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Sample records for peroxy radical diurnal

  1. Rapid Hydrogen Shift Reactions in Acyl Peroxy Radicals

    DEFF Research Database (Denmark)

    Knap, Hasse Christian; Jørgensen, Solvejg

    2017-01-01

    -shift with X = 6, 7, 8, or 9) in the hydroperoxy acyl peroxy radicals, this H-shift is a reversible reaction and it scrambles between two peroxides, hydroperoxy acyl peroxy and peroxy peroxoic acid radicals. The forward reaction rate constants of the 1,X-OOH H-shift reactions are estimated to be above 103 s–1...... with transition state theory corrected with Eckart quantum tunnelling correction. The ratio between the forward and reverse reaction rate constant of the 1,X-OOH H-shift reactions is around ∼105. Therefore, the equilibrium is pushed toward the production of peroxy peroxoic acid radicals. These very fast 1,X-OOH H......We have used quantum mechanical chemical calculations (CCSD(T)-F12a/cc-pVDZ-F12//M06-2X/aug-cc-pVTZ) to investigate the hydrogen shift (H-shift) reactions in acyl peroxy and hydroperoxy acyl peroxy radicals. We have focused on the H-shift reactions from a hydroperoxy group (OOH) (1,X-OOH H...

  2. Missing Peroxy Radical Sources Within a Rural Forest Canopy

    Science.gov (United States)

    Wolfe, G. M.; Cantrell, C.; Kim, S.; Mauldin, R. L., III; Karl, T.; Harley, P.; Turnipseed, A.; Zheng, W.; Flocke, F.; Apel, E. C.; hide

    2013-01-01

    Organic peroxy (RO2) and hydroperoxy (HO2) radicals are key intermediates in the photochemical processes that generate ozone, secondary organic aerosol and reactive nitrogen reservoirs throughout the troposphere. In regions with ample biogenic hydrocarbons, the richness and complexity of peroxy radical chemistry presents a significant challenge to current-generation models, especially given the scarcity of measurements in such environments. We present peroxy radical observations acquired within a Ponderosa pine forest during the summer 2010 Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen - Rocky Mountain Organic Carbon Study (BEACHON-ROCS). Total peroxy radical mixing ratios reach as high as 180 pptv and are among the highest yet recorded. Using the comprehensive measurement suite to constrain a near-explicit 0-D box model, we investigate the sources, sinks and distribution of peroxy radicals below the forest canopy. The base chemical mechanism underestimates total peroxy radicals by as much as a factor of 3. Since primary reaction partners for peroxy radicals are either measured (NO) or under-predicted (HO2 and RO2, i.e. self-reaction), missing sources are the most likely explanation for this result. A close comparison of model output with observations reveals at least two distinct source signatures. The first missing source, characterized by a sharp midday maximum and a strong dependence on solar radiation, is consistent with photolytic production of HO2. The diel profile of the second missing source peaks in the afternoon and suggests a process that generates RO2 independently of sun-driven photochemistry, such as ozonolysis of reactive hydrocarbons. The maximum magnitudes of these missing sources (approximately 120 and 50 pptv min-1, respectively) are consistent with previous observations alluding to unexpectedly intense oxidation within forests. We conclude that a similar mechanism may underlie many such observations.

  3. Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002

    Directory of Open Access Journals (Sweden)

    Z. L. Fleming

    2006-01-01

    Full Text Available Peroxy radical (HO2+ΣRO2 measurements, using the PEroxy Radical Chemical Amplification (PERCA technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer chemistry. A suite of other chemical parameters (NO, NO2, NO3, CO, CH4, O3, VOCs, peroxides, photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HOx. A good correlation exists between j(HCHO.[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HOx source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO2] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO2/(HO2+ΣRO2 ratios are dependent on [NOx] ranging between 0.2 and 0.6, with the ratio increasing linearly with NOx. Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO3-alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv h-1. The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O3/dln(NO=1.0. The results imply that the N(O3 (the in-situ net photochemical rate of ozone

  4. Airborne measurement of peroxy radicals in the lower troposphere

    Science.gov (United States)

    Andrés Hernández, Maria Dolores; Horstjann, Markus; Kartal, Deniz; Krebsbach, Marc; Linke, Christian; Lichtenstern, Michael; Andrey, Javier; Burrows, John P.

    2013-04-01

    The importance of peroxy radicals in the tropospheric chemistry is well recognized in the scientific literature. Hydroxy- and organic peroxy radicals (HO2 and RO2, R being an organic chain) are key intermediates in the OH radical initiated oxidation of CO and SO2, of volatile organic compounds (VOC), in the ozonolysis of alkenes and photo-oxidation of carbonyl species. Peroxy radicals are responsible for the ozone production in the troposphere, the formation of peroxides and other oxidants. Although radical chemistry in the troposphere has been subject of intensive research in the past three decades, it is still very few known about the vertical distribution of peroxy radicals. Airborne observations are scarce in spite of their particular importance to improve the understanding of the tropospheric chemistry and the oxidising capacity of the atmosphere at different altitudes. In situ trace gas measurements were carried out in summer 2010 on board of the INTA (Instituto Nacional de Técnicas Aeroespaciales) C212 aircraft over Spain in the frame of the EUFAR project VERDRILLT (VERtical Distribution of Radicals In the Lower Layers of the Troposphere), and in cooperation with the DLR (Deutsches Zentrum für Luft- und Raumfahrt), the University of Wuppertal, the CEAM (Centro de Estudios Ambientales del Mediterráneo) and the UPV-EHU University in Bilbao. VERDRILLT aimed at getting a deeper understanding of the vertical distribution of peroxy radicals in the lower layers of the troposphere. Measurements were taken over urban areas and extensions of different vegetation under meteorological conditions favouring active photochemistry and convection from the ground into close atmospheric layers. Results and main findings will be presented and discussed.

  5. Peroxy Radical Measurements via Laser Induced Fluorescence

    Science.gov (United States)

    Trawny, Katrin; Tatum Ernest, Cheryl; Novelli, Anna; Elste, Thomas; Plaß-Dülmer, Christian; Rudolf, Markus; Martinez, Monica; Harder, Hartwig; Lelieveld, Jos

    2013-04-01

    We present a newly built Laser Induced Fluorescence (LIF) system to measure the sum of all peroxy radicals (RO2) utilizing chemical conversion to OH. This instrument operates in two different modes: the ROx mode (sum of OH, HO2, and RO2) and the HOx mode (sum of OH and HO2). The HOx mode is used to derive the RO2 data from the ROx measurements. A model approach was used during instrumental development to identify the key parameters needed for the conversion process in front of the detection area and to optimize sensitivity. The instrument was then carefully characterized in various lab experiments, where it could be shown that the wall losses for HO2 are negligible and that nearly all HO2 is converted to OH in front of the detection zone. The pressure and temperature dependencies were also analyzed and assured that the instrument does not show any photolytical interference. As the instrument is calibrated with only one kind of peroxy radicals it was very important that the differences in sensitivity for different peroxy radicals are acceptable. Lab experiments as well as first results from the HOPE 2012 intensive field campaign, which took place in summer 2012 at the Global Atmosphere Watch (GAW) station of the German Weather Service, will be discussed.

  6. Peroxy Radical Measurements during PROPHET-AMOS 2016

    Science.gov (United States)

    Wood, E. C. D.; Deming, B.; Rollings, D.

    2016-12-01

    We present measurements of total peroxy radicals (HO2 + RO2) using the Ethane Chemical Amplifier (ECHAMP) technique during the PROPHET-AMOS project in Pellston, Michigan during July 2016. The C2H6/NO amplification chemistry occurred in FEP reaction chambers at the top of the PROPHET tower at a height of 34 m. The NO2 amplification product was transported through tubing to two cavity attenuated phase shift spectrometers (CAPS) housed inside the PROPHET laboratory. Two calibration sources were used: one based on water photolysis in the presence of isoprene and ozone actinometry, and another based on methyl iodide (CH3I) photolysis. The former was integrated into the inlet system, allowing for daily calibrations, whereas the latter was used twice during the campaign. Peak mixing ratios on warm, sunny days were approximately 40 ppt. Nighttime concentrations varied from below the instrumental detection limit to approximately 5 ppt. The measured peroxy radical concentrations will be compared to HO2 and HO2* mixing ratios measured by the Indiana University LIF-FAGE instrument.

  7. Alternative Chemical Amplification Methods for Peroxy Radical Detection

    Science.gov (United States)

    Wood, E. C. D.

    2014-12-01

    Peroxy radicals (HO2, CH3O2, etc.) are commonly detected by the chemical amplification technique, in which ambient air is mixed with high concentrations of CO and NO, initiating a chain reaction that produces 30 - 200 NO2 molecules per sampled peroxy radical. The NO2 is then measured by one of several techniques. With the exception of CIMS-based techniques, the chemical amplification method has undergone only incremental improvements since it was first introduced in 1982. The disadvantages of the technique include the need to use high concentrations of CO and the greatly reduced sensitivity of the amplification chain length in the presence of water vapor. We present a new chemical amplification scheme in which either ethane or acetaldehyde is used in place of CO, with the NO2 product detected using Cavity Attenuated Phase Shift spectroscopy (CAPS). Under dry conditions, the amplification factor of the alternative amplifiers are approximately six times lower than the CO-based amplifier. The relative humidity "penalty" is not as severe, however, such that at typical ambient relative humidity (RH) values the amplification factor is within a factor of three of the CO-based amplifier. Combined with the NO2 sensitivity of CAPS and a dual-channel design, the detection limit of the ethane amplifier is less than 2 ppt (1 minute average, signal-to-noise ratio 2). The advantages of these alternative chemical amplification schemes are improved safety, a reduced RH correction, and increased sensitivity to organic peroxy radicals relative to HO2.

  8. Investigation of the role of bicyclic peroxy radicals in the oxidation mechanism of toluene.

    Science.gov (United States)

    Birdsall, Adam W; Andreoni, John F; Elrod, Matthew J

    2010-10-07

    The products of the primary OH-initiated oxidation of toluene were investigated using the turbulent flow chemical ionization mass spectrometry technique under different oxygen, NO, and initial OH radical concentrations as well as a range of total pressures. The bicyclic peroxy radical intermediate, a key proposed intermediate species in the Master Chemical Mechanism (MCM) for the atmospheric oxidation of toluene, was detected for the first time. The toluene oxidation mechanism was shown to have a strong oxygen concentration dependence, presumably due to the central role of the bicyclic peroxy radical in determining the stable product distribution at atmospheric oxygen concentrations. The results also suggest a potential role for bicyclic peroxy radical + HO(2) reactions at high HO(2)/NO ratios. These reactions are postulated to be a source of the inconsistencies between environmental chamber results and predictions from the MCM.

  9. Peroxy Radical Measurements during the IRRONIC Field Project by C2H6 - NO Chemical Amplification

    Science.gov (United States)

    Wood, E. C. D.; Kundu, S.; Deming, B.; Lew, M.; Stevens, P. S.; Sklaveniti, S.; Dusanter, S.

    2015-12-01

    We present measurements of total peroxy radicals (HO2 + RO2) during the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC) field project in Bloomington, Indiana during July 2015. Peroxy radicals were measured by chemical amplification using ethane and nitric oxide in dual PFA reaction chambers, and the amplification product NO2 was quantified by cavity attenuated phase shift spectroscopy. On sunny days mid-day peroxy radical mixing ratios were typically between 20 and 70 ppt and were well correlated with "HO2*" measured by the Indiana University Laser-Induced Fluorescence with Fluorescence Assay by Gas Expansion (IU-FAGE) instrument. The ratio of total peroxy radicals (UMass) to the IU-FAGE HO2* measurements was greater than two. We also describe results from an informal intercomparison of the two instruments' calibration sources, which are based on acetone photolysis (UMass) and water photolysis (IU). In addition to sampling the IU calibration source in "amplification" mode, the UMass instrument also separately quantified the HO2 mixing ratio in the IU calibration gas by reaction with excess NO and subsequent quantification of the NO2 produced.

  10. Isomerization of Second-Generation Isoprene Peroxy Radicals

    DEFF Research Database (Denmark)

    D'Ambro, Emma L.; Møller, Kristian Holten; Lopez-Hilfiker, Felipe D.

    2017-01-01

    kinetics box model, we find that to explain the behavior of low-volatility products and SOA mass yields relative to input H2O2 concentrations, the second-generation dihydroxy hydroperoxy peroxy radical (C5H11O6·) must undergo an intramolecular H-shift with a net forward rate constant of order 0.1 s-1...... products under atmospheric conditions and, thus, on the importance of nonreactive gas-particle partitioning of isoprene oxidation products as an SOA source....

  11. Decay of peroxy radicals of methanol and isopropanol in the presence of copper ions and superoxide dismutase. Progress report, December 1, 1978--November 30, 1979

    International Nuclear Information System (INIS)

    Ilan, Y.A.; Ilan, Y.; Czapski, G.

    1979-01-01

    The decay of the peroxy radicals produced from methanol and isopropanol was followed in the presence and in the absence of Cu 2+ ions, and the enzyme Superoxide Dismutase. The results indicate that both Cu 2+ and Superoxide do not affect the decay of the alcohol peroxy radicals. They catalyze the decay of O - 2 radicals which are formed from the alcoholic peroxy radicals, and which absorb light at the same wavelengths region as these radicals. This catalysis enables the resolution of the decay of the alcoholic peroxy radicals, without the interference of absorption changes originating in the decay of HO 2 and O - 2 radicals

  12. Peroxy Radicals Observed in a Forested Environment with Time of Flight Mass Spectrometry

    Science.gov (United States)

    Cantrell, C. A.; Mauldin, L.; Nowak, J. B.

    2017-12-01

    Observations of peroxy radicals were made using time-of-flight chemical ionization mass spectrometry (ToF-CIMS) during the PROPHET-AMOS (Program for Research on Oxidants, Photochemistry, Emissions and Transport - Atmospheric Measurements of Oxidants in Summer) campaign in summer 2016 at the University of Michigan Biological Station (UMBS) in the northern lower peninsula of Michigan. The environment is one of high isoprene productivity and generally low NOx, depending on the origin of air masses that are sampled, and has been the subject of several comprehensive atmospheric observational studies. The ToF-CIMS was configured to measure OH, HO2+RO2, and extremely oxygenated volatile organic compounds (ELVOCs) in a cycle of about 5 minutes for each. This presentation examines the time- and chemical coordinate-dependent behavior of the peroxy radicals, and compares the observations with models that are constrained by observations of the controlling variables. The results are used to estimate factors such as the photochemical production rate of ozone and other atmospheric oxidation parameters for this remote forest site.

  13. Peroxy radical measurements during HOPE 2012

    Science.gov (United States)

    Trawny, K.; Tatum Ernest, C.; Novelli, A.; Elste, T.; Werner, A.; Englert, J.; Plass-Duelmer, C.; Rudolf, M.; Martinez, M.; Harder, H. D.; Lelieveld, J.

    2012-12-01

    We present the first ambient air measurements of a newly built Laser Induced Fluorescence (LIF) system to measure the sum of all peroxy radicals (RO2) utilizing chemical conversion to OH. This instrument operates in two different modes: the ROx mode (sum of OH, HO2, and RO2) and the HOx mode (sum of OH and HO2). The HOx mode is used to derive the RO2 data from the ROx measurements and is also compared to HOx measurements of a second LIF system. The HOPE 2012 intensive field campaign took place in summer 2012 at the Global Atmosphere Watch (GAW) station of the German Weather Service located approximately 60 km south-west of Munich and approximately 20 km away from the Alps at Hohenpeissenberg (988 m, 47° 48‧ N, 11° 0‧ E). Simultaneous side-by-side measurements of ROx were conducted on the roof platform of the observatory with two instruments using Chemical Ionization Mass Spectrometry (CIMS) and LIF. The RO2 measurements are compared to modeled data derived from the constrained box model CAABA/MECCA.

  14. Dynamics of Peroxy and Alkenyl Radicals Undergoing Competing Rearrangements in Biodiesel Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Dibble, Theodore S. [State Univ. of New York (SUNY), Syracuse, NY (United States)

    2016-03-24

    Biodiesel fuel is increasingly being used worldwide. Although we have a fair understanding of the molecular details of the chemistry of peroxy radicals derived from alkanes, biodiesel fuels contain ester and olefin groups which significantly impact the thermodynamics and kinetics of biodiesel ignition. The broader goal of this research is to carry out systematic computational studies of the elementary kinetics of the chemistry of ROO•, QOOH and •OOQOOH compounds that are models for biodiesel ignition.

  15. Atmospheric Peroxy Radical Measurements by Chemical Amplification - Cavity Attenuated Phase Shift Spectroscopy

    Science.gov (United States)

    Wood, E. C.; Charest, J. R.

    2013-12-01

    We present a new chemical amplifier for the detection of peroxy radicals using Cavity Attenuated Phase Shift spectroscopy (CAPS) detection of NO2. The amplification scheme is similar to other chemical amplifiers and involves addition of CO (8%) and NO (3 ppm) to air sampled in a PFA tube. The chain length is quantified by amplification of a known concentration of methyl peroxy radicals (CH3O2) and peroxyacetyl radicals (CH3COO2) sampled by the instrument's reactor. The CH3O2 and CH3COO2 radicals are produced by photolysis of acetone at 254 nm and quantified by conversion to NO2 by reaction with excess NO. The chain length (CL) in dry air is over 200 and constant at RO2 concentrations under 500 ppt. The CL decreases by 55% at a relative humidity of 50%. A 0.95 cm (3/8') ID PFA tube, a 0.32 cm (1/8' ID) PFA tube, and a 0.48 cm ID quartz reactor give near-identical chain lengths and RH dependence, demonstrating the small importance of wall reactions (for clean tubing) as radical termination steps. The instrument comprises two independent inlets and CAPS detectors, allowing for simultaneous measurements in ROx mode (= NO2 + O3 + RO2 + HO2) and Ox mode (= NO2 + O3) thereby greatly reducing the effect of variations in background [Ox]. The 1σ precision of the instrument at constant background [Ox] and 0% relative humidity is 0.2 ppt ROx with 100 second averaging and increases to 0.3 ppt at an RH of 50%. The absolute uncertainty of the measurements is estimated as 20% and is affected by the accuracy of the NO2 calibration, the precision of the CAPS when calibrating at low RO2 concentrations, and the uncertainty in the photolysis quantum yield for the CH3CO + CH3 channel of acetone photolysis.

  16. Measurements of Peroxy Radicals and Related Species At A Rural Site During The Escompte Campaign

    Science.gov (United States)

    Pinceloup, S.; Laverdet, G.; Le Bras, G.

    The chemical amplifier technique has been used to measure peroxy radicals (RO2) concentrations at a rural site (Dupail), located 35 km North East of Marseille, during the ESCOMPTE campaign in June-July 2001. Daily profiles of RO2 and also ozone and NOx concentrations have been recorded everyday including those of the four in- tensive observation periods (IOP). The NOx levels were most of the time lower than a few ppbv, ie characteristic of a rural site. Typical diurnal profiles of RO2 were ob- served with maxima in the range 40-180 pptv. The RO2 signals were corrected from the influence of relative humidity based on calibration of the chemical amplifier in separate laboratory experiments under controlled water vapor concentrations. Prelim- inary interpretation of the data shows very different ratios of photochemically pro- duced/transported ozone related to meteorological conditions. Further interpretation of the data is underway integrating additional measurements of a large variety of hy- drocarbons as well as some hydroperoxides and aldehydes made at the site by other groups. The results of the comparison of calculated steady state concentrations of RO2 and ozone production rate with the measured values will be presented and discussed in relation with our understanding of the tropospheric ozone production.

  17. Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

    Energy Technology Data Exchange (ETDEWEB)

    D’Ambro, Emma L.; Møller, Kristian H.; Lopez-Hilfiker, Felipe D.; Schobesberger, Siegfried; Liu, Jiumeng; Shilling, John E.; Lee, Ben Hwan; Kjaergaard, Henrik G.; Thornton, Joel A.

    2017-04-11

    We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1. Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.

  18. Comments on the reactions of carbohydrate peroxy radicals in relation to the lyoluminescent behaviour of irradiated carbohydrates

    International Nuclear Information System (INIS)

    Baugh, P.J.; Mahjani, M.G.

    1977-01-01

    Reference is made to recent work on lyoluminescence: the emission of visible light from irradiated tissue equivalent solids such as carbohydrates when dissolved in aqueous solutions (Atari et al., Radiat. Effects; 17:45(1973); and ibid.; 20: 135 (1973); and Baugh et al., Int.J.Radiat.Phys. Chem.(in press)). In the present communication the consequences of the fast elimination of the hydroperoxy radicals from carbohydrate peroxy radicals are considered in a further study of the chemical reactions involved. (U.K.)

  19. UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Sehested, J.

    1994-01-01

    Alkyl and alkyl peroxy radicals from 1-butyl alcohol (TBA), HOC (CH3)2CH2. and HOC(CH3)2CH2O2. have been studied in the ps phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR...

  20. UV absorption spectra and kinetics for alkyl and alkyl peroxy radicals originating from di-tert-butyl ether

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.; Langer, S.

    1995-01-01

    Alkyl, (CH3)(3)COC(CH3)(2)CH2, and alkyl peroxy, (CH3)(3)COC(CH3)(2)CH2O2, radicals from di-tert-butyl ether (DTBE), have been studied in the gas phase at 296 K. A pulse radiolysis UV absorption technique was used to measure the spectra and kinetics. Absorption cross sections were quantified over...

  1. Photodissociation dynamics of the simplest alkyl peroxy radicals, CH3OO and C2H5OO, at 248 nm

    Science.gov (United States)

    Sullivan, Erin N.; Nichols, Bethan; Neumark, Daniel M.

    2018-01-01

    The photodissociation dynamics of the simplest alkyl peroxy radicals, methyl peroxy (CH3OO) and ethyl peroxy (C2H5OO), are investigated using fast beam photofragment translational spectroscopy. A fast beam of CH3OO- or C2H5OO- anions is photodetached to generate neutral radicals that are subsequently dissociated using 248 nm photons. The coincident detection of the photofragment positions and arrival times allows for the determination of mass, translational energy, and angular distributions for both two-body and three-body dissociation events. CH3OO exhibits repulsive O loss resulting in the formation of O(1D) + CH3O with high translational energy release. Minor two-body channels leading to OH + CH2O and CH3O + O(3P) formation are also detected. In addition, small amounts of H + O(3P) + CH2O are observed and attributed to O loss followed by CH3O dissociation. C2H5OO exhibits more complex dissociation dynamics, in which O loss and OH loss occur in roughly equivalent amounts with O(1D) formed as the dominant O atom electronic state via dissociation on a repulsive surface. Minor two-body channels leading to the formation of O2 + C2H5 and HO2 + C2H4 are also observed and attributed to a ground state dissociation pathway following internal conversion. Additionally, C2H5OO dissociation yields a three-body product channel, CH3 + O(3P) + CH2O, for which the proposed mechanism is repulsive O loss followed by the dissociation of C2H5O over a barrier. These results are compared to a recent study of tert-butyl peroxy (t-BuOO) in which 248 nm excitation results in three-body dissociation and ground state two-body dissociation but no O(1D) production.

  2. Theoretical investigation of the hydrogen shift reactions in peroxy radicals derived from the atmospheric decomposition of 3-methyl-3-buten-1-ol (MBO331)

    DEFF Research Database (Denmark)

    Knap, Hasse Christian; Jørgensen, Solvejg; Kjærgaard, Henrik Grum

    2015-01-01

    The hydroxy peroxy radical derived from the oxidation of 3-methyl-3-buten-1-ol (MBO331), can undergo four different hydrogen shift (H-shift) reactions. We have compared optimized geometries, barrier heights and reaction rate constants obtained with five different DFT functionals (BLYP, B3LYP, BHand...

  3. Artifacts Generated During Azoalkane Peroxy Radical Oxidative Stress Testing of Pharmaceuticals Containing Primary and Secondary Amines.

    Science.gov (United States)

    Nefliu, Marcela; Zelesky, Todd; Jansen, Patrick; Sluggett, Gregory W; Foti, Christopher; Baertschi, Steven W; Harmon, Paul A

    2015-12-01

    We report artifactual degradation of pharmaceutical compounds containing primary and secondary amines during peroxy radical-mediated oxidative stress carried out using azoalkane initiators. Two degradation products were detected when model drug compounds dissolved in methanol/water were heated to 40°C with radical initiators such as 2,2'-azobis(2-methylpropionitrile) (AIBN). The primary artifact was identified as an α-aminonitrile generated from the reaction of the amine group of the model drug with formaldehyde and hydrogen cyanide, generated as byproducts of the stress reaction. A minor artifact was generated from the reaction between the amine group and isocyanic acid, also a byproduct of the stress reaction. We report the effects of pH, initiator/drug molar ratio, and type of azoalkane initiator on the formation of these artifacts. Mass spectrometry and nuclear magnetic resonance were used for structure elucidation, whereas mechanistic studies, including stable isotope labeling experiments, cyanide analysis, and experiments exploring the effects of butylated hydroxyanisole addition, were employed to support the degradation pathways. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  4. Tropospheric chemistry of natural hydrocarbons, aldehydes, and peroxy radicals: Their connections to sulfuric acid production and climate effects

    International Nuclear Information System (INIS)

    Gaffney, J.S.; Marley, N.A.

    1993-05-01

    Recent work has shown that natural hydrocarbon emissions can significantly affect the levels of urban and regional tropospheric ozone. We report on the reactivities of these biogenic trace gases, particularly isoprene, focusing on their importance in the production of aldehydes and peroxy radicals, leading to increased levels of hydrogen over regional forests. Hydrogen peroxide can lead to the wet oxidation of sulfur dioxide to acidic sulfate in aerosols, fogs, and clouds. In turn, acidic sulfate can act to as a light scattering aerosol and a source of cloud condensation nuclei (CCN), potentially leading to global cooling. Aerosol sulfate and other dissolved organic and inorganic compounds can also play important roles as a greenhouse species in the lower troposphere

  5. Composite wastewater treatment by aerated electrocoagulation and modified peroxi-coagulation processes.

    Science.gov (United States)

    Kumar, Abhijeet; Nidheesh, P V; Suresh Kumar, M

    2018-08-01

    Treatment of composite wastewater generating from the industrial estates is a great challenge. The present study examines the applicability of aerated electrocoagulation and modified peroxi-coagulation processes for removing color and COD from composite wastewater. Iron plates were used as anodes and cathodes in both electrochemical processes and experiments were carried out in a working volume of 2 L. Aeration enhanced the efficiency of electrocoagulation process significantly. More than 50% of COD and 60% of color were removed after 1 h of electrocoagulation process operated at pH 3 and applied voltage of 1 V. Efficiency of the modified peroxi-coagulation process was significantly higher than that of aerated electrocoagulation. COD and color removal efficiencies of the modified peroxi-coagulation process were found as 77.7% and 97%, respectively after 1 h of electrolysis operated at 1 V, solution pH 3 and 50 mM hydrogen peroxide addition. This improved efficiency of modified peroxi-coagulation compared to aerated electrocoagulation is mainly due to the attack of in-situ generated hydroxyl radicals. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Absolute rate constants for the reaction of NO with a series of peroxy radicals in the gas at 295 K

    DEFF Research Database (Denmark)

    Sehested, J.; Nielsen, O.J.; Wallington, T.J.

    1993-01-01

    The rate constants for the reaction of NO with a series of peroxy radicals: CH3O2, C2H5O2, (CH3)3CCH2O2, (CH3)3CC(CH3)2CH2O2, CH2FO2, CH2ClO2, CH2BrO2, CHF2O2, CF2ClO2, CHF2CF2O2, CF3CF2O2, CFCl2CH2O2 and CF2ClCH2O2 were measured at 298 K and a total pressure of 1 atm. The rate constants were...

  7. Peroxy bleaches

    Energy Technology Data Exchange (ETDEWEB)

    Carson, P.A. [Unilever Research, Port Sunlight Laboratory (United States) and Chemistry Department, University of Manchester, Institute of Science and Technology (United States)]. E-mail: pcarson2005@aol.com; Fairclough, C.S. [Unilever Research, Port Sunlight Laboratory (United States); Mauduit, C. [Chemistry Department, University of Manchester, Institute of Science and Technology (United States); Colsell, M. [Chemistry Department, University of Manchester, Institute of Science and Technology (United States)

    2006-08-25

    Fabric laundering is now a sophisticated chemical process involving a variety of operations including bleaching. The chemistry of peroxy bleaches is described including the use of novel organic compounds to provide effective bleaching at the lower temperatures of modern wash cycles. The instability of peroxy compounds is illustrated using cameo case histories to relate theory and practice. Techniques available for determining their thermochemistry are summarised. A model is provided for hazard and risk assessment of development projects in general (particularly those involving new molecules, processes or formulations) from ideas phase through exploratory laboratory investigations to pilot plant scale-up and eventual manufacture and commercial exploitation. This paper is a prelude to Part 2, which describes the determination of thermodynamic and kinetic properties of peroxy bleaches and discusses the implication of the results in terms of precautions for their safe storage and incorporation into detergent formulations during processing.

  8. Peroxy bleaches

    International Nuclear Information System (INIS)

    Carson, P.A.; Fairclough, C.S.; Mauduit, C.; Colsell, M.

    2006-01-01

    Fabric laundering is now a sophisticated chemical process involving a variety of operations including bleaching. The chemistry of peroxy bleaches is described including the use of novel organic compounds to provide effective bleaching at the lower temperatures of modern wash cycles. The instability of peroxy compounds is illustrated using cameo case histories to relate theory and practice. Techniques available for determining their thermochemistry are summarised. A model is provided for hazard and risk assessment of development projects in general (particularly those involving new molecules, processes or formulations) from ideas phase through exploratory laboratory investigations to pilot plant scale-up and eventual manufacture and commercial exploitation. This paper is a prelude to Part 2, which describes the determination of thermodynamic and kinetic properties of peroxy bleaches and discusses the implication of the results in terms of precautions for their safe storage and incorporation into detergent formulations during processing

  9. Spectroscopic detection, characterization and dynamics of free radicals relevant to combustion processes

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Terry [The Ohio State Univ., Columbus, OH (United States)

    2015-06-04

    Combustion chemistry is enormously complex. The chemical mechanisms involve a multitude of elementary reaction steps and a comparable number of reactive intermediates, many of which are free radicals. Computer simulations based upon these mechanisms are limited by the validity of the mechanisms and the parameters characterizing the properties of the intermediates and their reactivity. Spectroscopy can provide data for sensitive and selective diagnostics to follow their reactions. Spectroscopic analysis also provides detailed parameters characterizing the properties of these intermediates. These parameters serve as experimental gold standards to benchmark predictions of these properties from large-scale, electronic structure calculations. This work has demonstrated the unique capabilities of near-infrared cavity ringdown spectroscopy (NIR CRDS) to identify, characterize and monitor intermediates of key importance in complex chemical reactions. Our studies have focussed on the large family of organic peroxy radicals which are arguably themost important intermediates in combustion chemistry and many other reactions involving the oxidation of organic compounds. Our spectroscopic studies have shown that the NIR Ã - ˜X electronic spectra of the peroxy radicals allows one to differentiate among chemical species in the organic peroxy family and also determine their isomeric and conformic structure in many cases. We have clearly demonstrated this capability on saturated and unsaturated peroxy radicals and β-hydroxy peroxy radicals. In addition we have developed a unique dual wavelength CRDS apparatus specifically for the purpose of measuring absolute absorption cross section and following the reaction of chemical intermediates. The utility of the apparatus has been demonstrated by measuring the cross-section and self-reaction rate constant for ethyl peroxy.

  10. Comparison of COD removal from pharmaceutical wastewater by electrocoagulation, photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes

    International Nuclear Information System (INIS)

    Farhadi, Sajjad; Aminzadeh, Behnoush; Torabian, Ali; Khatibikamal, Vahid; Alizadeh Fard, Mohammad

    2012-01-01

    Highlights: ► Hydrogen peroxide improves the performance of electrocoagulation process. ► UV light can be effective on the performance on peroxi-electrocoagulation and electrocoagulation processes. ► The optimal amount of hydrogen peroxide for peroxi-electrocoagulation process for COD removal from pharmaceutical wastewater is 300 mg/L. ► The optimal values of pH for electrocoagulation and peroxi-electrocoagulation are 7 and 3, respectively. - Abstract: This work makes a comparison between electrocoagulation (EC), photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes to investigate the removal of chemical oxygen demand (COD) from pharmaceutical wastewater. The effects of operational parameters such as initial pH, current density, applied voltage, amount of hydrogen peroxide and electrolysis time on COD removal efficiency were investigated and the optimum operating range for each of these operating variables was experimentally determined. In electrocoagulation process, the optimum values of pH and voltage were determined to be 7 and 40 V, respectively. Desired pH and hydrogen peroxide concentration in the Fenton-based processes were found to be 3 and 300 mg/L, respectively. The amounts of COD, pH, electrical conductivity, temperature and total dissolved solids (TDS) were on-line monitored. Results indicated that under the optimum operating range for each process, the COD removal efficiency was in order of peroxi-electrocoagulation > peroxi-photoelectrocoagulation > photoelectrocoagulation > electrocoagulation. Finally, a kinetic study was carried out using the linear pseudo-second-order model and results showed that the pseudo-second-order equation provided the best correlation for the COD removal rate.

  11. Comparison of COD removal from pharmaceutical wastewater by electrocoagulation, photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes

    Energy Technology Data Exchange (ETDEWEB)

    Farhadi, Sajjad, E-mail: sajjadfarhadi@ut.ac.ir [Department of Civil and Environmental Engineering, Graduate Faculty of Environment, University of Tehran (Iran, Islamic Republic of); Aminzadeh, Behnoush, E-mail: bamin@ut.ac.ir [Department of Civil and Environmental Engineering, Graduate Faculty of Environment, University of Tehran (Iran, Islamic Republic of); Torabian, Ali, E-mail: atorabi@ut.ac.ir [Department of Civil and Environmental Engineering, Graduate Faculty of Environment, University of Tehran (Iran, Islamic Republic of); Khatibikamal, Vahid, E-mail: vahidkhatibi@ut.ac.ir [Department of Civil and Environmental Engineering, Graduate Faculty of Environment, University of Tehran (Iran, Islamic Republic of); Alizadeh Fard, Mohammad, E-mail: malizadeh1987@ut.ac.ir [Department of Civil and Environmental Engineering, Graduate Faculty of Environment, University of Tehran (Iran, Islamic Republic of)

    2012-06-15

    Highlights: Black-Right-Pointing-Pointer Hydrogen peroxide improves the performance of electrocoagulation process. Black-Right-Pointing-Pointer UV light can be effective on the performance on peroxi-electrocoagulation and electrocoagulation processes. Black-Right-Pointing-Pointer The optimal amount of hydrogen peroxide for peroxi-electrocoagulation process for COD removal from pharmaceutical wastewater is 300 mg/L. Black-Right-Pointing-Pointer The optimal values of pH for electrocoagulation and peroxi-electrocoagulation are 7 and 3, respectively. - Abstract: This work makes a comparison between electrocoagulation (EC), photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes to investigate the removal of chemical oxygen demand (COD) from pharmaceutical wastewater. The effects of operational parameters such as initial pH, current density, applied voltage, amount of hydrogen peroxide and electrolysis time on COD removal efficiency were investigated and the optimum operating range for each of these operating variables was experimentally determined. In electrocoagulation process, the optimum values of pH and voltage were determined to be 7 and 40 V, respectively. Desired pH and hydrogen peroxide concentration in the Fenton-based processes were found to be 3 and 300 mg/L, respectively. The amounts of COD, pH, electrical conductivity, temperature and total dissolved solids (TDS) were on-line monitored. Results indicated that under the optimum operating range for each process, the COD removal efficiency was in order of peroxi-electrocoagulation > peroxi-photoelectrocoagulation > photoelectrocoagulation > electrocoagulation. Finally, a kinetic study was carried out using the linear pseudo-second-order model and results showed that the pseudo-second-order equation provided the best correlation for the COD removal rate.

  12. Direct detection of OH formation in the reactions of HO2 with CH3C(OO2 and other substituted peroxy radicals

    Directory of Open Access Journals (Sweden)

    J. N. Crowley

    2008-08-01

    Full Text Available This work details the first direct observation of OH as a product from (R1: HO2+CH3C(OO2→(products, which has generally been considered an atmospheric radical termination process. The technique of pulsed laser photolysis radical generation, coupled to calibrated laser induced fluorescence detection was used to measure an OH product yield for (R1 of α1(298 K=(0.5±0.2. This study of (R1 included the measurement of a rate coefficient k1(298 K=(1.4±0.5×10−11cm3 molecule−1 s−1, substantially reducing the uncertainties in modelling this important atmospheric reaction. OH was also detected as a product from the reactions of HO2 with three other carbonyl-containing peroxy radicals, albeit at smaller yield, e.g. (R2: HO2+CH3C(OCH2O2→(products, α2≈0.15. By contrast, OH was not observed (α<0.06 as a major product from reactions where carbonyl functionality was absent, e.g. HO2+HOCH2CH2O2 (R8, and HO2+CH3CH(OHCH2O2 (R9.

  13. Study of atmospheric photo-oxidation mechanisms by concentration measurements of peroxy radicals by chemical amplification in the laboratory and in the atmosphere; Etudes des mecanismes de photooxydation atmospherique par mesure des radicaux peroxyles par amplification chimique au laboratoire et dans l'atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Pinceloup, St.

    2002-10-01

    In this thesis, we have continued to develop and to automate a chemical amplifier, with which measurements of peroxy radicals (RO{sub 2}) under real and simulated atmosphere can be made in order to better understand the atmospheric oxidation processes. Firstly, some experiments in laboratory have confirmed the inhibitory effect of water vapour on the chain length of the chemical amplifier, which is a technique of measuring peroxy radicals used by the LCSR. We have shown that the decrease in the chain length is primarily due to the increase of the HO{sub 2} loss to the wall of the amplifier in presence of H2{sub O} and to the HO{sub 2} loss in the gas phase by a minority way of the reaction NO + HO{sub 2} producing HNO{sub 3}. This reaction was studied using a turbulent flow reactor coupled to an ion molecule reactor with mass spectrometric detection. Secondly, the photo-oxidation of formaldehyde has been studied in the atmospheric simulation chamber of the LISA at Creteil coupled with the chemical amplifier. This study has allowed us to determine realistic values of the photolysis constants of radical and molecular ways of formaldehyde and the thermal decomposition constant at 298 K of the adduct HOCH{sub 2}O{sub 2} formed by reaction of HO{sub 2} with HCHO, thanks to the peroxy radicals measurements effectuated. Finally, we have participated in the field campaign, ESCOMPTE, during which concentrations of RO{sub 2}, NO, NO{sub 2} and ozone were measured continuously at the Dupail site. The measured concentrations were typical of a rural site. Using these measurements and those accomplished by other teams, we have determined the production rate of ozone by the radical budget method. The results show that the local photochemical production was important on the Dupail site and controlled essentially by the nitrogen oxides (NO, NO{sub 2}) characterizing a site free of emissions. (author)

  14. Comparison of COD removal from pharmaceutical wastewater by electrocoagulation, photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes.

    Science.gov (United States)

    Farhadi, Sajjad; Aminzadeh, Behnoush; Torabian, Ali; Khatibikamal, Vahid; Alizadeh Fard, Mohammad

    2012-06-15

    This work makes a comparison between electrocoagulation (EC), photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes to investigate the removal of chemical oxygen demand (COD) from pharmaceutical wastewater. The effects of operational parameters such as initial pH, current density, applied voltage, amount of hydrogen peroxide and electrolysis time on COD removal efficiency were investigated and the optimum operating range for each of these operating variables was experimentally determined. In electrocoagulation process, the optimum values of pH and voltage were determined to be 7 and 40 V, respectively. Desired pH and hydrogen peroxide concentration in the Fenton-based processes were found to be 3 and 300 mg/L, respectively. The amounts of COD, pH, electrical conductivity, temperature and total dissolved solids (TDS) were on-line monitored. Results indicated that under the optimum operating range for each process, the COD removal efficiency was in order of peroxi-electrocoagulation > peroxi-photoelectrocoagulation > photoelectrocoagulation>electrocoagulation. Finally, a kinetic study was carried out using the linear pseudo-second-order model and results showed that the pseudo-second-order equation provided the best correlation for the COD removal rate. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Radical-induced oxidation of RAFT agents : a kinetic study

    NARCIS (Netherlands)

    Li, Changxi; He, Junpo; Zhou, Yanwu; Gu, Yuankai; Yang, Yuliang

    2011-01-01

    Radical-induced oxidn. of reversible addn.-fragmentation chain transfer (RAFT) agents is studied with respect to the effect of mol. structure on oxidn. rate. The radicals are generated by homolysis of either azobisisobutyronitrile or alkoxyamine and transformed in situ immediately into peroxy

  16. Small molecule n-(alpha-peroxy) indole compounds and methods of use

    KAUST Repository

    Wang, Xinbo; Lai, Zhiping; Pan, Yupeng; Huang, Kuo-Wei; Wang, Zhigang

    2017-01-01

    The invention relates to novel N-(α-peroxy)indole compounds of Formula I and methods for use. (I) The N-(α-peroxy)indole compounds described herein are useful for treating or preventing parasitic infections, bacterial infections, and cancer in subjects. The methods include administering an N-(α-peroxy)indole compound as described herein to a subject. Also described herein are methods for synthesizing N-(α-peroxy )indole compounds.

  17. Small molecule n-(alpha-peroxy) carbazole compounds and methods of use

    KAUST Repository

    Wang, Xinbo; Lai, Zhiping; Pan, Yupeng; Huang, Kuo-Wei

    2017-01-01

    The invention relates to novel N-(α-peroxy)carbazole compounds of Formula I and methods for use. (I) The N-(α-peroxy)carbazole compounds described herein are useful for treating or preventing parasitic infections, bacterial infections, and cancer in subjects. The methods include administering an N-(α-peroxy)carbazole compound as described herein to a subject. Also described herein are methods for synthesizing N-(α-peroxy)carbazole compounds.

  18. Small molecule n-(alpha-peroxy) indole compounds and methods of use

    KAUST Repository

    Wang, Xinbo

    2017-11-16

    The invention relates to novel N-(α-peroxy)indole compounds of Formula I and methods for use. (I) The N-(α-peroxy)indole compounds described herein are useful for treating or preventing parasitic infections, bacterial infections, and cancer in subjects. The methods include administering an N-(α-peroxy)indole compound as described herein to a subject. Also described herein are methods for synthesizing N-(α-peroxy )indole compounds.

  19. Small molecule n-(alpha-peroxy) carbazole compounds and methods of use

    KAUST Repository

    Wang, Xinbo

    2017-11-16

    The invention relates to novel N-(α-peroxy)carbazole compounds of Formula I and methods for use. (I) The N-(α-peroxy)carbazole compounds described herein are useful for treating or preventing parasitic infections, bacterial infections, and cancer in subjects. The methods include administering an N-(α-peroxy)carbazole compound as described herein to a subject. Also described herein are methods for synthesizing N-(α-peroxy)carbazole compounds.

  20. Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

    International Nuclear Information System (INIS)

    Bors, W.; Saran, M.; Michel, C.

    1982-01-01

    The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

  1. Thermochemistry and kinetics for 2-butanone-1-yl radical (CH2·C(═O)CH2CH3) reactions with O2.

    Science.gov (United States)

    Sebbar, N; Bozzelli, J W; Bockhorn, H

    2014-01-09

    Thermochemistry of reactants, intermediates, transition state structures, and products along with kinetics on the association of CH2·C(═O)CH2CH3 (2-butanone-1-yl) with O2 and dissociation of the peroxy adduct isomers are studied. Thermochemical properties are determined using ab initio (G3MP2B3 and G3) composite methods along with density functional theory (B3LYP/6-311g(d,p)). Entropy and heat capacity contributions versus temperature are determined from structures, vibration frequencies, and internal rotor potentials. The CH2·C(═O)CH2CH3 radical + O2 association results in a chemically activated peroxy radical with 27 kcal mol(-1) excess of energy. The chemically activated adduct can react to stabilized peroxy or hydroperoxide alkyl radical adducts, further react to lactones plus hydroxyl radical, or form olefinic ketones and a hydroperoxy radical. Kinetic parameters are determined from the G3 composite methods derived thermochemical parameters, and quantum Rice-Ramsperger-Kassel (QRRK) analysis to calculate k(E) with master equation analysis to evaluate falloff in the chemically activated and dissociation reactions. One new, not previously reported, peroxy chemistry reaction is presented. It has a low barrier path and involves a concerted reaction resulting in olefin formation, H2O elimination, and an alkoxy radical.

  2. A pulse radiolysis study of the OH radical induced autoxidation of methanesulfinic acid

    DEFF Research Database (Denmark)

    Sehested, K.; Holcman, J.

