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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. The distribution of radioactive ( 3H, 14C) and stable ( 2H, 18O) isotopes in precipitation, surface and groundwaters of NW Yugoslavia

    NASA Astrophysics Data System (ADS)

    Horvatinčić, Nada; Krajcar-Bronić, Ines; Pezdič, Jože; Srdoč, Dušan; Obelić, Bogomil

    1986-11-01

    The isotopic measurements ( 2H, 3H, 18O) of precipitiation in Zagreb (since 1976) and Ljubljana (since 1981) in NW Yugoslavia show seasonal variations typical of the Northern hemisphere. Continuous measurements of tritium concentration in the Sava River ca 10 km upstream from Zagreb have been performed since 1976. Data show a smooth line without periodical changes, but a steady decrease is obvious. The sampling place is situated ca 30 km downstream from the Kr\\vsko Nuclear Power Plant. No change in tritium concentration due to the operation of the power plant has been observed. A comprehensive program of monitoring of the 14C activity in air CO 2 as well as in vegetables, cereals and tree-rings in the surroundings of the Nuclear Power Plant Kr\\vsko has been carried out since 1984. The measurement of 2H and 18O in karst springs of the Korana River catchmet area (Plitvice National Park) gave a meteoric water line equal to δ2H = 7.9 δ18O + 8.5, which is typical of the NW part of Yugoslavia. A fairly constant concentration of 2H and 18O in spring water indicates a thorough mixing of water in the karst aquifers. The mean residence time (MRT) of karst water was determined by measuring monthly tritium activity of spring water. The MRT is very short, ranging between 1 and 4 years on average.

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

    SciTech Connect

    1999-11-09

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

  4. 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.

  5. 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

  6. 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

  7. 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.

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

    PubMed

    Allen, D M

    2004-01-01

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

  9. 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.

  10. 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

  11. Thermal neutron capture cross sections for 16,171,18O and 2H

    NASA Astrophysics Data System (ADS)

    Firestone, R. B.; Revay, Zs.

    2016-04-01

    Thermal neutron capture γ -ray spectra for 16,17,18O and 2H have been measured with guided cold neutron beams from the Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRM II) reactor and the Budapest Research Reactor (BRR) on natural and O,1817 enriched D2O targets. Complete neutron capture γ -ray decay schemes for the 16,17,18O(n ,γ ) reactions were measured. Absolute transition probabilities were determined for each reaction by a least-squares fit of the γ -ray intensities to the decay schemes after accounting for the contribution from internal conversion. The transition probability for the 870.76-keV γ ray from 16O(n ,γ ) was measured as Pγ(871 )=96.6 ±0.5 % and the thermal neutron cross section for this γ ray was determined as 0.164 ±0.003 mb by internal standardization with multiple targets containing oxygen and stoichiometric quantities of hydrogen, nitrogen, and carbon whose γ -ray cross sections were previously standardized. The γ -ray cross sections for the O,1817(n ,γ ) and 2H(n ,γ ) reactions were then determined relative to the 870.76-keV γ -ray cross section after accounting for the isotopic abundances in the targets. We determined the following total radiative thermal neutron cross sections for each isotope from the γ -ray cross sections and transition probabilities; σ0(16O )=0.170 ±0.003 mb; σ0(17O )=0.67 ±0.07 mb; σ0(18O )=0.141 ±0.006 mb; and σ0(2H )=0.489 ±0.006 mb.

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

    PubMed

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

    2014-01-01

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

  13. 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).

  14. 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

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

    PubMed

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

    2016-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  17. Determination of δ2H and δ18O in mineral water based on Cavity Ring-Down Spectrometry

    NASA Astrophysics Data System (ADS)

    Tonietto, G.; Godoy, J.; Godoy, M. L.

    2013-12-01

    Stable isotopes of water are proven indicators, tracers and recorders of processes that affect the hydrologic cycle. Measurements of the stable isotope ratios (δ2H, δ18O and δ17O) of both liquid water and water vapor are widely used in hydrology, atmospheric sciences, and biogeochemistry to determine the migration of water through an ecosystem. Application of the method to Brazilian bottled mineral water has shown that it is possible to trace the origin of the water to at least the state level within Brazilian geographical regions. National and regional meteoric water lines were constructed with substantial differences between geographical regions, in particular for the central region of the country, with a slope coefficient of approximately seven and no deuterium excess. The repeatability, reproducibility and accuracy of the direct measurement of δ2H and δ18O isotopes in water samples were evaluated using Cavity Ring-Down Spectrometry, and values comparable with the Isotopic Ratio Mass Spectrometry were obtained. Memory effect correction was negligible after five successive injections, and the time for each sample analysis was approximately 7 minutes. The new high throughput method measures isotopologues of water with a typical precision of better than 0.15‰ for δ18O and better than 0.6‰ for δ2H.

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2015-07-01

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

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  2. Multi-isotope labelling (13C, 18O, 2H) for studying organic matter cycling within plant-soil systems

    NASA Astrophysics Data System (ADS)

    Studer, M. S.; Abiven, S.; Schmidt, M. W. I.; Siegwolf, R. T. W.

    2012-04-01

    Carbon cycling has become of major interest for the understanding and mitigation of global climatic change. Terrestrial ecosystems have a large carbon sequestration potential, but many processes and fluxes of organic matter (OM) cycling within the plant-soil system are not yet well understood [1]. The dynamics of OM cycling within the plant soil-system are determined by environmental parameters, as well as chemical quality of OM input. A well-known technique to study OM dynamics is to label OM inputs with stable isotopes (e.g 13C). Changes in OM quality in the plant and in the soil can be assessed by compound specific isotopic analysis [2]. These techniques give a precise insight of the OM composition, but are laborious and expensive. Here we suggest a new multi-isotope labelling technique using stable 13C in combination with stable 18O and 2H isotopes, which provides information on OM quality by simple bulk material analysis. The method is based on the creation of an isotopic van Krevelen diagram, which is used to describe different compound groups by plotting the atomic ratios of O/C vs. H/C [3]. We could show that new assimilates can be labelled with 13C, 18O and 2H by adding the stable isotopes (continuously) in the gaseous phase (CO2 and water vapour) to the plants atmosphere. The label has been traced within the bulk material of different compartments of the plant-soil system (e.g. leaves, stems, roots, bulk soil). Our first results showed that after 2, 8 and 14 days of labelling the 18O/13C(new) ratio was notably different in leaf, stem and root tissue (0.0024, 0.0011 and 0.0007, respectively), suggesting a change in OM quality towards more C-rich compounds. d2H analysis will follow and an isotopic van Krevelen diagram will be produced (18O/13C(new) vs. 2H/13C(new)) to describe the changes in OM quality. The new multi-isotope labelling approach represent a powerful tool to address open questions in plant and soil research such as the allocation of organic

  3. 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

  4. Continuous Arctic Ocean Water Vapor Isotope Ratio (δ18O and δ2H) Measurements During a Summer Icebreaker Expedition

    NASA Astrophysics Data System (ADS)

    Klein, E. S.; Welker, J. M.

    2015-12-01

    Warming in the Arctic is reducing sea ice, which may result in changes to the water cycle through increased atmospheric humidity. Here we present the first continuous record of water vapor isotope ratio (δ18O, δ2H, d-excess) measurements from the sub-Arctic and Arctic Ocean during ship transit through both open water and sea ice. As water vapor isotopes were collected across a spectrum of sea ice conditions, the influence of sea ice and availability of open water moisture sources on Arctic Ocean water vapor isotope values (particularly d-excess) is examined. Isotope values reveal characteristics about water availability at vapor sources, as influenced by presence of sea ice (e.g., ice covered arid or open water humid sources), and air parcel trajectory. Higher d-excess values were generally associated with more northern Arctic, ice covered, and arid vapor sources. Conversely, lower d-excess values were related to more southern, open water, and humid vapor sources. Additionally, water vapor isotopes while sea ice was present were generally characterized by more depleted δ18O and δ2H and higher d-excess values, relative to open water values. These water vapor isotope values also present information about potential shifts in moisture sources in an increasingly ice free Arctic Ocean. Understanding these shifts is important to learning about both modern and past patterns of Arctic atmospheric water movement and distribution.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    A regionalized cluster-based water isotope prediction (RCWIP) approach, based on the Global Network of Isotopes in Precipitation (GNIP), was demonstrated for the purposes of predicting point- and large-scale spatio-temporal patterns of the stable isotope composition (δ2H, δ18O) of precipitation around the world. Unlike earlier global domain and fixed regressor models, RCWIP predefined 36 climatic cluster domains and tested all model combinations from an array of climatic and spatial regressor variables to obtain the best predictive approach to each cluster domain, as indicated by root-mean-squared error (RMSE) and variogram analysis. Fuzzy membership fractions were thereafter used as the weights to seamlessly amalgamate results of the optimized climatic zone prediction models into a single predictive mapping product, such as global or regional amount-weighted mean annual, mean monthly, or growing-season δ18O2H in precipitation. Comparative tests revealed the RCWIP approach outperformed classical global-fixed regression-interpolation-based models more than 67% of the time, and clearly improved upon predictive accuracy and precision. All RCWIP isotope mapping products are available as gridded GeoTIFF files from the IAEA website (www.iaea.org/water) and are for use in hydrology, climatology, food authenticity, ecology, and forensics.

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

    A Regionalized Climatic Water Isotope Prediction (RCWIP) approach, based on the Global Network for Isotopes in Precipitation (GNIP), was demonstrated for the purposes of predicting point- and large-scale spatiotemporal patterns of the stable isotope compositions of water (δ2H, δ18O) in precipitation around the world. Unlike earlier global domain and fixed regressor models, RCWIP pre-defined thirty-six climatic cluster domains, and tested all model combinations from an array of climatic and spatial regressor variables to obtain the best predictive approach to each cluster domain, as indicated by RMSE and variogram analysis. Fuzzy membership fractions were thereafter used as the weights to seamlessly amalgamate results of the optimized climatic zone prediction models into a single predictive mapping product, such as global or regional amount-weighted mean annual, mean monthly or growing-season δ18O2H in precipitation. Comparative tests revealed the RCWIP approach outperformed classical global-fixed regression-interpolation based models more than 67% of the time, and significantly improved upon predictive accuracy and precision. All RCWIP isotope mapping products are available as gridded GeoTIFF files from the IAEA website (www.iaea.org/water) and are for use in hydrology, climatology, food authenticity, ecology, and forensics.

  7. Using environmental isotopes 2H and 18O for identification of infiltration processes in floodplain ecosystems of the River Elbe.

    PubMed

    Böhnke, R; Geyer, S; Kowski, P

    2002-03-01

    We examined a floodplain area in the middle section of the river Elbe Valley with regard to hydrogeological and hydrological processes using isotopic methods. Over two years, river water and groundwater have been analysed for temporal and spatial chemical and isotopic (delta2H and delta18O) changes. By these methods we assessed the flow dynamics of the river-groundwater infiltration system. At low and mean river stages there is a general hydraulic gradient from the higher areas at the margin of the valley towards the floodplain. During floods river water infiltrates into the adjacent aquifer not primarily through the river banks but first through surface water inflow from north to south, via depressions and gullies from the back of the floodplain. The early stage of river water infiltration is characterized by a sharp decrease in conductivity and in concentrations of SO4(2-) and Cl- in the hydraulically connected shallow aquifer. delta2H and delta18O values show a similar tendency. We observed a significant minimum in stable isotope ratios during the flood in March 1999. Using a simple mixing equation it was calculated that the groundwater in the upper, shallow aquifer consists of around 70% river water in the transition zone (well 13) during flooding.

  8. 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

  9. 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

  10. 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. PMID:27237686

  11. 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.

  12. 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.

  13. Improved water δ2H and δ18O calibration and calculation of measurement uncertainty using a simple software tool.

    PubMed

    Gröning, Manfred

    2011-10-15

    The calibration of all δ(2)H and δ(18)O measurements on the VSMOW/SLAP scale should be performed consistently, based on similar principles, independent of the instrumentation used. The basic principles of a comprehensive calibration strategy are discussed taking water as example. The most common raw data corrections for memory and drift effects are described. Those corrections result in a considerable improvement in data consistency, especially in laboratories analyzing samples of quite variable isotopic composition (e.g. doubly labelled water). The need for a reliable uncertainty assessment for all measurements is discussed and an easy implementation method proposed. A versatile evaluation method based on Excel macros and spreadsheets is presented. It corrects measured raw data for memory and drift effects, performs the calibration and calculates the combined standard uncertainty for each measurement. It allows the easy implementation of the discussed principles in any user laboratory. Following these principles will improve the comparability of data among laboratories. PMID:21913248

  14. 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.

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

    NASA Astrophysics Data System (ADS)

    West, J. B.

    2012-12-01

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

  16. Groundwater residence time and palaeohydrology in the Otway Basin, South Australia: 2H, 18O and 14C data

    NASA Astrophysics Data System (ADS)

    Love, A. J.; Herczeg, A. L.; Leaney, F. W.; Stadter, M. F.; Dighton, J. C.; Armstrong, D.

    1994-01-01

    Stable isotopes (δ 2H, δ 18O and δ 13C) and radiocarbon ( 14C) have been used in conjunction with chemical data to evaluate recharge mechanisms, groundwater residence time and palaeohydrology within the confined Dilwyn sand aquifer in the Gambier Embayment of the Otway Basin. This aquifer does not receive recharge down-gradient of the hydraulic hinge-line and data have been interpreted along two discrete flow lines. The mean residence time of groundwater (determined by 14C) in the confined aquifer from the hydraulic hinge position to the sea (a distance of about 50 km) along an inferred flow path is approximately 12 800 years. The corresponding hydraulic travel time calculated from Darcy's law is approximately 49 000 years. The apparent discrepancy may be a result of eustatic sea-level lowering during the last glacial. Because the groundwater system is hydraulically connected to the sea, lower sea-level would result in increased gradients and a decrease in groundwater residence time. Variations in stable isotopic composition along flow lines suggest a number of recharge mechanisms. Stable isotope data indicate progressive depletion of 2H and 18O in the groundwaters over the past 30 000 years. Groundwaters older than about 10 000 years B.P. were recharged either during a cooler climate climatic regime (lower precipitation/evapotranspiration and temperature) and/or the vapour source(s) had travelled over greater continental mass than those recharged over the past 10 000 years. Lower chloride concentrations in some of the older groundwaters indicate lower evapotranspiration rates in the recharge areas before 10 000 years ago.

  17. 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).

  18. 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.

  19. 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

  20. 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

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

    PubMed

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

    2012-11-20

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

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

    PubMed

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

    2012-11-20

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

  3. 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.

  4. 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).

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

    PubMed

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

    2011-11-15

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

  6. Determination of delta2H and delta18O in saline oil-associated waters: the question of simple vacuum distillation of water samples prior to isotopic analyses.

    PubMed

    Porowski, Adam; Kowski, Peter

    2008-06-01

    The paper deals with analytical and procedural aspects of delta18O and delta2H determination in saline oil-associated waters. The main objective of the study was to show experimentally the qualitative and quantitative applicability of the simple vacuum distillation of saline oil-associated waters while routine procedures of water isotopic analyses are applied. Additionally, two standard off-line techniques of delta2H determination in water - the zinc and the chromium method - have been compared. Each time a typical isotope salt effect has been tracked on the Dead Sea water. The results clearly show that application of the simple vacuum distillation improve the accuracy and reproducibility of delta2H determinations, especially in chromium off-line technique which appeared to be more sensitive to water salinity. The simple vacuum distillation does not improve the quality of delta18O determinations in the range of water salinities studied. Its application to high concentrated brines (for example, Dead Sea water) decreases the time of equilibration but still propagate the isotopic error connected with low water activity (in the case of 18O/16O ratio) and the incomplete water extraction from the remaining salts (in the case of 2H/1H ratio); in consequence, its time-consuming application seems to be baseless.

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

    NASA Astrophysics Data System (ADS)

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

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

  8. 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.

  9. The effect of carbonic anhydrase on the kinetics and equilibrium of the oxygen isotope exchange in the CO2-H2O system: Implications for δ18O vital effects in biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Uchikawa, Joji; Zeebe, Richard E.

    2012-10-01

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

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

    USGS Publications Warehouse

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

    2016-01-01

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

  11. 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.

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

    PubMed

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

    2009-02-01

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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

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

    SciTech Connect

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

    2012-11-20

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

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

    SciTech Connect

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

    2014-04-20

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

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

    PubMed

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

    2016-06-27

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

  1. AZTECAN C3PO: Arizona Three-millimeter Educational C18O And N2H+ Cold Core Census of Planck Objects

    NASA Astrophysics Data System (ADS)

    Walker-LaFollette, Amanda; Shirley, Y. L.; Hardegree-Ullman, K. K.; Towner, A. P. M.; Wallace, S. C.; Smith, C. W.; Turner, J. D.; Robertson, A. N.; Austin, C. L.; Small, L. C.; Carleton, T. M.; McGraw, A. M.; Daugherty, M. J.; Guvenen, B. C.; Johnson, K. L.; Crawford, B. E.; Smart, B. M.

