared in a single step from [(3)H]methyl iodide in 45% yield. [(13)C,(2)H3,(15)N]SCH 466036 was prepared in two steps from [(15)N]hydroxylamine and [(13)C,(2)H3]methyl iodide with an overall yield of 16%. [(14)C]SCH 466036 was prepared in seven steps from [(14)C]potassium cyanide in an overall yield of 13%.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. The δ(18) O and δ(2) H of water in the leaf growth-and-differentiation zone of grasses is close to source water in both humid and dry atmospheres.

    PubMed

    Liu, Hai Tao; Schäufele, Rudi; Gong, Xiao Ying; Schnyder, Hans

    2017-04-03

    The oxygen and hydrogen isotope composition of water in the leaf growth-and-differentiation zone, LGDZ, (δ(18) OLGDZ , δ(2) HLGDZ ) of grasses influences the isotopic composition of leaf cellulose (oxygen) and wax (hydrogen) - important for understanding (paleo)environmental and physiological information contained in these biological archives - but is presently unknown. This work determined δ(18) OLGDZ and δ(2) HLGDZ , (18) O- and (2) H-enrichment of LGDZ (∆(18) OLGDZ and ∆(2) HLGDZ ), and the (18) O- and (2) H-enrichment of leaf blade water (∆(18) OLW, ∆(2) HLW ) in two C3 and three C4 grasses grown at high and low vapor pressure deficit (VPD). The proportion of unenriched water (px ) in the LGDZ ranged from 0.9 to 1.0 for (18) O and 1.0 to 1.2 for (2) H. VPD had no effect on the proportion of (18) O- and (2) H-enriched water in the LGDZ, and species effects were small or nonsignificant. Deuterium discrimination caused depletion of (2) H in LGDZ water, increasing (apparent) px -values > 1.0 in some cases. The isotopic composition of water in the LGDZ was close to that of source water, independent of VPD and much less enriched than previously supposed, but similar to reported xylem water in trees. The well-constrained px will be useful in future investigations of oxygen and hydrogen isotopic fractionation during cellulose and wax synthesis, respectively.

  12. Measuring fast variations of δ^{18}O and δ^2H in atmospheric water vapour using laser spectroscopy: an instrument inter-comparison and characterisation study

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

    Fast variations of stable water isotopes in water vapour have become measurable lately using novel laser spectroscopic techniques. This allows us to perform process-based investigations of the atmospheric water cycle at the time scales of significant weather events. An important prerequisite for such studies implying automatic field measurements lasting for several weeks or even months is a detailed knowledge about sources of uncertainty and instrument properties. We present 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 Resarch). The old versions (L1115-i, WVIA) and the new versions (L2130-i, WVIA-EP) of both systems were tested. The uncertainty components of the measurements were assessed in laboratory experiments, focussing on 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. Knowledge from our laboratory experiments was used to setup a one-week field campaign for comparing measurements of the ambient isotope signals from the L1115-i and WVIA systems. The optimal calibration strategy determined for both instruments was applied as well as the correction functions for water vapour mixing ratio effects. Using this field measurement data we address the question of how well the deuterium excess (d=δ2H-8δ18O) of atmospheric water vapour can be determined with laser spectroscopy. The deuterium excess is an interesting parameter for process-based atmospheric water cycle studies, which depends on humidity and temperature conditions at source location of water vapour. Up to now only very few high-time-resolution measurements of deuterium excess exist. Our concurrent measurements of atmospheric isotopes in water vapour

  13. 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

  14. 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.

  15. Nqrs Data for C3H10INO6 [C3H7NO2·HIO3·(1/2)(H2O)] (Subst. No. 0642)

    NASA Astrophysics Data System (ADS)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C3H10INO6 [C3H7NO2·HIO3·(1/2)(H2O)] (Subst. No. 0642)

  16. Evaporation and concentration gradients created by episodic river recharge in a semi-arid zone aquifer: Insights from Cl-, δ18O, δ2H, and 3H

    NASA Astrophysics Data System (ADS)

    Meredith, K. T.; Hollins, S. E.; Hughes, C. E.; Cendón, D. I.; Chisari, R.; Griffiths, A.; Crawford, J.

    2015-10-01

    This study has significantly advanced our understanding of the origin of groundwater recharge in a semi-arid zone region of the Darling River catchment, Australia. The generally accepted hypothesis in arid zone environments in Australia that river water forms the primary groundwater recharge source has proven difficult to monitor. This is due to the time lags between large floods, the remoteness and expense of studying these hydrologically complex systems in detail. In addition, the highly episodic nature of dryland rivers complicates the interpretation of the groundwater signal. A range of hydrochemical tracers (chloride, oxygen-18, deuterium and tritium) measured in rain, river water, soil water and groundwater were used in this multi-year study to trace the pathways of groundwater recharge under wet and dry climatic conditions. The evaporation and Cl concentrations observed in the unsaturated zone confirmed that small volumetric inputs from periodic rainfall were not the major recharge mechanism. Sampling which included an overbank flooding event in March 2012 provided firm evidence for groundwater originating from high flow episodic river recharge. The use of long-term environmental data to understand how economically important water resources respond to climate change with increasing temperatures is considered essential for future sustainability.

  17. 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.

  18. 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.

  19. Secondary isotope effects in liquid chromatography behaviour of 2H and 3H labelled solutes and solvents.

    PubMed

    Valleix, Alain; Carrat, Sandrine; Caussignac, Céline; Léonce, Estelle; Tchapla, Alain

    2006-05-26

    water in mobile phases of the same composition (%, w/w) is compared. Independent of the nature of the organic modifier (methanol, acetonitrile or ethanol), the effect of replacing H2O with 2H2O in the mobile phase, is an increase in the retention factors and an improvement in the chromatographic resolution of isotopologue pairs. This increase in the resolution is not accompanied by a change in the chromatographic selectivity. The measurement of liquid-liquid extraction coefficients proves that the effect is mainly due to the modification of the phase ratio. In general the effect of 2H-labelled solvents (2H2O and C2H3CN) as mobile phase components, compared to their isotopically non-modified isomers, can be rationalized on the basis of their lower polarisabilities. Overall the use of perdeuterated rather than isotopically non-modified solvents as mobile phase components leads to the most efficient separation systems.

  20. 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.

  1. 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.

  2. 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.

  3. Synthesis and chemiluminescence of copolymers of 5-amino-8-vinyl-phthalazine-1,4(2H,3H)-dione with methyl methacrylate or styrene, and of alpha, omega-bis[5-amino-phthalazine-1,4(2H,3H)-dion-]8-yl alkanes [= alpha, omega-bis(6-luminyl) alkanes]: investigations on an intramolecular 'distance effect'.

    PubMed

    Gundermann, K D; Lieske, D; Haase, B; Hartmann-Azanza Baca, B

    1987-09-01

    Oligomers of 5-amino-8-vinyl-phthalazine-1,4(2H,3H)-dione exhibit about 0.05% of the chemiluminescence quantum yield of the corresponding 'monomer unit', i.e. 5-amino-8-ethyl-phthalazine-1,4(2H,3H)-dione which has a similar quantum yield to luminol. The quantum yields of copolymers of 5-amino-8-vinyl-phthalazine-1,4(2H,3H)-dione (1a) with methyl methacrylate or with styrene increase up to 1000-fold, relative to the quantum yield of oligomers of (1a). Thus the monomer units of methyl methacrylate or styrene appear to act as 'spacers' between the lumigenic groups. alpha, omega-Bis[(5-amino-phthalazine-1,4(2H,3H)-dion-)8-yl] alkanes show an analogue 'distance' effect: the chemiluminescence quantum yield increases with increasing alkane chain length. As the fluorescence of the corresponding amino phthalates (which are intermediates in the synthesis of the phthalazine diones) is only slightly influenced by the distance between the lumigenic groups it is suggested that a mainly chemical 'distance effect' is working here: the smaller the intramolecular distance between the hydrazide groups the more inhibition exists in respect of the oxidative reaction producing the luminol-type chemiluminescence.

  4. Volumetric Properties of the Mixture 2-Chloroethanol C2H5ClO + C3H6O2 Methyl ethanoate (VMSD1511, LB4797_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 2-Chloroethanol C2H5ClO + C3H6O2 Methyl ethanoate (VMSD1511, LB4797_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).

  5. 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.

  6. First field-based observations of δ 2H and δ 18O values of event-based precipitation, rivers and other water bodies in the Dzungarian Gobi, SW Mongolia

    PubMed Central

    Burnik Šturm, Martina; Ganbaatar, Oyunsaikhan; Voigt, Christian C.; Kaczensky, Petra

    2017-01-01

    ABSTRACT For certain remote areas like Mongolia, field-based precipitation, surface and ground water isotopic data are scarce. So far no such data exist for the Mongolian Gobi desert, which hinders the understanding of isotopic fractionation processes in this extreme, arid region. We collected 26 event-based precipitation samples, 39 Bij river samples, and 75 samples from other water bodies in the Dzungarian Gobi in SW Mongolia over a period of 16 months for hydrogen and oxygen stable isotope analysis. δ 2H and δ 18O values in precipitation show high seasonal variation and cover an extreme range: 175 ‰ for δ 2H and 24 ‰ for δ 18O values. The calculated local meteoric water line (LMWL) shows the isotopic characteristics of precipitation in an arid region. Individual water samples fall into one of three groups: within, above or below the 95 % confidence interval of LMWL. Data presented provide a basis for future studies in this region. PMID:27733073

  7. First field-based observations of δ(2)H and δ(18)O values of event-based precipitation, rivers and other water bodies in the Dzungarian Gobi, SW Mongolia.

    PubMed

    Burnik Šturm, Martina; Ganbaatar, Oyunsaikhan; Voigt, Christian C; Kaczensky, Petra

    2017-05-01

    For certain remote areas like Mongolia, field-based precipitation, surface and ground water isotopic data are scarce. So far no such data exist for the Mongolian Gobi desert, which hinders the understanding of isotopic fractionation processes in this extreme, arid region. We collected 26 event-based precipitation samples, 39 Bij river samples, and 75 samples from other water bodies in the Dzungarian Gobi in SW Mongolia over a period of 16 months for hydrogen and oxygen stable isotope analysis. δ(2)H and δ(18)O values in precipitation show high seasonal variation and cover an extreme range: 175 ‰ for δ(2)H and 24 ‰ for δ(18)O values. The calculated local meteoric water line (LMWL) shows the isotopic characteristics of precipitation in an arid region. Individual water samples fall into one of three groups: within, above or below the 95 % confidence interval of LMWL. Data presented provide a basis for future studies in this region.

  8. 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.

  9. 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

  10. Preparation and studies of new crystals in the K3H(SO4)2-(NH4)3H(SO4)2-H2O system

    NASA Astrophysics Data System (ADS)

    Dmitricheva, E. V.; Makarova, I. P.; Grebenev, V. V.; Dolbinina, V. V.; Verin, I. A.

    2014-05-01

    To elucidate the effect of isomorphic substitution on the kinetics of phase transitions, single crystals of (K x (NH4)1- x ) m H n (SO4)( m + n)/2 · yH2O solid solutions are grown from the K3H(SO4)2-(NH4)3H(SO4)2-H2O system, whose end members are known to undergo superprotonic phase transitions of fundamentally different kinetics. The chemical composition of the single crystals grown is determined by energy dispersive X-ray microanalysis. The thermal and optical behavior of (K,NH4)9H7(SO4)8 · H2O single crystals is studied in the temperature range 295-420 K and the crystal structure at 295 K is determined. A comparison of the results of the studies with data for crystal K9H7(SO4)8 · H2O published earlier shows that the substitution of ammonium for potassium atoms lowers the temperature of the structural phase transition by 8 K.

  11. DNA damage induced by 4,6,8,9-tetramethyl-2H-furo[2,3-h]quinolin-2-one, a new furocoumarin analog: photochemical mechanisms.

    PubMed

    Bordin, F; Baccichetti, F; Marzano, C; Carlassare, F; Miolo, G; Chilin, A; Guiotto, A

    2000-03-01

    Some photochemical and photobiological properties of 4,6,8,9-tetramethyl-2H-furo[2,3-h]quinolin-2-one (HFQ) were studied in comparison with its isomer 1,4,6,8-tetramethyl-2H-furo[2,3-h]quinolin-2-one (FQ) and 8-methoxypsoralen (8-MOP). The HFQ photobinds to DNA forming furan-side monoadducts (MAHFQ) that have molecular structure very similar to those of FQ (MAFQ). Unlike MA8-MOP and MAFQ, MAHFQ no longer photoreact. The HFQ, like FQ, produces moderate amounts of singlet oxygen but no superoxide anions. The HFQ and FQ induce numbers of DNA-protein cross-links (DPC), much more plentiful than those of 8-MOP (about two and seven times, respectively) but no interstrand cross-links. The mechanism of DPC formation was studied in vivo in mammalian cells by alkaline elution and in vitro using a new test mixing histones and DNA from calf thymus. The latter is a very useful technique for the double irradiation protocol. The DNA (or histones) are separately exposed to a first UVA dose in the presence of the sensitizer; then, after its unbound molecules have been removed, histones (or DNA) are added to assemble the chromatin-like complex that is irradiated again. According to in vitro and in vivo methods, DPC appear to be formed by FQ and 8-MOP by a biphotonic process that starts with monoadduct induction in DNA, followed by their conversion into DPC. In the resulting lesions, the sensitizer molecule forms a covalent bridge between the two macromolecules (DPC at length greater than zero). Instead, HFQ induces DPC by a monophotonic process; thus, HFQ is probably not a physical part of the bridge between DNA and proteins, which may be linked together directly, like DPC at zero length induced by UVC.

  12. DNA damage induced by 4,6,8,9-tetramethyl-2H-furo[2,3-h]quinolin-2-one, a new furocoumarin analog: biological consequences.

    PubMed

    Marzano, C; Baccichetti, F; Carlassare, F; Chilin, A; Lora, S; Bordin, F

    2000-03-01

    4,6,8,9-Tetramethyl-2H-furo[2,3-h]quinolin-2-one (HFQ) and its isomer FQ (1,4,6,8-tetramethyl-2H-furo[2,3-h]quinolin-2-one) showed very strong antiproliferative activity in mammalian cells, about two times greater than 8-methoxypsoralen (8-MOP). Both compounds induced DNA-protein cross-links (DPC) but not interstrand cross-links. The FQ generated DPC in a biphotonic process, yielding a new kind of diadduct, whereas HFQ induced DPC by a monophotonic one, probably without its physical participation in the covalent bridge. These lesions gave different toxic responses. Sensitization of FQ led to extensive DNA fragmentation and to a number of chromosomal aberrations. Conversely, HFQ seemed to be completely inactive and 8-MOP gave intermediate results. A strict relationship between DPC formation and induction of chromosomal aberrations was observed. The HFQ did not induce light skin erythemas, whereas FQ was more phototoxic than 8-MOP, thus suggesting that FQ lesions, DPC in particular, may be implicated in skin phototoxicity. Ehrlich ascites cells, a transplantable mouse tumor, inactivated by furoquinolinone sensitization and injected into healthy mice, protected them from a successive challenge by viable tumor cells. This response appeared to be based on an immune mechanism. Comparable amounts of base substitution revertants were scored when testing furoquinolinones and 8-MOP in bacteria but no DPC were detected. This suggests that classic mutagenesis tests on bacteria are insufficient to give adequate information on furocoumarin genotoxicity. Given its features, HFQ can be regarded as an interesting new agent for psoralen plus UVA photochemotherapy and photopheresis.

  13. 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

  14. 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

    RationaleAlthough 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.MethodsA 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 (δ17O, δ18O, and δ2H 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.ResultsCost-free LIMS for Lasers 2015 enables users to obtain improved δ17O, δ18O, and δ2H values with liquid-water LAS instruments, even those with under-performing syringes. For example, LAS δ2HVSMOW 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.ConclusionsLIMS for Lasers 2015 enables users to create systematic, well-founded instrument templates, import δ2H, δ17O, and δ18O 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 perform long-term QA/QC audits

  15. Precision measurements of {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He total cross sections at Big Bang nucleosynthesis energies

    SciTech Connect

    Leonard, D.S.; Karwowski, H.J.; Brune, C.R.; Fisher, B.M.; Ludwig, E.J.

    2006-04-15

    Recent Wilkinson Microwave Anisotropy Probe (WMAP) measurements have determined the baryon density of the Universe {omega}{sub b} with a precision of about 4%. With {omega}{sub b} tightly constrained, comparisons of Big Bang nucleosynthesis (BBN) abundance predictions to primordial abundance observations can be made and used to test BBN models and/or to further constrain abundances of isotopes with weak observational limits. To push the limits and improve constraints on BBN models, uncertainties in key nuclear reaction rates must be minimized. To this end, we made new precise measurements of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He total cross sections at lab energies from 110 to 650 keV. A complete fit was performed in energy and angle to both angular distribution and normalization data for both reactions simultaneously. By including parameters for experimental variables in the fit, error correlations between detectors, reactions, and reaction energies were accurately tabulated by computational methods. With uncertainties around 2%{+-}1% scale error, these new measurements significantly improve on the existing data set. At relevant temperatures, by using the data of the present work, both reaction rates are found to be about 7% higher than those in the widely used NACRE (nuclear astrophysics compilation of reaction rates) database. These data will thus lead not only to reduced uncertainties, but also to modifications in the BBN abundance predictions.

  16. 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.

  17. Precise and accurate isotope fractionation factors (α17O, α18O and αD) for water and CaSO4·2H2O (gypsum)

    NASA Astrophysics Data System (ADS)

    Gázquez, Fernando; Evans, Nicholas P.; Hodell, David A.

    2017-02-01

    Gypsum (CaSO4·2H2O) is a hydrated mineral containing crystallization water, also known as gypsum hydration water (GHW). We determined isotope fractionation factors (α17O, α18O and αD) between GHW and free water of the mother solution in the temperature range from 3 °C to 55 °C at different salinities and precipitation rates. The hydrogen isotope fractionation factor (αDgypsum-water) increases by 0.0001 units per °C between 3 °C and 55 °C and salinities <150 g/L of NaCl. The αDgypsum-water is 0.9812 ± 0.0007 at 20 °C, which is in good agreement with previous estimates of 0.981 ± 0.001 at the same temperature. The α18Ogypsum-water slightly decreases with temperature by 0.00001 per °C, which is not significant over much of the temperature range considered for paleoclimate applications. Between 3 °C and 55 °C, α18Ogypsum-water averages 1.0035 ± 0.0002. This value is more precise than that reported previously (e.g. 1.0041 ± 0.0004 at 25 °C) and lower than the commonly accepted value of 1.004. We found that NaCl concentrations below 150 g/L do not significantly affect α18Ogypsum-water, but αDgypsum-water increases linearly with NaCl concentrations even at relatively low salinities, suggesting a salt correction is necessary for gypsum formed from brines. Unlike oxygen isotopes, the αDgypsum-water is affected by kinetic effects that increase with gypsum precipitation rate. As expected, the relationship of the fractionation factors for 17O and 18O follows the theoretical mass-dependent fractionation on Earth (θ = 0.529 ± 0.001). We provide specific examples of the importance of using the revised fractionation factors when calculating the isotopic composition of the fluids.

  18. 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

  19. 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

  20. Syntheses of 24R,25-dihydroxy-(6,19,19-3H)vitamin D3 and 24R,25-dihydroxy-(6,19,19-2H)vitamin D3

    SciTech Connect

    Yamada, S.; Shimizu, M.; Fukushima, K.; Niimura, K.; Maeda, Y. )

    1989-08-01

    24R,25-Dihydroxy-(6,19,19-3H)vitamin D3 with a specific activity of 54 Ci/mmol and 24R,25-dihydroxy-(6,19,19-2H)vitamin D3 with 2.6 deuterium atoms/mol were synthesized in four steps starting from 24R,25-Dihydroxyvitamin D3 via its sulfur dioxide adduct.

  1. 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

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false 6-Ethoxy-2-(6-ethoxy-3-oxobenzo thien-2(3H)-ylidene) benzo thiophen-3 (2H)-one. 73.3123 Section 73.3123 Food and Drugs FOOD AND DRUG ADMINISTRATION... to exceed the minimum reasonably required to accomplish the intended coloring effect....

  2. 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

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false 6-Ethoxy-2-(6-ethoxy-3-oxobenzo thien-2(3H)-ylidene) benzo thiophen-3 (2H)-one. 73.3123 Section 73.3123 Food and Drugs FOOD AND DRUG ADMINISTRATION... to exceed the minimum reasonably required to accomplish the intended coloring effect....

  3. 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.

  4. The reaction C sub 3 H sub 3 sup + + C sub 2 H sub 2 and the structural isomers of C sub 5 H sub 5 sup +

    SciTech Connect

    Feng, Jikang; Leszczynski, J.; Weiner, B.; Zerner, M.C. )

    1989-06-21

    The authors study here the isomers of C{sub 5}H{sub 5}{sup +} and possible reactions between C{sub 3}H{sub 3}{sup +} and acetylene that lead to the formation of C{sub 5}H{sub 5}{sup +} using quantum chemical means. They find very many stable C{sub 5}H{sub 5}{sup +} isomers, the most stable being the vinylcyclopropenylium cation. A pyramidal form is calculated to be quite stable as are distorted planar cyclopentadienyl cations. Nonplanar distortions in these five-membered rings, however, do not appear stable. With an eye toward identification of these species in sooting flames and in Fourier transform ion cyclotron resonance experiments, they report the calculated vibrational and electronic spectra of these species. They also study reactions of C{sub 3}H{sub 3}{sup +} with acetylene, attempting to model the nucleation step in the formation of soot. They find that the cyclic form of C{sub 3}H{sub 3}{sup +} does not react with acetylene without sizeable barrier, whereas the linear propargyl cation reacts with acetylene without barrier to form many different C{sub 5}H{sub 5+} tautomers, some of which are quite stable. They discuss these findings in conjunction with the results of experiments on these systems.

  5. 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.

  6. Isolation and structures of sulfonium salts derived from thioethers: [{o-C(6)H(4)(CH(2)SMe)(2)}H][NbF(6)] and [{[9]aneS(3)}H][NbF(6)].

    PubMed

    Jura, Marek; Levason, William; Reid, Gillian; Webster, Michael

    2009-10-07

    Two very unusual sulfonium salts, [{o-C(6)H(4)(CH(2)SMe)(2)}H][NbF(6)] and [{[9]aneS(3)}H][NbF(6)], obtained from reaction of the thioethers with NbF(5) in CH(2)Cl(2) solution, are reported and their structures described; the eight-coordinate tetrafluoro Nb(v) cation of the dithioether is obtained from the same reaction.

  7. Low-energy SiC2H6+ and SiC3H9+ ion beam productions by the mass-selection of fragments produced from hexamethyldisilane for SiC film formations

    NASA Astrophysics Data System (ADS)

    Yoshimura, Satoru; Sugimoto, Satoshi; Murai, Kensuke; Kiuchi, Masato

    2016-12-01

    We have been attempting to produce low-energy ion beams from fragments produced through the decomposition of hexamethyldisilane (HMD) for silicon carbide (SiC) film formations. We mass-selected SiC2H6+ and SiC3H9+ ions from fragments produced from HMD, and finally produced low-energy SiC2H6+ and SiC3H9+ ion beams. The ion energy was approximately 100 eV. Then, the ion beams were irradiated to Si(100) substrates. The temperature of the Si substrate was 800°C during the ion irradiation. The X-ray diffraction and Raman spectroscopy of the substrates obtained following SiC2H6+ ion irradiation demonstrated the occurrence of 3C-SiC deposition. On the other hand, the film deposited by the irradiation of SiC3H9+ ions included diamond-like carbon in addition to 3C-SiC.

  8. 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

  9. Three whole-wood isotopic reference materials, USGS54, USGS55, and USGS56, for δ2H, δ13C, δ15N, and δ18O measurements

    USGS Publications Warehouse

    Qi, Haiping; Coplen, Tyler B.; Jordan, James A.

    2016-01-01

    Comparative measurements of stable hydrogen and oxygen isotopes in wood are hampered by the lack of proper reference materials (RMs). The U.S. Geological Survey (USGS) has prepared three powdered, whole-wood RMs, USGS54 (Pinus contorta, Canadian lodgepole pine), USGS55 (Cordia cf. dodecandra, Mexican ziricote), and USGS56 (Berchemia cf. zeyheri, South African red ivorywood). The stable isotopes of hydrogen, oxygen, carbon, and nitrogen in these RMs span ranges as δ2HVSMOW from –150.4 to –28.2 mUr or ‰, as δ18OVSMOW from + 17.79 to + 27.23 mUr, as δ13CVPDB from –27.13 to –24.34 mUr, and as δ15N AIR-N2 from –2.42 to + 1.8 mUr. These RMs will enable users to normalize measurements of wood samples to isotope–delta scales, and they are intended primarily for the normalization of δ2H and δ18O measurements of unknown wood samples. However, they also are suitable for normalization of stable isotope measurements of carbon and nitrogen in wood samples. In addition, these RMs are suitable for inter-laboratory calibration for the dual-water suilibration procedure for the measurements of δ2HVSMOW values of non-exchangeable hydrogen. The isotopic compositions with 1-σ uncertainties, mass fractions of each element, and fractions of exchangeable hydrogen of these materials are:USGS54 (Pinus contorta, Canadian Lodgepole pine)δ2HVSMOW = –150.4 ± 1.1 mUr (n = 29), hydrogen mass fraction = 6.00 ± 0.04 % (n = 10)Fraction of exchangeable hydrogen = 5.4 ± 0.6 % (n = 29)δ18OVSMOW = + 17.79 ± 0.15 mUr (n = 18), oxygen mass fraction = 40.4 ± 0.2 % (n = 6)δ13CVPDB = –24.43 ± 0.02 mUr (n = 18), carbon mass fraction = 48.3 ± 0.4 % (n = 12)δ15NAIR-N2 = –2.42 ± 0.32 mUr (n = 17), nitrogen mass fraction = 0.05 % (n = 4)USGS55 (Cordia cf. dodecandra, Mexican ziricote)δ2HVSMOW = –28.2 ± 1.7 mUr (n = 30), hydrogen mass fraction = 5.65 ± 0.06 % (n = 10)Fraction of exchangeable

  10. Control of open-framework structures through template⋯template interactions? Syntheses and structures of C 2H 7N 4OṡZnCl(HPO 4) and (C 2H 7N 4O) 2ṡZn 3(H 2O)(HPO 3) 4

    NASA Astrophysics Data System (ADS)

    Harrison, William T. A.

    2006-03-01

    The syntheses and structures of C 2H 7N 4OṡZnCl(HPO 4) and (C 2H 7N 4O) 2ṡZn 3(H 2O)(HPO 3) 4 are reported. Both phases arose in solution mediated reactions by way of the controlled, in situ, preparation of the cationic [C 2H 7N 4O] + guanylurea template by the slow hydrolysis of the neutral 2-cyanoguanidine starting material. C 2H 7N 4OṡZnCl(HPO 4) contains anionic [ZnCl(HPO 4)] - 6 3-topology polyhedral layers built up from vertex-sharing ZnO 3Cl and HPO 4 polyhedra. (C 2H 7N 4O) 2ṡZn 3(H 2O)(HPO 3) 4 is also layered and contains ZnO 4, ZnO 3(H 2O) and HPO 3 polyhedra sharing vertices by way of Zn sbnd O sbnd P bonds. In both structures, the guanylurea template participates in numerous template-to-framework and also template-to-template hydrogen bonds. Strikingly, the arrangement of template-to-template H bonds is different in the two structures, and also different to that seen earlier in C 2H 7N 4OṡZnPO 4. Crystal data: C 2H 7N 4OṡZnCl(HPO 4), M=299.91, monoclinic, Cc (No. 9), a=4.8823(2) Å, b=25.4781(11) Å, c=8.0335(4) Å, β=105.496(1)°, V=962.98(7) Å; Z=4. (C 2H 7N 4O) 2ṡZn 3(H 2O)(HPO 3) 4, M=740.27, triclinic, P1¯ (No. 2), a=9.0022(5) Å, b=9.5211(5) Å, c=13.4933(7) Å, α=94.986(1)°, β=94.111(1)°, γ=99.051(1)°, V=1133.51(1) Å; Z=2.

  11. The neural inductive signal is transferred to ectoblast in 1-2 h but a continued contact with mesoblast for 2-3 h is essential for neuralization in the chick area pellucida.

    PubMed

    Joshi-Banka, D; Deshmukh, S; Modak, S P

    2001-09-01

    In the area pellucida of the chick gastrula, the Hensen's node (HN) graft must contact the competent ectoblast for at least 4 h to promote neural induction. When we removed the grafted HN after 1 to 3 h and replaced it by a non-inducing post nodal (PN) fragment, a 1-2 h contact with HN was found to be sufficient to promote neural induction. When HN graft was removed after 3 or 4 h and replaced by PN, the neural inductive response was substantially improved towards formation of archencephalic structures. Thus, our results indicate that neural induction takes place in two steps. In the first step, a contact with HN for 1-2 h is sufficient to transferthe inductive signal which is stabilized through a second step involving continued cell-cell contact with even non-inducing PN mesoblast.

  12. 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.

  13. 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.

  14. The crystal and molecular structure of N{sub 2}H{sub 5}[M(N{sub 2}H{sub 3}COO){sub 3}].H{sub 2}O (M-bar {l_brace}Co, Zn{r_brace}) isomorphic compounds-an X-ray crystallographic, vibrational spectroscopic and quantum-chemical study

    SciTech Connect

    Jesih, Adolf; Rahten, Anka; Benkic, Primoz; Skapin, Tomaz; Pejov, Ljupco . E-mail: ljupcop@iunona.pmf.ukim.edu.mk; Petrusevski, Vladimir M.