    1996-01-01

    Methanesulfinic acid, CH3SO2H, reacts with OH radicals at pH 7 forming CH3SO2 radicals with a rate constant k = (6.0 +/- 1.0) x 10(9) M(-1) s(-1). The CH3SO2 radical absorbs at 325 nm with an extinction coefficient of 900 +/- 100 M(-1) cm(-1) and disappears in a second order self-reaction with k...... takes place. During the course of the chain oxidation a peroxyacid, presumably methaneperoxymonosulfonic acid, is formed and accumulated. This acid absorbs in the UV and eventually decays by reaction with excess methanesulfinic acid k = 5 x 10(3) M(-1) s(-1). The final product of the chain autoxidation...... = (1.0 +/- 0.2) x 10(9) M(-1) s(-1). This radical reacts with oxygen, k = (1.2 +/- 0.3) x 10(9) M(-1) s(-1), forming a peroxy radical which absorbs in the UV below 300 nm. The peroxy radical reacts in turn with methanesulfinic acid reforming the CH3SO2 radical whereby a chain oxidation of sulfinic acid...

  3. Understanding in situ ozone production in the summertime through radical observations and modelling studies during the Clean air for London project (ClearfLo)

    Science.gov (United States)

    Whalley, Lisa K.; Stone, Daniel; Dunmore, Rachel; Hamilton, Jacqueline; Hopkins, James R.; Lee, James D.; Lewis, Alastair C.; Williams, Paul; Kleffmann, Jörg; Laufs, Sebastian; Woodward-Massey, Robert; Heard, Dwayne E.

    2018-02-01

    Measurements of OH, HO2, RO2i (alkene and aromatic-related RO2) and total RO2 radicals taken during the ClearfLo campaign in central London in the summer of 2012 are presented. A photostationary steady-state calculation of OH which considered measured OH reactivity as the OH sink term and the measured OH sources (of which HO2+ NO reaction and HONO photolysis dominated) compared well with the observed levels of OH. Comparison with calculations from a detailed box model utilising the Master Chemical Mechanism v3.2, however, highlighted a substantial discrepancy between radical observations under lower NOx conditions ([NO] model was missing a significant peroxy radical sink; the model overpredicted HO2 by up to a factor of 10 at these times. Known radical termination steps, such as HO2 uptake on aerosols, were not sufficient to reconcile the model-measurement discrepancies alone, suggesting other missing termination processes. This missing sink was most evident when the air reaching the site had previously passed over central London to the east and when elevated temperatures were experienced and, hence, contained higher concentrations of VOCs. Uncertainties in the degradation mechanism at low NOx of complex biogenic and diesel related VOC species, which were particularly elevated and dominated OH reactivity under these easterly flows, may account for some of the model-measurement disagreement. Under higher [NO] (> 3 ppbv) the box model increasingly underpredicted total [RO2]. The modelled and observed HO2 were in agreement, however, under elevated NO concentrations ranging from 7 to 15 ppbv. The model uncertainty under low NO conditions leads to more ozone production predicted using modelled peroxy radical concentrations ( ˜ 3 ppbv h-1) versus ozone production from peroxy radicals measured ( ˜ 1 ppbv h-1). Conversely, ozone production derived from the predicted peroxy radicals is up to an order of magnitude lower than from the observed peroxy radicals as [NO

  4. Peroxy bleaches

    International Nuclear Information System (INIS)

    Carson, P.A.; Fairclough, C.S.; Mauduit, C.; Colsell, M.

    2006-01-01

    The thermodynamic and kinetic properties of a series of inorganic and organic peroxy bleaches were determined using adiabatic rate calorimetry and isothermal microcalorimetry. Results are compared to calculated oxygen balance values. The decomposition of the majority of the compounds is complex. Data indicate the need for cooling during the storage and transport for some materials evaluated. Although no overall structure/activity relationship could be established because of the diversity of molecular architectures studied, a combination of decomposition and activation energy data provides a means for hazard and risk classification

  5. Plasma thiobarbituric acid reactivity: reaction conditions and the role of iron, antioxidants and lipid peroxy radicals on the quantitation of plasma lipid peroxides

    Energy Technology Data Exchange (ETDEWEB)

    Wade, C.R.; van Rij, A.M.

    1988-01-01

    The effects of Fe/sup 3 +/, lipid peroxy radicals and the antioxidant butylated hydroxytoluene on the 2-thiobarbituric (TBA) acid quantitation of plasma lipid peroxides were investigated. Whole plasma and plasma fractions prepared by trichloroacetic acid (TCA) protein precipitation and lipid extraction, demonstrated markedly differing TBA reactivities in the presence or absence of added Fe/sup 3 +/. Examination of the spectral profiles of the TBA reacted whole plasma and TCA precipitated fractions demonstrated the presence of interfering compounds which gave rise to an artifactual increase in lipid peroxide concentrations. In contrast the TBA reacted lipid extracts had low levels of interfering compounds that could be removed by our previously described high pressure liquid chromatographic method. Further characterization of the TBA reactivity of the lipid extract showed that Fe/sup 3 +/ at an optimal concentration of 0.5 mM was necessary for the quantitative decomposition of the lipid peroxides to the TBA reactive product malondialdehyde (MDA). However the presence of Fe/sup 3 +/ resulted in further peroxidation of any unsaturated lipids present.

  6. The research progress of several kinds of free radical scavengers

    International Nuclear Information System (INIS)

    Qian Liren; Huang Yuecheng; Cai Jianming

    2009-01-01

    Ionization radiation can generate free radicals in biological system, which could induce lipid peroxi-dation, biomacromolecule and biomembrane damage, lost of cell function, cell cycle disturbance, genetic mutation and so on. The scavenging free radicals can protect organism from radiation damage. Many radio-protective agents, such as amylase, hydroxyl-benzene derivatives, hormone, vitamin, have great abilities to protect organism from radiation via scavenging free radicals. In this paper, we mainly review the free radical scavenging effects of several kinds of radio-protective agents. (authors)

  7. One electron transfer redox potentials of free radicals. I. The oxygen-superoxide system. Progress report, September 1, 1975--July 1, 1976

    International Nuclear Information System (INIS)

    Ilan, Y.A.; Czapski, G.; Meisel, D.

    1976-01-01

    The method of determination of Redox potentials of radicals, using the pulse radiolysis technique, is outlined. The method is based on the determination of equilibria constants of electron transfer reactions between the radicals and appropriate acceptors. The limitations of this technique are discussed. The redox potentials of several quinones--semi-quinones are calculated, as well as the standard redox potential of the peroxy radical. E 0 /sub O 2 /O 2 /sup -/ = -0.33 V and the redox oxidation properties of the peroxy radical in various systems and pH are discussed. The value determined for the redox potentials of O 2 /O 2 - is higher by more than 0.2 volts than earlier estimates, which has important implications on the possible role of O 2 - in biological processes of O 2 fixation

  8. Formation of gas-phase π-allyl radicals from propylene over bismuth oxide and γ-bismuth molybdate catalysts

    International Nuclear Information System (INIS)

    Martir, W.; Lunsford, J.H.

    1981-01-01

    Gas-phase π-allyl radicals were produced when propylene reacted over Bi 2 O 3 and γ-bismuth molybdate catalysts at 723 K. The pressure in the catalyst zone was varied between 5 x 10 -3 and 1 torr. The radicals were detected by EPR spectroscopy together with a matrix isolation technique in which argon was used as the diluent. The matrix was formed on a sapphire rod at 12 K which was located 33-cm downstream from the catalyst. Bismuth oxide was more effective in the production of gas-phase allyl radicals than γ-bismuth molybdate. By contrast α-bismuth molybdate was ineffective in forming allyl radicals and MoO 3 acted as a sink for radicals which were produced elsewhere in the system. Comparison of the π-allyl radical and the stable product concentrations over Bi 2 O 3 revealed that gas-phase radical recombination reactions served as a major pathway for the formation of 1,5-hexadiene. Addition of small amounts of gas-phase oxygen increased the concentration of allyl radicals, and at greater oxygen levels allyl peroxy radicals were detected. Because of the effect of temperature on the equilibrium between allyl and allyl peroxy radicals, the latter product must be formed in the cooler part of the system

  9. The Diurnal Variation of Hydrogen, Nitrogen, and Chlorine Radicals: Implications for the Heterogeneous Production of HNO2

    Science.gov (United States)

    Salawitch, R. J.; Wofsy, S. C.; Wennberg, P. O.; Cohen, R. C.; Anderson, J. G.; Fahey, D. W.; Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Stimpfle, R. M.; hide

    1994-01-01

    In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower stratosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N205 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and H02 observed near sunrise and sunset. The morning burst of [OH] and [HO2] coincides with the rise of [NO] from photolysis of N02, suggesting a new source of HO, that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allows for the heterogeneous production of HN02 results in an excellent simulation of the diurnal variations of [OH] and [HO2].

  10. OH, HO2, and HO2* Radical Chemistry During PROPHET-AMOS 2016: Measurements and Model Comparison

    Science.gov (United States)

    Bottorff, B.; Lew, M.; Rickly, P.; Stevens, P. S.

    2017-12-01

    The hydroxyl (OH) and peroxy radicals, both the hydroperoxy radical (HO2) and organic peroxy radicals (RO2), play an important role in atmospheric chemistry. In addition to controlling lifetimes of many trace gases important to issues of global climate change, reactions of these radicals can also lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in remote forest environments have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOX conditions. In the summer of 2016, OH, HO2 and HO2* (HO2 + αRO2) radicals were measured using the Indiana University Laser-Induced Fluorescence Fluorescence Assay by Gas Expansion (LIF-FAGE) technique as part of the Program for Research on Oxidants: PHtochemistry, Emissions, and Transport- Atmospheric Measurements of Oxidants in Summer (PROPHET-AMOS). This campaign took place in a forested area in northern Michigan characterized by high mixing ratios of isoprene and low mixing ratios of NOX. Ambient measurements from this campaign will be compared to previous measurements at this site and to modeled predictions using both the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism. Potential interferences associated with the OH measurements will also be examined.

  11. Radicals in the marine boundary layer during NEAQS 2004: a model study of day-time and night-time sources and sinks

    Directory of Open Access Journals (Sweden)

    R. Sommariva

    2009-05-01

    Full Text Available This paper describes a modelling study of several HOx and NOx species (OH, HO2, organic peroxy radicals, NO3 and N2O5 in the marine boundary layer. A model based upon the Master Chemical Mechanism (MCM was constrained to observations of chemical and physical parameters made onboard the NOAA ship R/V Brown as part of the New England Air Quality Study (NEAQS in the summer of 2004. The model was used to calculate [OH] and to determine the composition of the peroxy radical pool. Modelled [NO3] and [N2O5] were compared to in-situ measurements by Cavity Ring-Down Spectroscopy. The comparison showed that the model generally overestimated the measurements by 30–50%, on average.

    The model results were analyzed with respect to several chemical and physical parameters, including uptake of NO3 and N2O5 on fog droplets and on aerosol, dry deposition of NO3 and N2O5, gas-phase hydrolysis of N2O5 and reactions of NO3 with NMHCs and peroxy radicals. The results suggest that fog, when present, is an important sink for N2O5 via rapid heterogeneous uptake. The comparison between the model and the measurements were consistent with values of the heterogeneous uptake coefficient of N2O5N2O5>1×10−2, independent of aerosol composition in this marine environment. The analysis of the different loss processes of the nitrate radical showed the important role of the organic peroxy radicals, which accounted for a significant fraction (median: 15% of NO3 gas-phase removal, particularly in the presence of high concentrations of dimethyl sulphide (DMS.

  12. One-Pot Synthesis of N-(α-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere

    KAUST Repository

    Wang, Xinbo; Pan, Yupeng; Huang, Kuo-Wei; Lai, Zhiping

    2015-01-01

    A facile one-pot synthesis of N-(α-peroxy)indole and N-(α-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction

  13. Kinetics of the Reaction of CH3O2 Radicals with OH Studied over the 292-526 K Temperature Range.

    Science.gov (United States)

    Yan, Chao; Kocevska, Stefani; Krasnoperov, Lev N

    2016-08-11

    Reaction of methyl peroxy radicals with hydroxyl radicals, CH3O2 + OH → CH3O + HO2 (1a) and CH3O2 + OH → CH2OO + H2O (1b) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 292-526 K temperature range and pressure 1 bar (bath gas He). Hydroxyl radicals were generated in the reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N2O at 193.3 nm, with H2O. Methyl peroxy radicals were generated in the reaction of methyl radicals, CH3, produced in the photolysis of acetone at 193.3 nm, and subsequent reaction of CH3 with O2. Temporal profiles of OH were monitored via transient absorption of light from a DC discharge H2O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The overall rate constant of the reaction is k1a+1b = (8.4 ± 1.7) × 10(-11)(T/298 K)(-0.81) cm(3) molecule(-1) s(-1) (292-526 K). The branching ratio of channel 1b at 298 K is less than 5%.

  14. Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air.

    Science.gov (United States)

    Zhao, Yue; Wingen, Lisa M; Perraud, Véronique; Greaves, John; Finlayson-Pitts, Barbara J

    2015-05-21

    Ozonolysis of alkenes is an important source of secondary organic aerosol (SOA) in the atmosphere. However, the mechanisms by which stabilized Criegee intermediates (SCI) react to form and grow the particles, and in particular the contributions from oligomers, are not well understood. In this study, ozonolysis of trans-3-hexene (C6H12), as a proxy for small alkenes, was investigated with an emphasis on the mechanisms of particle formation and growth. Ozonolysis experiments were carried out both in static Teflon chambers (18-20 min reaction times) and in a glass flow reactor (24 s reaction time) in the absence and presence of OH or SCI scavengers, and under different relative humidity (RH) conditions. The chemical composition of polydisperse and size-selected SOA particles was probed using different mass spectrometric techniques and infrared spectroscopy. Oligomers having SCI as the chain unit are found to be the dominant components of such SOA particles. The formation mechanism for these oligomers suggested by our results follows the sequential addition of SCI to organic peroxy (RO2) radicals, in agreement with previous studies by Moortgat and coworkers. Smaller particles are shown to have a relatively greater contribution from longer oligomers. Higher O/C ratios are observed in smaller particles and are similar to those of oligomers resulting from RO2 + nSCI, supporting a significant role for longer oligomers in particle nucleation and early growth. Under atmospherically relevant RH of 30-80%, water vapor suppresses oligomer formation through scavenging SCI, but also enhances particle nucleation. Under humid conditions, or in the presence of formic or hydrochloric acid as SCI scavengers, peroxyhemiacetals are formed by the acid-catalyzed particle phase reaction between oligomers from RO2 + nSCI and a trans-3-hexene derived carbonyl product. In contrast to the ozonolysis of trans-3-hexene, oligomerization involving RO2 + nSCI does not appear to be prevalent in the

  15. The Atmospheric Oxidation of Volatile Organic Compounds Through Hydrogen Shift Reactions

    DEFF Research Database (Denmark)

    Knap, Hasse Christian

    a radical is denoted as a H-shift reaction. Quantum chemical calculations were carried out to investigate the potential energy surface of the H-shift reactions and the subsequent decomposition pathways. The transition state theory including the Eckart quantum tunneling correction have been used to calculate...... the reaction rate constants of the H-shift reactions. The autoxidation of volatile organic compounds is an important oxidation mechanism that produces secondary organic aerosols (SOA) and recycles hydroxyl (OH) radicals. The autoxidation cycle produces a second generation peroxy radical (OOQOOH) through...... a series of H-shift reactions and O2 attachments. I have investigated the H-shift reactions in two OOQOOH radicals (hydroperoxy peroxy radicals and hydroperoxy acyl peroxy radicals). The H-shift reaction rate constants have been compared with the bimolecular reaction rate constants of the peroxy radicals...

  16. In situ characterization of Ti-peroxy gel during formation on titanium surfaces in hydrogen peroxide containing solutions

    International Nuclear Information System (INIS)

    Muyco, Julie J.; Gray, Jeremy J.; Ratto, Timothy V.; Orme, Christine A.; McKittrick, Joanna; Frangos, John

    2006-01-01

    Three possible functions of Ti-peroxy gel are: reduction of the inflammatory response through the reduction of hydrogen peroxide and other reactive oxygen species; creation of a favorable surface for calcium phosphate nucleation; and as a transitional layer between the compliant surrounding tissue and the stiff titanium. Traditional surface characterization techniques operate in high vacuum environments that alter the actual sample-solution interface. Our studies used techniques that allowed samples to remain in solution and be observed over time. Atomic force microscopy (AFM) force-distance curves, electrochemical impedance spectroscopy (EIS), and Raman spectroscopy were each used in situ to define kinetic and mechanical properties of Ti-peroxy gel as it formed over time on titanium during exposure to hydrogen peroxide. Our studies enabled us to monitor real-time changes in the native oxide layer on titanium in hydrogen peroxide containing solution, including the formation of a Ti-peroxy gel layer above the native oxide. Peaks attributed to Ti-peroxy gel were seen to emerge over the course of several hours using in situ Raman spectroscopy. Force-distance curves suggest a layer that thickens with time on the titanium sample surface. EIS data showed that changes in the surface layers could be monitored in solution over time

  17. One-Pot Synthesis of N-(α-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere

    KAUST Repository

    Wang, Xinbo

    2015-11-06

    A facile one-pot synthesis of N-(α-peroxy)indole and N-(α-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction discovered, a new synthetic proposal for Fumitremorgin A and Verruculogen is introduced. Such a protocol could be easily handled and scaled up in an open atmosphere with a wide substrate scope, enabling the construction of a new molecule library.

  18. Spin trapping study on the nature of radicals generated by X radiolysis and peroxidation of linolenic acid

    International Nuclear Information System (INIS)

    Azizova, O.A.; Osipov, A.N.; Zubarev, V.E.; Yakhyaev, A.V.; Vladimirov, Yu.A.; Savov, V.M.; Kagan, V.E.

    1983-01-01

    The radicals of linolenic acid and their spin adducts (SA) with PBN formed during X radiolysis of linolenic acid and in lipid peroxidation with ferrous ions were investigated and identified. It was found that in the absence of oxygen in pure linolenic acid at 77 K X irradiation produces alkyl and carboxyl radicals. In the presence of the spin trap alkyl radical spin adducts were formed. Irradiation of linolenic acid in the presence of oxygen at 77 K also resulted in the formation of alkyl radicals. These radicals were transformed into peroxy radicals in the interaction of alkyl radical with oxygen upon heating to 117 K. In the presence of spin trap X irradiation of linolenic acid and heating of the sample up to 300 K gave rise to EPR spectra of SA alkyl and unidentified radicals. Lipid peroxidation of linolenic acid induced by ferrous ions in the presence of spin trap also formed radicals and SA of linolenic acid. The spectral parameters of SA generated with ferrous ions in lipid peroxidation and of those generated during X radiolysis do not differ. The similarity of spectral parameters of SA in these two cases suggests a similarity in the structure of linolenic acid radicals. (author)

  19. Mechanisms for formation of organic acids in gas-phase reactions of ozone and hydroxyl radical with dialkenes and unsaturated carbonyls

    Science.gov (United States)

    Chien, Chao-Jung

    2001-07-01

    Carboxylic acids are ubiquitous throughout the troposphere and may contribute significant fractions of the free acidity in some remote areas. One of the important sources of these carboxylic acids is thought to be photochemical transformation of biogenic hydrocarbons such as isoprene. For the work reported here, atmospheric samples from University of North Carolina dual outdoor environmental chamber under simulated urban atmospheric conditions were analyzed for carboxylic acids. Both OH radicals and O3 initiated photooxidation reaction experiments were performed for isoprene, along with its structural analogs, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene, and their primary photooxidation products, methacrolein, acrolein, and methyl vinyl ketone. Among the detected carboxylic acids were formic, acetic, and several multifunctional carboxylic acids, including methacrylic, acrylic, glyoxylic, and glycolic acids. Quantification of most carboxylic acid products was also established. Formation yields of carboxylic acids from the reactions of O3 with studied compounds were determined, and time-concentration series of the reactants and carboxylic acid products were measured to facilitate mechanism formulation. While the reaction mechanisms of Criegee biradicals arising from decomposition of primary ozonides are proposed to account for the observed carboxylic acid products in the ozonolysis of unsaturated hydrocarbons, reactions of peroxy acyl radicals with HO2 and/or other peroxy radicals are thought to be responsible for the formation of carboxylic acids during the OH-initiated reactions in the presence of NOx. In this study, smog chamber simulations have also been performed for selected compounds using Morpho, a photochemical kinetic simulation software package. Explicit photochemical mechanisms with O 3 and OH radicals that lead to formation of carboxylic acids were elaborated and implemented, and the simulation results were compared with those from other chemical

  20. Enthalpies of vaporization of some acetylene peroxy derivatives of carboranes-12

    International Nuclear Information System (INIS)

    Dibrivnyj, V.N.; Pistun, Z.E.; Van-Chin-Syan, Yu.Ya.; Yuvchenko, A.P.; Zvereva, T.D.

    1999-01-01

    Temperature dependences of saturated vapor pressure and vaporization enthalpies of five acetylene peroxy derivatives of carboranes-12 are determined by the Knudsen effusion method. Enthalpies and melting points of crystals, as well as temperatures of liquid compounds decomposition start are determined by the method of differential scanning calorimetry. Comparison of evaporation enthalpies determined in the study confirms the conclusions on non-additive character of intermolecular interaction in carboranes and their derivatives, which have been made previously [ru

  1. Peroxy defects in Rocks and H2O2 formation on the early Earth

    Science.gov (United States)

    Gray, A.; Balk, M.; Mason, P.; Freund, F.; Rothschild, L.

    2013-12-01

    An oxygen-rich atmosphere appears to have been a prerequisite for complex life to evolve on Earth and possibly elsewhere in the Universe. The question is still shrouded in uncertainty how free oxygen became available on the early Earth. Here we study processes of peroxy defects in silicate minerals which, upon weathering, generate mobilized electronic charge carriers resulting in oxygen formation in an initially anoxic subsurface environment. Reactive Oxygen Species (ROS) are precursors to molecular oxygen during this process. Due to their toxicity they may have strongly influenced the evolution of life. ROS are generated during hydrolysis of peroxy defects, which consist of pairs of oxygen anions. A second pathway for formation occurs during (bio) transformations of iron sulphide minerals. ROS are produced and consumed by intracellular and extracellular reactions of Fe, Mn, C, N, and S species. We propose that despite an overall reducing or neutral oxidation state of the macroenvironment and the absence of free O2 in the atmosphere, microorganisms on the early Earth had to cope with ROS in their microenvironments. They were thus under evolutionary pressure to develop enzymatic and other defenses against the potentially dangerous, even lethal effects of ROS and oxygen. We have investigated how oxygen might be released through weathering and test microorganisms in contact with rock surfaces. Our results show how early Life might have adapted to oxygen. Early microorganisms must have "trained" to detoxify ROS prior to the evolution of aerobic metabolism and oxygenic photosynthesis. A possible way out of this dilemma comes from a study of igneous and high-grade metamorphic rocks, whose minerals contain a small but significant fraction of oxygen anions in the valence state 1- , forming peroxy links of the type O3Si-OO-SiO3 [1, 2]. As water hydrolyzes the peroxy links hydrogen peroxide, H2O2, forms. Continued experimental discovery of H2O2 formation at rock

  2. Rare earths: preparation of spectro chemically pure standards, study of their carbonates and synthesis of a new compound series - the peroxy carbonates

    International Nuclear Information System (INIS)

    Queiroz, Carlos Alberto da Silva

    1996-05-01

    In this work the following studies are concerned: I) preparation of lanthanum, cerium, praseodymium, neodymium and samarium oxides for use as spectro chemically pure standards; II) behavior of the rare earth (La, Ce, Pr, Nd, Sm) carbonates soluble in ammonium carbonate and mixture of ammonium carbonate/ammonium hydroxide, and III) synthesis and characterization of rare earth peroxy carbonates - a new series of compounds. Data for the synthesis and characterization of the rare earths peroxy carbonates described for the first time in this work are presented and discussed. With the aid of thermal analysis (TG-DTG) the thermal stability and the stoichiometric composition for new compounds were established and a mechanism of thermal decomposition was proposed. The peroxy carbonate was prepared by the addition of hydrogen peroxyde to the complexed soluble rare earths carbonates. These studies included also the determinations of active oxygen, the total rare earth oxide by gravimetry and complexometry and the C, H and N contents by microanalysis. The new compounds were also investigated by infrared spectroscopy. (author)

  3. Development of thermoresponsive non-woven 3D scaffold for smart cell culture

    CSIR Research Space (South Africa)

    Mahlangu, T

    2012-10-01

    Full Text Available morphology of the NWF scaffolds. 2-2-Diphenyl-1-picrylhydrazyl (DPPH), a stable free radical, was used to quantify the amount of peroxy free radicals on the oNWF. Scheme 1: A schematic representation showing the possible mechanism for oxyfluorination... 2: Typical ATR-FTIR spectra of pNWF, oNWF, PP-g-PNIPAAm (gNWF) and PNIPAAm homopolymer It is well-known that oxyfluorination produces peroxy free radicals on polymer surfaces. After oxyfluorination, new bands were observed on the oNWF at 3 700...

  4. Evaluation of free radical scavenging capacity and antioxidative damage effect of resveratrol-nanostructured lipid carriers

    Science.gov (United States)

    Jin, Ju; Shi, Fan; Li, Qiu-wen; Li, Pei-shan; Chen, Tong-sheng; Wang, Yi-fei; Wang, Zhi-ping

    2016-03-01

    Cellular damage induced by free-radicals like reactive oxygen species has been implicated in several diseases. 2, 2-azobis(2-amidino-propane) dihydrochloride(AAPH) generates two potent ROS capable of inducing lipid peroxidation: alkoxy radical(RO-) and peroxy radical(ROO-). These radicals are similar to those that are physiologically active and thus might initiate a cascade of intracellular toxic events leading to oxidation, lipid peroxidation, DNA damage and subsequent cell death. Hence naturally anti-oxidant play a vital role in combating these conditions. In this study, resveratrol loaded nanostructured lipid carriers (Res-NLC) was prepared by hot melting and then high pressure homogenization technique. The effects of Res-NLC on free radical scavenging capacity and antioxidative damage is investigated. The particle size and zeta potential of Res-NLC were 139.3 ± 1.7 nm and -11.21 ± 0.41 mV, respectively. By free radical scavenging assays, the IC50 value of Res-NLC were 19.25, 5.29 μg/mL with DPPH, ABTS assay respectively, and 0.161 mg ferrous sulfate/1 mg Res-NLC with FRAP assay; and by AAPH-induced oxidative injury cell model assay, Res-NLC showed the strong protective effect against the human liver tumor HepG2 cell oxidative stress damage. These results indicated that the antioxidant properties of Res-NLC hold great potential used as an alternative to more toxic synthetic antioxidants as an additive in food, cosmetic and pharmaceutical preparations for the oxidative diseases treatment.

  5. Peroxi-coagulation degradation of C.I. Basic Yellow 2 based on carbon-PTFE and carbon nanotube-PTFE electrodes as cathode

    International Nuclear Information System (INIS)

    Zarei, Mahmoud; Salari, Darioush; Niaei, Aligoli; Khataee, Alireza

    2009-01-01

    The electrochemical treatment of solutions containing C.I. Basic Yellow 2 (BY2) in aqueous solutions with carbon-PTFE (polytetrafluoroethylene) and carbon nanotube (CNT)-PTFE electrodes as cathode has been studied. The fabricated electrodes were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The amount of electrogenerated H 2 O 2 on the surface of these electrodes was investigated, too. The results showed that the amount of H 2 O 2 obtained with the CNT-PTFE electrode was nearly three times higher than that of carbon-PTFE electrode. The decolorization efficiency of BY2 in peroxi-coagulation process reached 62% and 96% in the first 10 min by carbon-PTFE and CNT-PTFE electrodes at 100 mA, respectively. The effect of operational parameters such as applied current, initial pH and initial dye concentration was studied in an attempt to reach higher decolorization efficiency. The degradation and mineralization of BY2 using CNT-PTFE electrode were followed by total organic carbon (TOC) and GC-MS analysis. The results of TOC measurements indicated that peroxi-coagulation with carbon-PTFE allowed 81% mineralization after 6 h of electrolysis; whereas peroxi-coagulation with CNT-PTFE yields 92% mineralization under the same conditions. GC-MS analysis verified the identity of intermediates and a reaction pathway based on them was proposed.

  6. Degradation and biodegradability improvement of the olive mill wastewater by peroxi-electrocoagulation/electrooxidation-electroflotation process with bipolar aluminum electrodes.

    Science.gov (United States)

    Esfandyari, Yahya; Mahdavi, Yousef; Seyedsalehi, Mahdi; Hoseini, Mohammad; Safari, Gholam Hossein; Ghozikali, Mohammad Ghanbari; Kamani, Hossein; Jaafari, Jalil

    2015-04-01

    Olive mill wastewater is considered as one of the most polluting effluents of the food industry and constitutes a source of important environmental problems. In this study, the removal of pollutants (chemical oxygen demand (COD), biochemical oxygen demand (BOD5), polyphenols, turbidity, color, total suspended solids (TSS), and oil and grease) from olive oil mill processing wastewater by peroxi-electrocoagulation/electrooxidation-electroflotation process with bipolar aluminum electrodes was evaluated using a pilot continuous reactor. In the electrochemical unit, aluminum (Al), stainless steel, and RuO2/Ti plates were used. The effects of pH, hydrogen peroxide doses, current density, NaCl concentrations, and reaction times were studied. Under optimal conditions of pH 4, current density of 40 mA/m(2), 1000 mg/L H2O2, 1 g/L NaCl, and 30-min reaction time, the peroxi-electrochemical method yielded very effective removal of organic pollution from the olive mill wastewater diluted four times. The treatment process reduced COD by 96%, BOD5 by 93.6%, total, polyphenols by 94.4%, color by 91.4%, turbidity by 88.7, suspended solids by 97% and oil and grease by 97.1%. The biodegradability index (BOD5/COD) increased from 0.29 to 0.46. Therefore, the peroxi-electrocoagulation/electrooxidation-electroflotation process is considered as an effective and feasible process for pre-treating olive mill wastewater, making possible a post-treatment of the effluent in a biological system.

  7. Suppression of new particle formation from monoterpene oxidation by NOx

    Science.gov (United States)

    Wildt, J.; Mentel, T. F.; Kiendler-Scharr, A.; Hoffmann, T.; Andres, S.; Ehn, M.; Kleist, E.; Müsgen, P.; Rohrer, F.; Rudich, Y.; Springer, M.; Tillmann, R.; Wahner, A.

    2014-03-01

    The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory setup. At high NOx conditions ([BVOC] / [NOx] 23 ppb) new particle formation was suppressed. Instead, photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. When [NO] was reduced back to levels below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF to be slowed by orders of magnitude compared to analogous experiments at low NOx conditions ([NOx] ~300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF. This suggests that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent approaching -2. This exponent indicated that the overall peroxy radical concentration must have been similar when NPF occurred. Thus, permutation reactions of first-generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy-radical-like intermediates limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was substantially less sensitive to NOx concentrations. If at all, yields were reduced by about an order of magnitude only at very high NOx concentrations.

  8. Atmospheric implications of simultaneous nighttime measurements of NO3 radicals and hono

    International Nuclear Information System (INIS)

    Pitts, J.N. Jr.; Biermann, H.W.; Atkinson, R.; Winer, A.M.

    1984-01-01

    Atmospheric concentrations of gaseous HONO and the NO 3 radical were measured simultaneously for the first time using long path differential optical absorption spectroscopy. Diurnal profiles are reported for two successive nights following days of moderate pollution at Riverside, California, together with concurrent measurements of NO 2 , O 3 and NO concentrations and an upper limit for HCHO levels. These measurements permit an examination of selected aspects of the nighttime atmospheric chemistry of HONO and the NO 3 radical and related species. Our data do not support a recently proposed homogeneous gas phase mechanism for HONO formation initiated by the reaction of the NO 3 radical with HCHO

  9. Products of BVOC oxidation: ozone and organic aerosols

    Science.gov (United States)

    Wildt, Jürgen; Andres, Stefanie; Carriero, Giulia; Ehn, Mikael; Fares, Silvano; Hoffmann, Thorsten; Hacker, Lina; Kiendler-Scharr, Astrid; Kleist, Einhard; Paoletti, Elena; Pullinen, Iida; Rohrer, Franz; Rudich, Yinon; Springer, Monika; Tillmann, Ralf; Wahner, Andreas; Wu, Cheng; Mentel, Thomas

    2015-04-01

    Biogenic Volatile Organic Compounds (BVOC) are important precursors in photochemical O3 and secondary organic aerosol (SOA) formation. We conducted a series of laboratory experiments with OH-induced oxidation of monoterpenes to elucidate pathways and efficiencies of O3 and SOA formation. At high NOx conditions ([BVOC] / [NOx] monoterpene mixes emitted from different plant species we observed increasing ozone formation with increasing [NOX]. Between 2 and 3 O3-molecules were formed from 1 monoterpene when ozone formation was BVOC limited. Under such high NOX conditions, new particle formation was suppressed. Increasing [BVOC] / [NOX] ratios caused increasing efficiency of new particle formation indicating that peroxy radicals are the key intermediates in both, photochemical ozone- and new particle formation. The classical chemistry of peroxy radicals is well established (e.g. Master Chemical Mechanism). Peroxy radicals are produced by addition of molecular oxygen to the alkyl radical formed after OH attack at the BVOC. They either react with NO which leads to ozone formation or they react with other peroxy radicals and form chemically stable products (hydroperoxides, alkoholes and ketones). Much less knowledge exists on such reactions for Highly Oxidized Peroxy Radicals, (HOPR). Such HOPR were observed during ozonolysis of several volatiles and, in case of monoterpenes as precursors, they can contain more than 12 Oxygen atoms (Mentel et al., 2015). Although the OH-initiated formation of HOPR is yet not fully understood, their basic gas phase reactions seem to follow classical photochemical rules. In reactions with NO they can act as precursor for O3 and in reactions with other HOPR or with classical less oxidized peroxy radicals they can form highly oxidized stable products and alkoxy radicals. In addition, HOPR-HOPR reactions lead to the formation of dimers that, in case of monoterpenes as reactants, consist of a skeleton with 20 carbon atoms. These dimers seem to

  10. Novel Profluorescent Nitroxides for Monitoring Alkyl Radical Reactions During Radiation Degradation

    International Nuclear Information System (INIS)

    George, G.

    2006-01-01

    Hindered amine stabilizers (HAS) are effective at retarding the photo-oxidative and high energy radiation degradation of PP and in certain circumstances, also thermo-oxidative degradation. The effectiveness of HAS as retarders of oxidation relies on the oxidation of the N-C bond by polymer hydroperoxide, ROOH, to form the nitroxyl group -NO which is the scavenger of polymer alkyl radicals, R. This reaction, which produces the alkoxy amine: -NO-R, must be competitive with the reaction of R with oxygen (which gives the chain-carrying peroxy radical, RO 2 ) if this stabilization mechanism is to be important in the inhibition of radiation-induced oxidative degradation of polyolefins by HAS. The rate of this reaction is high and in solution the rate coefficient is from 1 to 9x10 8 l mol - 1 s - 1. The efficient radical trapping by nitroxides has been widely employed in spin-trapping studies by electron spin resonance (esr) spectroscopy]. In addition to the hindered piperidine structure of commercial HAS, more rigid aromatic systems have been studied that are more stable to oxidative degradation and are more efficient at scavenging alkyl radicals. One such family is the iso-indoline nitroxide system, TMDBIO, shown below which, as it contains the phenanthrene fluorophore, is termed phenanthrene nitroxide. This nitroxide only becomes fluorescent when it reacts with alkyl radicals or is reduced and is termed profluorescent. TMDBIO has a vanishingly small fluorescence quantum yield (φ∼10 - 4) due to the enhanced intersystem crossing from the first excited singlet state to the ground state due to electron exchange interactions of the nitroxyl radical. When the nitroxide traps an alkyl radical, R, the resulting alkoxy amine is fluorescent (φ∼10 - 1) and the emission intensity is a measure of the number of reactions that have occurred. This property may be exploited by using quantitative fluorescence spectroscopy to follow the reaction of the nitroxide with alkyl radicals

  11. Investigation of reactions and species dominating low temperature combustion - Final report

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, T.; Radi, P.; Knopp, G.; Tulej, M.

    2007-07-01

    This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Paul Scherrer Institute PSI in Switzerland on the quantitative description of ignition. processes and the influence of peroxy radicals that determine ignition and speciation of the intermediates initially present and, thereby, the progress of subsequent reactions. The authors note that for the preparation of peroxy radicals, a dedicated molecular beam apparatus has been built by the PSI's 'Molecular Dynamics' group. A novel radical source is operational. In many cases, specific radicals can be prepared with high selectivity. A description of flame chemistry is being worked on that can reliably predict the speciation of intermediate products during ignition. Laser-based measurement techniques are being applied at PSI to measure the static and dynamic properties of alkyl peroxy radicals in order to accurately describe their reaction behaviour in combustion processes. A dedicated synchrotron beam line is installed at the Swiss Light Source (SLS) that extends the available range of spectroscopic measurements into the VUV (vacuum-ultraviolet) wavelength domain. The results obtained are presented and discussed.

  12. Developments in laser-induced fluorescence spectroscopy for quantitative in situ measurements of free radicals in the troposphere

    Science.gov (United States)

    Heard, Dwayne

    2015-04-01

    Photo-oxidation in the troposphere is highly complex, being initiated by short lived free radical species, in the daytime dominated by the hydroxyl radical, OH. Chemical oxidation cycles, which also involve peroxy radicals (HO2 and RO2), remove natural or anthropogenic emissions (for example methane) and generate a range of secondary products, for example ozone, nitrogen dioxide, acidic and multifunctional organic species, and secondary organic aerosol, which impact on human health and climate. Owing to their short lifetime in the atmosphere, the abundance of radicals is determined solely by their rate of chemical production and loss, and not by transport. Field measurements of the concentrations of radicals and comparison with calculations using a numerical model therefore constitutes one of the very best ways to test whether the chemistry in each of these locations is understood and accurately represented in the model. Validation of the chemistry is important, as the predictions of climate and air quality models containing this chemistry are used to drive the formulation of policy and legislation. However, in situ measurements of radical species, owing to their very low abundance (often sub part per trillion) and short lifetimes (pulse repetition rate tunable laser systems, will be discussed, together with calibration methods to make signals absolute, and identification of potential interferences. LIF instruments have been operated on ground, ship and aircraft platforms at a number of locations worldwide, and examples from recent fieldwork involving the Leeds instruments will be presented.

  13. Novel process window for the safe and continuous synthesis of tert.-butyl peroxy pivalate in a micro reactor

    NARCIS (Netherlands)

    Illg, T.; Hessel, V.; Löb, P.; Schouten, J.C.

    2011-01-01

    In this paper, the two step synthesis of tert.-butyl peroxy pivalate using two different flow regimes is introduced, in particular the use of "segmented flow" and the concept of "dispersed flow". The use of the segmented flow process, in this case, is challenging due to the very low interfacial

  14. Peroxy-Titanium Complex-based inks for low temperature compliant anatase thin films.

    Science.gov (United States)

    Shabanov, N S; Asvarov, A Sh; Chiolerio, A; Rabadanov, K Sh; Isaev, A B; Orudzhev, F F; Makhmudov, S Sh

    2017-07-15

    Stable highly crystalline titanium dioxide colloids are of paramount importance for the establishment of a solution-processable library of materials that could help in bringing the advantages of digital printing to the world of photocatalysis and solar energy conversion. Nano-sized titanium dioxide in the anatase phase was synthesized by means of hydrothermal methods and treated with hydrogen peroxide to form Peroxy-Titanium Complexes (PTCs). The influence of hydrogen peroxide on the structural, optical and rheological properties of titanium dioxide and its colloidal solutions were assessed and a practical demonstration of a low temperature compliant digitally printed anatase thin film given. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Measurement of interferences associated with the detection of the hydroperoxy radical in the atmosphere using laser-induced fluorescence

    Science.gov (United States)

    Lew, Michelle M.; Dusanter, Sebastien; Stevens, Philip S.

    2018-01-01

    One technique used to measure concentrations of the hydroperoxy radical (HO2) in the atmosphere involves chemically converting it to OH by addition of NO and subsequent detection of OH. However, some organic peroxy radicals (RO2) can also be rapidly converted to HO2 (and subsequently OH) in the presence of NO, interfering with measurements of ambient HO2 radical concentrations. This interference must be characterized for each instrument to determine to what extent various RO2 radicals interfere with measurements of HO2 and to assess the impact of this interference on past measurements. The efficiency of RO2-to-HO2 conversion for the Indiana University laser-induced fluorescence-fluorescence assay by gas expansion (IU-FAGE) instrument was measured for a variety of RO2 radicals. Known quantities of OH and HO2 radicals were produced from the photolysis of water vapor at 184.9 nm, and RO2 radicals were produced by the reaction of several volatile organic compounds (VOCs) with OH. The conversion efficiency of RO2 radicals to HO2 was measured when NO was added to the sampling cell for conditions employed during several previous field campaigns. For these conditions, approximately 80 % of alkene-derived RO2 radicals and 20 % of alkane-derived RO2 radicals were converted to HO2. Based on these measurements, interferences from various RO2 radicals contributed to approximately 35 % of the measured HO2 signal during the Mexico City Metropolitan Area (MCMA) 2006 campaign (MCMA-2006), where the measured VOCs consisted of a mixture of saturated and unsaturated species. However, this interference can contribute more significantly to the measured HO2 signal in forested environments dominated by unsaturated biogenic emissions such as isoprene.

  16. High-Pressure Limit Rate Rules for α-H Isomerization of Hydroperoxyalkylperoxy Radicals

    KAUST Repository

    Mohamed, Samah Y

    2018-03-09

    Hydroperoxyalkylperoxy (OOQOOH) radical isomerization is an important low-temperature chain branching reaction within the mechanism of hydrocarbon oxidation. This isomerization may proceed via the migration of the α-hydrogen to the hydroperoxide group. In this work, a combination of high level composite methods - CBS-QB3, G3 and G4 - is used to determine the high-pressure-limit rate parameters for the title reaction. Rate rules for H-migration reactions proceeding through 5-, 6-, 7- and 8-membered ring transitions states are determined. Migrations from primary, secondary and tertiary carbon sites to the peroxy group are considered. Chirality is also investigated by considering two diastereomers for reactants and transition states with two chiral centers. This is important since chirality may influence the energy barrier of the reaction as well as the rotational energy barriers of hindered rotors in chemical species and transition states. The effect of chirality and hydrogen bonding interactions in the investigated energies and rate constants is studied. The results show that while the energy difference between two diastereomers ranges from 0.1 - 3.2 kcal, chirality hardly affects the kinetics, except at low temperatures (atmospheric conditions) or when two chiral centers are present in the reactant. Regarding the effects of the peroxy group position and the H-migration ring size, it is found that in most cases, the 1,5 and 1,6 H-migration reactions have similar rates at low temperatures (below ~830K) since the 1,6 H-migration proceeds via a cyclohexane-like transition state similar to that of the 1,5 H-migration.

  17. Observation and Modelling of the OH, HO2 and RO2 Radicals at a Regional Site of Beijing in Winter 2016.

    Science.gov (United States)

    Tan, Z.; Lu, K.; Ma, X.; Bohn, B.; Hofzumahaus, A.; Broch, S.; Fuchs, H.; Holland, F.; Liu, Y.; Li, X.; Novelli, A.; Rohrer, F.; Wang, H.; Wu, Y.; Shao, M.; Zeng, L.; Kiendler-Scharr, A.; Wahner, A.; Zhang, Y.

    2017-12-01

    A comprehensive field campaign was carried out in winter 2016 in the campus of UCAS (University of Chinese Academy of Science), located in a small town 60 km northeast of urban Beijing. Concentrations of OH, HO2 and RO2 radicals as well as the total OH reactivity were measured by a laser induced fluorescence instrument. Maximum hourly averaged OH, HO2 and RO2 radical concentrations were (3±2)×106cm-3, (8±6)×107 cm-3 and (7±5)×107 cm-3, respectively. These radical concentrations were smaller than those observed during summer because of the reduced solar radiation. A chemical modulation device to separate atmospheric OH radicals from any interfering species was applied for few days showing negligible interference for both clean and polluted air masses.HONO and HCHO photolysis were found to be the most important primary sources of ROx radicals. CO and NOx were the important OH reactants which contributed more than half of the total OH reactivity. The relative high OH concentrations in polluted episode enabled a fast oxidation of fresh emitted pollutants and the formation of secondary air products. The observed radical concentrations were compared with the results from a chemical box model. The model is capable of reproducing radical concentrations for moderate NOx conditions but larger discrepancies are observed for both low and high NOx regimes for the peroxy radical concentrations. The underestimation of RO2 radical concentrations for high NOx conditions is discussed in the context of recent campaigns.

  18. High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction

    Science.gov (United States)

    Weidman, Jared D.; Allen, Ryan T.; Moore, Kevin B.; Schaefer, Henry F.