    2012-05-01

    The Planck satellite is studying the power spectrum of the Cosmic Microwave Background (CMB), and has found foreground contamination including dust emission from the Galaxy. The Planck Cold Core Team has been cataloging and characterizing this foreground emission. An initial catalog of over 10,000 objects, the Cold Core Census of Planck Objects (C3PO), was released from the first year of data. A subset of 915 cold cores with dust temperatures of Td < 14K and SNR > 15 was selected from this catalog, and called the Early Cold Core (ECC) Catalog. Ground-based follow-up observations of these cores are needed to determine their size, mass, source geometry (filamentary, multiple cores, etc.), and kinematic properties (degree of turbulence, etc.). Using the Arizona Radio Observatory 12m radio telescope, we mapped a sub-sample of the ECC at 1‧ resolution in the dense gas tracers C18O J=1-0 and N2H+ J=1-0. These tracers complement each other, with CO depleting in very cold, dense environments where N2H+ may be abundant. While we detected most of the cores observed in C18O, we find that N2H+ emission is very weak toward many Planck cold cores. We present here the initial results from our mapping survey. This project is the main component of Amanda Walker-LaFollette’s NASA Space Grant internship research.

  2. 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.

  3. 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.

  4. Quantification of competing H3PO4 versus HPO3 + H2O neutral losses from regioselective 18O-labeled phosphopeptides.

    PubMed

    Cui, Li; Yapici, Ipek; Borhan, Babak; Reid, Gavin E

    2014-01-01

    Abundant neutral losses of 98 Da are often observed upon ion trap CID-MS/MS of protonated phosphopeptide ions. Two competing fragmentation pathways are involved in this process, namely, the direct loss of H3PO4 from the phosphorylated residue and the combined losses of HPO3 and H2O from the phosphorylation site and from an additional site within the peptide, respectively. These competing pathways produce product ions with different structures but the same m/z values, potentially limiting the utility of CID-MS(3) for phosphorylation site localization. To quantify the relative contributions of these pathways and to determine the conditions under which each pathway predominates, we have examined the ion trap CID-MS/MS fragmentation of a series of regioselective (18)O-phosphate ester labeled phosphopeptides prepared using novel solution-phase amino acid synthesis and solid-phase peptide synthesis methodologies. By comparing the intensity of the -100 Da (-H3PO3 (18)O) versus -98 Da (-[HPO3 + H2O]) neutral loss product ions formed upon MS/MS, quantification of the two pathways was achieved. Factors that affect the extent of formation of the competing neutral losses were investigated, with the combined loss pathway predominantly occurring under conditions of limited proton mobility, and with increased combined losses observed for phosphothreonine compared with phosphoserine-containing peptides. The combined loss pathway was found to be less dominant under ion activation conditions associated with HCD-MS/MS. Finally, the contribution of carboxylic acid functional groups and backbone amide bonds to the water loss in the combined loss fragmentation pathway was determined via methyl esterification and by examination of a phosphopeptide lacking side-chain hydroxyl groups.

  5. Quantification of Competing H3PO4 Versus HPO3 + H2O Neutral Losses from Regioselective 18O-Labeled Phosphopeptides

    NASA Astrophysics Data System (ADS)

    Cui, Li; Yapici, Ipek; Borhan, Babak; Reid, Gavin E.

    2014-01-01

    Abundant neutral losses of 98 Da are often observed upon ion trap CID-MS/MS of protonated phosphopeptide ions. Two competing fragmentation pathways are involved in this process, namely, the direct loss of H3PO4 from the phosphorylated residue and the combined losses of HPO3 and H2O from the phosphorylation site and from an additional site within the peptide, respectively. These competing pathways produce product ions with different structures but the same m/z values, potentially limiting the utility of CID-MS3 for phosphorylation site localization. To quantify the relative contributions of these pathways and to determine the conditions under which each pathway predominates, we have examined the ion trap CID-MS/MS fragmentation of a series of regioselective 18O-phosphate ester labeled phosphopeptides prepared using novel solution-phase amino acid synthesis and solid-phase peptide synthesis methodologies. By comparing the intensity of the -100 Da (-H3PO3 18O) versus -98 Da (-[HPO3 + H2O]) neutral loss product ions formed upon MS/MS, quantification of the two pathways was achieved. Factors that affect the extent of formation of the competing neutral losses were investigated, with the combined loss pathway predominantly occurring under conditions of limited proton mobility, and with increased combined losses observed for phosphothreonine compared with phosphoserine-containing peptides. The combined loss pathway was found to be less dominant under ion activation conditions associated with HCD-MS/MS. Finally, the contribution of carboxylic acid functional groups and backbone amide bonds to the water loss in the combined loss fragmentation pathway was determined via methyl esterification and by examination of a phosphopeptide lacking side-chain hydroxyl groups.

  6. 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. 

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

    NASA Astrophysics Data System (ADS)

    Koeniger, Paul; Himmelsbach, Thomas

    2016-04-01

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

  8. 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.

  9. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  11. 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

  12. 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).

  13. 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

  14. 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%. PMID:24285525

  15. 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

  16. 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

  17. 2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: international collaborative study report.

    PubMed

    Thomas, Freddy; Jamin, Eric

    2009-09-01

    An international collaborative study of isotopic methods applied to control the authenticity of vinegar was organized in order to support the recognition of these procedures as official methods. The determination of the 2H/1H ratio of the methyl site of acetic acid by SNIF-NMR (site-specific natural isotopic fractionation-nuclear magnetic resonance) and the determination of the 13C/12C ratio, by IRMS (isotope ratio mass spectrometry) provide complementary information to characterize the botanical origin of acetic acid and to detect adulterations of vinegar using synthetic acetic acid. Both methods use the same initial steps to recover pure acetic acid from vinegar. In the case of wine vinegar, the determination of the 18O/16O ratio of water by IRMS allows to differentiate wine vinegar from vinegars made from dried grapes. The same set of vinegar samples was used to validate these three determinations. The precision parameters of the method for measuring delta13C (carbon isotopic deviation) were found to be similar to the values previously obtained for similar methods applied to wine ethanol or sugars extracted from fruit juices: the average repeatability (r) was 0.45 per thousand, and the average reproducibility (R) was 0.91 per thousand. As expected from previous in-house study of the uncertainties, the precision parameters of the method for measuring the 2H/1H ratio of the methyl site were found to be slightly higher than the values previously obtained for similar methods applied to wine ethanol or fermentation ethanol in fruit juices: the average repeatability was 1.34 ppm, and the average reproducibility was 1.62 ppm. This precision is still significantly smaller than the differences between various acetic acid sources (delta13C and delta18O) and allows a satisfactory discrimination of vinegar types. The precision parameters of the method for measuring delta18O were found to be similar to the values previously obtained for other methods applied to wine and

  18. 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

  19. Iron-Catalyzed Directed C(sp(2))-H and C(sp(3))-H Functionalization with Trimethylaluminum.

    PubMed

    Shang, Rui; Ilies, Laurean; Nakamura, Eiichi

    2015-06-24

    Conversion of a C(sp(2))-H or C(sp(3))-H bond to the corresponding C-Me bond can be achieved by using AlMe3 or its air-stable diamine complex in the presence of catalytic amounts of an inorganic iron(III) salt and a diphosphine along with 2,3-dichlorobutane as a stoichiometric oxidant. The reaction is applicable to a variety of amide substrates bearing a picolinoyl or 8-aminoquinolyl directing group, enabling methylation of a variety of (hetero)aryl, alkenyl, and alkyl amides. The use of the mild aluminum reagent prevents undesired reduction of iron and allows the reaction to proceed with catalyst turnover numbers as high as 6500. PMID:26061014

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

    NASA Astrophysics Data System (ADS)

    Chae, K. Y.; Guimarães, V.

    2015-11-01

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

  1. 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.

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

    PubMed

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

    2016-08-01

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

  3. 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

  4. 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

  5. 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.

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

    PubMed

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

    2015-01-01

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

  7. Elaborating the phase behaviour of ethylene oxide oligomers and analogues in 2H, 3H-perfluoropentane.

    PubMed

    Griffiths, Peter C; Côte, Marie; Rogueda, Philippe G A

    2008-10-01

    Pressure metered dose inhalers (pMDIs) are seen as an attractive option for the delivery of active molecules to the bloodstream via the lungs. Formulation issues are important as it is necessary to disperse the active substance into a volatile propellant. The phase behaviour of a range of common formulation agents - excipients - in 2H, 3H-perfluoropentane is reported here, focussing on the effects of simple elaboration of a central ethylene-oxide (EO) moiety. The base series of hydroxyl terminated EO fragments exhibited lower consolute solution temperature (LCST) behaviour that was strongly molecular weight-dependent. Substitution of methyl groups in place of the hydroxyl groups at the terminus of the EO fragment had a pronounced effect on the solubility of the oligomeric or polymeric material, the material becoming fully miscible with the HPFP. Substitution of methyl groups along the backbone of the hydroxyl terminated EO greatly enhanced the solubility of the materials, but the exhibited phase behaviour was still that of LCST. Longer alkyl groups at the terminus of the EO were found to promote the solubility compared to the hydroxyl terminated material, but to a relatively smaller degree compared with the methyl group. It is hoped that these simple "design rules" should facilitate the development of designer excipients tailored for a particular application. PMID:18601989

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  9. 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

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

    PubMed

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

    2013-02-01

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

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  15. Theoretical study of the bonding of Sc, Y, and La singly charged and dipositive ions to C2H2, C2H4, and C3H6

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1991-01-01

    The interaction of the Sc and Y singly-charged and dipositive ions with C2H2, C2H4, and C3H6 is studied using electronic structure calculations that include high levels of electron correlation. These results are compared with comparable calculations performed previously for La(+) and La(2+). For C2H2 and C2H4, all three metal ions insert into the C-C pi bond, making a three-membered ring. The optimal structures for the MC3H6(+) ions all involve rearrangement to make a four-membered ring. The strength of the metal-ligand bond for the singly charged ions follows the order La greater than Sc equal to about Y. In contrast, the bonds involving the dipositive ions are electrostatic, so that the binding energy increases as the size of the ion decreases, leading to the trend Sc greater than Y greater than La.

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

    PubMed

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

    2012-10-01

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

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

    PubMed

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

    2016-06-01

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

  20. Catalytic functionalization of low reactive C(sp(3))-H and C(sp(2))-H bonds of alkanes and arenes by carbene transfer from diazo compounds.

    PubMed

    Caballero, Ana; Díaz-Requejo, M Mar; Fructos, Manuel R; Olmos, Andrea; Urbano, Juan; Pérez, Pedro J

    2015-12-21

    The direct functionalization of low reactive C(sp(3))-H and C(sp(2))-H bonds of alkanes and arenes, respectively, by metal-induced carbene transfer from diazo compounds is reviewed. To date, this methodology has enabled the incorporation of CR(1)R(2) moieties from N2[double bond, length as m-dash]CR(1)R(2) in a chemo, regio, enantio or diastereoselective manner in those substrates with the appropriate selection of metal and ligands.

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

    PubMed

    Raghunath, P; Lin, M C

    2013-10-24

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  3. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  5. 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.

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

    SciTech Connect

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

    1982-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

  8. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1212, LB5136_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1212, LB5136_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'heat of Mixing and Solution of Ethanol C2H6O + C3H6O3 Dimethyl carbonate (HMSD1121, LB4328_H)' providing data from direct calorimetric measurement of molar excess enthalpy at variable mole fraction and constant pressure and temperature.

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'heat of Mixing and Solution of Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (HMSD1111, LB4314_H)' providing data from direct low-pressure calorimetric measurement of molar excess enthalpy at variable mole fraction and constant temperature.

  11. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1111, LB5133_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1111, LB5133_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1511, LB4270_V)' providing data from direct measurement of low-pressure thermodynamic speed of sound at variable mole fraction and constant temperature, in the single-phase region(s).

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1212, LB4258_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1111, LB4250_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Ethanol C2H6O + C3H3N Propenenitrile (VMSD1511, LB4925_V)' providing data from direct measurement of low-pressure thermodynamic speed of sound at variable mole fraction and constant temperature, in the single-phase region(s).

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Ethanol C2H6O + C3H3N Propenenitrile (VMSD1212, LB4917_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture 1,2-Dichloroethane C2H4Cl2 + C3H3N Propenenitrile (EVLM1211, LB5647_E)' providing data from direct measurement of temperature at variable mole fraction in liquid phase and constant pressure.

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1111, LB4256_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1212, LB4257_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1511, LB4264_V)' providing data from direct measurement of low-pressure thermodynamic speed of sound at variable mole fraction and constant temperature, in the single-phase region(s).

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1412, LB4276_V)' providing data by calculation of isentropic compressibility from low-pressure density and thermodynamic speed of sound data at variable mole fraction and constant temperature, in the single-phase region(s).

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Ethanenitrile C2H3N + C3H3N Propenenitrile (VMSD1412, LB4277_V)' providing data by calculation of isentropic compressibility from low-pressure density and thermodynamic speed of sound data at variable mole fraction and constant temperature, in the single-phase region(s).

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Ethanol C2H6O + C3H3N Propenenitrile (VMSD1111, LB4908_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

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

    PubMed Central

    2015-01-01

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

  5. 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.

  6. 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.

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

    SciTech Connect

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

    2011-02-20

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

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

    SciTech Connect

    M. Viviani; R. Schiavilla; A. Kievsky

    1996-02-01

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

  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. 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

  11. 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

  12. 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.

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

    PubMed

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

    2015-12-31

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

  14. Synthesis, cytotoxic activity, and tubulin polymerization inhibitory activity of new pyrrol-2(3H)-ones and pyridazin-3(2H)-ones.

    PubMed

    Abbas, Samar Hafez; Abuo-Rahma, Gamal El-Din A A; Abdel-Aziz, Mohamed; Aly, Omar M; Beshr, Eman A; Gamal-Eldeen, Amira M

    2016-06-01

    A series of new pyrrol-2(3H)-ones 4a-f and pyridazin-3(2H)-ones 7a-f were synthesized and characterized using different spectroscopic tools. Some of the tested compounds revealed moderate activity against 60 cell lines. The E form of the pyrrolones 4 showed good cytotoxic activity than both the Z form and the corresponding open amide form. Furthermore, the in vitro cytotoxic activity against HepG2 and MCF-7 cell lines revealed that compounds (E)4b, 6f and 7f showed good cytotoxic activity against HepG2 with IC50 values of 11.47, 7.11 and 14.80μM, respectively. Compounds (E)4b, 6f, 7d and 7f showed a pronounced inhibitory effect against cellular localization of tubulin. Flow cytometric analysis indicated that HepG2 cells treated with (E)4b showed a predominated growth arrest at the S-phase compared to that of G2/M-phase. Molecular modeling study using MOE® program indicated that most of the target compounds showed good binding of β-subunit of tubulin with the binding free energy (dG) values about -10kcal/mole.

  15. Preparation of sup 2 H- and sup 3 H-labeled phaseic acid and dihydrophaseic acid as standards for determination of abscisic acid metabolites in tomato fruit

    SciTech Connect

    Kubik, M.; Buta, J.G. )

    1990-05-01

    There have been reports that the level of abscisic acid (ABA) increases during the cold storage of tomatoes. However, the important ABA metabolites, phaseic acid (PA) and dihydrophaseic acid (DPA) were never quantitatively determined in such a system. In order to obtain the labeled standards for quantitative determination of those compounds by GC-MS-SIM, we fed bean plants with 6,6,6-({sup 2}H{sub 3})-ABA (mean isotopic enrichment 60%) with addition of about 10{sup 5} Bq per mg of ({sup 3}H)-ABA. After 100 hours the plants were harvested and extracted with acetone. The extract were purified by solvent partitioning and, Prep-Sep amino column and on an HPLC C{sub 18} reverse phase column. Two major radioactive metabolites of ABA were obtained and identified by GC-MS as PA and DPA. Some results on the quantitation of ABA, PA and DPA in tomato fruit after cold storage will be presented.

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

    NASA Astrophysics Data System (ADS)

    Disselkamp, R.; Bernstein, E. R.

    1993-03-01

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

  17. An isotope (18O, 15N, and 2H) technique to investigate the metal ion interactions between the phosphoryl group and amino acid side chains by electrospray ionization mass spectrometry.

    PubMed

    Gao, Xiang; Hu, Xiaomei; Zhu, Jun; Zeng, Zhiping; Han, Daxiong; Tang, Guo; Huang, Xiantong; Xu, Pengxiang; Zhao, Yufen

    2011-04-01

    Cationic metal ion-coordinated N-diisopropyloxyphosphoryl dipeptides (DIPP-dipeptides) were analyzed by electrospray ionization multistage tandem mass spectrometry (ESI-MS(n)). Two novel rearrangement reactions with hydroxyl oxygen or carbonyl oxygen migrations were observed in ESI-MS/MS of the metallic adducts of DIPP-dipeptides, but not for the corresponding protonated DIPP-dipeptides. The possible oxygen migration mechanisms were elucidated through a combination of MS/MS experiments, isotope ((18)O, (15)N, and (2)H) labeling, accurate mass measurements, and density functional theory (DFT) calculations at the B3LYP/6-31 G(d) level. It was found that lithium and sodium cations catalyze the carbonyl oxygen migration more efficiently than does potassium and participation through a cyclic phosphoryl intermediate. In addition, dipeptides having a C-terminal hydroxyl or aromatic amino acid residue show a more favorable rearrangement through carbonyl oxygen migration, which may be due to metal cation stabilization by the donation of lone pair of the hydroxyl oxygen or aromatic π-electrons of the C-terminal amino acid residue, respectively. It was further shown that the metal ions, namely lithium, sodium, and potassium cations, could play a novel directing role for the migration of hydroxyl or carbonyl oxygen in the gas phase. This discovery suggests that interactions between phosphorylated biomolecules and proteins might involve the assistance of metal ions to coordinate the phosphoryl oxygen and protein side chains to achieve molecular recognition.