    2004-12-01

    A systematic study of N{sub 2}H{sub 5}[M(N{sub 2}H{sub 3}COO){sub 3}].H{sub 2}O (M-bar {l_brace}Co, Zn{r_brace}) type of compounds, which are typical model systems for transition metal complexes with {alpha}-amino acids (the latter are not obtainable in crystalline form), was carried out. The crystal structures of these compounds were solved by X-ray crystallographic methods. FTIR spectra at room and low temperature ({approx}100K) as well as Raman spectra at room temperature were recorded, and analyzed in details. Also, the geometries of the Zn(N{sub 2}H{sub 3}COO){sub 3}{sup -} and N{sub 2}H{sub 5}{sup +} species were fully optimized at ab initio HF and B3LYP/6-31+G(d,p) level of theory, and subsequent vibrational analyses were performed on the basis of which several important reassignments of the IR and Raman bands were proposed. In order to study the binding energetics and the ligand-cation charge-transfer interactions within the Zn(N{sub 2}H{sub 3}COO){sub 3}{sup -} complex, NBO analysis was carried out, employing the second-order perturbation theory analysis of the Fock matrix (i.e., its Kohn-Sham analog) within the NBO basis.

  15. 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.

  16. 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.

  17. Beam-energy dependence and updated test of the Trojan-horse nucleus invariance via a measurement of the 2H(d ,p )3H reaction at low energies

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    The 2H(d ,p )3H bare nucleus astrophysical S (E ) factor has been measured indirectly at energies from about 500 keV down to several keV by means of the Trojan-horse method applied to the 2H(6Li,p t )4He quasifree reaction induced at 11 MeV. The obtained results are compared with direct data as well as with previous indirect investigation of the same binary reactions. It shows that the precision of S (E ) data in the low-energy range extracted via the same Trojan-horse nuclei [6Li=(d ⊕α )] becomes better when the incident energy of the virtual binary process decreases from high value down to the lower Gamow energy range, which near the zero-quasi-free-energy point. The very good agreement between data extracted from different Trojan-horse nuclei [6Li=(d ⊕α ) vs 3He=(d ⊕p )] gives a strong updated test for the independence of the binary indirect cross section on the chosen Trojan-horse nucleus at low energies.

  18. 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.

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

    NASA Astrophysics Data System (ADS)

    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 (2 H- and 3 H-pyrazole) of 7 in Auroras A and B (PDB ID: 4AF3) crystal structures. This docking study shows that the major 3 H-pyrazole tautomer of 7 binds in Aurora A stronger than in Aurora B.

  20. 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.

  1. 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.

  2. Difference between ²JC2H3 and ²JC3H2 spin-spin couplings in heterocyclic five- and six-membered rings as a probe for studying σ-ring currents: a quantum chemical analysis.

    PubMed

    Contreras, Rubén H; dos Santos, Francisco P; Ducati, Lucas C; Tormena, Cláudio F

    2010-12-01

    Adequate analyses of canonical molecular orbitals (CMOs) can provide rather detailed information on the importance of different σ-Fermi contact (FC) coupling pathways (FC term transmitted through the σ-skeleton). Knowledge of the spatial distribution of CMOs is obtained by expanding them in terms of natural bond orbitals (NBOs). Their relative importance for transmitting the σ-FC contribution to a given spin-spin coupling constants (SSCCs) is estimated by resorting to the expression of the FC term given by the polarisation propagator formalism. In this way, it is possible to classify the effects affecting such couplings in two different ways: delocalisation interactions taking place in the neighbourhood of the coupling nuclei and 'round the ring' effects. The latter, associated with σ-ring currents, are observed to yield significant differences between the FC terms of (2)J(C2H3) and (2)J(C3H2) SSCCs which, consequently, are taken as probes to gauge the differences in σ-ring currents for the five-membered rings (furan, thiophene, selenophene and pyrrol) and also for the six-membered rings (benzene, pyridine, protonated pyridine and N-oxide pyridine) used in the present study.

  3. 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.

  4. Synthesis and biological evaluation of novel 5-alkyl-2-arylthio-6-((3,4-dihydroquinolin-1(2H)-yl)methyl)pyrimidin-4(3H)-ones as potent non-nucleoside HIV-1 reverse transcriptase inhibitors.

    PubMed

    Zhang, Jing; Zhan, Peng; Wu, Jingde; Li, Zhenyu; Jiang, Yan; Ge, Weiying; Pannecouque, Christophe; De Clercq, Erik; Liu, Xinyong

    2011-07-15

    A series of novel S-DABO analogues of 5-alkyl-2-arylthio-6-((3,4-dihydroquinolin-1(2H)-yl)methyl)pyrimidin-4(3H)-ones were synthesized and evaluated as inhibitors of human immunodeficiency virus type-1 (HIV-1). Among them, the most potent HIV-1 inhibitors were compounds 6c1,6c6, and 6b1 (EC(50)=0.24 ± 0.05, 0.38 ± 0.13, 0.39 ± 0.05 μM, respectively), which possess improved or similar HIV-1 inhibitory activity compared with nevirapine (NVP) (EC(50)=0.21 μM) and delavirdine (DLV) (EC(50)=0.32 μM). None of these compounds were active against HIV-2 replication. Furthermore, enzyme inhibitory assays were performed with selected derivatives against HIV-1 wtRT, confirming that the main target of these compounds is the HIV-1 RT and these new S-DABOs are acting as NNRTIs. The preliminary structure-activity relationship (SAR) of these new congeners is discussed briefly and rationalized by docking studies.

  5. A new inorganic-organic hybrid material Al-SBA-15-TPI/H6P2W18O62 catalyzed one-pot, three-component synthesis of 2H-indazolo[2,1-b]phthalazine-triones.

    PubMed

    Tayebee, R; Amini, M M; Pouyamanesh, S; Aliakbari, A

    2015-03-28

    A new inorganic-organic hybrid material Al-SBA-15-TPI/H6P2W18O62 was prepared and fully characterized by SEM, XRD, FT-IR, TGA-DTA, and UV-Vis spectroscopic techniques. Then, the prepared nanomaterial was used as a simple, cost-effective, and reusable heterogeneous catalyst for the synthesis of 2H-indazolo[2,1-b]phthalazine-1,6,11(13H)-trione derivatives by a one-pot, three-component condensation reaction of phthalhydrazide, cyclic diones, and aromatic aldehydes under solvent free conditions at 100 °C in a short time. This methodology has proven to be efficient and environmentally benign in terms of high yields and low reaction times and offers significant improvements with regard to the scope of transformation and simplicity of operation by avoiding expensive or corrosive catalysts.

  6. Solute-fluid coupling and energy dissipation in supercritical fluids: 9-cyanoanthracene in C{sub 2}H{sub 6}, CO{sub 2}, and CF{sub 3}H

    SciTech Connect

    Rice, J.K.; Niemeyer, E.D.; Bright, F.V.

    1996-05-16

    We report on the coupling and dissipation of energy between a model fluorescent solute, 9-cyanoanthracene (9CA), and several supercritical fluid solvents. To this end, we have determined experimentally the fluorescence quantum yields and excited-state fluorescence lifetimes for dilute solutions of 9CA in supercritical C{sub 2}H{sub 6}, CO{sub 2}, and CF{sub 3}H. The 9CA quantum yield is substantially less than unity at lower fluid densities; it approaches unity only at the high-density, liquid-like region. The 9CA excited-state lifetime is also shortened significantly in the low-density region. The radiative (k{sub r}) and nonradiative (k{sub nr}) decay rates for 9CA are found to be strongly density dependent. In the low-density region, the nonradiative rate dominates; however, in the high-density region the 9CA de-excitation follows the radiative pathway. To yield agreement between the experimental k{sub r} data and the Strickler-Berg predictions, we require there to be changes in the total 9CA molar absorptivity with denisity. Recent experiments on anthracene and pyrene in supercritical CO{sub 2} demonstrate that the average solute molar absorptivity is indeed a function of fluid density. The strong density dependence of the nonradiative decay rate is interpreted in terms of an increase in fluid density leading to an increase in the energy gap ({Delta}E) between T{sub 2} and S{sub 1} states. 69 refs., 10 figs., 1 tab.

  7. 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.

  8. Difference between 2 h and 3 h 75 g glucose tolerance test in the diagnosis of gestational diabetes mellitus (GDM): results from a national survey on prevalence of GDM.

    PubMed

    Gao, Xue-Lian; Wei, Yu-Mei; Yang, Hui-Xia; Xu, Xian-Ming; Fan, Ling; He, Jing; Liu, Ning; Zhao, San-Cun; Hu, Ya-Li; Yang, Zi; Zhang, Yun-Ping; Liu, Xing-Hui; Chen, Xu; Zhang, Jian-Ping; Gou, Wen-Li; Xiao, Mei; Wu, Hai-Rong; Zhang, Mei-Hua

    2010-09-01

    The possibility of the 2 h oral glucose tolerance test (OGTT) as an alternative to the 3 h OGTT was investigated based on data from a national survey on pregnancy-associated diabetes. Data were retrieved from 4179 pregnant women who had OGTT performed after an abnormal 50 g glucose challenge test (GCT). All of the 4 glucose levels during their OGTT were collected and analyzed. According to American Diabetes Association (ADA) gestational diabetes mellitus (GDM) diagnostic criteria, among the 4179 pregnant women who required OGTT, 3429 (82.1%) were normal and 750 (17.9%) were diagnosed as GDM. If the 3rd h glucose levels were omitted from OGTT, 79 cases of GDM (10.5%) would be overlooked. No trend was shown where women with more risk factors were more likely to be overlooked if the 3rd h test was omitted (χ2 for trend=0.038, P>0.05). No significant differences were found in the rate of cesarean section (CS), preterm births or macrosomia between the 79 cases and those with normal OGTT results and in the gestational weeks when OGTT was performed. It shows that in order to diagnose one woman with GDM, another 52 pregnant women would have an innocent 3rd h glucose test. Omission of the 3rd h glucose test in OGTT might be reasonable due to its convenience, better compliance and a small number of possibly miss-diagnosed cases, and their pregnancy outcomes have no significant difference from those of normal pregnant women.

  9. 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.

  10. Palladium-catalyzed through-space C(sp(3))-H and C(sp(2))-H bond activation by 1,4-palladium migration: efficient synthesis of [3,4]-fused oxindoles.

    PubMed

    Piou, Tiffany; Bunescu, Ala; Wang, Qian; Neuville, Luc; Zhu, Jieping

    2013-11-18

    Palladium two step: Linear anilides were converted into the title compounds in good to excellent yields through a palladium-catalyzed domino carbopalladation/1,4-palladium shift sequence. The C(sp(3) )-H activation involves a seven-membered palladacycle, and is chemoselective in the presence of competitive C(sp(2) )H bonds. DMA=N,N-dimethylacetamide, OPiv=pivalate.

  11. Surface and catalytic elucidation of Rh/gamma-Al2O3 catalysts during NO reduction by C3H8 in the presence of excess O2, H2O, and SO2.

    PubMed

    Pekridis, G; Kaklidis, N; Komvokis, V; Athanasiou, C; Konsolakis, M; Yentekakis, I V; Marnellos, G E

    2010-03-25

    The present study aims at exploring the surface and catalytic behavior of Rh/gamma-Al(2)O(3) catalysts during the selective reduction of NO by C(3)H(8) in the presence of excess oxygen, H(2)O, and SO(2) with particular emphasis on identifying the elementary steps that describe the reaction mechanism. To this end, detailed activity and stability tests were employed and a precise kinetic analysis was carried out at differential conditions to elucidate the effect of each reactant, including H(2)O and SO(2), on the total reaction rate. At the same time, temperature programmed desorption (TPD) studies in combination with in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy were carried out under various reaction conditions to correlate the catalytic performance of Rh/gamma-Al(2)O(3) catalyst with its corresponding surface chemistry. The results reveal that in the absence of H(2)O and SO(2), the reaction follows a typical "reduction" type mechanism, where the active intermediates (NO(X), carboxylates, isocyanates) are interacting to yield the final products. In this reaction sequence the formation of carboxylate (C(x)H(y)O(z)) species is considered as the rate determining step. Water affects in a different way the NO and C(3)H(8) conversion performance of Rh/gamma-Al(2)O(3) catalyst; its effect is totally reversible in the case of C(3)H(8) oxidation, while the NO reduction was permanently affected mainly due to the oxidation of Rh active sites. In contrast, SO(2) poisons both reactions irreversibly via the formation of strongly adsorbed sulfate compounds, which hinder the adsorption and consequently the activation of reactants.

  12. Microcrystalline phase transformation from ZrF4·HF·2H2O to ZrO2 through the intermediate phases ZrF4·3H2O, ZrF4·H2O, Zr2OF6·H2O and ZrF4

    NASA Astrophysics Data System (ADS)

    Dey, C. C.

    2014-09-01

    The behavior of hydrated zirconium fluoride has been studied by perturbed angular correlation spectroscopy. It is found that the crystalline compound ZrF4·HF·2H2O, formed initially by drying solution of Zr metal in concentrated HF, transforms spontaneously to ZrF4·3H2O. This trihydrated compound dehydrates to ZrF4 through the intermediate monohydrates ZrF4·H2O and Zr2OF6·H2O. The compound ZrF4 finally transforms to ZrO2 at ∼343 K. Different crystalline phases of ZrF4·HF·2H2O, ZrF4·3H2O, ZrF4·H2O, Zr2OF6·H2O, ZrF4 and ZrO2 have been identified and characterized by PAC spectroscopy. From previous PAC measurements, the intermediate ZrF4·H2O and Zr2OF6·H2O were not observed and the dehydration from ZrF4·3H2O to ZrF4 was found to be routed directly. Present measurements by PAC exhibits dissimilar crystal structures for ZrF4·3H2O and ZrF4·H2O unlike the crystal structures found in hafnium analogous compounds.

  13. Copper diphosphonates with zero-, one- and two-dimensional structures: ferrimagnetism in layer compound Cu3(ImhedpH)(2).2H2O [ImhedpH4=(1-C3H3N2)CH2C(OH)(PO3H2)2].

    PubMed

    Cao, Deng-Ke; Xie, Xiao-Ji; Li, Yi-Zhi; Zheng, Li-Min

    2008-10-07

    Reactions of CuSO4 with 2-(1-imidazole)-1-hydroxy-1,1'-ethylidenediphosphonic acid (ImhedpH4) under hydrothermal conditions at different temperatures lead to four new metal phosphonates: Cu(ImhedpH3)2(H2O).2H2O (), Cu(ImhedpH3)2 (), Cu3(ImhedpH2)2(ImhedpH3)(2).4H2O (), and Cu3(ImhedpH)(2).2H2O (). Compounds and have mononuclear structures in which the Cu atoms adopt square pyramidal and square planar geometries, respectively. In compound , a chain structure is observed where the Cu3(ImhedpH2)2(ImhedpH3)2 trimer units are connected by edge-sharing of the {Cu2O5} square pyramids. Compound exhibits a layer structure made up of Cu3(ImhedpH)2 trimer units. The connection of trimers through corner-sharing of {Cu1O4} and {CPO3} tetrahedra results in a two-dimensional layer containing 8- and 16-membered rings. The imidazole groups are grafted on the two sides of the layer. Magnetic studies reveal that ferromagnetic interactions are mediated in , while for compound , ferrimagnetism is observed below 5.8 K.

  14. Measurement of /sup 2/H/sub 2/O by IR absorbance in doubly labeled H/sub 2/O studies of energy expenditure

    SciTech Connect

    Karasov, W.H.; Han, L.R.; Munger, J.C.

    1988-07-01

    The energy expenditure of animals in their natural surroundings can be determined by measuring the turnover in body water of isotopes of oxygen and hydrogen. We evaluated the use of infrared spectrophotometry for measuring /sup 2/H/sub 2/O in small (20-microliters) water samples also labeled with 18O. For /sup 2/H/sub 2/O over the enrichment range of 0.1-1 atom%, there was a linear relationship between infrared absorbance and /sup 2/H/sub 2/O enrichment. /sup 2/H/sub 2/O enrichments could be measured with a precision and accuracy of less than or equal to 1%, using this relationship. The presence of /sup 18/O in water samples in enrichments of up to 1 atom% had no significant effect on measurement of /sup 2/H/sub 2/O by infrared absorbance. We measured the simultaneous turnover rates of /sup 2/H/sub 2/O and /sup 3/H in mice and turtles also labeled with 18O. Our results validated the use of infrared absorbance in doubly labeled water measures of energy expenditure and indicated that the fractionation factors in vivo for /sup 2/H/sub 2/O and /sup 3/H do not differ.

  15. Metal phosphonates based on aminomethylenediphosphonate: Syntheses and characterization of Na{sub 4}Zn{l_brace}NH{sub 3}CH(PO{sub 3}){sub 2}{r_brace}{sub 2}.4H{sub 2}O, Ni{l_brace}NH{sub 3}CH(PO{sub 3}H){sub 2}{r_brace}{sub 2}.xH{sub 2}O and NaNi{sub 2}{l_brace}NH{sub 3}CH(PO{sub 3})(PO{sub 3}H{sub 0.5}){r_brace}{sub 2}(H{sub 2}O){sub 2}.2H{sub 2}O

    SciTech Connect

    Bao Songsong; Wang Tianwei; Li Yizhi; Zheng Limin . E-mail: lmzheng@nju.edu.cn

    2006-02-15

    This paper describes the syntheses of three transition metal diphosphonate compounds: Na{sub 4}Zn{l_brace}NH{sub 3}CH(PO{sub 3}){sub 2}{r_brace}{sub 2}.4H{sub 2}O (1), Ni{l_brace}NH{sub 3}CH(PO{sub 3}H){sub 2}{r_brace}{sub 2}.xH{sub 2}O (2) and NaNi{sub 2}{l_brace}NH{sub 3}CH(PO{sub 3})(PO{sub 3}H{sub 0.5}){r_brace}{sub 2}(H{sub 2}O){sub 2}.2H{sub 2}O (3). Compound 1 contains chains of [Zn{l_brace}NH{sub 3}CH(PO{sub 3}){sub 2}{r_brace}{sub 2}]{sub n}{sup 4n-} made up of corner-sharing ZnO{sub 6} octahedra and CPO{sub 3} tetrahedra, which are further connected by tetramers of edge-sharing NaO{sub 6} octahedra, forming a three-dimensional open-framework structure. Compound 2 shows a square-grid layer structure where the NiO{sub 6} octahedra are corner shared with CPO{sub 3} tetrahedra. The adjacent layers are linked by strong inter-layer hydrogen bonds, resulting in a three-dimensional open-network structure with channels where the lattice water molecules reside. The structure of compound 3 is analogous to that of NaCo{sub 2}{l_brace}NH{sub 3}CH(PO{sub 3})(PO{sub 3}H{sub 0.5}){r_brace}{sub 2}(H{sub 2}O){sub 2}.xH{sub 2}O in which layers of Ni{sub 2}{l_brace}NH{sub 3}CH(PO{sub 3})(PO{sub 3}H{sub 0.5}){r_brace}{sub 2}(H{sub 2}O){sub 2} are connected by NaO{sub 6} linkages into an open-framework structure. The magnetic studies show that weak antiferromagnetic interactions are mediated between the nickel ions in compounds 2 and 3. Crystal data for 1: triclinic, space group P-1, a=5.551(2)A, b=6.166(2)A, c=12.424(4)A, {alpha}=92.422(6){sup o}, {beta}=92.687(7){sup o}, {gamma}=93.926(6){sup o}, V=423.3(2)A{sup 3}, Z=2. For 2: triclinic, space group P-1, a=9.043(1)A, b=9.180(1)A, c=9.271(1)A, {alpha}=89.693(3){sup o}, {beta}=70.202(3){sup o}, {gamma}=89.530(3){sup o}, V=724.1(2)A{sup 3}, Z=2.

  16. ON THE FORMATION AND ISOMER SPECIFIC DETECTION OF PROPENAL (C{sub 2}H{sub 3}CHO) AND CYCLOPROPANONE (c-C{sub 3}H{sub 4}O) IN INTERSTELLAR MODEL ICES—A COMBINED FTIR AND REFLECTRON TIME-OF-FLIGHT MASS SPECTROSCOPIC STUDY

    SciTech Connect

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

    2015-11-20

    The formation routes of two structural isomers—propenal (C{sub 2}H{sub 3}CHO) and cyclopropanone (c-C{sub 3}H{sub 4}O)—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 (C{sub 2}H{sub 3}CHO) and cyclopropanone (c-C{sub 3}H{sub 4}O)—in ethylene (C{sub 2}H{sub 4})—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.

  17. 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

  18. The CW-CRDS spectra of the 16O/18O isotopologues of ozone between 5930 and 6340 cm-1—Part 3: 16O18O18O and 18O16O18O

    NASA Astrophysics Data System (ADS)

    De Backer, M.-R.; Barbe, A.; Starikova, E.; Tyuterev, Vl. G.; Mondelain, D.; Kassi, S.; Campargue, A.

    2013-09-01

    Our systematic investigation of the high sensitivity CW-Cavity Ring Down Spectra of 16O/18O ozone isotopologues at high vibrational excitation continues with the study of the 16O18O18O and 18O16O18O species. The first two papers of this series were devoted to the analysis of the same four bands of the 16O16O18O and 16O18O16O species in the 5930-6340 cm-1domain. Here, after a brief reminder of relevant experiment and theory, we report the analyses of two bands of 16O18O18O, vibrationally assigned as 2ν2+5ν3 and 2ν1+2ν2+3ν3_2 and three bands of 18O16O18O, assigned to 2ν1+2ν2+3ν3_1, 5ν1+ν3 and 3ν1+ν2+3ν3.They correspond to the highest vibration excitations observed so far for the 16O18O18O and 18O16O18O isotopologues. Altogether for the two new bands of 16O18O18O, 1214 rovibrational transitions were assigned up to Jmax=29 and for the three new bands of 18O16O18O, 948 rovibrational transitions were assigned up to Jmax=27. Observed line positions were fitted with root-mean squares deviations ranging from 0.005 to 0.011 cm-1, using effective Hamiltonian models accounting for dark state perturbations. The derived band centres and rotational constants are in good agreement with new theoretical calculations from the molecular potential function. The corresponding lists of 3365 lines are provided as Supplementary material.

  19. δ18O anchoring to VPDB: calcite digestion with 18O-adjusted ortho-phosphoric acid.

    PubMed

    Wendeberg, Magnus; Richter, Jürgen M; Rothe, Michael; Brand, Willi A

    2011-04-15

    For anchoring CO(2) isotopic measurements on the δ(18)O(VPD-CO2) scale, the primary reference material (NBS 19 calcite) needs to be digested using concentrated ortho-phosphoric acid. During this procedure, great care must be taken to ensure that the isotopic composition of the liberated gas is accurate. Apart from controlling the reaction temperature to ±0.1 °C, the potential for oxygen isotope exchange between the produced CO(2) and water must be kept to a minimum. The water is usually assumed to reside on the walls in the headspace of the reaction vessel. We demonstrate here that a large fraction of the exchange may also occur with water inside the acid. Our results indicate that both exchange reactions have a significant impact on the results and may have largely been responsible for scale inconsistencies between laboratories in the past. The extent of CO(2)/H(2)O oxygen exchange depends on the concentration (amount of free water) in the acid. For acids with a nominal H(3)PO(4) mass fraction of less than 102%, oxygen isotope exchange can create a substantial isotopic bias during high-precision measurements with the degree of the alteration being proportional to the effective isotopic contrast between the acid and the CO(2) released from the calcite. Water evaporating from the acid at 25 °C has a δ(18)O value of -34.5‰ relative to the isotopic composition of the whole acid. This large fractionation is likely to occur in two steps; by exchange with phosphate, water inside the acid is decreased in oxygen-18 relative to the bulk acid by ∼ -22‰. This water is then fractionated further during evaporation. Oxygen exchange with both water inside the acid and water condensate in the headspace can contribute to the measured isotopic signature depending on the experimental parameters. The system employed for this study has been specifically designed to minimize oxygen exchange with water. However, the amount of altered CO(2) for a 95% H(3)PO(4) at 25 °C still

  20. The Hydrothermal NH 4/V/P/H 2O and K/v/p/n(c 2H 5) 3/H 2O Systems at 473 K and the Crystal Structures of NH 4VOPO 4and (nh 4) 3V 2O 3(VO)(PO 4) 2(HPO 4)

    NASA Astrophysics Data System (ADS)

    Schindler, Michael; Joswig, Werner; Baur, Werner H.

    1997-12-01

    An examination of the NH 4/VO 5/P/H 2O system at 473 K under hydrothermal conditions yielded the (NH 4) 3V 2O 3(VO)(PO 4) 2(HPO 4) and NH 4VOPO 4phases. The crystal structure of the first compound is isotypical with the corresponding Tl +and K +phases. The cations NH +4and Tl +have similar coordinations against oxygen. The investigation of the crystal structure of the second compound (space group Pn2 n) shows it to be related to other ABO TO 4phases of the potassium titanyl phosphate type with A=Na +, Ag +, NH +4, Rb +, K +, and Tl +, and B=Ti 4+, V 4+, Sn 4+, Fe 4+, Ge 4+, Ga 3+, Zr 4+, Sb 5+, and Nb 5+, and T=P 5+, Ge 4+, Si 4+, and As 5+, but none of them crystallize in space group Pn2 n. In the K/V/P/N(C 2H 5) 3/H 2O system, three different K phases were found: K 0.5VOPO 4·1.5H 2O, KVOPO 4, and K-FVP-1 (Frankfurt vanadium phosphate, one, or for short, FVP-1). The microporous K-FVP-1 compound was synthesized in a similar pH range as the isotypic Na-FVP-1 phase. The V 4+/V 5+ratio of K-FVP-1 varies from 3.5(1)/1.5(1) to 1.6(1)/3.4(1) and the corresponding lattice constants range from 16.0013(6) to 15.7665(4) Å.

  1. Distinguishing sources of ground water recharge by using delta2H and delta18O.

    PubMed

    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.

  2. 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.

  3. 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.

  4. Evolution of low-18O Icelandic crust

    NASA Astrophysics Data System (ADS)

    Pope, Emily C.; Bird, Dennis K.; Arnórsson, Stefán

    2013-07-01

    The Krafla central volcano in the neovolcanic zone of Iceland hosts a chemically diverse suite of magmas characterized by anomalously low δ18O values. A rhyolite magma intercepted by the Iceland Deep Drilling Project (IDDP) exploratory well at 2.1 km depth provided a unique opportunity to investigate the origins of an unerupted rhyolite melt in the primarily basaltic central volcano at Krafla. Here we compare whole rock hydrogen and oxygen isotopes of this melt to those of lavas within and near the caldera of the Krafla central volcano ranging from recent fissure eruptions to Plio--Pleistocene age (including analyses of 18 new samples, plus previously published values) in order to evaluate the petrogenesis of low-18O magmas within the neovolcanic zone of Iceland. Oxygen isotope values of the IDDP-1 melt (δ18O=+3.2±0.2‰) are within the range of Krafla eruptives that have a bimodal composition of olivine-tholeiite and rhyolite (δ18O=+1.6‰ to +4.5‰). Lavas show significantly more variability in hydrogen isotope values (δD=-161‰ to -92‰) than the IDDP-1 melt (-121±2‰), whose δD is comparable to local hydrothermal epidote (-127 to -108‰), and show significantly lower water contents than IDDP-1 (0.1-1.1 wt%, in contrast to ~1.8 wt%). Basaltic to dacitic lavas from the proximal Heidarspordur ridge volcanic zone have δ18O between +3.4‰ and +4.2‰ and δD between -105‰ and -99‰. Uniformity of oxygen isotopes in the Heidarspordur ridge lavas suggests that their magmatic compositional variations are a consequence of fractional crystallization. The δD of the glass sampled by IDDP-1 unequivocally identifies the source of silicic low-18O melts like those erupted from within the caldera of the Krafla volcano as anatexis of meteoric-hydrothermally altered basalts resulting from the intrusion of mantle-derived basaltic magma. Finally, mantle-derived basalts in both the Krafla central volcano and Heidarspordur ridge (MgO>5 wt%) have δ18O values lower

  5. Measurements of 18O18O and 17O18O in the atmosphere and the role of isotope-exchange reactions

    NASA Astrophysics Data System (ADS)

    Yeung, Laurence Y.; Young, Edward D.; Schauble, Edwin A.

    2012-09-01

    Of the six stable isotopic variants of O2, only three are measured routinely. Observations of natural variations in 16O18O/16O16O and 16O17O/16O16O ratios have led to insights in atmospheric, oceanographic, and paleoclimate research. Complementary measurements of the exceedingly rare 18O18O and 17O18O isotopic variants might therefore broaden our understanding of oxygen cycling. Here we describe a method to measure natural variations in these multiply substituted isotopologues of O2. Its accuracy is demonstrated by measuring isotopic effects for Knudsen diffusion and O2 electrolysis in the laboratory that are consistent with theoretical predictions. We then report the first measurements of 18O18O and 17O18O proportions relative to the stochastic distribution of isotopes (i.e., Δ36 and Δ35 values, respectively) in tropospheric air. Measured enrichments in 18O18O and 17O18O yield Δ36 = 2.05 ± 0.24‰ and Δ35 = 1.4 ± 0.5‰ (2σ). Based on the results of our electrolysis experiment, we suggest that autocatalytic O(3P) + O2 isotope exchange reactions play an important role in regulating the distribution of 18O18O and 17O18O in air. We constructed a box model of the atmosphere and biosphere that includes the effects of these isotope exchange reactions, and we find that the biosphere exerts only a minor influence on atmospheric Δ36 and Δ35 values. O(3P) + O2 isotope exchange in the stratosphere and troposphere is therefore expected to govern atmospheric Δ36 and Δ35 values on decadal timescales. These results suggest that the `clumped' isotopic composition of atmospheric O2in ice core records is sensitive to past variations in atmospheric dynamics and free-radical chemistry.

  6. O18O and C18O observations of ρ Ophiuchi A

    NASA Astrophysics Data System (ADS)

    Liseau, R.; Larsson, B.; Bergman, P.; Pagani, L.; Black, J. H.; Hjalmarson, Å.; Justtanont, K.