    2018-05-01

    Numerous processes in atmospheric and combustion chemistry produce the vinoxy radical (•CH2CHO). To understand the fate of this radical and to provide reliable energies needed for kinetic modeling of such processes, we have examined its reaction with O2 using highly reliable theoretical methods. Utilizing the focal point approach, the energetics of this reaction and subsequent reactions were obtained using coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set limit. These extrapolated energies were appended with several corrections including a treatment of full triples and connected quadruple excitations, i.e., CCSDT(Q). In addition, this study models the initial vinoxy radical + O2 reaction for the first time with multireference methods. We predict a barrier for this reaction of approximately 0.4 kcal mol-1. This result agrees with experimental findings but is in disagreement with previous theoretical studies. The vinoxy radical + O2 reaction produces a 2-oxoethylperoxy radical which can undergo a number of unimolecular reactions. Abstraction of a β-hydrogen (a 1,4-hydrogen shift) and dissociation back to reactants are predicted to be competitive to each other due to their similar barriers of 21.2 and 22.3 kcal mol-1, respectively. The minimum-energy β-hydrogen abstraction pathway produces a hydroperoxy radical (QOOH) that eventually decomposes to formaldehyde, CO, and •OH. Two other unimolecular reactions of the peroxy radical are α-hydrogen abstraction (38.7 kcal mol-1 barrier) and HO2• elimination (43.5 kcal mol-1 barrier). These pathways lead to glyoxal + •OH and ketene + HO2• formation, respectively, but they are expected to be uncompetitive due to their high barriers.

  19. Reaction between peroxynitrite and boronates: EPR spin-trapping, HPLC analyses, and quantum mechanical study of the free radical pathway

    Science.gov (United States)

    Sikora, Adam; Zielonka, Jacek; Lopez, Marcos; Dybala-Defratyka, Agnieszka; Joseph, Joy; Marcinek, Andrzej; Kalyanaraman, Balaraman

    2013-01-01

    Recently we showed that peroxynitrite (ONOO−) reacts directly and rapidly with aromatic and aliphatic boronic acids (k ≈ 106 M−1s−1). Product analyses and substrate consumption data indicated that ONOO− reacts stoichiometrically with boronates, yielding the corresponding phenols as the major product (~85–90%), and the remaining products (10–15%) were proposed to originate from free radical intermediates (phenyl and phenoxyl radicals). Here we investigated in detail the minor, free radical pathway of boronate reaction with ONOO−. The electron paramagnetic resonance (EPR) spin-trapping technique was used to characterize the free radical intermediates formed from the reaction between boronates and ONOO−. Using 2-methyl-2-nitrosopropane (MNP) and 5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO) spin traps, phenyl radicals were trapped and detected. Although phenoxyl radicals were not detected, the positive effects of molecular oxygen, and inhibitory effects of hydrogen atom donors (acetonitrile, and 2-propanol) and general radical scavengers (GSH, NADH, ascorbic acid and tyrosine) on the formation of phenoxyl radical-derived nitrated product, suggest that phenoxyl radical was formed as the secondary species. We propose that the initial step of the reaction involves the addition of ONOO− to the boron atom in boronates. The anionic intermediate undergoes both heterolytic (major pathway) and homolytic (minor pathway) cleavage of the peroxy (O-O) bond to form phenol and nitrite as a major product (via a non-radical mechanism), or a radical pair PhB(OH)2O•−…•NO2 as a minor product. It is conceivable that phenyl radicals are formed by the fragmentation of PhB(OH)2O•− radical anion. According to the DFT quantum mechanical calculations, the energy barrier for the dissociation of PhB(OH)2O•− radical anion to form phenyl radicals is only a few kcal/mol, suggesting rapid and spontaneous fragmentation of PhB(OH)2O•− radical anion

  20. Reassessing the atmospheric oxidation mechanism of toluene

    Science.gov (United States)

    Ji, Yuemeng; Zhao, Jun; Terazono, Hajime; Misawa, Kentaro; Levitt, Nicholas P.; Li, Yixin; Lin, Yun; Peng, Jianfei; Wang, Yuan; Duan, Lian; Pan, Bowen; Zhang, Fang; Feng, Xidan; An, Taicheng; Marrero-Ortiz, Wilmarie; Secrest, Jeremiah; Zhang, Annie L.; Shibuya, Kazuhiko; Molina, Mario J.; Zhang, Renyi

    2017-08-01

    Photochemical oxidation of aromatic hydrocarbons leads to tropospheric ozone and secondary organic aerosol (SOA) formation, with profound implications for air quality, human health, and climate. Toluene is the most abundant aromatic compound under urban environments, but its detailed chemical oxidation mechanism remains uncertain. From combined laboratory experiments and quantum chemical calculations, we show a toluene oxidation mechanism that is different from the one adopted in current atmospheric models. Our experimental work indicates a larger-than-expected branching ratio for cresols, but a negligible formation of ring-opening products (e.g., methylglyoxal). Quantum chemical calculations also demonstrate that cresols are much more stable than their corresponding peroxy radicals, and, for the most favorable OH (ortho) addition, the pathway of H extraction by O2 to form the cresol proceeds with a smaller barrier than O2 addition to form the peroxy radical. Our results reveal that phenolic (rather than peroxy radical) formation represents the dominant pathway for toluene oxidation, highlighting the necessity to reassess its role in ozone and SOA formation in the atmosphere.

  1. Diurnal and semi-diurnal tidal currents in the deep mid-Arabian sea

    Digital Repository Service at National Institute of Oceanography (India)

    Shenoi, S.S.C.; Gouveia, A.D.; Shetye, S.R.

    Current meter records from two depths, approximately 1000 m, at three mooring in the deep mid-Arabian Sea were used to study tidal components. Tidal ellipses for the semi-diurnal (M2, S2 and K2) and the diurnal (K1 and P1) tidal constituents have...

  2. 3D analysis of high ozone production rates observed during the ESCOMPTE campaign

    Science.gov (United States)

    Coll, Isabelle; Pinceloup, Stéphanie; Perros, Pascal E.; Laverdet, Gérard; Le Bras, Georges

    2005-03-01

    The development of environmental policies to reduce the ozone levels around large agglomerations requires a good understanding of the development of ozone episodes. In particular, it is necessary to know the location and photochemical activity of the plume where ozone is formed. Measurement campaigns make it possible not only to characterize the concentration fields of ozone and its precursors but also to identify the zones of strong ozone production, by means of specific measurements and kinetic calculations. The combination of the observation-based data with numerical simulations allows to better characterize photochemical pollution. This paper presents a study carried out within the ESCOMPTE program and based on the determination of ozone production rates by experimental and numerical methods: ground measurements of peroxy radicals, NO x at a rural site, airborne measurements of NO X and O 3, Eulerian modeling. The reported case is of particular interest since it corresponds to an episode with very different photochemical situations. The diurnal variations of the peroxy radical concentration are analyzed in relation to those of ozone and its precursors. Ozone production rates— P(O 3)-are studied over one particular day. The results show particularly high concentrations of RO 2+HO 2 at ground level (up to 200 pptv) under the influence of the urban and industrial plume, but also highlight very high production rates of ozone (60 to 80 ppbv h -1) a few tens of kilometers from the sources. The results show satisfactory agreement between the various approaches. Modeling provides a four-dimensional (4D) description of the plumes, in particular the relation between the ozone precursor concentrations and P(O 3) on the ground.

  3. Impact of resolving the diurnal cycle in an ocean-atmosphere GCM. Pt. 1: a diurnally forced OGCM

    Energy Technology Data Exchange (ETDEWEB)

    Bernie, D.J. [University of Reading, National Centre for Atmospheric Science - Climate, Department of Meteorology, Reading (United Kingdom); Laboratoire d' Oceanographie et du Climat, Experimentation et Approches Numeriques, IPSL, Paris (France); Met Office Hadley Centre, Exeter, EX1 3PB (United Kingdom); Guilyardi, E. [University of Reading, National Centre for Atmospheric Science - Climate, Department of Meteorology, Reading (United Kingdom); Laboratoire d' Oceanographie et du Climat, Experimentation et Approches Numeriques, IPSL, Paris (France); Madec, G. [Laboratoire d' Oceanographie et du Climat, Experimentation et Approches Numeriques, IPSL, Paris (France); Slingo, J.M.; Woolnough, S.J. [University of Reading, National Centre for Atmospheric Science - Climate, Department of Meteorology, Reading (United Kingdom)

    2007-11-15

    The diurnal cycle is a fundamental time scale in the climate system, at which the upper ocean and atmosphere are routinely observed to vary. Current climate models, however, are not configured to resolve the diurnal cycle in the upper ocean or the interaction of the ocean and atmosphere on these time scales. This study examines the diurnal cycle of the tropical upper ocean and its climate impacts. In the present paper, the first of two, a high vertical resolution ocean general circulation model (OGCM), with modified physics, is developed which is able to resolve the diurnal cycle of sea surface temperature (SST) and current variability in the upper ocean. It is then validated against a satellite derived parameterization of diurnal SST variability and in-situ current observations. The model is then used to assess rectification of the intraseasonal SST response to the Madden-Julian oscillation (MJO) by the diurnal cycle of SST. Across the equatorial Indo-Pacific it is found that the diurnal cycle increases the intraseasonal SST response to the MJO by around 20%. In the Pacific, the diurnal cycle also modifies the exchange of momentum between equatorially divergent Ekman currents and the meridionally convergent geostrophic currents beneath, resulting in a 10% increase in the strength of the Ekman cells and equatorial upwelling. How the thermodynamic and dynamical impacts of the diurnal cycle effect the mean state, and variability, of the climate system cannot be fully investigated in the constrained design of ocean-only experiments presented here. The second part of this study, published separately, addresses the climate impacts of the diurnal cycle in the coupled system by coupling the OGCM developed here to an atmosphere general circulation model. (orig.)

  4. Concentrations of OH and HO2 radicals during NAMBLEX: measurements and steady state analysis

    Directory of Open Access Journals (Sweden)

    S. C. Smith

    2006-01-01

    Full Text Available OH and HO2 concentrations were measured simultaneously at the Mace Head Atmospheric Research Station in the summer of 2002 during the NAMBLEX (North Atlantic Marine Boundary Layer EXperiment field campaign. OH was measured by laser-induced fluorescence employing the FAGE (Fluorescence Assay by Gas Expansion technique, with a mean daytime detection limit of 2.7×105 molecule cm−3 (5 min acquisition period; signal-to-noise ratio = 1. HO2 was detected as OH following its chemical conversion through addition of NO, with a mean detection limit of 4.4×106 molecule cm−3. The diurnal variation of OH was measured on 24 days, and that of HO2 on 17 days. The local solar noon OH concentrations ranged between (3–8×106 molecule cm−3, with a 24 h mean concentration of 9.1×105 molecule cm−3. The local solar noon HO2 concentrations were (0.9–2.1×108 molecule cm−3 (3.5–8.2 pptv, with a 24 h mean concentration of 4.2×107 molecule cm−3 (1.6 pptv. HO2 radicals in the range (2–3×107 molecule cm−3 were observed at night. During NAMBLEX, a comprehensive suite of supporting measurements enabled a detailed study of the behaviour of HOx radicals under primarily clean marine conditions. Steady state expressions are used to calculate OH and HO2 concentrations and to evaluate the effect of different free-radical sources and sinks. The diurnally averaged calculated to measured OH ratio was 1.04±0.36, but the ratio displays a distinct diurnal variation, being less than 1 during the early morning and late afternoon/evening, and greater than 1 in the middle of the day. For HO2 there was an overprediction, with the agreement between calculated and measured concentrations improved by including reaction with measured IO and BrO radicals and uptake to aerosols. Increasing the concentration of IO radicals included in the calculations to above that measured by a DOAS instrument with an absorption path located mainly over the ocean, reflecting the

  5. UV absorption spectra, kinetics and mechanisms of the self-reaction of CHF2O2 radicals in the gas phase at 298-K

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Ellermann, T.; Bartkiewicz, E.

    1992-01-01

    The ultraviolet-absorption spectrum and the self-reaction of CHF2O2 radicals have been studied in the gas phase at 298 K using the pulse radiolysis technique and long-pathlength Fourier transform infrared spectroscopy. Absorption cross sections were quantified over the wavelength range 220-280 nm....... The measured cross section near the absorption maximum was sigma(CHF2O2)(240 nm) = (2.66 +/- 0.46) x 10(-18) cm2 molecule-1. The absorption cross section data were used to derive the observed self-reaction rate constant for the reaction CHF2O2 + CHF2O2 --> products, defined as d[R]/dt = 2k(1obs)[CHF2O2]2, k(1......obs) = (5.0 +/- 0.7) x 10(-12) cm3 molecule-1 s-1 (+/- 2-sigma). The only carbon-containing product observed by FTIR spectroscopy was FC(O)F. These results are discussed with respect to previous studies of peroxy radicals....

  6. Modeling the oxidative capacity of the atmosphere of the south coast air basin of California. 2. HOx radical production.

    Science.gov (United States)

    Griffin, Robert J

    2004-02-01

    The production of HOx radicals in the South Coast Air Basin of California is investigated during the smog episode of September 9, 1993 using the California Institute of Technology (CIT) air-quality model. Sources of HOx(hydroxyl, hydroperoxy, and organic peroxy radicals) incorporated into the associated gas-phase chemical mechanism include the combination of excited-state singlet oxygen (formed from ozone (O3) photolysis (hv)) with water, the photolysis of nitrous acid, hydrogen peroxide (H2O2), and carbonyl compounds (formaldehyde (HCHO) or higher aldehydes and ketones), the consumption of aldehydes and alkenes (ALK) by the nitrate radical, and the consumption of alkenes by O3 and the oxygen atom (O). At a given time or location for surface cells and vertical averages, each route of HOx formation may be the greatest contributor to overall formation except HCHO-hv, H2O2-hv, and ALK-O, the latter two of which are insignificant pathways in general. The contribution of the ALK-O3 pathway is dependent on the stoichiometric yield of OH, but this pathway, at least for the studied smog episode, may not be as generally significant as previous research suggests. Future emissions scenarios yield lower total HOx production rates and a shift in the relative importance of individual pathways.

  7. Diurnal patterns of productivity of arbuscular mycorrhizal fungi revealed with the Soil Ecosystem Observatory.

    Science.gov (United States)

    Hernandez, Rebecca R; Allen, Michael F

    2013-10-01

    Arbuscular mycorrhizal (AM) fungi are the most abundant plant symbiont and a major pathway of carbon sequestration in soils. However, their basic biology, including their activity throughout a 24-h day : night cycle, remains unknown. We employed the in situ Soil Ecosystem Observatory to quantify the rates of diurnal growth, dieback and net productivity of extra-radical AM fungi. AM fungal hyphae showed significantly different rates of growth and dieback over a period of 24 h and paralleled the circadian-driven photosynthetic oscillations observed in plants. The greatest rates (and incidences) of growth and dieback occurred between noon and 18:00 h. Growth and dieback events often occurred simultaneously and were tightly coupled with soil temperature and moisture, suggesting a rapid acclimation of the external phase of AM fungi to the immediate environment. Changes in the environmental conditions and variability of the mycorrhizosphere may alter the diurnal patterns of productivity of AM fungi, thereby modifying soil carbon sequestration, nutrient cycling and host plant success. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

  8. Sequential study on reactive blue 29 dye removal from aqueous solution by peroxy acid and single wall carbon nanotubes: experiment and theory

    Directory of Open Access Journals (Sweden)

    Jahangiri-Rad Mahsa

    2013-01-01

    Full Text Available Abstract The majority of anthraquinone dye released to the environment come from antrapogenic sources. Several techniques are available for dyes' removal. In this study removal of reactive blue 29 (RB29 by an advanced oxidation process sequenced with single wall carbon nanotubes was investigated. Advanced oxidation process was optimized over a period of 60 minutes by changing the ratio of acetic acid to hydrogen peroxide, the compounds which form peroxy acid. Reduction of 20.2% -56.4% of reactive blue 29 was observed when the ratio of hydrogen peroxide/acetic acid/dye changed from 344/344/1 to 344/344/0.08 at different times (60, 120 and 180 min. The optimum ratio of acetic acid/hydrogen peroxide/dye was found to be 344/344/0.16 over 60 min. The resultant then was introduced for further removal by single wall carbon nanotubes(SWCNTs as adsorbent. The adsorption of reactive blue 29 onto SWCNTs was also investigated. Langmuir, Freundlich and BET isotherms were determined and the results revealed that the adsorption of RB29 onto SWCNTs was well explained by BET model and changed to Freundlich isotherm when SWCNTs was used after the application of peroxy acid. Kinetic study showed that the equilibrium time for adsorption of RB 29 on to SWCNT is 4 h. Experiments were carried out to investigate adsorption kinetics, adsorbent capacity and the effect of solution pH on the removal of reactive blue29. The pseudo-second order kinetic equation could best describe the sorption kinetics. The most efficient pH for color removal (amongst pH=3, 5 and 8 was pH= 5. Further studies are needed to identify the peroxy acid degradation intermediates and to investigate their effects on SWCNTs.

  9. Antimalarial activity of synthetic 1,2,4-trioxanes and cyclic peroxy ketals, a quantum similarity study

    Science.gov (United States)

    Gironés, X.; Gallegos, A.; Carbó-Dorca, R.

    2001-12-01

    In this work, the antimalarial activity of two series of 20 and 7 synthetic 1,2,4-trioxanes and a set of 20 cyclic peroxy ketals are tested for correlation search by means of Molecular Quantum Similarity Measures (MQSM). QSAR models, dealing with different biological responses (IC90, IC50 and ED90) of the parasite Plasmodium Falciparum, are constructed using MQSM as molecular descriptors and are satisfactorily correlated. The statistical results of the 20 1,2,4-trioxanes are deeply analyzed to elucidate the relevant structural features in the biological activity, revealing the importance of phenyl substitutions.

  10. Application of thermal-dissociation laser induced fluorescence (TD-LIF to measurement of HNO3, Σalkyl nitrates, Σperoxy nitrates, and NO2 fluxes using eddy covariance

    Directory of Open Access Journals (Sweden)

    D. K. Farmer

    2006-01-01

    Full Text Available Nitrogen exchange between the atmosphere and biosphere directly influences atmospheric composition. While much is known about mechanisms of NO and N2O emissions, instrumentation for the study of mechanisms contributing to exchange of other major nitrogen species is quite limited. Here we describe the application of a new technique, thermal dissociation-laser induced fluorescence (TD-LIF, to eddy covariance measurements of the fluxes of NO2, total peroxy acyl and peroxy nitrates, total alkyl and multifunctional alkyl nitrates, and nitric acid. The technique offers the potential for investigating mechanisms of exchange of these species at the canopy scale over timescales from days to years. Examples of flux measurements at a ponderosa pine plantation in the mid-elevation Sierra Nevada Mountains in California are reported and used to evaluate instrument performance.

  11. Diurnal blood pressure changes.

    Science.gov (United States)

    Asayama, Kei; Satoh, Michihiro; Kikuya, Masahiro

    2018-05-23

    The definition of diurnal blood pressure changes varies widely, which can be confusing. Short-term blood pressure variability during a 24-h period and the dipping status of diurnal blood pressure can be captured by ambulatory blood pressure monitoring, and these metrics are reported to have prognostic significance for cardiovascular complications. Morning blood pressure surge also indicates this risk, but its effect may be limited to populations with specific conditions. Meanwhile, the combined use of conventional office blood pressure and out-of-office blood pressure allows us to identify people with white-coat and masked hypertension. Current home devices can measure nocturnal blood pressure during sleep more conveniently than ambulatory monitoring; however, we should pay attention to blood pressure measurement conditions regardless of whether they are in a home, ambulatory, or office setting. The relatively poor reproducibility of diurnal blood pressure changes, including the nocturnal fall of blood pressure, is another underestimated issue to be addressed. Although information on diurnal blood pressure changes is expected to be used more effectively in the future, we should also keep in mind that blood pressure levels have remained central to the primary and secondary prevention of blood pressure-related cardiovascular diseases in clinical practice.

  12. Diurnal variations of Titan

    Science.gov (United States)

    Cui, J.; Galand, M.; Yelle, R. V.; Vuitton, V.; Wahlund, J.-E.; Lavvas, P. P.; Mueller-Wodarg, I. C. F.; Kasprzak, W. T.; Waite, J. H.

    2009-04-01

    We present our analysis of the diurnal variations of Titan's ionosphere (between 1,000 and 1,400 km) based on a sample of Ion Neutral Mass Spectrometer (INMS) measurements in the Open Source Ion (OSI) mode obtained from 8 close encounters of the Cassini spacecraft with Titan. Though there is an overall ion depletion well beyond the terminator, the ion content on Titan's nightside is still appreciable, with a density plateau of ~700 cm-3 below ~1,300 km. Such a plateau is associated with the combination of distinct diurnal variations of light and heavy ions. Light ions (e.g. CH5+, HCNH+, C2H5+) show strong diurnal variation, with clear bite-outs in their nightside distributions. In contrast, heavy ions (e.g. c-C3H3+, C2H3CNH+, C6H7+) present modest diurnal variation, with significant densities observed on the nightside. We propose that the distinctions between light and heavy ions are associated with their different chemical loss pathways, with the former primarily through "fast" ion-neutral chemistry and the latter through "slow" electron dissociative recombination. The INMS data suggest day-to-night transport as an important source of ions on Titan's nightside, to be distinguished from the conventional scenario of auroral ionization by magnetospheric particles as the only ionizing source on the nightside. This is supported by the strong correlation between the observed night-to-day ion density ratios and the associated ion lifetimes. We construct a time-dependent ion chemistry model to investigate the effects of day-to-night transport on the ionospheric structures of Titan. The predicted diurnal variation has similar general characteristics to those observed, with some apparent discrepancies which could be reconciled by imposing fast horizontal thermal winds in Titan's upper atmosphere.

  13. Treatment of an azo dye effluent by peroxi-coagulation and its comparison to traditional electrochemical advanced processes.

    Science.gov (United States)

    do Vale-Júnior, Edilson; da Silva, Djalma R; Fajardo, Ana S; Martínez-Huitle, Carlos A

    2018-04-05

    Peroxi-coagulation (PC) is an interesting new process that has not been widely studied in the literature. This work presents the application of this technology to treat an azo dye synthetic effluent, studying the effect of different parameters including initial pH, current density (j), initial dye concentration and supporting electrolyte. The two former variables significantly affected the colour removal of the wastewater, followed by the initial dye concentration and the kind of electrolyte, in a lesser extent. The optimum operating conditions achieved were initial pH of 3.0, j = 33.3 mA cm -2 , 100 mg L -1 of methyl orange (MO) and Na 2 SO 4 as supporting electrolyte. The performance of PC was also compared to other electrochemical advanced processes, under similar experimental conditions. Results indicate that the kinetic decay of the MO increases in the following order: electrocoagulation (EC) oxidation (EO) with electrogenerated H 2 O 2 oxidant character of the homogenous OH radicals generated by EF and PC approaches. The EO process with production of H 2 O 2 (EO-H 2 O 2 ) is limited by mass transport and the EC, as a separation method, takes longer times to achieve similar removal results. Energy requirements about 0.06 kWh g COD -1 , 0.09 kWh g COD -1 , 0.7 kWh g COD -1 and 0.1 kWh g COD -1 were achieved for PC, EF, EO-H 2 O 2 and EC, respectively. Degradation intermediates were monitored and carboxylic acids were detected for PC and EF processes, being rapidly removed by the former technology. PC emerges as a promising and competitive alternative for wastewaters depollution, among other oxidative approaches. Copyright © 2018 Elsevier Ltd. All rights reserved.

  14. Diurnal and semi-diurnal tidal structures due to O2, O3 and H2O ...

    Indian Academy of Sciences (India)

    from World Meteorological Organization (WMO. 1986), while the Rayleigh scattering cross section was calculated using the formula of Nicolet (1984). ..... Figure 5(a) exhibits the exponential growth of diurnal amplitude with altitude, at low to mid lat- itudes. At high latitudes, the diurnal amplitude decreases with altitude due to ...

  15. Oxidation and Free Radical Decay in Vitamin E-stabilized, Radiation Cross-linked UHMWPE

    International Nuclear Information System (INIS)

    Oral, E.

    2006-01-01

    folds where they are able to abstract a hydrogen atom from nearby amorphous chains or react with diffused oxygen. This would lead to an increase in polyenyl and peroxy free radicals, respectively, giving a sharp singlet. The rate of the change of alkyl/allyl type free radicals was faster in αTPE. It is possible that some α-T co-crystallized with UHMWPE, increasing the mobility of the chains resulting in efficient quenching of the free radicals. αTPE showed the same free radical evolution as control UHMWPE, suggesting that the mechanism of decay of the free radicals was similar. However, this was not accompanied by oxidation in αTPE, supporting the chain-breaking antioxidant activity of α-T. Real-time oxidation behavior of αTPE was consistent with that observed with accelerated aging. This new UHMWPE is oxidation resistant and is expected to maintain its mechanical properties in the long-term

  16. Impact of resolving the diurnal cycle in an ocean-atmosphere GCM. Pt. 2. A diurnally coupled CGCM

    Energy Technology Data Exchange (ETDEWEB)

    Bernie, D.J. [Met Office Hadley Centre, Exeter (United Kingdom); University of Reading, National Centre for Atmospheric Science-Climate, Department of Meteorology, Reading (United Kingdom); Numeriques, IPSL, Laboratoire d' Oceanographie et du Climat, Experimentation et Approches, Paris (France); Guilyardi, E. [University of Reading, National Centre for Atmospheric Science-Climate, Department of Meteorology, Reading (United Kingdom); Numeriques, IPSL, Laboratoire d' Oceanographie et du Climat, Experimentation et Approches, Paris (France); Madec, G. [Numeriques, IPSL, Laboratoire d' Oceanographie et du Climat, Experimentation et Approches, Paris (France); Slingo, J.M.; Woolnough, S.J.; Cole, J. [University of Reading, National Centre for Atmospheric Science-Climate, Department of Meteorology, Reading (United Kingdom)

    2008-12-15

    Coupled ocean atmosphere general circulation models (GCM) are typically coupled once every 24 h, excluding the diurnal cycle from the upper ocean. Previous studies attempting to examine the role of the diurnal cycle of the upper ocean and particularly of diurnal SST variability have used models unable to resolve the processes of interest. In part 1 of this study a high vertical resolution ocean GCM configuration with modified physics was developed that could resolve the diurnal cycle in the upper ocean. In this study it is coupled every 3 h to atmospheric GCM to examine the sensitivity of the mean climate simulation and aspects of its variability to the inclusion of diurnal ocean-atmosphere coupling. The inclusion of the diurnal cycle leads to a tropics wide increase in mean sea surface temperature (SST), with the strongest signal being across the equatorial Pacific where the warming increases from 0.2 C in the central and western Pacific to over 0.3 C in the eastern equatorial Pacific. Much of this warming is shown to be a direct consequence of the rectification of daily mean SST by the diurnal variability of SST. The warming of the equatorial Pacific leads to a redistribution of precipitation from the Inter tropical convergence zone (ITCZ) toward the equator. In the western Pacific there is an increase in precipitation between Papa new guinea and 170 E of up to 1.2 mm/day, improving the simulation compared to climatology. Pacific sub tropical cells are increased in strength by about 10%, in line with results of part 1 of this study, due to the modification of the exchange of momentum between the equatorially divergent Ekman currents and the geostropic convergence at depth, effectively increasing the dynamical response of the tropical Pacific to zonal wind stresses. During the spring relaxation of the Pacific trade winds, a large diurnal cycle of SST increases the seasonal warming of the equatorial Pacific. When the trade winds then re-intensify, the increase in

  17. One-electron oxidation of BD84, an ellipticine antitumor derivative

    International Nuclear Information System (INIS)

    Sekaki, A.; Gardes-Albert, M.; Houee-Levin, C.; Ferradini, C.; Rivalle, C.; Bisagni, E.; Hickel, B.

    1991-01-01

    The one-electron oxidation of BD84, an ellipticine-related drug, has been studied by pulse radiolysis using OH· radicals as oxidizing agents. In the absence of oxygen, R· radicals are formed. They disappear by recombination. In the presence of oxygen, R· radicals react with O 2 to give peroxy radicals RO 2 ·, which decay by a second-order process. These results are compared to those obtained for other ellipticine derivatives [fr

  18. Observations of the diurnal and seasonal trends in nitrogen oxides in the western Sierra Nevada

    Directory of Open Access Journals (Sweden)

    J. G. Murphy

    2006-01-01

    Full Text Available Observations of speciated nitrogen oxides, namely NO2, total peroxy nitrates (ΣPNs, total alkyl nitrates (ΣANs, and HNO3 by thermal dissociation laser induced fluorescence (TD-LIF, and supporting chemical and meteorological measurements at Big Hill (1860 m, a high elevation site in California's Sierra Nevada Mountains, are described. From May through October, terrain-driven winds in the region routinely bring air from Sacramento, 100 km southwest of the site, upslope over oak and pine forests to Big Hill during the day, while at night, the site often samples clean, dry air characteristic of the free troposphere. Winter differs mainly in that the meteorology does not favour the buildup of Sacramento's pollution over the Sierra Nevada range, and the urban-influenced air that is seen has been less affected by biogenic VOC emissions, resulting in longer lifetime for NO2 and a predominance of the inorganic forms of nitrogen oxides. Summertime observations at Big Hill can be compared with those from Granite Bay, a Sacramento suburb, and from the University of California's Blodgett Forest Research Station to examine the evolution of nitrogen oxides and ozone within the urban plume. Nitrogen oxide radicals (NO and NO2, which dominate total nitrogen oxides (NOy at Granite Bay, are rapidly converted into HNO3, ΣPNs, and ΣANs, such that these compounds contribute 29, 30, and 21% respectively to the NOy budget in the plume at Big Hill. Nevertheless, the decreasing concentrations of NO2 as the plume is advected to Big Hill lead to decreases in the production rate of HNO3 and ozone. The data also demonstrate the role that temperature plays in sequestering NO2 into peroxy nitrates, effectively decreasing the rate of ozone production. The important contribution of ΣANs to NOy in the region suggests that they should be considered with regards to export of NOy from the boundary layer. Nocturnal observations of airmasses characteristic of the

  19. Specific diurnal EMG activity pattern observed in occlusal collapse patients: relationship between diurnal bruxism and tooth loss progression.

    Directory of Open Access Journals (Sweden)

    Shigehisa Kawakami

    Full Text Available AIM: The role of parafunctional masticatory muscle activity in tooth loss has not been fully clarified. This study aimed to reveal the characteristic activity of masseter muscles in bite collapse patients while awake and asleep. MATERIALS AND METHODS: Six progressive bite collapse patients (PBC group, six age- and gender-matched control subjects (MC group, and six young control subjects (YC group were enrolled. Electromyograms (EMG of the masseter muscles were continuously recorded with an ambulatory EMG recorder while patients were awake and asleep. Diurnal and nocturnal parafunctional EMG activity was classified as phasic, tonic, or mixed using an EMG threshold of 20% maximal voluntary clenching. RESULTS: Highly extended diurnal phasic activity was observed only in the PBC group. The three groups had significantly different mean diurnal phasic episodes per hour, with 13.29±7.18 per hour in the PBC group, 0.95±0.97 per hour in the MC group, and 0.87±0.98 per hour in the YC group (p<0.01. ROC curve analysis suggested that the number of diurnal phasic episodes might be used to predict bite collapsing tooth loss. CONCLUSION: Extensive bite loss might be related to diurnal masticatory muscle parafunction but not to parafunction during sleep. CLINICAL RELEVANCE SCIENTIFIC RATIONALE FOR STUDY: Although mandibular parafunction has been implicated in stomatognathic system breakdown, a causal relationship has not been established because scientific modalities to evaluate parafunctional activity have been lacking. PRINCIPAL FINDINGS: This study used a newly developed EMG recording system that evaluates masseter muscle activity throughout the day. Our results challenge the stereotypical idea of nocturnal bruxism as a strong destructive force. We found that diurnal phasic masticatory muscle activity was most characteristic in patients with progressive bite collapse. PRACTICAL IMPLICATIONS: The incidence of diurnal phasic contractions could be used for

  20. 40 CFR 1060.105 - What diurnal requirements apply for equipment?

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 32 2010-07-01 2010-07-01 false What diurnal requirements apply for... EQUIPMENT Emission Standards and Related Requirements § 1060.105 What diurnal requirements apply for... for controlling diurnal emissions: (1) If you are subject to both running loss and diurnal emission...

  1. Specific Diurnal EMG Activity Pattern Observed in Occlusal Collapse Patients: Relationship between Diurnal Bruxism and Tooth Loss Progression

    Science.gov (United States)

    Kawakami, Shigehisa; Kumazaki, Yohei; Manda, Yosuke; Oki, Kazuhiro; Minagi, Shogo

    2014-01-01

    Aim The role of parafunctional masticatory muscle activity in tooth loss has not been fully clarified. This study aimed to reveal the characteristic activity of masseter muscles in bite collapse patients while awake and asleep. Materials and Methods Six progressive bite collapse patients (PBC group), six age- and gender-matched control subjects (MC group), and six young control subjects (YC group) were enrolled. Electromyograms (EMG) of the masseter muscles were continuously recorded with an ambulatory EMG recorder while patients were awake and asleep. Diurnal and nocturnal parafunctional EMG activity was classified as phasic, tonic, or mixed using an EMG threshold of 20% maximal voluntary clenching. Results Highly extended diurnal phasic activity was observed only in the PBC group. The three groups had significantly different mean diurnal phasic episodes per hour, with 13.29±7.18 per hour in the PBC group, 0.95±0.97 per hour in the MC group, and 0.87±0.98 per hour in the YC group (pbruxism as a strong destructive force. We found that diurnal phasic masticatory muscle activity was most characteristic in patients with progressive bite collapse. Practical implications The incidence of diurnal phasic contractions could be used for the prognostic evaluation of stomatognathic system stability. PMID:25010348

  2. Measurements of free radicals in a megacity during the Clean Air for London Project

    Science.gov (United States)

    Heard, Dwayne; Whalley, Lisa; Stone, Daniel; Clancy, Noel; Lee, James; Kleffman, Jorg; Laufs, Sebastian; Bandy, Brian

    2013-04-01

    Free radicals control the photo-oxidative chemistry of the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3, multifunctional species and particulates. Here we present measurements of OH, HO2 and RO2 radicals and OH reactivity recorded at North Kensington, Central London, during two Intensive Operational Periods (IOPs) of the Clear Air for London (Clearflo) project in the summer and winter of 2012. OH and HO2 were measured using laser-induced fluorescence (LIF) spectroscopy at low pressure (the FAGE technique), and RO2 was measured using the recently developed ROXLIF technique, which utilises an external flow-reactor interfaced to FAGE, and which is able to discriminate between HO2 and organic peroxy radicals. Through control of reagent gases we are further able to provide a separate measurement of those RO2 species which are known to give an interference for HO2 measurements (namely alkene, aromatic and large-chain alkane derived RO2). OH reactivity was measured using laser-flash photolysis combined with FAGE. Low concentrations of radicals were observed during the winter IOP, with mixing ratios of [OH] ~ 0.04 pptv, [HO2] ~ 0.4 pptv, and [RO2] ~ 1.6 pptv at noon, all displaying a negative correlation with NO. The photolysis of O3 and subsequent reaction of O(1D) with H2O vapour was only a minor contribution to radical production in winter, with photolysis of HONO a major radical source. The summer IOP coincided with the London Olympic Games, with a number of pollution events, with ozone peaking at 100 ppbv (exceeding EU air quality directives) and elevated radical concentrations (peak [OH] ~ 0.14 pptv, [HO2] ~ 4 pptv, [RO2] ~ 6.4 pptv) being observed. The net rate of ozone production was calculated from radical observations and agreed well with measured ozone production, suggesting that advection/dilution by continental air-masses was not playing a significant role in determining ozone

  3. Investigation of reactions and species dominating low temperature combustion - Final report

    Energy Technology Data Exchange (ETDEWEB)

    Radi, P.; Knopp, G.; Johnson, M.; Boedi, A.; Gerber, T.

    2009-12-15

    This report for the Swiss Federal Office of Energy (SFOE) presents the results of work done at the Paul Scherrer Institute (PSI) in Switzerland. The project 'Investigation of reactions and species dominating low temperature combustion' involves the characterisation of species that govern ignition. A base established for the spectroscopic investigation of peroxy radicals is discussed. The two-fold aim of this project is discussed which includes the measurement of molecular features such as binding energies and dissociation patterns of well-studied and spectroscopically accessible molecules and radicals as well as the application of the measurement techniques to alkyl peroxy radicals. This was done in order to improve the database of a class of molecules playing a dominant role in combustion and atmospheric chemistry. Several experimental techniques that are to be developed to achieve these aims are looked at. Achievements made are discussed and future work to be carried out is noted.

  4. Formation, Evaporation, and Hydrolysis of Organic Nitrates from Nitrate Radical Oxidation of Monoterpenes

    Science.gov (United States)

    Ng, N. L.; Takeuchi, M.; Eris, G.; Berkemeier, T.; Boyd, C.; Nah, T.; Xu, L.

    2017-12-01

    Organic nitrates play an important role in the cycling of NOx and secondary organic aerosol (SOA) formation, yet their formation mechanisms and fates remain highly uncertain. The interactions of biogenic VOCs with NO3 radicals represent a direct way for positively linking anthropogenic and biogenic emissions. Results from ambient studies suggest that organic nitrates have a relatively short lifetime, though corresponding laboratory data are limited. SOA and organic nitrates produced at night may evaporate the following morning due to increasing temperatures or dilution of semi-volatile compounds. Once formed, organic nitrates can also undergo hydrolysis in the presence of particle water. In this work, we investigate the formation, evaporation, and hydrolysis of organic nitrates generated from the nitrate radical oxidation of a-pinene, b-pinene, and limonene. Experiments are conducted in the Georgia Environmental Chamber facility (GTEC) under dry and humid conditions and different temperatures. Experiments are also designed to probe different peroxy radical pathways (RO2+HO2 vs RO2+NO3). Speciated gas-phase and particle-phase organic nitrates are continuously monitored by a Filter Inlet for Gases and AEROsols High Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (FIGAERO-HR-ToF-CIMS). Bulk aerosol composition is measured by a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). A large suite of highly oxygenated gas- and particle-phase organic nitrates are formed rapidly. We find a resistance to aerosol evaporation when it is heated. The extent of organic nitrate hydrolysis in the humid experiments is evaluated. The dynamics of the speciated organic nitrates over the course of the experiments will also be discussed. Results from this chamber study provide fundamental data for understanding the dynamics of organic nitrate aerosols over its atmospheric lifetime.

  5. Diurnal changes in ocean color sensed in satellite imagery

    Science.gov (United States)

    Arnone, Robert; Vandermuelen, Ryan; Soto, Inia; Ladner, Sherwin; Ondrusek, Michael; Yang, Haoping

    2017-07-01

    Measurements of diurnal changes in ocean color in turbid coastal regions in the Gulf of Mexico were characterized using above water spectral radiometry from a National Aeronautics and Space Administration (aerosol robotic network-WaveCIS CSI-06) site that can provide 8 to 10 observations per day. Satellite capability to detect diurnal changes in ocean color was characterized using hourly overlapping afternoon orbits of the visual infrared imaging radiometer suite (VIIRS) Suomi National Polar-orbiting Partnership ocean color sensor and validated with in situ observations. The monthly cycle of diurnal changes was investigated for different water masses using VIIRS overlaps. Results showed the capability of satellite observations to monitor hourly color changes in coastal regions that can be impacted by vertical movement of optical layers, in response to tides, resuspension, and river plume dispersion. The spatial variability of VIIRS diurnal changes showed the occurrence and displacement of phytoplankton blooming and decaying processes. The diurnal change in ocean color was above 20%, which represents a 30% change in chlorophyll-a. Seasonal changes in diurnal ocean color for different water masses suggest differences in summer and winter responses to surface processes. The diurnal changes observed using satellite ocean color can be used to define the following: surface processes associated with biological activity, vertical changes in optical depth, and advection of water masses.

  6. Rare earths: preparation of spectro chemically pure standards, study of their carbonates and synthesis of a new compound series - the peroxy carbonates; Terras-raras: obtencao de padroes espectroquimicos, estudo dos carbonatos e sintese dos peroxicarbonatos. Uma nova serie de compostos

    Energy Technology Data Exchange (ETDEWEB)

    Queiroz, Carlos Alberto da Silva

    1996-05-01

    In this work the following studies are concerned: I) preparation of lanthanum, cerium, praseodymium, neodymium and samarium oxides for use as spectro chemically pure standards; II) behavior of the rare earth (La, Ce, Pr, Nd, Sm) carbonates soluble in ammonium carbonate and mixture of ammonium carbonate/ammonium hydroxide, and III) synthesis and characterization of rare earth peroxy carbonates - a new series of compounds. Data for the synthesis and characterization of the rare earths peroxy carbonates described for the first time in this work are presented and discussed. With the aid of thermal analysis (TG-DTG) the thermal stability and the stoichiometric composition for new compounds were established and a mechanism of thermal decomposition was proposed. The peroxy carbonate was prepared by the addition of hydrogen peroxyde to the complexed soluble rare earths carbonates. These studies included also the determinations of active oxygen, the total rare earth oxide by gravimetry and complexometry and the C, H and N contents by microanalysis. The new compounds were also investigated by infrared spectroscopy. (author)

  7. Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China: results from the Mt. Waliguan Observatory

    Directory of Open Access Journals (Sweden)

    L. K. Xue

    2013-09-01

    Full Text Available The chemistry of the natural atmosphere and the influence by long-range transport of air pollution are key issues in the atmospheric sciences. Here we present two intensive field measurements of volatile organic compounds (VOCs in late spring and summer of 2003 at Mt. Waliguan (WLG, 36.28° N, 100.90° E, 3816 m a.s.l., a baseline station in the northeast part of the Qinghai-Tibetan Plateau. Most VOC species exhibited higher concentrations in late spring than in summer. A typical diurnal variation was observed with higher nighttime levels, in contrast to results from other mountainous sites. Five different air masses were identified from backward trajectory analysis showing distinct VOC speciation. Air masses originating from the central Eurasian continent contained the lowest VOC levels compared to the others that were impacted by anthropogenic emissions from China and the Indian subcontinent. A photochemical box model based on the Master Chemical Mechanism (version 3.2 and constrained by a full suite of measurements was developed to probe the photochemistry of atmosphere at WLG. Our results show net ozone production from in situ photochemistry during both late spring and summer. Oxidation of nitric oxide (NO by the hydroperoxyl radical (HO2 dominates the ozone production relative to the oxidation by the organic peroxy radicals (RO2, and the ozone is primarily destroyed by photolysis and reactions with the HOx (HOx = OH + HO2 radicals. Ozone photolysis is the predominant primary source of radicals (ROx = OH + HO2 + RO2, followed by the photolysis of secondary oxygenated VOCs and hydrogen peroxides. The radical losses are governed by the self and cross reactions among the radicals. Overall, the findings of the present study provide insights into the background chemistry and the impacts of pollution transport on the pristine atmosphere over the Eurasian continent.

  8. The nature of the initiating centres for grafting in air-irradiated perfluoro polymers

    International Nuclear Information System (INIS)

    Bozzi, A.; Chapiro, A.

    1987-01-01

    Grafting of acrylic acid on polytetrafluoroethylene has been performed using films of the polymer gamma-irradiated in air and then treated with aqueous acrylic acid. It is concluded that the initiating centres are peroxides POOP', where P' is a small perfluorinated fragment, and also trapped peroxy radicals PO 2 radical which undergo deoxygenation. Homopolymerization is suppressed by polymerization inhibitors. (author)

  9. Multiple origin of diurnality in geckos: evidence from eye lens crystallins

    Science.gov (United States)

    Röll, Beate

    2001-05-01

    The large lizard family Gekkonidae comprises about 90 genera (1000 species). While most geckos are nocturnal, the members of about 15 genera are diurnal. All of these species are 'tertiarily' diurnal, i.e. they are descended from 'secondarily' nocturnal ancestors. They have adapted to a diurnal lifestyle in quite different ways, as can be deduced by the crystallin proteins in their lenses. Evaluation of the heterogeneous lens crystallin compositions of diurnal geckos reveals that there are at least three lineages that regained diurnality independently.