  18. 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.

  19. 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

  20. Cometary implications of the internal energy distributions of the C2 and C3 radicals produced in the photolysis of the C2H and C3H2

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

    The C2 and C3 radicals are prominent emission in the visible region of cometary spectra. Observational evidence exists that suggests these radicals are formed as granddaughter fragments in the photolysis of more stable molecules. Likely candidates for these parent molecules ar C2H2, C3H4 (allene), and CH3C2H (propyne). Recent laboratory studies were performed on all of these parent molecules and they indicate that they can indeed produce the observed cometary radicals. In the case of C2H2, the laboratory evidence suggest that C2 is formed via the following mechanisms: (1) C2H2 + photon(193 nm) yields C2H + H; and (2) C2H + photon(193 nm) yields C2 + H. Evidence is presented to show that the C2 radical produced in the second reaction occurs in a variety of electronic, vibrational, and rotational states. It is argued that this is a result of conical intersections in the potential energy curves and the density of states associated with these curves. Since this is a property of the C2H radical similar initial product state distributions are expected to occur in comets. This means that any models of the C2 emission may have to start off with rotationally excited C2 radicals in both the singlet and the triplet manifolds. When C3H4 (allene) and CH3C2H (propyne) were photolyzed, the C3 radical is formed. In the allene case, laboratory evidence shows that the C3 radical is formed via the following mechanism: (1) C3H4 + photon(193 nm) yields C3H2 + H2; and (2) C3H2 + photon(193 nm) yields C3 + H2. More C3 is formed in the case of allene than in the propyne case, even though the absorption cross section for propyne is a factor of 2 larger. This suggests that competing dissociation pathways are present during the photolysis of propyne that are not available to allene. The observed quantum state distributions of the C3 product were the same for both parent molecules, indicating that the same intermediate state is involved. These observations can be understood if the excited

  1. Fast Switching of CO3(-)(H2O)n and O2(-)(H2O)n reactant ions in dopant-assisted negative photoionization ion mobility spectrometry for explosives detection.

    PubMed

    Cheng, Shasha; Wang, Weiguo; Zhou, Qinghua; Chen, Chuang; Peng, Liying; Hua, Lei; Li, Yang; Hou, Keyong; Li, Haiyang

    2014-03-01

    Ion mobility spectrometry (IMS) has become the most deployed technique for on-site detection of trace explosives, and the reactant ions generated in the ionization source are tightly related to the performances of IMS. Combination of multiform reactant ions would provide more information and is in favor of correct identification of explosives. Fast switchable CO3(-)(H2O)n and O2(-)(H2O)n reactant ions were realized in a dopant-assisted negative photoionization ion mobility spectrometer (DANP-IMS). The switching could be achieved in less than 2 s by simply changing the gas flow direction. Up to 88% of the total reactant ions were CO3(-)(H2O)n in the bidirectional mode, and 89% of that were O2(-)(H2O)n in the unidirectional mode. The characteristics of combination of CO3(-)(H2O)n and O2(-)(H2O)n were demonstrated by the detection of explosives, including 2,4,6-trinitrotoluene (TNT), cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), ammonium nitrate fuel oil (ANFO), and black powder (BP). For TNT, RDX, and BP, product ions with different reduced mobility values (K0) were observed with CO3(-)(H2O)n and O2(-)(H2O)n, respectively, which is a benefit for the accurate identification. For ANFO, the same product ions with K0 of 2.07 cm(2) V(-1) s(-1) were generated, but improved peak-to-peak resolution as well as sensitivity were achieved with CO3(-)(H2O)n. Moreover, an improved peak-to-peak resolution was also obtained for BP with CO3(-)(H2O)n, while the better sensitivity was obtained with O2(-)(H2O)n.

  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, 2013 CFR

    2013-04-01

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

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

    Code of Federal Regulations, 2012 CFR

    2012-04-01

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

  4. 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, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 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, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION...

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

    PubMed

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

    2012-04-01

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

  6. 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.

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

    PubMed

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

    2012-04-01

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

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

    SciTech Connect

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

    2011-09-16

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

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

    SciTech Connect

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

    2009-08-15

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

  10. Infrared matrix isolation studies of hydrogen bonds involving C-H bonds: CF 3H, (CF 2H) 2O and CF 3OCF 2H with selected bases

    NASA Astrophysics Data System (ADS)

    Jeng, Mei-Lee H.; Ault, Bruce S.

    1991-06-01

    Hydrogen bonded complexes of fluoroform and fluoromethylethers with halide anions and amines have been isolated at 15 K in argon matrices and characterized by IR spectroscopy. The observed red shifts of the CH stretching mode were significantly less than for analogous alkyne complexes. For a given alkane, the magnitude of shifts for complexes with the halide anions were greater than complexes with neutral amines, consistent with the greater basicity of the halide anions. The perturbed and shifted CH bending mode and its overtone were also observed, as well as perturbations to the CF stretching and bending modes. The spectral evidence tentatively suggests a monodentate hydrogen bond for the (CF 2H) 2O•F - complex, rather than the bidentate structure inferred from ion cyclotron resonance data.

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

    SciTech Connect

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

    2009-10-20

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

  12. 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

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

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture 1,1,2,2-Tetrachloroethane C2H2Cl4 + C3H3N Propenenitrile (EVLM1211, LB5648_E)' providing data from direct measurement of temperature at variable mole fraction in liquid phase and constant pressure.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  15. 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.

  16. 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.

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

    SciTech Connect

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

    2013-05-06

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

  18. Theoretical studies of the local structures and electron paramagnetic resonance parameters for Cu2+ center in Zn(C3H3O4)2(H2O)2 single crystal

    NASA Astrophysics Data System (ADS)

    Zhang, Hua-Ming; Xiao, Wen-Bo; Wan, Xiong

    2014-07-01

    The electron paramagnetic resonance (EPR) parameters (g factors gxx, gyy, gzz and hyperfine structure constants Axx, Ayy, Azz) are interpreted by taking account of the admixture of d-orbitals in the ground state wave function of the Cu2+ ion in a Zn(C3H3O4)2(H2O)2 (DABMZ) single crystal. Based on the calculation, local structural parameters of the impurity Cu2+ center were obtained (i.e. Ra≈1.92 Å, Rb≈1.96 Å, Rc≈1.99 Å). The theoretical EPR parameters based on the above Cu2+-O2- bond lengths in the DABMZ crystal show good agreement with the observed values and some improvements have been made as compared with those in the previous studies.

  19. Synthesis and structure of new light-resistant bactericide bis(nitrilotrismethylenephosphonato)diaquatetrasilver monohydrate {Ag4[NH(CH2PO3H)3]2(H2O)2} · H2O

    NASA Astrophysics Data System (ADS)

    Somov, N. V.; Chausov, F. F.

    2016-01-01

    A new four-core silver complex {Ag4[NH(CH2PO3H)3]2(H2O)2} · H2O has been synthesized and investigated. Its crystallographic characteristics are sp. gr. Pbar 1, Z = 1, a = 7.5806(2) Å, b = 8.4946(2) Å, c = 10.1092(3) Å, α = 81.087(2)°, β = 88.356(2)°, γ = 82.132(2)°. The ligand in the form of zwitterion is hexdentate. The complex is chelating; each silver atom closes an eight-membered cycle Ag-O-P-C-N-C-P-O. Simultaneously, two ligand molecules form six bridge bonds with neighboring formula units. Silver atoms form a polycyclic cluster Ag4O6, the configuration of which is stabilized by coordination and hydrogen bonds.

  20. 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.

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

    PubMed

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

    2000-05-01

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

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

    PubMed

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

    2015-01-01

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

  3. 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.

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

    PubMed

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

    2014-11-24

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

  5. 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.

  6. X-ray absorption spectroscopy comparison of the active site structures of Phanerochaete chrysosporium lignin peroxidase isoenzymes H2, H3, H4, H5, H8, and H10.

    PubMed

    Sinclair, R; Copeland, B; Yamazaki, I; Powers, L

    1995-10-10

    The iron heme and its immediate environment can provide information that is pivotal to our understanding of the structural and mechanistic features that confer unusual properties to the heme peroxidases. X-ray absorption spectroscopy (XAS), which is ideally suited for the investigation of the local environment and electronic structure of the heme iron of hemeproteins, has been used to characterize a variety of lignin peroxidase and manganese-dependent peroxidase isoenzymes produced by the white rot fungus Phanerochaete chrysosporium. The data suggest no differences within the error in the first coordination shell of iron for the isoenzymes H2, H3, H4, H5, H8, and H10 examined in this study. The pyrrole nitrogens are at a distance of 2.05 +/- 0.015 A, and the proximal histidine nitrogens are at 1.93 +/- 0.02 A, while the sixth ligands are located at 2.17 +/- 0.03 A. Significant differences are observed in higher coordination shells which may be related to conformational differences in the heme.

  7. 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.

    PubMed

    Adly, Omima M I

    2012-09-01

    Metal complexes of Ni(II), Co(II), Cd(II), VO(IV) and UO(2)(VI) as well as several Cu(II) salts, including Cl(-),NO(3)(-),AcO(-),ClO(4)(-) and SO(4)(-2) with a tridentate O(2)N donor Schiff base ligand (H(2)L), 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.

  8. Spectral characterization, molecular modeling and antimicrobial studies on hydrazone metal complexes of 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)dione and S-methyl dithiocarbazate.

    PubMed

    Taha, Ali; Emara, Adel A A; Mashaly, Mahmoud M; Adly, Omima M I

    2014-09-15

    Metal complexes of copper(II), nickel(II), cobalt(II), oxovanadium(IV), chromium(III) and cadmium(II) with a new bridged ONS dibasic tridentate hydrazone (H2L) derived from 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione with S-methyl dithiocarbazate have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, spectral (infrared, electronic, mass, 1H NMR and ESR) studies as well as thermal gravimetric analysis (TGA). The synthesized complexes have dimeric structures with the general formula [ML(NO3)m(H2O)x]2·nH2O·zMeOH, L=dianion of the hydrazone, m=0-1, x=0-2, n=0-4 and z=0-1. The metal complexes exhibited square planar, tetrahedral and octahedral geometrical arrangements, the molar conductivity data indicates that all complexes are neutral. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition stages of some complexes. Structural parameters of the ligand and its metal complexes have been theoretically computed on the basis of semiempirical PM3 level and the results were correlated with their experimental data. Antibacterial activities of the free ligand and its metal complexes were screened against various organisms.

  9. Spectral characterization, molecular modeling and antimicrobial studies on hydrazone metal complexes of 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)dione and S-methyl dithiocarbazate

    NASA Astrophysics Data System (ADS)

    Taha, Ali; Emara, Adel A. A.; Mashaly, Mahmoud M.; Adly, Omima M. I.

    2014-09-01

    Metal complexes of copper(II), nickel(II), cobalt(II), oxovanadium(IV), chromium(III) and cadmium(II) with a new bridged ONS dibasic tridentate hydrazone (H2L) derived from 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione with S-methyl dithiocarbazate have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, spectral (infrared, electronic, mass, 1H NMR and ESR) studies as well as thermal gravimetric analysis (TGA). The synthesized complexes have dimeric structures with the general formula [ML(NO3)m(H2O)x]2·nH2O·zMeOH, L = dianion of the hydrazone, m = 0-1, x = 0-2, n = 0-4 and z = 0-1. The metal complexes exhibited square planar, tetrahedral and octahedral geometrical arrangements, the molar conductivity data indicates that all complexes are neutral. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition stages of some complexes. Structural parameters of the ligand and its metal complexes have been theoretically computed on the basis of semiempirical PM3 level and the results were correlated with their experimental data. Antibacterial activities of the free ligand and its metal complexes were screened against various organisms.

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

    NASA Astrophysics Data System (ADS)

    Bhoj, Ananth N.; Kushner, Mark J.

    2008-08-01

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

  11. 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.

  12. 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.

  13. 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.

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

    SciTech Connect

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

    1999-09-01

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

  15. Electrosynthesis of Rh2(dpf)4(R) where dpf = N,N'-diphenylformamidinate anion and R = CH3, C2H5, C3H7, C4H9 or C5H11.

    PubMed

    Bear, J L; Van Caemelbecke, E; Ngubane, S; Da-Riz, V; Kadish, K M

    2011-03-21

    The electrosynthesis of Rh(2)(dpf)(4)(R) where dpf is the N,N'-diphenylformamidinate anion and R = CH(3), C(2)H(5), C(3)H(7), C(4)H(9) or C(5)H(11) was carried out in THF containing 0.2 M tetra-n-butylammonium perchlorate (TBAP) and one of several alkyl iodides represented as RI. The initial step in the reaction involved a one-electron reduction of the Rh(2)(4+) unit in Rh(2)(dpf)(4) to its Rh(2)(3+) form followed by a homogeneous reaction involving electrogenerated [Rh(2)(dpf)(4)](-) and the alkyl iodide in solution to give Rh(2)(dpf)(4)(R). The homogeneously generated Rh(2)(5+) product was then immediately reduced by a second electron at the potential where [Rh(2)(dpf)(4)(R)](-) is generated, giving [Rh(2)(dpf)(4)(R)](-) which contains a Rh(2)(4+) center as a final product of an electrochemical ECE mechanism. The electrosynthesized [Rh(2)(dpf)(4)(CH(3))](-) derivative could be reoxidized to Rh(2)(dpf)(4)(CH(3)) on the reverse potential sweep and both forms of the CH(3) bonded derivative were in situ characterized by cyclic voltammetry combined with UV-visible and/or ESR spectroscopy. The reversible Rh(2)(4+/3+) process of Rh(2)(dpf)(4) is located at E(1/2) = -1.11 V in THF, 0.2 M TBAP while the electrogenerated Rh(2)(dpf)(4)(R) products are substantially easier to reduce, with E(p) values for the Rh(2)(5+/4+) couples ranging from -0.50 to -0.54 V vs. SCE depending upon the specific R group.

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

    PubMed

    Adly, Omima M I

    2011-09-01

    Metal complexes with the general formula [ML(H2O)(CH3OH)x]·nH2O·(CH3OH)y(NO3)z [M=Cu(II), Ni(II), Co(II), VO(IV), Cr(III), Cd(II), Zn(II) or UO2(VI); x=0-2; y=0,1; z=0,1; n=0-2, 6 and L=hydrazone (H2L) derived from condensation of thiosemicarbazide with 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione. The synthesized ligand and its metal complexes have been characterized on the basis of elemental analyses, spectral and magnetic studies as well as thermal gravimetric analysis (TGA). The deprotonated ligand acts as a dibasic tridentate (ONS) via phenolate oxygen, azomethine (CN), and thiolate (C-S) groups. Copper(II) complex exhibits square planar geometry. Nickel(II), chromium(III) and dioxouranium(VI) complexes exhibit octahedral geometry. Cobalt(II), cadmium(II) and zinc(II) complexes showed tetrahedral geometry, whereas oxovanadium(IV) reveals square pyramidal geometry. Thermal analysis are investigated and showed either three or four thermal decomposition steps. Kinetic parameters (Ea, A, ΔH, ΔS and ΔG) of the thermal decomposition stages have been evaluated using Coats-Redfern equations. The molecular parameters of the ligand and its metal complexes have been calculated and correlated with the experimental data such as IR and TGA results.

  17. Low temperature rate coefficients for reactions of the butadiynyl radical, C4H, with various hydrocarbons. Part I: reactions with alkanes (CH4, C2H6, C3H8, C4H10).

    PubMed

    Berteloite, Coralie; Le Picard, Sébastien D; Balucani, Nadia; Canosa, André; Sims, Ian R

    2010-04-21

    The kinetics of the reactions of the linear butadiynyl radical, C4H (CCCCH), with methane, ethane, propane and butane have been studied over the temperature range of 39-300 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. The rate coefficients, except for the reaction with methane, show a negative temperature dependence and can be fitted with the following expressions over the temperature range of this study: k(C2H6) = 0.289 x 10(-10) (T/298 K)(-1.23) exp(-24.8 K/T) cm3 molecule(-1) s(-1); k(C3H8) = 1.06 x 10(-10) (T/298 K)(-1.36) exp(-56.9 K/T) cm3 molecule(-1) s(-1); k(C4H10) = 2.93 x 10(-10) (T/298 K)(-1.30) exp(-90.1 K/T) cm3 molecule(-1) s(-1). The rate coefficients for the reaction with methane were measured only at 200 K and 300 K yielding a positive temperature dependence: k(CH4) = 1.63 x 10(-11) exp(-610 K/T) cm3 molecule(-1) s(-1). Possible reaction mechanisms and product channels are discussed in detail for each of these reactions. Potential implications of these results for models of low temperature chemical environments, in particular cold interstellar clouds and planetary atmospheres such as that of Titan, are considered.