    2010-02-01

    Context. Contrary to theoretical expectation, surprisingly low concentrations of molecular oxygen, O2, have been found in the interstellar medium. Telluric absorption makes ground based O2 observations essentially impossible and observations had to be done from space. Millimetre-wave telescopes on space platforms were necessarily small, which resulted in large, several arcminutes wide, beam patterns. Observations of the (NJ = 11-10) ground state transition of O2 with the Odin satellite resulted in a ≳ 5σ detection toward the dense core ρ {Oph A}. At the frequency of the line, 119 GHz, the Odin telescope has a beam width of 10', larger than the size of the dense core. Aims: The precise nature of the emitting source and its exact location and extent are therefore unknown. The current investigation is intended to remedy this. Methods: Although the Earth's atmosphere is entirely opaque to low-lying O2 transitions, it allows ground based observations of the much rarer 16O18O in favourable conditions and at much higher angular resolution with larger telescopes. In addition, ρ {Oph A} exhibits both multiple radial velocity systems and considerable velocity gradients. Extensive mapping of the region in the proxy C18O (J = 3-2) line can be expected to help identify the O2 source on the basis of its line shape and Doppler velocity. Line opacities were determined from observations of optically thin 13C18O (J = 3-2). During several observing periods, two C18O intensity maxima in ρ {Oph A} were searched for O18O in the (21-01) line at 234 GHz with the 12 m APEX telescope. These positions are associated also with peaks in the mm-continuum emission from dust. Results: Our observations resulted in an upper limit on the integrated O18O intensity of int T*A d\\upsilon < 0.01 K km s-1 (3 σ) into the 26.6 arcsec beam. Together with the C18O data, this leads to a ratio of N(C18O)/N(O18O) > 16. Combining Odin's O2 with the present O18O observations we infer an O2 abundance 5

  7. Oxidation of potentials of the Me(IV)-Me(III) couple and the thermodynamics of the reactions Me/sup 3 +/ + H/sup +/ reversible Me/sup 4 +/ + 1/2H/sub 2/ (Me = Bk, Ce) in different media

    SciTech Connect

    Timofeev, G.A.; Chistyakov, V.M.; Erin, E.A.; Baranov, A.A.

    1987-11-01

    The values of the real oxidation potentials E/sub p//sup 0/ of the couples Bk(IV)-Bk(III) in solutions of perchloric, nitric, and phosphoric acids, potassium phosphotungstate, and sodium and potassium carbonates are measured by differential coulopotentiometry. It is shown that when solutions of sulfuric acid phosphoric acids, potassium phosphotungstate, and sodium and potassium carbonates are used in place of perchloric and nitric acids the E/sub p//sup 0/ value moves in the negative direction for both berkelium and cerium, which indicates strong complexation of ions of these elements. The thermodynamic parameters ..delta..G, ..delta..H, and ..delta..S of the reaction Me/sup 3 +/ + H/sup +/ reversible Me/sup 4 +/ + 12 H/sub 2/ (Me = Bk, Ce) are determined

  8. 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.

  9. Chironomid δ 18O as a proxy for past lake water δ 18O: a Lateglacial record from Rotsee (Switzerland)

    NASA Astrophysics Data System (ADS)

    Verbruggen, F.; Heiri, O.; Reichart, G.-J.; Lotter, A. F.

    2010-08-01

    We explored whether the stable oxygen isotope composition (δ 18O) of fossil chironomid remains can be used to reconstruct past variations in lake water δ 18O from Lateglacial and early Holocene sediments from Rotsee (Switzerland). A sediment core from the former littoral zone of the lake was examined since it contained both high concentrations of chironomid remains and abundant authigenic carbonates and therefore allowed a direct comparison of chironomid δ 18O with values measured on bulk carbonates. Since carbonate particles adhering to chironomid remains potentially affect 18O measurements we tested two methods to chemically remove residual carbonates. Trials with isotopically heavy and light acid solutions indicated that treatment with hydrochloric acid promoted oxygen exchange between chironomid remains and the water used during pretreatment. In contrast, a buffered 2 M ammonium chloride (NH 4Cl) solution did not seem to affect chironomid δ 18O to a significant extent. Fossil chironomid δ 18O was analyzed for the Rotsee record both using standard palaeoecological methods and after pretreatment with NH 4Cl. Samples prepared using standard techniques showed a poor correlation with δ 18O of bulk carbonate ( r2 = 0.14) suggesting that carbonate contamination of the chironomid samples obscured the chironomid δ 18O signature. Samples pretreated with NH 4Cl correlated well with bulk carbonate δ 18O ( r2 = 0.67) and successfully tracked the well-known Lateglacial changes in δ 18O. Chironomid δ 18O indicated depleted lake water δ 18O during the Oldest Dryas period, the Aegelsee and Gerzensee Oscillations, and the Younger Dryas, whereas enriched δ 18O values were associated with sediments deposited during the Lateglacial interstadial and the early Holocene. Differences in the amplitude of variations in bulk carbonate and chironomid δ 18O are attributed to differential temperature effects on oxygen isotope fractionation during the formation of carbonates and

  10. 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.

  11. 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.

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

    PubMed

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

    2015-06-03

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

  13. Decadal patterns in δ18O of atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Zakem, E.; White, J. W.

    2010-12-01

    The stable oxygen isotope 18O is unique to isotope ecology in that it links the hydrosphere to the carbon cycle. Since land biosphere fluxes are the dominant influences on 18O of atmospheric CO2, particularly on shorter times scales, analysis of atmospheric δ18O trends can provide useful insight into the terrestrial carbon cycle. The isotopic values imprinted by leaf water and soil water exchanges with CO2 out-compete those from ocean exchange, fossil fuel and biomass burning, and stratospheric reactions. The opposing isotopic imprints of photosynthesis and ecosystem respiration therefore control the majority of atmospheric 18O concentration. The resulting seasonal cycle in δ18O data of peaks during early summer, when photosynthesis dominates, and lows during early winter, when respiration dominates, has been clearly established. However, the reasons for the interannual variability of atmospheric 18O remain unknown. Studies have shown that the size and isotopic value of the “retrodiffusion” flux- the CO2 that enters and exits leaves without being fixed by photosynthesis- is a function of stomatal conductance, which is affected by the relative humidity in the surrounding atmosphere. We observe that data from numerous global sites shows a global decadal oscillation in δ18O, suggesting a climatological forcing. We compare decadal trends in δ18O with climate oscillations and the 11-year solar cycle, as well as relative humidity records, examining correlations and proposing associated mechanisms. Understanding the decadal patterns in atmospheric 18O of CO2 will shed light on global terrestrial carbon fluxes and the carbon-water interaction on decadal time scales, potentially helping to scale human versus natural impacts on this coupled system.

  14. Organic-Inorganic Hybrid Materials Based on Basket-like {Ca⊂P6Mo18O73} Cages.

    PubMed

    Zhang, He; Yu, Kai; Lv, Jing-hua; Gong, Li-hong; Wang, Chun-mei; Wang, Chun-xiao; Sun, Di; Zhou, Bai-Bin

    2015-07-20

    Four basket-like organic-inorganic hybrids, formulated as [{Cu(II)(H2O)2}{Ca4(H2O)4(HO0.5)3(en)2}{Ca⊂P6Mo4(V)Mo14(VI)O73}]·7H2O (1), (H4bth)[{Fe(II)(H2O)}{Ca⊂P6Mo18(VI)O73}]·4H2O (2), (H2bih)3[{Cu(II)(H2O)2}{Ca⊂P6Mo2(V)Mo16(VI)O73}]·2H2O (3), (H2bib)3[{Fe(II)(H2O)2}{Ca⊂P6Mo2(V) Mo16(VI)O73}]·4H2O (4), (bth = 1,6-bis(triazole)hexane; bih = 1,6-bis(imidazol)hexane; bib = 1,4-bis(imidazole)butane) have been hydrothermally synthesized and fully characterized. Compounds 1-4 contain polyoxoanion [Ca⊂P6Mon(V)Mo18-n(VI)O73]((6+n)-) (n = 0, 2, or 4) (abbreviated as {P6Mo18O73}) as a basic building block, which is composed of a "basket body" {P2Mo14} unit and a "handle"-liked {P4Mo4} fragment encasing an alkaline-earth metal Ca(2+) cation in the cage. Compound 1 exhibits an infrequent 2D layer structure linked by the Cu(H2O)2 linker and an uncommon tetranuclear calcium complex, while compound 2 is 8-connected 2-D layers connected by binuclear {Fe2(H2O)3} segaments, which are observed for the first time as 2-D basket-like assemblies. Compounds 3 and 4 are similar 1D Z-typed chains bonded by M(H2O)2 units (M = Cu for 3 and Fe for 4). The optical band gaps of 1-4 reveal their semiconductive natures. They exhibit universal highly efficient degradation ability for typical dyes such as methylene blue, methyl orange, and rhodamine B under UV light. The lifetime and catalysis mechanism of the catalysts have been investigated. The compounds also show good bifunctional electrocatalytic behavior for oxidation of amino acids and reduction of NO2(-).

  15. Estimate of recharge of a rising water table in semiarid Niger from 3H and 14C modeling.

    PubMed

    Favreau, Guillaume; Leduc, Christian; Marlin, Christelle; Dray, Martial; Taupin, Jean-Denis; Massault, Marc; Le, GalLaSalleCorinne; Babic, Milanka

    2002-01-01

    A hydrodynamic survey carried out in semiarid southwest Niger revealed an increase in the unconfined ground water reserves of approximately 10% over the last 50 years due to the clearing of native vegetation. Isotopic samplings (3H, 18O, 2H for water and 14C, 13C for the dissolved inorganic carbon) were performed on about 3500 km2 of this silty aquifer to characterize recharge. Stable isotope analyses confirmed the indirect recharge process that had already been shown by hydrodynamic surveys and suggested the tracers are exclusively of atmospheric origin. An analytical model that takes into account the long-term rise in the water table was used to interpret 3H and 14C contents in ground water. The natural, preclearing median annual renewal rate (i.e., recharge as a fraction of the saturated aquifer volume) lies between 0.04% and 0.06%. For representative characteristics of the aquifer (30 m of saturated thickness, porosity between 10% and 25%), this implies a recharge of between 1 and 5 mm/year, which is much lower than the estimates of 20 to 50 mm/year for recent years, obtained using hydrological and hydrodynamic methods and the same aquifer parameters. Our study, therefore, reveals that land clearing in semiarid Niger increased ground water recharge by about one order of magnitude.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  17. Analysis and theoretical modeling of 18O enriched carbon dioxide spectrum by CRDS near 1.35 μm: (II) 16O13C18O, 16O13C17O, 12C18O2, 17O12C18O, 12C17O2, 13C18O2 and 17O13C18O

    NASA Astrophysics Data System (ADS)

    Karlovets, E. V.; Campargue, A.; Kassi, S.; Tashkun, S. A.; Perevalov, V. I.

    2017-04-01

    This contribution is the second part of the analysis of the room temperature absorption spectrum of 18O enriched carbon dioxide by very high sensitivity Cavity Ring Down spectroscopy between 6977 and 7918 cm-1 (1.43-1.26 μm). Overall, more than 8600 lines belonging to 166 bands of eleven carbon dioxide isotopologues were rovibrationnally assigned. In a first part (Kassi et al. J Quant Spectrosc Radiat Transfer 187 (2017) 414-425, http://dx.doi.org/10.1016/j.jqsrt.2016.09.002), the results relative to mono-substituted isotopologues, 16O12C18O, 16O12C17O, 12C16O2 and 13C16O2, were presented. This second contribution is devoted to the multiply-substituted isotopologues or clumped isotopologues of particular importance in geochemistry: 16O13C18O, 16O13C17O, 12C18O2, 17O12C18O, 12C17O2, 13C18O2 and 17O13C18O. On the basis of the predictions of effective Hamiltonian models, a total of 3195 transitions belonging to 73 bands were rovibrationnally assigned for these seven species. Among the 73 observed bands, 55 are newly reported. All the identified bands correspond to ΔP=10 and 11 series of transitions, where P= 2V1+V2+3V3 is the polyad number (Vi are vibrational quantum numbers). The accurate spectroscopic parameters of 70 bands have been determined from the standard band-by-band analysis. Global fits of the measured line intensities of the ΔP=10 series of transitions of 17O12C18O and 16O13C18O and of the ΔP=11 series of transitions of 12C18O2, 17O12C18O, 16O13C18O and 13C18O2 were performed to determine the corresponding sets of the effective dipole moment parameters.

  18. 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

  19. Muon Capture on ^3H

    NASA Astrophysics Data System (ADS)

    Golak, Jacek; Skibiński, Roman; Witała, Henryk; Topolnicki, Kacper; Kamada, Hiroyuki; Nogga, Andreas; Marcucci, Laura E.

    2017-01-01

    The μ ^- + ^3H → ν _μ + n + n + n capture reaction is studied under full inclusion of final-state interactions with the AV18 nucleon-nucleon potential and the Urbana IX three-nucleon force. We employ the single nucleon weak current operator comprising the dominant relativistic corrections to obtain first estimates of the total capture rates based on realistic forces. Our results are compared with older theoretical predictions.

  20. 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.

  1. 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...

  2. K9[H4V18O42(NO2)]•14H2O•4N2H4

    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'.

  3. K9[H4V18O42(Br)]•14H2O•4N2H4

    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'.

  4. 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...

  5. The use of groundwater tracers, including {sup 36}Cl, {delta}{sup 18}O, and {delta}{sup 2}JH, in the study fo the Magothy aquifer, Maryland

    SciTech Connect

    Bond, C.A.; Mignerey, A.C.; Helz, G.R.

    1995-12-01

    The recent conclusion of a study of groundwater from the Magothy Formation, Maryland allows for an examination of processes occurring in this aquifer system. Water samples were gathered from a wide area along flow paths estimated from hydrological parameters and analyzed for the major cations and anions, nutrients, and {sup 87}Sr/{sup 86}Sr ratios, in addition to {sup 36}Cl, {delta}{sup 18}O, and {delta}{sup 2}H. Also, three samples that contained anomalously high {sup 36}Cl/Cl ratios were analyzed for {sup 3}H in an attempt to determine possible sources for those readings. A comparison of the results of this study to those of a previous study conducted by this group of the overlying Aquia Aquifer will also be given. The potential of inter-aquifer mixing between the two systems in some areas and of matching {sup 36}Cl and Cl{sup -} values to sea level rise and fall will be discussed.

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

    PubMed Central

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

    2015-01-01

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

  7. Theoretical exploration of hydrogen loss from Al3H9.

    PubMed

    Nold, Christopher P; Head, John D

    2012-05-03

    The Al(3)H(9) and Al(3)H(7) potential energy surfaces were explored using quantum chemistry calculations to investigate the H(2) loss mechanism from Al(3)H(9), which provide new insights into hydrogen production from bulk alane, [AlH(3)](x), a possible energy storage material. We present results of B3LYP/6-311++G(d,p) calculations for the various Al(3)H(9) and Al(3)H(7) optimized local minima and transition state structures along with some reaction pathways for their interconversion. We find the energy for Al(3)H(9) decomposition into Al(2)H(6) and AlH(3) is slightly lower than that for H(2) loss and Al(3)H(7) formation, but the calculations show that H(2) loss from Al(3)H(9) is a lower energy process than for losing hydrogen from either Al(2)H(6) or AlH(3). We found four transition state structures and reaction pathways for Al(3)H(9) → Al(3)H(7) + H(2), where the lowest energy activation barrier is around 25-73 kJ/mol greater than the experimental value for H(2) loss from bulk alane. Intrinsic reaction coordinate calculations show that the H(2) loss pathway involves considerable rearrangement of the H atom positions around a single Al center. Three of the pathways start with the formation of an AlH(3) moiety, which then enables a terminal H on the AlH(3) to get within 1.1 to 1.2 Å of a nearby bridging H atom. The bridging and terminal H atoms eventually combine to form H(2) and leave Al(3)H(9). One implication of these H(2) loss reaction pathways is that, since the H atoms in bulk alanes are all at bridging positions, if a similar H(2) loss mechanism were to apply to bulk alane, then H(2) loss would most likely occur on the bulk alane surface or at a defect site where there should be more terminal H atoms available for reaction with nearby bridging H atoms.

  8. Effect of sequence of administration on the pharmacokinetic interaction between the anticholinergic drug biperiden and [3H]quinuclidinyl benzylate or [3H]N-methylscopolamine in rats.

    PubMed

    Ishizaki, J; Yokogawa, K; Nakashima, E; Takayasu, T; Ohshima, T; Ichimura, F

    1998-02-01

    In rats the pharmacokinetic interactions between the anticholinergic drug biperiden and [3H]quinuclidinyl benzylate ([3H]QNB) or [3H]N-methylscopolamine ([3H]NMS) is affected by the sequence in which the drugs are administered. Drug concentrations in various tissues were determined after intravenous administration of [3H]QNB or [3H]NMS (325 ng kg(-1)). Biperiden (6.4 mg kg(-1)) was administered either 5 min before, concomitantly with or 20 min after injection of [3H]QNB or [3H]NMS. When biperiden was administered concomitantly with or before [3H]QNB, distribution of [3H]QNB among the regions of the brain and other tissues was reduced; at 4 h the ratio of the distribution of [3H]QNB for experimental animals to that for control animals ranged from 0.15 to 0.9. When biperiden was administered after [3H]QNB, the distribution of [3H]QNB in the brain and other tissues was significantly higher than for the other two treatments (P < 0.01). However, for [3H]NMS the sequence of administration had no effect on the distribution of the drug in the brain and other tissues except for the kidney. In-vitro, in crude synaptosomal membranes, the amount of [3H]QNB at 2 h relative to the control concentration at equilibrium was 87% when biperiden was added before [3H]QNB and 56% when biperiden was added after [3H]QNB. In both instances the concentration of [3H]NMS reached equilibrium within 30 min. These findings suggest that the difference between the rate constant of association and dissociation at the possible site of action gives rise to the effect of the sequence of administration on the pharmacokinetic interaction.

  9. 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...

  10. 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.

  11. Forward modeling of δ18O in Andean ice cores

    NASA Astrophysics Data System (ADS)

    Hurley, J. V.; Vuille, M.; Hardy, D. R.

    2016-08-01

    Tropical ice core archives are among the best dated and highest resolution from the tropics, but a thorough understanding of processes that shape their isotope signature as well as the simulation of observed variability remain incomplete. To address this, we develop a tropical Andean ice core isotope forward model from in situ hydrologic observations and satellite water vapor isotope measurements. A control simulation of snow δ18O captures the mean and seasonal trend but underestimates the observed intraseasonal variability. The simulation of observed variability is improved by including amount effects associated with South American cold air incursions, linking synoptic-scale disturbances and monsoon dynamics to tropical ice core δ18O. The forward model was calibrated with and run under present-day conditions but can also be driven with past climate forcings to reconstruct paleomonsoon variability. The model is transferable and may be used to render a (paleo)climatic context at other ice core locations.

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

    SciTech Connect

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

    1980-01-01

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

  13. 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

  14. CAF-1-induced oligomerization of histones H3/H4 and mutually exclusive interactions with Asf1 guide H3/H4 transitions among histone chaperones and DNA.

    PubMed

    Liu, Wallace H; Roemer, Sarah C; Port, Alex M; Churchill, Mair E A

    2012-12-01

    Anti-silencing function 1 (Asf1) and Chromatin Assembly Factor 1 (CAF-1) chaperone histones H3/H4 during the assembly of nucleosomes on newly replicated DNA. To understand the mechanism of histone H3/H4 transfer among Asf1, CAF-1 and DNA from a thermodynamic perspective, we developed and employed biophysical approaches using full-length proteins in the budding yeast system. We find that the C-terminal tail of Asf1 enhances the interaction of Asf1 with CAF-1. Surprisingly, although H3/H4 also enhances the interaction of Asf1 with the CAF-1 subunit Cac2, H3/H4 forms a tight complex with CAF-1 exclusive of Asf1, with an affinity weaker than Asf1-H3/H4 or H3/H4-DNA interactions. Unlike Asf1, monomeric CAF-1 binds to multiple H3/H4 dimers, which ultimately promotes the formation of (H3/H4)(2) tetramers on DNA. Thus, transition of H3/H4 from the Asf1-associated dimer to the DNA-associated tetramer is promoted by CAF-1-induced H3/H4 oligomerization.

  15. A dipseudoacid, C 16H 18O 6

    NASA Astrophysics Data System (ADS)

    Liskin, Dmitriy V.; Valente, Edward J.

    2008-04-01

    Pseudoacids, or cyclic oxocarboxylic acids commonly form non-planar, complementary and non-cooperative, dimeric hydrogen-bonds. A dehydration resistant arylpyran dipseudoacid, C 16H 18O 6, has been synthesized and characterized. Crystals of trans-4,4,8,8-tetramethyl-3,7-dihydroxy-1,2,3,4,5,6,7,8-octahydro-2,6-dioxaanthracen-1,5-dione occur in the monoclinic system and form linear hydrogen-bonded chains; it has an elevated melting point without decomposition at 574.6 K.

  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. Immobilization of Ag(i) into a metal-organic framework with -SO3H sites for highly selective olefin-paraffin separation at room temperature.

    PubMed

    Chang, Ganggang; Huang, Minhui; Su, Ye; Xing, Huabin; Su, Baogen; Zhang, Zhiguo; Yang, Qiwei; Yang, Yiwen; Ren, Qilong; Bao, Zongbi; Chen, Banglin

    2015-02-18

    Introduction of Ag(i) ions into a sulfonic acid functionalized MOF ((Cr)-MIL-101-SO3H) significantly enhances its interactions with olefin double bonds, leading to its much higher selectivities for the separation of C2H4-C2H6 and C3H6-C3H8 at room temperature over the original (Cr)-MIL-101-SO3H and other adsorbents at room temperature.

  18. 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

  19. 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

  20. Dynamically biased statistical model for the ortho/para conversion in the H2+H3+ --> H3++ H2 reaction

    NASA Astrophysics Data System (ADS)

    Gómez-Carrasco, Susana; González-Sánchez, Lola; Aguado, Alfredo; Sanz-Sanz, Cristina; Zanchet, Alexandre; Roncero, Octavio

    2012-09-01

    In this work we present a dynamically biased statistical model to describe the evolution of the title reaction from statistical to a more direct mechanism, using quasi-classical trajectories (QCT). The method is based on the one previously proposed by Park and Light [J. Chem. Phys. 126, 044305 (2007), 10.1063/1.2430711]. A recent global potential energy surface is used here to calculate the capture probabilities, instead of the long-range ion-induced dipole interactions. The dynamical constraints are introduced by considering a scrambling matrix which depends on energy and determine the probability of the identity/hop/exchange mechanisms. These probabilities are calculated using QCT. It is found that the high zero-point energy of the fragments is transferred to the rest of the degrees of freedom, what shortens the lifetime of H_5^+ complexes and, as a consequence, the exchange mechanism is produced with lower proportion. The zero-point energy (ZPE) is not properly described in quasi-classical trajectory calculations and an approximation is done in which the initial ZPE of the reactants is reduced in QCT calculations to obtain a new ZPE-biased scrambling matrix. This reduction of the ZPE is explained by the need of correcting the pure classical level number of the H_5^+ complex, as done in classical simulations of unimolecular processes and to get equivalent quantum and classical rate constants using Rice-Ramsperger-Kassel-Marcus theory. This matrix allows to obtain a ratio of hop/exchange mechanisms, α(T), in rather good agreement with recent experimental results by Crabtree et al. [J. Chem. Phys. 134, 194311 (2011), 10.1063/1.3587246] at room temperature. At lower temperatures, however, the present simulations predict too high ratios because the biased scrambling matrix is not statistical enough. This demonstrates the importance of applying quantum methods to simulate this reaction at the low temperatures of astrophysical interest.

  1. Terahertz spectroscopy of ground state HD18O

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  2. 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.

  3. 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.

  4. Transformation of ENSO-related rainwater to dripwater δ18O variability by vadose water mixing

    NASA Astrophysics Data System (ADS)

    Moerman, Jessica W.; Cobb, Kim M.; Partin, Judson W.; Meckler, A. Nele; Carolin, Stacy A.; Adkins, Jess F.; Lejau, Syria; Malang, Jenny; Clark, Brian; Tuen, Andrew A.

    2014-11-01

    Speleothem oxygen isotopes (δ18O) are often used to reconstruct past rainfall δ18O variability, and thereby hydroclimate changes, in many regions of the world. However, poor constraints on the karst hydrological processes that transform rainfall signals into cave dripwater add significant uncertainty to interpretations of speleothem-based reconstructions. Here we present several 6.5 year, biweekly dripwater δ18O time series from northern Borneo and compare them to local rainfall δ18O variability. We demonstrate that vadose water mixing is the primary rainfall-to-dripwater transformation process at our site, where dripwater δ18O reflects amount-weighted rainfall δ18O integrated over the previous 3-10 months. We document large interannual dripwater δ18O variability related to the El Niño-Southern Oscillation (ENSO), with amplitudes inversely correlated to dripwater residence times. According to a simple stalagmite forward model, asymmetrical ENSO extremes produce significant offsets in stalagmite δ18O time series given different dripwater residence times. Our study highlights the utility of generating multiyear, paired time series of rainfall and dripwater δ18O to aid interpretations of stalagmite δ18O reconstructions.

  5. The in vitro biological activities of synthetic 18-O-methyl mycalamide B, 10-epi-18-O-methyl mycalamide B and pederin.

    PubMed

    Richter, A; Kocienski, P; Raubo, P; Davies, D E

    1997-04-01

    Mycalamides A and B, which were originally isolated from a marine sponge, show close structural similarity to the insect toxin pederin, and exhibit potent cytotoxicity and antitumour activity. Detailed investigation of the clinical potential of these compounds has been hampered because they are available in only minute quantities from natural sources. We now describe the biological activities of 18-O-methyl mycalamide B, 10-epi-18-O-methyl mycalamide and pederin, all prepared by total synthesis. The activities of 18-O-methyl mycalamide B and pederin were virtually indistinguishable when evaluated in DNA or protein synthesis assays, and in cytotoxicity assays using human carcinoma cell lines (IC50s 0.2-0.6 nM). In all assays, 10-epi-18-O-methyl mycalamide B was 10(3) times less toxic than its diastereoisomer, demonstrating that the cytotoxicity of 18-O-methyl mycalamide B is inseparable from its ability to inhibit protein synthesis. Short-term exposure of squamous carcinoma cells to 18-O-methyl mycalamide B or pederin caused an irreversible inhibition of cellular proliferation and induced cellular necrosis. In contrast, the antiproliferative effects of the compounds on human fibroblasts were reversible and there was no evidence of necrosis. Demonstration that 18-O-methyl mycalamide B and the synthetically less complex molecule, pederin, show some tumour cell toxicity indicates that this novel class of compounds should be subjected to preclinical evaluation.

  6. Experimental and theoretical investigations of the sulfite-based polyoxometalate cluster redox series: alpha- and beta-[Mo(18)O(54)(SO(3))(2)](4-/5-/6-).

    PubMed

    Baffert, Carole; Boas, John F; Bond, Alan M; Kögerler, Paul; Long, De-Liang; Pilbrow, John R; Cronin, Leroy

    2006-11-15

    The synthesis, isolation and structural characterization of the sulfite polyoxomolybdate clusters alpha-(D(3h))(C(20)H(44)N)(4){alpha-[Mo(18)O(54)(SO(3))(2)]}CH(3)CN and beta-(D(3d))(C(20)H(44)N)(4){beta-[Mo(18)O(54)(SO(3))(2)]}CH(3)CN is presented. Voltammetric studies in acetonitrile (0.1 M Hx(4)NClO(4), Hx(4)N=tetra-n-hexylammonium) reveal the presence of an extensive series of six one-electron reduction processes for both isomers. Under conditions of bulk electrolysis, the initial [Mo(18)O(54)(SO(3))(2)](4-/5-) and [Mo(18)O(54)(SO(3))(2)](5-/6-) processes produce stable [Mo(18)O(54)(SO(3))(2)](5-) and [Mo(18)O(54)(SO(3))(2)](6-) species, respectively, and the same reduced species may be produced by photochemical reduction. Spectroelectrochemical data imply that retention of structural form results upon reduction, so that both alpha and beta isomers are available at each of the 4-, 5-, and 6-redox levels. However, the alpha isomer is the thermodynamically favored species in both the one- and two-electron-reduced states, with beta-->alpha isomerization being detected in both cases on long time scales (days). EPR spectra also imply that increasing localization of the unpaired electron occurs over the alpha- and beta-[Mo(18)O(54)(SO(3))(2)](5-) frameworks as the temperature approaches 2 K where the EPR spectra show orthorhombic symmetry with different g and hyperfine values for the alpha and beta isomers. Theoretical studies support the observation that it is easier to reduce the alpha cluster than the beta form and also provide insight into the driving force for beta-->alpha isomerization in the reduced state. Data are compared with that obtained for the well studied alpha-[Mo(18)O(54)(SO(4))(2))](4-) sulfate cluster.

  7. 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.

  8. Assessment of phospholipid deacylation-reacylation cycles by H/sub 2/ /sup 18/O incorporation

    SciTech Connect

    Kuwae, T.; Schmid, P.C.; Johnson, S.B.; Schmid, H.H.O.

    1987-05-01

    Quantitative estimation of metabolic turnover involving hydrolysis is possible with the use of H/sub 2/ /sup 18/O which readily equilibrates throughout subcellular compartments and thus obviates many problems associated with the use of exogenous metabolites. Incubation of cells in H/sub 2/ /sup 18/O results in the time-dependent incorporation of /sup 18/O into ester carbonyls of glycerophospholipids. Preparation of methyl esters by alkaline methanolysis preserves the carbonyl oxygen and hydrogenation prior to analysis by gas-chromatography/mass-spectrometry simplifies determination of /sup 18/O//sup 16/O ratios. Mouse peritoneal exudate cells incorporate /sup 18/O from H/sub 2/ /sup 18/O into acyl groups of phosphatidylcholine (PC) and phosphatidylinositol (PI), and smaller amounts into phosphatidylethanolamine (PE) and phosphatidylserine (PS). Acyl groups at the sn-1 position of PC and PE show about the same rate of turnover as those at the sn-2 position. Considering the route of /sup 18/O incorporation via free fatty acid derived through ester hydrolysis in 40% H/sub 2/ /sup 18/O, acyl turnover may exceed 20% per hour. Turnover of 2-O-acyl groups in the plasmalogen analog of PE, as assayed by /sup 18/O incorporation, is drastically lower than in diacylPE. This indicates either a much lower rate of hydrolysis, or reacylation of lysoplasmalogen by direct acyl transfer not involving free fatty acid.