  10. Diurnal variation of tropospheric temperature at a tropical station

    Directory of Open Access Journals (Sweden)

    K. Revathy

    2001-08-01

    Full Text Available The vertical velocity in the troposphere-lower stratosphere region measured using MST radar has been utilized to evaluate the temperature profile in the region. The diurnal variation of the tropospheric temperature on one day in August 1998 at the tropical station Gadanki (13.5° N, 79.2° E has been studied using the MST radar technique. The diurnal variation of the temperature revealed a prominent diurnal variation with the peak in the afternoon hours increasingly delayed in altitude. The tropopause temperature and altitude exhibited a clear diurnal cycle.Key words. Atmospheric composition and structure (pressure, density and temperature; troposphere - composition and chemistry; instruments and technique

  11. Sticking of HO2 on fatty acids aggregates

    Science.gov (United States)

    Vardanega, Delphine; Briquez, Stéphane; Duflot, Denis; Monnerville, Maurice; Toubin, Céline

    2015-04-01

    Models of atmospheric chemistry are widely used to perform projections of future changes in the chemical composition of the global troposphere, including changes in climate related greenhouse gases and aerosol particles. However, large uncertainties are still associated with the chemistry implemented in these models, which in turn can lead to inaccurate long-term predictions. The proposed work seeks to improve our understanding of the oxidative capacity of the atmosphere, which drives the lifetime of trace gases, and therefore atmospheric composition. Recent measurements [1] of free radicals made in forested environments characterized by low levels of nitrogen oxides (NOx = NO and NO2) indicate that current models of atmospheric chemistry tend to overestimate the concentration of peroxy radicals (HO2 and RO2). An overestimation of peroxy radicals is an important issue since these radicals are the main precursors of the hydroxyl radical (OH), the most important atmospheric oxidant during daytime. This issue could lead to a significant overestimation of the oxidative capacity of the global atmosphere since more than 86% of the Earth surface is covered by forests, oceans, and polar regions. An analysis of this dataset indicates that the missing sink could be due to an underestimation of the rates of RO2+HO2 reactions, and/or the uptake of peroxy radicals onto aerosol particles. A thorough evaluation of scientific studies published in the literature shows that there is a lack of kinetic and mechanistic data to correctly assess the contribution of these two loss pathways of peroxy radicals in low NOx environments. Classical molecular dynamics simulations, using the Gromacs package [2], are performed to study the interaction of HO2 with organic (carboxylic acid) aerosols. The effect of the presence of water molecules on the surface are also be investigated. These calculations provide theoretical values for observable quantities such as uptake and mass accommodation

  12. Diurnal cortisol after early institutional care—Age matters

    Directory of Open Access Journals (Sweden)

    Jessica E. Flannery

    2017-06-01

    Full Text Available Several studies have shown that young children who have experienced early caregiving adversity (e.g. previously institutionalization (PI exhibit flattened diurnal cortisol slopes; however, less is known about how these patterns might differ between children and adolescents, since the transition between childhood and adolescence is a time of purported plasticity in the hypothalamic-pituitary-adrenal (HPA axis. PI youth experience a massive improvement in caregiving environment once adopted into families; therefore we anticipated that a developmental increase in HPA axis plasticity during adolescence might additionally allow for an enhanced enrichment effect by the adoptive family. In a cross-sectional sample of 197 youths (PI and Comparison; 4–15 years old we observed age-related group differences in diurnal slope. First replicating previous findings, PI children exhibited flattened diurnal slope. This group difference, however, was not observed in adolescents. Moderation analyses showed that pubertal development, increased time with family, and early adoption contributed to the steeper diurnal cortisol slope in PI adolescents. These findings add support to existing theories positing that the transition between middle childhood and adolescence may mark an additional sensitive period for diurnal cortisol patterning, allowing PI youth to benefit from the enriched environment provided by adoptive parents during this period of development.

  13. Informal Conference on Photochemistry Held in Atlanta, Georgia on 26 April-1 May, 1992

    Science.gov (United States)

    1992-05-01

    of the kinetics of such reactions. We have measured rate constants for the neopentyl peroxy radical, generating the alkyl radical by laser flash... glycol diacetate) > Ketones(acetone.acetophenone) > Ethers(tetrahydrofuran. dioxane). Nltrlles(acetonltrlle).Halogenated hydrocarbons (carbon...the best solvent to synthesis of CBDA. especially ethyl acetate (Y63% /KW Hr) and ethylene glycol diacetate (Y55,/lW Hr).i (2) TEMPERATURE CBDA yield

  14. Barrierless Reactions with Loose Transition States Govern the Yields and Lifetimes of Organic Nitrates Derived from Isoprene

    Science.gov (United States)

    The chemical reaction mechanism of NO addition to two β and δ isoprene hydroxy–peroxy radical isomers is examined in detail using density functional theory, coupled cluster methods, and the energy resolved master equation formalism to provide estimates of rate co...

  15. Mid-infrared quantum cascade laser spectroscopy probing of the ...

    Indian Academy of Sciences (India)

    Aparajeo Chattopadhyay

    2018-05-07

    May 7, 2018 ... cm3 molecule. −1 s. −1 ... Quantum cascade laser; time-resolved mid-infrared spectroscopy; transient absorption; peroxy radicals .... peak of the laser emission profile. .... cal with O2 is a termolecular reaction (Eq. 3) and the.

  16. Diurnal Variations of Airborne Pollen and Spores in Taipei City, Taiwan

    Directory of Open Access Journals (Sweden)

    Yueh-Lin Yang

    2003-09-01

    Full Text Available The diurnal variation of airborne pollen and spores in Taipei City, Taiwan, was investigated during a two-year survey from 1993 to 1994. The pollen and spores were sampled using a Burkard seven-day volumetric pollen trap. The diurnal trends of the total amount of pollen and spores in 1993 and in 1994 were similar to each other, and peaked at 3 to 10 o’clock. The diurnal patterns of airborne pollen and spores of Broussonetia, Fraxinus, Cyathea and Gramineae in 1993 were similar to those in 1994. High concentrations of Broussonetia and Fraxinus were obtained from midnight to the next morning. Cyathea spores peaked from morning till noon, and Gramineae peaked in the afternoon. The diurnal patterns of airborne pollen of Bischofia, Juniperus, Mallotus, Morus, Trema and Urticaceae in 1993 were different to those in 1994. Regular diurnal patterns also associated with the taxa, which produce large pollen or spores, such as Gramineae and Cyathea. In contrast, Bischofia, Juniperus, Mallotus, Morus, Trema and Urticaceae produce relatively small pollen and the diurnal patterns of their airborne pollen were found irregular. The source plants Broussonetia and Fraxinus were close to the collection site so the diurnal patterns of their airborne pollen were regular, suggesting that the diurnal fluctuations of the pollen or spores in air might be affected by the source of plants and the sizes of pollen or spores. The transportation of the smaller pollen or spores in air is probably more easily affected by instability of air currents; they are therefore more likely to exhibit irregular diurnal patterns.

  17. Diurnal variations of tritium uptake by plants

    International Nuclear Information System (INIS)

    Hettinger, M.; Diabate, S.; Strack, S.

    1991-02-01

    The influence of the diurnal cycle is important for the behaviour of environmental tritium in the vegetation. A mathematical model has been used to calculate the deposition of tritium in plants as a function of diurnal variations of climatic parameters. The necessary physiological parameters (relationship of net photosynthesis and growth) were derived from growth experiments for tomatoes and maize. In chamber experiments, tomato and maize plants were exposed to tritium with natural diurnal variations of the climatic conditions. Within the range of standard deviations the measured concentrations of tritium in tissue free water of tomatoes correspond well to the estimated values. Furthermore, the incorporation into non-exchangeable organically bound tritium (OBT nx) can be sufficiently modelled and explained. There are deviations from the estimated concentrations in some parts of maize leaves. (orig.) [de

  18. Atmospheric diurnal variations observed with GPS radio occultation soundings

    Directory of Open Access Journals (Sweden)

    F. Xie

    2010-07-01

    Full Text Available The diurnal variation, driven by solar forcing, is a fundamental mode in the Earth's weather and climate system. Radio occultation (RO measurements from the six COSMIC satellites (Constellation Observing System for Meteorology, Ionosphere and Climate provide nearly uniform global coverage with high vertical resolution, all-weather and diurnal sampling capability. This paper analyzes the diurnal variations of temperature and refractivity from three-year (2007–2009 COSMIC RO measurements in the troposphere and stratosphere between 30° S and 30° N. The RO observations reveal both propagating and trapped vertical structures of diurnal variations, including transition regions near the tropopause where data with high vertical resolution are critical. In the tropics the diurnal amplitude in refractivity shows the minimum around 14 km and increases to a local maximum around 32 km in the stratosphere. The upward propagating component of the migrating diurnal tides in the tropics is clearly captured by the GPS RO measurements, which show a downward progression in phase from stratopause to the upper troposphere with a vertical wavelength of about 25 km. At ~32 km the seasonal variation of the tidal amplitude maximizes at the opposite side of the equator relative to the solar forcing. The vertical structure of tidal amplitude shows strong seasonal variations and becomes asymmetric along the equator and tilted toward the summer hemisphere in the solstice months. Such asymmetry becomes less prominent in equinox months.

  19. Diurnal changes in ocean color in coastal waters

    Science.gov (United States)

    Arnone, Robert; Vandermeulen, Ryan; Ladner, Sherwin; Ondrusek, Michael; Kovach, Charles; Yang, Haoping; Salisbury, Joseph

    2016-05-01

    Coastal processes can change on hourly time scales in response to tides, winds and biological activity, which can influence the color of surface waters. These temporal and spatial ocean color changes require satellite validation for applications using bio-optical products to delineate diurnal processes. The diurnal color change and capability for satellite ocean color response were determined with in situ and satellite observations. Hourly variations in satellite ocean color are dependent on several properties which include: a) sensor characterization b) advection of water masses and c) diurnal response of biological and optical water properties. The in situ diurnal changes in ocean color in a dynamic turbid coastal region in the northern Gulf of Mexico were characterized using above water spectral radiometry from an AErosol RObotic NETwork (AERONET -WavCIS CSI-06) site that provides up to 8-10 observations per day (in 15-30 minute increments). These in situ diurnal changes were used to validate and quantify natural bio-optical fluctuations in satellite ocean color measurements. Satellite capability to detect changes in ocean color was characterized by using overlapping afternoon orbits of the VIIRS-NPP ocean color sensor within 100 minutes. Results show the capability of multiple satellite observations to monitor hourly color changes in dynamic coastal regions that are impacted by tides, re-suspension, and river plume dispersion. Hourly changes in satellite ocean color were validated with in situ observation on multiple occurrences during different times of the afternoon. Also, the spatial variability of VIIRS diurnal changes shows the occurrence and displacement of phytoplankton blooms and decay during the afternoon period. Results suggest that determining the temporal and spatial changes in a color / phytoplankton bloom from the morning to afternoon time period will require additional satellite coverage periods in the coastal zone.

  20. Characteristics of diurnal pattern of global photosynthetically-active ...

    African Journals Online (AJOL)

    A two year data (September 1992 August 1994) on photosynhetically-active radiation (PAR) measured at Ilorin (Lat.: 832´N. Long.:434´E) using LI-190SA quantum sensor are analysed both on daily and monthly mean diurnal bases. This was done with the aim of characterizing the diurnal pattern of this radiation at this ...

  1. Specific diurnal EMG activity pattern observed in occlusal collapse patients: relationship between diurnal bruxism and tooth loss progression.

    Science.gov (United States)

    Kawakami, Shigehisa; Kumazaki, Yohei; Manda, Yosuke; Oki, Kazuhiro; Minagi, Shogo

    2014-01-01

    The role of parafunctional masticatory muscle activity in tooth loss has not been fully clarified. This study aimed to reveal the characteristic activity of masseter muscles in bite collapse patients while awake and asleep. Six progressive bite collapse patients (PBC group), six age- and gender-matched control subjects (MC group), and six young control subjects (YC group) were enrolled. Electromyograms (EMG) of the masseter muscles were continuously recorded with an ambulatory EMG recorder while patients were awake and asleep. Diurnal and nocturnal parafunctional EMG activity was classified as phasic, tonic, or mixed using an EMG threshold of 20% maximal voluntary clenching. Highly extended diurnal phasic activity was observed only in the PBC group. The three groups had significantly different mean diurnal phasic episodes per hour, with 13.29±7.18 per hour in the PBC group, 0.95±0.97 per hour in the MC group, and 0.87±0.98 per hour in the YC group (pstability.

  2. Model independent result on possible diurnal effect in DAMA/LIBRA-phase1

    Energy Technology Data Exchange (ETDEWEB)

    Bernabei, R.; D' Angelo, S.; Di Marco, A. [Universita di Roma ' ' Tor Vergata' ' , Dipt. di Fisica, Rome (Italy); INFN, Sezione Roma ' ' Tor Vergata' ' , Rome (Italy); Belli, P. [INFN, Sezione Roma ' ' Tor Vergata' ' , Rome (Italy); Cappella, F.; D' Angelo, A.; Prosperi, D. [Universita di Roma ' ' La Sapienza' ' , Dipt. di Fisica, Rome (Italy); INFN, Sezione Roma, Rome (Italy); Caracciolo, V.; Castellano, S.; Cerulli, R. [INFN, Laboratori Nazionali del Gran Sasso, Assergi (Italy); Dai, C.J.; He, H.L.; Kuang, H.H.; Ma, X.H.; Sheng, X.D.; Wang, R.G. [Chinese Academy of Sciences, Institute of High Energy Physics, Beijing (China); Incicchitti, A. [INFN, Sezione Roma, Rome (Italy); Montecchia, F. [INFN, Sezione Roma ' ' Tor Vergata' ' , Rome (Italy); Universita di Roma ' ' Tor Vergata' ' , Dipt. di Ingegneria Civile e Ingegneria Informatica, Rome (Italy); Ye, Z.P. [Chinese Academy of Sciences, Institute of High Energy Physics, Beijing (China); University of Jing Gangshan, Jiangxi (China)

    2014-03-15

    The results obtained in the search for possible diurnal effect in the single-hit low energy data collected by DAMA/LIBRA-phase1 (total exposure 1.04 ton x year) deep underground at the Gran Sasso National Laboratory (LNGS) of the INFN are presented. At the present level of sensitivity the presence of any significant diurnal variation and of diurnal time structures in the data can be excluded for both the cases of solar and sidereal time. In particular, the diurnal modulation amplitude expected, because of the Earth diurnal motion, on the basis of the DAMA dark matter annual modulation results is below the present sensitivity. (orig.)

  3. Model independent result on possible diurnal effect in DAMA/LIBRA-phase1

    International Nuclear Information System (INIS)

    Bernabei, R.; D'Angelo, S.; Di Marco, A.; Belli, P.; Cappella, F.; D'Angelo, A.; Prosperi, D.; Caracciolo, V.; Castellano, S.; Cerulli, R.; Dai, C.J.; He, H.L.; Kuang, H.H.; Ma, X.H.; Sheng, X.D.; Wang, R.G.; Incicchitti, A.; Montecchia, F.; Ye, Z.P.

    2014-01-01

    The results obtained in the search for possible diurnal effect in the single-hit low energy data collected by DAMA/LIBRA-phase1 (total exposure 1.04 ton x year) deep underground at the Gran Sasso National Laboratory (LNGS) of the INFN are presented. At the present level of sensitivity the presence of any significant diurnal variation and of diurnal time structures in the data can be excluded for both the cases of solar and sidereal time. In particular, the diurnal modulation amplitude expected, because of the Earth diurnal motion, on the basis of the DAMA dark matter annual modulation results is below the present sensitivity. (orig.)

  4. Peroxy acetyl nitrate intercalibration. Final report. Step EV4V-CT90-0222

    Energy Technology Data Exchange (ETDEWEB)

    Krognes, T; Toupance, G; Glavas, S [and others

    1994-06-01

    The report deals with intercalibration of PAN (peroxy acetyl nitrate). PAN is a highly reactive and thermally unstable photo oxidant. It is formed in the atmosphere when a mixture of nitrogen oxides and organic compounds is irradiated by sunlight. It is an important reservoir for nitrogen oxides in the atmosphere. PAN interferes with many types of NO{sub x} monitors. In large cities and industrial areas PAN is an important component of photochemical ``smog``. It may cause irritation of respiratory organs, and in some cases cause plant damage. One country (Italy) presently has passed legislation that includes PAN among the air quality parameters that shall be monitored in polluted areas. Good monitoring and calibration methods are required to fulfill the purpose of such legislation. The emission of nitrogen oxides (NO{sub x}) is subjected to international treaties. To control the effect of such treaties, monitoring and modelling of NO{sub x} components is required. PAN is not the major component, but a significant part of this picture in central European areas. In arctic areas, PAN is a major component of NO{sub v}, and a large contributor to NO{sub x}. 6 figs., 2 tabs.

  5. Diurnal Salivary Alpha-amylase Dynamics among Dementia Family Caregivers

    Science.gov (United States)

    Liu, Yin; Granger, Douglas A.; Kim, Kyungmin; Klein, Laura C.; Almeida, David M.; Zarit, Steven H.

    2016-01-01

    Objective The study examined diurnal regulation of salivary alpha-amylase (sAA) in association with daily stressors, adult day services (ADS) use, and other caregiving characteristics. Methods A sample of 165 family caregivers of individuals with dementia (IWD) completed an 8-day diary study. Caregivers provided 5 saliva samples across the 8 days. On some days, caregivers provided all or most of the care. On other days, their relative attended ADS for part of the day. A 3-level unconditional linear spline model was fit to describe the typical sAA diurnal rhythms. Predictors were then added to the unconditional model to test the hypotheses on ADS use and daily stressors. Results Daily ADS use did not have an effect on diurnal sAA regulation. However, controlling for daily ADS use, greater ADS use over the 8 days was associated with a more prominent rise between 30 minutes after wake-up and before lunch, and a more prominent decline between before lunch and late afternoon. Fewer ADS days were associated with a more flattened sAA diurnal rhythm. Additionally, greater daily care-related stressor exposures had a within-person association with lower sAA levels in the late afternoon. Care-related stressor exposures had significant within- and between-person associations with sAA diurnal slopes. Furthermore, daily positive experiences had a significant between-person association with sAA diurnal slopes. Conclusions Caring for a disabled family member may heighten the vulnerability to potential physiological conditions. Respite from care stressors from ADS use may have some biobehavioral benefits on sAA regulations. PMID:27786517

  6. Isoprene photochemistry over the Amazon rainforest.

    Science.gov (United States)

    Liu, Yingjun; Brito, Joel; Dorris, Matthew R; Rivera-Rios, Jean C; Seco, Roger; Bates, Kelvin H; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N; Kim, Saewung; Goldstein, Allen H; Guenther, Alex B; Manzi, Antonio O; Souza, Rodrigo A F; Springston, Stephen R; Watson, Thomas B; McKinney, Karena A; Martin, Scot T

    2016-05-31

    Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (Amazon rainforest.

  7. Diurnal variations in H2O2, O3, PAN, HNO3 and aldehyde concentrations and NO/NO2 ratios at Rishiri Island, Japan: Potential influence from iodine chemistry

    International Nuclear Information System (INIS)

    Kanaya, Yugo; Tanimoto, Hiroshi; Matsumoto, Jun; Furutani, Hiroshi; Hashimoto, Shigeru; Komazaki, Yuichi; Tanaka, Shigeru; Yokouchi, Yoko; Kato, Shungo; Kajii, Yoshizumi; Akimoto, Hajime

    2007-01-01

    The presence of iodine chemistry, hypothesized due to the overprediction of HO 2 levels by a photochemical box model at Rishiri Island in June 2000, was quantitatively tested against the observed NO/NO 2 ratios and the net production rates of ozone. The observed NO/NO 2 ratios were reproduced reasonably well by considering the conversion of NO to NO 2 by IO, whose amount was calculated so as to reproduce the observed HO 2 levels. However, the net production rates of ozone were calculated to be negative when such high mixing ratios of IO were considered, which was inconsistent with the observed buildup of ozone during daytime. These results suggest that iodine chemistry may not be the sole mechanism for the reduced mixing ratios of HO 2 , or that 'hot spots' for iodine chemistry were present. Diurnal variations in the mixing ratios of HCHO, CH 3 CHO, peroxy acetyl nitrate (PAN) and HNO 3 observed during the study are presented along with the simulated ones. The box model simulations suggest that the effect of iodine chemistry on these concentrations is small and that important sources of CH 3 CHO and sinks of PAN are probably missing from our current understanding of the tropospheric chemistry mechanism

  8. Radical fashion and radical fashion innovation

    NARCIS (Netherlands)

    Zhang, D.; Benedetto, Di A.C.

    2010-01-01

    This is a study of the related concepts of radical fashion and radical fashion innovation. Radical fashions are defined here as those that may never enter the market at all, and exist primarily on runway shows, in exhibitions and in publicity; by contrast, radical fashion innovations may be very

  9. Long-term stability of diurnal salivary cortisol and alpha-amylase secretion patterns.

    Science.gov (United States)

    Skoluda, Nadine; La Marca, Roberto; Gollwitzer, Mario; Müller, Andreas; Limm, Heribert; Marten-Mittag, Birgitt; Gündel, Harald; Angerer, Peter; Nater, Urs M

    2017-06-01

    This study aimed to investigate long-term stability and variability of diurnal cortisol and alpha-amylase patterns. Diurnal cortisol and alpha-amylase secretion patterns were assessed on a single workday with three waves of measurement across a total time period of 24months in 189 participants. Separate hierarchical linear models were analyzed, with and without a number of potential predictor variables (age, BMI, smoking, chronic stress, stress reactivity). While low long-term stability was found in diurnal cortisol, the stability of diurnal alpha-amylase was moderate across the time period of 24months. Several predictor variables had a positive impact on diurnal cortisol and alpha-amylase secretion patterns averaged across waves. Our findings underpin the notion that long-term stability is not necessarily warranted in longitudinal studies. It is important to choose an appropriate study design when attempting to disentangle clinically and biologically relevant changes from naturally occurring variations in diurnal cortisol and alpha-amylase. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Diurnal Change of Soil Carbon Flux of Binhai New District

    Science.gov (United States)

    Wang, T. F.; Mao, T. Y.; Ye, W.

    2018-05-01

    In order to investigate the factors influencing diurnal change of soil carbon flux of Binhai New District. Field observation experiments were carried out by using LC pro-SD photosynthetic apparatus. The diurnal changes of soil carbon flux and its environmental factors such as atmosphere temperature and soil temperature were analysed. The results indicated that soil carbon flux appeared single diurnal pattern. The diurnal average of soil carbon flux ranked from 0.2761 to 2.3367μmo1/m2/s. Soil carbon flux varied significantly among different land use regimes(Pequations (Pquadratic correlations between soil carbon flux and soil temperature (10cm). And soil temperature could account for more than 32.27% of the soil carbon flux changes (P<0.05, R2=0.3227-0.7465).

  11. Investigation of the oxidation of methyl vinyl ketone (MVK) by OH radicals in the atmospheric simulation chamber SAPHIR

    Science.gov (United States)

    Fuchs, Hendrik; Albrecht, Sascha; Acir, Ismail-Hakki; Bohn, Birger; Breitenlechner, Martin; Dorn, Hans-Peter; Gkatzelis, Georgios I.; Hofzumahaus, Andreas; Holland, Frank; Kaminski, Martin; Keutsch, Frank N.; Novelli, Anna; Reimer, David; Rohrer, Franz; Tillmann, Ralf; Vereecken, Luc; Wegener, Robert; Zaytsev, Alexander; Kiendler-Scharr, Astrid; Wahner, Andreas

    2018-06-01

    The photooxidation of methyl vinyl ketone (MVK) was investigated in the atmospheric simulation chamber SAPHIR for conditions at which organic peroxy radicals (RO2) mainly reacted with NO (high NO case) and for conditions at which other reaction channels could compete (low NO case). Measurements of trace gas concentrations were compared to calculated concentration time series applying the Master Chemical Mechanism (MCM version 3.3.1). Product yields of methylglyoxal and glycolaldehyde were determined from measurements. For the high NO case, the methylglyoxal yield was (19 ± 3) % and the glycolaldehyde yield was (65 ± 14) %, consistent with recent literature studies. For the low NO case, the methylglyoxal yield reduced to (5 ± 2) % because other RO2 reaction channels that do not form methylglyoxal became important. Consistent with literature data, the glycolaldehyde yield of (37 ± 9) % determined in the experiment was not reduced as much as implemented in the MCM, suggesting additional reaction channels producing glycolaldehyde. At the same time, direct quantification of OH radicals in the experiments shows the need for an enhanced OH radical production at low NO conditions similar to previous studies investigating the oxidation of the parent VOC isoprene and methacrolein, the second major oxidation product of isoprene. For MVK the model-measurement discrepancy was up to a factor of 2. Product yields and OH observations were consistent with assumptions of additional RO2 plus HO2 reaction channels as proposed in literature for the major RO2 species formed from the reaction of MVK with OH. However, this study shows that also HO2 radical concentrations are underestimated by the model, suggesting that additional OH is not directly produced from RO2 radical reactions, but indirectly via increased HO2. Quantum chemical calculations show that HO2 could be produced from a fast 1,4-H shift of the second most important MVK derived RO2 species (reaction rate constant 0

  12. Postradiation destruction of dextran in solutions

    International Nuclear Information System (INIS)

    Bondarenko, N.T.; Sharpatyj, V.A.

    1989-01-01

    Methods of pH-metry, UV absorption and ESR spectroscopy were used to study the oxidation destruction of dextran solutions, stored in the air after gamma irradiation ( 60 Co) bydoses of up to 200 kGy. It is shown that polymer destruction under mentioned conditions is initiated by hydroperoxide decomposition with successive radical transformation into peroxides. Experimentally observed periodical change of acidity of irradiated dextran solutions is also explained by transformations of peroxy radicals

  13. Mechanism of antioxidant interaction on polymer oxidation by thermal and radiation ageing

    International Nuclear Information System (INIS)

    Seguchi, Tadao; Tamura, Kiyotoshi; Shimada, Akihiko; Sugimoto, Masaki; Kudoh, Hisaaki

    2012-01-01

    The mechanism of polymer oxidation by radiation and thermal ageing was investigated for the life evaluation of cables installed in radiation environments. The antioxidant as a stabilizer was very effective for thermal oxidation with a small content in polymers, but was not effective for radiation oxidation. The ionizing radiation induced the oxidation to result in chain scission even at low temperature, because the free radicals were produced and the antioxidant could not stop the oxidation of radicals with the chain scission. A new mechanism of antioxidant effect for polymer oxidation was proposed. The effect of antioxidant was not the termination of free radicals in polymer chains such as peroxy radicals, but was the depression of initial radical formation in polymer chains by thermal activation. The antioxidant molecule was assumed to delocalize the activated energy in polymer chains by the Boltzmann statics (distribution) to result in decrease in the probability of radical formation at a given temperature. The interaction distance (delocalization volume) by one antioxidant molecule was estimated to be 5–10 nm by the radius of sphere in polymer matrix, though the value would depend on the chemical structure of antioxidant. - Highlights: ► Interaction of antioxidant on polymer oxidation is discussed for thermal and radiation ageings. ► Antioxidant is very effective for thermal oxidation, but not for radiation induced oxidation. ► Interaction of antioxidant is not the termination reaction of radicals on polymers. ► Antioxidant is supposed to reduce the provability of polymer radical formation by thermal activation. ► Mechanism of polymer oxidation may not be chain reaction via peroxy radical and hydro-peroxide.

  14. Characterisation and quantification of regional diurnal SST cycles from SEVIRI

    DEFF Research Database (Denmark)

    Karagali, Ioanna; Høyer, J.L.

    2014-01-01

    seas. Six years of SST fields from SEVIRI are validated against the Advanced Along-Track Scanning Radiometer (AATSR) Reprocessed for Climate (ARC) data set. The overall SEVIRI–AATSR bias is −0.07 K, and the standard deviation is 0.51 K, based on more than 53×106 matchups. Identification of the diurnal...... in the tropics. Longer diurnal warming duration is identified in the high latitudes compared to the tropics. The maximum monthly mean diurnal signal can be up to 0.5K in specific regions....

  15. Radical chemistry at a rural site (Wangdu) in the North China Plain: observation and model calculations of OH, HO2 and RO2 radicals

    Science.gov (United States)

    Tan, Zhaofeng; Fuchs, Hendrik; Lu, Keding; Hofzumahaus, Andreas; Bohn, Birger; Broch, Sebastian; Dong, Huabin; Gomm, Sebastian; Häseler, Rolf; He, Lingyan; Holland, Frank; Li, Xin; Liu, Ying; Lu, Sihua; Rohrer, Franz; Shao, Min; Wang, Baolin; Wang, Ming; Wu, Yusheng; Zeng, Limin; Zhang, Yinsong; Wahner, Andreas; Zhang, Yuanhang

    2017-01-01

    production at high NOx found in this study is consistent with the results from other field campaigns in urban environments, which underlines the need for better understanding of the peroxy radical chemistry for high NOx conditions.

  16. Modeling the diurnal tide with dissipation derived from UARS/HRDI measurements

    Directory of Open Access Journals (Sweden)

    M. A. Geller

    1997-09-01

    Full Text Available This paper uses dissipation values derived from UARS/HRDI observations in a recently published diurnal-tide model. These model structures compare quite well with the UARS/HRDI observations with respect to the annual variation of the diurnal tidal amplitudes and the size of the amplitudes themselves. It is suggested that the annual variation of atmospheric dissipation in the mesosphere-lower thermosphere is a major controlling factor in determining the annual variation of the diurnal tide.

  17. The 1988 Arctic Survey, Diurnal Study (Sunrise and Sunset) and Peak Altitude (22 km) Flights for the In Situ Detection of ClO and BrO from the NASA ER-2 Aircraft

    Science.gov (United States)

    Anderson, James G.

    1996-01-01

    Two critical areas of research were addressed successfully by this research. The first involves NASA ER-2 airborne observations of ClO and BrO radical destruction of ozone within the arctic vortex. The second involves the analysis of diurnal variations in ClO, to test the production and loss rates of ClO that constitutes the test for coupling reactions between the chlorine and nitrogen systems. We discuss results from this research in order.

  18. Progress in Research on Diurnal and Semidiurnal Earth Rotation Change

    Science.gov (United States)

    Xu, Xueqing

    2015-08-01

    We mainly focus on the progress of research on high frequency changes in the earth rotation. Firstly, we review the development course and main motivating factors of the diurnal and semidiurnal earth rotation change. In recent decades, earth orientation has been monitored with increasing accuracy by advanced space-geodetic techniques, including lunar and satellite laser ranging, very long baseline interferometry and the global positioning system. We are able to obtain the Earth Rotation Parameters (ERP, polar motion and rotation rate changes) by even 1 to 2 hours observation data, form which obvious diurnal and semidiurnal signals can be detected, and compare them with the predicted results by the ocean model. Both the amplitude and phase are in good agreement in the main diurnal and semidiurnal wave frequency, especially for the UT1, whose compliance is 90%, and 60% for polar motion, there are 30% motivating factor of the diurnal and semidiurnal polar motion have not been identified. Then we comprehensively review the different types of global ocean tidal correction models since the last eighties century, as well as the application research on diurnal and semidiurnal polar motion and UT1, the current ocean tidal correction models have 10% to 20% uncertainty, and need for further refinement.

  19. Interannual and Intraseasonal Variability of the Diurnal Tide

    Science.gov (United States)

    Riggin, D. M.; Ortland, D. A.; Lieberman, R. S.; Oberheide, J.; Murayama, Y.; Hocking, W. K.; Vincent, R. A.; Reid, I. M.; Kumar, G. K.; Batista, P. P.; Clemesha, B. R.

    2013-12-01

    Temporal variations in the amplitude of the diurnal tide (DT) have been observed by radars with a seasonal dependence that is typically semiannual in the tropics. During some years the wind variation departs from the normal seasonal behavior with anomalously large amplitudes compared to most other years. This anomaly often takes the form of a greatly enhanced boreal spring equinoctal maximum. The boreal spring of 2008 is a example of this behavior. Diurnal amplitudes in the meridional winds are shown in the figure below for the first 6 months of 2008. Note that the diurnal tide undergoes a sharp increase in amplitude up to 80 ms-1 during this event. The characteristics of this event are diagnosed in a variety of global data sets. These include our own physics-based assimilation of SABER temperatures, and gridded analyses from the national weather services (NCAR/NCEP and ECMWF). Tidal amplitude variations are sometimes attributed to nonlinear interaction. However, this type of interaction would be expected to produce non-migrating tides, e.g., westward-2 or standing. SABER data show that the amplitude anomaly is mainly in the migrating DT. The global data sets allow us to explore properties of the anomaly, such as its origin, evolution in time, and associated momentum flux. In addition to this case study, we also investigate the general characteristics of DT interannual variability during the years of the SABER mission (2002-present). Diurnal tide momentum deposition plays a significant role in controlling the zonal mean wind in the mesosphere, We demonstrate its importance in driving the mesospheric semiannual oscillation (MSAO). Diurnal tide wind amplitudes in the meridional component observed at two radar sites, Rarotonga, Cook Islands (22.1°S, 159.8°W), and at Guanacaste, Costa Rica (10.3°N, 85.6°W).

  20. Diurnal variations of summer precipitation over the regions east to Tibetan Plateau

    Science.gov (United States)

    Wu, Yang; Huang, Anning; Huang, Danqing; Chen, Fei; Yang, Ben; Zhou, Yang; Fang, Dexian; Zhang, Lujun; Wen, Lijuan

    2017-12-01

    Based on the hourly gauge-satellite merged precipitation product with the horizontal resolution of 0.1° latitude/longitude during 2008-2014, diurnal variations of the summer precipitation amount (PA), frequency (PF), and intensity (PI) with different duration time over the regions east to Tibetan Plateau have been systematically revealed in this study. Results indicate that the eight typical precipitation diurnal patterns identified by the cluster analysis display pronounced regional features among the plateaus, basins, plains, hilly and coastal areas. The precipitation diurnal cycles are significantly affected by the sub-grid terrain fluctuations. The PA, PF and PI of the total rainfall show much more pronounced double diurnal peaks with the sub-grid topography standard deviation (SD) decreased. Meanwhile, the diurnal peaks of PA and PF (PI) strengthen (weaken) with the sub-grid topography SD enhanced. Over the elevated mountain ranges, southeastern hilly and coastal regions, the PA and PF diurnal patterns of the total rainfall generally show predominant late-afternoon peaks, which are closely associated with the short-duration (≤slant 3 h) rainfall. Along the Tibetan Plateau to its downstream, the diurnal peaks of PA, PF and PI for the total rainfall all exhibit obvious eastward phase time delay mainly due to the diurnal evolutions of long-duration (> 6 h) rainfall. However, the 4-6 h rainfall leads to the eastward phase time delay of the total rainfall along the Taihang Mountains to its downstream. Further mechanism analysis suggests that the midnight to morning diurnal evolution of the long-duration rainfall is closely associated with the diurnal variations of the upward branches of thermally driven mountain-plain solenoids and the water vapor transport associated with the accelerated nocturnal southwesterly winds. The late-afternoon peak of the short-duration PA over the southeastern hilly and coastal regions is ascribed to the strong local thermal

  1. Biophysical information in asymmetric and symmetric diurnal bidirectional canopy reflectance

    Science.gov (United States)

    Vanderbilt, Vern C.; Caldwell, William F.; Pettigrew, Rita E.; Ustin, Susan L.; Martens, Scott N.; Rousseau, Robert A.; Berger, Kevin M.; Ganapol, B. D.; Kasischke, Eric S.; Clark, Jenny A.

    1991-01-01

    The authors present a theory for partitioning the information content in diurnal bidirectional reflectance measurements in order to detect differences potentially related to biophysical variables. The theory, which divides the canopy reflectance into asymmetric and symmetric functions of solar azimuth angle, attributes asymmetric variation to diurnal changes in the canopy biphysical properties. The symmetric function is attributed to the effects of sunlight interacting with a hypothetical average canopy which would display the average diurnal properties of the actual canopy. The authors analyzed radiometer data collected diurnally in the Thematic Mapper wavelength bands from two walnut canopies that received differing irrigation treatments. The reflectance of the canopies varied with sun and view angles and across seven bands in the visible, near-infrared, and middle infrared wavelength regions. Although one of the canopies was permanently water stressed and the other was stressed in mid-afternoon each day, no water stress signature was unambiguously evident in the reflectance data.

  2. Diurnal changes in epidermal UV transmittance of plants in naturally high UV environments.

    Science.gov (United States)

    Barnes, Paul W; Flint, Stephan D; Slusser, James R; Gao, Wei; Ryel, Ronald J

    2008-06-01

    Studies were conducted on three herbaceous plant species growing in naturally high solar UV environments in the subalpine of Mauna Kea, Hawaii, USA, to determine if diurnal changes in epidermal UV transmittance (T(UV)) occur in these species, and to test whether manipulation of the solar radiation regime could alter these diurnal patterns. Additional field studies were conducted at Logan, Utah, USA, to determine if solar UV was causing diurnal T(UV) changes and to evaluate the relationship between diurnal changes in T(UV) and UV-absorbing pigments. Under clear skies, T(UV), as measured with a UV-A-pulse amplitude modulation fluorometer for leaves of Verbascum thapsus and Oenothera stricta growing in native soils and Vicia faba growing in pots, was highest at predawn and sunset and lowest at midday. These patterns in T(UV) closely tracked diurnal changes in solar radiation and were the result of correlated changes in fluorescence induced by UV-A and blue radiation but not photochemical efficiency (F(v)/F(m)) or initial fluorescence yield (F(o)). The magnitude of the midday reduction in T(UV) was greater for young leaves than for older leaves of Verbascum. Imposition of artificial shade eliminated the diurnal changes in T(UV) in Verbascum, but reduction in solar UV had no effect on diurnal T(UV) changes in Vicia. In Vicia, the diurnal changes in T(UV) occurred without detectable changes in the concentration of whole-leaf UV-absorbing compounds. Results suggest that plants actively control diurnal changes in UV shielding, and these changes occur in response to signals other than solar UV; however, the underlying mechanisms responsible for rapid changes in T(UV) remain unclear.

  3. Autoxidation of hydrazones. Some new insights.

    Science.gov (United States)

    Harej, Maja; Dolenc, Darko

    2007-09-14

    Autoxidation of hydrazones is a generally occurring reaction, leading mostly to the formation of alpha-azohydroperoxides. All structural kinds of hydrazones, having at least one hydrogen atom on nitrogen, are prone to autoxidation; however, there are marked differences in the rate of the reaction. Hydrazones of aliphatic ketones are 1-2 orders of magnitude more reactive than analogous derivatives of aromatic ketones. Even less reactive are the hydrazones of chalcones, which function also as efficient inhibitors of autoxidation of other hydrazones. These differences can be attributed to the reduction of the rate of the addition of oxygen to a hydrazonyl radical, which is a reversible reaction. In the case of conjugated ketones, it becomes endothermic, making this elementary step slow down and the chain termination reactions become important. Substituents influence the stability of hydrazonyl radicals and, consequently, the bond dissociation energies of the N-H bonds. In acetophenone phenylhydrazones, the substituents placed on the ring of hydrazine moiety exhibit a higher effect (Hammett rho = -2.8) than those on the ketone moiety (rho = -0.82), which denotes higher importance of the structure with spin density concentrated on nitrogen in delocalized hydrazonyl radical. Electronic effects of the substituents also affect the transition state for the abstraction of hydrogen atom by electrophilic peroxy radicals; NBO analysis display a negative charge transfer of about 0.4 eu from hydrazone to a peroxy radical in the transition state.

  4. Individual Differences in Diurnal Preference and Time-of-Exercise Interact to Predict Exercise Frequency.

    Science.gov (United States)

    Hisler, Garrett C; Phillips, Alison L; Krizan, Zlatan

    2017-06-01

    Diurnal preference (and chronotype more generally) has been implicated in exercise behavior, but this relation has not been examined using objective exercise measurements nor have potential psychosocial mediators been examined. Furthermore, time-of-day often moderates diurnal preference's influence on outcomes, and it is unknown whether time-of-exercise may influence the relation between chronotype and exercise frequency. The current study examined whether individual differences in diurnal preference ("morningness-eveningness") predict unique variance in exercise frequency and if commonly studied psychosocial variables mediate this relation (i.e., behavioral intentions, internal exercise control, external exercise control, and conscientiousness). Moreover, the study sought to test whether individuals' typical time-of-exercise moderated the impact of diurnal preference on exercise frequency. One hundred twelve healthy adults (mean age = 25.4; SD = 11.6 years) completed baseline demographics and then wore Fitbit Zips® for 4 weeks to objectively measure exercise frequency and typical time-of-exercise. At the end of the study, participants also self-reported recent exercise. Diurnal preference predicted both self-reported exercise and Fitbit-recorded exercise frequency. When evaluating mediators, only conscientiousness emerged as a partial mediator of the relation between diurnal preference and self-reported exercise. In addition, time-of-exercise moderated diurnal preference's relation to both self-reported exercise and Fitbit-recorded exercise frequency such that diurnal preference predicted higher exercise frequency when exercise occurred at a time that was congruent with one's diurnal preference. Based on these findings, diurnal preference is valuable, above and beyond other psychological constructs, in predicting exercise frequency and represents an important variable to incorporate into interventions seeking to increase exercise.

  5. Diurnal variation of the human adipose transcriptome and the link to metabolic disease

    Directory of Open Access Journals (Sweden)

    Lamb John

    2009-02-01

    Full Text Available Abstract Background Circadian (diurnal rhythm is an integral part of the physiology of the body; specifically, sleep, feeding behavior and metabolism are tightly linked to the light-dark cycle dictated by earth's rotation. Methods The present study examines the effect of diurnal rhythm on gene expression in the subcutaneous adipose tissue of overweight to mildly obese, healthy individuals. In this well-controlled clinical study, adipose biopsies were taken in the morning, afternoon and evening from individuals in three study arms: treatment with the weight loss drug sibutramine/fasted, placebo/fed and placebo/fasted. Results The results indicated that diurnal rhythm was the most significant driver of gene expression variation in the human adipose tissue, with at least 25% of the genes having had significant changes in their expression levels during the course of the day. The mRNA expression levels of core clock genes at a specific time of day were consistent across multiple subjects on different days in all three arms, indicating robust diurnal regulation irrespective of potential confounding factors. The genes essential for energy metabolism and tissue physiology were part of the diurnal signature. We hypothesize that the diurnal transition of the expression of energy metabolism genes reflects the shift in the adipose tissue from an energy-expending state in the morning to an energy-storing state in the evening. Consistent with this hypothesis, the diurnal transition was delayed by fasting and treatment with sibutramine. Finally, an in silico comparison of the diurnal signature with data from the publicly-available Connectivity Map demonstrated a significant association with transcripts that were repressed by mTOR inhibitors, suggesting a possible link between mTOR signaling, diurnal gene expression and metabolic regulation. Conclusion Diurnal rhythm plays an important role in the physiology and regulation of energy metabolism in the adipose

  6. Changing On Diurnal Cycle Of Rainfall In Northern Coastal Of West Java

    Science.gov (United States)

    Yulihastin, E.; Hadi, T. W.; Ningsih, N. S.

    2017-12-01

    The floods event in the north of Java was largely due to persistent of rainfall that occurred in the morning which indicated of deviation of diurnal pattern of rainfall. The shift of the phase of diurnal rainfall cycle using TRMM satellite hourly data of 3B41RT on the rainy period of 2000-2016 exhibits over land from Late Afternoon-Early Midnight (LA-EM) to morning. The peak of the cycle changes from diurnal to semidiurnal with a peak occurring in LA-EM and morning. Location of rainfall which usually occurs in the oceans shifted into near coastal area. The classification of diurnal rainfall cycles based on composite analysis shows four types: Normal (N) Type (45.6%) with one peak rainfall occurring in the afternoon until night, Diurnal (D) Type (26%) with one peak and phase opposite to normal type, Semidiurnal (SD) Type (6.5 %) with two peaks and the main peak occurring in the afternoon until night, Third Diurnal (TD) Type (21.7%) with three peaks and the main peak occurs in the morning. The classification was confirmed using the objective method of Empirical Mode Decomposition (EMD) and obtained three IMFs representing three diurnal cycle modes of Type TD (67.8%) with the main rain peak taking place in the afternoon, Type D with rain peak occurring in the early hours (18.9%), and SD type (9.9%) with the first peak occurred in the afternoon. For D Type, the results also prove that the diurnal cycle with significant deviations in amplitude occurred in February 2002, 2004, 2008, 2014, wich is the maximum rainfall occurs in the EM. It also seems that in those years, rainfall intensity is concentrated on the northern coast of West Java while in the Java Sea rainfall was minimum.

  7. Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling.

    Science.gov (United States)

    Hoyermann, Karlheinz; Mauß, Fabian; Olzmann, Matthias; Welz, Oliver; Zeuch, Thomas

    2017-07-19

    Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity. Their reactivity is central to our understanding of how volatile organic compounds are degraded in the atmosphere and converted into secondary organic aerosol. Moreover, they sensitively determine ignition timing in internal combustion engines. The intention of this perspective article is to provide the reader with information about the general mechanisms of reactions initiated by addition of atomic and molecular oxygen to alkyl radicals and ozone to alkenes. We will focus on critical branching points in the subsequent reaction mechanisms and discuss them from a consistent point of view. As a first example of our integrated approach, we will show how experiment, theory, and kinetic modeling have been successfully combined in the first infrared detection of Criegee intermediates during the gas phase ozonolysis. As a second example, we will examine the ignition timing of n-heptane/air mixtures at low and intermediate temperatures. Here, we present a reduced, fuel size independent kinetic model of the complex chemistry initiated by peroxy radicals that has been successfully applied to simulate standard n-heptane combustion experiments.

  8. Seasonal variation in diurnal atmospheric grass pollen concentration profiles

    DEFF Research Database (Denmark)

    Peel, Robert George; Ørby, Pia Viuf; Skjøth, Carsten Ambelas

    2014-01-01

    the time of day when peak concentrations are most likely to occur using seasonally averaged diurnal profiles. Atmospheric pollen loads are highly dependent upon emissions, and different species of grass are known to flower and emit pollen at different times of the day and during different periods......In this study, the diurnal atmospheric grass pollen concentration profile within the Danish city of Aarhus was shown to change in a systematic manner as the pollen season progressed. Although diurnal grass pollen profiles can differ greatly from day-to-day, it is common practice to establish...... of the pollen season. Pollen concentrations are also influenced by meteorological factors - directly through those parameters that govern pollen dispersion and transport, and indirectly through the weather-driven flowering process. We found that three different profiles dominated the grass pollen season...