  18. 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.

  19. Synthesis and antitumor activity of some 2, 3-disubstituted quinazolin-4(3H)-ones and 4, 6- disubstituted- 1, 2, 3, 4-tetrahydroquinazolin-2H-ones.

    PubMed

    Abdel Gawad, Nagwa M; Georgey, Hanan H; Youssef, Riham M; El-Sayed, Nehad A

    2010-12-01

    The synthesis of some new 3-substituted quinazolin-4(3H)-ones and 3,4-dihydro-quinazolin-2(1H)-one derivatives and their biological evaluation as antitumor agents using the National Cancer Institute (NCI), disease oriented antitumor screening protocol are investigated. Compounds 2-[2-(4-chlorophenyl)-2-oxo-ethylthio]-3-(4-methoxyphenyl)quinazolin-4(3H)-one (3b), and 3-(4-chlorophenyl)-2-[2-(4-methoxyphenyl)-2-oxo-ethylthio]quinazolin-4(3H)-one (3d), are broad-spectrum antitumors showing effectiveness toward numerous cell lines that belong to different tumor subpanels, Compounds 3b, 3d are the most active members in this study. Those two quinazoline analogues could be considered as useful templates for future development to obtain more potent antitumor agent(s).

  20. 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.

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

    SciTech Connect

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

    2013-07-15

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

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. Theoretical study of isoelectronic molecules: B6H10, 2-CB5H9, 2,3-C2B4H8, 2,3,4-C3B3H7, and 2,3,4,5-C4B2H6.

    PubMed

    Tian, Shan Xi

    2005-07-28

    Isoelectronic molecules regarding B6H10, 2-CB5H9, 2,3-C2B4H8, 2,3,4-C3B3H7, and 2,3,4,5-C4B2H6 are studied by the density functional B3LYP/6-311G(d,p) method and the electron propagator theory in the partial third-order quasiparticale approximation, as well as the extrapolated calculation with the coupled-cluster CCSD(T) theory. The calculated ionization potentials are in good agreement with the experimental data from photoelectron spectroscopy. Valence structures are characterized with natural orbital bond (NBO) theory, exhibiting the multiple three-center two-electron bonds B-H-B, B-B-B, C-B-B, B-C-B, and C-B-C, and chemical bond rearrangements in the cations. PMID:16834005

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

    PubMed

    Swiatek, Mirosława; Kufelnicki, Aleksander

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

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

  9. Syntheses of 3-[(Alkylamino)methylene]-6-methylpyridine-2,4(1H,3H)-diones, 3-Substituted 7-Methyl-2H-pyrano[3,2-c]pyridine-2,5(6H)-dione Fluorescence Probes, and Tetrahydro-1H,9H-2,10-dioxa-9-azaanthracen-1-ones

    PubMed Central

    Prior, Allan M.; Gunaratna, Medha J.; Kikuchi, Daisuke; Desper, John; Kim, Yunjeong; Chang, Kyeong-Ok; Maezawa, Izumi; Jin, Lee-Way; Hua, Duy H.

    2014-01-01

    Various condensation and ring-closing reactions were used for the syntheses of 3-[(alkylamino)methylene]-6-methylpyri-dine-2,4(1H,3H)-diones, bicyclic pyridinones, and tricyclic morpholinopyrones. For instance, 3-[(dialkylamino)methylene]-6-methylpyridine-2,4(1H,3H)-diones were synthesized from the condensation of dialkylamines and 3-formyl-4-hydroxy-6-methylpyridin-2(1H)-one. 3-Formyl-4-hydroxy-6-methylpyridin-2(1H)-one, derived from 3-formyl-4-hydroxy-6-methylpyridin-2(1H)-one, was used to construct a number of bicyclic pyridinones via a one-pot Knoevenagal and intramolecular lactonization reaction. Tricyclic morpholinopyrones were assembled from a dialkylation reaction involving a dinucleophile, 3-amino-4-hydroxy-6-methyl-2H-pyran-2-one, and a dielectrophile, trans-3,6-dibromocyclohexene. Depending on the reaction conditions, isomers of the tricyclic molecules can be selectively produced, and their chemical structures were unequivocally determined using single-crystal X-ray analyses and 2D COSY spectroscopy. The fluorescently active bicyclic pyridinone compounds show longer absorption (368–430 nm; maximum) and emission wavelengths (450–467 nm) than those of 7-amino-4-methylcoumarin (AMC; λabs,max = 350 nm; λem = 430 nm) suggesting these molecules, such as 3-(2-aminoacetyl)-7-methyl-2H-pyrano[3,2-c]pyridine-2,5(6H)-dione, can be employed as fluorescence activity based probes for tracing biological pathways. PMID:25177061

  10. Part 1. Spectrophotometric determination of trace mercury (II) in dental-unit wastewater and fertilizer samples using the novel reagent 6-hydroxy-3-(2-oxoindolin-3-ylideneamino)-2-thioxo-2H-1,3-thiazin-4(3H)-one and the dual-wavelength beta-correction spectrophotometry.

    PubMed

    Hamza, A; Bashammakh, A S; Al-Sibaai, A A; Al-Saidi, H M; El-Shahawi, M S

    2010-06-15

    A simple and low cost method was developed and validated for the determination of trace mercury (II) ions in dental-unit wastewater and fertilizer samples. The method was based upon the reaction of mercury (II) ions with the novel reagent 6-hydroxy-3-(2-oxoindolin-3-ylideneamino)-2-thioxo-2H-1,3-thiazin-4(3H)-one, the formed complex shows an absorption maximum at 505 nm (lambda(max)) in Britton-Robinson (B-R) buffer (pH 4-6).The corrected absorbance of the formed complex at lambda(max) was obtained employing beta-correction spectrophotometric method. Beer's-Lambert law and Ringbom's plots of the colored Hg-reagent complex were obeyed in the concentration range of 0.2-2.0 and 0.32-0.96 microg mL(-1) mercury (II) ions, respectively with a relative standard deviation in the range of 2.1+/-1.3%. The limits of detection (LOD) and quantification (LOQ) of the procedure were 0.026 and 0.086 microg mL(-1) Hg(2+), respectively. The proposed method was applied for the analysis of mercury (II) in dental-unit wastewater and fertilizer samples. The validation of the method was tested by comparison with the data obtained by the inductively coupled plasma-mass spectrometry (ICP-MS). The statistical treatment of data in terms of Student's t-tests and variance ratio f-tests has revealed no significance differences. PMID:20149525

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

    SciTech Connect

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

    2009-07-15

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

  12. 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.

  13. 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.

  14. 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.

  15. Molecular and cluster structures in 18O

    NASA Astrophysics Data System (ADS)

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

    2010-01-01

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

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

    SciTech Connect

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

    1996-05-14

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

  20. 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.

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

    SciTech Connect

    Xie Yiming Chen Wentong; Wu Jihuai

    2008-08-15

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

  2. 18O and 226Ra in the Minjiang River estuary, China and their hydrological implications

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  3. Rapid and convenient preparation of (4-/sup 3/H)NADP and stereospecifically tritiated NADP/sup 3/H

    SciTech Connect

    Moran, R.G.; Sartori, P.; Reich, V.

    1984-04-01

    The enzymatic preparation and chromatographic purification of (4-/sup 3/H)NADP and NADPH stereospecifically labeled with /sup 3/H on either the A or B faces at position 4 have been simplified. Commercially available (1-/sup 3/H)glucose was used as a starting material for the sequential synthesis of (4B-/sup 3/H)NADPH, (4-/sup 3/H)NADP, and (4A-/sup 3/H)NADPH. These products were rapidly purified by step elution of DEAE-cellulose minicolumns so that (4B-/sup 3/H)NADPH was produced and purified from (1-/sup 3/H)glucose in 2 h, (4-/sup 3/H)NADP in 5 h, and (4A-/sup 3/H)NADPH in 8 h. Yields of these products were 65 to 88% starting with (1-/sup 3/H)glucose. Analysis of the products by high-performance liquid chromatography indicated radiochemical purities of 82-95% for these compounds and specific activities equivalent to that of the starting material (10-15 Ci/mmol). 15 references.

  4. Use of 18O-labelled leucine and phenylalanine to measure protein turnover in muscle cell cultures and possible futile cycling during aminoacylation.

    PubMed Central

    Fuller, J C; Nissen, S L; Huiatt, T W

    1993-01-01

    Amino acids labelled with 18(O) on both carboxy oxygen atoms have the potential for use as non-recyclable tracers to measure protein turnover. During protein synthesis one of the labelled oxygen atoms is removed, and thus release of the mono-labelled amino acid could be used to determine proteolysis. Primary cultures of embryonic-chick skeletal-muscle cells were used to test the use of 18(O2)-labelled Leu to measure proteolysis. For 9-day cultures, prelabelled on days 2-8 with medium containing one-half the Leu as [18O2]Leu and one-half as [2H3]Leu, release of [18(O)]Leu was less than 50% that of [2H]Leu over 24 h, suggesting a loss of the 18O label by a mechanism other than protein synthesis. Medium containing [18(O2)]Leu, [2H3]Leu, [18O2]Phe and [13C]Phe was then incubated with 9-day cultures to compare the rate of loss of the 18(O)-label from Leu and Phe with the rate of uptake of the non-carboxy-oxygen-labelled amino acids. Results for Leu demonstrated an 81% loss of the 18(O) label compared with a 33% decrease in [2H]Leu over 12 h. Loss of the 18(O) label was four times as great for Leu as for Phe. Loss of the 18(O) label was not decreased by addition of cycloheximide or by addition of a 3-fold excess of Ile, Val and Tyr; thus the loss of label was not due to protein synthesis alone or to misbinding to incorrect tRNAs. Infusion of the isotopes into pigs showed that the 18(O) label of Leu was not lost during transamination to alpha-ketoisocaproate (alpha-oxoisohexanoate). The most probable explanation is that the 18(O) label is lost as a result of the enzymic deacylation of tRNA, that this process is substantially faster for Leu than for Phe, and that this represents a potentially costly futile cycle for Leu. Images Scheme 2 PMID:8373357

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  6. 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.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  9. 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

  10. Ultrathin W18O49 nanowire assemblies for electrochromic devices.

    PubMed

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

    2013-08-14

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

  11. 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.

  12. Materials Data on RbNa3Mo2H18O17 (SG:176) by Materials Project

    SciTech Connect

    Kristin Persson

    2014-07-09

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  13. 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...

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

    PubMed

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

    1991-03-01

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

  15. 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...

  16. 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

  17. 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.

  18. 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...

  19. C18O Depletion in Starless Cores in Taurus

    NASA Astrophysics Data System (ADS)

    Ford, Amanda Brady; Shirley, Yancy L.

    2011-02-01

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

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

    PubMed

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

    2006-11-01

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

  1. 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.

  2. /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.

  3. 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

  4. 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.

  5. 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.

  6. Biological concentration of /sup 3/H

    SciTech Connect

    Moghissi, A.A.; Bretthauer, E.W.; Patzer, R.G.

    1987-10-01

    In a three-year study, the possible biological concentration of /sup 3/H in rabbits was investigated. Tritiated water was used to grow alfalfa that was used exclusively as feed for the rabbits. Feed and water were kept at a constant /sup 3/H-to-/sup 1/H ratio. The foundation group consisted of 18 female rabbits maintained on a /sup 3/H diet for 2 wk before mating. The subsequent generations were maintained with tritiated water and feed. At appropriate intervals, animals were sacrificed and selected tissues were analyzed for /sup 3/H. The specific activity of /sup 3/H in aqueous and organic fractions of tissues of all the animals remained essentially equal to that in the original water and feed. Results of this experiment indicate that under the steady-state equilibrium conditions of the experiment, no preferential concentration of /sup 3/H in animals occurred.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  8. 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.

  9. Formation of nitric oxide and nitrous oxide in electron-irradiated H(2)18O/N2 ice mixtures--evidence for the existence of free oxygen atoms in interstellar and solar system analog ices.

    PubMed

    Zheng, Weijun; Kim, Y Seol; Kaiser, Ralf I

    2011-09-21

    We investigated the irradiation of low temperature H(2)(18)O/N(2) ice mixtures with energetic electrons in an ultrahigh vacuum chamber. The newly formed species, such as nitric oxide (N(18)O), nitrous oxide (NN(18)O), hydrogen peroxide (H(2)(18)O(2)) and hydrazine (N(2)H(4)), were identified in the experiments with infrared absorption spectroscopy and mass spectrometry. The results suggest that the unimolecular decomposition of water molecules within water ices at 10 K can lead to the formation of transient, suprathermal oxygen atoms. These oxygen atoms may play an important role in the formation of oxygen-containing biomolecules such as amino acids and sugar, as well as the decomposition of the biomolecules in the ices.

  10. Astronomical identification of the C3H radical

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

  11. Climatological significance of δ18O in north Tibetan ice cores

    NASA Astrophysics Data System (ADS)

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

    1996-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Awad, Sadek

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  15. 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.

  16. 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

  17. $sup 18$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.

  18. Predictable components in global speleothem δ18O

    NASA Astrophysics Data System (ADS)

    Fischer, Matt J.

    2016-01-01

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

  19. 18O isotopic separation of stream nitrate sources in mid-Appalachian forested watersheds

    NASA Astrophysics Data System (ADS)

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

    2001-10-01

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

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

    PubMed

    Thiem, Ines; Lüpke, Matthias; Seifert, Hermann

    2004-09-01

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

  1. 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.

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

    NASA Astrophysics Data System (ADS)

    Sano, Masaki; Xu, Chenxi; Nakatsuka, Takeshi

    2012-06-01

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

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

    PubMed Central

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

    2014-01-01

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

  4. 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. 

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

    NASA Astrophysics Data System (ADS)

    Comas-Bru, Laia; McDermott, Frank

    2015-11-01

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

  6. 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.

  7. 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

  8. 13C18O in Earth's Atmosphere: a New Proxy for Constraining CO Budget

    NASA Astrophysics Data System (ADS)

    Guo, W.; Eiler, J. M.

    2005-12-01

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

  9. Relations between 3H-estradiol uptake and receptor content of estrogen responsive tissues of castrated female rat.

    PubMed

    Gómez-Benitez, J; Sosa-González, A; Díaz-Chico, B N

    1984-09-01

    The time course of 3H-Estradiol-17 beta (3H-E2) uptake, and estrogen receptor content in estrogen responsive tissues were studied between 0 and 12 h after injection of 0.5 microgram/kg of 3H-E2 or cold E2 injection to castrated adult female rats. The plasma concentration of 3H-E2 between 10 min and 2 h after injection was in the range of the plasma E2 level of cyclic rat. The total 3H-E2 uptake was well correlated with the receptor content in all tissues. The rank order of 3H-E2 uptake was: uterus (Ut) greater than anterior pituitary (Ap) greater than hypothalamus (Ht) greater than plasma. The cytosol 3H-E2 uptake showed its maximal level 10 min after injection in all tissues. Parallel time course between plasma 3H-E2 and cytosol uptake was obtained for each separate tissue. The nuclear 3H-E2 uptake showed its maximal values 2 h after injection with a subsequent decline. Cytosolic estrogen receptor (Rc) content showed a depletion-replenishment cycle after cold E2 injection in all tissues. Nuclear estrogen receptor (Rn) content in Ut increased progressively from 0 to 14 h after injection, but in Ap it showed its maximal level 2 h after injection, declining afterwards. In Ap, nuclear 3H-E2 uptake and Rn level showed parallel time courses. The maximal level of both parameters coinciding with the time of maximal Rc depletion. However, the Rn level in Ut increases more slowly at greater length than the nuclear 3H-E2 uptake, both processes being divergent. These findings are interpreted as the expression of tissular differences in the rate of nuclear receptor formation from the Rc-E complex previously translocated into nucleus and attached to chromatin.

  10. 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.

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

    PubMed

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

    2009-03-15

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

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

    PubMed Central

    Klingler, Diana; Hardt, Markus

    2013-01-01

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

  13. 18O 16O ratios in cherts associated with the saline lake deposits of East Africa

    USGS Publications Warehouse

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

    1973-01-01

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

  14. 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.

  15. 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...

  16. 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...

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

    EPA Science Inventory

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

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    PubMed

    Marshall, John D; Monserud, Robert A

    2006-08-01

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

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

    SciTech Connect

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

    1983-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

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

    PubMed

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

    2016-07-01

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

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

    PubMed

    Heller, Hartmut; Schuster, Klaus-Dieter

    2007-01-01

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

  4. 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.

  5. 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.

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

    PubMed

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

    2016-07-01

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

  7. 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.

  8. 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

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

    NASA Astrophysics Data System (ADS)

    Vinther, B. M.