  9. 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.

  10. Predictable components in global speleothem δ18O

    NASA Astrophysics Data System (ADS)

    Fischer, Matt J.

    2016-01-01

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

  11. $sup 18$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.

  12. Investigations of intramolecular hydrogen bonding in three types of Schiff bases by 2H and 3H NMR isotope effects.

    PubMed

    Schilf, Wojciech; Bloxsidge, James P; Jones, John R; Lu, Shui-Yu

    2004-06-01

    Hydrogen bonding within the structures of three Schiff bases (1-3), obtained by condensation of 4-methoxy-, 5-methoxy- and 4,6-dimethoxysalicylaldehyde with methylamine, was investigated by measuring deuterium and tritium NMR isotope effects. The primary deuterium and tritium isotope effects (delta(XH)-delta(XD/T)) and secondary one-bond nitrogen deuterium effect appear to be very useful parameters for defining the character of intramolecular hydrogen bonds. The tritium isotope effects were also determined for nitrogen-hydrogen one-bond coupling constants for both 4-methoxy and 4,6-dimethoxy derivatives. These parameters are seen to be highly sensitive to hydrogen bond characteristics and can be used to distinguish localized and tautomeric hydrogen bonds.

  13. 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.

  14. 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

  15. 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.

  16. 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

    2014-02-28

    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.

  17. 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. 

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    about 80% of the oxygen atoms in C6 position are isotopically exchanged during cellulose synthesis (Waterhouse et al., 2013). It is worth mentioning that in paleolimnological studies dealing with lacustrine sediments, no evapotranspirative 18O enrichment of leaf water has to be considered provided that the hemicelluloses are primarily of aquatic origin (Zech et al., in press). In cases where evaporative 18O enrichment of lake water is negligible and lake water resembles precipitation, this can largely simplify the paleoclimatic interpretation because then the apparent 18O fractionation between precipitation and the lacustrine δ18Ohemicellulose record can be assumed to have been constant (Fig. 4). By contrast, in terrestrial records it will be challenging or even impossible to disentangle δ18Oprecipitation variability from possible variability of evapotranspirative 18O enrichment of leaf water based on δ18Ohemicellulose records alone. Zech et al. (2013) therefore suggested that the most promising approach in biomarker-based paleohydrology and paleoclimate research may be the combination of δ18Ohemicellulose and δ2Hn-alkane records, with n-alkanes serving as leaf wax-derived lipid biomarkers. Such a combined approach allows estimating the evapotranspirative 18O and 2H leaf water enrichment by using an Craig-Gordon-modelled evaporation line and thus in turn allows reconstructing δ18Oprecipitation and δ2Hprecipitation.

  19. Isotope 18 O 16 O Ratio Measurements of Water Vapor by use of Photoacoustic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Matsumi, Yutaka; Kishigami, Masahiro; Tanaka, Noriyuki; Kawasaki, Masahiro; Inoue, Gen

    1998-09-01

    We applied a photoacoustic spectroscopy technique to isotope ratio measurements of 16 O and 18 O in water-vapor samples, using a pulsed tunable dye laser pumped by a Nd:YAG laser. The fourth overtone bands (4 OH ) of water molecules near 720 nm were investigated. We identified the absorption lines of H 2 16 O and H 2 18 O in the photoacoustic spectra that we measured by using an 18 O-enriched water sample and the HITRAN database. We measured the difference in the 18 O 16 O isotope ratios for normal distilled water and Antarctic ice, using the photoacoustic method. The value obtained for the difference between the two samples is 18 O 32 16 , where the indicated deviation was a 1 value among 240-s measurements, whereas the value measured with a conventional isotope mass spectrometer was 18 O 28 2 . This method is demonstrated to have the potential of a transportable system for in situ and quick measurements of the H 2 18 O H 2 16 O ratio in the environment.

  20. Stable (2)H isotope analysis of modern-day human hair and nails can aid forensic human identification.

    PubMed

    Fraser, Isla; Meier-Augenstein, Wolfram

    2007-01-01

    Continuous-flow isotope ratio mass spectrometry (CF-IRMS) was used to compare (2)H isotopic composition at natural abundance level of human scalp hair and fingernail samples collected from subjects worldwide with interpolated delta(2)H precipitation values at corresponding locations. The results showed a strong correlation between delta(2)H values of meteoric water and hair (r(2) = 0.86), while the corresponding correlation for nails was not as strong (r(2) = 0.6). Offsets of -180 per thousand and -127 per thousand were observed when calculating solutions of the linear regression analyses for delta(2)H vs. delta(18)O correlation plots of hair and nail samples, respectively. Compared with the +10 per thousand offset of the global meteoric water line equation these findings suggested that delta(18)O data from hair and nail would be of limited diagnostic value. The results of this pilot study provide for the first time tentative correlations of (2)H isotopic composition of human hair and nails with local water. Linear regression analyses for measured delta(2)H values of human hair and nails vs. water yielded delta(2)H(hair) = 0.49 x delta(2)H(water) - 35 and delta(2)H(nails) = 0.38 x delta(2)H(water) - 49, respectively. The results suggest that (2)H isotopic analysis of hair and nail samples can be used to provide information regarding an individual's recent geographical life history and, hence, location. The benefit of this technique is to aid identification of victims of violent crime and mass disasters in circumstances where traditional methods such as DNA and fingerprinting cannot be brought to bear (or at least not immediately).

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  2. 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.

  3. Adrenergic receptor and catecholamine distribution in rat cerebral cortex: binding studies with [3H]prazosin, [3H]idazoxan and [3H]dihydroalprenolol.

    PubMed

    Diop, L; Brière, R; Grondin, L; Reader, T A

    1987-02-03

    The tritiated adrenergic antagonists [3H]dihydroalprenolol ([3H]DHA; beta-receptors), [3H]prazosin ([3H]PRZ; alpha 1-receptors), and [3H]idazoxan ([3H]IDA; alpha 2-receptors) were used to determine the distribution of these sites in 5 defined areas of the adult rat cerebral cortex. The highest density of [3H]PRZ binding was found in the prefrontal cortex, with a lower and homogeneous distribution for the frontal, parietal, occipital and temporal areas. The [3H]IDA binding sites were fairly uniform for all areas, except for the temporal cortex where it was very dense. In contrast, beta-adrenoceptors labelled by [3H]DHA were very homogeneous for all the regions examined. The functional significance of the distribution of alpha 1, alpha 2 and beta-adrenoceptors is discussed in relation to the catecholamine innervation and monoamine contents measured by high performance liquid chromatography.

  4. Dehydrocoupling of dimethylamine borane catalyzed by Rh(PCy3)2H2Cl.

    PubMed

    Sewell, Laura J; Huertos, Miguel A; Dickinson, Molly E; Weller, Andrew S; Lloyd-Jones, Guy C

    2013-04-15

    The Rh(III) species Rh(PCy3)2H2Cl is an effective catalyst (2 mol %, 298 K) for the dehydrogenation of H3B·NMe2H (0.072 M in 1,2-F2C6H4 solvent) to ultimately afford the dimeric aminoborane [H2BNMe2]2. Mechanistic studies on the early stages in the consumption of H3B·NMe2H, using initial rate and H/D exchange experiments, indicate possible dehydrogenation mechanisms that invoke turnover-limiting N-H activation, which either precedes or follows B-H activation, to form H2B═NMe2, which then dimerizes to give [H2BNMe2]2. An additional detail is that the active catalyst Rh(PCy3)2H2Cl is in rapid equilibrium with an inactive dimeric species, [Rh(PCy3)H2Cl]2. The reaction of Rh(PCy3)2H2Cl with [Rh(PCy3)H2(H2)2][BAr(F)4] forms the halide-bridged adduct [Rh(PCy3)2H2(μ-Cl)H2(PCy3)2Rh][BAr(F)4] (Ar(F) = 3,5-(CF3)2C6H3), which has been crystallographically characterized. This dinuclear cation dissociates on addition of H3B·NMe2H to re-form Rh(PCy3)2H2Cl and generate [Rh(PCy3)2H2(η(2)-H3B·NMe2H)][BAr(F)4]. The fate of the catalyst at low catalyst loadings (0.5 mol %) is also addressed, with the formation of an inactive borohydride species, Rh(PCy3)2H2(η(2)-H2BH2), observed. On addition of H3B·NMe2H to Ir(PCy3)2H2Cl, the Ir congener Ir(PCy3)2H2(η(2)-H2BH2) is formed, with concomitant generation of the salt [H2B(NMe2H)2]Cl.

  5. True absorption and scattering of pions on 16O and 18O

    NASA Astrophysics Data System (ADS)

    Navon, I.; Piasetzky, E.; Ashery, D.; Altman, A.; Azuelos, G.; Schlepütz, F. W.; Walter, H. K.

    1980-10-01

    The inclusive pion inelastic scattering and true absorption cross sections on 16O and 18O were measured at 165 MeV for π± and at 315 MeV for π+. The results show large effects of the two neutrons in 18O on the absorption and inelastic scattering cross sections at the resonance energy. In particular, the inelastic scattering of π+ from 18O is considerably smaller than from 16O and this effect is attributed to the coupling between the reaction channels.

  6. [3H]Ethynylbicycloorthobenzoate ([3H]EBOB) binding in recombinant GABAA receptors.

    PubMed

    Yagle, Monica A; Martin, Michael W; de Fiebre, Christopher M; de Fiebre, NancyEllen C; Drewe, John A; Dillon, Glenn H

    2003-12-01

    Ethynylbicycloorthobenzoate (EBOB) is a recently developed ligand that binds to the convulsant site of the GABAA receptor. While a few studies have examined the binding of [3H]EBOB in vertebrate brain tissue and insect preparations, none have examined [3H]EBOB binding in preparations that express known configurations of the GABAA receptor. We have thus examined [3H]EBOB binding in HEK293 cells stably expressing human alpha1beta2gamma2 and alpha2beta2gamma2 GABAA receptors, and the effects of CNS convulsants on its binding. The ability of the CNS convulsants to displace the prototypical convulsant site ligand, [35S]TBPS, was also assessed. Saturation analysis revealed [3H]EBOB binding at a single site, with a K(d) of approximately 9 nM in alpha1beta2gamma2 and alpha2beta2gamma2 receptors. Binding of both [3H]EBOB and [35S]TBPS was inhibited by dieldrin, lindane, tert-butylbicycloorthobenzoate (TBOB), PTX, TBPS, and pentylenetetrazol (PTZ) at one site in a concentration-dependent fashion. Affinities were in the high nM to low microM range for all compounds except PTZ (low mM range), and the rank order of potency for these convulsants to displace [3H]EBOB and [35S]TBPS was the same. Low [GABA] stimulated [3H]EBOB binding, while higher [GABA] (greater than 10 microM) inhibited [3H]EBOB binding. Overall, our data demonstrate that [3H]EBOB binds to a single, high affinity site in alpha1beta2gamma2 and alpha2beta2gamma2 GABAA receptors, and modulation of its binding is similar to that seen with [35S]TBPS. [3H]EBOB has a number of desirable traits that may make it preferable to [35S]TBPS for analysis of the convulsant site of the GABAA receptor.

  7. 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...

  8. 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...

  9. 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.

  10. K9[H3V18O42(H2O)]•14H2O•4N2H4

    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. Water isotope ratio (δ2H and δ18O) measurements in atmospheric moisture using an optical feedback cavity enhanced absorption laser spectrometer

    NASA Astrophysics Data System (ADS)

    Iannone, Rosario Q.; Romanini, Daniele; Cattani, Olivier; Meijer, Harro A. J.; Kerstel, Erik R. Th.

    2010-05-01

    Water vapor isotopes represent an innovative and excellent tool for understanding complex mechanisms in the atmospheric water cycle over different time scales, and they can be used for a variety of applications in the fields of paleoclimatology, hydrology, oceanography, and ecology. We use an ultrasensitive near-infrared spectrometer, originally designed for use on airborne platforms in the upper troposphere and lower stratosphere, to measure the water deuterium and oxygen-18 isotope ratios in situ, in ground-level tropospheric moisture, with a high temporal resolution (from 300 s down to less than 1 s). We present some examples of continuous monitoring of near-surface atmospheric moisture, demonstrating that our infrared laser spectrometer could be used successfully to record high-concentration atmospheric water vapor mixing ratios in continuous time series, with a data coverage of ˜90%, interrupted only for daily calibration to two isotope ratio mass spectrometry-calibrated local water standards. The atmospheric data show that the water vapor isotopic composition exhibits a high variability that can be related to weather conditions, especially to changes in relative humidity. Besides, the results suggest that observed spatial and temporal variations of the stable isotope content of atmospheric water vapor are strongly related to water vapor transport in the atmosphere.

  12. 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...

  13. 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...

  14. 18O labeling of chlorophyll d in Acaryochloris marina reveals that chlorophyll a and molecular oxygen are precursors.

    PubMed

    Schliep, Martin; Crossett, Ben; Willows, Robert D; Chen, Min

    2010-09-10

    The cyanobacterium Acaryochloris marina was cultured in the presence of either H(2)(18)O or (18)O(2), and the newly synthesized chlorophylls (Chl a and Chl d) were isolated using high performance liquid chromatography and analyzed by mass spectroscopy. In the presence of H(2)(18)O, newly synthesized Chl a and d, both incorporated up to four isotopic (18)O atoms. Time course H(2)(18)O labeling experiments showed incorporation of isotopic (18)O atoms originating from H(2)(18)O into Chl a, with over 90% of Chl a (18)O-labeled at 48 h. The incorporation of isotopic (18)O atoms into Chl d upon incubation in H(2)(18)O was slower compared with Chl a with approximately 50% (18)O-labeled Chl d at 115 h. The rapid turnover of newly synthesized Chl a suggested that Chl a is the direct biosynthetic precursor of Chl d. In the presence of (18)O(2) gas, one isotopic (18)O atom was incorporated into Chl a with approximately the same kinetic incorporation rate observed in the H(2)(18)O labeling experiment, reaching over 90% labeling intensity at 48 h. The incorporation of two isotopic (18)O atoms derived from molecular oxygen ((18)O(2)) was observed in the extracted Chl d, and the percentage of double isotopic (18)O-labeled Chl d increased in parallel with the decrease of non-isotopic-labeled Chl d. This clearly indicated that the oxygen atom in the C3(1)-formyl group of Chl d is derived from dioxygen via an oxygenase-type reaction mechanism.

  15. 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...

  16. Investigating the past and recent δ18O-accumulation relationship seen in Greenland ice cores

    NASA Astrophysics Data System (ADS)

    Buchardt, S. L.; Clausen, H. B.; Vinther, B. M.; Dahl-Jensen, D.

    2012-08-01

    Decadal means of δ18O and accumulation rates from 52 ice core sites in Greenland are presented. The accumulation rates are derived from annual layers determined in the δ18O curve. Investigation of the δ18O-accumulation relationship across the ice divide reveals a significant Foehn effect with anticorrelation of δ18O and accumulation on the lee side of the divide in Southern Greenland, while no effect is seen in Central Greenland. Furthermore, the sensitivity of accumulation rate to changes in temperature is found to be smaller in Northern Greenland than in the central and southern parts. Four sites in the data set contain sufficient recent data that the period of observed temperature rise from the 1990's and onwards can be investigated. All four sites are located close to the ice divide in Northern Greenland and while three sites show increased temperatures, none show evidence of increased accumulation.

  17. Robust electrocatalysts from metal doped W18O49 nanofibers for hydrogen evolution.

    PubMed

    Zhao, Yuanyuan; Tang, Qunwei; Yang, Peizhi; He, Benlin

    2017-04-03

    We report here robust electrocatalysts from metal doped W18O49 nanofibers (NFs) for high-efficiency hydrogen evolution. By tuning Pd dosages, the optimal 5 at% Pd doped W18O49 NFs yield an onset overpotential of only 65 mV and exchange current densities up to 2.36 × 10(-3) mA cm(-2). Moreover, the resultant electrocatalyst is relatively stable during persistent operation.

  18. 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.

  19. 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.

  20. The relationship between phytolith- and plant-water δ 18O values in grasses

    NASA Astrophysics Data System (ADS)

    Webb, Elizabeth A.; Longstaffe, Fred J.

    2003-04-01

    Information regarding climatic conditions during plant growth is preserved by the oxygen-isotope composition of biogenic silica (phytoliths) deposited in grasses. The O-isotope compositions of phytoliths and the plant water from which they precipitate are dependent on soil-water δ 18O values, relative humidity, evapotranspiration rates, and temperature. Plant water and phytoliths from two grass species, Ammophila breviligulata (C 3) and Calamovilfa longifolia (C 4) at Pinery Provincial Park in southwestern Ontario, Canada, were examined to determine the variability in their δ 18O values. Stem water was unfractionated from soil-water in oxygen isotopic composition and the δ 18O values of stem silica provide a good proxy for the soil water available to roots during the growing season. Greater spatial and temporal variation in the δ 18O values of water in the top 5 cm of the soil, and their enhanced sensitivity to evaporative 18O enrichment, are reflected in the generally higher δ 18O values of water in the shallow roots and rhizomes of these grasses. Water within the sheath and lower and upper leaf tissues experiences continual evaporation, becoming progressively enriched in 18O as it moves towards the tip of the leaf. However, the water from which leaf silica precipitates has not acquired the extreme 18O enrichment predicted using steady-state models, or measured for midday or average daily leaf water. Possible explanations for this behaviour include preferential deposition of silica at night; the existence of a secluded water fraction within the leaf, which experiences smaller diurnal variations in isotopic composition than leaf water at sites of evaporation; kinetic isotope effects during rapid precipitation of leaf silica; and incomplete exchange between the oxygen in the silicic acid and the leaf water.

  1. 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.

  2. 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.

  3. Regional and global benthic δ18O stacks for the last glacial cycle

    NASA Astrophysics Data System (ADS)

    Lisiecki, Lorraine E.; Stern, Joseph V.

    2016-10-01

    Although detailed age models exist for some marine sediment records of the last glacial cycle (0-150 ka), age models for many cores rely on the stratigraphic correlation of benthic δ18O, which measures ice volume and deep ocean temperature change. The large amount of data available for the last glacial cycle offers the opportunity to improve upon previous benthic δ18O compilations, such as the "LR04" global stack. Not only are the age constraints for the LR04 stack now outdated but a single global alignment target neglects regional differences of several thousand years in the timing of benthic δ18O change during glacial terminations. Here we present regional stacks that characterize mean benthic δ18O change for 8 ocean regions and a volume-weighted global stack of data from 263 cores. Age models for these stacks are based on radiocarbon data from 0 to 40 ka, correlation to a layer-counted Greenland ice core from 40 to 56 ka, and correlation to radiometrically dated speleothems from 56 to 150 ka. The regional δ18O stacks offer better stratigraphic alignment targets than the LR04 global stack and, furthermore, suggest that the LR04 stack is biased 1-2 kyr too young throughout the Pleistocene. Finally, we compare global and regional benthic δ18O responses with sea level estimates for the last glacial cycle.

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

    NASA Astrophysics Data System (ADS)

    Jasechko, Scott

    2016-08-01

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

  5. 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.

  6. 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

  7. Variable sea ice contributions to seawater δ18O on glacial-interglacial timescales

    NASA Astrophysics Data System (ADS)

    Brennan, C. E.; Weaver, A. J.; Eby, M.; Meissner, K. J.

    2011-12-01

    The oxygen isotope composition of seawater varies in time, mainly based on the amount of (depleted) ice stored on continents. Oxygen isotope records derived from ocean sediment cores serve as indicators of changes in both seawater temperature and continental ice volume. Seawater δ18O may contain a variable signature of sea ice production, especially at high latitudes. Sea ice growth produces isotopically enriched ice and depleted brine. Over glacial-interglacial cycles, changes in the sites and rates of sea ice production (and by extension sea ice meltwater and brine export) hold the potential to shift local to regional seawater isotopic chemistry. Neglecting variability in sea ice production may therefore superimpose error upon reconstructions employing high latitude δ18O records. We examine the effects of variability in sea ice production between glacial and interglacial climate states on seawater δ18O in the University of Victoria Earth System Climate Model. Oxygen isotopes are implemented in all components (ocean, atmosphere, land surface, and sea ice) of the coupled model. The role of glacial-interglacial sea ice variability is investigated in a set of model experiments. Here we isolate the seawater δ18O field due only to sea ice in the model. By contrasting the seawater δ18O fields due to sea ice resulting from the glacial and interglacial climates, we investigate the potential for variable sea ice formation to shift seawater δ18O.

  8. 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.

  9. 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

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

    NASA Astrophysics Data System (ADS)

    Nowak, A.

    2015-12-01

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

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  15. Large Volume 18O-depleted Rhyolitic Volcanism: the Bruneau-Jarbidge Volcanic Field, Idaho

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

    The Bruneau-Jarbidge (BJ) volcanic field is located in southern Idaho at the intersection of the western and eastern arms of the Snake River Plain. The BJ region is an oval structural basin of about 6000 km2, and is likely a system of nested caldera and collapse structures similar to, though larger than, the Yellowstone Volcanic Plateau. BJ rocks are high-temperature rhyolite tuffs, high-temperature rhyolite lavas, and volumetrically minor basalts. Exposed volumes of individual rhyolite units range up to greater than 500 km3. We have analyzed feldspar and, where present, quartz from 30 rhyolite units emplaced throughout the history of the BJ center. All, including the Cougar Point Tuff, are 18O depleted (δ 18OFSP = -1.3 to 3.7‰ ), while petrographically, temporally, and chemically similar lavas erupted along the nearby Owyhee Front have "normal" rhyolite magmatic δ 18O values of 7 - 9‰ . There is no evidence for significant modification of δ 18O values by post-eruptive alteration. No correlation exists between δ 18O and age, magmatic temperature, major element composition or trace element abundances among depleted BJ rhyolites. The BJ and WSRP rhyolites possess the geochemical characteristics (depressed Al, Ca, Eu, and Sr contents, high Ga/Al and K/Na) expected of liquids derived from shallow melting of calc-alkaline granitoids with residual plagioclase and orthopyroxene (Patino-Douce, Geology v.25 p.743-746, 1997). The classic Yellowstone low δ 18O rhyolites are post-caldera collapse lavas, but at BJ, both lavas and caldera-forming ignimbrites are strongly 18O-depleted. The total volume of low δ 18O rhyolite may be as high as 10,000 km3, requiring massive involvement of meteoric-hydrothermally altered crust in rhyolite petrogenesis. Regional hydrothermal modification of the crust under the thermal influence of the Yellowstone hotspot apparently preceded voluminous rhyolite generation at Bruneau-Jarbidge.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  17. Low-lying states of Li 3H: Is there an ion-pair minimum?

    NASA Astrophysics Data System (ADS)

    Talbi, Dahbia; Saxon, Roberta P.

    1989-05-01

    The 1 1A', 1 1A″, 1 3A', and 1 3A″ states of Li 3H have been investigated at the MCSCF/SOCI level. The global minimum is a planar conformation of 1A' symmetry. A local minimum on the same potential surface at a C 3v pyramidal geometry, of mixed ion-pair and covalent character, is found at a relative energy of 20.30 kcal/mol. The barrier height for isomerization is predicted to be 1.3 kcal/mol. The correlation diagram linking states of Li 3H to those of Li 3 + H, LiH + Li 2 and Li 2H + Li is presented.

  18. Oxygen isotope evolution of the Lake Owyhee volcanic field, Oregon, and implications for the low-δ18O magmatism of the Snake River Plain-Yellowstone hotspot and other low-δ18O large igneous provinces

    NASA Astrophysics Data System (ADS)

    Blum, Tyler B.; Kitajima, Kouki; Nakashima, Daisuke; Strickland, Ariel; Spicuzza, Michael J.; Valley, John W.

    2016-11-01

    The Snake River Plain-Yellowstone (SRP-Y) hotspot track represents the largest known low-δ18O igneous province; however, debate persists regarding the timing and distribution of meteoric hydrothermal alteration and subsequent melting/assimilation relative to hotspot magmatism. To further constrain alteration relations for SRP-Y low-δ18O magmatism, we present in situ δ18O and U-Pb analyses of zircon, and laser fluorination δ18O analyses of phenocrysts, from the Lake Owyhee volcanic field (LOVF) of east-central Oregon. U-Pb data place LOVF magmatism between 16.3 and 15.4 Ma, and contain no evidence for xenocrystic zircon. LOVF δ18O(Zrc) values demonstrate (1) both low-δ18O and high-δ18O caldera-forming and pre-/post-caldera magmas, (2) relative increases in δ18O between low-δ18O caldera-forming and post-caldera units, and (3) low-δ18O magmatism associated with extension of the Oregon-Idaho Graben. The new data, along with new compilations of (1) in situ zircon δ18O data for the SRP-Y, and (2) regional δ18O(WR) and δ18O(magma) patterns, further constrain the thermal and structural associations for hydrothermal alteration in the SRP-Y. Models for low-δ18O magmatism must be compatible with (1) δ18O(magma) trends within individual SRP-Y eruptive centers, (2) along axis trends in δ18O(magma), and (3) the high concentration of low-δ18O magmas relative to the surrounding regions. When considered with the structural and thermal evolution of the SRP-Y, these constraints support low-δ18O magma genesis originating from syn-hotspot meteoric hydrothermal alteration, driven by hotspot-derived thermal fluxes superimposed on extensional tectonics. This model is not restricted to continental hotspot settings and may apply to several other low-δ18O igneous provinces with similar thermal and structural associations.

  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.

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

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

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

  3. Using 18O as a Tracer of Oxygen in the Photochemical Alteration of Dissolved Organic Matter

    NASA Astrophysics Data System (ADS)

    Davis, J. A.; Stubbins, A.; Helms, J.; Dias, R. F.; Mopper, K.

    2006-12-01

    The biogeochemical cycling of dissolved organic matter (DOM) in natural waters is affected by numerous processes, including photochemical alteration. Photochemical processes result in the net oxidation and mineralization of DOM concomitant with dissolved oxygen consumption and production of dissolved inorganic carbon (DIC; principally CO2). The photochemical oxygen budget is not well constrained while DIC production accounts for nearly all the dissolved oxygen consumed, conflicting data suggests that more than half of the oxygen consumed is required to account for observed DOM oxidation and hydrogen peroxide production. An alternate source of oxygen is required to balance this budget; water itself may provide the answer. In order to determine the source of oxygen, a number of time series irradiations were performed using Great Dismal Swamp water (southeast Virginia) with 18O enrichments as either dissolved oxygen or water. Early results, upon irradiation in a UV solar simulator, show significant incorporation of 18O-enriched oxygen into high molecular weight (HMW) DOM from both sources. While the majority of the incorporated oxygen originated from the dissolved oxygen, at least 5 percent originated from water. Data will be presented showing the rate and degree of incorporation of 18O-enriched oxygen from both sources as well as the production of 18O-enriched carbon dioxide. The movement of 18O label will be discussed in relation to shifts in spectral qualities, including photobleaching and spectral slope, of the irradiated samples and selective incorporation as detailed by FT-ICRMS.

  4. Comparison of δ18O measurements in Nitrate by different combustion techniques

    USGS Publications Warehouse

    Revesz, Kinga; Böhlke, John Karl

    2002-01-01

    Three different KNO3 salts with δ18O values ranging from about −31 to +54‰ relative to VSMOW were used to compare three off-line, sealed glass tube combustion methods (widely used for isotope studies) with a more recently developed on-line carbon combustion technique. All methods yielded roughly similar isotope ratios for KNO3 samples with δ18O values in the midpoint of the δ18O scale near that of the nitrate reference material IAEA-NO-3 (around +21 to +25‰). This reference material has been used previously for one-point interlaboratory and intertechnique calibrations. However, the isotope ratio scale factors by all of the off-line combustion techniques are compressed such that they are between 0.3 and 0.7 times that of the on-line combustion technique. The contraction of the δ18O scale in the off-line preparations apparently is caused by O isotope exchange between the sample and the glass combustion tubes. These results reinforce the need for nitrate reference materials with δ18O values far from that of atmospheric O2, to improve interlaboratory comparability.

  5. Isotope parameters (δD, δ18O) and sources of freshwater input to Kara Sea

    NASA Astrophysics Data System (ADS)

    Dubinina, E. O.; Kossova, S. A.; Miroshnikov, A. Yu.; Fyaizullina, R. V.

    2017-01-01

    The isotope characteristics (δD, δ18O) of Kara Sea water were studied for quantitative estimation of freshwater runoff at stations located along transect from Yamal Peninsula to Blagopoluchiya Bay (Novaya Zemlya). Freshwater samples were studied for glaciers (Rose, Serp i Molot) and for Yenisei and Ob estuaries. As a whole, δD and δ18O are higher in glaciers than in river waters. isotope composition of estuarial water from Ob River is δD =-131.4 and δ18O =-17.6‰. Estuarial waters of Yenisei River are characterized by compositions close to those of Ob River (-134.4 and-17.7‰), as well as by isotopically "heavier" compositions (-120.7 and-15.8‰). Waters from studied section of Kara Sea can be product of mixing of freshwater (δD =-119.4, δ18O =-15.5) and seawater (S = 34.9, δD = +1.56, δ18O = +0.25) with a composition close to that of Barents Sea water. isotope parameters of water vary significantly with salinity in surface layer, and Kara Sea waters are desalinated along entire studied transect due to river runoff. concentration of freshwater is 5-10% in main part of water column, and <5% at a depth of >100 m. maximum contribution of freshwater (>65%) was recorded in surface layer of central part of sea.