  9. Regimes of Diurnal Variation of Summer Rainfall over Subtropical East Asia

    Energy Technology Data Exchange (ETDEWEB)

    Yuan W.; Lin W.; Yu, R.; Zhang, M.; Chen, H.; Li, J.

    2012-05-01

    Using hourly rain gauge records and Tropical Rainfall Measuring Mission 3B42 from 1998 to 2006, the authors present an analysis of the diurnal characteristics of summer rainfall over subtropical East Asia. The study shows that there are four different regimes of distinct diurnal variation of rainfall in both the rain gauge and the satellite data. They are located over the Tibetan Plateau with late-afternoon and midnight peaks, in the western China plain with midnight to early-morning peaks, in the eastern China plain with double peaks in late afternoon and early morning, and over the East China Sea with an early-morning peak. No propagation of diurnal phases is found from the land to the ocean across the coastlines. The different diurnal regimes are highly correlated with the inhomogeneous underlying surface, such as the plateau, plain, and ocean, with physical mechanisms consistent with the large-scale 'mountain-valley' and 'land-sea' breezes and convective instability. These diurnal characteristics over subtropical East Asia can be used as diagnostic metrics to evaluate the physical parameterization and hydrological cycle of climate models over East Asia.

  10. Preeclampsia prediction in type 1 diabetes and diurnal blood pressure methodology

    DEFF Research Database (Denmark)

    Lauszus, Finn

    2016-01-01

    of the papers with the best, validated methodology on BP measurements, which is by no way guaranteed in numerous recent publications. Inherent characteristics of the measurements to be considered are reproducibility, consistency, precision, and trend over scale of measurement. Studies on these issues suggest....... Preeclampsia is associated with urinary albumin excretion rate, reduced night/day ratio, and elevated diurnal blood pressure from first trimester and onwards. However, due to blunting of the diurnal variation, the night/day rhythm provides no good prediction of preeclampsia. Diurnal measurement is a valuable...

  11. Seasonal and diurnal variations of ocular pressure in ocular hypertensive subjects in Pakistan.

    Science.gov (United States)

    Qureshi, I A; Xiao, R X; Yang, B H; Zhang, J; Xiang, D W; Hui, J L

    1999-05-01

    Studies have been shown that intraocular pressure (IOP) shows a diurnal variation in ocular hypertensive subjects, but the amount of change differs from study to study. In recent years it has been noted that intraocular pressure is a dynamic function and is subjected to many influences both acutely and over the long term. The variability in the results may be due to negligence of factors that can affect IOP. Moreover, seasonal variations in the ocular hypertensive subjects have never been described. After placing control on those factors that can affect IOP, this study investigated seasonal and diurnal variations in IOP of ocular hypertensive subjects. IOP was measured each month over the course of 12 months with the Goldmann applanation tonometer in 91 ocular hypertensive male subjects. To see the diurnal changes, subjects were asked to stay in the hospital for 24 hours. The average IOP in the winter months was higher than those in spring, summer, and autumn. The IOP difference between winter and summer was (mean +/- sem) 2.9 +/- 0.9 mmHg (p < 0.001). The peak of mean IOP in diurnal variation curve (25.7 +/- 1.2 mmHg) appeared in the morning when the subjects had just awaken. The mean diurnal variation was found to be 4.2 +/- 0.6 mmHg (p < 0.001). This study confirms that seasons influence IOP and it shows diurnal variations. As compared to other nations, diurnal variations in ocular hypertensive subjects seem to be somewhat less in Pakistan. Knowledge of the seasonal and diurnal variations in IOP may help glaucoma screeners.

  12. Dopamine transporters govern diurnal variation in extracellular dopamine tone

    OpenAIRE

    Ferris, Mark J.; España, Rodrigo A.; Locke, Jason L.; Konstantopoulos, Joanne K.; Rose, Jamie H.; Chen, Rong; Jones, Sara R.

    2014-01-01

    The mechanism for diurnal (i.e., light/dark) oscillations in extracellular dopamine tone in mesolimbic and nigrostriatal systems is unknown. This is because, unlike other neurotransmitter systems, variation in dopamine tone does not correlate with variation in dopamine cell firing. The current research pinpoints the dopamine transporter as a critical governor of diurnal variation in both extracellular dopamine tone and the intracellular availability of releasable dopamine. These data describe...

  13. Diurnal variations of Titan's ionosphere

    Science.gov (United States)

    Cui, J.; Galand, M.; Yelle, R. V.; Vuitton, V.; Wahlund, J.-E.; Lavvas, P. P.; Müller-Wodarg, I. C. F.; Cravens, T. E.; Kasprzak, W. T.; Waite, J. H.

    2009-06-01

    We present our analysis of the diurnal variations of Titan's ionosphere (between 1000 and 1300 km) based on a sample of Ion Neutral Mass Spectrometer (INMS) measurements in the Open Source Ion (OSI) mode obtained from eight close encounters of the Cassini spacecraft with Titan. Although there is an overall ion depletion well beyond the terminator, the ion content on Titan's nightside is still appreciable, with a density plateau of ˜700 cm-3 below ˜1300 km. Such a plateau is a combined result of significant depletion of light ions and modest depletion of heavy ones on Titan's nightside. We propose that the distinctions between the diurnal variations of light and heavy ions are associated with their different chemical loss pathways, with the former primarily through “fast” ion-neutral chemistry and the latter through “slow” electron dissociative recombination. The strong correlation between the observed night-to-day ion density ratios and the associated ion lifetimes suggests a scenario in which the ions created on Titan's dayside may survive well to the nightside. The observed asymmetry between the dawn and dusk ion density profiles also supports such an interpretation. We construct a time-dependent ion chemistry model to investigate the effect of ion survival associated with solid body rotation alone as well as superrotating horizontal winds. For long-lived ions, the predicted diurnal variations have similar general characteristics to those observed. However, for short-lived ions, the model densities on the nightside are significantly lower than the observed values. This implies that electron precipitation from Saturn's magnetosphere may be an additional and important contributor to the densities of the short-lived ions observed on Titan's nightside.

  14. Differences in ocular parameters between diurnal and nocturnal raptors.

    Science.gov (United States)

    Beckwith-Cohen, Billie; Horowitz, Igal; Bdolah-Abram, Tali; Lublin, Avishai; Ofri, Ron

    2015-01-01

    To establish and compare normal ocular parameters between and within diurnal and nocturnal raptor groups. Eighty-eight ophthalmically normal raptors of six nocturnal and 11 diurnal species were studied. Tear production was measured using Schirmer tear test (STT) and phenol red thread test (PRTT), and applanation tonometry was conducted. Ultrasonographic measurements of axial length (AL), mediolateral axis (ML), vitreous body (VB), and pecten length (PL) were recorded, and conjunctival cultures were obtained. A weak correlation (R = 0.312, P = 0.006) was found between PRTT and STT. Tear production was significantly lower in nocturnal species (P raptors were positive for mycology or bacteriology, either on culture or PCR. The most common infectious agent isolated was Staphylococcus spp. Phenol red thread test and STT are both valid methods to measure tear production; however, a separate baseline must be determined for each species using these methods, as the results of one method cannot be extrapolated to the other. Due to significant differences observed within diurnal and nocturnal species, it appears that a more intricate division should be used when comparing these parameters for raptors, and the classification of diurnal or nocturnal holds little significance in the baseline of these data. © 2013 American College of Veterinary Ophthalmologists.

  15. Satellite, climatological, and theoretical inputs for modeling of the diurnal cycle of fire emissions

    Science.gov (United States)

    Hyer, E. J.; Reid, J. S.; Schmidt, C. C.; Giglio, L.; Prins, E.

    2009-12-01

    The diurnal cycle of fire activity is crucial for accurate simulation of atmospheric effects of fire emissions, especially at finer spatial and temporal scales. Estimating diurnal variability in emissions is also a critical problem for construction of emissions estimates from multiple sensors with variable coverage patterns. An optimal diurnal emissions estimate will use as much information as possible from satellite fire observations, compensate known biases in those observations, and use detailed theoretical models of the diurnal cycle to fill in missing information. As part of ongoing improvements to the Fire Location and Monitoring of Burning Emissions (FLAMBE) fire monitoring system, we evaluated several different methods of integrating observations with different temporal sampling. We used geostationary fire detections from WF_ABBA, fire detection data from MODIS, empirical diurnal cycles from TRMM, and simple theoretical diurnal curves based on surface heating. Our experiments integrated these data in different combinations to estimate the diurnal cycles of emissions for each location and time. Hourly emissions estimates derived using these methods were tested using an aerosol transport model. We present results of this comparison, and discuss the implications of our results for the broader problem of multi-sensor data fusion in fire emissions modeling.

  16. Diurnal-and sex-related difference of metallothionein expression in mice

    Directory of Open Access Journals (Sweden)

    Zhang Dan

    2012-07-01

    Full Text Available Abstract Background Metallothionein (MT is a small, cysteine-rich, metal-binding protein that plays an important role in protecting against toxicity of heavy metal and chemicals. This study was aimed to define diurnal and sex variation of MT in mice. Methods Adult mice were maintained in light- and temperature-controlled facilities for 2 weeks with light on at 8:00 and light off at 20:00. The blood, liver, and kidneys were collected every 4 h during the 24 h period. Total RNA was isolated, purified, and subjected to real-time RT-PCR analysis and MT protein was determined by western blot and the Cd/hemoglobin assay. Results The diurnal variations in mRNA levels of MT-1 and MT-2in liver were dramatic, up to a 40-foldpeak/trough ratio. MT mRNA levels in kidneys and blood also showed diurnal variation, up to 5-fold peak/trough ratio. The diurnal variation of MT mRNAs resembled the clock gene albumin site D-binding protein (Dbp, and was anti-phase to the clock gene Brain and Muscle ARNT-like Protein 1 (Bmal1 in liver and kidneys. The peaks of MT mRNA levels were higher in females than in males. Hepatic MT protein followed a similar pattern, with about a 3-fold difference. Conclusion MT mRNA levels and protein showed diurnal- and sex-variation in liver, kidney, and blood of mice, which could impact the body defense against toxic stimuli.

  17. SST diurnal variability in the North Sea and the Baltic Sea

    DEFF Research Database (Denmark)

    Karagali, Ioanna; Høyer, Jacob; Hasager, Charlotte Bay

    2012-01-01

    (σ) between 0.4K and 0.9K. The 5year record with daytime temperature anomalies is used to derive robust statistical description of duration, spatial extent, proximity to coast and water depth of the diurnal warming events. Seasonal and inter-annual variations in the diurnal warming are also...... quantified. Daytime anomalies exceeding 2K are identified during the spring and summer months of every year, peaking at 1500 LT. Events with daily anomalies exceeding 5K are observed. Areas where diurnal variability is often observed coincide with areas of frequently observed low winds and turbid waters...

  18. Heliospheric Modulation of Galactic Cosmic Rays; Diurnal Variability Abstract Details

    Science.gov (United States)

    Kalu, D. F.; Okpala, K. C.

    2017-12-01

    We have studied the variability of Cosmic rays flux during solar quiet days at mid and high latitudes in the Northern Hemisphere. By using the five (5) quietest days for each month and the five disturbed days for each month, the monthly mean diurnal variation of cosmic ray anisotropy have been derived for the period 1999-2015, which covers part of cycles 23, and cycle 24. This study seeks to understand the heliospheric contribution to the variation of these Cosmic rays on quietest days, three stations (Inuvik, Moscow, Rome) Neutron Monitors were employed. This study seeks to understand the important features of the high latitude and mid latitude diurnal wave, and how solar and geomagnetic activity may be influencing the wave characteristics. Cosmic ray wave characteristics were obtained by discrete Fourier transform (DFT). The mean, diurnal amplitude, phase and dispersion for each month's diurnal wave were calculated and profiled. There was clear indication that the terrestrial effect on the variability of the monthly mean was more associated with geomagnetic activity rather than rigidity of the cosmic rays. Correlation of the time series of these wave characteristic with solar and geomagnetic activity index showed better association with solar activity.

  19. Quality assessment of coffee beans with ESR and gamma-ray irradiation

    International Nuclear Information System (INIS)

    Ikeya, Motoji; Baffa, F.O.; Mascarenhas, Sergio

    1989-01-01

    Peroxy radical formation in raw coffee beans of different qualities and origins from all over the world has been studied with electron spin resonance (ESR) analysis. The γ-ray equivalent absorbed dose (ED) which creates the same concentration of radicals is obtained by the additive γ-ray irradiation of the coffee beans. The ED and the cup quality is somewhat inversely related suggesting that the peroxidation of the unsaturated fatty acid is somewhat indicative of the degree of the aromatic decomposition and rancidity. (author)

  20. Synthesis and Characterization of Titanium Supported on High Order Nanoporous Silica and Application for Direct Oxidation of Benzene to Phenol

    OpenAIRE

    Alireza Badiei; Javad Gholami; Yeganeh Khaniani

    2009-01-01

    Direct oxidation of benzene to phenol in liquid phase by H2O2 peroxide was examined over Ti/ LUS-1 catalyst in methanol and acetic acid as solvents. The maximum yield and selectivity of the phenol produced was obtained in the presence of acetic acid. It can be attributed to the stabilization of H2O2 as peroxy acetic acid species in the radical mechanism for this reaction. Acetic acid interacts with hydrogen peroxide over Ti/LUS-1 and produces acetoxy radicals.

  1. Synthesis and Characterization of Titanium Supported on High Order Nanoporous Silica and Application for Direct Oxidation of Benzene to Phenol

    Directory of Open Access Journals (Sweden)

    Alireza Badiei

    2009-01-01

    Full Text Available Direct oxidation of benzene to phenol in liquid phase by H2O2 peroxide was examined over Ti/ LUS-1 catalyst in methanol and acetic acid as solvents. The maximum yield and selectivity of the phenol produced was obtained in the presence of acetic acid. It can be attributed to the stabilization of H2O2 as peroxy acetic acid species in the radical mechanism for this reaction. Acetic acid interacts with hydrogen peroxide over Ti/LUS-1 and produces acetoxy radicals.

  2. A Comparative Study of the Radical-scavenging Activity of the Phenolcarboxylic Acids Caffeic Acid, p-Coumaric Acid, Chlorogenic Acid and Ferulic Acid, With or Without 2-Mercaptoethanol, a Thiol, Using the Induction Period Method

    Directory of Open Access Journals (Sweden)

    Seiichiro Fujisawa

    2008-10-01

    Full Text Available Phenolcarboxylic acid antioxidants do not act in vivo as radical-scavengers in isolation, but rather together with GSH (glutathione, a coantioxidant, they constitute an intricate antioxidant network. Caffeic acid, p-coumaric acid, ferulic acid and chlorogenic acid with or without 2-mercaptoethanol (ME, as a substitute for GSH, was investigated by the induction period (IP method for polymerization of methyl methacrylate (MMA initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN, a source of alkyl radicals, R. and benzoyl peroxide (BPO, a source of peroxy radicals, PhCOO. using differential scanning calorimetry (DSC. Upon PhCOO. radical scavenging, the stoichiometric factors (n, number of free radical trapped by one mole of antioxidant for caffeic acid, ferulic acid, p-coumaric acid and chlorogenic acid were 2.4, 1.8, 1.7 and 0.9, whereas upon R. radical scavenging, the corresponding values were 1.3, 1.2, 1.0 and 0.8, respectively. Antioxidants with n values close to 2 suggest the stepwise formation of semiquinone radicals and quinones. By contrast, those with n values close to 1 suggest the formation of dimers after single-electron oxidation, possibly due to recombination of corresponding aryloxy radicals. The ratio of the rate constant of inhibition to that of propagation (kinh/kp declined in the order chlorogenic acid > p-coumaric acid > ferulic acid > caffeic acid. The ratio of the observed IP for the phenolcarboxylic acid/2-mercapto-ethanol (ME mixture (1:1 molar ratio (A to the calculated IP (the simple sum of phenol acid antioxidant and ME (B was investigated. Upon R. scavenging, the caffeic acid or p-coumaric acid/ME mixture was A/B > 1, particularly the former was 1.2, suggesting a synergic effect. By contrast, upon PhCOO. scavenging, the corresponding mixture was A/B < 1, particularly the latter was 0.7, suggesting an antagonistic effect. Upon both radicals scavenging, the A/B for the ferulic acid or chlorogenic acid

  3. Isoprene photochemistry over the Amazon rainforest

    Science.gov (United States)

    Liu, Yingjun; Brito, Joel; Dorris, Matthew R.; Rivera-Rios, Jean C.; Seco, Roger; Bates, Kelvin H.; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N.; Kim, Saewung; Goldstein, Allen H.; Guenther, Alex B.; Manzi, Antonio O.; Souza, Rodrigo A. F.; Springston, Stephen R.; Watson, Thomas B.; McKinney, Karena A.

    2016-01-01

    Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4–0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest. PMID:27185928

  4. Spectral and diurnal variations in clear sky planetary albedo

    Science.gov (United States)

    Briegleb, B.; Ramanathan, V.

    1982-01-01

    Spectral and diurnal variations in the clear sky planetary albedo of the earth are calculated using a radiative transfer model to obtain January and July values for a 5 deg x 5 deg global grid. The model employs observed climatological values of temperatures, humidities, snow and sea-ice cover. The diurnal cycle of clear sky albedo is calculated in the following intervals: 0.2-0.5, 0.5-0.7, and 0.7-4 microns. Observed ozone distribution is specified as a function of latitude and season. The 0.2-0.5 micron spectral albedo is 10-20% higher than the total albedo for all latitudes because of Rayleigh scattering; the 0.5-0.7 micron albedo differs from the total albedo by 1-2% for most latitudes, while the 0.7-4 micron albedo is 5-10% lower than the total because of strong atmospheric absorption. Planetary albedo decreases from morning to local noon, with diurnal variations being particularly strong over water.

  5. Modelling of diurnal cycle under climate change

    Energy Technology Data Exchange (ETDEWEB)

    Eliseev, A V; Bezmenov, K V; Demchenko, P F; Mokhov, I I; Petoukhov, V K [Russian Academy of Sciences, Moscow (Russian Federation). Inst. of Atmospheric Physics

    1996-12-31

    The observed diurnal temperature range (DTR) displays remarkable change during last 30 years. Land air DTR generally decreases under global climate warming due to more significant night minimum temperature increase in comparison with day maximum temperature increase. Atmosphere hydrological cycle characteristics change under global warming and possible background aerosol atmosphere content change may cause essential errors in the estimation of DTR tendencies of change under global warming. The result of this study is the investigation of cloudiness effect on the DTR and blackbody radiative emissivity diurnal range. It is shown that in some cases (particularly in cold seasons) it results in opposite change in DTR and BD at doubled CO{sub 2} atmosphere content. The influence of background aerosol is the same as the cloudiness one

  6. Modelling of diurnal cycle under climate change

    Energy Technology Data Exchange (ETDEWEB)

    Eliseev, A.V.; Bezmenov, K.V.; Demchenko, P.F.; Mokhov, I.I.; Petoukhov, V.K. [Russian Academy of Sciences, Moscow (Russian Federation). Inst. of Atmospheric Physics

    1995-12-31

    The observed diurnal temperature range (DTR) displays remarkable change during last 30 years. Land air DTR generally decreases under global climate warming due to more significant night minimum temperature increase in comparison with day maximum temperature increase. Atmosphere hydrological cycle characteristics change under global warming and possible background aerosol atmosphere content change may cause essential errors in the estimation of DTR tendencies of change under global warming. The result of this study is the investigation of cloudiness effect on the DTR and blackbody radiative emissivity diurnal range. It is shown that in some cases (particularly in cold seasons) it results in opposite change in DTR and BD at doubled CO{sub 2} atmosphere content. The influence of background aerosol is the same as the cloudiness one

  7. Atmospheric chemistry of hydrofluorocarbons and hydrochlorofluorocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Sehested, J

    1995-03-01

    Pulse radiolysis coupled with a time resolved UV absorption detection system and a FTIR spectrometer coupled to a 140 l reaction chamber was used to study the degradation of HCFCs and HFCs in the atmosphere. Reaction rates for a series of reactions of HFCs and HCFCs were investigated: F + RH, R + O{sub 2} + RO{sub 2} + NO, and RO{sub 2} + NO{sub 2} + M, together with UV absorption spectra of the halogenated alkyl (R) and halogenated alkyl peroxy radicals (RO{sub 2}). The products following the self reactions for RO{sub 2} radicals for RO{sub 2} = CF{sub 3}CF{sub 2}O{sub 2}, CF{sub 2}HCF{sub 2}O{sub 2}, CF{sub 3}CH{sub 2}O{sub 2}, CFH{sub 2}CFHO{sub 2}, CF{sub 3}O{sub 2}, and CF{sub 3}C(O)O{sub 2} were investigated by the FTIR setup. The results show that the self reaction of halogenated peroxy radicals give the alkoxy radical, RO, as product. The atmospheric fate of these radicals were C-C bond cleavage for CF{sub 3}CF{sub 2}O, CHF{sub 2}CF{sub 2}O, CFH{sub 2}CHFO, and CF{sub 3}C(O)O; while CF{sub 3}CH{sub 2}O radicals rect with O{sub 2} to give CF{sub 3}CHO and HO{sub 2}. the reaction between CFH{sub 2}O{sub 2} and HO{sub 2} was shown to give 29{+-}7 % CH{sub 2}FCOOH and 72{+-}11 % HCOF as the carbon containing products. (Abstract Truncated)

  8. Diurnal variation of summer precipitation over the Tibetan Plateau. A cloud-resolving simulation

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Jianyu; Zhang, Bing; Wang, Minghuan [China Meteorological Administration, Wuhan (China). Wuhan Inst. of Heavy Rain; Wang, Huijuan [Weather Modification Office of Hubei Province, Wuhan (China)

    2012-07-01

    In this study, the Weather Research and Forecasting model was used to simulate the diurnal variation in summer precipitation over the Tibetan Plateau (TP) at a cloudresolving scale. Compared with the TRMM, precipitation data shows that the model can well simulate the diurnal rainfall cycle with an overall late-afternoon maximum precipitation in the central TP and a nighttime maximum in the southern edge. The simulated diurnal variations in regional circulation and thermodynamics are in good correspondence with the precipitation diurnal cycles in the central and southern edge of TP, respectively. A possible mechanism responsible for the nocturnal precipitation maximum in the southern edge has been proposed, indicating the importance of the TP in regulating the regional circulation and precipitation. (orig.)

  9. Diurnal rhythm in serum levels of inhibin B in normal men

    DEFF Research Database (Denmark)

    Carlsen, E; Olsson, C; Petersen, J H

    1999-01-01

    in the early morning hours and lower values in the late afternoon and evening. We did not find evidence for a role of FSH in this diurnal variation of inhibin B. However, covariation with serum levels of testosterone and estradiol suggested that these hormones might play a role in the diurnal rhythm of inhibin...

  10. Diurnal Reflectance Changes in Vegetation Observed with AVIRIS

    Science.gov (United States)

    Vanderbilt, V. C.; Ambrosia, V. G.; Ustin, S. L.

    1998-01-01

    Among the most important short-term dynamic biological processes are diurnal changes in canopy water relations. Plant regulation of water transport through stomatal openings affects other gaseous transport processes, often dramatically decreasing photosynthetic fixation of carbon dioxide during periods of water stress. Water stress reduces stomatal conductance of water vapor through the leaf surface and alters the diurnal timing of stomatal opening. Under non-water stressed conditions, stomates typically open soon after dawn and transpire water vapor throughout the daylight period. During stress periods, stomates may close for part of the day, generally near mid-day. Under prolonged stress conditions, stomatal closure shifts to earlier times during the day; stomates may close by mid-morning and remain closed until the following morning - or remain closed entirely. Under these conditions the relationship between canopy greenness (e.g., measured with a vegetation index or by spectral mixture analysis) and photosynthetic fixation of carbon is lost and the remotely sensed vegetation metric is a poor predictor of gas exchange. Prediction of stomatal regulation and exchange of water and trace gases is critical for ecosystem and climate models to correctly estimate budgets of these gases and understand or predict other processes like gross and net ecosystem primary production. Plant gas exchange has been extensively studied by physiologists at the leaf and whole plant level and by biometeorologists at somewhat larger scales. While these energy driven processes follow a predictable if somewhat asymmetric diurnal cycle dependent on soil water availability and the constraints imposed by the solar energy budget, they are nonetheless difficult to measure at the tree and stand levels using conventional methods. Ecologists have long been interested in the potential of remote sensing for monitoring physiological changes using multi-temporal images. Much of this research has

  11. Diurnal and stress-reactive dehydroepiandrosterone levels and telomere length in youth.

    Science.gov (United States)

    Dismukes, Andrew R; Meyer, Vanessa J; Shirtcliff, Elizabeth A; Theall, Katherine P; Esteves, Kyle C; Drury, Stacy S

    2016-05-01

    The current investigation examined the association between the aging-related biomarkers dehydroepiandrosterone (DHEA) and telomere length (TL) in community-recruited African-American youth. The examination of DHEA included stress reactive, basal and diurnal sampling, in order to elucidate the underlying physiological process that may overlap with TL. One hundred and two participants completed the Trier Social Stressor Test for children (TSST-C). TL was obtained from all youth from buccal swabs on the same day as the TSST-C. Saliva samples from 83 participants were obtained over the course of two additional days to measure waking and diurnal levels of DHEA. DHEA diurnal slope was a robust predictor of TL (B=0.516, P<0.05), while other DHEA values were not significantly associated with TL. This study is one of the first studies to examine basal, diurnal and reactivity measurements of DHEA in youth. Furthermore, this is the first study, to our knowledge, to demonstrate a positive association between DHEA, a putative anti-aging hormone, and TL, an indicator of cellular aging. © 2016 The authors.

  12. Diurnal and stress-reactive dehydroepiandrosterone levels and telomere length in youth

    Directory of Open Access Journals (Sweden)

    Andrew R Dismukes

    2016-05-01

    Full Text Available The current investigation examined the association between the aging-related biomarkers dehydroepiandrosterone (DHEA and telomere length (TL in community-recruited African-American youth. The examination of DHEA included stress reactive, basal and diurnal sampling, in order to elucidate the underlying physiological process that may overlap with TL. One hundred and two participants completed the Trier Social Stressor Test for children (TSST-C. TL was obtained from all youth from buccal swabs on the same day as the TSST-C. Saliva samples from 83 participants were obtained over the course of two additional days to measure waking and diurnal levels of DHEA. DHEA diurnal slope was a robust predictor of TL (B=0.516, P<0.05, while other DHEA values were not significantly associated with TL. This study is one of the first studies to examine basal, diurnal and reactivity measurements of DHEA in youth. Furthermore, this is the first study, to our knowledge, to demonstrate a positive association between DHEA, a putative anti-aging hormone, and TL, an indicator of cellular aging.

  13. The diurnal pattern of microwave backscattering by wheat

    International Nuclear Information System (INIS)

    Brisco, B.; Brown, R.J.; Koehler, J.A.; Sofko, G.J.; McKibben, M.J.

    1990-01-01

    A truck-mounted Ku-, C-, and L-band scatterometer system was used to obtain diurnal multiparameter radar backscatter measurements of wheat in August 1987 and June and July 1988. Concurrent field measurements of plant and soil moisture content were made in support of the radar data. Analyses of these data demonstrate the sensitivity of the microwave signals to the daily movement of water in the soil/plant system. The dependence of frequency, incidence angle, and polarization are discussed in relationship to the diurnal and seasonal changes in the soil and plant water content. The results are used to identify potential agronomic applications and future research requirements. (author)

  14. Latitudinal and longitudinal dependence of the cosmic ray diurnal anisotropy during 2001-2014

    International Nuclear Information System (INIS)

    Tezari, Anastasia; Mavromichalaki, Helen; Katsinis, Dimitrios; Kanellakopoulos, Anastasios; Kolovi, Sofia; Plainaki, Christina; National and Kapodistrian Univ. of Athens; Andriopoulou, Maria

    2016-01-01

    The diurnal anisotropy of cosmic ray intensity for the time period 2001 to 2014 is studied, covering the maximum and the descending phase of solar cycle 23, the minimum between solar cycles 23 and 24, and the ascending phase and maximum of solar cycle 24. Cosmic ray intensity data from 11 neutron monitor stations located at different places around the Northern Hemisphere obtained from the high-resolution Neutron Monitor Database (NMDB) were used. Special software was developed for the calculations of the amplitude and the phase of the diurnal anisotropy vectors on annual and monthly basis using Fourier analysis and for the creation of the harmonic dial diagrams. The geomagnetic bending for each station was taken into account in our calculations determined from the asymptotic cones of each station via the Tsyganenko96 (Tsyganenko and Stern, 1996) magnetospheric model. From our analysis, it was resulted that there is a different behavior of the diurnal anisotropy vectors during the different phases of the solar cycles depending on the solar magnetic field polarity. The latitudinal and longitudinal distribution of the cosmic ray diurnal anisotropy was also examined by grouping the stations according to their geographic coordinates, and it was shown that diurnal variation is modulated not only by the latitude but also by the longitude of the stations. The diurnal anisotropy during strong events of solar and/or cosmic ray activity is discussed.

  15. Latitudinal and longitudinal dependence of the cosmic ray diurnal anisotropy during 2001-2014

    Energy Technology Data Exchange (ETDEWEB)

    Tezari, Anastasia; Mavromichalaki, Helen; Katsinis, Dimitrios; Kanellakopoulos, Anastasios; Kolovi, Sofia [National and Kapodistrian Univ. of Athens (Greece). Nuclear and Particle Physics Dept.; Plainaki, Christina [INAF-IAPS, Rome (Italy); National and Kapodistrian Univ. of Athens (Greece). Nuclear and Particle Physics Dept.; Andriopoulou, Maria [Austrian Academy of Sciences, Graz (Austria). Space Research Inst.

    2016-07-01

    The diurnal anisotropy of cosmic ray intensity for the time period 2001 to 2014 is studied, covering the maximum and the descending phase of solar cycle 23, the minimum between solar cycles 23 and 24, and the ascending phase and maximum of solar cycle 24. Cosmic ray intensity data from 11 neutron monitor stations located at different places around the Northern Hemisphere obtained from the high-resolution Neutron Monitor Database (NMDB) were used. Special software was developed for the calculations of the amplitude and the phase of the diurnal anisotropy vectors on annual and monthly basis using Fourier analysis and for the creation of the harmonic dial diagrams. The geomagnetic bending for each station was taken into account in our calculations determined from the asymptotic cones of each station via the Tsyganenko96 (Tsyganenko and Stern, 1996) magnetospheric model. From our analysis, it was resulted that there is a different behavior of the diurnal anisotropy vectors during the different phases of the solar cycles depending on the solar magnetic field polarity. The latitudinal and longitudinal distribution of the cosmic ray diurnal anisotropy was also examined by grouping the stations according to their geographic coordinates, and it was shown that diurnal variation is modulated not only by the latitude but also by the longitude of the stations. The diurnal anisotropy during strong events of solar and/or cosmic ray activity is discussed.

  16. Using a 1-D model to reproduce diurnal SST signals

    DEFF Research Database (Denmark)

    Karagali, Ioanna; Høyer, Jacob L.

    2014-01-01

    The diurnal variability of SST has been extensively studied as it poses challenges for validating and calibrating satellite sensors, merging SST time series, oceanic and atmospheric modelling. As heat is significantly trapped close to the surface, the diurnal signal’s maximum amplitude is best...... captured by radiometers. The availability of infra-red retrievals from a geostationary orbit allows the hourly monitoring of the diurnal SST evolution. When infra-red SSTs are validated with in situ measurements a general mismatch is found, associated with the different reference depth of each type...... of measurement. A generally preferred approach to bridge the gap between in situ and remotely obtained measurements is through modelling of the upper ocean temperature. This ESA supported study focuses on the implementation of the 1 dimensional General Ocean Turbulence Model (GOTM), in order to resolve...

  17. Reproducibility of summertime diurnal precipitation over northern Eurasia simulated by CMIP5 climate models

    Science.gov (United States)

    Hirota, N.; Takayabu, Y. N.

    2015-12-01

    Reproducibility of diurnal precipitation over northern Eurasia simulated by CMIP5 climate models in their historical runs were evaluated, in comparison with station data (NCDC-9813) and satellite data (GSMaP-V5). We first calculated diurnal cycles by averaging precipitation at each local solar time (LST) in June-July-August during 1981-2000 over the continent of northern Eurasia (0-180E, 45-90N). Then we examined occurrence time of maximum precipitation and a contribution of diurnally varying precipitation to the total precipitation.The contribution of diurnal precipitation was about 21% in both NCDC-9813 and GSMaP-V5. The maximum precipitation occurred at 18LST in NCDC-9813 but 16LST in GSMaP-V5, indicating some uncertainties even in the observational datasets. The diurnal contribution of the CMIP5 models varied largely from 11% to 62%, and their timing of the precipitation maximum ranged from 11LST to 20LST. Interestingly, the contribution and the timing had strong negative correlation of -0.65. The models with larger diurnal precipitation showed precipitation maximum earlier around noon. Next, we compared sensitivity of precipitation to surface temperature and tropospheric humidity between 5 models with large diurnal precipitation (LDMs) and 5 models with small diurnal precipitation (SDMs). Precipitation in LDMs showed high sensitivity to surface temperature, indicating its close relationship with local instability. On the other hand, synoptic disturbances were more active in SDMs with a dominant role of the large scale condensation, and precipitation in SDMs was more related with tropospheric moisture. Therefore, the relative importance of the local instability and the synoptic disturbances was suggested to be an important factor in determining the contribution and timing of the diurnal precipitation. Acknowledgment: This study is supported by Green Network of Excellence (GRENE) Program by the Ministry of Education, Culture, Sports, Science and Technology

  18. Waste water processing with radiation; destruction of organic pollution in water

    International Nuclear Information System (INIS)

    Micic, O.

    1977-06-01

    The mechanism of phenol degradation in irradiated aqueous solutions has been studied by means of pulse radiolysis and kinetic absorption spectrometry. G(-phenol) value depends on the dose rate, phenol concentration and the presence of oxygen in solution. The phenol peroxy radical formed during radiolysis is unstable and does not initiate chain reactions. It is the O 2 - radical that reacts with phenol to initiate an autodegradation chain. Rate constants for individual steps in the chain reaction scheme have been determined in both de-aerated and oxygenated solutions

  19. DIURNAL CHANGES IN LEAF PHOTOSYNTHESIS AND RELATIVE WATER CONTENT OF GRAPEVINE

    Directory of Open Access Journals (Sweden)

    Monica Popescu

    2014-11-01

    Full Text Available Variation in light intensity, air temperature and relative air humidity leads to diurnal variations of photosynthetic rate and leaf relative water content. In order to determine the diurnal changes in net photosynthetic rate of vine plants and influence of the main environmental factors, gas exchange in the vine leaves were measure using a portable plant CO2 analysis package. The results show that diurnal changes in photosynthetic rate could be interpreted as single-peak curve, with a maximum at noon (10.794 μmol CO2 m-2 s-1. Leaf relative water content has maximum value in the morning; the values may slightly decrease during the day (day of June, with normal temperature, no rain, no water restriction in soil.

  20. Diurnal variation of zooplankton off Versova (Bombay)

    Digital Repository Service at National Institute of Oceanography (India)

    Gajbhiye, S.N.; Nair, V.R.; Desai, B.N.

    Physicochemical parameters and diurnal variaion of zooplankton were studied off Versova on 17/18 February 1981. Salinity and dissolved oxygen showed limited variation during the period of study. Nutrient values followed the tidal rhythm and high...

  1. Diurnal and Nocturnal Pollination of Marginatocereus marginatus (Pachycereeae: Cactaceae) in Central Mexico

    Science.gov (United States)

    DAR, SALEEM; ARIZMENDI, Ma. del CORO; VALIENTE-BANUET, ALFONSO

    2006-01-01

    • Background and Aims Chiropterophillous and ornithophillous characteristics can form part of a single reproductive strategy in plants that have flowers with diurnal and nocturnal anthesis. This broader pollination strategy can ensure seed set when pollinators are scarce or unpredictable. This appears to be true of hummingbirds, which presumably pollinate Marginatocereus marginatus, a columnar cactus with red nocturnal and diurnal flowers growing as part of dense bat-pollinated columnar cacti forests in arid regions of central Mexico. The aim of this study was to study the floral biology of M. marginatus, and evaluate the effectiveness of nocturnal vs. diurnal pollinators and the contribution of each pollinator group to overall plant fitness. • Methods Individual flower buds were marked and followed to evaluate flower phenology and anthesis time. Flowers and nectar production were measured. An exclusion experiment was conducted to measure the relative contribution of nocturnal and diurnal pollinators to seed set. • Key Results Marginatocereus marginatus has red hermaphroditic flowers with nocturnal and diurnal anthesis. The plant cannot produce seeds by selfing and was pollinated during the day by hummingbirds and during the night by bats, demonstrating that both pollinator groups were important for plant reproduction. Strong pollen limitation was found in the absence of one of the pollinator guilds. • Conclusions Marginatocereus marginatus has an open pollination system in which both diurnal and nocturnal pollinators are needed to set seeds. This represents a fail-safe pollination system that can ensure both pollination, in a situation of low abundance of one of the pollinator groups (hummingbirds), and high competition for nocturnal pollinators with other columnar cacti that bloom synchronously with M. marginatus in the Tehuacan Valley, Mexico. PMID:16394025

  2. Diurnal cortisol slopes and mental and physical health outcomes: A systematic review and meta-analysis.

    Science.gov (United States)

    Adam, Emma K; Quinn, Meghan E; Tavernier, Royette; McQuillan, Mollie T; Dahlke, Katie A; Gilbert, Kirsten E

    2017-09-01

    Changes in levels of the stress-sensitive hormone cortisol from morning to evening are referred to as diurnal cortisol slopes. Flatter diurnal cortisol slopes have been proposed as a mediator between chronic psychosocial stress and poor mental and physical health outcomes in past theory and research. Surprisingly, neither a systematic nor a meta-analytic review of associations between diurnal cortisol slopes and health has been conducted to date, despite extensive literature on the topic. The current systematic review and meta-analysis examined associations between diurnal cortisol slopes and physical and mental health outcomes. Analyses were based on 179 associations from 80 studies for the time period up to January 31, 2015. Results indicated a significant association between flatter diurnal cortisol slopes and poorer health across all studies (average effect size, r=0.147). Further, flatter diurnal cortisol slopes were associated with poorer health in 10 out of 12 subtypes of emotional and physical health outcomes examined. Among these subtypes, the effect size was largest for immune/inflammation outcomes (r=0.288). Potential moderators of the associations between diurnal cortisol slopes and health outcomes were examined, including type of slope measure and study quality indices. The possible roles of flatter slopes as either a marker or a mechanism for disease etiology are discussed. We argue that flatter diurnal cortisol slopes may both reflect and contribute to stress-related dysregulation of central and peripheral circadian mechanisms, with corresponding downstream effects on multiple aspects of biology, behavior, and health. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Diurnal variation in soil respiration under different land uses on Taihang Mountain, North China

    Science.gov (United States)

    Liu, Xiuping; Zhang, Wanjun; Zhang, Bin; Yang, Qihong; Chang, Jianguo; Hou, Ke

    2016-01-01

    The aim of this paper is to evaluate the diurnal variation in soil respiration under different land use types on Taihang Mountain, North China, and to understand its response to environmental factors (e.g., soil temperature and moisture) and forest management. Diurnal variations in soil respiration from plantations (Robinia pseudoacacia, Punica granatum, and Ziziphus jujuba), naturally regenerated forests (Vitex negundo var. heterophylla), grasslands (Bothriochloa ischaemum), and farmlands (winter wheat/summer maize) were measured using an LI-8100 automated soil CO2 flux system from May 2012 to April 2013. The results indicated that land use type had a significant effect on the diurnal variation of soil respiration. The diurnal soil respiration from farmlands was highest, followed by Ziziphus jujube, R. pseudoacacia, P. granatum, the lower soil CO2 efflux was found from B. ischaemum and V. negundo var. heterophylla. The diurnal soil respiration across different land use types was significantly affected by soil temperature and moisture, and their interaction. Precipitation-stimulated soil respiration increased more in soil with low water content and less in soil with high water content. The lower diurnal soil respiration from naturally regenerated forests suggests that naturally regenerated vegetation is the optimal vegetation type for reducing global warming.

  4. Diurnal variations of indoor radon progeny for Bangalore metropolitan, India

    International Nuclear Information System (INIS)

    Nagesh, V.; Sathish, L.A.; Nagaraja, K.; Sundareshan, S.

    2010-01-01

    Radon progenies are identified as major causes of the lung cancer if the activity is above its normal. It has not been clear whether radon poses a similar risk of causing lung cancer in humans exposed at generally lower levels found in homes, but a number of indoor radon survey have been carried out in recent years around the world. In view of this an attempt has been made for the measurement of diurnal variation of indoor radon levels for the environment of Bangalore metropolitan, India. The Radon progeny concentrations in terms of working level were measured using Kusnetz's method. The patterns of daily and annual changes in indoor Radon concentration have been observed in a general way for many years. However, understanding of the physical basis for these changes had to await the development of continuous monitors and a more complete knowledge of transport processes in the atmosphere. Over a continent, heating of the ground surface by the Sun during the day and cooling by radiation during the night causes a marked diurnal change in temperature near the surface. As a result cool air near the ground will accumulate radon isotopes from surface flux during the night; while during the day the warm air will be transported upward carrying radon with it. Many buildings show diurnal radon variations. Concentrations are relatively higher during night than daytime. This is influenced by the outdoor-indoor temperature contrast. This effect can be enhanced in buildings with strong diurnal use patterns. Buildings that have high average radon concentrations, but are only occupied for part of the day, may need to be measured during occupied periods to determine if there is significant diurnal radon variation. The results are discussed in detail. (author)

  5. Global distributions of diurnal and semi-diurnal tides: observations from HRDI-UARS of the MLT region

    Directory of Open Access Journals (Sweden)

    A. H. Manson

    2002-11-01

    Full Text Available HRDI (High Resolution Doppler Interferometer-UARS winds data have been analyzed in 4° latitude by 10° longitude cells at 96 km to obtain global contour maps of solar-tidal amplitudes and phases, and also mean winds. The solstices June–July (1993, December–January (1993–1994, and one equinox September–October (1994 are shown.  The 24-h diurnal tide that maximizes near the 20–25° latitude has significant seasonal changes with equinoctial maxima, and very clear longitudinal variability. Maxima are very clear over the oceans. In contrast, the 12-h semi-diurnal tides that maximize near the 40–55° latitude have very strong seasonal changes with winter maxima, and more modest longitudinal changes. The similarities with MLT (mesosphere-lower thermosphere radar observations (90 km and the GSWM (Global Scale Wave Model are very satisfactory. The mean winds are consistent with expectations and show clear poleward flow from summer to winter hemispheres in the solstices.Key words. Meteorology and atmospheric dynamics (middle atmosphere dynamics; waves and tides Radio science (remote sensing

  6. Monthly variations of diurnal rainfall in north coast of West Java Indonesia during boreal winter periods

    Science.gov (United States)

    Yulihastin, E.; Trismidianto

    2018-05-01

    Diurnal rainfall during the active monsoon period is usually associated with the highest convective activity that often triggers extreme rainfall. Investigating diurnal rainfall behavior in the north coast of West Java is important to recognize the behavioral trends of data leading to such extreme events in strategic West Java because the city of Jakarta is located in this region. Variability of diurnal rainfall during the period of active monsoon on December-January-February (DJF) composite during the 2000-2016 period was investigated using hourly rainfall data from Tropical Rainfall Measuring Mission (TRMM) 3B41RT dataset. Through the Empirical Mode Decomposition method was appears that the diurnal rain cycle during February has increased significantly in its amplitude and frequency. It is simultaneously shows that the indication of extreme rainfall events is related to diurnal rain divergences during February shown through phase shifts. The diurnal, semidiurnal, and terdiurnal cycles appear on the characteristics of the DJF composite rainfall data during the 2000-2016 period.The significant increases in amplitude occurred during February are the diurnal (IMF 3) and terdiurnal (IMF 1) of rainfall cycles.