    2012-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  11. 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.

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

    NASA Astrophysics Data System (ADS)

    Jasechko, Scott

    2016-08-01

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

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    SciTech Connect

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

    2010-08-12

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

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  18. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    NASA Technical Reports Server (NTRS)

    Wilson, S.; Green, S.

    1980-01-01

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

  1. Experimental and theoretical study on the thermal decomposition of C3H6 (propene).

    PubMed

    Hung, Wei-Chung; Tsai, Chieh-Ying; Matsui, Hiroyuki; Wang, Niann-Shiah; Miyoshi, Akira

    2015-02-26

    The mechanism of the thermal unimolecular decomposition of C3H6 (propene) is studied both theoretically and experimentally. The potential energy surfaces for possible reaction pathways are investigated by CBS-QB3 level of quantum chemical calculations, and RRKM/master-equation calculation is performed for the main channels. The time evolutions of H atoms are observed experimentally by using a highly sensitive detection technique (ARAS, detection limit ≈ 10(11) atoms cm(-3)) behind reflected shock waves (0.5-1.0 ppm C3H6 diluted in Ar, 1450-1710 K at 2.0 atm). The objective of this study is to examine the main product channels by combining the experimental and theoretical investigations on the yield and the rates of H atom production. Present quantum chemical calculations identify reactions (1a-1d) as the candidates of product channels: C3H6 → aC3H5 (allyl radical) + H (1a), C3H6 → CH3 + C2H3 (vinyl radical) (1b), C3H6 → CH4 + :CCH2 (singlet vinyldene radical) (1c), and C3H6 → C3H4 (allene) + H2 (1d). The RRKM calculations reveal the branching fractions for (1a), (1b), and (1c) to be approximately 0.8, 0.2, and 0.01, respectively. Reaction (1d) and other product channels are negligible (< 0.1 %), and the pressure dependence of the branching fraction is small under the present experimental conditions. The experimental yield of H atoms (1.7-2.0) is consistent with the theoretical branching fractions considering the H-atom production from the rapid subsequent thermal decomposition of a C3H5 and C2H3. From the observed time profiles of H atoms, the rate of overall thermal decomposition of C3H6 can be evaluated as Ln(k1/s(-1)) = (38.05 ± 1.18) - (48.91 ± 1.85) × 10(3) K/T, which is in excellent agreement with the theoretical prediction.

  2. Uptake of [3H]-nicotine and [3H]-noradrenaline by cultured chromaffin cells.

    PubMed Central

    Ceña, V.; García, A. G.; Montiel, C.; Sánchez-García, P.

    1984-01-01

    Three day-old cultured bovine adrenal chromaffin cells incubated at room temperature with Krebs-HEPES solution containing different concentrations of [3H]-nicotine, took up and retained increasing amounts of the drug by a mechanism that did not saturate. Concentrations of cold nicotine as high as 100 microM did not alter the amount of [3H]-nicotine retained by cells. Imipramine, cocaine, tetracaine or mecamylamine, at concentrations (10 microM) that blocked the catecholamine secretory effects of nicotine completely, did not modify the uptake of [3H]-nicotine. Both imipramine and cocaine drastically inhibited [3H]-noradrenaline uptake by cells in a concentration-dependent manner (IC50S of 0.08 and 1 microM, respectively). These data indicate that the secretory effects of nicotine are not coupled to its previous uptake into cells, and are evidence in favour of a site of action for nicotine located in or at the surface of the chromaffin cell membrane. PMID:6704577

  3. 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  6. Synthesis of [2H7]indatraline.

    PubMed

    Allmendinger, L; Wanner, K T

    2014-11-01

    Deuterium-labelled indatraline was synthesized in high efficiency employing a Friedel-Crafts alkylation of [(2)H6]benzene with (E)-3-(3,4-dichlorophenyl)acrylic acid as a key step. The desired labelling of the final compound was ascertained in two ways, by incorporation of [(2)H6]benzene in the target molecule and additionally by deuterium transfer to the non-deuterated aryl moiety of the Friedel-Crafts alkylation product from [(2)H6]benzene, the latter thus serving as reagent and solvent. PMID:25382822

  7. 3H-nicotine, 3H-flunitrazepam, and 3H-cocaine incorporation into melanin: a model for the examination of drug-melanin interactions.

    PubMed

    Claffey, D J; Stout, P R; Ruth, J A

    2001-10-01

    To explore drug-melanin interactions, we examined the in vitro tyrosinase-mediated formation of melanin from tyrosine in the presence of the 3H-cocaine (3H-COC), 3H-flunitrazepam (3H-FLU), and 3H-nicotine (3H-NIC) at 10-100,000 ng/mL. Polymerization in the presence of 10 or 100 ng/mL of each drug resulted in almost complete drug incorporation into the melanin pellet. Only 12% (3H-NIC) to 28% (3H-FLU) of the pellet-associated radioactivity could be released upon treatment with 6 M HCl. At 1000-100,000 ng/mL, between 20 and 50% of label became melanin-associated. In each case a significant percentage of melanin-associated radioactivity was resistant to treatment with 6 M HCl. Nicotine-associated radioactivity in the polymer was subject to much greater quenching than was 3H-COC or 3H-FLU, suggesting a much tighter association with the melanin. The subsequent demonstration of a covalent adduct of a melanin intermediate and nicotine has demonstrated the utility of this polymerization system as a model for further chemical characterization of drug-melanin interactions.

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

    USGS Publications Warehouse

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

    2004-01-01

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

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

    SciTech Connect

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

    2014-05-09

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

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

    PubMed

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

    2010-03-01

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

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

    SciTech Connect

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

    1981-11-16

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

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

    PubMed

    Clementz, Mark T; Sewall, Jacob O

    2011-04-22

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

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

    PubMed

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

    2009-07-14

    The stratospheric CO(2) oxygen isotope budget is thought to be governed primarily by the O((1)D)+CO(2) isotope exchange reaction. However, there is increasing evidence that other important physical processes may be occurring that standard isotopic tools have been unable to identify. Measuring the distribution of the exceedingly rare CO(2) isotopologue (16)O(13)C(18)O, in concert with (18)O and (17)O abundances, provides sensitivities to these additional processes and, thus, is a valuable test of current models. We identify a large and unexpected meridional variation in stratospheric (16)O(13)C(18)O, observed as proportions in the polar vortex that are higher than in any naturally derived CO(2) sample to date. We show, through photochemical experiments, that lower (16)O(13)C(18)O proportions observed in the midlatitudes are determined primarily by the O((1)D)+CO(2) isotope exchange reaction, which promotes a stochastic isotopologue distribution. In contrast, higher (16)O(13)C(18)O proportions in the polar vortex show correlations with long-lived stratospheric tracer and bulk isotope abundances opposite to those observed at midlatitudes and, thus, opposite to those easily explained by O((1)D)+CO(2). We believe the most plausible explanation for this meridional variation is either an unrecognized isotopic fractionation associated with the mesospheric photochemistry of CO(2) or temperature-dependent isotopic exchange on polar stratospheric clouds. Unraveling the ultimate source of stratospheric (16)O(13)C(18)O enrichments may impose additional isotopic constraints on biosphere-atmosphere carbon exchange, biosphere productivity, and their respective responses to climate change.

  15. 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.

  16. 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.

  17. Comprehensive inter-laboratory calibration of reference materials for delta18O versus VSMOW using various on-line high-temperature conversion techniques.

    PubMed

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

    2009-04-01

    reports the delta(18)O values of two or more internationally distributed nitrates (USGS 34, IAEA-NO-3, and USGS 35), 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 delta(18)O values at a later time should it become necessary.The high-temperature reduction technique for analyzing delta(18)O and delta(2)H 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. Comprehensive inter-laboratory calibration of reference materials for delta18O versus VSMOW using various on-line high-temperature conversion techniques.

    PubMed

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

    2009-04-01

    reports the delta(18)O values of two or more internationally distributed nitrates (USGS 34, IAEA-NO-3, and USGS 35), 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 delta(18)O values at a later time should it become necessary.The high-temperature reduction technique for analyzing delta(18)O and delta(2)H 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. PMID:19263478

  19. 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

  20. ({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.

  1. 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."

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

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

    PubMed Central

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

    2012-01-01

    Next-generation screening of disease-related metabolomic phenotypes requires monitoring of both metabolite levels and turnover rates. Stable isotope 18O-assisted 31P nuclear magnetic resonance (NMR) and mass spectrometry uniquely allows simultaneous measurement of phosphometabolite levels and turnover rates in tissue and blood samples. The 18O labeling procedure is based on the incorporation of one 18O into Pi from [18O]H2O with each act of ATP hydrolysis and the distribution of 18O-labeled phosphoryls among phosphate-carrying molecules. This enables simultaneous recording of ATP synthesis and utilization, phosphotransfer fluxes through adenylate kinase, creatine kinase, and glycolytic pathways, as well as mitochondrial substrate shuttle, urea and Krebs cycle activity, glycogen turnover, and intracellular energetic communication. Application of expanded 18O-labeling procedures has revealed significant differences in the dynamics of G-6-P[18O] (glycolysis), G-3-P[18O] (substrate shuttle), and G-1-P[18O] (glycogenolysis) between human and rat atrial myocardium. In human atria, the turnover of G-3-P[18O], which defects are associated with the sudden death syndrome, was significantly higher indicating a greater importance of substrate shuttling to mitochondria. Phosphometabolomic profiling of transgenic hearts deficient in adenylate kinase (AK1−/−), which altered levels and mutations are associated to human diseases, revealed a stress-induced shift in metabolomic profile with increased CrP[18O] and decreased G-1-P[18O] metabolic dynamics. The metabolomic profile of creatine kinase M-CK/ScCKmit−/−-deficient hearts is characterized by a higher G-6-[18O]P turnover rate, G-6-P levels, glycolytic capacity, γ/β-phosphoryl of GTP[18O] turnover, as well as β-[18O]ATP and β-[18O]ADP turnover, indicating altered glycolytic, guanine nucleotide, and adenylate kinase metabolic flux. Thus, 18O-assisted gas chromatography-mass spectrometry and 31P NMR provide a suitable

  4. 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.

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

    PubMed

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

    2016-01-01

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

  6. 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.

  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. 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.

  9. 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

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

    PubMed

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Clayton, D. D.

    2004-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Killingley, John S.; Lutcavage, Molly

    1983-03-01

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

  13. 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...

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

    PubMed

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

    2011-02-01

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

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

    SciTech Connect

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

    2015-08-15

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

  16. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 13C-18O bonding (Δ47) in deep-sea corals: a calibration study

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  3. 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.

  4. 18O/16O studies of fossil fissure fumaroles from the Valley of Ten Thousand Smokes, Alaska

    NASA Astrophysics Data System (ADS)

    Warner Holt, Elizabeth; Taylor, Hugh

    2001-03-01

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

  5. 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

  6. 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

  7. 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.

  8. /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.

  9. 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

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    DOE PAGES

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

    2015-09-17

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

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

    PubMed

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

    2015-10-01

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

  14. Molecular-beam experiments for photodissociation of propenal at 157 nm and quantum-chemical calculations for migration and elimination of hydrogen atoms in systems C3H4O and C3H3O

    NASA Astrophysics Data System (ADS)

    Chin, Chih-Hao; Chaudhuri, Chanchal; Lee, Shih-Huang

    2011-07-01

    We investigated the dynamics of photodissociation of propenal (acrolein, CH2CHCHO) at 157 nm in a molecular beam and of migration and elimination of hydrogen atoms in systems C3H4O and C3H3O using quantum-chemical calculations. Compared with the previous results of photodissociation of propenal at 193 nm, the major difference is that the C3H3O fragment present at the 193-nm photolysis disappears at the 157-nm photolysis whereas the C3H2O fragment absent at 193 nm appears at 157 nm. Optimized structures and harmonic vibrational frequencies of molecular species with gross formula C3H2-4O were computed at the level of B3LYP/6-311G(d,p) and total energies of those molecules at optimized structures were computed at the level of CCSD(T)/6-311+G(3df,2p). Based on the calculated potential-energy surfaces, we deduce that the C3H3O fragment observed in the photolysis of propenal at 193 nm is probably CHCCHOH (2A″) and/or CH2CCOH (2A″) produced from an intermediate hydroxyl propadiene (CH2CCHOH) following isomerization. Adiabatic and vertical ionization potentials of eight isomers of C3H3O and two isomers of C3H2O were calculated; CHCCHOH (2A″) and CH2CCOH (2A″) have ionization potentials in good agreement with the experimental value of ˜7.4 eV. We also deduce that all the nascent C3H3O fragments from the photolysis of propenal at 157 nm spontaneously decompose mainly to C2H3 + CO and C3H2O + H because of the large excitation energy. This work provides profound insight into the dynamics of migration and elimination of hydrogen atoms of propenal optically excited in the vacuum-ultraviolet region.

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

    PubMed Central

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

    1994-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Holt, Elizabeth Warner; Taylor, Hugh P.

    2001-06-01

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

  17. Dissociative recombination of N2H+

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-04-01

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

  19. 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.

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

    PubMed

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

    2007-05-01

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

  1. 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.

  2. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

    Gillon, Jim; Yakir, Dan

    2001-03-01

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

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

    PubMed Central

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

    2007-01-01

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

  6. 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.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-11-01

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

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  11. Radiotoxicities of (/sup 3/H)thymidine and of (/sup 3/H)arginine compared in mouse embryos in vitro

    SciTech Connect

    Mueller, W.U.S.; Streffer, C.; Molls, M.; Glueck, L.

    1987-05-01

    Tritium that is bound to organic molecules is of special risk for living systems, in particular when such molecules are components of the cell nucleus. Therefore, (/sup 3/H)thymidine and (/sup 3/H)arginine were studied for radiotoxicity in early mammalian embryo development. Starting with the two-cell stage, mouse embryos were incubated in vitro with (/sup 3/H)thymidine or (/sup 3/H)arginine at either 370 Bq/ml (10 nCi/ml) or 925 Bq/ml (25 nCi/ml). Development in vitro was followed up to the formation of the inner cell mass at 192 h postconception (p.c.). There was no difference in radiotoxicity of the two substances with respect to cell proliferation; however, formation of blastocysts, hatching of blastocysts, trophoblast outgrowth, and formation of inner cell mass were impaired more strongly by (/sup 3/H)arginine than by (/sup 3/H)thymidine when the external exposure concentrations were the same. Similarly, micronuclei were seen in blastocysts at 96 h p.c. at higher frequency after incubation with (/sup 3/H)arginine. However, uptake of (/sup 3/H)arginine by the embryos was considerably faster than that of (/sup 3/H)thymidine, and this most probably accounts for the apparent difference in radiotoxicity.

  12. 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.

  13. /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.

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

    PubMed

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

    2013-11-01

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

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

    PubMed Central

    Brown, S B; King, R F

    1978-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

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

    PubMed

    Hartard, Britta; Máguas, C; Lakatos, M

    2008-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-06-01

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

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

    NASA Astrophysics Data System (ADS)

    Gai, Moshe

    1992-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2003-07-01

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

  2. 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.

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

    SciTech Connect

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

    1989-01-01

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

  4. Autoradiographic analysis of 3H-glutamate, 3H-dopamine, and 3H-GABA accumulation in rabbit retina after kainic acid treatment

    SciTech Connect

    Hampton, C.K.; Redburn, D.A.

    1983-01-01

    We have previously reported that exposure of isolated rabbit retina to 10(-3) M kainic acid produces profound morphological changes in specific retinal neurons (Hampton et al, 1981). We noted specific swelling of horizontal cell bodies and neurites, necrosis of cell bodies in the amacrine and ganglion cell layers, and swelling of elements in the inner plexiform layer. We now report a differential sensitivity to kainic acid of specific subclasses of amacrine cells autoradiographically labeled with 3H-glutamate, 3H-GABA, or 3H-dopamine. Three different effects were observed: (1) Labeling of neurons after incubation in 3H-glutamate was uniformly reduced while labeling of glia was much less affected. (2) The accumulation of 3H-dopamine was also decreased by kainic acid in two of the three labeled bands of the inner plexiform layer. The outermost labeled band was insensitive to kainic acid at the highest concentration tested (10(-2) M). These findings provide a basis for the subclassification of dopaminergic amacrine cells into at least two subclasses based on their sensitivity to kainic acid. (3) Kainic acid caused a dramatic increase in the labeling of GABAergic amacrine cell bodies and their terminals. This increased intensity may reflect a compensatory increase in uptake activity in response to kainic acid-induced depletion of endogenous GABA stores. These results confirm the highly toxic nature of kainic acid and demonstrate a high degree of specificity and complexity in its action in the retina.

  5. 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.

  6. Localization of [3H]nicotine, [3H]cytisine, [3H]epibatidine, and [125I]alpha-bungarotoxin binding sites in the brain of Macaca mulatta.