  6. Clay aquitards as archives of holocene paleoclimate: delta18O and thermal profiling.

    PubMed

    Hendry, M Jim; Woodbury, A D

    2007-01-01

    Paleoclimatic conditions in the Holocene were reconstructed from a detailed vertical profile of pore water delta(18)O and a series of downhole thermal profiles at a thick, hydrogeologically simple, aquitard research site in the Northern Great Plains of Saskatchewan. Reconstructions were obtained using the theory of one-dimensional diffusive transport and an empirical Bayesian inversion technique. Inversion of the delta(18)O profile shows that input signal consists of a sudden increase of +6 per thousand (corresponding to a temperature increase of about 18 degrees C) at about 12,000 years before present (BP), after which no measurable change in delta(18)O is apparent to present day. This research shows, at this location, that there is no evidence of large amplitude temperature shifts in the Holocene and supports the commonly used assumption in ground water studies of constant atmospheric delta(18)O values throughout the Holocene. Inversion of the temperature profiles suggests the ground surface temperature increased primarily in the last half of the 20th century, with a peak temperature (about 3 degrees C) circa 1990. For both profiles, the ability to resolve historical variability decays rapidly with time. For the temperature profiles, the decay in resolution precluded the development of reliable estimates of climatic conditions prior to about 1950 and, in the case of the delta(18)O profile, it prevented the precise definition of climate changes (e.g., Hypsithermal and Little Ice Age) in the Holocene.

  7. 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.

  8. Reconstructing seawater δ 18O from paired coral δ 18O and Sr/Ca ratios: Methods, error analysis and problems, with examples from Tahiti (French Polynesia) and Timor (Indonesia)

    NASA Astrophysics Data System (ADS)

    Yudawati Cahyarini, Sri; Pfeiffer, Miriam; Timm, Oliver; Dullo, Wolf-Christian; Schönberg, Dieter Garbe

    2008-06-01

    We compare several statistical routines that may be used to calculate δ 18O sw and SSS from paired coral Sr/Ca and δ 18O measurements. Typically, the δ 18O coral-SST relationship is estimated by linear regression of coral δ 18O vs. SST. If this method is applied, evidence should be given that at a particular site SST and SSS do not co-vary. In the tropical oceans, SST and δ 18O sw (SSS) often co-vary, and this will bias the estimate of the regression slope of δ 18O coral-SST. Using a stochastic model, we show that covariance leads to a bias in the coefficients of the univariate regression equations. As the slope of the δ 18O coral-SST relationship has known, we propose to insert this value for γ1 in the regression models. This requires that the constants of the regression equations are removed. To omit the constants, we propose to center the regression equations (i.e., to remove the mean values from the variables). The statistical error propagation is calculated to assess our ability to resolve past variations in δ 18O sw (SSS). At Tahiti, we find that the combined analytical uncertainties of coral δ 18O and Sr/Ca equal the amplitude of the seasonal cycle of δ 18O sw (SSS). Therefore, we cannot resolve the seasonal cycle of SSS at Tahiti. At Timor, the error of reconstructed δ 18O sw (SSS) is lower than the magnitude of seasonal variations of δ 18O sw (SSS), and the seasonal cycle of δ 18O sw (SSS) can be resolved.

  9. 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.

  10. Microwave-assisted 18O-labeling of proteins catalyzed by formic acid.

    PubMed

    Liu, Ning; Wu, Hanzhi; Liu, Hongxia; Chen, Guonan; Cai, Zongwei

    2010-11-01

    Oxygen exchange may occur at carboxyl groups catalyzed by acid. The reaction, however, takes at least several days at room temperature. The long-time exchanging reaction often prevents its application from protein analysis. In this study, an (18)O-labeling method utilizing microwave-assisted acid hydrolysis was developed. After being dissolved in (16)O/(18)O (1:1) water containing 2.5% formic acid, protein samples were exposed to microwave irradiation. LC-MS/MS analysis of the resulted peptide mixtures indicated that oxygen in the carboxyl groups from glutamic acid, aspartic acid, and the C-terminal residues could be efficiently exchanged with (18)O within less than 15 min. The rate of back exchange was so slow that no detectable back exchange could be found during the HPLC run.

  11. Pion-induced nucleon knockout reactions on 16O and 18O

    NASA Astrophysics Data System (ADS)

    Piasetzky, E.; Altman, A.; Lichtenstadt, J.; Yavin, A. I.; Ashery, D.; Bertl, W.; Felawka, L.; Walter, H. K.; Schlepütz, F. W.; Powers, K. J.; Winter, R. G.; Pluym, J. V. D.

    1982-12-01

    The (π+, π+p), (π-, π-p), and (π-, π-n) reactions on 16O and 18O were studied at 165 MeV by coincidence measurements of the outgoing particles. The cross sections for the (π-, π-n) reaction is larger on 18O than on 16O, whereas those for the (π+, π+p) and the (π-, π-p) reactions are smaller, most likely because of the coupling between the absorption and the scattering channels. NUCLEAR REACTIONS (π+/-, π+/-p) (π-, π-n) coin. Measurements on 16O18O E=165 MeV; deduced coupling between the absorption and the scattering channels.

  12. 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.

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

    SciTech Connect

    Morrison, J.; Valley, J.W.

    1985-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  15. 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

  16. A 3D microporous covalent organic framework with exceedingly high C3H8/CH4 and C2 hydrocarbon/CH4 selectivity.

    PubMed

    Ma, Heping; Ren, Hao; Meng, Shuang; Yan, Zhuojun; Zhao, Huanyu; Sun, Fuxing; Zhu, Guangshan

    2013-10-28

    Here we present a new 3D microporous COF with a uniform pore size (0.64 nm). MCOF-1 exhibits high adsorption selectivity towards C3H8, C2H6 and C2H4 over CH4 owing to the pore size and preferential adsorption.

  17. ({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.

  18. 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

  19. Isotopic effects in the ( π±, 2N) reactions on 16O and 18O

    NASA Astrophysics Data System (ADS)

    Altman, A.; Ashery, D.; Piasetzky, E.; Lichtenstadt, J.; Yavin, A. I.; Bertl, W.; Felawka, L.; Walter, H. K.; Powers, R. J.; Winter, R. G.; v. d. Pluym, J.

    1984-09-01

    The ( π+, 2p), ( π+, pn) and ( π-, pn) reactions on 16O and 18O were studied at 165 MeV. The cross section for the ( π+, 2p) reaction on 18O is larger than that for 16O be only 5% ± 3%, while the total π+ absorption cross section is larger by 17% ± 5%. This supports the assumption that two-nucleon absorption occurs mainly on nucleons in the same shell. It is further concluded that Δ++n → pp is not only absorption mechanism that couples strongly to the nucleon knock out reactions.

  20. 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.

  1. Microwave Spectrum of a Silicon Monoxide Isotopomer: 28Si18O

    NASA Astrophysics Data System (ADS)

    Cho, Se-Hyung; Saito, Shuji

    1998-03-01

    The rotational transitions of 28Si18O in the ground vibrational state were observed by laboratory microwave spectroscopy for astronomical use. The SiO molecules were generated in a free-space absorption cell by dc-glow discharge in a mixture of tetra-methyl silane, Si(CH3)4, and 18O2. Ten rotational transitions were precisely measured in the 40-444 GHz region. The rotational and centrifugal distortion constants were determined by a least-squares analysis of measured line frequencies: B0=20176.4394(43) and D0=0.025809(32) MHz, with the 3 σ deviations in parentheses.

  2. 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.

  3. 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."

  4. THz spectroscopy of D2H+

    NASA Astrophysics Data System (ADS)

    Yu, S.; Pearson, J. C.; Amano, T.; Matsushima, F.

    2017-01-01

    We extended the measurements of the rotational transitions of D2H+ up to 3 THz by using the JPL frequency multiplier chains and a TuFIR system at Toyama. D2H+ was generated in an extended negative glow discharge cell cooled to liquid nitrogen temperature. We observed five new THz lines. All the available rotational transition frequencies together with the combination differences derived from the three fundamental bands were subject to least square analysis to determine the molecular constants. New THz measurements are definitely useful for better characterization of spectroscopic properties. The improved molecular constants provide better predictions of other unobserved rotational transitions.

  5. A continuous-flow crushing device for on-line delta2H analysis of fluid inclusion water in speleothems.

    PubMed

    Vonhof, Hubert B; van Breukelen, Martin R; Postma, Onno; Rowe, Peter J; Atkinson, Tim C; Kroon, Dick

    2006-01-01

    A method for the isotope analysis of fluid inclusion water in speleothem calcite is presented. The technique is based on a commercially available continuous-flow pyrolysis furnace (ThermoFinnigan TC-EA). The main adaptation made to the standard TC-EA configuration is the addition of a crusher and cold trap unit, which is connected to the carrier gas inlet at the top of the TC-EA reactor tube. A series of tests conducted with this device shows that: (1) standard waters, injected in the crusher, and passed through a cryogenic trapping routine, yield accurate delta(2)H values; (2) crushed cubes of speleothem calcite from two Peruvian caves with rather dissimilar seepage water delta(2)H values yield fluid inclusion delta(2)H values in good accordance with these drip waters. The clear advantage of this continuous-flow technique for fluid inclusion isotope analysis is that it is relatively quick compared with other techniques. Since the conditions of water sample introduction into the TC-EA are identical for delta(2)H and delta(18)O analysis, we expect that only limited adaptations to the extraction procedure are required to provide delta(18)O analysis of fluid inclusion samples with the same device.

  6. Following 18O uptake in scCO2–H2O mixtures with Raman spectroscopy

    SciTech Connect

    Windisch, Charles F.; Schaef, Herbert T.; Martin, Paul F.; Owen, Antionette T.; McGrail, B. Peter

    2012-03-01

    The kinetics of 18O/16O isotopic exchange in scCO2 containing liquid water was followed with Raman spectroscopy using a specially designed high-pressure optical cell. Characteristic bands from the C16O18O and C18O2 molecules were identified in the supercritical phase and measured in the spectra as a function of time after introducing liquid H218O into scC16O2. Temporal dependence indicated the isotopic exchange was diffusion-limited in our cell for both molecules, and that the chemical reactions within the liquid phase were comparatively rapid. However, the ratio of concentrations of the 18O-labeled CO2 molecules, C18O2/C16O18O, was much higher than expected in the supercritical phase, suggesting the role of an intermediate step, possibly desorption, in moderating the concentrations of these species in the liquid water phase.

  7. 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.

  8. 13CO/C18O Gradients across the Disks of Nearby Spiral Galaxies

    NASA Astrophysics Data System (ADS)

    Jiménez-Donaire, María J.; Cormier, Diane; Bigiel, Frank; Leroy, Adam K.; Gallagher, Molly; Krumholz, Mark R.; Usero, Antonio; Hughes, Annie; Kramer, Carsten; Meier, David; Murphy, Eric; Pety, Jérôme; Schinnerer, Eva; Schruba, Andreas; Schuster, Karl; Sliwa, Kazimierz; Tomicic, Neven

    2017-02-01

    We use the IRAM Large Program EMPIRE and new high-resolution ALMA data to measure 13CO(1-0)/C18O(1-0) intensity ratios across nine nearby spiral galaxies. These isotopologues of 12CO are typically optically thin across most of the area in galaxy disks, and this ratio allows us to gauge their relative abundance due to chemistry or stellar nucleosynthesis effects. Resolved 13CO/C18O gradients across normal galaxies have been rare due to the faintness of these lines. We find a mean 13CO/C18O ratio of 6.0 ± 0.9 for the central regions of our galaxies. This agrees well with results in the Milky Way, but differs from results for starburst galaxies (3.4 ± 0.9) and ultraluminous infrared galaxies (1.1 ± 0.4). In our sample, the 13CO/C18O ratio consistently increases with increasing galactocentric radius and decreases with increasing star formation rate surface density. These trends could be explained if the isotopic abundances are altered by fractionation; the sense of the trends also agrees with those expected for carbon and oxygen isotopic abundance variations due to selective enrichment by massive stars.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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.

  11. 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...

  12. Investigating the past and recent δ18O-accumulation relationship seen in Greenland ice cores

    NASA Astrophysics Data System (ADS)

    Buchardt, S. L.; Clausen, H. B.; Vinther, B. M.; Dahl-Jensen, D.

    2012-12-01

    Decadal means of δ18O and accumulation rates from 52 ice core locations in Greenland are presented. The accumulation rates are derived from annual layers determined in the δ18O curve. Investigation of the δ18O-accumulation relationship across the ice divide reveals a significant Foehn effect with anticorrelation of δ18O and accumulation rate on the lee side of the divide in Southern Greenland, while no effect is seen in Central Greenland. Furthermore, the sensitivity of accumulation rate to changes in temperature is found to be smaller in Northern Greenland than in the central and southern parts. Four records in the data set contain sufficient recent data that the period of observed temperature rise from the 1990s and onwards can be investigated. All four records are from locations close to the ice divide in Northern Greenland and while three of them show increased temperatures, no conclusive statement can be made about the accumulation rate from these data.

  13. 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.

  14. 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

  15. The enigma of effective path length for (18) O enrichment in leaf water of conifers.

    PubMed

    Roden, John; Kahmen, Ansgar; Buchmann, Nina; Siegwolf, Rolf

    2015-12-01

    The Péclet correction is often used to predict leaf evaporative enrichment and requires an estimate of effective path length (L). Studies to estimate L in conifer needles have produced unexpected patterns based on Péclet theory and leaf anatomy. We exposed seedlings of six conifer species to different vapour pressure deficits (VPD) in controlled climate chambers to produce steady-state leaf water enrichment (in (18) O). We measured leaf gas exchange, stable oxygen isotopic composition (δ(18) O) of input and plant waters as well as leaf anatomical characteristics. Variation in bulk needle water δ(18) O was strongly related to VPD. Conifer needles had large amounts of water within the vascular strand that was potentially unenriched (up to 40%). Both standard Craig-Gordon and Péclet models failed to accurately predict conifer leaf water δ(18) O without taking into consideration the unenriched water in the vascular strand and variable L. Although L was linearly related to mesophyll thickness, large within-species variation prevented the development of generalizations that could allow a broader use of the Péclet effect in predictive models. Our results point to the importance of within needle water pools and isolating mechanisms that need further investigation in order to integrate Péclet corrections with 'two compartment' leaf water concepts.

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

    USGS Publications Warehouse

    Donnelly-Nolan, J. M.

    1998-01-01

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

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

    PubMed

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

    2016-06-21

    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.

  18. Variations of 17O/ 16O and 18O/ 16O in meteoric waters

    NASA Astrophysics Data System (ADS)

    Luz, Boaz; Barkan, Eugeni

    2010-11-01

    The variations of δ 17O and δ 18O in recent meteoric waters and in ice cores have proven to be an important tool for investigating the present and past hydrologic cycle. In order to close significant information gaps in the present distribution of δ 17O and δ 18O of meteoric water, we have run precise measurements, with respect to VSMOW, on samples distributed globally from low to high latitudes. Based on the new and existing data, we present the Global Meteoric Water Line (GMWL) for δ 17O and δ 18O as: ln(δ17O+1)=0.528ln(δ18O+1)+0.000033(R2=0.99999) In addition to meteoric water, we carried out the first measurements of seawater from the Pacific and Atlantic oceans with respect to VSMOW. The obtained results show that the slope of the trend line ln(δ 17O + 1) vs. ln(δ 18O + 1) of seawater samples is 0.528, the same as for meteoric water, but the regression intercept is -5 per meg. Thus, the positive intercept in the GMWL indicates an excess of 17O in meteoric waters with respect to the ocean. An excess (or depletion) of 17O in water is defined as: 17O-excess=ln(δ17O+1)-0.528(δ18O+1) Most meteoric water samples have positive 17O-excess of varying magnitudes with an average of 37 per meg with respect to VSMOW. We explain how these positive values originate from evaporation of sea water into marine air, which is undersaturated in water vapor, and how subsequent increase of 17O-excess occurs when atmospheric vapor condenses to form liquid and solid precipitation. We also clarify the effect of excessive evaporation on 17O-excess. Finally, based on the new results on 17O-excess of seawater we recalculated the relationship of δ 17O vs. δ 18O in vapor diffusion in air as 18α diff = 1.0096.

  19. 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

  20. 13C 18O clumping in speleothems: Observations from natural caves and precipitation experiments

    NASA Astrophysics Data System (ADS)

    Daëron, M.; Guo, W.; Eiler, J.; Genty, D.; Blamart, D.; Boch, R.; Drysdale, R.; Maire, R.; Wainer, K.; Zanchetta, G.

    2011-06-01

    The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ 18O. Interpreting speleothem δ 18O records in terms of absolute paleotemperatures and δ 18O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ47 (a geochemical variable reflecting the statistical overabundance of 13C 18O bonds in CO 2 evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ47 value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation. Here we report Δ47 values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ47 and heavier δ 18O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ47 disequilibrium and that of δ 18O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ 18O and Δ47 values, probably inherited from prior degassing within the cave system. In addition

  1. 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

  2. VizieR Online Data Catalog: NGC 1333-IRAS 4A C18O, NO and O2 spectra (

    NASA Astrophysics Data System (ADS)

    Yildiz, U. A.; Acharyya, K.; Goldsmith, P. F.; van Dishoeck, E. F.; Melnick, G.; Snell, R.; Liseau, R.; Chen, J.-H.; Pagani, L.; Bergin, E.; Caselli, P.; Herbst, E.; Kristensen, L. E.; Visser, R.; Lis, D. C.; Gerin, M.

    2013-10-01

    Files contain the observations of O2, C18O 1- C18O 5-4, and NO toward NGC 1333 IRAS 4A low mass protostar. C18O 1-0 and 3-2 observations conducted in mapping mode, therefore they were convolved to 44-arcsec beam in order to compare with the Herschel-HIFI observations of molecular oxygen. (2 data files).

  3. Cellulose δ18O is an index of leaf-to-air vapor pressure difference (VPD) in tropical plants

    PubMed Central

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

    2011-01-01

    Cellulose in plants contains oxygen that derives in most cases from precipitation. Because the stable oxygen isotope composition, δ18O, of precipitation is associated with environmental conditions, cellulose δ18O should be as well. However, plant physiological models using δ18O suggest that cellulose δ18O is influenced by a complex mix of both climatic and physiological drivers. This influence complicates the interpretation of cellulose δ18O values in a paleo-context. Here, we combined empirical data analyses with mechanistic model simulations to i) quantify the impacts that the primary climatic drivers humidity (ea) and air temperature (Tair) have on cellulose δ18O values in different tropical ecosystems and ii) determine which environmental signal is dominating cellulose δ18O values. Our results revealed that ea and Tair equally influence cellulose δ18O values and that distinguishing which of these factors dominates the δ18O values of cellulose cannot be accomplished in the absence of additional environmental information. However, the individual impacts of ea and Tair on the δ18O values of cellulose can be integrated into a single index of plant-experienced atmospheric vapor demand: the leaf-to-air vapor pressure difference (VPD). We found a robust relationship between VPD and cellulose δ18O values in both empirical and modeled data in all ecosystems that we investigated. Our analysis revealed therefore that δ18O values in plant cellulose can be used as a proxy for VPD in tropical ecosystems. As VPD is an essential variable that determines the biogeochemical dynamics of ecosystems, our study has applications in ecological-, climate-, or forensic-sciences. PMID:21245322

  4. 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.

  5. Disequilibrium δ18O values in microbial carbonates as a tracer of metabolic production of dissolved inorganic carbon

    NASA Astrophysics Data System (ADS)

    Thaler, Caroline; Millo, Christian; Ader, Magali; Chaduteau, Carine; Guyot, François; Ménez, Bénédicte

    2017-02-01

    Carbon and oxygen stable isotope compositions of carbonates are widely used to retrieve paleoenvironmental information. However, bias may exist in such reconstructions as carbonate precipitation is often associated with biological activity. Several skeleton-forming eukaryotes have been shown to precipitate carbonates with significant offsets from isotopic equilibrium with water. Although poorly understood, the origin of these biologically-induced isotopic shifts in biogenic carbonates, commonly referred to as ;vital effects;, could be related to metabolic effects that may not be restricted to mineralizing eukaryotes. The aim of our study was to determine whether microbially-mediated carbonate precipitation can also produce offsets from equilibrium for oxygen isotopes. We present here δ18O values of calcium carbonates formed by the activity of Sporosarcina pasteurii, a carbonatogenic bacterium whose ureolytic activity produces ammonia (thus increasing pH) and dissolved inorganic carbon (DIC) that precipitates as solid carbonates in the presence of Ca2+. We show that the 1000 lnαCaCO3-H2O values for these bacterially-precipitated carbonates are up to 24.7‰ smaller than those expected for precipitation at isotopic equilibrium. A similar experiment run in the presence of carbonic anhydrase (an enzyme able to accelerate oxygen isotope equilibration between DIC and water) resulted in δ18O values of microbial carbonates in line with values expected at isotopic equilibrium with water. These results demonstrate for the first time that bacteria can induce calcium carbonate precipitation in strong oxygen isotope disequilibrium with water, similarly to what is observed for eukaryotes. This disequilibrium effect can be unambiguously ascribed to oxygen isotope disequilibrium between DIC and water inherited from the oxygen isotope composition of the ureolytically produced CO2, probably combined with a kinetic isotope effect during CO2 hydration/hydroxylation. The fact that

  6. Growth of 18O isotopically enriched ZnO nanorods by two novel VPT methods

    NASA Astrophysics Data System (ADS)

    Gray, Ciarán; Trefflich, Lukas; Röder, Robert; Ronning, Carsten; Henry, Martin O.; McGlynn, Enda

    2017-02-01

    We have developed two novel vapour phase transport methods to grow ZnO nanorod arrays isotopically enriched with 18O. Firstly, a three-step process used to grow natural and Zn-enriched ZnO nanorods has been further modified, by replacing the atmospheric O2 with enriched 18O2, in order to grow 18O-enriched ZnO nanorods using this vapour-solid method on chemical bath deposited buffer layers. In addition, 18O-enriched ZnO nanorods were successfully grown using 18O isotopically enriched ZnO source powders in a vapour-liquid-solid growth method. Scanning electron microscopy studies confirmed the success of both growth methods in terms of nanorod morphology, although in the case of the vapour-liquid-solid samples, the nanorods' c-axes were not vertically aligned due to the use of a non-epitaxial substrate. Raman and PL studies indicated clearly that O-enrichment was successful in both cases, although the results indicate that the enrichment is at a lower level in our samples compared to previous reports with the same nominal enrichment levels. The results of our studies also allow us to comment on both levels of enrichment achieved and on novel effects of the high temperature growth environment on the nanorod growth, as well as suggesting possible mechanisms for such effects. Very narrow photoluminescence line widths, far narrower than those reported previously in the literature for isotopically enriched bulk ZnO, are seen in both the vapour-solid and vapour-liquid-solid nanorod samples demonstrating their excellent optical quality and their potential for use in detailed optical studies of defects and impurities using low temperature photoluminescence.

  7. 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.

  8. 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

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

    USGS Publications Warehouse

    Anderson, Lesleigh

    2011-01-01

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

  12. 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.

  13. Binding of [3H]-prazosin and [3H]-dihydroergocryptine to rat cardiac alpha-adrenoceptors.

    PubMed Central

    Guicheney, P.; Meyer, P.

    1981-01-01

    1 [3H]-prazosin binds specifically to a single class of alpha-adrenoceptors in rat cardiac membranes (KD25 degrees C = 0.2 nM). 2 That these receptors are of the alpha 1-type was indicated by competition studies, i.e. alpha 1-antagonists such as prazosin and (2-(2,6-dimethoxyphenoxyethyl) aminomethyl-1, 4-benzodioxane (WB 4101) were more potent than the alpha 2-antagonists, yohimbine and piperoxan in inhibiting [3H]-prazosin binding. 3 A comparative study of [3H]-prazosin binding and [3H]-dihydroergocryptine binding to cardiac membranes showed that both [3H]-prazosin and [3H]-dihydroergocryptine (at low concentrations) bind to alpha 2-adrenoceptors, while [3H]-dihydroergocryptine (at higher concentrations) also binds to another class of sites. PMID:6269682

  14. 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

  15. 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

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

    USGS Publications Warehouse

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

    2001-01-01

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

  17. Leaf morphological effects predict effective path length and enrichment of 18O in leaf water of different Eucalyptus species

    NASA Astrophysics Data System (ADS)

    Kahmen, A.; Merchant, A.; Callister, A.; Dawson, T. E.; Arndt, S. K.

    2006-12-01

    Stable isotopes have been a valuable tool to study water or carbon fluxes of plants and ecosystems. In particular oxygen isotopes (δ18O) in leaf water or plant organic material are now beginning to be established as a simple and integrative measure for plant - water relations. Current δ18O models, however, are still limited in their application to a broad range of different species and ecosystems. It remains for example unclear, if species-specific effects such as different leaf morphologies need to be included in the models for a precise understanding and prediction of δ18O signals. In a common garden experiment (Currency Creek Arboretum, South Australia), where over 900 different Eucalyptus species are cultivated in four replicates, we tested effects of leaf morphology and anatomy on δ18O signals in leaf water of 25 different species. In particular, we determined for all species enrichment in 18O of mean lamina leaf water above source water (Δ18O) as related to leaf physiology as well as leaf thickness, leaf area, specific leaf area and weight and selected anatomical properties. Our data revealed that diurnal Δ18O in leaf water at steady state was significantly different among the investigated species and with differences up to 10% at midday. Fitting factors (effective path length) of leaf water Δ18O models were also significantly different among the investigated species and were highly affected by species-specific morphological parameters. For example, leaf area explained a high percentage of the differences in effective path length observed among the investigated species. Our data suggest that leaf water δ18O can act as powerful tool to estimate plant - water relations in comparative studies but that additional leaf morphological parameters need to be considered in existing δ18O models for a better interpretation of the observed δ18O signals.

  18. 18O Labeling of Chlorophyll d in Acaryochloris marina Reveals That Chlorophyll a and Molecular Oxygen Are Precursors*

    PubMed Central

    Schliep, Martin; Crossett, Ben; Willows, Robert D.; Chen, Min

    2010-01-01

    The cyanobacterium Acaryochloris marina was cultured in the presence of either H218O or 18O2, and the newly synthesized chlorophylls (Chl a and Chl d) were isolated using high performance liquid chromatography and analyzed by mass spectroscopy. In the presence of H218O, newly synthesized Chl a and d, both incorporated up to four isotopic 18O atoms. Time course H218O labeling experiments showed incorporation of isotopic 18O atoms originating from H218O into Chl a, with over 90% of Chl a 18O-labeled at 48 h. The incorporation of isotopic 18O atoms into Chl d upon incubation in H218O was slower compared with Chl a with ∼50% 18O-labeled Chl d at 115 h. The rapid turnover of newly synthesized Chl a suggested that Chl a is the direct biosynthetic precursor of Chl d. In the presence of 18O2 gas, one isotopic 18O atom was incorporated into Chl a with approximately the same kinetic incorporation rate observed in the H218O labeling experiment, reaching over 90% labeling intensity at 48 h. The incorporation of two isotopic 18O atoms derived from molecular oxygen (18O2) was observed in the extracted Chl d, and the percentage of double isotopic 18O-labeled Chl d increased in parallel with the decrease of non-isotopic-labeled Chl d. This clearly indicated that the oxygen atom in the C31-formyl group of Chl d is derived from dioxygen via an oxygenase-type reaction mechanism. PMID:20610399

  19. 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

  20. 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

  1. 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

    2015-10-05

    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.

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

    DOE PAGES

    Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; ...

    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

  3. /sup 2/H-NMR studies of hypocotyl cell walls of germinating beams supplied with perdeuterated myo-inositol

    SciTech Connect

    Sasaki, K.; Wallace, J.C.; MacKay, A.L.; Balza, F.; Taylor, I.E.P.

    1987-04-01

    When myo-(2-/sup 3/H) inositol (MI) was supplied to bean seeds by imbibition, only uronic acid, arabinose and xylose residues of cell wall polysaccharides were labeled. To study the structural mobility of the uronic acid- and/or pentose-rich polysaccharides in cell wall using /sup 2/H-NMR, the authors supplied perdeuterated MI with (2-/sup 3/H) MI to germinating bean seeds. Perdeuterated MI was prepared by the /sup 1/H-/sup 2/H exchange reaction of MI in deuterium oxide with Raney nickel. During the exchange reaction, extensive epimerization occurred and at least 6 inositol epimers in addition to MI were identified in the reaction mixture of GC/MS. The perdeuterated MI was completely resolved from other inositol epimers and purified by anion-exchange chromatography using Dowex 1 (borate form) and by crystallization. The /sup 2/H-NMR analysis resolved the /sup 2/H-labeled hypocotyl cell walls into two components (rigid and mobile components). They also report the distribution of /sup 2/H and /sup 3/H from perdeuterated and (2-/sup 3/H) MI in the cell wall sugar residues.

  4. Expeditious diastereoselective synthesis of elaborated ketones via remote Csp3-H functionalization

    NASA Astrophysics Data System (ADS)

    Shu, Wei; Lorente, Adriana; Gómez-Bengoa, Enrique; Nevado, Cristina

    2017-01-01

    The quest for selective C-H functionalization reactions, able to provide new strategic opportunities for the rapid assembly of molecular complexity, represents a major focus of the chemical community. Examples of non-directed, remote Csp3-H activation to forge complex carbon frameworks remain scarce due to the kinetic stability and thus intrinsic challenge associated to the chemo-, regio- and stereoselective functionalization of aliphatic C-H bonds. Here we describe a radical-mediated, directing-group-free regioselective 1,5-hydrogen transfer of unactivated Csp3-H bonds followed by a second Csp2-H functionalization to produce, with exquisite stereoselectivity, a variety of elaborated fused ketones. This study demonstrates that aliphatic acids can be strategically harnessed as 1,2-diradical synthons and that secondary aliphatic C-H bonds can be engaged in stereoselective C-C bond-forming reactions, highlighting the potential of this protocol for target-oriented natural product and pharmaceutical synthesis.