  7. Diurnal variations in H{sub 2}O{sub 2}, O{sub 3}, PAN, HNO{sub 3} and aldehyde concentrations and NO/NO{sub 2} ratios at Rishiri Island, Japan: Potential influence from iodine chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Kanaya, Yugo [Frontier Research Center for Global Change, Japan Agency for Marine-Earth Science and Technology, 3173-25 Showa-machi, Kanazawa-ku, Yokohama, Kanagawa 236-0001 (Japan)]. E-mail: yugo@jamstec.go.jp; Tanimoto, Hiroshi [National Institute for Environmental Studies, Tsukuba (Japan); Matsumoto, Jun [Integrated Research Institute, Tokyo Institute of Technology, Yokohama (Japan); Furutani, Hiroshi [Department of Chemistry and Biochemistry, University of California, San Diego (United States); Hashimoto, Shigeru [National Institute for Environmental Studies, Tsukuba (Japan); Komazaki, Yuichi [Frontier Research Center for Global Change, Japan Agency for Marine-Earth Science and Technology, 3173-25 Showa-machi, Kanazawa-ku, Yokohama, Kanagawa 236-0001 (Japan); Tanaka, Shigeru [Department of Applied Chemistry, Keio University, Yokohama (Japan); Yokouchi, Yoko [National Institute for Environmental Studies, Tsukuba (Japan); Kato, Shungo [Department of Applied Chemistry, Graduate School of Engineering, Tokyo Metropolitan University, Hachioji (Japan); Kajii, Yoshizumi [Department of Applied Chemistry, Graduate School of Engineering, Tokyo Metropolitan University, Hachioji (Japan); Akimoto, Hajime [Frontier Research Center for Global Change, Japan Agency for Marine-Earth Science and Technology, 3173-25 Showa-machi, Kanazawa-ku, Yokohama, Kanagawa 236-0001 (Japan)

    2007-04-15

    The presence of iodine chemistry, hypothesized due to the overprediction of HO{sub 2} levels by a photochemical box model at Rishiri Island in June 2000, was quantitatively tested against the observed NO/NO{sub 2} ratios and the net production rates of ozone. The observed NO/NO{sub 2} ratios were reproduced reasonably well by considering the conversion of NO to NO{sub 2} by IO, whose amount was calculated so as to reproduce the observed HO{sub 2} levels. However, the net production rates of ozone were calculated to be negative when such high mixing ratios of IO were considered, which was inconsistent with the observed buildup of ozone during daytime. These results suggest that iodine chemistry may not be the sole mechanism for the reduced mixing ratios of HO{sub 2}, or that 'hot spots' for iodine chemistry were present. Diurnal variations in the mixing ratios of HCHO, CH{sub 3}CHO, peroxy acetyl nitrate (PAN) and HNO{sub 3} observed during the study are presented along with the simulated ones. The box model simulations suggest that the effect of iodine chemistry on these concentrations is small and that important sources of CH{sub 3}CHO and sinks of PAN are probably missing from our current understanding of the tropospheric chemistry mechanism.

  8. Diurnal periodicity in the activity of the common sole, solea vulgaris quensel

    NARCIS (Netherlands)

    Kruuk, H.

    1963-01-01

    1. 1. The diurnal rhythm in the trawl catch of Solea vulgaris Quensel gave rise to this investigation into the diurnal activity rhythm of the fish. 2. 2. Periodicity in the food intake of the Sole in its natural habitat was studied by analyses of the contents of the intestines. Food intake

  9. Hydroxyl-radical-induced oxidation of cyclic dipeptides: Reactions of free peptide radicals and their peroxyl radicals

    International Nuclear Information System (INIS)

    Mieden, O.J.

    1989-01-01

    In the course of this study investigations were carried out into the reactions of hydroxyl radicals and hydrogen atoms with cyclic dipeptides as well as the subsequent reactions of peptide radicals and their peroxyl radicals in aqueous solution. The radiolysis products formed in the absence and presence of oxygen or transient metal complexes were characterized and determined on a quantitative basis. The linking of information from product analyses to the kinetic data for transient species obtained by time-resolving UV/VIS and conductivity measurements (pulse radiolysis) as well as computer-assisted simulations of individual events during the reaction permitted an evaluation of the mechanisms underlying the various processes and an identification of interim products with short life-times, which did or did not belong to the group of radicals. Through the characterization of key reactions of radicals and peroxyl radicals of this substance class a major advance has been made towards a better understanding of the role of radicals in the peptide compound and the mechanisms involved in indirect radiation effects on long-chain peptides and proteins. (orig.) [de

  10. A radical approach to radical innovation

    NARCIS (Netherlands)

    D. Deichmann (Dirk); J.C.M. van den Ende (Jan)

    2014-01-01

    textabstractInnovation pays. Amazon, Apple, Facebook, Google – nearly every one of today’s most successful companies has a talent for developing radical new ideas. But how best to encourage radical initiative taking from employees, and does their previous success or failure at it play a role?

  11. Scale interactions on diurnal toseasonal timescales and their relevanceto model systematic errors

    Directory of Open Access Journals (Sweden)

    G. Yang

    2003-06-01

    Full Text Available Examples of current research into systematic errors in climate models are used to demonstrate the importance of scale interactions on diurnal,intraseasonal and seasonal timescales for the mean and variability of the tropical climate system. It has enabled some conclusions to be drawn about possible processes that may need to be represented, and some recommendations to be made regarding model improvements. It has been shown that the Maritime Continent heat source is a major driver of the global circulation but yet is poorly represented in GCMs. A new climatology of the diurnal cycle has been used to provide compelling evidence of important land-sea breeze and gravity wave effects, which may play a crucial role in the heat and moisture budget of this key region for the tropical and global circulation. The role of the diurnal cycle has also been emphasized for intraseasonal variability associated with the Madden Julian Oscillation (MJO. It is suggested that the diurnal cycle in Sea Surface Temperature (SST during the suppressed phase of the MJO leads to a triggering of cumulus congestus clouds, which serve to moisten the free troposphere and hence precondition the atmosphere for the next active phase. It has been further shown that coupling between the ocean and atmosphere on intraseasonal timescales leads to a more realistic simulation of the MJO. These results stress the need for models to be able to simulate firstly, the observed tri-modal distribution of convection, and secondly, the coupling between the ocean and atmosphere on diurnal to intraseasonal timescales. It is argued, however, that the current representation of the ocean mixed layer in coupled models is not adequate to represent the complex structure of the observed mixed layer, in particular the formation of salinity barrier layers which can potentially provide much stronger local coupling between the atmosphere and ocean on diurnal to intraseasonal timescales.

  12. Radicalization In Pakistan And The Spread Of Radical Islam In Pakistan

    Directory of Open Access Journals (Sweden)

    Bahir ahmad

    2015-08-01

    Full Text Available ABSTRACT It is pertinent to mention that radicalism is not intrinsic to Islam and radical interpretations of the religion or for that matter may occur within any way of life and religion Saikal 2003 and yet the question remains as to why Muslims in certain geographical regions have more radical approaches towards their religion and also that what are the causes of such radicalization. Becoming a radical Muslim is not even a matter of a day nor is it a sudden process. There are several reasons behind making a person radical peaceful angry smiling or tolerant. For knowing the reason behind radicalization or radicals persons one has to understand the causes. Tracing these causes is one of the ways to eliminate such behavior. The first step in the elimination of the radical sentiments in a person is to develop peace in his personality Fair Malhotra amp Shapiro 2010. The chapter which has been addressed here is going to shed light on the roots and symptoms of the radicalism. There will be a brief discussion on how the roots of radicalism can be traced and can be eliminated. The assessment and discussion will be conducted on the parameters of the economy media politics and theology from social cultural point of view. According to the analysis of Ahrari 2000 political factor is one of the major and direct factors which have resulted in causing of the radicalism. These factors however intertwine with one another. Radical actions cannot take place only because of the political factors.

  13. Work, Stress, and Diurnal Bruxism: A Pilot Study among Information Technology Professionals in Bangalore City, India

    Directory of Open Access Journals (Sweden)

    S. K. Rao

    2011-01-01

    Full Text Available The study assessed the prevalence of diurnal bruxism among information technology (IT professionals and explored plausible predictors associated with the parafunctional habit. A cross-sectional study was designed and IT professionals were invited to participate. The inclusion criteria composed of participants in service for at least one year, having natural dentition, no history of cervical or facial injury and not undergoing orthodontic therapy. The participants (N=147 were interviewed by a trained interviewer to record information. A pre-tested questionnaire that included questions related to work, stress symptoms and diurnal bruxism was completed by each participant. The prevalence of self-reported diurnal bruxism was 59%. Bivariate analyses revealed that work (<0.05 and work experience (<0.05 were significantly associated with self-reported diurnal bruxism. In the binary logistic regression analysis stress (Odds Ratio [OR] =5.9, 95% Confidence Interval [CI] 2.6–13.3 was identified to be a strong predictor of diurnal bruxism. Professionals with 11 or more years of experience were less likely to report diurnal bruxism (OR=0.04, 95% CI 0.00–0.43 than those with 1 to 5 years of work experience. The study revealed that stress and less work experience were associated with diurnal bruxism among IT professionals in Bangalore city.

  14. Pathophysiology of diurnal drooling in Parkinson's disease

    NARCIS (Netherlands)

    Kalf, J.G.; Munneke, M.; Engel-Hoek, L. van den; Swart, B.J.M. de; Borm, G.F.; Bloem, B.R.; Zwarts, M.J.

    2011-01-01

    Drooling is an incapacitating feature of Parkinson's disease. Better pathophysiological insights are needed to improve treatment. In this study, we tested the hypothesis that the cause of drooling is multifactorial. We examined 15 patients with Parkinson's disease with distinct diurnal saliva loss

  15. Global distributions of diurnal and semi-diurnal tides: observations from HRDI-UARS of the MLT region

    Directory of Open Access Journals (Sweden)

    A. H. Manson

    Full Text Available HRDI (High Resolution Doppler Interferometer-UARS winds data have been analyzed in 4° latitude by 10° longitude cells at 96 km to obtain global contour maps of solar-tidal amplitudes and phases, and also mean winds. The solstices June–July (1993, December–January (1993–1994, and one equinox September–October (1994 are shown. 

    The 24-h diurnal tide that maximizes near the 20–25° latitude has significant seasonal changes with equinoctial maxima, and very clear longitudinal variability. Maxima are very clear over the oceans. In contrast, the 12-h semi-diurnal tides that maximize near the 40–55° latitude have very strong seasonal changes with winter maxima, and more modest longitudinal changes. The similarities with MLT (mesosphere-lower thermosphere radar observations (90 km and the GSWM (Global Scale Wave Model are very satisfactory. The mean winds are consistent with expectations and show clear poleward flow from summer to winter hemispheres in the solstices.

    Key words. Meteorology and atmospheric dynamics (middle atmosphere dynamics; waves and tides Radio science (remote sensing

  16. Robust fitting of diurnal brightness temperature cycle

    CSIR Research Space (South Africa)

    Udahemuka, G

    2007-11-01

    Full Text Available for a pixel concerned. Robust fitting of observed Diurnal Temperature Cycle (DTC) taken over a day of a given pixel without cloud cover and other abnormally conditions such as fire can give a data based brightness temperature model for a given pixel...

  17. Diurnal cortisol rhythms, fatigue and psychosocial factors in five-year survivors of ovarian cancer.

    Science.gov (United States)

    Cuneo, Michaela G; Schrepf, Andrew; Slavich, George M; Thaker, Premal H; Goodheart, Michael; Bender, David; Cole, Steve W; Sood, Anil K; Lutgendorf, Susan K

    2017-10-01

    Fatigue is a challenge in ovarian cancer survivorship and greatly impacts quality of life. In other cancer populations, fatigue has been associated with abnormal diurnal cortisol patterns. However, little is known about biological and behavioral factors in 5+-year ovarian cancer survivors and potential mechanisms underlying persistent fatigue have not been investigated in this population. Moreover, relationships between neuroendocrine and psychosocial factors in 5+-year ovarian cancer survivors have not been studied. We addressed these issues by examining relationships between diurnal cortisol rhythms, fatigue, life stress, and social support in 30 survivors of ovarian cancer who were assessed at least 5 years (mean=6.20years) following their primary diagnosis. Flatter diurnal cortisol slopes were associated with higher levels of fatigue, suggesting a role for HPA-axis dysregulation in sustained fatigue experienced by survivors. Moreover, greater cumulative lifetime stressor exposure (p=0.023) and stressor severity (p=0.004) were associated with flatter diurnal cortisol slopes, while higher social attachment (p=0.001) was associated with steeper diurnal cortisol slopes. These findings suggest that ovarian cancer survivors with greater lifetime stress exposure or lower social attachment may be at increased risk for circadian rhythm disruption, which in turn is associated with fatigue. Future research should examine relationships of clinical stage and inflammatory cytokines to cortisol rhythms and fatigue in long-term ovarian cancer survivors, as well as investigating the clinical significance of abnormal diurnal cortisol profiles in this population. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Enhanced Oxidation of Isoprene and Monoterpenes in High and Low NOx Conditions

    Science.gov (United States)

    Tokarek, T. W.; Gilman, J.; Lerner, B. M.; Koss, A.; Yuan, B.; Taha, Y. M.; Osthoff, H. D.; Warneke, C.; De Gouw, J. A.

    2015-12-01

    In the troposphere, the photochemical oxidation of volatile organic compounds (VOCs) is primarily initiated by their reactions with the hydroxyl radical (OH) which yields peroxy radicals (HO2 and RO2). Concentrations of OH and the rates of VOC oxidation depend on the efficiency of peroxy radical recycling to OH. Radical recycling mainly occurs through reaction of HO2 with NO to produce NO2 and, ultimately, ozone (O3). Hence, the rate of VOC oxidation is dependent on NOx (=NO+NO2) concentration. The Shale Oil and Natural Gas Nexus (SONGNEX) campaign was conducted from March 17 to April 29, 2015 with the main goal of identifying and quantifying industrial sources of pollutants throughout the United States, in particular those associated with the production of oil and natural gas. In this work, a case study of biogenic VOC oxidation within and outside a power plant plume in the Haynesville basin near the border of Texas and Louisiana is presented. Isoprene, monoterpenes and their oxides were measured by H3O+ chemical ionization mass spectrometry (H3O+ CIMS) in high time resolution (1 s). Further, an improved Whole Air Sampler (iWAS) was used to collect samples for post-flight analysis by gas chromatography mass spectrometric detection (GC-MS) and yielded speciated quantification of biogenic VOCs. The monoterpene oxide to monoterpene ratio follows the spatial extent of the plume as judged by another tracer (NOx), tracking the enhancement of oxidation rates by NOx. The observations are rationalized with the aid of box modeling using the Master Chemical Mechanism (MCM).

  19. Manipulating radicals: Using cobalt to steer radical reactions

    OpenAIRE

    Chirilă, A.

    2017-01-01

    This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

  20. Effect of storage conditions on graft of polypropylene non-woven fabric induced by electron beam

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jin Young; Jeun, Joon Pyo; Kang, Phil Hyun [Radiation Research Dvision for Industry and Environment, Korea Atomic Energy Research Institute, Jeongeup(Korea, Republic of)

    2015-05-15

    In this study, we fabricated effect of storage conditions on graft of polypropylene (PP) non-woven fabric induced by electron beam. The electron beam irradiations on PP non-woven fabric were carried out over a range of irradiation doses from 25 to 100 kGy to make free radicals on fabric surface. The radical measurement was established by electron spin resonance (ESR) for confirming the changes of the alkyl radical and peroxy radical according to effect of storage time, storage temperature and atmosphere. It was observed that the free radicals were increased with irradiation dose and decreased with storage time due to the continuous oxidation. However, the radical extinction was significantly delayed due to reduced mobility of radicals at extremely low temperature. The degree of graft based on the analysis of ESR was investigated. The conditions of graft reaction were set at a temperature: 60 degrees Celcius, reaction time: 6 hours and styrene monomer concentration: 20 wt%.

  1. Free radical inactivation of trypsin

    International Nuclear Information System (INIS)

    Cudina, Ivana; Jovanovic, S.V.

    1988-01-01

    Reactivities of free radical oxidants, radical OH, Br2-anion radical and Cl 3 COO radical and a reductant, CO2-anion radical, with trypsin and reactive protein components were determined by pulse radiolysis of aqueous solutions at pH 7, 20 0 C. Highly reactive free radicals, radical OH, Br2-anion radical and CO2-anion radical, react with trypsin at diffusion controlled rates. Moderately reactive trichloroperoxy radical, k(Cl 3 COO radical + trypsin) preferentially oxidizes histidine residues. The efficiency of inactivation of trypsin by free radicals is inversely proportional to their reactivity. The yields of inactivation of trypsin by radical OH, Br2-anion radical and CO2-anion radical are low, G(inactivation) = 0.6-0.8, which corresponds to ∼ 10% of the initially produced radicals. In contrast, Cl 3 COO radical inactivates trypsin with ∼ 50% efficiency, i.e. G(inactivation) = 3.2. (author)

  2. Studying Diurnal Variations of Aerosols with NASA MERRA-2 Reanalysis Data

    Science.gov (United States)

    Shen, Suhung; Ostrenga, Dana M.; Zeng, Jian; Vollmer, Bruce E.

    2018-01-01

    Aerosols play an important role in atmospheric dynamics, climate variations, and Earth's energy cycle by altering the radiation balance in the atmosphere through interaction with clouds, providing fertilizer for forests and canopy, and as a supply of iron to the ocean over long time periods. Studies suggest that much of the feedback between dust aerosols and dynamics is associated with diurnal and synoptic scale variability. However, the lack of sub-daily resolution of aerosols from satellite observations makes it difficult to study the diurnal characteristics, especially over tropical and subtropical regions. Investigation of this topic utilizes over 37 years of simulated global aerosol products from NASA atmospheric reanalysis, in the second Modern-Era Retrospective analysis for Research and Applications (MERRA-2) data set, available from NASA Goddard Earth Science Data and Information Services Center (GES DISC). MERRA-2 covers the period 1980-present, and is continuing as an ongoing climate analysis. Aerosol assimilation is included throughout the period, using data from MODIS, MISR, AERONET, and AVHRR (in the pre-EOS period). The aerosols are assimilated using the MERRA-2 aerosol model, which interacts directly with radiation parameterization, and is radiatively coupled with atmospheric model dynamics in the Goddard Earth Observing System Model, Version 5 (GEOS-5). Hourly, monthly, and monthly diurnal data are available at spatial resolution of 0.5o x 0.625o (latitude x longitude). By using MERRA-2 hourly and monthly diurnal products, different aerosol diurnal variabilities are observed over North America, Africa, Asia, and Australia, that may be due to different meteorological conditions and aerosol sources. The presentation will also provide an overview of MERRA-2 data services at GES DISC, such as how to find and download data, and how to quickly visualize and analyze data online with Giovanni.

  3. The impact of negative family-work spillover on diurnal cortisol.

    Science.gov (United States)

    Zilioli, Samuele; Imami, Ledina; Slatcher, Richard B

    2016-10-01

    Both dimensions of the work-family interface, work-to-family and family-to-work spillover, have important implications for health and well-being. Despite the importance of these associations, very little is known about the physiological mechanisms through which the interplay between family and work experiences are translated into long-lasting consequences for health. This study investigated both positive and negative aspects of each spillover dimension on diurnal cortisol secretion patterns in a large panel study of working adults between the ages of 33 and 80. Greater negative family-to-work (NFW) spillover predicted lower wake-up cortisol values and a flatter (less "healthy") diurnal cortisol slope. This effect was evident even after controlling for the effects of the other spillover dimensions. These findings indicate that not all aspects of the work-family interface might impact stress physiology to the same extent and suggest that diurnal cortisol may be an important pathway through which negative aspects of the work-family interface leave their mark on health. (PsycINFO Database Record (c) 2016 APA, all rights reserved).

  4. natalensis) and diurn'al (Rhabdomys pumilio)

    African Journals Online (AJOL)

    The thermo neutral zone for both speCies was found to be at T. = 32 ± 1 °e. Below the lower critical point. Vo. for the diurnal species (R. pumilio) was significantly higher. (p

  5. Central melanopsin projections in the diurnal rodent, Arvicanthis niloticus

    Directory of Open Access Journals (Sweden)

    Jennifer Lou Langel

    2015-07-01

    Full Text Available The direct effects of photic stimuli on behavior are very different in diurnal and nocturnal species, as light stimulates an increase in activity in the former and a decrease in the latter. Studies of nocturnal mice have implicated a select population of retinal ganglion cells that are intrinsically photosensitive (ipRGCs in mediation of these acute responses to light. ipRGCs are photosensitive due to the expression of the photopigment melanopsin; these cells use glutamate and pituitary adenylate cyclase-activating polypeptide (PACAP as neurotransmitters. PACAP is useful for the study of central ipRGC projections because, in the retina, it is found exclusively within melanopsin cells. Little is known about the central projections of ipRGCs in diurnal species. Here, we first characterized these cells in the retina of the diurnal Nile grass rat using immunohistochemistry (IHC. The same basic subtypes of melanopsin cells that have been described in other mammals were present, but nearly 25% of them were displaced, primarily in its superior region. PACAP was present in 87.7% of all melanopsin cells, while 97.4% of PACAP cells contained melanopsin. We then investigated central projections of ipRGCs by examining the distribution of immunoreactive PACAP fibers in intact and enucleated animals. This revealed evidence that these cells project to the suprachiasmatic nucleus, lateral geniculate nucleus (LGN, pretectum and superior colliculus. This distribution was confirmed with injections of cholera toxin subunit β coupled with Alexa Fluor 488 in one eye and Alexa Flour 594 in the other, combined with IHC staining of PACAP. These studies also revealed that the ventral and dorsal LGN and the caudal olivary pretectal nucleus receive less innervation from ipRGCs than that reported in nocturnal rodents. Overall, these data suggest that although ipRGCs and their projections are very similar in diurnal and nocturnal rodents, they may not be identical.

  6. Analysis of Hydroperoxides in solid Polyethylene by NMR and EPR Spectroscopy

    International Nuclear Information System (INIS)

    Assink, Roger A.; Celina, Mathias C.; Dunbar, Timothy D.; Alam, Todd M.; Clough, Roger Lee; Gillen, Kenneth T.

    2000-01-01

    The authors have shown that the hydroperoxide species in γ-irradiated 13 C-polyethylene can be directly observed by 13 C MAS NMR spectroscopy. The experiment was performed without the need for special sample preparation such as chemical derivatization or dissolution. Annealing experiments were employed to study the thermal decomposition of the hydroperoxide species and to measure an activation energy of 98 kJ/mol. EPR spectroscopy suggests that residual polyenyl and alkylperoxy radicals are predominantly trapped in interracial or crystalline regions, while the peroxy radicals observed after UV-photolysis of hydroperoxides are in amorphous regions

  7. Impact of assimilation window length on diurnal features in a Mars atmospheric analysis

    Directory of Open Access Journals (Sweden)

    Yongjing Zhao

    2015-05-01

    Full Text Available Effective simulation of diurnal variability is an important aspect of many geophysical data assimilation systems. For the Martian atmosphere, thermal tides are particularly prominent and contribute much to the Martian atmospheric circulation, dynamics and dust transport. To study the Mars diurnal variability and Mars thermal tides, the Geophysical Fluid Dynamics Laboratory Mars Global Climate Model with the 4D-local ensemble transform Kalman filter (4D-LETKF is used to perform an analysis assimilating spacecraft temperature retrievals. We find that the use of a ‘traditional’ 6-hr assimilation cycle induces spurious forcing of a resonantly enhanced semi-diurnal Kelvin waves represented in both surface pressure and mid-level temperature by forming a wave 4 pattern in the diurnal averaged analysis increment that acts as a ‘topographic’ stationary forcing. Different assimilation window lengths in the 4D-LETKF are introduced to remove the artificially induced resonance. It is found that short assimilation window lengths not only remove the spurious resonance, but also push the migrating semi-diurnal temperature variation at 50 Pa closer to the estimated ‘true’ tides even in the absence of a radiatively active water ice cloud parameterisation. In order to compare the performance of different assimilation window lengths, short-term to mid-range forecasts based on the hour 00 and 12 assimilation are evaluated and compared. Results show that during Northern Hemisphere summer, it is not the assimilation window length, but the radiatively active water ice clouds that influence the model prediction. A ‘diurnal bias correction’ that includes bias correction fields dependent on the local time is shown to effectively reduce the forecast root mean square differences between forecasts and observations, compensate for the absence of water ice cloud parameterisation and enhance Martian atmosphere prediction. The implications of these results for

  8. Simulation of the Universal-Time Diurnal Variation of the Global Electric Circuit Charging Rate

    Science.gov (United States)

    Mackerras, D.; Darvenzia, M.; Orville, R. E.; Williams, E. R.; Goodman, S. J.

    1999-01-01

    A global lightning model that includes diurnal and annual lightning variation, and total flash density versus latitude for each major land and ocean, has been used as the basis for simulating the global electric circuit charging rate. A particular objective has been to reconcile the difference in amplitude ratios [AR=(max-min)/mean] between global lightning diurnal variation (AR approx. = 0.8) and the diurnal variation of typical atmospheric potential gradient curves (AR approx. = 0.35). A constraint on the simulation is that the annual mean charging current should be about 1000 A. The global lightning model shows that negative ground flashes can contribute, at most, about 10-15% of the required current. For the purpose of the charging rate simulation, it was assumed that each ground flash contributes 5 C to the charging process. It was necessary to assume that all electrified clouds contribute to charging by means other than lightning, that the total flash rate can serve as an indirect indicator of the rate of charge transfer, and that oceanic electrified clouds contribute to charging even though they are relatively inefficient in producing lightning. It was also found necessary to add a diurnally invariant charging current component. By trial and error it was found that charging rate diurnal variation curves in Universal time (UT) could be produced with amplitude ratios and general shapes similar to those of the potential gradient diurnal variation curves measured over ocean and arctic regions during voyages of the Carnegie Institute research vessels.

  9. Diurnal tides in the Arctic Ocean

    Science.gov (United States)

    Kowalik, Z.; Proshutinsky, A. Y.

    1993-01-01

    A 2D numerical model with a space grid of about 14 km is applied to calculate diurnal tidal constituents K(1) and O(1) in the Arctic Ocean. Calculated corange and cotidal charts show that along the continental slope, local regions of increased sea level amplitude, highly variable phase and enhanced currents occur. It is shown that in these local regions, shelf waves (topographic waves) of tidal origin are generated. In the Arctic Ocean and Northern Atlantic Ocean more than 30 regions of enhanced currents are identified. To prove the near-resonant interaction of the diurnal tides with the local bottom topography, the natural periods of oscillations for all regions have been calculated. The flux of energy averaged over the tidal period depicts the gyres of semitrapped energy, suggesting that the shelf waves are partially trapped over the irregularities of the bottom topography. It is shown that the occurrence of near-resonance phenomenon changes the energy flow in the tidal waves. First, the flux of energy from the astronomical sources is amplified in the shelf wave regions, and afterwards the tidal energy is strongly dissipated in the same regions.

  10. Light exposure influences the diurnal oscillation of gut microbiota in mice.

    Science.gov (United States)

    Wu, Guangyan; Tang, Wenli; He, Yan; Hu, Jingjuan; Gong, Shenhai; He, Zhanke; Wei, Guoquan; Lv, Liyi; Jiang, Yong; Zhou, Hongwei; Chen, Peng

    2018-05-03

    The gut microbiota exhibit diurnal compositional and functional oscillations that influence the host homeostasis. However, the upstream factors that affect the microbial oscillations remain elusive. Here, we focused on the potential impact of light exposure, the main factor that affects the host circadian oscillation, on the diurnal oscillations of intestinal microflora to explore the upstream factor that governs the fluctuations of the gut microbes. The gut microbiota of the mice that were underwent regular light/dark (LD) cycles exhibited a robust rhythm at both compositional and functional level, in all parts of the intestine. Comparably, constant darkness (DD) led to the loss of the rhythmic oscillations in almost all parts of the intestine. Additionally, the abundance of Clostridia in DD conditions was dramatically enhanced in the small intestine. Our data indicated light exposure is the upstream factor that governs the regular diurnal fluctuations of gut microbiota in vivo. Copyright © 2018. Published by Elsevier Inc.

  11. Diurnal and circadian expression profiles of glycerolipid biosynthetic genes in Arabidopsis.

    Science.gov (United States)

    Nakamura, Yuki; Andrés, Fernando; Kanehara, Kazue; Liu, Yu-chi; Coupland, George; Dörmann, Peter

    2014-01-01

    Glycerolipid composition in plant membranes oscillates in response to diurnal change. However, its functional significance remained unclear. A recent discovery that Arabidopsis florigen FT binds diurnally oscillating phosphatidylcholine molecules to promote flowering suggests that diurnal oscillation of glycerolipid composition is an important input in flowering time control. Taking advantage of public microarray data, we globally analyzed the expression pattern of glycerolipid biosynthetic genes in Arabidopsis under long-day, short-day, and continuous light conditions. The results revealed that 12 genes associated with glycerolipid metabolism showed significant oscillatory profiles. Interestingly, expression of most of these genes followed circadian profiles, suggesting that glycerolipid biosynthesis is partially under clock regulation. The oscillating expression profile of one representative gene, PECT1, was analyzed in detail. Expression of PECT1 showed a circadian pattern highly correlated with that of the clock-regulated gene GIGANTEA. Thus, our study suggests that a considerable number of glycerolipid biosynthetic genes are under circadian control.

  12. Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

    International Nuclear Information System (INIS)

    Fujimura, T.; Hayakawa, N.; Kuriyama, I.

    1978-01-01

    The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed. (author)

  13. Guest Editorial: Processes of Radicalization and De-Radicalization

    Directory of Open Access Journals (Sweden)

    Donatella Della Porta

    2012-05-01

    Full Text Available The study of radicalization and de-radicalization, understood as processes leading towards the increased or decreased use of political violence, is central to the question of how political violence emerges, how it can be prevented, and how it can be contained. The focus section of this issue of the International Journal of Conflict and Violence addresses radicalization and de-radicalization, seeking to develop a more comprehensive understanding of the processes, dynamics, and mechanisms involved and taking an interdisciplinary approach to overcome the fragmentation into separate disciplines and focus areas. Contributions by Pénélope Larzillière, Felix Heiduk, Bill Kissane, Hank Johnston, Christian Davenport and Cyanne Loyle, Veronique Dudouet, and Lasse Lindekilde address repressive settings, legitimacy, institutional aspects, organizational outcomes, and dynamics in Europe, Asia, Africa, and North and South America.

  14. Evaluation of the sensitivity of the Amazonian diurnal cycle to convective intensity in reanalyses

    Science.gov (United States)

    Itterly, Kyle F.; Taylor, Patrick C.

    2017-02-01

    Model parameterizations of tropical deep convection are unable to reproduce the observed diurnal and spatial variability of convection in the Amazon, which contributes to climatological biases in the water cycle and energy budget. Convective intensity regimes are defined using percentiles of daily minimum 3-hourly averaged outgoing longwave radiation (OLR) from Clouds and the Earth's Radiant Energy System (CERES). This study compares the observed spatial variability of convective diurnal cycle statistics for each regime to MERRA-2 and ERA-Interim (ERA) reanalysis data sets. Composite diurnal cycle statistics are computed for daytime hours (06:00-21:00 local time) in the wet season (December-January-February). MERRA-2 matches observations more closely than ERA for domain averaged composite diurnal statistics—specifically precipitation. However, ERA reproduces mesoscale features of OLR and precipitation phase associated with topography and the propagation of the coastal squall line. Both reanalysis models are shown to underestimate extreme convection.

  15. Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

    2009-08-01

    The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

  16. Seasonal and Diurnal Variations of Atmospheric Non-Methane Hydrocarbons in Guangzhou, China

    Directory of Open Access Journals (Sweden)

    Longfeng Li

    2012-05-01

    Full Text Available In recent decades, high ambient ozone concentrations have become one of the major regional air quality issues in the Pearl River Delta (PRD region. Non-methane hydrocarbons (NMHCs, as key precursors of ozone, were found to be the limiting factor in photochemical ozone formation for large areas in the PRD. For source apportioning of NMHCs as well as ozone pollution control strategies, it is necessary to obtain typical seasonal and diurnal patterns of NMHCs with a large pool of field data. To date, few studies have focused on seasonal and diurnal variations of NMHCs in urban areas of Guangzhou. This study explored the seasonal variations of most hydrocarbons concentrations with autumn maximum and spring minimum in Guangzhou. The diurnal variations of most anthropogenic NMHCs typically showed two-peak pattern with one at 8:00 in the morning and another at 20:00 in the evening, both corresponding to traffic rush hours in Guangzhou, whereas isoprene displayed a different bimodal diurnal curve. Propene, ethene, m, p-xylene and toluene were the four largest contributors to ozone formation in Guangzhou, based on the evaluation of individual NMHCs’ photochemical reactivity. Therefore, an effective strategy for controlling ozone pollution may be achieved by the reduction of vehicle emissions in Guangzhou.

  17. Moderation of genetic and environmental influences on diurnal preference by age in adult twins.

    Science.gov (United States)

    Barclay, Nicola L; Watson, Nathaniel F; Buchwald, Dedra; Goldberg, Jack

    2014-03-01

    Diurnal preference changes across the lifespan. However, the mechanisms underlying this age-related shift are poorly understood. The aim of this twin study was to determine the extent to which genetic and environmental influences on diurnal preference are moderated by age. Seven hundred and sixty-eight monozygotic and 674 dizygotic adult twin pairs participating in the University of Washington Twin Registry completed the reduced Morningness-Eveningness Questionnaire as a measure of diurnal preference. Participants ranged in age from 19 to 93 years (mean = 36.23, SD = 15.54) and were categorized on the basis of age into three groups: younger adulthood (19-35 years, n = 1715 individuals), middle adulthood (36-64 years, n = 1003 individuals) and older adulthood (65+ years, n = 168 individuals). Increasing age was associated with an increasing tendency towards morningness (r = 0.42, p influences for the total sample as well as for each age group separately. Additive genetic influences accounted for 52%[46-57%], and non-shared environmental influences 48%[43-54%], of the total variance in diurnal preference. In comparing univariate genetic models between age groups, the best-fitting model was one in which the parameter estimates for younger adults and older adults were equated, in comparison with middle adulthood. For younger and older adulthood, additive genetic influences accounted for 44%[31-49%] and non-shared environmental influences 56%[49-64%] of variance in diurnal preference, whereas for middle adulthood these estimates were 34%[21-45%] and 66%[55-79%], respectively. Therefore, genetic influences on diurnal preference are attenuated in middle adulthood. Attenuation is likely driven by the increased importance of work and family responsibilities during this life stage, in comparison with younger and older adulthood when these factors may be less influential in determining sleep-wake timing. These findings have implications for studies

  18. Seasonal and diurnal variations of atmospheric mercury across the US determined from AMNet monitoring data

    Directory of Open Access Journals (Sweden)

    X. Lan

    2012-11-01

    Full Text Available Speciated atmospheric mercury observations collected over the period from 2008 to 2010 at the Environmental Protection Agency and National Atmospheric Deposition Program Atmospheric Mercury Network sites (AMNet were analyzed for its spatial, seasonal, and diurnal characteristics across the US. Median values of gaseous elemental mercury (GEM, gaseous oxidized mercury (GOM and particulate bound mercury (PBM at 11 different AMNet sites ranged from 148–226 ppqv (1.32–2.02 ng m−3, 0.05–1.4 ppqv (0.47–12.4 pg m−3 and 0.18–1.5 ppqv (1.61–13.7 pg m−3, respectively. Common characteristics of these sites were the similar median levels of GEM as well as its seasonality, with the highest mixing ratios occurring in winter and spring and the lowest in fall. However, discernible differences in monthly average GEM were as large as 30 ppqv, which may be caused by sporadic influence from local emission sources. The largest diurnal variation amplitude of GEM occurred in the summer. Seven rural sites displayed similar GEM summer diurnal patterns, in that the lowest levels appeared in the early morning, and then the GEM mixing ratio increased after sunrise and reached its maxima at noon or in the early afternoon. Unlike GEM, GOM exhibited higher mixing ratios in spring and summer. The largest diurnal variation amplitude of GOM occurred in spring for most AMNet sites. The GOM diurnal minima appeared before sunrise and maxima appeared in the afternoon. The increased GOM mixing ratio in the afternoon indicated a photochemically driven oxidation of GEM resulting in GOM formation. PBM exhibited diurnal fluctuations in summertime. The summertime PBM diurnal pattern displayed daily maxima in the early afternoon and lower mixing ratios at night, implying photochemical production of PBM in summer.

  19. Analysis of the Diurnal Variation of the Global Electric Circuit Obtained From Different Numerical Models

    Science.gov (United States)

    Jánský, Jaroslav; Lucas, Greg M.; Kalb, Christina; Bayona, Victor; Peterson, Michael J.; Deierling, Wiebke; Flyer, Natasha; Pasko, Victor P.

    2017-12-01

    This work analyzes different current source and conductivity parameterizations and their influence on the diurnal variation of the global electric circuit (GEC). The diurnal variations of the current source parameterizations obtained using electric field and conductivity measurements from plane overflights combined with global Tropical Rainfall Measuring Mission satellite data give generally good agreement with measured diurnal variation of the electric field at Vostok, Antarctica, where reference experimental measurements are performed. An approach employing 85 GHz passive microwave observations to infer currents within the GEC is compared and shows the best agreement in amplitude and phase with experimental measurements. To study the conductivity influence, GEC models solving the continuity equation in 3-D are used to calculate atmospheric resistance using yearly averaged conductivity obtained from the global circulation model Community Earth System Model (CESM). Then, using current source parameterization combining mean currents and global counts of electrified clouds, if the exponential conductivity is substituted by the conductivity from CESM, the peak to peak diurnal variation of the ionospheric potential of the GEC decreases from 24% to 20%. The main reason for the change is the presence of clouds while effects of 222Rn ionization, aerosols, and topography are less pronounced. The simulated peak to peak diurnal variation of the electric field at Vostok is increased from 15% to 18% from the diurnal variation of the global current in the GEC if conductivity from CESM is used.

  20. Variability of Diurnal Temperature Range During Winter Over Western Himalaya: Range- and Altitude-Wise Study

    Science.gov (United States)

    Shekhar, M. S.; Devi, Usha; Dash, S. K.; Singh, G. P.; Singh, Amreek

    2018-04-01

    The current trends in diurnal temperature range, maximum temperature, minimum temperature, mean temperature, and sun shine hours over different ranges and altitudes of Western Himalaya during winter have been studied. Analysis of 25 years of data shows an increasing trend in diurnal temperature range over all the ranges and altitudes of Western Himalaya during winter, thereby confirming regional warming of the region due to present climate change and global warming. Statistical studies show significant increasing trend in maximum temperature over all the ranges and altitudes of Western Himalaya. Minimum temperature shows significant decreasing trend over Pir Panjal and Shamshawari range and significant increasing trend over higher altitude of Western Himalaya. Similarly, sunshine hours show significant decreasing trend over Karakoram range. There exists strong positive correlation between diurnal temperature range and maximum temperature for all the ranges and altitudes of Western Himalaya. Strong negative correlation exists between diurnal temperature range and minimum temperature over Shamshawari and Great Himalaya range and lower altitude of Western Himalaya. Sunshine hours show strong positive correlation with diurnal temperature range over Pir Panjal and Great Himalaya range and lower and higher altitudes.

  1. Psychosocial determinants of diurnal alpha-amylase among healthy Quebec workers.

    Science.gov (United States)

    Marchand, Alain; Juster, Robert-Paul; Lupien, Sonia J; Durand, Pierre

    2016-04-01

    Salivary alpha-amylase (sAA) is a stress-sensitive biomarker the shows promise as an indirect proxy of sympathetic-adrenal-medullary axis activities that are otherwise difficult to discern non-invasively. This comprehensive study investigated diurnal sAA in association with numerous psychosocial characteristics related to mental health, work stress, and non-work stress. Participants included 395 workers (56.1% women, age: M=41.3, SD=10.81) from across 34 distinct workplaces. Diurnal sAA was sampled over two non-consecutive work days at awakening, 30 min after awakening, 14h00, 16h00, and bedtime. Well-validated psychometrics and survey items were used to measure mental health (psychological distress, depression, burnout, work characteristics) (task design, demands, social relations, gratifications), and non-work characteristics (marital/parental status, economic statuses, marital and parental stress, work-family conflicts). Preliminary results revealed that men showed occasionally higher sAA concentrations than women. Multilevel regressions were used to analyze sAA concentrations nested according to levels (i) for each time-point, (ii) between workers, and (iii) across workplaces while covarying for time of awakening, sex, age, cigarette smoking, alcohol consumption, regular physical activity, psychotropic drug use, and body mass index. Main results revealed that psychological demands, support from colleagues, interpersonal conflicts, job recognition and job insecurity appear to be associated with diurnal sAA, while non-work factors did not. Our findings showing a distinct diurnal profile for sAA replicate and expand those of Nater et al. (2007, Psychoneuroendocrinology 32, 392-401), providing further evidence that sAA is associated to subjective psychosocial factors. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Pathophysiology of diurnal drooling in Parkinson’s disease

    NARCIS (Netherlands)

    Lenie van den Engel-Hoek; Johanna Kalf; Bastiaan Bloem; George Borm; Machiel Zwarts; Bert de Swart; Marten Munneke

    2011-01-01

    Drooling is an incapacitating feature of Parkinson's disease. Better pathophysiological insights are needed to improve treatment. In this study, we tested the hypothesis that the cause of drooling is multifactorial. We examined 15 patients with Parkinson's disease with distinct diurnal saliva loss

  3. Diurnality as an energy-saving strategy: energetic consequences of temporal niche switching in small mammals

    NARCIS (Netherlands)

    van der Vinne, V.; Gorter, J.A.; Riede, S.J.; Hut, R.A.

    2015-01-01

    Endogenous daily (circadian) rhythms allow organisms to anticipate daily changes in the environment. Most mammals are specialized to be active during the night (nocturnal) or day (diurnal). However, typically nocturnal mammals become diurnal when energetically challenged by cold or hunger. The

  4. Diurnality as an energy-saving strategy : energetic consequences of temporal niche switching in small mammals

    NARCIS (Netherlands)

    van der Vinne, Vincent; Gorter, Jenke A; Riede, Sjaak J; Hut, Roelof A

    Endogenous daily (circadian) rhythms allow organisms to anticipate daily changes in the environment. Most mammals are specialized to be active during the night (nocturnal) or day (diurnal). However, typically nocturnal mammals become diurnal when energetically challenged by cold or hunger. The

  5. Melatonin-induced CBF/DREB1s are essential for diurnal change of disease resistance and CCA1 expression in Arabidopsis.

    Science.gov (United States)

    Shi, Haitao; Wei, Yunxie; He, Chaozu

    2016-03-01

    Melatonin (N-acetyl-5-methoxytryptamine) is an important regulator of circadian rhythms and immunity in animals. However, the diurnal changes of endogenous melatonin and melatonin-mediated diurnal change of downstream responses remain unclear in Arabidopsis. Using the publicly available microarray data, we found that the transcript levels of two melatonin synthesis genes (serotonin N-acetyltransferase (SNAT) and caffeate O-methyltransferase (COMT)) and endogenous melatonin level were regulated by diurnal cycles, with different magnitudes of change. Moreover, the transcripts of C-repeat-binding factors (CBFs)/Drought response element Binding 1 factors (DREB1s) were co-regulated by exogenous melatonin and diurnal changes, indicating the possible correlation among clock, endogenous melatonin level and AtCBFs expressions. Interestingly, diurnal change of plant immunity against Pst DC3000 and CIRCADIANCLOCK ASSOCIATED 1 (CCA1) expression were largely lost in AtCBFs knockdown line-amiR-1. Taken together, this study identifies the molecular pathway underlying the diurnal changes of immunity in Arabidopsis. Notably, the diurnal changes of endogenous melatonin may regulate corresponding changes of AtCBF/DREB1s expression and their underlying diurnal cycle of plant immunity and AtCCA1. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  6. Concurrent and longitudinal associations between diurnal cortisol and body mass index across adolescence.

    Science.gov (United States)

    Ruttle, Paula L; Javaras, Kristin N; Klein, Marjorie H; Armstrong, Jeffrey M; Burk, Linnea R; Essex, Marilyn J

    2013-06-01

    Childhood and adolescent obesity have reached epidemic levels; however, little is known about the psychobiological underpinnings of obesity in youth and whether these differ from the mechanisms identified in adults. The current study examines concurrent (i.e., measured at the same point in time) and longitudinal (i.e., using earlier cortisol measures to predict later body mass index [BMI]) associations between diurnal cortisol and BMI across adolescence. Adolescent diurnal cortisol was measured over 3 days at each 11, 13, and 15 years. Hierarchical linear modeling was used to extract average measures of predicted morning, afternoon, evening levels of cortisol and the diurnal slope at each assessment. Adolescent BMI (kg/m(2)) was measured at 11, 13, 15, and 18 years. Sex, family socioeconomic status, mother's BMI, pubertal status, and adolescent mental health were examined as possible confounding variables. Linear regressions revealed that blunted patterns of adolescent cortisol were associated with increased measures of BMI across adolescence both concurrently and longitudinally, particularly when examining measures of cortisol in early adolescence. Multinomial logistic regressions extended the linear regression findings beyond BMI scores to encompass categories of obesity. The current study builds on previous research documenting diurnal cortisol-obesity findings in adults by demonstrating similar findings exist both concurrently and longitudinally in adolescents. Findings suggest the association between cortisol and BMI is developmentally influenced and that blunted diurnal cortisol patterns can be identified in overweight individuals at a younger age than previously thought. Copyright © 2013 Society for Adolescent Health and Medicine. Published by Elsevier Inc. All rights reserved.

  7. Diurnal variation of cosmic ray intensity I. Two approaches to the study

    International Nuclear Information System (INIS)

    Sari, J.W.; Venkatesan, D.; Lanzerotti, L.J.; Maclennan, C.G.