    PubMed

    Han, Zhi-Yan; Zoli, Michele; Cardona, Ana; Bourgeois, Jean-Pierre; Changeux, Jean-Pierre; Le Novère, Nicolas

    2003-06-16

    We determined the localization of [(3)H]nicotine, [(3)H]cytisine, [(3)H]epibatidine, and [(125)I]alpha-bungarotoxin binding sites in the brain of rhesus monkey by means of receptor autoradiography. The labelings by [(3)H]nicotine, [(3)H]cytisine, and [(3)H]epibatidine were highly concordant, except for epibatidine. Layer IV of some cortical areas, most thalamic nuclei, and presubiculum displayed high levels of labeling for the three ligands. Moderate levels of binding were detected in the subiculum, the septum, and the mesencephalon. Low levels were present in layers I-II and VI of the cortex, the cornu Ammonis, the dentate gyrus, and the amygdala. In addition, the level of epibatidine labeling was very high in the epithalamic nuclei and the interpeduncular nucleus, whereas labeling by nicotine and cytisine was very weak in the same regions. The distribution of [(125)I]alpha-bungarotoxin binding differed from the binding of the three agonists. The labeling was dense in layer I of most cortical areas, dentate gyrus, stratum lacunosum-moleculare of CA1 field, several thalamic nuclei, and medial habenula. A moderate labeling was found in layers V and VI of the prefrontal and frontal cortices, layer IV of primary visual cortex, amygdala, septum, hypothalamus, and some mesencenphalic nuclei. A weak signal was also detected in subiculum, claustrum, stratum oriens, and stratum lucidum of cornu Ammonis and also in some mesencephalic nuclei. The distribution of nicotine, cytisine, and epibatidine bindings corresponds broadly to the patterns observed in rodents, with the marked exception of the epithalamus. However, in monkey, those distributions match the distribution of alpha2 messenger RNA, rather than that of alpha4 transcripts as it exists in rodent brains. The distribution of the binding sites for alpha-bungarotoxin is larger in the brain of rhesus monkeys than in rodent brain, suggesting a more important role of alpha7 receptors in primates.

  7. Thz Spectroscopy of D_2H^+

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Pearson, John; Amano, Takayoshi

    2015-06-01

    Pure rotational transitions of D_2H^+ observed by high-resolution spectroscopy have been limited so far to the J = 110-101 transition at 691.7 GHz, J=220-211 at 1.370 THz, and J=111-000 at 1.477 THz. As this ion is a light asymmetric-top molecule, spectroscopic characterization and prediction of other rotational transition frequencies are not straightforward. In this presentation, we extended the measurements up to 2 THz by using the JPL frequency multiplier chains, and observed three new THz lines and re-measured the three known transitions. D_2H^+ was generated in an extended negative glow discharge cell cooled to liquid nitrogen temperature. Six rotational transition frequencies together with the combination differences derived from 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. T. Hirao and T. Amano, Ap. J.,597, L85 (2003) K. M. Evenson et al cited by O. L. Polyansky and A. R. W. McKellar, J. Chem. Phys., 92, 4039 (1990) O. Asvany et al, Phys. Rev. Lett., 100, 233004 (2008)

  8. Characteristics of [3H]sultopride binding to rat brain.

    PubMed

    Mizuchi, A; Kitagawa, N; Saruta, S; Miyachi, Y

    1982-10-15

    The binding of [3H]sultopride, a benzamide drug, to rat brain was investigated in vitro. Specific [3H]sultopride binding was observed in dopaminergic regions: striatum, nucleus accumbens, olfactory tubercle, substantia nigra, frontal cortex and anterior pituitary. Specific [3H]sultopride binding to striatum was saturable and had one high affinity binding site with a KD of 5.8 nM and a total density of receptors 25.7 pmol/g. [3H]Sultopride binding was stereoselectively displaced by (-)- and (+)-sultopride. Inhibition studies indicated that all neuroleptic drugs and dopamine were capable of displacing sultopride from its binding sites. A highly significant correlation was observed between IC50 values against [3H]sultopride and those against [3H]spiperone binding. Specific [3H]sultopride binding was highly dependent on the presence of sodium ions. The results suggest that the characteristics of sultopride binding sites seem to be similar to those of the D2-receptor labeled by spiperone and haloperidol. The sultopride binding site was highly dependent on the presence of sodium ions and may thus be characterized as a sodium-dependent D2-receptor.

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

    SciTech Connect

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

    1987-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  11. 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.

  12. Characterization of [3H]palmitate- and [3H]ethanolamine-labelled proteins in the multicellular parasitic trematode Schistosoma mansoni.

    PubMed Central

    Wiest, P M; Tisdale, E J; Roberts, W L; Rosenberry, T L; Mahmoud, A A; Tartakoff, A M

    1988-01-01

    Biosynthetic labelling experiments with cercariae and schistosomula of the multicellular parasitic trematode Schistosoma mansoni were performed to determine whether [3H]palmitate or [3H]ethanolamine was incorporated into proteins. Parasites incorporated [3H]palmitate into numerous proteins, as judged by SDS/polyacrylamide-gel electrophoresis and fluorography. The radiolabel was resistant to extraction with chloroform, but sensitive to alkaline hydrolysis, indicating the presence of an ester bond. Further investigation of the major 22 kDa [3H]palmitate-labelled species showed that the label could be recovered in a Pronase fragment which bound detergent and had an apparent molecular mass of 1200 Da as determined by gel filtration on Sephadex LH-20. Schistosomula incubated with [3H]ethanolamine for up to 24 h incorporated this precursor into several proteins; labelled Pronase fragments recovered from the three most intensely labelled proteins were hydrophilic and had a molecular mass of approx. 200 Da. Furthermore, reductive methylation of such fragments showed that the [3H]ethanolamine bears a free amino group, indicating the lack of an amide linkage. We also evaluated the effect of phosphatidylinositol-specific phospholipase C from Staphylococcus aureus: [3H]palmitate-labelled proteins of schistosomula and surface-iodinated proteins were resistant to hydrolysis with this enzyme. In conclusion, [3H]palmitate and [3H]ethanolamine are incorporated into distinct proteins of cercariae and schistosomula which do not bear glycophospholipid anchors. The [3H]ethanolamine-labelled proteins represent a novel variety of protein modification. Images Fig. 1. Fig. 3. Fig. 5. PMID:3178767

  13. East China Sea δ18O Record Detects Millennial-Scale Changes in the East Asian Summer Monsoon

    NASA Astrophysics Data System (ADS)

    Gleeman, E.; Clemens, S. C.; Lawman, A. E.; Kubota, Y.; Holbourn, A. E.; Martin, A.

    2015-12-01

    The East Asian Summer Monsoon (EASM) brings heavy summer rainfall to some of Asia's most densely-populated areas, impacting agricultural production and water resources. Sediment cores were recovered from International Ocean Drilling Program Site U1429 in the East China Sea (31° 37.04' N, 128° 59.50' E, 732 mbsl). This location receives runoff from the Yangtze River, which serves as a major drainage system for monsoon-induced precipitation. Hence, the δ18O record of planktonic foraminifera at Site U1429 reflects changes in regional, monsoon-driven salinity. The top 100 meters of core at Site U1429 were sampled at a preliminary resolution of 15 cm and processed to isolate the planktonic foraminifer Globigerinoides ruber for δ18O mass spectrometry analyses. Abrupt, millennial-scale regional climate variability in the EASM and its linkage to orbital forcings have been reconstructed using stratigraphic analysis of δ18O. The sub-orbital scale structure of the δ18O record over the past 400 kyr matches the structures of both the composite speleothem δ18O from eastern China (Sanbao and Hulu caves) and the planktonic δ18O record from northern South China Sea Site 1146. The similarities between these δ18O records indicate a strong regional response to monsoon forcing. Removal of the temperature component of the δ18O signal by using Mg/Ca (G. ruber) paleothermometry will provide a record of changes in the δ18O composition of seawater in response to Yangtze River runoff.

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

    NASA Astrophysics Data System (ADS)

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

    2008-06-01

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

  15. Crossed-beam radical-radical reaction dynamics of O(3P)+C3H3-->H(2S)+C3H2O

    NASA Astrophysics Data System (ADS)

    Kwon, Lee-Kyoung; Nam, Mi-Ja; Youn, Sung-Eui; Joo, Sun-Kyu; Lee, Hohjai; Choi, Jong-Ho

    2006-05-01

    The radical-radical oxidation reaction, O(P3)+C3H3(propargyl)→H(S2)+C3H2O (propynal), was investigated using vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed-beam configuration, together with ab initio and statistical calculations. The barrierless addition of O(P3) to C3H3 is calculated to form energy-rich addition complexes on the lowest doublet potential energy surface, which subsequently undergo direct decomposition steps leading to the major reaction products, H +C3H2O (propynal). According to the nascent H-atom Doppler-profile analysis, the average translational energy of the products and the fraction of the average transitional energy to the total available energy were determined to be 5.09±0.36kcal/mol and 0.077, respectively. On the basis of a comparison with statistical prior calculations, the reaction mechanism and the significant internal excitation of the polyatomic propynal product can be rationalized in terms of the formation of highly activated, short-lived addition-complex intermediates and the adiabaticity of the excess available energy along the reaction coordinate.

  16. An Observational Investigation of the Identity of B11244 (l-C3H+/C3H-)

    NASA Astrophysics Data System (ADS)

    McGuire, Brett A.; Carroll, P. Brandon; Gratier, Pierre; Guzmán, Viviana; Pety, Jerome; Roueff, Evelyne; Gerin, Maryvonne; Blake, Geoffrey A.; Remijan, Anthony J.

    2014-03-01

    Pety et al. have reported the detection of eight transitions of a closed-shell, linear molecule (B11244) in observations toward the Horsehead photodissociation region (PDR), which they attribute to the l-C3H+ cation. Recent high-level ab initio calculations have called this assignment into question; the anionic C3H- molecule has been suggested as a more likely candidate. Here, we examine observations of the Horsehead PDR, Sgr B2(N), TMC-1, and IRC+10216 in the context of both l-C3H+ and C3H-. We find no observational evidence of Ka = 1 lines, which should be present were the carrier indeed C3H-. Additionally, we find a strong anticorrelation between the presence of known molecular anions and B11244 in these regions. Finally, we discuss the formation and destruction chemistry of C3H- in the context of the physical conditions in the regions. Based on these results, we conclude there is little evidence to support the claim that the carrier is C3H-.

  17. (/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.

  18. Autoradiographic localization of (3H) gepirone in the rat brain

    SciTech Connect

    Bennett, J.E.; Matheson, G.K. )

    1990-02-26

    Gepirone is an anxiolytic compound active at the 5-HT{sub 1A} receptor site. The purpose of this study was to locate the ({sup 3}H)gepirone in the rat brain and to determine the quantity of gepirone in these locations. Male Sprague-Dawley rats were injected with (3H)gepirone (200 {mu}Ci/kg, i.v.) and decapitated 10 minutes later. To determine specific binding some animals were pretreated with cold gepirone (1 mg/kg) 15 minutes before the (3H)gepirone treatment. The brains were removed, frozen, sectioned, and fixed in formaldehyde vapors. Tritium sensitive film was exposed to the sections for 106 days. Using computerized imaging technology data were obtained from 104 brain sites. Overall, the quantity of (3H)gepirone in each site correlated proportionally with known 5-HT{sub 1A} (in vitro) receptor binding.

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

    SciTech Connect

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

    1989-10-01

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

  20. 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

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

  2. 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

  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

  4. (/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.

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

    PubMed Central

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

    1980-01-01

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

  6. 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.

  7. Application of a quantum cascade laser for time-resolved, in situ probing of CH4/H2 and C2H2/H2 gas mixtures during microwave plasma enhanced chemical vapor deposition of diamond.

    PubMed

    Cheesman, A; Smith, J A; Ashfold, M N R; Langford, N; Wright, S; Duxbury, G

    2006-03-01

    First illustrations of the utility of pulsed quantum cascade lasers for in situ probing of the chemistry prevailing in microwave plasma activated hydrocarbon/Ar/H2 gas mixtures used for diamond thin film growth are reported. CH4 and C2H2 molecules, and their interconversion, have been monitored by line-of-sight single pass absorption methods, as a function of process conditions (e.g., choice of input hydrocarbon (CH4 or C2H2), hydrocarbon mole fraction, total gas pressure, and applied microwave power). The observed trends can be rationalized, qualitatively, within the framework of the previously reported modeling of the gas-phase chemistry prevailing in hot filament activated hydrocarbon/H2 gas mixtures (Ashfold et al. Phys. Chem. Chem. Phys. 2001, 3, 3471). Column densities of vibrationally excited C2H2(v5=1) molecules at low input carbon fractions are shown to be far higher than expected on the basis of local thermodynamic equilibrium. The presence of vibrationally excited C2H2 molecules (C2H2(double dagger)) can be attributed to the exothermicity of the C2H3 + H <==> C2H2 + H2 elementary reaction within the overall multistep CH4 --> C2H2 conversion. Diagnostic methods that sample just C2H2(v=0) molecules thus run the risk of underestimating total C2H2 column densities in hydrocarbon/H2 mixtures operated under conditions where the production rate of C2H2(double dagger) molecules exceeds their vibrational relaxation (and thermal equilibration) rates.

  8. Binding of [3H]palmitate to BSA.

    PubMed

    Elmadhoun, B M; Wang, G Q; Templeton, J F; Burczynski, F J

    1998-10-01

    Determination of the BSA-palmitate high-affinity binding constant (Ka) traditionally relied on the heptane-water partitioning technique. We used this technique to calculate Ka for the BSA-[3H]palmitate complex, to determine if Ka was independent of protein concentration, and to determine if the unbound [3H]palmitate concentration is constant at different BSA concentrations using constant BSA-to-palmitate molar ratios (range 1:1 to 1:4). After extensive extraction of non-[3H]palmitate radiolabeled substances, the heptane-to-buffer partition ratio, in the absence of BSA, was 702 +/- 19 (mean +/- SD, n = 6). This value was much lower than the predicted value of 1,376 and was highly dependent on which phase (organic or aqueous) initially contained the [3H]palmitic acid. The data were consistent with the notion of self-association of [3H]palmitate in the aqueous phase. Ka for the BSA-[3H]palmitate complex was determined to be similar (2.2 +/- 0.1) x 10(8) M-1 (mean +/- SD, P > 0.05) at all BSA concentrations studied. At each BSA-to-palmitate molar ratio, the equilibrium unbound ligand concentration was constant only at low BSA concentrations (<10 microM) and at low BSA-to-palmitate molar ratios (i.e., 1:1 and 1:2). At higher BSA concentrations and molar ratios, the unbound ligand concentration increased with an increase in protein concentration. Hepatocyte uptake using the manufacturer-supplied radiolabeled product was significantly higher than with the purified product, suggesting that a non-[3H]palmitate radiolabel is also a substrate for the uptake process.

  9. Spatial variability of δ18O-PO4 in soils.

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  10. Impacts of Tibetan Plateau uplift on atmospheric dynamics and associated precipitation δ18O

    NASA Astrophysics Data System (ADS)

    Botsyun, Svetlana; Sepulchre, Pierre; Risi, Camille; Donnadieu, Yannick

    2016-06-01

    Palaeoelevation reconstructions of mountain belts have become a focus of modern science since surface elevation provides crucial information for understanding both geodynamic mechanisms of Earth's interior and the influence of mountain growth on climate. Stable oxygen isotopes palaeoaltimetry is one of the most popular techniques nowadays, and relies on the difference between δ18O of palaeo-precipitation reconstructed using the natural archives, and modern measured values for the point of interest. Our goal is to understand where and how complex climatic changes linked with the growth of mountains affect δ18O in precipitation. For this purpose, we develop a theoretical expression for the precipitation composition based on the Rayleigh distillation and the isotope-equipped atmospheric general circulation model LMDZ-iso outputs. Experiments with reduced height over the Tibetan Plateau and the Himalayas have been designed. Our results show that the isotopic composition of precipitation is very sensitive to climate changes related to the growth of the Himalayas and Tibetan Plateau. Specifically our simulations suggest that only 40 % of sampled sites for palaeoaltimetry depict a full topographic signal, and that uplift-related changes in relative humidity (northern region) and precipitation amount (southern region) could explain absolute deviations of up to 2.5 ‰ of the isotopic signal, thereby creating biases in palaeoelevation reconstructions.

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

    SciTech Connect

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

    1980-01-30

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

  12. Millennial-scale features in ?18O from a stalagmite in the eastern United States

    NASA Astrophysics Data System (ADS)

    Hardt, B. F.; Doctor, D. H.; Gao, Y.; Rowe, H. D.; Cheng, H.; Edwards, R.

    2013-12-01

    The oxygen isotope record of calcite from a stalagmite collected from Grand Caverns in Virginia, USA shows evidence of millennial-scale variability that appears to be coherent with Dansgaard/Oeschger events observed in Greenland ice. Sample GC-S02 grew from 82 - 13 ka BP and ranges in δ18O composition from -8 to -4 ‰ (VPDB) with multiple instances of millennial-scale changes in excess of 1‰. As δ18O in GC-S02 is more positive during MIS 2 than MIS 3, change in mean annual temperature is not a likely explanation for the observed variability. The carbon and oxygen isotopic records of calcite are independent and show no evidence of covaration (r = -0.1). Changes in the seasonal timing of precipitation provides an alternate explanation for the data, particularly given the potential for warm- and cool-season precipitation to come from different sources (Gulf of Mexico versus the Atlantic ocean). Grand Caverns is located in the Shenandoah River watershed within the Appalachian Great Valley, suggesting a meaningful role for Atlantic moisture. The age model is based on high-precision U-Th ages, making this record a potential benchmark for the region.