  5. Expeditious diastereoselective synthesis of elaborated ketones via remote Csp(3)-H functionalization.

    PubMed

    Shu, Wei; Lorente, Adriana; Gómez-Bengoa, Enrique; Nevado, Cristina

    2017-01-13

    The quest for selective C-H functionalization reactions, able to provide new strategic opportunities for the rapid assembly of molecular complexity, represents a major focus of the chemical community. Examples of non-directed, remote Csp(3)-H activation to forge complex carbon frameworks remain scarce due to the kinetic stability and thus intrinsic challenge associated to the chemo-, regio- and stereoselective functionalization of aliphatic C-H bonds. Here we describe a radical-mediated, directing-group-free regioselective 1,5-hydrogen transfer of unactivated Csp(3)-H bonds followed by a second Csp(2)-H functionalization to produce, with exquisite stereoselectivity, a variety of elaborated fused ketones. This study demonstrates that aliphatic acids can be strategically harnessed as 1,2-diradical synthons and that secondary aliphatic C-H bonds can be engaged in stereoselective C-C bond-forming reactions, highlighting the potential of this protocol for target-oriented natural product and pharmaceutical synthesis.

  6. Dual sources of water overprinting on the low zircon δ18O metamorphic country rocks: Disequilibrium constrained through inverse modelling of partial reequilibration

    PubMed Central

    Wei, Chun-Sheng; Zhao, Zi-Fu

    2017-01-01

    Since water is only composed of oxygen and hydrogen, δ18O and δ2H values are thus utilized to trace the origin of water(s) and quantify the water-rock interactions. While Triassic high pressure (HP) and ultrahigh pressure (UHP) metamorphic rocks across the Dabie-Sulu orogen in central-eastern China have been well documented, postcollisional magmatism driven hydrothermal systems are little known. Here we show that two sources of externally derived water interactions were revealed by oxygen isotopes for the gneissic country rocks intruded by the early Cretaceous postcollisional granitoids. Inverse modellings indicate that the degree of disequilibrium (doD) of meteoric water interactions was more evident than that of magmatic one (−65 ± 1o vs. −20 ± 2°); the partial reequilibration between quartz and alkali feldspar oxygen isotopes with magmatic water was achieved at 340 °C with a water/rock (W/R) ratio of about 1.2 for an open-hydrothermal system; two-stage meteoric water interactions were unraveled with reequilibration temperatures less than 300 °C and W/R ratios around 0.4. The lifetime of fossil magmatic hydrothermal system overprinted on the low zircon δ18O orthogneissic country rocks was estimated to maintain up to 50 thousand years (Kyr) through oxygen exchange modellings. Four-stage isotopic evolutions were proposed for the magmatic water interacted gneiss. PMID:28091552

  7. Dual sources of water overprinting on the low zircon δ18O metamorphic country rocks: Disequilibrium constrained through inverse modelling of partial reequilibration

    NASA Astrophysics Data System (ADS)

    Wei, Chun-Sheng; Zhao, Zi-Fu

    2017-01-01

    Since water is only composed of oxygen and hydrogen, δ18O and δ2H values are thus utilized to trace the origin of water(s) and quantify the water-rock interactions. While Triassic high pressure (HP) and ultrahigh pressure (UHP) metamorphic rocks across the Dabie-Sulu orogen in central-eastern China have been well documented, postcollisional magmatism driven hydrothermal systems are little known. Here we show that two sources of externally derived water interactions were revealed by oxygen isotopes for the gneissic country rocks intruded by the early Cretaceous postcollisional granitoids. Inverse modellings indicate that the degree of disequilibrium (doD) of meteoric water interactions was more evident than that of magmatic one (‑65 ± 1o vs. ‑20 ± 2°) the partial reequilibration between quartz and alkali feldspar oxygen isotopes with magmatic water was achieved at 340 °C with a water/rock (W/R) ratio of about 1.2 for an open-hydrothermal system; two-stage meteoric water interactions were unraveled with reequilibration temperatures less than 300 °C and W/R ratios around 0.4. The lifetime of fossil magmatic hydrothermal system overprinted on the low zircon δ18O orthogneissic country rocks was estimated to maintain up to 50 thousand years (Kyr) through oxygen exchange modellings. Four-stage isotopic evolutions were proposed for the magmatic water interacted gneiss.

  8. Dual sources of water overprinting on the low zircon δ(18)O metamorphic country rocks: Disequilibrium constrained through inverse modelling of partial reequilibration.

    PubMed

    Wei, Chun-Sheng; Zhao, Zi-Fu

    2017-01-16

    Since water is only composed of oxygen and hydrogen, δ(18)O and δ(2)H values are thus utilized to trace the origin of water(s) and quantify the water-rock interactions. While Triassic high pressure (HP) and ultrahigh pressure (UHP) metamorphic rocks across the Dabie-Sulu orogen in central-eastern China have been well documented, postcollisional magmatism driven hydrothermal systems are little known. Here we show that two sources of externally derived water interactions were revealed by oxygen isotopes for the gneissic country rocks intruded by the early Cretaceous postcollisional granitoids. Inverse modellings indicate that the degree of disequilibrium (doD) of meteoric water interactions was more evident than that of magmatic one (-65 ± 1(o) vs. -20 ± 2°); the partial reequilibration between quartz and alkali feldspar oxygen isotopes with magmatic water was achieved at 340 °C with a water/rock (W/R) ratio of about 1.2 for an open-hydrothermal system; two-stage meteoric water interactions were unraveled with reequilibration temperatures less than 300 °C and W/R ratios around 0.4. The lifetime of fossil magmatic hydrothermal system overprinted on the low zircon δ(18)O orthogneissic country rocks was estimated to maintain up to 50 thousand years (Kyr) through oxygen exchange modellings. Four-stage isotopic evolutions were proposed for the magmatic water interacted gneiss.

  9. Effects of delta9-THC on the synaptosomal uptake of 3H-tryptophan and 3H-choline.

    PubMed

    Johnson, K M; Dewey, W L

    1978-01-01

    The in vitro addition of (-)-delta9-tetrahydrocannabinol (delta9-THC) resulted in a dose-responsive inhibition of the high-affinity specific synaptosomal uptake of both 3H-tryptophan and 3H-choline in mouse forebrain crude synaptosomal preparations. The approximate concentrations of delta9-THC required to cause a 50% inhibition of the uptake of 3H-tryptophan and 3H-choline were 33 and 16 muM, respectively. Kinetic analysis showed that inhibition of both compounds were consistent with a noncompetitive mechanism. The pretreatment of mice with doses of 10, 30 or 100 mg/kg delta9-THC had no effect on the subsequent in vitro synaptosomal uptake of either 3H-tryptophan or 3H-choline into forebrain synaptosomes.

  10. 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.

  11. 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; 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.

  12. 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.

  13. Dynamics of 16,18O-induced reactions using Ni, Ge and Mo targets

    NASA Astrophysics Data System (ADS)

    Rajni; Kaur, Gurvinder; Sharma, Manoj K.

    2016-11-01

    Dynamical cluster decay model (DCM) based on the collective clusterization approach is employed to explore the dynamics of various even-mass Zr isotopes formed in 16O-induced reactions. In reference to the measured fusion cross-section data, various decay modes contributing towards 86,88,90,92Zr∗ nuclei are investigated. Also, the role of deformations and orientation degree of freedom is analyzed by comparing results with spherical choice of fragmentation. In addition to this, the effect of entrance channel is explored for 92Zr∗ and 76Kr∗ nuclei formed in 16O and 18O-induced reactions. Besides this, the dynamics of relatively heavier mass Sn isotopes is exercised using 16O and 18O projectiles. The DCM calculated decay cross-sections find good agreement with available experimental data.

  14. 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.

  15. 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.

  16. The δ18O record of phanerozoic abiotic marine calcite cements

    NASA Astrophysics Data System (ADS)

    Lohmann, Kyger C.; Walker, James C. G.

    Monomineralic, abiotic marine cements formed in low-latitude Phanerozoic reefs provide the direction and amplitude of secular variation of δ13C and δ18O in marine calcite and defines two end member compositions — 580 to 360 my (-7 to -5‰ δ18OPDB) and 360 to present (-3 to 0‰ δ18OPDB). 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 δ13C and 3-4‰ offset in δ18O. The abruptness of such change, and its overall correlation with variations in 87Sr/86Sr, δ34S, δ13C, and Li/Al ratios in marine sediments suggests a primary offset in marine water composition.

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

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  18. Plio-Pleistocene ice volume, Antarctic climate, and the global delta18O record.

    PubMed

    Raymo, M E; Lisiecki, L E; Nisancioglu, Kerim H

    2006-07-28

    We propose that from approximately 3 to 1 million years ago, ice volume changes occurred in both the Northern and Southern Hemispheres, each controlled by local summer insolation. Because Earth's orbital precession is out of phase between hemispheres, 23,000-year changes in ice volume in each hemisphere cancel out in globally integrated proxies such as ocean delta18O or sea level, leaving the in-phase obliquity (41,000 years) component of insolation to dominate those records. Only a modest ice mass change in Antarctica is required to effectively cancel out a much larger northern ice volume signal. At the mid-Pleistocene transition, we propose that marine-based ice sheet margins replaced terrestrial ice margins around the perimeter of East Antarctica, resulting in a shift to in-phase behavior of northern and southern ice sheets as well as the strengthening of 23,000-year cyclicity in the marine delta18O record.

  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. 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.

  1. 13C-18O isotope signatures and ‘clumped isotope’ thermometry in foraminifera and coccoliths

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

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

  3. Carbonate clumped isotope constraints on Silurian ocean temperature and seawater δ18O

    NASA Astrophysics Data System (ADS)

    Cummins, Renata C.; Finnegan, Seth; Fike, David A.; Eiler, John M.; Fischer, Woodward W.

    2014-09-01

    Much of what we know about the history of Earth's climate derives from the chemistry of carbonate minerals in the sedimentary record. The oxygen isotopic compositions (δ18O) of calcitic marine fossils and cements have been widely used as a proxy for past seawater temperatures, but application of this proxy to deep geologic time is complicated by diagenetic alteration and uncertainties in the δ18O of seawater in the past. Carbonate clumped isotope thermometry provides an independent estimate of the temperature of the water from which a calcite phase precipitated, and allows direct calculation of the δ18O of the water. The clumped isotope composition of calcites is also highly sensitive to recrystallization and can help diagnose different modes of diagenetic alteration, enabling evaluation of preservation states and identification of the most pristine materials from within a sample set-critical information for assessing the quality of paleoproxy data generated from carbonates. We measured the clumped isotope composition of a large suite of calcitic fossils (primarily brachiopods and corals), sedimentary grains, and cements from Silurian (ca. 433 Ma) stratigraphic sections on the island of Gotland, Sweden. Substantial variability in clumped isotope temperatures suggests differential preservation with alteration largely tied to rock-buffered diagenesis, complicating the generation of a stratigraphically resolved climate history through these sections. Despite the generally high preservation quality of samples from these sections, micro-scale observations of calcite fabric and trace metal composition using electron backscatter diffraction and electron microprobe analysis suggest that only a subset of relatively pristine samples retain primary clumped isotope signatures. These samples indicate that Silurian tropical oceans were likely warm (33 ± 7 °C) and similar in oxygen isotopic composition to that estimated for a "modern" ice-free world (δ18OVSMOW of -1.1 ± 1

  4. 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.

  5. Letter: Observation of the 16O/18O exchange during electrospray ionization.

    PubMed

    Kostyukevich, Yury; Kononikhin, Alexey; Popov, Igor; Nikolaev, Eugene

    2015-01-01

    Isotopic exchange approach coupled to high-resolution mass spectrometry has become the power analytical approach for a wide range of analytical and bioanalyticall applications. Considerable efforts have been dedicated to developing fast exchange techniques directly in the ionization source. But all such methods are limited to the hydrogen/deuterium exchange approaches. In this paper we demonstrate that certain types of oxygen atoms can also be exchanged for (18)O on the time scale of the ionization process. Using HIO(3) and NaIO(4) and by infusing the heavy water H(2)(18)O in the ESI source we have demonstrated that it is possible to obtain a high level of oxygen exchange. It was observed that the rate of this exchange depends to a large extent on the temperature of the desolvating capillary of the mass spectrometer. Several other species, such as peptides, oligonucleotides and low weight organic molecules, were subjected to in-ESI (16)O/(18)O exchange but the exchange was not observed.

  6. 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.

  7. NanoSIMS50 analyses of Ar/18O2 plasma-treated Escherichia coli bacteria

    NASA Astrophysics Data System (ADS)

    Clément, F.; Lecoq, E.; Duday, D.; Belmonte, T.; Audinot, J.-N.; Lentzen, E.; Penny, C.; Cauchie, H.-M.; Choquet, P.

    2011-11-01

    Reactive oxygen species (ROS) can be produced by electrical discharges and can be transported in uncharged regions by gas flows, in the so-called afterglows. These species are well known to have bactericidal effects but interaction mechanisms that occur with living micro-organisms remain misunderstood. In order to better understand these interactions, new analysis approaches are necessary. High-lateral-resolution secondary ion mass spectrometry (NanoSIMS) is one of the most promising ways of retrieving additional information on bacteria plasma inactivation mechanisms by combining isotopic imaging of plasma-treated bacteria and the use of 18O2 as process gas. Indeed, this technology combines a lateral resolution of a few tens of nanometres that is sufficient to image the interior of bacteria, and a high mass resolution allowing detection of isotopes present in low quantities (a few ppm or lower) within the bacteria. The present paper deals with Ar-18O2 (2%) plasma treatment, through low-pressure microwave late afterglows, of Escherichia coli bacteria and their elemental and isotopic imaging by NanoSIMS. E. coli bacteria have been exposed to this reactive medium for varying treatment duration while keeping all other parameters unchanged. Our main goal is to determine whether the quantity of 18O fixed in treated bacteria and the NanoSIMS50 lateral resolution are sufficient to give additional information on E. coli bacteria-plasma interaction.

  8. Terahertz spectroscopy of N18O and isotopic invariant fit of several nitric oxide isotopologs

    NASA Astrophysics Data System (ADS)

    Müller, Holger S. P.; Kobayashi, Kaori; Takahashi, Kazumasa; Tomaru, Kazuko; Matsushima, Fusakazu

    2015-04-01

    A tunable far-infrared laser sideband spectrometer was used to investigate a nitric oxide sample enriched in 18O between 0.99 and 4.75 THz. Regular, electric dipole transitions were recorded between 0.99 and 2.52 THz, while magnetic dipole transitions between the 2Π1/2 and 2Π3/2 spin-ladders were recorded between 3.71 and 4.75 THz. These data were combined with lower frequency data of N18 O (unlabeled atoms refer to 14 N and 16 O, respectively), with rotational data of NO, 15 NO, N17 O, and 15 N18 O, and with heterodyne infrared data of NO to be subjected to one isotopic invariant fit. Rotational, fine and hyperfine structure parameters were determined along with vibrational, rotational, and Born-Oppenheimer breakdown corrections. The resulting spectroscopic parameters permit prediction of rotational spectra suitable for the identification of various nitric oxide isotopologs especially in the interstellar medium by means of rotational spectroscopy.

  9. Constraining past seawater δ18O and temperature records developed from foraminiferal geochemistry

    NASA Astrophysics Data System (ADS)

    Thirumalai, Kaustubh; Quinn, Terrence M.; Marino, Gianluca

    2016-10-01

    Paired measurements of magnesium-to-calcium ratios (Mg/Ca) and the stable oxygen isotopic composition (δ18O) in foraminifera have significantly advanced our knowledge of the climate system by providing information on past temperature and seawater δ18O (δ18Osw, a proxy for salinity and ice volume). However, multiple sources of uncertainty exist in transferring these downcore geochemical data into quantitative paleoclimate reconstructions. Here we develop a computational toolkit entitled Paleo-Seawater Uncertainty Solver (PSU Solver) that performs bootstrap Monte Carlo simulations to constrain these various sources of uncertainty. PSU Solver calculates temperature and δ18Osw, and their respective confidence intervals using an iterative approach with user-defined errors, calibrations, and sea-level curves. Our probabilistic approach yields reduced uncertainty constraints compared to theoretical considerations and commonly used propagation exercises. We demonstrate the applicability of PSU Solver for published records covering three timescales: the late Holocene, the last deglaciation, and the last glacial period. We show that the influence of salinity on Mg/Ca can considerably alter the structure and amplitude of change in the resulting reconstruction and can impact the interpretation of paleoceanographic time series. We also highlight the sensitivity of the records to various inputs of sea-level curves, transfer functions, and uncertainty constraints. PSU Solver offers an expeditious yet rigorous approach to test the robustness of past climate variability inferred from paired Mg/Ca-δ18O measurements.

  10. Elemental and isotopic ( 29Si and 18O) tracing of glass alteration mechanisms

    NASA Astrophysics Data System (ADS)

    Valle, Nathalie; Verney-Carron, Aurélie; Sterpenich, Jérôme; Libourel, Guy; Deloule, Etienne; Jollivet, Patrick

    2010-06-01

    To better understand glass alteration mechanisms, especially alteration layers formation, leaching experiments of a borosilicate glass (SON68) doped with a different rare earth element (La, Ce, or Nd) with solutions rich in 29Si and 18O were carried out. The coupled analyses of glass, alteration products, and solution led to a complete elemental and isotopic ( 29Si and 18O) budget. They revealed different behaviours of elements that depend not only on their structural role in the glass, but also on their affinity for alteration products (gel, phyllosilicates, phosphates). However, analyses of both glass and solution are not sufficient to describe the real exchanges occurring between glass and solution. The use of 29Si and 18O tracers gives new insights on the formation of alteration layers. During alteration the phyllosilicates records the isotopic variations of the leaching solution. Their isotopic signatures highlight a mechanism of dissolution/precipitation, which implies equilibrium between the secondary phases and the solution. On the other hand the gel isotopic signature, that is intermediate between the glass and the solution, substantiates the hypothesis that the gel is formed by hydrolysis/condensation reactions. This mechanism can thus explain the influence of the gel formation conditions (alteration conditions, solution saturation) on the structure (reorganisation) and texture (porosity) of this layer and on its protective effect. These hydrolysis/condensation reactions are also certainly involved in the aluminosilicate glass alteration and in the formation of palagonite.

  11. Observation of the pi...H hydrogen-bonded ternary complex, (C(2)H(4))(2)H(2)O, using matrix isolation infrared spectroscopy.

    PubMed

    Thompson, Matthew G K; Lewars, Errol G; Parnis, J Mark

    2005-10-27

    FTIR absorption spectra of water-containing ethene:Ar matrices, with compositions of ethene up to 1:10 ethene:Ar, have been recorded. Systematically increasing the concentration of ethene reveals features in the spectra consistent with the known 1:1 ethene:water complex, which subsequently disappear on further increase in ethene concentration. At high concentrations of ethene, new features are observed at 3669 and 3585 cm(-1), which are red-shifted with respect to matrix-isolated nu(3) and nu(1) O-H stretching modes of water and the 1:1 ethene:water complex. These shifts are consistent with a pi...H interaction of a 2:1 ethene:water complex of the form (C(2)H(4)...H-O-H...C(2)H(4)). The analogous (C(2)D(4))(2)H(2)O complex shows little shifting from positions associated with (C(2)H(4))(2)H(2)O, while the (C(2)H(4))(2)D(2)O isotopomer shows large shifts to 2722.3 and 2617.2 cm(-1), having identical nu(3)(H(2)O)/nu(3)(D(2)O) and nu(1)(H(2)O)/nu(1)(D(2)O) values when compared with monomeric water isotopomers. Features at 3626.1 and 2666.2 cm(-1) are also observed and are attributed to (C(2)H(4))(2)HDO. DFT calculations at the B3LYP/6-311+G(d,p) level for each isotopomer are presented, and the predicted vibrational frequencies are directly compared with experimental values. The interaction energy for the formation of the 2:1 ethene:water complex from the 1:1 ethene:water complex is also presented.

  12. 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.

  13. 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.

  14. /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.

  15. Binding of [3H]idazoxan and of its methoxy derivative [3H] RX821002 in human fat cells: [3H]idazoxan but not [3H] RX821002 labels additional non-alpha 2-adrenergic binding sites.

    PubMed

    Langin, D; Paris, H; Lafontan, M

    1990-06-01

    Binding studies were carried out in human fat cell membranes with two alpha 2-adrenergic antagonists, [3H]idazoxan and its methoxy derivative [3H]RX821002. Inhibition studies with epinephrine enantiomers indicate that [3H]RX821002 only binds to alpha 2-adrenoceptors, whereas [3H]idazoxan labels alpha 2-adrenoceptors and additional nonadrenergic sites (NAIBS). NAIBS and alpha 2-adrenoceptors display different affinities towards drugs from various chemical families. Imidazoline and some guanidine derivatives exhibit a high affinity for NAIBS. Pharmacological studies of human NAIBS indicate that they are slightly different from those previously reported in the rabbit, suggesting the existence of several subtypes of NAIBS. Furthermore, NAIBS are different from the previously described "imidazoline-preferring sites." [3H]idazoxan and [3H]RX821002 saturation analyses were performed in human adipocytes from different anatomical locations, in order to compare the number of NAIBS and alpha 2-adrenoceptors. Although there was an important variation in NAIBS and alpha 2-adrenoceptor numbers in the studied samples, a very poor correlation was obtained between the Bmax values of the two sites. Moreover, alkylation of alpha 2-adrenoceptors by phenoxybenzamine produces a 90% reduction in accessible [3H]RX821002 binding sites, without modification of [3H]idazoxan binding. These data show that NAIBS are not closely related to the alpha 2-adrenergic molecule. In addition, benextramine appears to be a reversible competitor at NAIBS. [3H]idazoxan binding, but not [3H]RX821002 binding, is sensitive to K+, suggesting that the domains involved in the ligand-NAIBS interaction are different from those involved in the ligand-alpha 2-adrenoceptor interaction.

  16. Laser Fluorination of Meteorites--Small Sample Analysis of delta17O and delta18O

    NASA Astrophysics Data System (ADS)

    Franchi, I. A.; Akagi, T.; Pillinger, C. T.

    1992-07-01

    The importance of oxygen isotope analysis in the field of meteoritics has been firmly established over the past 15 to 20 years, almost exclusively by Clayton and co-workers at the University of Chicago. The ability of the now classical oxygen three isotope plot to distinguish between fractionation and mixing processes has meant that such analyses are particularly powerful in helping to establish the generic relationships between different classes of meteorites. Conventionally, oxygen gas is usually extracted from the samples in nickel, or similar, reaction bombs at temperatures up to 700 degrees C in the presence of a powerful oxidizing reagent. Due to the nature of these experiments relatively large samples are required (35 mg or more) and the maximum temperatures used make analyses of more refractory minerals difficult if not dangerous. In the past two years a number of laboratories have been developing laser fluorination techniques. Such a technique greatly helps to reduce the blank, allow higher reaction temperatures, and speed up the reaction times, resulting in smaller sample size requirements, and potentially in situ analysis. However, to date this has only been applied to delta^18O analyses where the oxygen is analysed as CO2. We report here the development of a laser fluorination technique capable of running small samples for delta^17O and delta^18O using oxygen gas. The laser used is a 25W CO2 laser (10.6 micrometer radiation) and the reagent is ClF3. The sample size requirements are currently 0.5 to 1.0 mg. Replicate analyses of NBS-28 quartz has yielded precision on delta^18O and delta^17O of +-0.15 and +-0.17o/oo respectively and with other terrestrial samples define the expected fractionation line. The results of the first application of this technique to meteorite samples are shown in the figures. The LL6 Appley Bridge has been analyzed four times (Fig. 1a) giving mean values for delta^17O and delta^18O of +3.94o/oo (+-0.14) and +4.99o/oo (+-0

  17. /sup 3/H-imipramine uptake into rat striatal slices and imipramine-induced /sup 3/H-dopamine efflux

    SciTech Connect

    Saito, R.; Kawasaki, K.; Ono, N.; Kamiya, H.

    1983-04-01

    The effect of imipramine on spontaneous efflux of radiolabelled dopamine (DA) from slices of rat striatum was examined by a superfusion method. Imipramine at concentrations of 10 - 100 microM enhanced the efflux of DA accumulated in a high-affinity uptake system in a concentration-dependent manner. This efflux of /sup 3/H-DA was not affected by conditions (Ca/sup 2 +/-free medium, 100 microM bretylium and 30 microM tetrodotoxin) which inhibited the release of /sup 3/H-DA by electrical stimulation. Furthermore, this imipramine-induced /sup 3/H-DA efflux was temperature-dependent. The uptake of /sup 3/H-imipramine into striatal slices was determined. This uptake was concentration- and temperature-dependent and increased linearly. These results are discussed in relation to the hypothesis that /sup 3/H-DA efflux by imipramine is connected with uptake of imipramine.

  18. Assimilation of 3H in photosynthesizing leaves exposed to HTO.

    PubMed

    Guenot, J; Belot, Y

    1984-12-01

    Potato and wine grape plants were exposed for a period of 4 h to tritiated water vapor, and simultaneously to 14CO2 which served as a tracer for photosynthetic assimilation. During and after exposure, foliar samples were collected in which the exchangeable and nonexchangeable fractions of organic 3H were determined, taking care that the exchangeable fraction should not be lost to atmosphere. It was demonstrated that about 20% of the organic H in vegetation could be exchanged with 3H of tissue water, and that nonexchangeable 3H was fixed by photosynthesis. The kinetic behavior of the 2 forms was very different.

  19. 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.

  20. δ18O records in water vapor and an ice core from the eastern Pamir Plateau: Implications for paleoclimate reconstructions

    NASA Astrophysics Data System (ADS)

    Yu, Wusheng; Tian, Lide; Risi, Camille; Yao, Tandong; Ma, Yaoming; Zhao, Huabiao; Zhu, Haifeng; He, You; Xu, Baiqing; Zhang, Hongbo; Qu, Dongmei

    2016-12-01

    This study is the first to examine δ18O in daily water vapor at Taxkorgan on the eastern Pamir Plateau. The results show that changes in observed and simulated δ18O values in water vapor/precipitation at the event scale (using a LMDZ-iso model) were mainly affected by temperature. The influences of humidity, precipitation amount, and different moisture sources, such as the westerlies, local evaporated moisture, and polar air masses, on δ18O values are comparatively weak. The combination of the δ18O record from the Muztagata ice core, 58 km away from the study area, and the LMDZ-iso simulated annual δ18O pattern in precipitation at Taxkorgan also demonstrated that temperature, and particularly the temperature of the regions over which the southern branch of the westerlies flows, is the most important factor controlling δ18O variations. The results from this study area, which is dominated by the westerlies throughout the year, are markedly different from those derived from parts of the Tibetan Plateau that are dominated by the combined influences of the westerlies in winter and the Indian monsoon in summer. The results suggested that the eastern Pamir Plateau is an ideal location to reconstruct past temperature variations and that the δ18O records preserved in ice cores from the region are a suitable and robust proxy for temperature.

  1. 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.

  2. Renal Aldosterone Receptors: Studies with [3H]Aldosterone and the Anti-Mineralocorticoid [3H]Spirolactone (SC-26304)

    PubMed Central

    Marver, Diana; Stewart, John; Funder, John W.; Feldman, David; Edelman, Isidore S.

    1974-01-01

    In vivo, a spirolactone (SC-26304) inhibited the effects of aldosterone on urinary K+:Na+ ratios and the binding of [3H]aldosterone to renal cytoplasmic and nuclear receptors. Cytoplasmic binding of [3H]aldosterone and [3H]spirolactone (SC-26304) was similar in magnitude and involved the same set of sites. Under three sets of conditions—(i) in the intact rat, (ii) in kidney slices, and (iii) in reconstitution studies (mixing prelabeled cytoplasm with either purified renal nuclei or chromatin), [3H]spirolactone (SC-26304) did not yield specific nuclear complexes in contrast to the reproducible generation of these complexes with [3H]aldosterone. In glycerol density gradients, cytoplasmic [3H]aldosterone receptor complexes sedimented at 8.5 S and 4 S in low concentrations of salt and at 4.5 S in high concentrations of salt. Cytoplasmic [3H]spirolactone (SC-26304) receptor complexes sedimented at 3 S in low concentrations of salt and 4 S in high concentrations of salt. These results are discussed in terms of an allosteric model of the receptor system. Images PMID:4364539

  3. (/sup 3/H) clonidine binding to rat hippocampal membranes

    SciTech Connect

    George, C.R.

    1982-02-01

    Alpha adrenergic receptor subtypes in rat hippocampal membranes were studied, using (/sup 3/H) clonidine as the radioactive ligand. On the basis of competitive binding studies, using the selective antagonist-prazosin, WB-4101, and yohimbine, (/sup 3/H) clonidine appeared to bind to a population of presynaptic sites that are pharmacologically similar to receptors previously classified as alpha 2. A computerized model that linearized and produced the best possible fit to the experimental data points indicated that (/sup 3/H) clonidine binds to a single population of receptors possessing equal affinity for the ligand. Binding data also indicated that rat hippo-campus contains significantly fewer (/sup 3/H)clonidine binding sites than rat cortex.