    1978-01-01

    The investigation has been carried out over the past two decades by either of two approaches: the traditional Fourier series method and the more recently introduced power spectral method. A comparison of the two approaches is essential to the proper understanding of the results derived from them. The present study, for the first time, adopts both approaches for investigating the data from the Sulfur Mountain super neutron monitor for the period of mid-December 1965 to April 1966 (extending over five solar rotations), when interplanetary magnetic field data from Pioneer 6 were also available. Problems relating to the analyses of both data sets on a day-to-day basis and on a statistical basis over a number of days are discussed. The power spectral analysis method cannot provide information on the phase of the diurnal variation or information on the diurnal amplitude on a day-to-day basis. This method provides excellent estimates of the diurnal anisotropy amplitude provides a measure of the ambient anisotropy amplitude. The Fourier series method can yield reliable measures of the amplitude and phase on a day-to-day basis, provided the time series is reasonably stationary. This method cannot estimate the ambient anisotropy amplitude which, for small amplitudes, contributes to large uncertainties in the Fourier coefficients. We find that there is a general agreement between the observed diurnal variation and that predicted theoretically. However, for most of the periods examined the ratio of the perpendicular diffusion coefficient to the parallel diffusion coefficient is rather small (K 1 /K < or approx. =0.1). As such the diurnal variation amplitude is generally most sensitive to the interplanetary field direction and the solar wind velocity and not to the calculated values of the diffusion coefficients. Further tests of the theory are discussed

  8. Habitat selection and diurnal refugia of gray foxes in southwestern Georgia, USA.

    Directory of Open Access Journals (Sweden)

    Nicholas R Deuel

    Full Text Available Understanding habitat selection of gray foxes (Urocyon cinereoargenteus is essential to evaluate their potential response to changes in land use and predator communities. Few studies have evaluated temporal habitat selection or explicitly identified habitats used by gray foxes for diurnal refugia. We used GPS collars to obtain location data for 34 gray foxes (20 males and 14 females from February 2014 to December 2015 to evaluate temporal (seasonal and diel habitat selection and selection of diurnal refugia in southwestern Georgia, USA. We analyzed habitat selection at 2 levels, selection of a core area within the home range and selection of locations within the home range. Habitat selection was non-random (P 0.05. Hardwoods, human use (i.e., areas associated with regular human activity such as buildings, lawns, parking areas, etc., and roads were selected (P 0.05. Selection of habitats for diurnal refugia did not vary seasonally or by sex (P > 0.05, with foxes selecting (P < 0.05 areas near hardwood forests, roads, agriculture, human use, pastures/food plots, and shrub scrub habitats. Gray foxes were observed on the ground while resting, and we found no evidence of gray foxes diurnally resting in trees. Our results suggest that on our study area, gray foxes are an edge species that prefer forests with a hardwood component in areas near human use and roads.

  9. Radical Change by Entrepreneurial Design

    National Research Council Canada - National Science Library

    Roberts, Nancy C

    1998-01-01

    .... How radical change in public policy has occurred in the past is then documented. We find examples of radical change by chance, radical change by consensus, radical change by learning, and radical change by entrepreneurial design...

  10. Bats as prey of diurnal birds: a global perspective.

    Czech Academy of Sciences Publication Activity Database

    Mikula, P.; Morelli, Federico; Lučan, R. K.; Jones, D. N.; Tryjanowski, P.

    2016-01-01

    Roč. 46, č. 3 (2016), s. 160-174 ISSN 0305-1838 Institutional support: RVO:60077344 Keywords : avian predation hypothesis * bats * diurnal birds * nocturnality * predation Subject RIV: EG - Zoology Impact factor: 3.286, year: 2016

  11. Sleep duration partially accounts for race differences in diurnal cortisol dynamics.

    Science.gov (United States)

    Peterson, Laurel M; Miller, Karissa G; Wong, Patricia M; Anderson, Barbara P; Kamarck, Thomas W; Matthews, Karen A; Kirschbaum, Clemens; Manuck, Stephen B

    2017-05-01

    Emerging research demonstrates race differences in diurnal cortisol slope, an indicator of hypothalamic-pituitary-adrenocortical (HPA)-axis functioning associated with morbidity and mortality, with African Americans showing flatter diurnal slopes than their White counterparts. Sleep characteristics are associated with both race and with HPA-axis functioning. The present report examines whether sleep duration may account for race differences in cortisol dynamics. Participants were 424 employed African American and White adults (mean age = 42.8 years, 84.2% White, 53.6% female) with no cardiovascular disease (Adult Health and Behavior Project-Phase 2 [AHAB-II] cohort, University of Pittsburgh). Cortisol slope was calculated using 4 salivary cortisol readings, averaged over each of 4 days. Demographic (age, sex), psychosocial (socioeconomic status [SES], affect, discrimination), and health behaviors (smoking, alcohol use, physical activity) variables were used as covariates, and sleep (self-report and accelerometry) was also assessed. African Americans had flatter slopes than Whites (F(1, 411) = 10.45, B = .02, p = .001) in models adjusting for demographic, psychosocial, and health behavior covariates. Shorter actigraphy-assessed total sleep time was a second significant predictor of flatter cortisol slopes (F(1, 411) = 25.27, B = -.0002, p race and diurnal slope [confidence interval = .05 (lower = .014, upper .04)]. African Americans have flatter diurnal cortisol slopes than their White counterparts, an effect that may be partially attributable to race differences in nightly sleep duration. Sleep parameters should be considered in further research on race and cortisol. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

  12. Evaluation of NASA GEOS-ADAS Modeled Diurnal Warming Through Comparisons to SEVIRI and AMSR2 SST Observations

    Science.gov (United States)

    Gentemann, C. L.; Akella, S.

    2018-02-01

    An analysis of the ocean skin Sea Surface Temperature (SST) has been included in the Goddard Earth Observing System (GEOS) - Atmospheric Data Assimilation System (ADAS), Version 5 (GEOS-ADAS). This analysis is based on the GEOS atmospheric general circulation model (AGCM) that simulates near-surface diurnal warming and cool skin effects. Analysis for the skin SST is performed along with the atmospheric state, including Advanced Very High Resolution Radiometer (AVHRR) satellite radiance observations as part of the data assimilation system. One month (September, 2015) of GEOS-ADAS SSTs were compared to collocated satellite Spinning Enhanced Visible and InfraRed Imager (SEVIRI) and Advanced Microwave Scanning Radiometer 2 (AMSR2) SSTs to examine how the GEOS-ADAS diurnal warming compares to the satellite measured warming. The spatial distribution of warming compares well to the satellite observed distributions. Specific diurnal events are analyzed to examine variability within a single day. The dependence of diurnal warming on wind speed, time of day, and daily average insolation is also examined. Overall the magnitude of GEOS-ADAS warming is similar to the warming inferred from satellite retrievals, but several weaknesses in the GEOS-AGCM simulated diurnal warming are identified and directly related back to specific features in the formulation of the diurnal warming model.

  13. Radial frequency diagram (sunflower) for the analysis of diurnal cycle parameters: Solar energy application

    International Nuclear Information System (INIS)

    Božnar, Marija Zlata; Grašič, Boštjan; Mlakar, Primož; Soares, Jacyra; Pereira de Oliveira, Amauri; Costa, Tássio Santos

    2015-01-01

    Graphical abstract: A new type of graphical presentation showing diurnal cycle of solar energy forecast. The application is possible for other parameters related to weather and green energy production. - Highlights: • The diurnal cycle of solar energy is important for the management of the electrical grid. • A solar plant’s average production depends on the statistical features of solar radiation. • The new tool – the “sunflower”, is proposed for solar energy availability representation. • The sunflower identifies and quantifies information with a clear diurnal cycle. • The sunflower diagram has been developed from the “wind rose” diagram. - Abstract: Many meteorological parameters present a natural diurnal cycle because they are directly or indirectly dependent on sunshine exposure. The solar radiation diurnal pattern is important to energy production, agriculture, prognostic models, health and general climatology. This article aims at introducing a new type of radial frequency diagram – hereafter called sunflower – for the analysis of solar radiation data in connection with energy production and also for climatological studies. The diagram is based on two-dimensional data sorting. Firstly data are sorted into classes representing hours in a day. Then the data in each hourly class is sorted into classes of the observed variable values. The relative frequencies of the value classes are shown as sections on each hour’s segment in a radial diagram. The radial diagram forms a unique pattern for each analysed dataset. Therefore it enables the quick detection of features and the comparison of several such patterns belonging to the different datasets being analysed. The sunflower diagram enables a quick and comprehensive understanding of the information about diurnal cycle of the solar radiation data. It enables in a graphical form, quick screening and long-term statistics of huge data quantities when searching for their diurnal features and

  14. Maize global transcriptomics reveals pervasive leaf diurnal rhythms but rhythms in developing ears are largely limited to the core oscillator.

    Directory of Open Access Journals (Sweden)

    Kevin R Hayes

    Full Text Available BACKGROUND: Plant diurnal rhythms are vital environmental adaptations to coordinate internal physiological responses to alternating day-night cycles. A comprehensive view of diurnal biology has been lacking for maize (Zea mays, a major world crop. METHODOLOGY: A photosynthetic tissue, the leaf, and a non-photosynthetic tissue, the developing ear, were sampled under natural field conditions. Genome-wide transcript profiling was conducted on a high-density 105 K Agilent microarray to investigate diurnal rhythms. CONCLUSIONS: In both leaves and ears, the core oscillators were intact and diurnally cycling. Maize core oscillator genes are found to be largely conserved with their Arabidopsis counterparts. Diurnal gene regulation occurs in leaves, with some 23% of expressed transcripts exhibiting a diurnal cycling pattern. These transcripts can be assigned to over 1700 gene ontology functional terms, underscoring the pervasive impact of diurnal rhythms on plant biology. Considering the peak expression time for each diurnally regulated gene, and its corresponding functional assignment, most gene functions display temporal enrichment in the day, often with distinct patterns, such as dawn or midday preferred, indicating that there is a staged procession of biological events undulating with the diurnal cycle. Notably, many gene functions display a bimodal enrichment flanking the midday photosynthetic maximum, with an initial peak in mid-morning followed by another peak during the afternoon/evening. In contrast to leaves, in developing ears as few as 47 gene transcripts are diurnally regulated, and this set of transcripts includes primarily the core oscillators. In developing ears, which are largely shielded from light, the core oscillator therefore is intact with little outward effect on transcription.

  15. Generation of diurnal variation for influent data for dynamic simulation.

    Science.gov (United States)

    Langergraber, G; Alex, J; Weissenbacher, N; Woerner, D; Ahnert, M; Frehmann, T; Halft, N; Hobus, I; Plattes, M; Spering, V; Winkler, S

    2008-01-01

    When using dynamic simulation for fine tuning of the design of activated sludge (AS) plants diurnal variations of influent data are required. For this application usually only data from the design process and no measured data are available. In this paper a simple method to generate diurnal variations of wastewater flow and concentrations is described. The aim is to generate realistic influent data in terms of flow, concentrations and TKN/COD ratios and not to predict the influent of the AS plant in detail. The work has been prepared within the framework of HSG-Sim (Hochschulgruppe Simulation, http://www.hsgsim.org), a group of researchers from Germany, Austria, Luxembourg, Poland, the Netherlands and Switzerland. (c) IWA Publishing 2008.

  16. The games radicals play : special issue on free radicals and radical ions

    OpenAIRE

    Walton, J.C.; Williams, F.

    2015-01-01

    Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and a...

  17. Spectroscopic studies of neutral and chemically oxidized species of β-carotene, lycopene and norbixin in CH2Cl2: Fluorescence from intermediate compounds

    International Nuclear Information System (INIS)

    Alwis, D.D.D.H; Chandrika, U.G.; Jayaweera, P.M.

    2015-01-01

    Radical cations, dications and oxidized intermediate species of three carotenoids, namely, β-carotene, lycopene and norbixin, were generated in CH 2 Cl 2 solutions via chemical oxidation using anhydrous FeCl 3 . UV–vis, fluorescence and fluorescence-excitation spectroscopic studies were performed to understand and compare the nature of intermediate species generated during the chemical oxidation process and subsequent degradation. The intense emission observed at 550 nm can be assigned to the S 2 →S 0 (1 1 B u →1 1 A g ) transition of the carotenoid molecules. The 350 nm excitation during the oxidation process for β-carotene, lycopene and norbixin exhibit intense fluorescence peaks at 492 nm, 493 nm and 500 nm, respectively. These peaks are assigned to intermediate peroxy/epoxy compounds of the three molecules that are formed with molecular oxygen prior to the formation of oxidized short-chain stable compounds. - Highlights: • Fluorescence and UV–vis studies on β-carotene, lycopene and norbixin. • Oxidation, induced by FeCl 3 in CH 2 Cl 2 shows blue shifted fluorescence peaks. • Fluorescence peaks were assigned to intermediate peroxy/epoxy forms of carotenoids. • The D0→D3 transition of radical cations are observed in the near IR region

  18. Time resolved resonance Raman spectra of anilino radical and aniline radical cation

    International Nuclear Information System (INIS)

    Tripathi, G.N.R.; Schuler, R.H.

    1987-01-01

    We report, in this paper, submicrosecond time resolved resonance Raman spectra of anilino radical and its radical cation as observed in pulse radiolytic studies of the oxidation of aniline in aqueous solution. By excitation in resonance with the broad and weak electronic transition of anilino radical at 400 nm (ε--1250 M -1 cm -1 ) we have observed, for the first time, the vibrational features of this radical. The Wilson ν 8 /sub a/ ring stretching mode at 1560 cm -1 is most strongly resonance enhanced. The ν 7 /sub a/ CN stretching band at 1505 cm -1 , which is shifted to higher frequency by 231 cm -1 with respect to aniline, is also prominent. The frequency of this latter mode indicates that the CN bond in the radical has considerable double bond character. The Raman spectrum of aniline radical cation, excited in resonance with the --425 nm electronic absorption (ε--4000 M -1 cm -1 ), shows features which are similar to phenoxyl radical. Most of the observed frequencies of this radical in solution are in good agreement with vibrational energies determined by recent laser photoelectron spectroscopic studies in the vapor phase. The bands most strongly enhanced in the resonance Raman spectrum are, however, weak in the photoelectron spectrum. While the vibrational frequencies observed for anilino radical and its isoelectronic cation are quite similar, the resonance enhancement patterns are very different. In particular the ν 14 b 2 mode of anilino radical observed at 1324 cm -1 is highly resonance enhanced because of strong vibronic coupling between the 400 nm 2 A 2 -- 2 B 1 and the higher 2 B 1 -- 2 B 1 electronic transitions

  19. Diurnal Human Activity and Introduced Species Affect Occurrence of Carnivores in a Human-Dominated Landscape.

    Directory of Open Access Journals (Sweden)

    Dario Moreira-Arce

    Full Text Available Diurnal human activity and domestic dogs in agro-forestry mosaics should theoretically modify the diurnal habitat use patterns of native carnivores, with these effects being scale-dependent. We combined intensive camera trapping data with Bayesian occurrence probability models to evaluate both diurnal and nocturnal patterns of space use by carnivores in a mosaic of land-use types in southern Chile. A total of eight carnivores species were recorded, including human-introduced dogs. During the day the most frequently detected species were the culpeo fox and the cougar. Conversely, during the night, the kodkod and chilla fox were the most detected species. The best supported models showed that native carnivores responded differently to landscape attributes and dogs depending on both the time of day as well as the spatial scale of landscape attributes. The positive effect of native forest cover at 250 m and 500 m radius buffers was stronger during the night for the Darwin's fox and cougar. Road density at 250 m scale negatively affected the diurnal occurrence of Darwin´s fox, whereas at 500 m scale roads had a stronger negative effect on the diurnal occurrence of Darwin´s foxes and cougars. A positive effect of road density on dog occurrence was evidenced during both night and day. Patch size had a positive effect on cougar occurrence during night whereas it affected negatively the occurrence of culpeo foxes and skunks during day. Dog occurrence had a negative effect on Darwin's fox occurrence during day-time and night-time, whereas its negative effect on the occurrence of cougar was evidenced only during day-time. Carnivore occurrences were not influenced by the proximity to a conservation area. Our results provided support for the hypothesis that diurnal changes to carnivore occurrence were associated with human and dog activity. Landscape planning in our study area should be focused in reducing both the levels of diurnal human activity in

  20. Diurnal Human Activity and Introduced Species Affect Occurrence of Carnivores in a Human-Dominated Landscape.

    Science.gov (United States)

    Moreira-Arce, Dario; Vergara, Pablo M; Boutin, Stan

    2015-01-01

    Diurnal human activity and domestic dogs in agro-forestry mosaics should theoretically modify the diurnal habitat use patterns of native carnivores, with these effects being scale-dependent. We combined intensive camera trapping data with Bayesian occurrence probability models to evaluate both diurnal and nocturnal patterns of space use by carnivores in a mosaic of land-use types in southern Chile. A total of eight carnivores species were recorded, including human-introduced dogs. During the day the most frequently detected species were the culpeo fox and the cougar. Conversely, during the night, the kodkod and chilla fox were the most detected species. The best supported models showed that native carnivores responded differently to landscape attributes and dogs depending on both the time of day as well as the spatial scale of landscape attributes. The positive effect of native forest cover at 250 m and 500 m radius buffers was stronger during the night for the Darwin's fox and cougar. Road density at 250 m scale negatively affected the diurnal occurrence of Darwin´s fox, whereas at 500 m scale roads had a stronger negative effect on the diurnal occurrence of Darwin´s foxes and cougars. A positive effect of road density on dog occurrence was evidenced during both night and day. Patch size had a positive effect on cougar occurrence during night whereas it affected negatively the occurrence of culpeo foxes and skunks during day. Dog occurrence had a negative effect on Darwin's fox occurrence during day-time and night-time, whereas its negative effect on the occurrence of cougar was evidenced only during day-time. Carnivore occurrences were not influenced by the proximity to a conservation area. Our results provided support for the hypothesis that diurnal changes to carnivore occurrence were associated with human and dog activity. Landscape planning in our study area should be focused in reducing both the levels of diurnal human activity in native forest remnants

  1. Wheel running improves REM sleep and attenuates stress-induced flattening of diurnal rhythms in F344 rats.

    Science.gov (United States)

    Thompson, Robert S; Roller, Rachel; Greenwood, Benjamin N; Fleshner, Monika

    2016-05-01

    Regular physical activity produces resistance to the negative health consequences of stressor exposure. One way that exercise may confer stress resistance is by reducing the impact of stress on diurnal rhythms and sleep; disruptions of which contribute to stress-related disease including mood disorders. Given the link between diurnal rhythm disruptions and stress-related disorders and that exercise both promotes stress resistance and is a powerful non-photic biological entrainment cue, we tested if wheel running could reduce stress-induced disruptions of sleep/wake behavior and diurnal rhythms. Adult, male F344 rats with or without access to running wheels were instrumented for biotelemetric recording of diurnal rhythms of locomotor activity, heart rate, core body temperature (CBT), and sleep (i.e. REM, NREM, and WAKE) in the presence of a 12 h light/dark cycle. Following 6 weeks of sedentary or exercise conditions, rats were exposed to an acute stressor known to disrupt diurnal rhythms and produce behaviors associated with mood disorders. Prior to stressor exposure, exercise rats had higher CBT, more locomotor activity during the dark cycle, and greater %REM during the light cycle relative to sedentary rats. NREM and REM sleep were consolidated immediately following peak running to a greater extent in exercise, compared to sedentary rats. In response to stressor exposure, exercise rats expressed higher stress-induced hyperthermia than sedentary rats. Stressor exposure disrupted diurnal rhythms in sedentary rats; and wheel running reduced these effects. Improvements in sleep and reduced diurnal rhythm disruptions following stress could contribute to the health promoting and stress protective effects of exercise.

  2. Familial circadian rhythm disorder in the diurnal primate, Macaca mulatta.

    Directory of Open Access Journals (Sweden)

    Irina V Zhdanova

    Full Text Available In view of the inverse temporal relationship of central clock activity to physiological or behavioral outputs in diurnal and nocturnal species, understanding the mechanisms and physiological consequences of circadian disorders in humans would benefit from studies in a diurnal animal model, phylogenetically close to humans. Here we report the discovery of the first intrinsic circadian disorder in a family of diurnal non-human primates, the rhesus monkey. The disorder is characterized by a combination of delayed sleep phase, relative to light-dark cycle, mutual desynchrony of intrinsic rhythms of activity, food intake and cognitive performance, enhanced nighttime feeding or, in the extreme case, intrinsic asynchrony. The phenotype is associated with normal length of intrinsic circadian period and requires an intact central clock, as demonstrated by an SCN lesion. Entrainment to different photoperiods or melatonin administration does not eliminate internal desynchrony, though melatonin can temporarily reinstate intrinsic activity rhythms in the animal with intrinsic asynchrony. Entrainment to restricted feeding is highly effective in animals with intrinsic or SCN lesion-induced asynchrony. The large isolated family of rhesus macaques harboring the disorder provides a powerful new tool for translational research of regulatory circuits underlying circadian disorders and their effective treatment.

  3. No diurnal variation in rate or carbon isotope composition of soil respiration in a boreal forest

    International Nuclear Information System (INIS)

    Betson, N.R.; Gottlicher, S.G.; Hogberg, P.; Hall, M.; Wallin, G.; Richter, A.

    2007-01-01

    This study evaluated the diurnal variability in the rate and stable carbon isotope ratio ((delta) 13 C) of soil respiration in a northern boreal forest, measured with opaque chambers after the removal of understory vegetation. The experiment was conducted in June and August 2004 at the Picea abies L. Karst-dominated Flakaliden Research Forest in northern Sweden, using unfertilized girdled-tree plots and unfertilized non-girdled tree plots. Soil respiration and (delta) 13 C of soil-respired carbon dioxide (CO 2 ) were measured every 4 hours on 6 plots, with a total of 11 sampling times over each 48 hour period. The purpose was to clarify an earlier study regarding the origin of diurnal patterns of soil CO 2 flux. This study explored whether the diurnal patterns were the result of photosynthetic CO 2 uptake during the day by the understory or whether there were underlying trends in soil respiration driven by plant root allocation. The sampling campaigns undertaken in this study investigated whether diurnal variations in soil respiration rate and (delta) 13 C exist in this ecosystem when no understory vegetation is present. Shoot photosynthesis and environmental parameters were measured simultaneously. Despite significant variations in climatic conditions and shoot photosynthetic rates in non-girdled trees, no diurnal patterns in soil respiration rates and (delta) 13 C were noted in either treatment. The lack of detectable diurnal changes in both treatments indicates that modeling of daily boreal forest carbon balances based on single instantaneous measurements are unlikely to be misconstrued by substantial diurnal trends. However, it was suggested that spatial variable should be accounted for, given the large standard errors. The impact of tree girdling on soil respiration rates also emphasized the significance of canopy photosynthesis in driving soil processes. 37 refs., 2 figs

  4. Standardised Resting Time Prior to Blood Sampling and Diurnal Variation Associated with Risk of Patient Misclassification

    DEFF Research Database (Denmark)

    Bøgh Andersen, Ida; Brasen, Claus L.; Christensen, Henry

    2015-01-01

    .9×10-7) and sodium (p = 8.7×10-16). Only TSH and albumin were clinically significantly influenced by diurnal variation. Resting time had no clinically significant effect. CONCLUSIONS: We found no need for resting 15 minutes prior to blood sampling. However, diurnal variation was found to have a significant......BACKGROUND: According to current recommendations, blood samples should be taken in the morning after 15 minutes' resting time. Some components exhibit diurnal variation and in response to pressures to expand opening hours and reduce waiting time, the aims of this study were to investigate...... the impact of resting time prior to blood sampling and diurnal variation on biochemical components, including albumin, thyrotropin (TSH), total calcium and sodium in plasma. METHODS: All patients referred to an outpatient clinic for blood sampling were included in the period Nov 2011 until June 2014 (opening...

  5. Moored surface buoy observations of the diurnal warm layer

    KAUST Repository

    Prytherch, J.

    2013-09-01

    An extensive data set is used to examine the dynamics of diurnal warming in the upper ocean. The data set comprises more than 4700 days of measurements at five sites in the tropics and subtropics, obtained from surface moorings equipped to make comprehensive meteorological, incoming solar and infrared radiation, and high-resolution subsurface temperature (and, in some cases, velocity) measurements. The observations, which include surface warmings of up to 3.4°C, are compared with a selection of existing models of the diurnal warm layer (DWL). A simple one-layer physical model is shown to give a reasonable estimate of both the magnitude of diurnal surface warming (model-observation correlation 0.88) and the structure and temporal evolution of the DWL. Novel observations of velocity shear obtained during 346 days at one site, incorporating high-resolution (1 m) upper ocean (5-15 m) acoustic Doppler current profile measurements, are also shown to be in reasonable agreement with estimates from the physical model (daily maximum shear model-observation correlation 0.77). Physics-based improvements to the one-layer model (incorporation of rotation and freshwater terms) are discussed, though they do not provide significant improvements against the observations reported here. The simplicity and limitations of the physical model are used to discuss DWL dynamics. The physical model is shown to give better model performance under the range of forcing conditions experienced across the five sites than the more empirical models. ©2013. American Geophysical Union. All Rights Reserved.

  6. Moored surface buoy observations of the diurnal warm layer

    KAUST Repository

    Prytherch, J.; Farrar, J. T.; Weller, R. A.

    2013-01-01

    An extensive data set is used to examine the dynamics of diurnal warming in the upper ocean. The data set comprises more than 4700 days of measurements at five sites in the tropics and subtropics, obtained from surface moorings equipped to make comprehensive meteorological, incoming solar and infrared radiation, and high-resolution subsurface temperature (and, in some cases, velocity) measurements. The observations, which include surface warmings of up to 3.4°C, are compared with a selection of existing models of the diurnal warm layer (DWL). A simple one-layer physical model is shown to give a reasonable estimate of both the magnitude of diurnal surface warming (model-observation correlation 0.88) and the structure and temporal evolution of the DWL. Novel observations of velocity shear obtained during 346 days at one site, incorporating high-resolution (1 m) upper ocean (5-15 m) acoustic Doppler current profile measurements, are also shown to be in reasonable agreement with estimates from the physical model (daily maximum shear model-observation correlation 0.77). Physics-based improvements to the one-layer model (incorporation of rotation and freshwater terms) are discussed, though they do not provide significant improvements against the observations reported here. The simplicity and limitations of the physical model are used to discuss DWL dynamics. The physical model is shown to give better model performance under the range of forcing conditions experienced across the five sites than the more empirical models. ©2013. American Geophysical Union. All Rights Reserved.

  7. Intramolecular transformation of thiyl radicals to α-aminoalkyl radicals: 'ab initio' calculations on homocystein

    International Nuclear Information System (INIS)

    Chhun, S.; Berges, J.; Bleton, V.; Abedinzadeh, Z.

    2000-01-01

    One-electron oxidation of thiols by oxidizing radicals leads to the formation of thiyl radical and carbon-centered radicals. It has been shown experimentally that in the absence of oxygen, the thiyl radicals derived from certain thiols of biological interest such as glutathion, cysteine and homocysteine decay rapidly by intramolecular rearrangement reactions into the carbon-centered radical. In the present work we have investigated theoretically the structure and the stability of thiyl and carbon-centered radicals of homocysteine in order to check the possibility of this rearrangement. (author)

  8. Diurnal variability of Synechococcus abundance in Sagami Bay, Japan

    Digital Repository Service at National Institute of Oceanography (India)

    Mitbavkar, S.; Saino, T.

    Synechococcus, the most dominant picophytoplankton in coastal regions, exhibits diurnal variations in the open ocean. The aim of this study was to assess its short-term population dynamics and cell cycle phases through DNA analysis in a coastal...

  9. Diurnal levels of immunoreactive erythropoietin in normal subjects and subjects with chronic lung disease

    Energy Technology Data Exchange (ETDEWEB)

    Miller, M.E.; Garcia, J.F.; Cohen, R.A.; Cronkite, E.P.; Moccia, G.; Acevedo, J.

    1981-10-01

    Serum levels of immunoreactive erythropoietin (Ep) were measured in 48 normal male and female volunteers, ages 20-60 years, to establish a control value for Ep of 18.5 +/- 5.0 (mean +/- SD) mU/ml. Levels of the hormone were also measured sequentially over a 24 h period of time in an additional 17 normal volunteers with no diurnal variation. Diurnal levels of immunoreactive Ep were also measured in 30 subjects, with chronic lung disease. These patients, in contrast to normal subjects exhibited a diurnal variation in the level of immunoreactive Ep with peak levels occurring at midnight. The only variable measured which correlated with the serum immunoreactive Ep level in subjects with chronic lung disease was the level of carboxyhaemoglobin (P less than 0.02).

  10. Free radical transfer in polymers

    International Nuclear Information System (INIS)

    Sonntag, C. von; Bothe, E.; Ulanski, P.

    1998-01-01

    For the present study of free-radical transfer in polymers pulse radiolysis and product studies have been carried out in aqueous solutions using thus far only the water-soluble polymers polyacrylic acid, polymethacrylic acid and polyvinyl alcohol. When OH radicals, generated in the radiolysis of N 2 O-saturated aqueous solutions, react with polymers the lifetime of the polymer radical thus created very much depends on the number of radicals per polymer chain. When there are a large number of radicals per chain their bimolecular decay may be faster than the corresponding (diffusion controlled) decay of monomeric radicals, but when the macromolecule contains only few or even just one radical their lifetime is considerably prolonged. Highly charged polymers such as polyacrylic acid at high pH attain a rod-like conformation which again favors a long lifetime of the radicals. Under such conditions, radical transfer reactions can occur. For example, in polyacrylic acid OH radicals generate two kinds of radicals side by side. The radical in β-position to the carboxylate group converts into the thermodynamically more stable α-radicals by an H-transfer reaction as can be followed by spectrophotometry. Besides radical transfer reactions β-fragmentation reactions occur causing chain scission. Such reactions can be followed in a pulse radiolysis experiment by conductometry, because counter ions are released upon chain scission. Such a process is especially effective in the case of polymethacrylic acid, where it results in a chain depolymerization. An intramolecular H-abstraction is also observed in the γ-radiolysis of polyacrylic acid with the corresponding peroxyl radicals. This causes a chain reaction to occur. The resulting hydroperoxides are unstable and decarboxylate given rise to acetylacetone-like products. In polyvinyl alcohol the peroxyl radicals in α-position to the alcohol function undergo HO 2 -elimination. This prevents a scission of the polymer chain in the

  11. Deregulated power prices: comparison of diurnal patterns

    International Nuclear Information System (INIS)

    Ying Li; Flynn, P.C.

    2004-01-01

    We examine electrical power price, and in particular its daily and average weekday vs. weekend pattern of change, for 14 deregulated markets. Power price in deregulated markets shows fundamentally different patterns. North American markets show a monotonic diurnal weekday price pattern, while all other markets studied show more than one price peak. Deregulated power markets differ in maximum vs. minimum daily average price and in average weekday to weekend price, in turn creating a different incentive for a consumer to time shift power consuming activities. Markets differ in the extent to which a small fraction of the days shapes the average diurnal pattern and value of price. Deregulated markets show a wide variation in the correlation between load and price. Some deregulated markets, most notably Britain and Spain, show patterns that are predictable and consistent, and hence that can encourage a customer to shape consumption behaviors. Other markets, for example South Australia, have patterns that are inconsistent and irregular, and hence are hard for a customer to interpret; a customer in such a market will have a higher incentive to escape risk through hedging mechanisms. (Author)

  12. Deregulated power prices: comparison of diurnal patterns

    International Nuclear Information System (INIS)

    Li Ying; Flynn, Peter C.

    2004-01-01

    We examine electrical power price, and in particular its daily and average weekday vs. weekend pattern of change, for 14 deregulated markets. Power price in deregulated markets shows fundamentally different patterns. North American markets show a monotonic diurnal weekday price pattern, while all other markets studied show more than one price peak. Deregulated power markets differ in maximum vs. minimum daily average price and in average weekday to weekend price, in turn creating a different incentive for a consumer to time shift power consuming activities. Markets differ in the extent to which a small fraction of the days shapes the average diurnal pattern and value of price. Deregulated markets show a wide variation in the correlation between load and price. Some deregulated markets, most notably Britain and Spain, show patterns that are predictable and consistent, and hence that can encourage a customer to shape consumption behaviors. Other markets, for example South Australia, have patterns that are inconsistent and irregular, and hence are hard for a customer to interpret; a customer in such a market will have a higher incentive to escape risk through hedging mechanisms

  13. Aging effect on radiation-induced degradation of polypropylene

    International Nuclear Information System (INIS)

    Imai, M.; Sekiguchi, M.; Tabei, M.; Yamada, Y.; Shimizu, H.

    1995-01-01

    PP sheets and films were irradiated with γ-ray and with high energy electron beam. The mechanical degradation, decay of peroxy radical and the variation of molecular weight with storage time were measured. The variation of molecular weight corresponded to mechanical degradation. The molecular weight of sheet sample at which elongation falls to zero was much higher than that of film sample. The relation between mechanical degradation and sample thickness was discussed. (author)

  14. Developing a Data Record of Lower Troposphere Temperature Profiles for Diurnal Land-Atmosphere Coupling Investigations

    Science.gov (United States)

    Lin, Z.; Li, D.

    2017-12-01

    The lower troposphere, including the planetary boundary layer, is strongly influenced by the land surface at diurnal scales. However, investigations of diurnal land-atmosphere coupling are significantly hindered by the lack of profile measurements that resolve the diurnal cycle. This study aims to bridge this gap by developing a decade-long (from 2007 to 2016) data record of diurnal temperature profiles in the lower troposphere (from the surface to about 4 km above the surface), which is based on the Aircrafts Communications Addressing and Reporting System (ACARS) meteorological observations. We first identify the number of profiles within an hour for each airport over the CONUS. At each airport, only data that passed at least level-1 quality check are retained. 40 airports out of 275 are then selected, which have data for more than 12 hours per day. These selected airports are mainly located along the east and west coasts, as expected. Because the data are recorded at irregular heights, we resample each profile in the lowest 4 km or so to pre-defined vertical coordinates. These temperature profiles are further bias-corrected by comparing to collocated radiosonde observations. This consistent data record of diurnal temperature profiles in the lower troposphere can be also used for regional climatology research, short-term weather forecasts, and numerical model evaluation.

  15. Development and evaluation of an empirical diurnal sea surface temperature model

    Science.gov (United States)

    Weihs, R. R.; Bourassa, M. A.

    2013-12-01

    An innovative method is developed to determine the diurnal heating amplitude of sea surface temperatures (SSTs) using observations of high-quality satellite SST measurements and NWP atmospheric meteorological data. The diurnal cycle results from heating that develops at the surface of the ocean from low mechanical or shear produced turbulence and large solar radiation absorption. During these typically calm weather conditions, the absorption of solar radiation causes heating of the upper few meters of the ocean, which become buoyantly stable; this heating causes a temperature differential between the surface and the mixed [or bulk] layer on the order of a few degrees. It has been shown that capturing the diurnal cycle is important for a variety of applications, including surface heat flux estimates, which have been shown to be underestimated when neglecting diurnal warming, and satellite and buoy calibrations, which can be complicated because of the heating differential. An empirical algorithm using a pre-dawn sea surface temperature, peak solar radiation, and accumulated wind stress is used to estimate the cycle. The empirical algorithm is derived from a multistep process in which SSTs from MTG's SEVIRI SST experimental hourly data set are combined with hourly wind stress fields derived from a bulk flux algorithm. Inputs for the flux model are taken from NASA's MERRA reanalysis product. NWP inputs are necessary because the inputs need to incorporate diurnal and air-sea interactive processes, which are vital to the ocean surface dynamics, with a high enough temporal resolution. The MERRA winds are adjusted with CCMP winds to obtain more realistic spatial and variance characteristics and the other atmospheric inputs (air temperature, specific humidity) are further corrected on the basis of in situ comparisons. The SSTs are fitted to a Gaussian curve (using one or two peaks), forming a set of coefficients used to fit the data. The coefficient data are combined with

  16. Diurnal sampling reveals significant variation in CO2 emission from a tropical productive lake.

    Science.gov (United States)

    Reis, P C J; Barbosa, F A R

    2014-08-01

    It is well accepted in the literature that lakes are generally net heterotrophic and supersaturated with CO2 because they receive allochthonous carbon inputs. However, autotrophy and CO2 undersaturation may happen for at least part of the time, especially in productive lakes. Since diurnal scale is particularly important to tropical lakes dynamics, we evaluated diurnal changes in pCO2 and CO2 flux across the air-water interface in a tropical productive lake in southeastern Brazil (Lake Carioca) over two consecutive days. Both pCO2 and CO2 flux were significantly different between day (9:00 to 17:00) and night (21:00 to 5:00) confirming the importance of this scale for CO2 dynamics in tropical lakes. Net heterotrophy and CO2 outgassing from the lake were registered only at night, while significant CO2 emission did not happen during the day. Dissolved oxygen concentration and temperature trends over the diurnal cycle indicated the dependence of CO2 dynamics on lake metabolism (respiration and photosynthesis). This study indicates the importance of considering the diurnal scale when examining CO2 emissions from tropical lakes.

  17. Large Eddy Simulation of the Diurnal Cycle in Southeast Pacific Stratocumulus

    Energy Technology Data Exchange (ETDEWEB)

    Caldwell, P; Bretherton, C

    2008-03-03

    This paper describes a series of 6 day large eddy simulations of a deep, sometimes drizzling stratocumulus-topped boundary layer based on forcings from the East Pacific Investigation of Climate (EPIC) 2001 field campaign. The base simulation was found to reproduce the observed mean boundary layer properties quite well. The diurnal cycle of liquid water path was also well captured, although good agreement appears to result partially from compensating errors in the diurnal cycles of cloud base and cloud top due to overentrainment around midday. At other times of the day, entrainment is found to be proportional to the vertically-integrated buoyancy flux. Model stratification matches observations well; turbulence profiles suggest that the boundary layer is always at least somewhat decoupled. Model drizzle appears to be too sensitive to liquid water path and subcloud evaporation appears to be too weak. Removing the diurnal cycle of subsidence had little effect on simulated cloud albedo. Simulations with changed droplet concentration and drizzle susceptibility showed large liquid water path differences at night, but differences were quite small at midday. Droplet concentration also had a significant impact on entrainment, primarily through droplet sedimentation feedback rather than through drizzle processes.

  18. Diurnal Cycle of Clouds and Precipitation at the ARM SGP Site

    Science.gov (United States)

    Zhao, W.; Marchand, R.; Fu, Q.

    2016-12-01

    Millimeter Wavelength Cloud Radar (MMCR) data from Dec. 1996 to Dec. 2010, collected at the U. S. Department of Energy Atmospheric Radiation Measurement (ARM) program site in the U.S. Southern Great Plains (SGP), are categorized into clouds (-40dBZe≤reflectivityCRM). Observational and simulated radar reflectivity are compared and further sorted into different atmospheric states identified by Evans (2014). Evans used a neutral network to take ERA-Interim state variables (i.e. horizontal winds, relative humidity, temperature at seven predetermined pressure level and surface pressure) on an 8×8 grid with 1.5º×1.5º spatial resolution centered on the SGP site and found twenty-one atmospheric states which represent specific synoptic conditions. We use these states to study the differences in the diurnal cycle between observations and simulations. Differences in the (mean) annual diurnal cycle between the observations and model are decomposed into errors in the daily mean, errors in the diurnal variation in each state, and errors due to difference in the frequency of occurrence of atmospheric states between ERA and the MMF. The magnitude of various error sources is assessed.

  19. Children's diurnal cortisol responses to negative events at school and home.

    Science.gov (United States)

    Bai, Sunhye; Robles, Theodore F; Reynolds, Bridget M; Repetti, Rena L

    2017-09-01

    This study examined the within-and between-person associations between daily negative events - peer problems, academic problems and interparental conflict - and diurnal cortisol in school-age children. Salivary cortisol levels were assessed four times per day (at wakeup, 30min later, just before dinner and at bedtime) on eight days in 47 youths ages 8-13 years old (60% female; M age=11.28, SD=1.50). The relative contributions of within- and between-person variances in each stressor were estimated in models predicting same-day diurnal cortisol slope, same-day bedtime cortisol, and next morning wakeup cortisol. Children who reported more peer problems on average showed flatter slopes of cortisol decline from wakeup to bedtime. However, children secreted more cortisol at wakeup following days when they had reported more peer or academic problems than usual. Interparental conflict was not significantly associated with diurnal cortisol. Findings from this study extend our understanding of short-term cortisol responses to naturally occurring problems in daily life, and help to differentiate these daily processes from the cumulative effects of chronic stress. Copyright © 2017. Published by Elsevier Ltd.

  20. Daily positive events and diurnal cortisol rhythms: Examination of between-person differences and within-person variation.

    Science.gov (United States)

    Sin, Nancy L; Ong, Anthony D; Stawski, Robert S; Almeida, David M

    2017-09-01

    Growing evidence from field studies has linked daily stressors to dysregulated patterns of diurnal cortisol. Less is known about whether naturally-occurring positive events in everyday life are associated with diurnal cortisol. The objectives of this study were to evaluate daily positive events as predictors of between-person differences and within-person (day-to-day) variations in diurnal cortisol parameters, in addition to daily positive events as buffers against the associations between daily stressors and cortisol. In the National Study of Daily Experiences, 1657 adults ages 33-84 (57% female) reported daily experiences during telephone interviews on 8 consecutive evenings. Saliva samples were collected 4 times per day on 4 interview days and assayed for cortisol. Multilevel models were used to estimate associations of daily positive events with cortisol awakening response (CAR), diurnal cortisol slope, and area under the curve (AUC). At the between-person level, people who experienced more frequent positive events exhibited a steeper diurnal cortisol slope, controlling for daily stressors, daily affect, and other covariates. At the within-person level, positive events in the morning (but not prior-night or afternoon/evening events) predicted steeper decline in cortisol across that day; positive events were also marginally associated with lower same-day AUC. Associations were not mediated by daily positive affect, and positive events did not buffer against stressor-related cortisol alterations. These findings indicate that individual differences and day-to-day variations in daily positive events are associated with diurnal cortisol patterns, independent of stressors and affect. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Aging, health behaviors, and the Diurnal rhythm and awakening response of salivary cortisol

    OpenAIRE

    Heaney, Jennifer L. J.; Phillips, Anna C.; Carroll, Douglas

    2012-01-01

    This study compared the awakening response and diurnal rhythm of cortisol in young versus older adults in relation to health behaviours. Older adults displayed significantly reduced cortisol upon awakening, a lower cortisol awakening response and a flatter diurnal profile represented by a reduced area under the curve and cortisol slope. There was also a significant interaction of age, cortisol and diet; younger adults with a higher fat and lower fruit and vegetable intake exhibited the flatte...

  2. Impact of biomass burning emission on total peroxy nitrates: fire plume identification during the BORTAS campaign

    Directory of Open Access Journals (Sweden)

    E. Aruffo

    2016-11-01

    Full Text Available Total peroxy nitrate ( ∑ PN concentrations have been measured using a thermal dissociation laser-induced fluorescence (TD-LIF instrument during the BORTAS campaign, which focused on the impact of boreal biomass burning (BB emissions on air quality in the Northern Hemisphere. The strong correlation observed between the  ∑ PN concentrations and those of carbon monoxide (CO, a well-known pyrogenic tracer, suggests the possible use of the  ∑ PN concentrations as marker of the BB plumes. Two methods for the identification of BB plumes have been applied: (1  ∑ PN concentrations higher than 6 times the standard deviation above the background and (2  ∑ PN concentrations higher than the 99th percentile of the  ∑ PNs measured during a background flight (B625; then we compared the percentage of BB plume selected using these methods with the percentage evaluated, applying the approaches usually used in literature. Moreover, adding the pressure threshold ( ∼  750 hPa as ancillary parameter to  ∑ PNs, hydrogen cyanide (HCN and CO, the BB plume identification is improved. A recurrent artificial neural network (ANN model was adapted to simulate the concentrations of  ∑ PNs and HCN, including nitrogen oxide (NO, acetonitrile (CH3CN, CO, ozone (O3 and atmospheric pressure as input parameters, to verify the specific role of these input data to better identify BB plumes.

  3. Glutathione--hydroxyl radical interaction: a theoretical study on radical recognition process.

    Directory of Open Access Journals (Sweden)

    Béla Fiser

    Full Text Available Non-reactive, comparative (2 × 1.2 μs molecular dynamics simulations were carried out to characterize the interactions between glutathione (GSH, host molecule and hydroxyl radical (OH(•, guest molecule. From this analysis, two distinct steps were identified in the recognition process of hydroxyl radical by glutathione: catching and steering, based on the interactions between the host-guest molecules. Over 78% of all interactions are related to the catching mechanism via complex formation between anionic carboxyl groups and the OH radical, hence both terminal residues of GSH serve as recognition sites. The glycine residue has an additional role in the recognition of OH radical, namely the steering. The flexibility of the Gly residue enables the formation of further interactions of other parts of glutathione (e.g. thiol, α- and β-carbons with the lone electron pair of the hydroxyl radical. Moreover, quantum chemical calculations were carried out on selected GSH/OH(• complexes and on appropriate GSH conformers to describe the energy profile of the recognition process. The relative enthalpy and the free energy changes of the radical recognition of the strongest complexes varied from -42.4 to -27.8 kJ/mol and from -21.3 to 9.8 kJ/mol, respectively. These complexes, containing two or more intermolecular interactions, would be the starting configurations for the hydrogen atom migration to quench the hydroxyl radical via different reaction channels.