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

    NASA Astrophysics Data System (ADS)

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

    1996-10-01

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

  14. 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.

  15. 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.

  16. 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.

  17. 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

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

    PubMed

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

    2013-10-01

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

  19. 18O depletion in monsoon rain relates to large scale organized convection rather than the amount of rainfall

    PubMed Central

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

    2014-01-01

    Oxygen isotopic variations in rainfall proxies such as tree rings and cave calcites from South and East Asia have been used to reconstruct past monsoon variability, mainly through the amount effect: the observed 18O depletion of rain with increasing amount, manifested as a negative correlation of the monthly amount of tropical rain with its δ18O, both measured at the same station. This relation exhibits a significant spatial variability, and at some sites (especially North-East and peninsular India), the rainfall proxies are not interpretable by this effect. We show here that relatively higher 18O-depletion in monsoon rain is not related necessarily to its amount, but rather, to large scale organized convection. Presenting δ18O analyses of ~654 samples of daily rain collected during summer 2012 across 9 stations in Kerala, southern India, we demonstrate that although the cross correlations between the amounts of rainfall in different stations is insignificant, the δ18O values of rain exhibit highly coherent variations (significant at P = 0.05). Significantly more 18O-depletion in the rain is caused by clouds only during events with a large spatial extent of clouds observable over in the south eastern Arabian Sea. PMID:25012535

  20. Thermal Decomposition of 2(3H) and 2(5H) Furanones: Theoretical Aspects.

    PubMed

    Würmel, Judith; Simmie, John M; Losty, Michelle M; McKenna, Cathal D

    2015-07-01

    The thermal decomposition reactions of 2(3H) and 2(5H) furanones and their methyl derivatives are explored. Theoretical calculations of the barriers, reaction enthalpies, and the properties of these and intermediate species are reported using the composite model chemistry CBS-QB3 and also the functional M06-2X allied to the 6-311++G(d,p) basis set. Thus, the bond dissociation enthalpies, ionization energies, and unimolecular chemical kinetic rate constants in the high-pressure limit were computed. We show that flow reactor experiments that intimated that heating the 2(3H) furanone converts it to the isomeric 2(5H) furanone occurs via a 1 → 2 H-transfer reaction to an open ring ketenoic aldehyde. The latter can then ring close to the other isomeric structure. The final products acrolein and carbon monoxide are only formed from 2(3H), and acrolein will further decompose to ethylene and CO. Comparable channels explain the interconversion of 5-methyl-2(3H) furanone to its 2(5H) isomer and to the formation of methyl vinyl ketone and CO. The influence of the methyl group at other positions on the ring is hardly of significance except in the case of 5-methyl-2(5H) furanone where a hydrogen atom transfer from the methyl group leads to the formation of a doubly unsaturated carboxylic compound, 2,4-pentadienoic acid. Studies of the UV photolysis of the parent compounds in both low-temperature inert argon matrices and in solution are broadly in accord with the thermal findings insofar as product formation is concerned and with our theoretical calculations. The dominant features of the early decomposition chemistry of these compounds are simple hydrogen transfer and simultaneous ring opening reactions, which do however result in some quite unusual species.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    Although the instrumental coupling of gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) for compound-specific δ18O analyses is commercially available for more than 10 years, this method is hardly applied by isotope researchers so far. Using GC-Py-IRMS, Zech and Glaser (2009) and Zech et al. (2013; 2012) developed and applied a method, which allows determining δ18O of hemicellulose-derived sugar biomarkers extracted from soils and sediments. However, the used methylboronic acid (MBA) derivatization is suitable only for pentoses and deoxyhexoses, not for hexoses. Here we present first GC-Py-IRMS results for TMS-(trimethylsilyl)-derivatives of plant sap-relevant sugars (glucose, fucose, sucrose, raffinose) and a polyalkohol (pinitol) produced using BSTFA (N,O-Bis(trimethylsilyl)trifluoroacetamide) as the derivatization reagent. Particularly, we focus on sucrose, which is the most important transport sugar in plants and hence of utmost relevance in plant physiology and in tree-ring studies. Replicate analyses of sucrose standards with known δ18O values suggest that the δ18O measurements are not stable over several days. A calibration (including a drift correction) against an external sucrose standard is hence essential when measuring sample batches. Furthermore, we observed a large dependence of the δ18O values on the analyte amount (area), which needs to be considered by a respective correction procedure. Tests with 18O-enriched water do not provide any evidence for oxygen exchange reactions between water and sucrose, glucose and raffinose. Finally we present the first application of compound-specific δ18O analyses from natural samples, namely from seven needle extracts (soluble carbohydrates) from a Siberian study area. Both the δ18O amplitude and values of sucrose are considerably higher (32.1‰ to 40.1‰) compared to the δ18O amplitude and values of bulk needle extract (24.6‰ to 27.2‰). We found positive correlation (although

  3. 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

  4. Variation of δ18O and δD in precipitation and stream waters across the Kashmir Himalaya (India) to distinguish and estimate the seasonal sources of stream flow

    NASA Astrophysics Data System (ADS)

    Jeelani, Gh.; Saravana Kumar, U.; Kumar, Bhishm

    2013-02-01

    SummaryThe spatial and temporal distribution of δ18O and δD measurements of precipitation and stream waters were used to distinguish various sources and components of stream flow and to estimate their residence times in snow dominated mountainous catchments of Kashmir Himalaya. A marked spatial and seasonal variability of stable isotopes of oxygen and hydrogen was observed in precipitation with δ18O and δD varied from -12.98‰ to -0.58‰ and -74.5‰ to -11.1‰, respectively during the period from November 2007 to January 2009. The seasonal changes in stable isotopes of precipitation with depleted and enriched 18O and 2H in January/March/May and July/September/November, respectively at each site are attributed to the seasonal changes in ambient temperature, precipitation, source of moisture and airmass trajectory. The mean altitude effect of -0.23‰ and -1.2‰ per 100 m change in elevation for δ18O and δD, respectively, was observed based on amount weighted mean precipitation isotopic composition data. Unlike precipitation, less variability of stable isotopes of streams was found with δ18O and δD ranging from -11.56‰ to -6.26‰ and -65.4‰ to -36.4‰, respectively, the depleted values being observed in the headwaters of the streams/tributaries and enriched values at lower elevations of the watersheds. The LMWL established for the Kashmir Himalayas, based on amount weighted monthly samples is δD = 7.59 (± 0.32) × δ18O + 11.79 (± 2.07) (r2 = 0.96) with lower slope and intercept than GMWL, is very close to the LMWL for the western Himalayas. The seasonal regression lines suggest the effect of evaporation with lower slopes and intercepts except in winter. The results suggest that the winter precipitation (snow) dominantly contributes the annual stream flow with average snowmelt contribution of about 29% in early spring, 66% in late spring, 61% in summer while the baseflow contribution is found in the order of 40% in autumn season. The mean stream

  5. 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.

  6. 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

  7. A calibration of the triple oxygen isotope fractionation in the SiO2-H2O system and applications to natural samples

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Gibbons, J. A.; Maltsev, O.; Atudorei, V.; Pack, A.; Sengupta, S.; Shock, E. L.; Knauth, L. P.

    2016-08-01

    It is now recognized that variations in the Δ17O of terrestrial materials resulting from purely mass dependent fractionations, though small, have geological significance. In this study, the δ18O and δ17O values of selected low temperature quartz and silica samples were measured in order to derive the quartz-water fractionation-temperature relationship for the three oxygen isotope system. A 18O/16O quartz-water fractionation equation valid for all temperatures was generated from published high temperature exchange experiments and low temperature empirical estimates and is given by 1000ln αqz-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.

  8. A calibration of the triple oxygen isotope fractionation in the SiO2-H2O system and applications to natural samples

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Gibbons, J. A.; Maltsev, O.; Atudorei, V.; Pack, A.; Sengupta, S.; Shock, E. L.; Knauth, L. P.

    2016-08-01

    It is now recognized that variations in the Δ17O of terrestrial materials resulting from purely mass dependent fractionations, though small, have geological significance. In this study, the δ18O and δ17O values of selected low temperature quartz and silica samples were measured in order to derive the quartz-water fractionation-temperature relationship for the three oxygen isotope system. A 18O/16O quartz-water fractionation equation valid for all temperatures was generated from published high temperature exchange experiments and low temperature empirical estimates and is given by 1000ln αqz-H2O18O /16O = 4.20 (0.11) ×106/T2 - 3.3 (0.2) × 1000/T (T in Kelvins). The equilibrium δ17O-δ18O relationship is given by the equation lnα17O/16O = θlnα18O/16O . The variation of θ with temperature for the quartz-water system was determined empirically using low temperature marine diatoms, microcrystalline quartz and a modern sinter sample. A best fit to the data give the equation θSiO2 - H2O = -(1.85 ± 0.04)/T + 0.5305 , indistinguishable from an earlier theoretical estimate. Application of the quartz-water triple isotope system to low temperature samples provides constraints on both temperature and composition of the water with which the silica last equilibrated. Authigenic quartz crystallization temperatures cluster around 50 °C, which are lower than many previous estimates. The combined δ18O and δ17O values of samples considered to be in equilibrium with ocean or meteoric waters can be used to estimate both formation temperatures and the δ18O value of the meteoric water. Unlike other multiple isotopes systems, such as combined H and O isotopes in cherts, the oxygen source and diagenetic potential for both 17O/16O and 18O/16O ratios are identical, simplifying interpretations from ancient samples.

  9. Tracking Cats: Problems with Placing Feline Carnivores on δ18O, δD Isoscapes

    PubMed Central

    Pietsch, Stephanie J.; Hobson, Keith A.; Wassenaar, Leonard I.; Tütken, Thomas

    2011-01-01

    Background Several felids are endangered and threatened by the illegal wildlife trade. Establishing geographic origin of tissues of endangered species is thus crucial for wildlife crime investigations and effective conservation strategies. As shown in other species, stable isotope analysis of hydrogen and oxygen in hair (δDh, δ18Oh) can be used as a tool for provenance determination. However, reliably predicting the spatial distribution of δDh and δ18Oh requires confirmation from animal tissues of known origin and a detailed understanding of the isotopic routing of dietary nutrients into felid hair. Methodology/Findings We used coupled δDh and δ18Oh measurements from the North American bobcat (Lynx rufus) and puma (Puma concolor) with precipitation-based assignment isoscapes to test the feasibility of isotopic geo-location of felidae. Hairs of felid and rabbit museum specimens from 75 sites across the United States and Canada were analyzed. Bobcat and puma lacked a significant correlation between H/O isotopes in hair and local waters, and also exhibited an isotopic decoupling of δ18Oh and δDh. Conversely, strong δD and δ18O coupling was found for key prey, eastern cottontail rabbit (Sylvilagus floridanus; hair) and white-tailed deer (Odocoileus virginianus; collagen, bone phosphate). Conclusions/Significance Puma and bobcat hairs do not adhere to expected pattern of H and O isotopic variation predicted by precipitation isoscapes for North America. Thus, using bulk hair, felids cannot be placed on δ18O and δD isoscapes for use in forensic investigations. The effective application of isotopes to trace the provenance of feline carnivores is likely compromised by major controls of their diet, physiology and metabolism on hair δ18O and δD related to body water budgets. Controlled feeding experiments, combined with single amino acid isotope analysis of diets and hair, are needed to reveal mechanisms and physiological traits explaining why felid hair does

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

    PubMed Central

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

    2015-01-01

    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. These interactions are also crucial for the inhibition of spurious transcription from within coding regions. 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. PMID:26109053

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

    PubMed

    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. These interactions are also crucial for the inhibition of spurious transcription from within coding regions. 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.

  12. a Computational Investigation of c-C3H2...HX(X = F, Cl, Br) H-Bonded Complexes

    NASA Astrophysics Data System (ADS)

    Varadwaj, Pradeep R.; Varadwaj, Arpita; Peslherbe, Gilles H.

    2011-06-01

    Cyclopropenylidene (c-C3H2) is of significant importance in interstellar chemistry and synthetic chemistry (e.g., transition metal and organic catalysis). Because of its peculiar structure, c-C3H2 can act as a hydrogen-bond donor or acceptor. In order to gain insight into this feature, the ground-state potential energy surfaces of singlet c-C3H2 complexed with hydrogen halides HX (X = F, Cl, Br) have been explored extensively by density-functional theory (B3LYP) and {ab initio} quantum chemistry (MP2) with a variety of basis sets, cc-pVxZ and aug-cc-pVxZ (x = D, T). The complexes characterized have the carbenic end of c-C3H2 H-bonded to HX, with some proton transfer occurring, the extent of which follows the order HF < HCl < HBr. Accompanying the complex formation are the dipole moment enhancement, the charge transfer, red shifts of the HX vibrational stretching frequencies together with the significant enhancement of band intensity and concomitant HX bond elongation. The nature of H-bonding in these complexes has been explored, based on energy decomposition schemes and the Bader's quantum theory of atoms-in-molecules, with the conclusion that c-C3H2 is a strong H-bond acceptor with respect to the hydrogen halides.

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

    PubMed

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

    2011-12-01

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

  14. 18O-Labeled Proteome Reference as Global Internal Standards for Targeted Quantification by Selected Reaction Monitoring-Mass Spectrometry

    SciTech Connect

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

    2011-10-11

    Selected reaction monitoring-mass spectrometry (SRM-MS) is an emerging technology for high throughput targeted protein quantification and verification in biological and biomarker discovery studies; however, the cost associated with the use of stable isotope labeled synthetic peptides as internal standards is prohibitive for quantitatively screening large numbers of candidate proteins as often required in the pre-verification phase of biomarker discovery. Herein we present the proof-of-concept experiments of using an 18O-labeled 'universal' reference as comprehensive internal standards for quantitative SRM-MS analysis. With an 18O-labeled whole proteome sample as reference, every peptide of interest will have its own corresponding heavy isotope labeled internal standard, thus providing an ideal approach for quantitative screening of a large number of candidates using SRM-MS. Our results showed that the 18O incorporation efficiency using a recently improved protocol was >99.5% for most peptides investigated, a level comparable to 13C/15N labeled synthetic peptides in terms of heavy isotope incorporation. The accuracy, reproducibility, and linear dynamic range of quantification were further assessed based on known ratios of standard proteins spiked into mouse plasma with an 18O-labeled mouse plasma reference. A dynamic range of four orders of magnitude in relative concentration was obtained with high reproducibility (i.e., coefficient of variance <10%) based on the 16O/18O peak area ratios. Absolute and relative quantification of C-reactive protein and prostate-specific antigen were demonstrated by coupling an 18O-labeled reference with standard additions of protein standards. Collectively, our results demonstrated that the use of 18O-labeled reference provides a convenient and effective strategy for quantitative SRM screening of large number of candidate proteins.

  15. LED-based Fourier transform spectroscopy of 16O12C18O and 12C18O2 in the 11,260-11,430 cm-1 range

    NASA Astrophysics Data System (ADS)

    Serdyukov, V. I.; Sinitsa, L. N.; Lugovskoi, A. A.; Borkov, Yu. G.; Tashkun, S. A.; Perevalov, V. I.

    2016-07-01

    The absorption spectrum of the 16O12C18O and 12C18O2 carbon dioxide isotopologues has been recorded in the 11,260- 11,430 cm-1 spectral range using Bruker IFS 125 HR Fourier transform spectrometer with resolution 0.05 cm-1 at temperature 297 K and path length 24 m. The 18O enriched sample of carbon dioxide at total pressure 96.5 mbar was used for these purposes. The spectrometer used LED emitter as a light source. This gave possibility to reach the minimal detectable absorption coefficient αmin~1.4×10-7 cm-1 using 23,328 scans. In the recorded spectrum we have assigned the 00051-00001 band for both 16O12C18O and 12C18O2 isotopologues using the predictions performed within the framework of the method of effective operators. The line positions and intensities of the observed bands are found. The comparison of the observed and predicted line positions and intensities is performed confirming good accuracy of the predictions. The spectroscopic parameters for the observed bands are determined.

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

    PubMed

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

    2006-01-27

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

  17. Two-neutron stripping in ({sup 18}O, {sup 16}O) and (t,p) reactions

    SciTech Connect

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

    2014-11-11

    The {sup 12}C({sup 18}O,{sup 16}O){sup 14}C reactions has been investigated at 84 MeV incident energy. The charged ejectiles produced in the reaction have been momentum analyzed and identified by the MAGNEX magnetic spectrometer. Q-value spectra have been extracted with an energy resolution of 160 keV (Full Width at Half Maximum) and several known bound and resonant states of {sup 14}C have been identified up to 15 MeV. In particular, excited states with dominant 2p - 4h configuration are the most populated. The absolute values of the cross sections have been extracted showing a striking similarity with those measured for the same transitions by (t,p) reactions. This indicates that the effect of the {sup 16}O core is negligible in the reaction mechanism.