  4. 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

  5. Quantitative Proteomic Approach for MicroRNA Target Prediction Based on 18O/16O Labeling

    PubMed Central

    Ma, Xuepo; Zhu, Ying; Huang, Yufei; Tegeler, Tony; Gao, Shou-Jiang; Zhang, Jianqiu

    2015-01-01

    MOTIVATION Among many large-scale proteomic quantification methods, 18O/16O labeling requires neither specific amino acid in peptides nor label incorporation through several cell cycles, as in metabolic labeling; it does not cause significant elution time shifts between heavy- and light-labeled peptides, and its dynamic range of quantification is larger than that of tandem mass spectrometry-based quantification methods. These properties offer 18O/16O labeling the maximum flexibility in application. However, 18O/16O labeling introduces large quantification variations due to varying labeling efficiency. There lacks a processing pipeline that warrants the reliable identification of differentially expressed proteins (DEPs). This motivates us to develop a quantitative proteomic approach based on 18O/16O labeling and apply it on Kaposi sarcoma-associated herpesvirus (KSHV) microRNA (miR) target prediction. KSHV is a human pathogenic γ-herpesvirus strongly associated with the development of B-cell proliferative disorders, including primary effusion lymphoma. Recent studies suggest that miRs have evolved a highly complex network of interactions with the cellular and viral transcriptomes, and relatively few KSHV miR targets have been characterized at the functional level. While the new miR target prediction method, photoactivatable ribonucleoside-enhanced cross-linking and immunoprecipitation (PAR-CLIP), allows the identification of thousands of miR targets, the link between miRs and their targets still cannot be determined. We propose to apply the developed proteomic approach to establish such links. METHOD We integrate several 18O/16O data processing algorithms that we published recently and identify the messenger RNAs of downregulated proteins as potential targets in KSHV miR-transfected human embryonic kidney 293T cells. Various statistical tests are employed for picking DEPs, and we select the best test by examining the enrichment of PAR-CLIP-reported targets with

  6. 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

  7. (/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.

  8. 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

  9. Tertiary delta 18O record and glacio-eustatic sea-level fluctuations.

    USGS Publications Warehouse

    Matthews, R.K.; Poore, R.Z.

    1980-01-01

    Previous interpretation of the Tertiary delta 18O record of planktic and benthic foraminifers has emphasized comparison to the modern ocean, assumed an ice-free world prior to middle Miocene time, and thereby calculated surprisingly cool temperatures for the tropical sea surface. We propose an alternative interpretation, which compares Tertiary data to average late Pleistocene, assumes constant tropical sea-surface temperature, and thereby estimates global ice volume. This approach suggests that Earth has had a significant ice budget (and therefore glacio-eustatic sea-level fluctuations) at least since Eocene and perhaps even throughout much of Cretaceous time. -Authors

  10. sup 18 O( sup 3 He, p ) sup 20 F reaction

    SciTech Connect

    Chowdhury, M.S.; Zaman, M.A.; Sen Gupta, H.M. )

    1992-12-01

    The {sup 18}O({sup 3}He,{ital p}){sup 20}F reaction has been studied at 18 MeV. Energy levels are measured up to {ital E}{sub {ital x}}{similar to}8.5 MeV and several new levels are observed. Angular distributions are measured for many of the levels and distorted wave Born approximation analyses are carried out. The {ital L} assignments are made and {ital J}{sup {pi}} limits are obtained.

  11. Stimulation of [3H] GABA and beta-[3H] alanine release from rat brain slices by cis-4-aminocrotonic acid.

    PubMed

    Chebib, M; Johnston, G A

    1997-02-01

    cis-4-Aminocrotonic acid (CACA; 100 microM), an analogue of GABA in a folded conformation, stimulated the passive release of [3H] GABA from slices of rat cerebellum, cerebral cortex, retina, and spinal cord and of beta-[3H]alanine from slices of cerebellum and spinal cord without influencing potassium-evoked release. In contrast, CACA (100 microM) did not stimulate the passive release of [3H]taurine from slices of cerebellum and spinal cord or of D-[3H]aspartate from slices of cerebellum and did not influence potassium-evoked release of [3H]-taurine from the cerebellum and spinal cord and D-[3H]-aspartate from the cerebellum. These results suggest that the effects of CACA on GABA and beta-alanine release are due to CACA acting as a substrate for a beta-alanine-sensitive GABA transport system, consistent with CACA inhibiting the uptake of beta-[3H]alanine into slices of rat cerebellum and cerebral cortex. The observed Ki for CACA against beta-[3H]alanine uptake in the cerebellum was 750 +/- 60 microM. CACA appears to be 10-fold weaker as a substrate for the transporter system than as an agonist for the GABAc receptor. The effects of CACA on GABA and beta-alanine release provide indirect evidence for a GABA transporter in cerebellum, cerebral cortex, retina, and spinal cord that transports GABA, beta-alanine, CACA, and nipecotic acid that has a similar pharmacological profile to that of the GABA transporter, GAT-3, cloned from rat CNS. The structural similarities of GABA, beta-alanine, CACA, and nipecotic acid are demonstrated by computer-aided molecular modeling, providing information on the possible conformations of these substances being transported by a common carrier protein.

  12. Washout of tritium from 3R-3(/sup 3/H)-L-aspartate in the aspartase reaction

    SciTech Connect

    Katz, B.M.; Cook, P.F.

    1987-05-01

    Bacterial aspartase catalyzes the reversible conversion of L-aspartate to fumarate and ammonia. Recent studies that made use of deuterium and /sup 15/N isotope effects suggested a carbanion intermediate mechanism in which C-N bond cleavage is rate determining. This could result in removal of a proton from the 3R position of aspartate at a rate of faster than the elimination of ammonia. 3R-3(/sup 3/H)-Aspartate was prepared enzymatically using aspartase from fumarate, ammonia and /sup 3/H/sub 2/O and aspartate isolated via chromatography on Dowex 50W x 8 at pH 1, eluting with 2N pyridine. The rate of /sup 3/H washout from this aspartate was then measured as a function of aspartate concentration and compared to the rate of production of fumarate. Tritium does washout of aspartate at a rate faster than fumarate is formed but the proton is apparently not rapidly equilibrated with solvent. The tritium washout experiments were supplemented using 3R-3(/sup 2/H)-aspartate prepared as above with /sup 2/H/sub 2/O replacing /sup 3/H/sub 2/O and monitoring the appearance of 3R-3(/sup 1/H)-aspartate via /sup 1/H-NMR. Results confirm the tritium washout results. Data are discussed in terms of the carbanion mechanism.

  13. 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.

  14. A Review of Climatic Controls on δ18o in Precipitation over the Tibetan Plateau: Observations and Simulations

    NASA Astrophysics Data System (ADS)

    Yao, T.; Masson-Delmotte, V.; Gao, J.; Risi, C. M.

    2014-12-01

    Located at the convergence of air masses between the westerlies and monsoon, the Tibetan Plateau (TP) undergoes complex water cycle processes, which need to be documented and understood through a combination of variant methodologies. The stable oxygen isotope ratio (δ18O) in precipitation is an integrated tracer of the atmospheric processes and has been used worldwide. Since the 1990s, an intensive effort has been dedicated to studying precipitation isotopic composition at more than 20 stations in the TP. Based on these observations, we establish a database of precipitation δ18O and use different models to evaluate the climatic drivers of present-day precipitation δ18O over the TP. The spatial and temporal patterns of precipitation δ18O and their relationships with temperature and precipitation reveal three distinct domains, respectively associated with the influence of the westerlies (Northern TP), Indian monsoon (Southern TP) and transition in between. The seasonal patterns of precipitation δ18O are diverse in different domains. High-resolution atmospheric models equipped with stable isotopes capture the spatial and temporal patterns of precipitation δ18O and their relationships with moisture transport from the westerlies and Indian monsoon. Only in the westerlies domain are atmospheric models able to represent qualitatively and quantitatively the relationships between climate and precipitation δ18O. More significant temperature effect exists when either the westerlies or Indian monsoon is the sole dominant atmospheric process. The observed and simulated altitude-δ18O relationships strongly depend on the season and the domain (monsoon or westerlies). Our results have crucial implications for the interpretation of the abundant stable isotope information derived from natural climatic archives over the TP such as ice cores, lake sediments or tree rings, and for the application of atmospheric simulations to quantifying paleo-climate and paleo

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

    NASA Astrophysics Data System (ADS)

    Allison, Nicola; Finch, Adrian A.; EIMF

    2010-10-01

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

  16. Biosynthetic experiments with tall plants under field conditions. 18O2 incorporation into humulone from Humulus lupulus.

    PubMed

    Hecht, Stefan; Kammhuber, Klaus; Reiner, Josef; Bacher, Adelbert; Eisenreich, Wolfgang

    2004-04-01

    Five segments of a large hop plant (Humulus lupulus var. Hallertauer Magnum) carrying several cones were enclosed in sealed glass vessels that were gassed with (18)O(2). After 14 days, the segments were harvested and humulone and cohumulone were analysed by NMR spectroscopy and mass spectroscopy. The oxygen atoms in position 6 of humulone and cohumulone showed 9% (18)O enrichment, respectively. It follows that the C-6 hydroxy groups were introduced by oxygenase catalysis.

  17. A δ18O isoscape for the shallow groundwater in the Baltic Artesian Basin

    NASA Astrophysics Data System (ADS)

    Raidla, Valle; Kern, Zoltan; Pärn, Joonas; Babre, Alise; Erg, Katrin; Ivask, Jüri; Kalvāns, Andis; Kohán, Balázs; Lelgus, Mati; Martma, Tõnu; Mokrik, Robert; Popovs, Konrāds; Vaikmäe, Rein

    2016-11-01

    The study presents a shallow groundwater isoscape for the Baltic region, which covers the major part of the Baltic Artesian Basin (BAB). BAB is an important palaeogroundwater reservoir, but prior to this study, little has been known about the spatial variability of δD and δ18O values in modern precipitation input across the region. To overcome this limitation, we hypothesized that the isotopic composition of shallow groundwater in the BAB could be used as a proxy for the mean weighted annual isotopic composition of local precipitation. However, the results of the study reveal many clear discrepancies between the isotopic composition of precipitation and shallow groundwater in the area. The isotopic composition of shallow groundwater is mostly biased towards isotopically depleted wintertime precipitation. We propose that the formation of shallow groundwater in the BAB area could be largely affected by variations in soil structure and land cover. The derived isoscape based on δ18O values of shallow groundwater in the BAB area is characterised by high spatial resolution and can therefore serve as a fairly reliable reference basis for further hydrogeological, ecological and forensic applications.

  18. 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.

  19. 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.

  20. Low 18O-contents in Arctic Neogloboquadrina pachyderma shells: A proxy of brine formation rate?

    NASA Astrophysics Data System (ADS)

    Hillaire-Marcel, C.; de Vernal, A.

    2006-12-01

    In the Arctic Ocean, the cold water foraminifera Neogloboquadrina pachyderma (Np), left as right coiled, likely forms its shell along the pycnocline between the cold, dilute, surface water and the warmer, saline North Atlantic Water (NAW), due to salinity conditions in the surface water mass below optimum values for the species (~ 35 psu;[1]). However, δ18O-values in Np shell still present negative offsets with isotopic equilibrium conditions for a calcite precipitated at mid-pycnocline depth. This offset ranges from 1 (Arctic seas) to 3 per mil (Canada Basin, East Siberian Sea), although temperature gradients along the pycnocline still result in predictable isotopic shifts from small (juvenile?) to large (mature?) shells [2]. The precise mechanism responsible for the 18O offset is not known, but it seems linked to rate of sea-ice formation or to its seasonal duration (e.g., [3]). The freezing of low 18O-content sea-surface waters rejects isotopically-light brines that sink to the pycnocline. We hypothesize that Np-shell growth occurs in such high- salinity/low-δ18O water droplets or thin layers sinking to the pycnocline. In vitro experiments [4] have indeed shown that formation of new shell-chambers could still occurs in salinities of up to 58 psu, and that some specimens could survive 82 psu for at least a week. Thus, in this hypothesis, isotopic offsets in Np would relate to the rate of brine formation. In the modern Arctic Ocean, mixing of these brines into NAW and export of surface water and sea ice into the North Atlantic would contribute maintaining steady-state conditions, thus resulting in an asymptotic offset value near 2.5/-3 per mil in Np shells. From this viewpoint, the greater offsets in the western Arctic and East Siberian Sea areas (up to 3 per mil), compared with the eastern Arctic Ocean (appr. 1 per mil), would reflect a difference in sea-ice formation rates along the shelves. Such isotopic offsets maintained in the Chukchi Sea during most of

  1. 18O depletion in monsoon rain relates to large scale organized convection rather than the amount of rainfall.

    PubMed

    Lekshmy, P R; Midhun, M; Ramesh, R; Jani, R A

    2014-07-11

    Oxygen isotopic variations in rainfall proxies such as tree rings and cave calcites from South and East Asia have been used to reconstruct past monsoon variability, mainly through the amount effect: the observed (18)O depletion of rain with increasing amount, manifested as a negative correlation of the monthly amount of tropical rain with its δ(18)O, both measured at the same station. This relation exhibits a significant spatial variability, and at some sites (especially North-East and peninsular India), the rainfall proxies are not interpretable by this effect. We show here that relatively higher (18)O-depletion in monsoon rain is not related necessarily to its amount, but rather, to large scale organized convection. Presenting δ(18)O analyses of ~654 samples of daily rain collected during summer 2012 across 9 stations in Kerala, southern India, we demonstrate that although the cross correlations between the amounts of rainfall in different stations is insignificant, the δ(18)O values of rain exhibit highly coherent variations (significant at P = 0.05). Significantly more (18)O-depletion in the rain is caused by clouds only during events with a large spatial extent of clouds observable over in the south eastern Arabian Sea.

  2. 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

  3. Modulation of [3H]MK-801 binding to NMDA receptors in vivo and in vitro.

    PubMed

    Murray, F; Kennedy, J; Hutson, P H; Elliot, J; Huscroft, I; Mohnen, K; Russell, M G; Grimwood, S

    2000-06-02

    [3H]MK-801 binding in vivo was used to determine the occupancy of NMDA receptor ligands shown to allosterically modulate binding in vitro. ED(50) values (mg/kg) were obtained for the channel blockers (+)-5-methyl-10,11-dihydro-5,4-dibenzo[a,d]cyclohepten-5,10-imine maleate ((+)-MK-801, 0.2), 1-(1-phenylcyclohexyl)piperidine (phencyclidine, PCP, 1.7) and ketamine (4.4). Antagonists at the glutamate (DL-(2-carboxypiperazine-4-yl)propyl-1-phosphonate (DL-CPP, 5.7)) and glycine site (7-Chloro-4-hydroxy-3-(3-phenoxy)-phenyl-2(H)quinolinone (L-701,324, 14.1), 3R(+)cis-4-methyl-pyrrollid-2-one (L-687,414, 15.1)) inhibited [3H]MK-801 binding in vivo to varying maximum levels (69%, 103% and 45%, respectively). NR2B subunit-selective compounds acting at the ifenprodil site inhibited [3H]MK-801 in vivo by a maximum of 52-72% and gave ED(50) values (mg/kg) of: (+/-)-(1S*, 2S*)-1-(4-hydroxyphenyl)-2-(4-hydroxy-4-phenylpiperidino)-1-propanol ((+/-)CP-101,606), 1.9; (+/-)-(3R, 4S)-3-[4-(4-fluorophenyl)-4-hydroxypiperidin-1-yl]chroman-4,7-diol ((+/-)CP-283,097), 1.8; (+/-)-(R*, S*)-alpha-(4-hydroxyphenyl)-beta-methyl-4-(phenylmethyl)-1-piperidine propanol ((+/-)Ro 25-6981), 1.0; ifenprodil, 6.0. The glycine site agonist D-serine stimulated binding to 151% of control with an ED(50) of 1.7 mg/kg. Results show that [3H]MK-801 binding in vivo may be used to measure receptor occupancy of ligands acting not only within the ion channel but also at modulatory sites on the NMDA receptor complex.

  4. Rabbit blastocysts accumulate [3H]prostaglandins in vitro.

    PubMed

    Jones, M A; Harper, M J

    1984-08-01

    Rabbit blastocysts obtained on days 5, 6, and 6.8 of pregnancy were incubated in vitro in Tyrode's buffer with 3H-labeled prostaglandins (PGs). Accumulation of PGs was studied, using Whatman GF/F filters to separate bound and free ligands. The uptake and efflux of [3H]PGs were studied as a function of PG type, incubation time, temperature, and effect of metabolic inhibitors as well as age and number of blastocysts. Blastocysts of the same age accumulated approximately the same amount of [3H]PGE2 and [3H]PGF2 alpha from their environment; however, there was no apparent saturation over a PG concentration range of 1-1000 nM. Both the uptake and efflux of PG were age dependent, with older blastocysts accumulating more PGs. Approximately 90% of the [3H]PGs appear to be transported into the blastocoelic fluid, with little PG remaining in the blastomeres. PG accumulation was relatively insensitive to azide, ouabain, cyanide, or bromcresol green, but was affected by incubation at 0 C or the addition of indomethacin (10 micrograms/ml). No catabolism of the accumulated PGs was observed. The release of PGE2 in general did not differ from that of PGF2 alpha, except on day 6.8 of pregnancy when PGE2 was released more rapidly than on day 6. We conclude that rabbit blastocysts can accumulate PGs from their environment, which may imply a storage potential in the blastocyst and release before implantation.

  5. 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

  6. 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

  7. 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...

  8. 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.

  9. Analytical potential energy surface and kinetics of the NH(3) + H --> NH(2) + H(2) hydrogen abstraction and the ammonia inversion reactions.

    PubMed

    Espinosa-Garcia, J; Corchado, J C

    2010-04-01

    Based on accurate electronic structure calculations, a new analytical potential energy surface (PES) was fitted to simultaneously describe the hydrogen abstraction reaction from ammonia by a hydrogen atom, and the ammonia inversion. Using a wide spectrum of properties of the reactive system (equilibrium geometries, vibrational frequencies, and relative energies of the stationary points, topology of the reaction paths, and points on the reaction swaths) as reference, the resulting analytical PES reproduces reasonably well the input ab initio information obtained at the CCSD(T)/cc-pVTZ level, which represents a severe test for the new surface. As a first application, on this analytical PES we perform an extensive kinetics study using variational transition-state theory with semiclassical transmission coefficients over a wide temperature range, 200-2000 K. For the hydrogen abstraction reaction, the forward rate constants reproduce the experimental measurements, while the reverse ones are slightly underestimated. Another severe test of the new surface is the analysis of the kinetic isotope effects (KIEs). The KIEs between unsubstituted and all deuterated reactions agree with experiment in the common temperature range. For the ammonia inversion reaction, the splitting of the degenerate vibrational levels of the double well due to the tunneling contribution, which is very important in this reaction representing 93% of the reactivity at 200 K, was calculated for the NH(3) and ND(3) species. The values found were 3.6 and 0.37 cm(-1), respectively, which although higher than experimental values, reproduce the experimental behavior on isotopic substitution.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  11. SPATIALLY RESOLVED l-C{sub 3}H{sup +} EMISSION IN THE HORSEHEAD PHOTODISSOCIATION REGION: FURTHER EVIDENCE FOR A TOP-DOWN HYDROCARBON CHEMISTRY

    SciTech Connect

    Guzmán, V. V.; Öberg, K. I.; Pety, J.; Goicoechea, J. R.; Gerin, M.; Roueff, E.; Gratier, P.

    2015-02-20

    Small hydrocarbons, such as C{sub 2}H, C{sub 3}H, and C{sub 3}H{sub 2} 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-C{sub 3}H{sup +}, in the Horsehead PDR with the Plateau de Bure Interferometer at high-angular resolution (6″). We compare with previous observations of C{sub 2}H and c-C{sub 3}H{sub 2} 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-C{sub 3}H{sup +}, C{sub 2}H, and c-C{sub 3}H{sub 2} 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 C{sub 2}H and c-C{sub 3}H{sub 2} abundances are underestimated by an order of magnitude. At this position, the l-C{sub 3}H{sup +} abundance is also underpredicted by the model but only by a factor of a few. In addition, contrary to the model predictions, l-C{sub 3}H{sup +} peaks further out in the PDR than the other hydrocarbons, C{sub 2}H and c-C{sub 3}H{sub 2}. 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.

  12. 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).

  13. 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

  14. Effects of linalool on [(3)H]MK801 and [(3)H] muscimol binding in mouse cortical membranes.

    PubMed

    Brum, L F; Elisabetsky, E; Souza, D

    2001-08-01

    Linalool is a monoterpene compound reported to be a major component of essential oils of several aromatic species. Several linalool-producing species are used in traditional medical systems for sedative purposes, including the interruption and prevention of seizures. Previous studies in mice revealed that linalool modulates glutamatergic (competitive antagonism of L-[(3)H]glutamate binding, delayed intraperitoneal NMDA-induced convulsions and blockade of intracerebroventricular Quin-induced convulsions) and GABAergic transmission (protection against pentylenetetrazol and picrotoxin-induced convulsions). To further clarify the anticonvulsive mechanisms of linalool, we studied the effects of linalool on binding of [(3)H]MK801 (NMDA antagonist) and [(3)H]muscimol (GABA(A) agonist) to mouse cortical membranes. Linalool showed a dose dependent non-competitive inhibition of [(3)H]MK801 binding (IC(50) = 2.97 mM) but no effect on [(3)H]muscimol binding. The data suggest that the anticonvulsant mode of action of linalool includes a direct interaction with the NMDA receptor complex. The data do not, however, support a direct interaction of linalool with GABA(A) receptors, although changes in GABA-mediated neuronal inhibition or effects on GABA release and uptake cannot be ruled out.

  15. Reconstructing early Cenozoic topography of the North American Cordillera from authigenic mineral δ18O-Moving beyond Rayleigh distillation

    NASA Astrophysics Data System (ADS)

    Feng, R.; Poulsen, C. J.; Werner, M.

    2012-12-01

    Elevation reconstructions of the North American Cordillera, inferred from the oxygen isotope composition (δ18O) of terrestrial sediments, suggest fast north-to-south migration of topography in the early Cenozoic (pre-49Ma to 28Ma). This interpretation assumes that sediments accurately record the δ18O of ancient precipitation, and that the isotopic fractionation of precipitating air masses are represented by a Rayleigh distillation model (RDM) with a single moisture source from the Pacific. In this study, we test this latter assumption using a global climate model with isotope tracking capability (ECHAM5-wiso). Four Eocene experiments are performed, with topography inferred from proxy δ18O, to investigate how southward propagation of topography affects the climate and δ18O of precipitation over North America. Our ECHAM5-wiso simulations, with prescribed topography scenarios, predict precipitation δ18O distributions that are consistent with maps of temporally binned proxy δ18O. At face value, these simulations confirm the paleoelevation inferences based on proxy δ18O. However, detailed analyses of our GCM results demonstrate that in response to surface uplift, precipitation δ18O is substantially affected by precipitation processes and climate changes that are not captured by Rayleigh distillation. These processes include shifts in local precipitation type between convective and large-scale and between rain and snow; intensification of low-level vapor recycling particularly on leeward slopes; changes in wind direction and moisture source; and changes in upward mixing intensity. Each of these processes can have large (≥ 2‰) influences on precipitation δ18O that are comparable in magnitude to surface uplift of hundreds to thousands of meters. In many regions, these processes compensate each other, explaining the apparent agreement between ECHAM5-wiso and proxy δ18O and, more broadly, between Rayleigh distillation estimates and observed δ18O

  16. 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.

  17. Association reactions at low pressure. III. The C2H2+/C2H2 system.

    PubMed

    Anicich, V G; Sen, A D; Huntress, W T; McEwan, M J

    1990-11-15

    The association reactions, C4H2(+) + C2H2 and C4H3(+) + C2H2 have been examined at pressures between 8 x 10(-8) and 1 x 10(-4) Torr at 298 K in an ion cyclotron resonance mass spectrometer. Association occurred via two different mechanisms. At pressures below approximately 2 x 10(-6) Torr, the association was bimolecular having rate coefficients k2 = 2.7 x 10(-10) cm3 s-1 and 2.0 x 10(-10) cm3 s-1 for C4H2+ and C4H3+, respectively. At pressures above approximately 2 x 10(-6) Torr, termolecular association was observed with rate coefficients, k3 = 5.7 x 10(-23) cm6 s-1 and 1.3 x 10(-23) cm6 s-1 for C4H2+ and C4H3+, respectively, when M = C2H2. The termolecular rate constants with N2, Ar, Ne, and He as the third body, M, are also reported. We propose that the low pressure bimolecular association process was the result of radiative stabilization of the complex and the termolecular association process was the result of collisional stabilization. Elementary rate coefficients were obtained and the lifetime of the collision complex was > or = 57 microseconds for (C6H4+)* and > or = 18 microseconds for (C6H5+)*. At pressures below 1 x 10(-6) Torr, approximately 11% of the (C6H4+)* were stabilized by photon emission and the remaining approximately 89% reverted back to reactants, while approximately 24% of the (C6H5+)* were stabilized by photon emission and the remaining approximately 76% reverted back to reactants. The ionic products of the C2H2(+) + C2H2 reaction, C4H2+ and C4H3+, were found to be formed with enough internal energy that they did not react by the radiative association channel until relaxed by several nonreactive collisions with the bath gas.

  18. 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.

  19. Structure–function studies of histone H3/H4 tetramer maintenance during transcription by chaperone Spt2

    DOE PAGES

    Chen, Shoudeng; Rufiange, Anne; Huang, Hongda; ...

    2015-06-15

    Cells use specific mechanisms such as histone chaperones to abrogate the inherent barrier that the nucleosome poses to transcribing polymerases. The current model postulates that nucleosomes can be transiently disrupted to accommodate passage of RNA polymerases and that histones H3 and H4 possess their own chaperones dedicated to the recovery of nucleosomes. Here, we determined the crystal structure of the conserved C terminus of human Suppressors of Ty insertions 2 (hSpt2C) chaperone bound to an H3/H4 tetramer. The structural studies demonstrate that hSpt2C is bound to the periphery of the H3/H4 tetramer, mimicking the trajectory of nucleosomal-bound DNA. These structuralmore » studies have been complemented with in vitro binding and in vivo functional studies on mutants that disrupt key intermolecular contacts involving two acidic patches and hydrophobic residues on Spt2C. We show that contacts between both human and yeast Spt2C with the H3/H4 tetramer are required for the suppression of H3/ H4 exchange as measured by H3K56ac and new H3 deposition. Furthermore, these interactions are also crucial for the inhibition of spurious transcription from within coding regions. In conclusion, together, our data indicate that Spt2 interacts with the periphery of the H3/H4 tetramer and promotes its recycling in the wake of RNA polymerase.« less

  20. Structure–function studies of histone H3/H4 tetramer maintenance during transcription by chaperone Spt2

    SciTech Connect

    Chen, Shoudeng; Rufiange, Anne; Huang, Hongda; Rajashankar, Kanagalaghatta R.; Nourani, Amine; Patel, Dinshaw J.

    2015-06-15

    Cells use specific mechanisms such as histone chaperones to abrogate the inherent barrier that the nucleosome poses to transcribing polymerases. The current model postulates that nucleosomes can be transiently disrupted to accommodate passage of RNA polymerases and that histones H3 and H4 possess their own chaperones dedicated to the recovery of nucleosomes. Here, we determined the crystal structure of the conserved C terminus of human Suppressors of Ty insertions 2 (hSpt2C) chaperone bound to an H3/H4 tetramer. The structural studies demonstrate that hSpt2C is bound to the periphery of the H3/H4 tetramer, mimicking the trajectory of nucleosomal-bound DNA. These structural studies have been complemented with in vitro binding and in vivo functional studies on mutants that disrupt key intermolecular contacts involving two acidic patches and hydrophobic residues on Spt2C. We show that contacts between both human and yeast Spt2C with the H3/H4 tetramer are required for the suppression of H3/ H4 exchange as measured by H3K56ac and new H3 deposition. Furthermore, these interactions are also crucial for the inhibition of spurious transcription from within coding regions. In conclusion, together, our data indicate that Spt2 interacts with the periphery of the H3/H4 tetramer and promotes its recycling in the wake of RNA polymerase.

  1. R-matrix description of particle energy spectra produced by low-energy 3H + 3H reactions

    DOE PAGES

    Brune, C. R.; Caggiano, J. A.; Sayre, D. B.; ...

    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

  2. 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.

  3. 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.

  4. [Pharmacokinetics and biodistribution of 3H-norcantharidin in mice].

    PubMed

    Wei, Chun-Min; Wang, Ben-Jie; Ma, Ya; Sun, Zi-Ping; Li, Xiao-Li; Guo, Rui-Chen

    2007-05-01

    A single dose of 3H-norcantharidin solution was intragastrically given, blood, tissues, urine and feces were collected as scheduled, and radioactivity in these samples was determined by tritium tracing method to investigate the pharmacokinetics, tissue distribution and excretion of norcantharidin in Kunming mice. The pharmacokinetic characteristics of norcantharidin were evaluated by DAS version 2.0. The blood concentration reached to maximum 0. 5 h after intragastric administration. The radioactivity in tissues was high in small intestine, gallbladder, stomach, adrenal gland, kidney, heart and uterus 15 minutes after administration, descending with time, and high in gallbladder, adrenal gland and uterus 3 hours post dosing. The 24 h accumulative excretion ratio of urine and feces were 65.40% and 1.33% respectively. 3H-norcantharidin was easily absorbed after orally given to mice, the radioactivity was high and existed for a long-time in gallbladder, adrenal gland and uterus, and low but also existed for a long-time in large intestine, thymus and fat tissue. 3H-norcantharidin was declined quickly in small intestine, stomach, kidney and heart, and occurred rarely in brain. Norcantharidin was excreted mainly by urinary route and seldom in feces, which may be the cause of the urinary stimulation side effects observed. Because the radioactivity measured were the sum of 3H labeled norcantharidin and its metabolites, further studies on the disposition of norcantharidin in mammal animals, on the separation or identification of metabolites and, if any, on their activities, are fairly needed.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Rabbit blastocysts accumulate (/sup 3/H)prostaglandins in vitro

    SciTech Connect

    Jones, M.A.; Harper, M.J.