  18. 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.; Bacher, A. D.; Hale, G. M.; Paris, M. W.

    2015-07-20

    An R-matrix model for three-body final states is presented and applied to a recent measurement of the neutron energy spectrum from the 3H + 3H→ 2n + α reaction. The calculation includes the n alpha and n n interactions in the final state, angular momentum conservation, antisymmetrization, and the interference between different channels. A good fit to the measured spectrum is obtained, where clear evidence for the 5He ground state is observed. The model is also used to predict the alpha-particle spectrum from 3H + 3H as well as particle spectra from 3He + 3He. The R-matrix approach presented heremore » is very general, and can be adapted to a wide variety of problems with three-body final states.« less

  19. Thermal Dehydrogenation of Base-Stabilized B2H5(+) Complexes and Its Role in C-H Borylation.

    PubMed

    Prokofjevs, Aleksandrs

    2015-11-01

    Thermally induced dehydrogenation of the H-bridged cation L2B2H5(+) (L=Lewis base) is proposed to be the key step in the intramolecular C-H borylation of tertiary amine boranes activated with catalytic amounts of strong "hydridophiles". Loss of H2 from L2B2H5(+) generates the highly reactive cation L2B2H3(+), which in its sp(2)-sp(3) diborane(4) form then undergoes either an intramolecular C-H insertion with B-B bond cleavage, or captures BH3 to produce L2B3H6(+). The effect of the counterion stability on the outcome of the reaction is illustrated by formation of LBH2C6F5 complexes through disproportionation of L2B2H5(+) HB(C6F5)3(-) . PMID:26377358

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

    USGS Publications Warehouse

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

    2004-01-01

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

  1. Historical droughts in northern Vietnam captured by variability in speleothem δ18O

    NASA Astrophysics Data System (ADS)

    Hardt, B. F.; McGee, D.; Burns, S. J.; Hieu, N.; Hieu, D. T.

    2015-12-01

    Speleothem records overlapping with the historical period offer valuable comparisons of documentary evidence with speleothem proxy data. These records provide opportunities to 'ground-truth' the paleo-record, fill in gaps in the historical record, and more confidently extent the paleo-record into deeper time. Here we present isotopic results from a stalagmite collected in northern Vietnam spanning 1200 to 1950 CE, a period with a rich historical record in Vietnam. This sample adds significantly to the relatively sparse paleoclimate record from Southeast Asia. The record includes several multi-decadal positive excursions of ≥1 per mille in calcite δ18O. A preliminary age model, based on six U/Th ages, suggests possible correspondence to noted droughts from the historical record, including the Angkor Droughts, the Ming Dynasty Drought, the Strange Parallels Drought, and the Victorian Holocaust Drought. As modeling studies indicate a strong correlation between rainfall δ18O and both the intensity of summer monsoon winds and summer rainfall over northern Vietnam (e.g., Liu et al., 2014), these excursions are consistent with a decrease in regional precipitation. The Vietnam record shows an overall negative trend during the Little Ice Age. The study site is located well south of the westerly wind belt, ruling out a shift between monsoonal and mid-latitude circulation systems as a likely explanation for the northern Vietnam record. We explore the correspondence between our record and other proxy data from Southeast Asia and suggest possible implications of the differences between Vietnamese and Chinese speleothem records during the Little Ice Age. References cited: Liu Z., Wen X., Brady E. C., Otto-Bliesner B., Yu G., Lu H., Cheng H., Wang Y., Zheng W., Ding Y., Edwards R. L., Cheng J., Liu W. and Yang H. (2014) Chinese cave records and the East Asia Summer Monsoon. Quaternary Science Reviews 83, 115-128.

  2. Body temperatures of modern and extinct vertebrates from 13C-18O bond abundances in bioapatite

    PubMed Central

    Eagle, Robert A.; Schauble, Edwin A.; Tripati, Aradhna K.; Tütken, Thomas; Hulbert, Richard C.; Eiler, John M.

    2010-01-01

    The stable isotope compositions of biologically precipitated apatite in bone, teeth, and scales are widely used to obtain information on the diet, behavior, and physiology of extinct organisms and to reconstruct past climate. Here we report the application of a new type of geochemical measurement to bioapatite, a “clumped-isotope” paleothermometer, based on the thermodynamically driven preference for 13C and 18O to bond with each other within carbonate ions in the bioapatite crystal lattice. This effect is dependent on temperature but, unlike conventional stable isotope paleothermometers, is independent from the isotopic composition of water from which the mineral formed. We show that the abundance of 13C-18O bonds in the carbonate component of tooth bioapatite from modern specimens decreases with increasing body temperature of the animal, following a relationship between isotope “clumping” and temperature that is statistically indistinguishable from inorganic calcite. This result is in agreement with a theoretical model of isotopic ordering in carbonate ion groups in apatite and calcite. This thermometer constrains body temperatures of bioapatite-producing organisms with an accuracy of 1–2 °C. Analyses of fossilized tooth enamel of both Pleistocene and Miocene age yielded temperatures within error of those derived from similar modern taxa. Clumped-isotope analysis of bioapatite represents a new approach in the study of the thermophysiology of extinct species, allowing the first direct measurement of their body temperatures. It will also open new avenues in the study of paleoclimate, as the measurement of clumped isotopes in phosphorites and fossils has the potential to reconstruct environmental temperatures. PMID:20498092

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

    PubMed

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

    2006-12-27

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

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

    PubMed Central

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

    2009-01-01

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

  5. An explanation for the 18O excess in Noelaerhabdaceae coccolith calcite

    NASA Astrophysics Data System (ADS)

    Hermoso, M.; Minoletti, F.; Aloisi, G.; Bonifacie, M.; McClelland, H. L. O.; Labourdette, N.; Renforth, P.; Chaduteau, C.; Rickaby, R. E. M.

    2016-09-01

    Coccoliths have dominated the sedimentary archive in the pelagic environment since the Jurassic. The biominerals produced by the coccolithophores are ideally placed to infer sea surface temperatures from their oxygen isotopic composition, as calcification in this photosynthetic algal group only occurs in the sunlit surface waters. In the present study, we dissect the isotopic mechanisms contributing to the "vital effect", which overprints the oceanic temperatures recorded in coccolith calcite. Applying the passive diffusion model of carbon acquisition by the marine phytoplankton widely used in biogeochemical and palaeoceanographic studies, our results suggest that the oxygen isotope offsets from inorganic calcite in fast dividing species Emiliania huxleyi and Gephyrocapsa oceanica originates from the legacy of assimilated 18O-rich CO2 that induces transient isotopic disequilibrium to the internal dissolved inorganic carbon (DIC) pool. The extent to which this intracellular isotopic disequilibrium is recorded in coccolith calcite (1.5 to +3‰ over a 10 to 25 °C temperature range) is set by the degree of isotopic re-equilibration between CO2 and water molecules before intracellular mineralisation. We show that the extent of re-equilibration is, in turn, set by temperature through both physiological (dynamics of the utilisation of the DIC pool) and thermodynamic (completeness of the re-equilibration of the relative 18O-rich CO2 influx) processes. At the highest temperature, less ambient aqueous CO2 is present for algal growth, and the consequence of carbon limitation is exacerbation of the oxygen isotope vital effect, obliterating the temperature signal. This culture dataset further demonstrates that the vital effect is variable for a given species/morphotype, and depends on the intricate relationship between the environment and the physiology of biomineralising algae.

  6. (/sup 3/H)glucosamine and (/sup 3/H)proline radioautography of embryonic mouse dental basement membrane

    SciTech Connect

    Osman, M.; Ruch, J.V.

    1981-01-01

    (/sup 3/H)proline and (/sup 3/H)glucosamine radioautography was performed to analyze the labeling pattern of mouse embryonic dental basement membrane before and during odontoblast terminal differentiation. Sixteen- and eighteen-day-old first lower molars and trypsin-isolated enamel organs, as well as EDTA-isolated dental papillae, were used. Continuous labeling for 12 to 24 hr was required with (/sup 3/H)proline to obtain a clear labeling of epithelial-mesenchymal junction in intact tooth germs or accumulation of surface label in trypsin-isolated enamel organs. With (/sup 3/H)glucosamine, after 6-hr labeling, the epithelial-mesenchymal junction was heavily labeled and the trypsin-isolated enamel organs accumulated substantial amounts of surface label, corresponding to the redeposited basement membrane. At Day 16 stage, these labels always had a uniform distribution and decreased during chase without any redistribution. At Day 18 stage, when the terminal differentiation of odontoblasts occurred the label accumulated in a unique pattern: much more label was at the epithelial surface corresponding to the top of the cusps than in the apical parts. During chase and only in intact tooth germs epithelial surfaces which had labeled poorly during pulse became labeled, but those labeling heavily during pulse lost label. This pattern existed only in the presence of mesenchyme. EDTA treatment of (/sup 3/H)glucosamine-labeled teeth enabled us to obtain isolated dental papillae with surface label. Distribution of this label was exactly the same as that for the epithelial-mesenchymal junction of intact teeth. During chase, these dental papillae completely lost the surface label. The mesenchyme seen to control the synthesis and/or the degradation of epithelially derived (/sup 3/H)glucosamine-labeled material.

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  8. Specific [(3)H]tryptophan binding sites in rat brain.

    PubMed

    Wong, P T; Lee, H S; Tan, C H; Teo, W L

    1989-01-01

    [(3)H]Tryptophan binds to a single population of sites in the rat cortical synaptosomal membranes. The binding is reversible and follows the law of mass action. By saturation studies using increasing concentration of [(3)H]tryptophan with decreasing specific radioactivity, the apparent K(d) obtained was approx. 0.8 ?M and the B(max) 110 pmol/mg protein. However, the IC(50) obtained for unlabelled tryptophan in displacing [(3)H]tryptophan binding (3.5 nM) was 0.26 ?M. All six naturally occurring aromatic amino acids studied displaced [(3)H]tryptophan binding with tryptophan and phenylalanine showing higher apparent affinity than histidine, tyrosine, dihydroxyphenylalanine and 5-hydroxytryptophan. These binding sites are proteins in nature as they are sensitive to trypsin and ?-chymotrypsin. It is observed that about 37% of the sites seem to be protected from the proteolytic enzymes by the membrane structure. Furthermore, they are extremely sensitive to phospholipase A(2) presumably because altered membrane phospholipids conduce a conformational change in the binding protein. A considerable degree of stereospecificity was demonstrated with the affinity for l-tryptophan about 90 times higher than that for d-tryptophan. The affinity for l-phenylalanine was 8 times higher than that for d-phenylalanine. Ligand specificity for the aromatic amino acids is remarkable as hydrocinnamic acid, 2-phenylethylamine, 5-hydroxytryptamine, histamine, dopamine, ?-aminobutyric acid, glutamic acid and taurine did not displace [(3)H]tryptophan binding. Therefore, these sites are termed aromatic amino acid binding sites (AABS). Whether or not AABS are involved in neuromodulation at the synapse awaits clarification. If so, the endogenous ligand for the AABS may well be tryptophan.

  9. 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.

  10. 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).

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

    NASA Astrophysics Data System (ADS)

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

    1996-09-01

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

  12. Electrochemical zinc insertion into W{sub 18}O{sub 49}: Synthesis and characterization of new bronzes

    SciTech Connect

    Martinez-de la Cruz, A.; Amador, U.; Rodriguez-Carvajal, J.; Garcia-Alvarado, F. . E-mail: flaga@ceu.es

    2005-10-15

    Divalent zinc ions have been electrochemically inserted into W{sub 18}O{sub 49}, producing zinc bronzes. Under our experimental conditions, W{sub 18}O{sub 49} accepts zinc reversibly as a guest up to 0.9 ions per formula. The reaction seems to proceed through the formation of a solid solution in which the W-O framework of the parent oxide is maintained. The location of the Zn{sup 2+} ions in the framework of W{sub 18}O{sub 49} has been determined by neutron diffraction on a chemically prepared sample having the composition Zn{sub 0.34}W{sub 18}O{sub 49}. As a main result, we found that Zn prefers to insert in one of the four types of quadrangular tunnels. More precisely, it is displaced from the center to occupy a low coordination site. This result indicates that a significant covalent character exists in the Zn-O bond. - Graphical Abstract: The structure of Zn{sub 0.36}W{sub 18}O{sub 49} projected along the b-axis.

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

    NASA Astrophysics Data System (ADS)

    Sanyal, Prasanta; Basu, Sayak

    2016-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-02-01

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

  15. Measurements of excess O3, CO2, CH4, C2H4, C2H2, HCN, NO, NH3, HCOOH, CH3COOH, HCHO, and CH3H in 1997 Alaskan biomass burning plumes by airborne Fourier transform infrared spectroscopy (AFTIR) [O3 CO2 CH4 C2H4 C2H2 NH3 CH3COOH CH3H

    NASA Astrophysics Data System (ADS)

    Goode, Jon G.; Yokelson, Robert J.; Ward, Darold E.; Susott, Ronald A.; Babbitt, Ronald E.; Davies, Mary Ann; Hao, Wei Min

    2000-09-01

    We used an airborne Fourier transform infrared spectrometer (AFTIR), coupled to a flow-through, air-sampling cell, on a King Air B-90 to make in situ trace gas measurements in isolated smoke plumes from four, large, boreal zone wildfires in interior Alaska during June 1997. AFTIR spectra acquired near the source of the smoke plumes yielded excess mixing ratios for 13 of the most common trace gases: water, carbon dioxide, carbon monoxide, methane, nitric oxide, formaldehyde, acetic acid, formic acid, methanol, ethylene, acetylene, ammonia and hydrogen cyanide. Emission ratios to carbon monoxide for formaldehyde, acetic acid, and methanol were 2.2±0.4%, 1.3±0.4%, and 1.4±0.1%, respectively. For each oxygenated organic compound, a single linear equation fits our emission factors from Alaska, North Carolina, and laboratory fires as a function of modified combustion efficiency (MCE). A linear equation for predicting the NH3/NOx emission ratio as a function of MCE fits our Alaskan AFTIR results and those from many other studies. AFTIR spectra collected in downwind smoke that had aged 2.2±1 hours in the upper, early plume yielded ΔO3/ΔCO ratios of 7.9±2.4% resulting from O3 production rates of ˜50 ppbv h-1. The ΔNH3/ΔCO ratio in another plume decreased to 1/e of its initial value in ˜2.5 hours. A set of average emission ratios and emission factors for fires in Alaskan boreal forests is derived. We estimate that the 1997 Alaskan fires emitted 46±11 Tg of CO2.

  16. 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.

  17. Arabidopsis C3H14 and C3H15 have overlapping roles in the regulation of secondary wall thickening and anther development.

    PubMed

    Chai, Guohua; Kong, Yingzhen; Zhu, Ming; Yu, Li; Qi, Guang; Tang, Xianfeng; Wang, Zengguang; Cao, Yingping; Yu, Changjiang; Zhou, Gongke

    2015-05-01

    Plant tandem CCCH zinc finger (TZF) proteins play diverse roles in developmental and adaptive processes. Arabidopsis C3H14 has been shown to act as a potential regulator of secondary wall biosynthesis. However, there is lack of direct evidence to support its functions in Arabidopsis. It is demonstrated here that C3H14 and its homologue C3H15 redundantly regulate secondary wall formation and that they additionally function in anther development. Plants with double, but not single, T-DNA mutants for C3H14 or C3H15 have few pollen grains and thinner stem secondary walls than the wild type. Plants homozygous for c3h14 and heterozygous for c3h15 [c3h14 c3h15(±)] have slightly thinner secondary walls than plants heterozygous for c3h14 and homozygous for c3h15 [c3h14(±) c3h15], and c3h14(±) c3h15 have lower fertility. Overexpression of C3H14 or C3H15 led to increased secondary wall thickness in stems and the ectopic deposition of secondary walls in various tissues, but did not affect anther morphology. Transcript profiles from the C3H14/15 overexpression and c3h14 c3h15 plants revealed marked changes in the expression of many genes associated with cell wall metabolism and pollen formation. Subcellular localization and biochemical analyses suggest that C3H14/15 might function at both the transcriptional and post-transcriptional levels.

  18. H3++H2 isotopic system at low temperatures: Microcanonical model and experimental study

    NASA Astrophysics Data System (ADS)

    Hugo, Edouard; Asvany, Oskar; Schlemmer, Stephan

    2009-04-01

    State-to-state thermal rate coefficients for reactions of all H3++H2 isotopic variants are derived and compared to new experimental data. The theoretical data are also sought for astrochemical modeling of cold environments (<50K). The rates are calculated on the basis of a microcanonical approach using the Langevin model and the conservation laws of mass, energy, angular momentum, and nuclear spin. Full scrambling of all five nuclei during the collision is assumed for the calculations and alternatively partial dynamical restrictions are considered. The ergodic principle of the collision is employed in two limiting cases, neglecting (weak ergodic limit) or accounting for explicit degeneracies of the reaction mechanisms (strong ergodic limit). The resulting sets of rate coefficients are shown to be consistent with the detailed balance and thermodynamical equilibrium constants. Rate coefficients