    1984-08-01

    Rabbit blastocysts obtained on days 5, 6, and 6.8 of pregnancy were incubated in vitro in Tyrode's buffer with /sup 3/H-labeled prostaglandins (PGs). Accumulation of PGs was studied, using Whatman GF/F filters to separate bound and free ligands. The uptake and efflux of (/sup 3/H)PGs were studied as a function of PG type, incubation time, temperature, and effect of metabolic inhibitors as well as age and number of blastocysts. Blastocysts of the same age accumulated approximately the same amount of (/sup 3/H)PGE2 and (/sup 3/H)PGF2 alpha from their environment; however, there was no apparent saturation over a PG concentration range of 1-1000 nM. Both the uptake and efflux of PG were age dependent, with older blastocysts accumulating more PGs. Approximately 90% of the (/sup 3/H)PGs appear to be transported into the blastocoelic fluid, with little PG remaining in the blastomeres. PG accumulation was relatively insensitive to azide, ouabain, cyanide, or bromcresol green, but was affected by incubation at 0 C or the addition of indomethacin (10 micrograms/ml). No catabolism of the accumulated PGs was observed. The release of PGE2 in general did not differ from that of PGF2 alpha, except on day 6.8 of pregnancy when PGE2 was released more rapidly than on day 6. The authors conclude that rabbit blastocysts can accumulate PGs from their environment, which may imply a storage potential in the blastocyst and release before implantation.

  10. The Chemistry of Mesitylgallium(3) Derivatives as Arene Ligands in Metal Carbonyl Complexes. Crystal and Molecular Structures of ((CO)3Mo(Eta 6- C6Me3H2))Ga(C6Me3H2)2 and ((CO)3Mo(Eta 6-C6Me3H2))2GA(C6Me3H2)

    DTIC Science & Technology

    1988-12-16

    useful neutral 6 6 6amphoteric ligands include PhB (NMe2 )2 , PhB (OMe)2 , PhB (C 5Ho10 ) and PhB (CH2CH(Me)C2H4 ) 6 . An anionic arene-transition metal...recrystallized from an appropriate solvent system. Synthesis of [(CO)3MoNes]2Ga~es. The complex [(CO) 3MoMes]2GaMes was prepared by refluxing a...2.22 (s, p-Me, 3 H); IR (DME, v(CO), cm- I) 1960 (sh, s), 1951 (vs), 1879 (vs). Anal. Caled: C, 50.35; H, 4.22. Found: C, 50.56; H, 4.24. Synthesis

  11. Variations of 18O/ 16O in plants from temperate peat bogs (Switzerland): implications for paleoclimatic studies

    NASA Astrophysics Data System (ADS)

    Ménot-Combes, Guillemette; Burns, Stephen J.; Leuenberger, Markus

    2002-09-01

    Despite the great potential of peat bogs as climatic archives, to date only few studies have focused on the climatic controls on cellulose isotopic composition in modern bog plants. This study attempts to calibrate plant-climate relationships by sampling a set of modern plant species (both vascular plants and mosses) and bog surface waters along an altitude transect in Switzerland. Isotopic analyses of water samples show that the δ 18O-values of surface bog waters follow the trend of precipitation despite significant scatter in the data set. Detailed sampling of surface waters within one bog shows that δ 18O-values vary widely and are closely related to the micro-topography of the bog surface. More enriched 18O/ 16O ratios in water samples collected from small raised hummocks than the ones collected from hollows are documented in both horizontal and vertical profiles. A δ 18O-δD plot indicates that the process leading to the isotopic enrichment of the uppermost surface waters is evaporation, greater above Sphagnum covered hummocks than above open pools. To investigate the implications of such high variability of source water for plant α-cellulose δ 18O-values, a detailed study of both surface water and α-cellulose δ 18O-values within one site is conducted. The large δ 18O variability observed in surface waters is found to be considerably smoothed in α-cellulose (by a factor of 5-10 depending on the plant species). This indicates that the water used by plant photosynthetic processes reflects the isotopic composition of the average annual precipitation. This points to a source water level for plants of a few decimeters where the variations are smaller than at the air-water interface. The response of the α-cellulose δ 18O to the environmental gradient along the altitude transect varies considerably from species to species. For most of the species studied, the δ 18O-values decrease with altitude, following the trends of δ 18O-values in precipitation and

  12. Comparing α-cellulose δ13C and δ18O to regional climate at Big Thicket National Preserve, Texas

    NASA Astrophysics Data System (ADS)

    Lewis, D. B.; Finkelstein, D. B.; Mora, C. I.; Grissino-Mayer, H. D.; Perfect, E.

    2009-12-01

    Few studies have investigated the relationship between tree-ring δ13C, δ18O, and regional climate in the southeastern U.S. In other regions, tree ring δ13C and δ18O have proven useful for analyzing temporal changes in precipitation, temperature, drought, and relative humidity. The purpose of this study was to characterize the relationships of regional climate with seasonally-resolved tree-ring cellulose δ13C and δ18O records from longleaf pine (Pinus palustris Mill.) trees at Big Thicket National Preserve (BTNP), Texas. BTNP is a semi-tropical area along the southeastern Texas Gulf Coast with a MAP of 1300 mm. Increment cores were collected from living trees in the Big Sandy Creek Unit (BSC) of BTNP, and four trees were randomly selected for isotopic analysis. The latewood (LW) portions of annual rings were removed in small slivers using a scalpel, and α-cellulose was extracted for a 26-year period (1982-2007). The δ13C series were compared to δ18O series from the same tree, and correlations ranged from 0.64 (BSC 005) to 0.18 (BSC 010). Single tree LW δ13C and δ18O chronologies were compared to regional climate records (Region 8, Upper Coast). Three of the four LW δ18O series were significantly correlated to fall (August-October) precipitation and the Palmer z-index, a measure of short-term (monthly) drought. BSC 010 δ18O exhibited no relationship with either climate parameter. Two of the δ13C series were correlated to fall precipitation and z-index. BSC 010 and BSC 015 were not significantly correlated. Averaging the four individual LW δ18O series into a single chronology resulted in significant correlations with fall precipitation (r = -0.60, p = 0.002) and z-index (r = -0.58, p = 0.002). Both relationships were slightly improved by removing BSC 010 from the chronology. The average δ13C chronology was also correlated to fall precipitation (r = -0.59, p = 0.001) and z-index (r = -0.57, p = 0.003). Neither isotope chronology was correlated to

  13. 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.

  14. P6Mo18O73 heteropolyanion and its four-copper complex: theoretical and experimental investigation.

    PubMed

    Zhang, Fu-Qiang; Zhang, Xian-Ming; Fang, Rui-Qin; Wu, Hai-Shun

    2010-09-21

    The non-classical KP(6)Mo(18)O(73) heteropolyanion has been studied by the density functional theory (DFT) method, and the calculated geometry compares well with the experimental one. In fully oxidized [KP(6)Mo(18)O(73)](7-) state, the d(xy)-orbitals centered at eight "belt" Mo sites in the lower part of the "basket" are the major contributors to the LUMO and LUMO+1, while the LUMO+2 orbital is mostly focused on the two polar parts. In contrast, the HOMOs indicates that the coordination of the KP(6)Mo(18) heteropolyanion to metal ions favorably occurs at the oxygen atoms from four external phosphates and two molybdates of the handle of the "basket". Compared with Wells-Dawson [P(2)Mo(18)O(62)](6-), the HOMO-LUMO gap in fully oxidized [KP(6)Mo(18)O(73)](7-) is much smaller, indicating much easier reduction that is consistent with the cyclic voltammogram. Both frontier orbitals and Mulliken analysis indicate that two of three blue electrons in [KP(6)Mo(18)O(73)](10-) (KP(6)Mo(18)-3e) have spin alpha while third blue electron has spin beta, in agreement with magnetic data. The four-copper complex of the non-classical KP(6)Mo(18)-3e heteropolyanion has been synthesized and structurally characterized; its structure supports the theoretical results such as reactivity and basicity of external oxygen sites.

  15. 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).

  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. Reactions of Fe+ and FeO+ with C2H2, C2H4, and C2H6: temperature-dependent kinetics.

    PubMed

    Ard, Shaun G; Melko, Joshua J; Fournier, Joseph A; Shuman, Nicholas S; Viggiano, Albert A

    2013-10-10

    We present the first temperature-dependent rate constants and branching ratios for the reactions of Fe(+) and FeO(+) with C2H2, C2H4, and C2H6 from 170 to 700 K. Fe(+) is observed to react only by association with the three hydrocarbons, with temperature dependencies of T(-2) to T(-3). FeO(+) reacts with C2H2 and C2H4 at the collision rate over the temperature range, and their respective product branchings show similar temperature dependences. In contrast, the reaction with ethane is collisional at 170 K but varies as T(-0.5), while the product branching remains essentially flat with temperature. These variations in reactivity are discussed in terms of the published reactive potential surfaces. The effectiveness of Fe(+) as an oxygen-transfer catalyst toward the three hydrocarbons is also discussed.

  18. 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.

  19. Collisions of slow polyatomic ions with surfaces: dissociation and chemical reactions of C2H2+*, C2H3+, C2H4+*, C2H5+, and their deuterated variants C2D2+* and C2D4+* on room-temperature and heated carbon surfaces.

    PubMed

    Jasík, Juraj; Zabka, Jan; Feketeova, Linda; Ipolyi, Imre; Märk, Tilmann D; Herman, Zdenek

    2005-11-17

    Interaction of C2Hn+ (n = 2-5) hydrocarbon ions and some of their isotopic variants with room-temperature and heated (600 degrees C) highly oriented pyrolytic graphite (HOPG) surfaces was investigated over the range of incident energies 11-46 eV and an incident angle of 60 degrees with respect to the surface normal. The work is an extension of our earlier research on surface interactions of CHn+ (n = 3-5) ions. Mass spectra, translational energy distributions, and angular distributions of product ions were measured. Collisions with the HOPG surface heated to 600 degrees C showed only partial or substantial dissociation of the projectile ions; translational energy distributions of the product ions peaked at about 50% of the incident energy. Interactions with the HOPG surface at room temperature showed both surface-induced dissociation of the projectiles and, in the case of radical cation projectiles C2H2+* and C2H4+*, chemical reactions with the hydrocarbons on the surface. These reactions were (i) H-atom transfer to the projectile, formation of protonated projectiles, and their subsequent fragmentation and (ii) formation of a carbon chain build-up product in reactions of the projectile ion with a terminal CH3-group of the surface hydrocarbons and subsequent fragmentation of the product ion to C3H3+. The product ions were formed in inelastic collisions in which the translational energy of the surface-excited projectile peaked at about 32% of the incident energy. Angular distributions of reaction products showed peaking at subspecular angles close to 68 degrees (heated surfaces) and 72 degrees (room-temperature surfaces). The absolute survival probability at the incident angle of 60 degrees was about 0.1% for C2H2+*, close to 1% for C2H4+* and C2H5+, and about 3-6% for C2H3+.

  20. Rate constant for the reaction C2H5 + HBr → C2H6 + Br.

    PubMed

    Golden, David M; Peng, Jingping; Goumri, A; Yuan, J; Marshall, Paul

    2012-06-21

    RRKM theory has been employed to analyze the kinetics of the title reaction, in particular, the once-controversial negative activation energy. Stationary points along the reaction coordinate were characterized with coupled cluster theory combined with basis set extrapolation to the complete basis set limit. A shallow minimum, bound by 9.7 kJ mol(-1) relative to C(2)H(5) + HBr, was located, with a very small energy barrier to dissociation to Br + C(2)H(6). The transition state is tight compared to the adduct. The influence of vibrational anharmonicity on the kinetics and thermochemistry of the title reaction were explored quantitatively. With adjustment of the adduct binding energy by ∼4 kJ mol(-1), the computed rate constants may be brought into agreement with most experimental data in the literature, including new room-temperature results described here. There are indications that at temperatures above those studied experimentally, the activation energy may switch from negative to positive.

  1. 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.

  2. Simple purification of recovered [18O]H2O by UV, ozone, and solid-phase extraction methods.

    PubMed

    Moon, Woo Yeon; Oh, Seung Jun; Cheon, Jun Hong; Chae, Won Seok; Lim, Sung Jae; Cho, Si Man; Moon, Dae Hyuk

    2007-06-01

    We have developed three methods for removing organic impurities as well as a solid-phase extraction (SPE) method for removing metallic and ionic impurities from recovered [18O]H2O. Preliminary experiments with [16O]H2O were used to determine the optimal purification conditions. These showed that UV irradiation rapidly (<4 h) eliminated low boiling point impurities such as acetonitrile and acetone with only a slight loss of mass. A combination of UV irradiation and purging with ozone removed high boiling point impurities such as ethanol and methanol more quickly than UV irradiation alone. UV irradiation followed by a SPE with [18O]H2O removed all organic and inorganic impurities. The purified [18O]H2O gave a saturation yield of 128.62+/-15.6 mCi/microA for [18F]fluoride and a 49.8+/-12.7% radiochemical yield for [18F]fluorodeoxyglucose.

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

    PubMed

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

    2006-11-01

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

  4. 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

  5. 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

  6. Conformational changes in the H3. H4 histone complex

    SciTech Connect

    Feldman, L.; Beaudette, N.V.; Stollar, B.D.; Fasman, G.D.

    1980-08-10

    The H3.H4 complex has been extracted from calf thymus chromatin in either 0.05 M NaOAc, pH 5.0, or in 2.0 M KCl, 0.1 M KPO/sub 4/, pH 6.7, and both forms have been shown to consist solely of histones H3 and H4 when examined on sodium dodecyl sulfate-polyacrylamide gels. Serological and circular dichroism analyses indicate the existence of structural differences between the two forms. Dilution of the high salt form of the complex into low salt produces a time-dependent conformational change which is related to reduction in the ..cap alpha.. helix content of the complex and which exposes antigenic sites on the complex. The existence of multiple forms of the H3.H4 complex may be related to the dynamic equilibrium of nucleosome structure in vivo.

  7. Silver-Catalyzed C(sp(3))-H Chlorination.

    PubMed

    Ozawa, Jun; Kanai, Motomu

    2017-03-17

    A silver-catalyzed chlorination of benzylic, tertiary, and secondary C(sp(3))-H bonds was developed. The reaction proceeded with as low as 0.2 mol % catalyst loading at room temperature under air atmosphere with synthetically useful functional group compatibility. The regioselectivity and reactivity tendencies suggest that the chlorination proceeded through a radical pathway, but an intermediate alkylsilver species cannot be ruled out.

  8. Synthesis of 2-Alkenyl-2H-indazoles from 2-(2-Carbonylmethyl)-2H-indazoles.

    PubMed

    Lin, Mei-Huey; Liang, Kung-Yu; Tsai, Chang-Hsien; Chen, Yu-Chun; Hsiao, Hung-Chang; Li, Yi-Syuan; Chen, Chung-Hao; Wu, Hau-Chun

    2016-02-19

    A procedure has been developed for synthesis of 2-alkenyl-2H-indazoles starting from 2-(2-carbonylmethyl)-2H-indazoles, which are prepared by gallium/aluminium- and aluminium-mediated, direct, regioselective alkylation of indazoles with α-bromocarbonyl compounds. The structure of 3-(2H-indazol-2-yl)-2H-chromen-2-one was proven by X-ray crystallography. The styrene- and coumarin-2H-indazoles produced by using the new method were found to have interesting fluorescence properties.

  9. Southern Tibetan Plateau ice core δ18O reflects abrupt shifts in atmospheric circulation in the late 1970s

    NASA Astrophysics Data System (ADS)

    Gao, Jing; Risi, Camille; Masson-Delmotte, Valerie; He, You; Xu, Baiqing

    2016-01-01

    Ice cores from the Tibetan Plateau provide high-resolution records of changes in the snow and ice isotopic composition. In the monsoon sector of southern Tibetan Plateau, their climatic interpretation has been controversial. Here, we present a new high-resolution δ18O record obtained from 2206 measurements performed at 2-3 cm depth resolution along a 55.1 m depth ice core retrieved from the Noijinkansang glacier (NK, 5950 m a.s.l.) that spans the period from 1864 to 2006 AD. The data are characterized by high δ18O values in the nineteenth century, 1910s and 1960s, followed by a drop in the late 1970s and a recent increasing trend. The comparison with regional meteorological data and with a simulation performed with the LMDZiso general circulation model leads to the attribution of the abrupt shift in the late 1970s predominantly to changes in regional atmospheric circulation, together with the impact of atmospheric temperature change. Correlation analyses suggest that the large-scale modes of variability (PDO and ENSO, i.e. Pacific Decadal Oscillation and El Nino-Southern Oscillation) play important roles in modulating NK δ18O changes. The NK δ18O minimum at the end of the 1970s coincides with a PDO phase shift, an inflexion point of the zonal index (representing the overall intensity of the surface westerly anomalies over middle latitudes) as well as ENSO, implying interdecadal modulation of the influence of the PDO/ENSO on the Indian monsoon on southern TP precipitation δ18O. While convective activity above North India controls the intra-seasonal variability of precipitation δ18O in southern TP, other processes associated with changes in large-scale atmospheric circulation act at the inter-annual scale.

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

    PubMed

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

    2013-01-01

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

  11. 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.

  12. (/sup 3/H)nitrendipine binding to adrenal capsular membranes

    SciTech Connect

    Finkel, M.S.; Aguilera, G.; Catt, K.J.; Keiser, H.R.

    1984-08-20

    The physiologic regulation of aldosterone secretion is dependent on extracellular calcium and appears to be mediated by increases in cytosolic free calcium concentration in the zona glomerulosa cell. A specific role for voltage-dependent calcium channels was suggested by previous studies with the calcium channel antagonist verapamil. The authors therefore studied the (/sup 3/H)nitrendipine calcium channel binding site in adrenal capsules. These studies revealed a single class of saturable, high affinity sites with K/sub D/ = .26 +/- .04 nM and B/sub max/ = 105 +/- 5.7 fmol/mg protein. Specific binding of (/sup 3/H)nitrendipine was inhibited by calcium channel antagonists with potencies nitrendipine = nifedipine >> verapamil, while diltiazem had no inhibitory effect. In the rat, binding sites for (/sup 3/H)nitrendipine were located in the adrenal capsule and medulla and were undetectable in the zona fasciculata. Physiologic studies with collagenase-dispersed adrenal glomerulosa cells demonstrated that nifedipine selectively inhibited angiotensin-II and potassium-stimulated steroidogenesis. These observations suggest both a pharmacologic and physiologic role for the nitrendipine binding site in aldosterone production. 17 references, 2 figures, 1 table.

  13. Preformance Analysis of NH3-H2O Absorption Cycle

    NASA Astrophysics Data System (ADS)

    Tsujimori, Atsushi; Ozaki, Eiichi

    Different from H2O-LiBr absorption cycle, it is necessary to have rectifier between generator and condenser in NH3-H2O absorption cycle, because there mixes some steam in refrigerant vapor in the process of regenerating refrigerant from the ammonia strong aqueous solution. And in some case ex. partial load or heating, the efficiency of rectifier might decrease, if the flow rate of refrigerant vapor and ammonia aqueous solution decrease. As a result, steam flow into condenser with ammonia refrigerant vapor, which reduces cycle COPs of cooling and heating. Accordingly in order to evaluate the effect of ammonia concentration in refrigerant for the performance of NH3-H2O absorption heat pump, the simple design approach of modeling condenser and evaporator is introduced in this paper. In the model, the calculation of heat rate in condenser and evaporator was simplified considering the characteristic of NH3-H2O liquid-vapor equilibrium. Then the simulation for cycle perforance based on GAX absorption cycle was made using the efficiency of rectifier that established the ammonia concentration in refrigerant and it was derived that 3 [%] decrease of ammonia concentration in refrigerant induced 15 [%] decrcase of cooling COP and 7 [%] decrease of heating COP and that there existed the most suitable circulation ratio for each ammonia concentration in refrigerant.

  14. Localization of 3H-diethylstilbestrol in skeletal muscle

    SciTech Connect

    Gruber, B.; Cohen, L.

    1981-11-01

    The localization of diethylstilbestrol (DES) in skeletal muscle was studied in CF1 mice and perfused rat hindlimbs. There was a slow accumulation of 3H-DES in mouse muscle from 4 to 24 hours following i.p. injection even though plasma DES was decreasing. Twenty-four hours after injection of 50 microCi 3H-DES (714 pmole) mouse gastrocnemius contained 8.9 x 10(-17) mole unaltered 3H-DES per mg muscle. Extrapolating to the entire skeletal muscle mass of the animal, this represents 0.15% of the radioactivity injected. The radioactivity in muscle was completely extracted with 95% ethanol or ether: ethanol (3:1), and both unaltered DES and DES-metabolites were present in the extracts. The fraction of radioactivity due to unaltered DES 4 hours after injection was 0.51 +/- 0.09 in muscle and 0.30 +/- 0.11 in plasma. Significant extrahepatic metabolism of DES was demonstrated in perfused isolated rat hindlimbs by the presence of DES-metabolites in the perfusate. The radioactivity extracted from the perfused muscle itself was unaltered DES. These results indicate that skeletal muscle is an important site of DES localization in rodents.

  15. Predicting paleoelevation of Tibet and the Himalaya from δ 18O vs. altitude gradients in meteoric water across the Nepal Himalaya

    NASA Astrophysics Data System (ADS)

    Garzione, Carmala N.; Quade, Jay; DeCelles, Peter G.; English, Nathan B.

    2000-11-01

    The δ 18O value of meteoric water varies with elevation, providing a means to reconstruct paleoelevation if the δ 18O values of paleowater are known. In this study, we determined the δ 18O values of water (δ 18O mw) from small tributaries along the Seti River and Kali Gandaki in the Nepal Himalaya. We found that δ 18O mw values decrease with increasing altitude for both transects. δ 18O mw vs. altitude along the Kali Gandaki in west-central Nepal fit a second order polynomial curve, consistent with increasing depletion of 18O with increasing elevation, as predicted by a Rayleigh-type fractionation process. This modern δ 18O mw vs. altitude relationship can be used to constrain paleoelevation from the δ 18O values of Miocene-Pliocene carbonate (δ 18O c) deposited in the Thakkhola graben in the southern Tibetan Plateau. Paleoelevations of 3800±480 m to 5900±350 are predicted for the older Tetang Formation and 4500±430 m to 6300±330 m for the younger Thakkhola Formation. These paleoelevation estimates suggest that by ˜11 Ma the southern Tibetan Plateau was at a similar elevation to modern.

  16. γ -ray spectroscopy of fission fragments produced in 208Pb(18O ,f )

    NASA Astrophysics Data System (ADS)

    Banerjee, P.; Ganguly, S.; Pradhan, M. K.; Moin Shaikh, Md.; Sharma, H. P.; Chakraborty, S.; Palit, R.; Pillay, R. G.; Nanal, V.; Saha, S.; Sethi, J.; Biswas, D. C.

    2015-08-01

    Prompt gamma-ray spectroscopy of fission fragments produced in the heavy-ion induced fusion-fission reaction 208Pb(18O,f ) at E =90 MeV has been performed. The relative isotopic yields of the fission fragments and the fragment mass distribution have been studied. Structures in the mass distribution have been discussed in the light of earlier results. Relative yields of several odd-A isotopes of Mo, Ru, Pd, and Cd and the odd-A isotones with N =62 and 64 have been studied along with the yields of the neighboring even-Z , even-N fragments and correlated to nuclear structural effects. The average total neutron multiplicity during fission has been measured to be 5.48 ±0.59 . The level schemes of the two neutron-rich nuclei 110Pd and 116Cd have been studied from γ -ray triple coincidence data. A large number of transitions, previously reported only from β -decay studies, have been observed in 110Pd for the first time. The yrast band in 116Cd has been extended up to spin (16+). In addition, a rotational sequence built upon an excited 5- state in 116Cd has been observed up to (13-). The level schemes have been discussed in the context of existing results, both experimental and theoretical, in the literature.

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

    PubMed Central

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

    2014-01-01

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

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

    SciTech Connect

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

    2014-11-11

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  20. A New Look at 29Al and 27Mg from the 18O + 14C Reaction

    NASA Astrophysics Data System (ADS)

    Tabor, Samuel; Dungan, Rutger; Volya, Alexander; Tripathi, Vandana; Abromeit, Brittany; Caussyn, David; Kravvaris, Konstantinos; Lubna, Rebeka; Tai, Pei-Luan

    2016-09-01

    It was possible to compare moderately high-spin states in a nearby pair of odd proton and odd neutron s-d shell nuclei by observing proton-gamma-gamma or alpha-gamma-gamma coincidences, respectively, following the fusion of long-lived radioactive 14C with neutron-rich 18O at a beam energy of 40 MeV using the FSU gamma detector array with digital data acquisition. Eight new states were seen in 29Al, all of which decay directly or indirectly to the 9/2 + level, the highest previously known spin in 29Al. Some of the new states form a very likely yrast M1 decay sequence from (15/2 +) down to the 5/2 + ground state. The new states are relatively well described by pure s-d shell model calculations using the USDA interaction. By contrast the 4 new states found in 27Mg are divided between positive and negative parities reaching up to (13/2 +) and (11/2-). Radiative decays of neutron unbound states in 27Mg will be discussed. Supported in part by NSF Grant No. 1401574.

  1. THE ABUNDANCE OF C{sub 3}H{sub 2} AND OTHER SMALL HYDROCARBONS IN THE DIFFUSE INTERSTELLAR MEDIUM

    SciTech Connect

    Liszt, Harvey; Sonnentrucker, Paule; Cordiner, Martin; Gerin, Maryvonne

    2012-07-10

    Hydrocarbons are ubiquitous in the interstellar medium, observed in diverse environments ranging from diffuse to molecular dark clouds and strong photon-dominated regions near H II regions. Recently, two broad diffuse interstellar bands (DIBs) at 4881 A and 5450 A were attributed to the linear version of propynylidene l-C{sub 3}H{sub 2}, a species whose more stable cyclic conformer c-C{sub 3}H{sub 2} has been widely observed in the diffuse interstellar medium at radio wavelengths. This attribution has already been criticized on the basis of indirect plausibility arguments because the required column densities are quite large, N(l-C{sub 3}H{sub 2})/E{sub B-V} =4 Multiplication-Sign 10{sup 14} cm{sup -2} mag{sup -1}. Here we present new measurements of N(l-C{sub 3}H{sub 2}) based on simultaneous 18-21 GHz Very Large Array absorption profiles of cyclic and linear C{sub 3}H{sub 2} taken along sight lines toward extragalactic radio-continuum background sources with foreground Galactic reddening E{sub B-V} = 0.1-1.6 mag. We find that N(l-C{sub 3}H{sub 2})/N(c-C{sub 3}H{sub 2}) Almost-Equal-To 1/15-1/40 and N(l-C{sub 3}H{sub 2})/E{sub B-V} Almost-Equal-To (2 {+-} 1) Multiplication-Sign 10{sup 11} cm{sup -2} mag{sup -1}, so that the column densities of l-C{sub 3}H{sub 2} needed to explain the DIBs are some three orders of magnitude higher than what is observed. We also find N(C{sub 4}H)/E{sub B-V} <1.3 Multiplication-Sign 10{sup 13} cm{sup -2} mag{sup -1} and N(C{sub 4}H{sup -})/E{sub B-V} <1 Multiplication-Sign 10{sup 11} cm{sup -2} mag{sup -1} (3{sigma}). Using available data for CH and C{sub 2}H we compare the abundances of small hydrocarbons in diffuse and dark clouds as a guide to their ability to contribute as DIB carriers over a wide range of conditions in the interstellar medium.

  2. SiO{sub 2}/SiC structures annealed in D{sub 2}{sup 18}O: Compositional and electrical effects

    SciTech Connect

    Pitthan, E. Corrêa, S. A.; Soares, G. V.; Boudinov, H. I.; Stedile, F. C.

    2014-03-17

    Effects of water vapor annealing on SiO{sub 2}/4H-SiC structures formed following different routes were investigated using water isotopically enriched in {sup 18}O and {sup 2}H (D). Isotopic exchange between oxygen from the water vapor and oxygen from SiO{sub 2} films deposited on 4H-SiC was observed in the whole depth of the films, differently from the behavior of SiO{sub 2} films thermally grown on 4H-SiC. The highest amount of D was obtained in the sample with the highest negative fixed charge concentration, suggesting that the D incorporation occurs in defects in the structure that exist prior to the annealing. As a consequence of the water annealing, a significant reduction in the negative effective charge in metal-oxide-semiconductor capacitors and the removal of the SiO{sub 2}/SiC interfacial region was observed, attributed to the reduction of the amount of SiO{sub x}C{sub y} compounds in the interfacial region.

  3. Distribution of 3H-8-MOP and its metabolites in rat organs after a single oral administration

    SciTech Connect

    Wulf, H.C.; Andreasen, M.P.

    1981-04-01

    Concentrations of 3H-8-methoxypsoralen (MOP), its lipid- and water soluble metabolites and tritiated water have been measured in rat serum, liver, kidney, and skin, using liquid scintillation, thin-layer chromatography and other techniques. Radioactivity in whole blood, plasma, ovary, adrenals, and pancreas has also been measured. The radioactivty has been measured up to 1 week after medication, while 3H-8-MOP and metabolite concentrations have been measured from 10 min to 24 h after medication with a single dose of 1 mg 3H-8-MOP in solution/kg bodyweight. Maximum 8-MOP concentrations were seen from 10 to 30 min after dosing. The concentrations in microgram/kg 10 min, 2 h, and 24 h after medication were as follows: serum--686, 57, 2.1; liver--489, 45, 3.3; kidney--1708, 139, 4.3; and skin--55, 16, 3.8. The concentrations of water soluble metabolites were very high in the liver and only slightly lower in the kidney. The concentrations of these metabolites might accumulate after doses repeated 4 times a week. 3H-8-MOP and its metabolites would not show similar accumulation. Most of the radioactivity present after 1 week is due to trititated water.

  4. Synthesis Of [2h, 13c]M [2h2m 13c], And [2h3,, 13c] Methyl Aryl Sulfones And Sulfoxides

    DOEpatents

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

    2004-07-20

    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 sulfones and [.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 sulfoxides, wherein the .sup.13 C methyl group attached to the sulfur of the sulfone or sulfoxide 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 methyl aryl sulfones and methyl aryl sulfoxides.

  5. 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.

  6. Influence of Changing Atmospheric Circulation on Precipitation δ