  4. Separating selection by diurnal and nocturnal pollinators on floral display and spur length in Gymnadenia conopsea.

    Science.gov (United States)

    Sletvold, Nina; Trunschke, Judith; Wimmergren, Carolina; Agren, Jon

    2012-08-01

    Most plants attract multiple flower visitors that may vary widely in their effectiveness as pollinators. Floral evolution is expected to reflect interactions with the most important pollinators, but few studies have quantified the contribution of different pollinators to current selection on floral traits. To compare selection mediated by diurnal and nocturnal pollinators on floral display and spur length in the rewarding orchid Gymnadenia conopsea, we manipulated the environment by conducting supplemental hand-pollinations and selective pollinator exclusions in two populations in central Norway. In both populations, the exclusion of diurnal pollinators significantly reduced seed production compared to open pollination, whereas the exclusion of nocturnal pollinators did not. There was significant selection on traits expected to influence pollinator attraction and pollination efficiency in both the diurnal and nocturnal pollination treatment. The relative strength of selection among plants exposed to diurnal and nocturnal visitors varied among traits and populations, but the direction of selection was consistent. The results suggest that diurnal pollinators are more important than nocturnal pollinators for seed production in the study populations, but that both categories contribute to selection on floral morphology. The study illustrates how experimental manipulations can link specific categories of pollinators to observed selection on floral traits, and thus improve our understanding of how species interactions shape patterns of selection.

  5. Diurnal variations in personal care products in seawater and mussels at three Mediterranean coastal sites.

    Science.gov (United States)

    Picot-Groz, Marina; Fenet, Hélène; Martinez Bueno, Maria Jesus; Rosain, David; Gomez, Elena

    2018-03-01

    The presence of personal care products (PCPs) in the marine environment is of major concern. PCPs, UV filters, and musks can enter the marine environment indirectly through wastewater or directly via recreational activities. We conducted this study to document patterns in the occurrence of seven PCPs at three coastal sites impacted by recreational activities during 1 day. The study focused on diurnal variations in these seven PCPs in seawater and indigenous mussels. In seawater, UV filters showed diurnal variations that mirrored variations in recreational activities at the sites. Ethylhexyl methoxycinnamate (EHMC) and octocrylene (OC) water concentrations increased from under the limit of quantification in the morning to 106 and 369 ng/L, respectively, when recreational activities were the highest. In mussels, diurnal variations in OC were observed, with the lowest concentrations recorded in the morning and then increasing throughout the day. As Mytilus spp. are widely used as sentinels in coastal pollution monitoring programs (mussel watch), our findings on diurnal variations could enhance sampling recommendations for recreational sites impacted by PCPs.

  6. Radiolysis of paracetamol in dilute aqueous solution

    Science.gov (United States)

    Szabó, László; Tóth, Tünde; Homlok, Renáta; Takács, Erzsébet; Wojnárovits, László

    2012-09-01

    Using radiolytic experiments hydroxyl radical (main reactant in advanced oxidation processes) was shown to effectively destroy paracetamol molecules. The basic reaction is attachment to the ring. The hydroxy-cyclohexadienyl radical produced in the further reactions may transform to hydroxylated paracetamol derivatives or to quinone type molecules and acetamide. The initial efficiency of aromatic ring destruction in the absence of dissolved O2 is c.a. 10%. The efficiency is 2-3 times higher in the presence of O2 due to its reaction with intermediate hydroxy-cyclohexadienyl radical and the subsequent ring destruction reactions through peroxi radical. Upon irradiation the toxicity of solutions at low doses increases with the dose and then at higher doses it decreases. This is due to formation of compounds with higher toxicity than paracetamol (e.g. acetamide, hidroquinone). These products, however, are highly sensitive to irradiation and degrade easily.

  7. Radiation Chemistry of Xenon Trioxide, Xenate and Perxenate and Photochemistry of Perxenate - A Pulse Radiolysis and Laser Flash-Photolysis Study

    DEFF Research Database (Denmark)

    Kläning, U. K.; Sehested, Knud; Wolff, T.

    1982-01-01

    O2–6 are assumed. HXeO3 and H3XeO2–6 are formed in reactions of the hydrated electron with XeO3 and HXeO3–6, respectively. HXeO4 and H3XeO2–7 are formed in reactions of the hydroxyl radical with XeO3 and HXeO3–6 in which the hydroxyl radical adds to a ligand oxygen atom to form peroxy compounds. HXe......O2–5 is formed in a reaction with the hydroxyl radical anion in which the hydroxyl radical anion adds to the xenon atom and by photolysis of HXeO3–6: HXeO3–6 [graphic omitted] HXeO2–5+ O–. XeV, XeVII and XeIX and corresponding iodine species in the oxidation states four, six and eight have similar...

  8. Development of a new free radical absorption capacity assay method for antioxidants: aroxyl radical absorption capacity (ARAC).

    Science.gov (United States)

    Nagaoka, Shin-ichi; Nagai, Kanae; Fujii, Yuko; Ouchi, Aya; Mukai, Kazuo

    2013-10-23

    A new free radical absorption capacity assay method is proposed with use of an aroxyl radical (2,6-di-tert-butyl-4-(4'-methoxyphenyl)phenoxyl radical) and stopped-flow spectroscopy and is named the aroxyl radical absorption capacity (ARAC) assay method. The free radical absorption capacity (ARAC value) of each tocopherol was determined through measurement of the radical-scavenging rate constant in ethanol. The ARAC value could also be evaluated through measurement of the half-life of the aroxyl radical during the scavenging reaction. For the estimation of the free radical absorption capacity, the aroxyl radical was more suitable than the DPPH radical, galvinoxyl, and p-nitrophenyl nitronyl nitroxide. The ARAC value in tocopherols showed the same tendency as the free radical absorption capacities reported previously, and the tendency was independent of an oxygen radical participating in the scavenging reaction and of a medium surrounding the tocopherol and oxygen radical. The ARAC value can be directly connected to the free radical-scavenging rate constant, and the ARAC method has the advantage of treating a stable and isolable radical (aroxyl radical) in a user-friendly organic solvent (ethanol). The ARAC method was also successfully applied to a palm oil extract. Accordingly, the ARAC method would be useful in free radical absorption capacity assay of antioxidative reagents and foods.

  9. Timing the tides: genetic control of diurnal and lunar emergence times is correlated in the marine midge Clunio marinus.

    Science.gov (United States)

    Kaiser, Tobias S; Neumann, Dietrich; Heckel, David G

    2011-05-20

    The intertidal zone of seacoasts, being affected by the superimposed tidal, diurnal and lunar cycles, is temporally the most complex environment on earth. Many marine organisms exhibit lunar rhythms in reproductive behaviour and some show experimental evidence of endogenous control by a circalunar clock, the molecular and genetic basis of which is unexplored. We examined the genetic control of lunar and diurnal rhythmicity in the marine midge Clunio marinus (Chironomidae, Diptera), a species for which the correct timing of adult emergence is critical in natural populations. We crossed two strains of Clunio marinus that differ in the timing of the diurnal and lunar rhythms of emergence. The phenotype distribution of the segregating backcross progeny indicates polygenic control of the lunar emergence rhythm. Diurnal timing of emergence is also under genetic control, and is influenced by two unlinked genes with major effects. Furthermore, the lunar and diurnal timing of emergence is correlated in the backcross generation. We show that both the lunar emergence time and its correlation to the diurnal emergence time are adaptive for the species in its natural environment. The correlation implies that the unlinked genes affecting lunar timing and the two unlinked genes affecting diurnal timing could be the same, providing an unexpectedly close interaction of the two clocks. Alternatively, the genes could be genetically linked in a two-by-two fashion, suggesting that evolution has shaped the genetic architecture to stabilize adaptive combinations of lunar and diurnal emergence times by tightening linkage. Our results, the first on genetic control of lunar rhythms, offer a new perspective to explore their molecular clockwork.

  10. Diurnal temperature asymmetries and fog at Churchill, Manitoba

    Science.gov (United States)

    Gough, William A.; He, Dianze

    2015-07-01

    A variety of methods are available to calculate daily mean temperature. We explore how the difference between two commonly used methods provides insight into the local climate of Churchill, Manitoba. In particular, we found that these differences related closely to seasonal fog. A strong statistically significant correlation was found between the fog frequency (hours per day) and the diurnal temperature asymmetries of the surface temperature using the difference between the min/max and 24-h methods of daily temperature calculation. The relationship was particularly strong for winter, spring and summer. Autumn appears to experience the joint effect of fog formation and the radiative effect of snow cover. The results of this study suggests that subtle variations of diurnality of temperature, as measured in the difference of the two mean temperature methods of calculation, may be used as a proxy for fog detection in the Hudson Bay region. These results also provide a cautionary note for the spatial analysis of mean temperatures using data derived from the two different methods particularly in areas that are fog prone.

  11. Diurnal variations in iron concentrations and expression of genes involved in iron absorption and metabolism in pigs.

    Science.gov (United States)

    Zhang, Yiming; Wan, Dan; Zhou, Xihong; Long, Ciming; Wu, Xin; Li, Lan; He, Liuqin; Huang, Pan; Chen, Shuai; Tan, Bie; Yin, Yulong

    2017-09-02

    Diurnal variations in serum iron levels have been well documented in clinical studies, and serum iron is an important diagnostic index for iron-deficiency anemia. However, the underlying mechanism of dynamic iron regulation in response to the circadian rhythm is still unclear. In this study, we investigated daily variations in iron status in the plasma and liver of pigs. The transcripts encoding key factors involved in iron uptake and homeostasis were evaluated. The results showed that iron levels in the plasma and liver exhibited diurnal rhythms. Diurnal variations were also observed in transcript levels of divalent metal transporter 1 (DMT1), membrane-associated ferric reductase 1 (DCYTB), and transferrin receptor (TfR) in the duodenum and jejunum, as well as hepcidin (HAMP) and TfR in the liver. Moreover, the results showed a network in which diurnal variations in systemic iron levels were tightly regulated by hepcidin and Tf/TfR via DCYTB and DMT1. These findings provide new insights into circadian iron homeostasis regulation. The diurnal variations in serum iron levels may also have pathophysiological implications for clinical diagnostics related to iron deficiency anemia in pigs. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Physiology of free radicals

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2011-01-01

    Full Text Available Free radicals imply that every atom, molecule, ion, group of atoms, or molecules with one or several non-paired electrons in outer orbital. Among these are: nitrogenoxide (NO•, superoxide-anion-radical (O2•-, hydroxyl radical (OH•, peroxyl radical (ROO•, alcoxyl radical (RO• and hydroperoxyl radical (HO2•. However, reactive oxygen species also include components without non-paired electrons in outer orbital (so-called reactive non-radical agents, such as: singlet oxygen (1O2, peroxynitrite (ONOO-, hydrogen-peroxide (H2O2, hypochloric acid (eg. HOCl and ozone (O3. High concentrations of free radicals lead to the development of oxidative stress which is a precondition for numerous pathological effects. However, low and moderate concentrations of these matter, which occur quite normally during cell metabolic activity, play multiple significant roles in many reactions. Some of these are: regulation of signal pathways within the cell and between cells, the role of chemoattractors and leukocyte activators, the role in phagocytosis, participation in maintaining, changes in the position and shape of the cell, assisting the cell during adaption and recovery from damage (e.g.caused by physical effort, the role in normal cell growth, programmed cell death (apoptosis and cell ageing, in the synthesis of essential biological compounds and energy production, as well as the contribution to the regulation of the vascular tone, actually, tissue vascularization.

  13. Diurnal Cycle of ITCZ Convection during the MJO Suppressed Phase in DYNAMO

    Science.gov (United States)

    Ciesielski, P. E.; Johnson, R. H.; Schubert, W. H.

    2017-12-01

    During the special observing period of the Dynamics of the MJO (DYNAMO) experiment, conducted over the Indian Ocean from 1 October to 30 November 2011, two sounding arrays - one north and one south of the equator, referred to here as the NSA and SSA, respectively - took 4-8 soundings/day. We augment this 3-h dataset with observations of radiation and rainfall to investigate the diurnal cycle of convection during the suppressed phase of the October MJO. During this 14-day period when convection was suppressed over the NSA but prominent over the SSA, the circulation over the sounding arrays could be characterized as a local Hadley cell embedded within a monsoonal flow. Strong rising motion was present within the ITCZ and compensating subsidence over the NSA. A prominent diurnal pulsing of this cell was observed, impacting conditions on both sides of the equator, with the cell running strongest in the early morning hours (05-08 LT) and notably weakening later in the day (17-20LT). The reduction in evening subsidence over the NSA may have assisted the moistening of the low to mid-troposphere there during the pre-onset stage of the MJO. Apparent heating Q1 within the ITCZ exhibits a diurnal evolution from early morning bottom-heavy profiles to weaker daytime top-heavy profiles. Making use of the weak temperature gradient approximation, results suggest that direct radiative effects played a dominant role in controlling diurnal variations of vertical motion and convection within the ITCZ while non-radiative processes were more prominent over the NSA.

  14. Engineering a horseradish peroxidase C stable to radical attacks by mutating multiple radical coupling sites.

    Science.gov (United States)

    Kim, Su Jin; Joo, Jeong Chan; Song, Bong Keun; Yoo, Young Je; Kim, Yong Hwan

    2015-04-01

    Peroxidases have great potential as industrial biocatalysts. In particular, the oxidative polymerization of phenolic compounds catalyzed by peroxidases has been extensively examined because of the advantage of this method over other conventional chemical methods. However, the industrial application of peroxidases is often limited because of their rapid inactivation by phenoxyl radicals during oxidative polymerization. In this work, we report a novel protein engineering approach to improve the radical stability of horseradish peroxidase isozyme C (HRPC). Phenylalanine residues that are vulnerable to modification by the phenoxyl radicals were identified using mass spectrometry analysis. UV-Vis and CD spectra showed that radical coupling did not change the secondary structure or the active site of HRPC. Four phenylalanine (Phe) residues (F68, F142, F143, and F179) were each mutated to alanine residues to generate single mutants to examine the role of these sites in radical coupling. Despite marginal improvement of radical stability, each single mutant still exhibited rapid radical inactivation. To further reduce inactivation by radical coupling, the four substitution mutations were combined in F68A/F142A/F143A/F179A. This mutant demonstrated dramatic enhancement of radical stability by retaining 41% of its initial activity compared to the wild-type, which was completely inactivated. Structure and sequence alignment revealed that radical-vulnerable Phe residues of HPRC are conserved in homologous peroxidases, which showed the same rapid inactivation tendency as HRPC. Based on our site-directed mutagenesis and biochemical characterization, we have shown that engineering radical-vulnerable residues to eliminate multiple radical coupling can be a good strategy to improve the stability of peroxidases against radical attack. © 2014 Wiley Periodicals, Inc.

  15. Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis.

    Science.gov (United States)

    De Boeck, Benoit; Herbert, Nicola M A; Harrington-Frost, Nicole M; Pattenden, Gerald

    2005-01-21

    Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu(3)SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu(3)SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the alpha,beta,gamma,delta-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

  16. Diurnal rhythms in psychological reward functioning in healthy young men: 'Wanting', liking, and learning.

    Science.gov (United States)

    Byrne, Jamie E M; Murray, Greg

    2017-01-01

    A range of evidence suggests that human reward functioning is partly driven by the endogenous circadian system, generating 24-hour rhythms in behavioural measures of reward activation. Reward functioning is multifaceted but literature to date is largely limited to measures of self-reported positive mood states. The aim of this study was to advance the field by testing for hypothesised diurnal variation in previously unexplored components of psychological reward: 'wanting', liking, and learning using subjective and behavioural measures. Risky decision making (automatic Balloon Analogue Risk Task), affective responsivity to positive images (International Affective Pictures System), uncued self-reported discrete emotions, and learning-contingent reward (Iowa Gambling Task) were measured at 10.00 hours, 14.00 hours, and 19.00 hours in a counterbalanced repeated measures design with 50 healthy male participants (aged 18-30). As hypothesised, risky decision making (unconscious 'wanting') and ratings of arousal towards positive images (conscious wanting) exhibited a diurnal waveform with indices highest at 14.00 hours. No diurnal rhythm was observed for liking (pleasure ratings to positive images, discrete uncued positive emotions) or in a learning-contingent reward task. Findings reaffirm that diurnal variation in human reward functioning is most pronounced in the motivational 'wanting' components of reward.

  17. Higher measured than modeled ozone production at increased NOx levels in the Colorado Front Range

    Directory of Open Access Journals (Sweden)

    B. C. Baier

    2017-09-01

    Full Text Available Chemical models must correctly calculate the ozone formation rate, P(O3, to accurately predict ozone levels and to test mitigation strategies. However, air quality models can have large uncertainties in P(O3 calculations, which can create uncertainties in ozone forecasts, especially during the summertime when P(O3 is high. One way to test mechanisms is to compare modeled P(O3 to direct measurements. During summer 2014, the Measurement of Ozone Production Sensor (MOPS directly measured net P(O3 in Golden, CO, approximately 25 km west of Denver along the Colorado Front Range. Net P(O3 was compared to rates calculated by a photochemical box model that was constrained by measurements of other chemical species and that used a lumped chemical mechanism and a more explicit one. Median observed P(O3 was up to a factor of 2 higher than that modeled during early morning hours when nitric oxide (NO levels were high and was similar to modeled P(O3 for the rest of the day. While all interferences and offsets in this new method are not fully understood, simulations of these possible uncertainties cannot explain the observed P(O3 behavior. Modeled and measured P(O3 and peroxy radical (HO2 and RO2 discrepancies observed here are similar to those presented in prior studies. While a missing atmospheric organic peroxy radical source from volatile organic compounds co-emitted with NO could be one plausible solution to the P(O3 discrepancy, such a source has not been identified and does not fully explain the peroxy radical model–data mismatch. If the MOPS accurately depicts atmospheric P(O3, then these results would imply that P(O3 in Golden, CO, would be NOx-sensitive for more of the day than what is calculated by models, extending the NOx-sensitive P(O3 regime from the afternoon further into the morning. These results could affect ozone reduction strategies for the region surrounding Golden and possibly other areas that do not comply with national ozone

  18. Insights into the diurnal cycle of global Earth outgoing radiation using a numerical weather prediction model

    Science.gov (United States)

    Gristey, Jake J.; Chiu, J. Christine; Gurney, Robert J.; Morcrette, Cyril J.; Hill, Peter G.; Russell, Jacqueline E.; Brindley, Helen E.

    2018-04-01

    A globally complete, high temporal resolution and multiple-variable approach is employed to analyse the diurnal cycle of Earth's outgoing energy flows. This is made possible via the use of Met Office model output for September 2010 that is assessed alongside regional satellite observations throughout. Principal component analysis applied to the long-wave component of modelled outgoing radiation reveals dominant diurnal patterns related to land surface heating and convective cloud development, respectively explaining 68.5 and 16.0 % of the variance at the global scale. The total variance explained by these first two patterns is markedly less than previous regional estimates from observations, and this analysis suggests that around half of the difference relates to the lack of global coverage in the observations. The first pattern is strongly and simultaneously coupled to the land surface temperature diurnal variations. The second pattern is strongly coupled to the cloud water content and height diurnal variations, but lags the cloud variations by several hours. We suggest that the mechanism controlling the delay is a moistening of the upper troposphere due to the evaporation of anvil cloud. The short-wave component of modelled outgoing radiation, analysed in terms of albedo, exhibits a very dominant pattern explaining 88.4 % of the variance that is related to the angle of incoming solar radiation, and a second pattern explaining 6.7 % of the variance that is related to compensating effects from convective cloud development and marine stratocumulus cloud dissipation. Similar patterns are found in regional satellite observations, but with slightly different timings due to known model biases. The first pattern is controlled by changes in surface and cloud albedo, and Rayleigh and aerosol scattering. The second pattern is strongly coupled to the diurnal variations in both cloud water content and height in convective regions but only cloud water content in marine

  19. Serum Hydroxyl Radical Scavenging Capacity as Quantified with Iron-Free Hydroxyl Radical Source

    Science.gov (United States)

    Endo, Nobuyuki; Oowada, Shigeru; Sueishi, Yoshimi; Shimmei, Masashi; Makino, Keisuke; Fujii, Hirotada; Kotake, Yashige

    2009-01-01

    We have developed a simple ESR spin trapping based method for hydroxyl (OH) radical scavenging-capacity determination, using iron-free OH radical source. Instead of the widely used Fenton reaction, a short (typically 5 seconds) in situ UV-photolysis of a dilute hydrogen peroxide aqueous solution was employed to generate reproducible amounts of OH radicals. ESR spin trapping was applied to quantify OH radicals; the decrease in the OH radical level due to the specimen’s scavenging activity was converted into the OH radical scavenging capacity (rate). The validity of the method was confirmed in pure antioxidants, and the agreement with the previous data was satisfactory. In the second half of this work, the new method was applied to the sera of chronic renal failure (CRF) patients. We show for the first time that after hemodialysis, OH radical scavenging capacity of the CRF serum was restored to the level of healthy control. This method is simple and rapid, and the low concentration hydrogen peroxide is the only chemical added to the system, that could eliminate the complexity of iron-involved Fenton reactions or the use of the pulse-radiolysis system. PMID:19794928

  20. Diurnal Periodicity in the Supply of Cell Wall Components during Wood Cell Wall Formation

    OpenAIRE

    細尾, 佳宏

    2012-01-01

    This review summarizes recent studies on the diurnal periodicity in wood cell wall formation, with a major focus on those that we have conducted. Differences in the innermost surface of developing secondary walls of differentiating conifer tracheids can be seen from day to night Cellulose microfibrils are clearly evident during the day, and amorphous material containing abundant hemicelluloses is prevalent at night. These findings suggest a diurnal periodicity in the supply of cell wall compo...

  1. Dementia and memory improvement due to histological changes in the brain hippocampus and hormone secretion of brain by lecithin administration

    OpenAIRE

    GU, Yeun-Hwa; YAMASHITA, Takenori; KANG, Ki-Mun

    2014-01-01

    Abstract : In this study, senescence accelerated mice (SAMP8 male, 8w), were used for the study of spatial recognition ability. We studied the effects on the brain hippocampus by administering lecithin (500 mg/kg, po). As compared to sham control group, the peroxy radical was inhibited significant in the lecithin administration group. The brain peroxidized fat level had a tendency to decrease was found in the lecithin group. Also, in the intracerebral serotonin concentration, was increased in...

  2. Tracking the MJO Convection and its Impact on the Diurnal Cycle over the Maritime Continent Using Satellite Observations

    Science.gov (United States)

    Kerns, B. W.; Chen, S. S.

    2017-12-01

    The Indo-Pacific Maritime Continent (MC) is the most active convection center in the tropics, and the most important modes of variability are the diurnal cycle and the Madden-Julian Oscillation (MJO). Previous studies have shown that the MC has strong diurnal variability compared with the rest of the tropics, and the diurnal cycle of convection over the MC is amplified during the passage of an MJO. One outstanding science question is how the passage of the active MJO affects the diurnal cycle. The atmospheric, upper ocean, and land surface forcing factors contributing to the diurnal cycle need to be clarified. In order to address this, large scale precipitation tracking (LPT) is used to identify MJO active and suppressed periods for 2000-2015. To document the diurnal cycle of convection during the active and suppressed periods, TRMM/GPM and mesoscale cloud cluster tracking are used. Finally, the LPT tracking is used to composite the satellite-estimated surface wind, humidity, temperature, cloud cover, and soil moisture over the islands for active versus suppressed MJO periods. In active MJO periods, the diurnal convection in the surrounding marginal seas is enhanced and the diurnal convection over land is decreased. The islands of the MC have greater soil moisture, more cloud cover, and do not warm up as much during the day, leading to a weaker afternoon maximum over land. But how is nocturnal convection over the sea increased? The largest, most mature convective cloud systems are found over the marginal seas in the early morning. This is hypothesized to mainly be a consequence of the longer life cycle of convective systems in the favorable large-scale active MJO. The propagation of the MJO across the MC is facilitated by the enhanced nocturnal deep convection over the sea. In contrast, In the suppressed period the convection is mostly daytime forced convection over land which is locked to the terrain.

  3. Radical transfer between proteins: role of tyrosine, tryptophan and protein peroxyl radicals

    International Nuclear Information System (INIS)

    Irwin, J.A.; Ostdal, H.; Davies, M.J.

    1998-01-01

    Reaction of the Fe(III) forms of the heme proteins myoglobin (Mb) and horseradish peroxidase (HRP) with H 2 O 2 gives rise to high-oxidation-state heme-derived species which can be described as a Fe(IV)-oxo porphyrin radical-cation ('Compound 1'). In the case of Mb, the Fe(IV)-oxo porphyrin radical-cation undergoes rapid electron transfer with the surrounding protein to give protein (globin)-derived radicals and an Fe(lV)-oxo species ('Compound 2'). The globin-derived radicals have been shown to be located at two (or more) sites: Tyr-103 or Trp-14, with the latter radical known to react with oxygen to give a Trp-derived peroxyl radical (Mb-Trp-OO*). With HRP, the Fe(lV)-oxo porphyrin radical-cation carries out two successive one-electron oxidation reactions at the exposed heme edge to give firstly 'Compound 2' [the Fe(lV)oxo species] and then the resting Fe(III) state of the enzyme. n this study we have investigated whether the Trp-14 peroxyl radical from Mb and the Compound 1 and 2 species from HRP (in the absence and presence of free Tyr) can oxidise amino acids, peptides and proteins. Such reactions constitute intermolecular protein-to-protein radical transfer reactions and hence protein chain-oxidation. We have also examined whether these oxidants react with antioxidants. Reaction of these heme-protein derived oxidants with amino acids, proteins and antioxidants has been carried out at room temperature for defined periods of time before freeze-quenching to 77K to halt reaction. The radical species present in the reaction system at the time of freezing were subsequently examined by EPR spectroscopy at 77K. Three free amino acids, Tyr, Trp and Cys (with Cys the least efficient) have been shown to react rapidly with Mb-Trp-OO*, as evidenced by the loss of the characteristic EPR features of Mb-Trp-OO* on inclusion of increasing concentrations of the amino acids. All other amino acids are much less reactive. Evidence has also been obtained for (inefficient) hydrogen

  4. A model for plasma modification of polypropylene using atmospheric pressure discharges

    CERN Document Server

    Dorai, R

    2003-01-01

    Atmospheric pressure plasmas are commonly used to improve the wetting and adhesion properties of polymers. In spite of their use, the mechanisms for achieving these properties are unclear. In this regard, we report on a computational investigation of the gas phase and surface kinetics during humid-air corona treatment of polypropylene (PP) and the resulting modification of its surface properties while varying energy deposition, relative humidity (RH), web speed, and gas temperature. Using results from a global plasma chemistry model validated against experiments, we found that increasing energy deposition increased the densities of alcohol, carbonyl, acid, and peroxy radicals on the PP surface. In doing so, significant amounts of gas phase O sub 3 and N sub x O sub y are produced. Increasing the RH increased the production of peroxy and acid groups, while decreasing those of alcohol and carbonyl groups. Production of O sub 3 decreased while that of HNO sub 3 increased. Increasing the temperature decreased the...

  5. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    It has been reported that a growing number of youngsters from Western Europe are engaging in conflicts motivated by religious and political conflicts in the Middle East. This paper explores the reasons behind this seemingly religious radicalization from the point of view of the youngsters...... youngsters and parents of youngsters who have chosen a radicalized path in life. The paper will shed light on how the sense of and yearning for belonging and recognition have to be taken into account in our understanding of homegrown religious radicalization...

  6. Absence of diurnal variation of C-reactive protein concentrations in healthy human subjects

    Science.gov (United States)

    Meier-Ewert, H. K.; Ridker, P. M.; Rifai, N.; Price, N.; Dinges, D. F.; Mullington, J. M.

    2001-01-01

    BACKGROUND: The concentration of C-reactive protein (CRP) in otherwise healthy subjects has been shown to predict future risk of myocardial infarction and stroke. CRP is synthesized by the liver in response to interleukin-6, the serum concentration of which is subject to diurnal variation. METHODS: To examine the existence of a time-of-day effect for baseline CRP values, we determined CRP concentrations in hourly blood samples drawn from healthy subjects (10 males, 3 females; age range, 21-35 years) during a baseline day in a controlled environment (8 h of nighttime sleep). RESULTS: Overall CRP concentrations were low, with only three subjects having CRP concentrations >2 mg/L. Comparison of raw data showed stability of CRP concentrations throughout the 24 h studied. When compared with cutoff values of CRP quintile derived from population-based studies, misclassification of greater than one quintile did not occur as a result of diurnal variation in any of the subjects studied. Nonparametric ANOVA comparing different time points showed no significant differences for both raw and z-transformed data. Analysis for rhythmic diurnal variation using a method fitting a cosine curve to the group data was negative. CONCLUSIONS: Our data show that baseline CRP concentrations are not subject to time-of-day variation and thus help to explain why CRP concentrations are a better predictor of vascular risk than interleukin-6. Determination of CRP for cardiovascular risk prediction may be performed without concern for diurnal variation.

  7. Reproductive biology of Echinopsis terscheckii (Cactaceae): the role of nocturnal and diurnal pollinators.

    Science.gov (United States)

    Ortega-Baes, P; Saravia, M; Sühring, S; Godínez-Alvarez, H; Zamar, M

    2011-01-01

    The aim of this study was to analyse the reproductive biology of Echinopsis terscheckii, a species endemic to northwest Argentina that has nocturnal flowers. We expected that this species had a generalised pollination system, with moths and diurnal visitors as the primary pollinators. To test this, we studied the floral biology, breeding system and floral visitors of this species and the effectiveness of nocturnal and diurnal visitors. Floral biology was defined based on floral morphology, floral cycle and nectar production of the flowers. The breeding system and relative contributions of diurnal and nocturnal visitors to fruit and seed set were analysed through field experiments. E. terscheckii flowers opened at sunset and closed the following day. The peak of nectar production occurred at midnight. Flowers were determined to be self-incompatible. Moths, bees and birds were identified as floral visitors. Moths were the most frequent visitors at night, whereas bees were the most frequent visitors during the day. Fruit production by diurnal pollinators was less than that by nocturnal pollinators; among all floral visitors, moths were the most effective pollinators. We have demonstrated for the first time that moths are the primary pollinators of columnar cacti of the genus Echinopsis. Our results suggest that moths might be important pollinators of columnar cactus species with nocturnal flowers in the extra-tropical deserts of South America. © 2010 German Botanical Society and The Royal Botanical Society of the Netherlands.

  8. Diurnal Patterns of Heterotrophic and Autotrophic Soil Respiration in Maize and Switchgrass Bioenergy Cropping Systems

    Science.gov (United States)

    von Haden, A.; Marin-Spiotta, E.; Jackson, R. D.; Kucharik, C. J.

    2016-12-01

    A high proportion of carbon lost from terrestrial ecosystems occurs via soil CO2 respiration. Soil respiration is comprised of two contrasting sources: heterotrophic respiration (RH) from the decomposition of organic matter and autotrophic respiration (RA) from plant root metabolism. Since the two sources of soil respiration vary widely in their origin, the controls of each source are also likely to differ. However, the challenge of partitioning soil respiration sources in situ has limited our mechanistic understanding of RH and RA. Our objective was to evaluate the in situ diurnal controls of RH and RA in maize (Zea mays L.) and switchgrass (Panicum virgatum L.) bioenergy cropping systems. We hypothesized that both RH and RA would follow diurnal soil temperature trends, but that RA would also respond to diel patterns of photosynthetically active radiation (PAR). We also expected that diurnal soil respiration patterns would vary significantly within the growing season. We evaluated our hypothesis with six diurnal soil respiration campaigns during the 2015 and 2016 growing seasons at Arlington, WI, USA. RH showed clear oscillating diel trends, typically peaking in the mid-afternoon when near-surface soil temperatures were highest. Diurnal RA patterns were more nuanced than RH, but were generally highest in the late afternoon and showed the most pronounced diel trends during peak growing season in July. RA also tended to spike in concert with PAR, but this effect was much more prominent in maize than switchgrass. Continuing efforts will attempt to quantitatively separate the effects of soil temperature and PAR on RA.

  9. Prenatal exposure to diurnal temperature variation and early childhood pneumonia.

    Science.gov (United States)

    Zeng, Ji; Lu, Chan; Deng, Qihong

    2017-04-01

    Childhood pneumonia is one of the leading single causes of mortality and morbidity in children worldwide, but its etiology still remains unclear. We investigate the association between childhood pneumonia and exposure to diurnal temperature variation (DTV) in different timing windows. We conducted a prospective cohort study of 2,598 children aged 3-6 years in Changsha, China. The lifetime prevalence of pneumonia was assessed by a questionnaire administered by the parents. Individual exposure to DTV during both prenatal and postnatal periods was estimated. Logic regression models was used to examine the association between childhood pneumonia and DTV exposure in terms of odds ratios (OR) and 95% confidence interval (CI). Lifetime prevalence of childhood pneumonia in preschool children in Changsha was high up to 38.6%. We found that childhood pneumonia was significantly associated with prenatal DTV exposure, with adjusted OR (95%CI) =1.19 (1.02-1.38), particularly during the second trimester. However, childhood pneumonia not associated with postnatal DTV exposure. Sensitivity analysis indicated that boys are more susceptible to the pneumonia risk of diurnal temperature variation than girls. We further observed that the prevalence of childhood pneumonia was decreased in recent years as DTV shrinked. Early childhood pneumonia was associated with prenatal exposure to the diurnal temperature variation (DTV) during pregnancy, particularly in the second trimester, which suggests fetal origin of childhood pneumonia. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Diurnal variation of precipitation over the Carolina Sandhills region

    Indian Academy of Sciences (India)

    State Climate Office of North Carolina, Raleigh, NC 27695-8208, USA. ∗ e-mail: ... of the weather forecast models experience problems in accounting for the ... effect of vegetation and soil contrasts on thermally induced flow is ... Sandhills; diurnal convection; heat flux gradients; cloud–radiation interaction. J. Earth Syst. Sci.

  11. Sexual orientation and diurnal cortisol patterns in a cohort of U.S. young adults.

    Science.gov (United States)

    Austin, S Bryn; Rosario, Margaret; McLaughlin, Katie A; Roberts, Andrea L; Gordon, Allegra R; Sarda, Vishnudas; Missmer, Stacey; Anatale-Tardiff, Laura; Scherer, Emily A

    2016-07-01

    Sexual minorities in the United States are at elevated risk of bullying, discrimination, and violence victimization, all stressors that have been linked to psychological and behavioral stress responses including depressive and anxious symptoms and substance use. Acute and chronic stressors may also elicit physiologic stress responses, including changes in the regulation of the hypothalamic-pituitary-adrenocortical (HPA) axis. Few studies, however, have examined the relationship between minority sexual orientation and diurnal cortisol patterns. The present study included 1670 young adults ages 18-32 years (69% female, 31% male) from the Growing Up Today Study, a prospective cohort of U.S. youth. Participants provided five saliva samples over one day to estimate diurnal cortisol patterns. Sexual orientation groups included: completely heterosexual with no same-sex partners (referent), completely heterosexual with same-sex partners/mostly heterosexual, and gay/lesbian/bisexual. Covariates included perceived stress and stressful life events in the past month. Sex-stratified multilevel models of log-transformed cortisol values were used to model diurnal cortisol patterns, and generalized estimating equations were used to model area under the curve (AUC), both with respect to ground (AUCg) and increase (AUCi). Among females, sexual minorities reported significantly more stressful life events in the past month than their heterosexual counterparts. In adjusted multilevel models, sexual orientation was not significantly associated with diurnal cortisol patterns or with AUCg or AUCi in either females or males. There were no significant interactions between sexual orientation and stressful life events. Time-varying negative mood was significantly associated with higher cortisol levels across the day for both female and male participants, after adjusting for all covariates. This study from a large cohort of U.S. young adults did not detect a relationship between sexual

  12. Laparoscopic radical trachelectomy.

    Science.gov (United States)

    Rendón, Gabriel J; Ramirez, Pedro T; Frumovitz, Michael; Schmeler, Kathleen M; Pareja, Rene

    2012-01-01

    The standard treatment for patients with early-stage cervical cancer has been radical hysterectomy. However, for women interested in future fertility, radical trachelectomy is now considered a safe and feasible option. The use of minimally invasive surgical techniques to perform this procedure has recently been reported. We report the first case of a laparoscopic radical trachelectomy performed in a developing country. The patient is a nulligravid, 30-y-old female with stage IB1 adenocarcinoma of the cervix who desired future fertility. She underwent a laparoscopic radical trachelectomy and bilateral pelvic lymph node dissection. The operative time was 340 min, and the estimated blood loss was 100mL. There were no intraoperative or postoperative complications. The final pathology showed no evidence of residual disease, and all pelvic lymph nodes were negative. At 20 mo of follow-up, the patient is having regular menses but has not yet attempted to become pregnant. There is no evidence of recurrence. Laparoscopic radical trachelectomy with pelvic lymphadenectomy in a young woman who desires future fertility may also be an alternative technique in the treatment of early cervical cancer in developing countries.

  13. Diurnal Patterns and Correlates of Older Adults' Sedentary Behavior.

    Directory of Open Access Journals (Sweden)

    Jelle Van Cauwenberg

    Full Text Available Insights into the diurnal patterns of sedentary behavior and the identification of subgroups that are at increased risk for engaging in high levels of sedentary behavior are needed to inform potential interventions for reducing older adults' sedentary time. Therefore, we examined the diurnal patterns and sociodemographic correlates of older adults' sedentary behavior(s.Stratified cluster sampling was used to recruit 508 non-institutionalized Belgian older adults (≥ 65 years. Morning, afternoon, evening and total sedentary time was assessed objectively using accelerometers. Specific sedentary behaviors, total sitting time and sociodemographic attributes were assessed using an interviewer-administered questionnaire.Participants self-reported a median of 475 (Q1-Q3 = 383-599 minutes/day of total sitting time and they accumulated a mean of 580 ± 98 minutes/day of accelerometer-derived sedentary time. Sedentary time was lowest during the morning and highest during the evening. Older participants were as sedentary as younger participants during the evening, but they were more sedentary during daytime. Compared to married participants, widowers were more sedentary during daytime. Younger participants (< 75 years, men and the higher educated were more likely to engage in (high levels of sitting while driving a car and using the computer. Those with tertiary education viewed 29% and 22% minutes/day less television compared to those with primary or secondary education, respectively. Older participants accumulated 35 sedentary minutes/day more than did younger participants and men accumulated 32 sedentary minutes/day more than did women.These findings highlight diurnal variations and potential opportunities to tailor approaches to reducing sedentary time for subgroups of the older adult population.

  14. Diurnal variations in the UV albedo of arctic snow

    Directory of Open Access Journals (Sweden)

    O. Meinander

    2008-11-01

    Full Text Available The relevance of snow for climate studies is based on its physical properties, such as high surface reflectivity. Surface ultraviolet (UV albedo is an essential parameter for various applications based on radiative transfer modeling. Here, new continuous measurements of the local UV albedo of natural Arctic snow were made at Sodankylä (67°22'N, 26°39'E, 179 m a.s.l. during the spring of 2007. The data were logged at 1-min intervals. The accumulation of snow was up to 68 cm. The surface layer thickness varied from 0.5 to 35 cm with the snow grain size between 0.2 and 2.5 mm. The midday erythemally weighted UV albedo ranged from 0.6 to 0.8 in the accumulation period, and from 0.5 to 0.7 during melting. During the snow melt period, under cases of an almost clear sky and variable cloudiness, an unexpected diurnal decrease of 0.05 in albedo soon after midday, and recovery thereafter, was detected. This diurnal decrease in albedo was found to be asymmetric with respect to solar midday, thus indicating a change in the properties of the snow. Independent UV albedo results with two different types of instruments confirm these findings. The measured temperature of the snow surface was below 0°C on the following mornings. Hence, the reversible diurnal change, evident for ~1–2 h, could be explained by the daily metamorphosis of the surface of the snowpack, in which the temperature of the surface increases, melting some of the snow to liquid water, after which the surface freezes again.

  15. The effects of the diurnal atmospheric variability on entry, descent and landing on Mars

    Directory of Open Access Journals (Sweden)

    Marčeta D.

    2014-01-01

    Full Text Available Landing on Mars is extremely challenging task due to the fact that the Martian atmosphere is the most hostile environment in the Solar system to perform the entry, descent and landing (EDL process, because it is thick enough to create substantial heating of the entry vehicle but not thick enough to reduce its velocity to the one necessary for safe landing. Beside this, the atmosphere is very dynamic mainly due to high eccentricity of the Martian orbit, obliquity of the orbital to the equatorial plane and close alignment of the winter solstice and the orbital perihelion. Although seasonal variations of atmospheric parameters are significantly larger than the diurnal, it is very important to analyze diurnal cycles as they can significantly change vertical and horizontal atmospheric profiles in very short time intervals. This can present a serious threat to missions which have very precise timings and specific requirements such as the requirement for the daytime landing to enable ground images acquisition during the descent and landing phase. A 3-degrees-of-freedom trajectory integration routine was combined with the Mars Global Reference Atmospheric Model (Mars-GRAM to identify the dependence of the EDL profiles on the diurnal cycles of atmospheric parameters throughout the Martian year. The obtained results show that the influence of the diurnal cycles is the largest at the equator and decreases relatively symmetrically towards the poles with a slightly stronger influence in the northern hemisphere. Also, there is a significant influence of the orbital position of Mars on the effect of diurnal atmospheric variations which causes that, around the orbital perihelion and winter solstice, there is some kind of inversion of the dependance of optimal entry timing on latitude of the landing site comparing to the rest of the Martian year. [Projekat Ministarstva nauke Republike Srbije, br. 176002

  16. Diurnal variability of inner-shelf circulation in the lee of a cape under upwelling conditions

    Science.gov (United States)

    Lamas, L.; Peliz, A.; Dias, J.; Oliveira, P. B.; Angélico, M. M.; Castro, J. J.; Fernandes, J. N.; Trindade, A.; Cruz, T.

    2017-07-01

    The nearshore circulation in the lee of a cape under upwelling conditions was studied using in-situ data from 3 consecutive summers (2006-2008). Focus was given to a period between 20 July and 04 August 2006 to study the diurnal variability of the cross-shelf circulation. This period was chosen because it had a steady upwelling-favourable wind condition modulated by a diurnal cycle much similar to sea breeze. The daily variability of the observed cross-shelf circulation consisted of three distinct periods: a morning period with a 3-layer vertical structure with onshore velocities at mid-depth, a mid-day period where the flow is reversed and has a 2-layer structure with onshore velocities at the surface and offshore flow below, and, lastly, in the evening, a 2-layer period with intensified offshore velocities at the surface and onshore flow at the bottom. The observed cross-shelf circulation showed a peculiar vertical shape and diurnal variability different from several other systems described in literature. We hypothesize that the flow reversal of the cross-shelf circulation results as a response to the rapid change of the wind magnitude and direction at mid-day with the presence of the cape north of the mooring site influencing this response. A numerical modelling experiment exclusively forced by winds simulated successfully most of the circulation at the ADCP site, especially the mid-day reversal and the evening's upwelling-type structure. This supports the hypothesis that the cross-shelf circulation at diurnal timescales is mostly wind-driven. By analysing the 3D circulation in the vicinity of Cape Sines we came to the conclusion that the diurnal variability of the wind and the flow interaction with topography are responsible for the circulation variability at the ADCP site, though only a small region in the south of the cape showed a similar diurnal variability. The fact that the wind diurnally undergoes relaxation and intensification strongly affects the

  17. Radical Evil

    Directory of Open Access Journals (Sweden)

    Carlos Manrique

    2007-12-01

    Full Text Available There is an aporia in Kant’s analysis of evil: he defines radical evilas an invisible disposition of the will, but he also demands an inferential connection between visible evil actions and this invisible disposition. This inference,however, undermines the radical invisibility of radical evil according to Kant’s own definition of the latter. Noting how this invisibility of moral worth is a distinctive feature of Kant’s approach to the moral problem, the paper then asks why, in the Groundwork, he nonetheless forecloses a question about evil that seems to be consistent with this approach. It is argued that to account for this aporia and this foreclosure, one has to interrogate the way in which the category of religion orients Kant’s incipient philosophy of history in Die Religion.

  18. Seasonal and diurnal variations of particulate nitrate and organic matter at the IfT research station Melpitz

    Directory of Open Access Journals (Sweden)

    L. Poulain

    2011-12-01

    Full Text Available Ammonium nitrate and several organic compounds such as dicarboxylic acids (e.g. succinic acid, glutaric acid, some Polycyclic Aromatic Hydrocarbon (PAHs or some n-alkanes are semi-volatile. The transition of these compounds between the gas and particulate phase may significantly change the aerosol particles radiative properties, the heterogeneous chemical properties, and, naturally, the total particulate mass concentration. To better assess these time-dependent effects, three intensive field experiments were conducted in 2008–2009 at the Central European EMEP research station Melpitz (Germany using an Aerodyne Aerosol Mass Spectrometer (AMS. Data from all seasons highlight organic matter as being the most important particulate fraction of PM1 in summer (59% while in winter, the nitrate fraction was more prevalent (34.4%. The diurnal variation of nitrate always showed the lowest concentration during the day while its concentration increased during the night. This night increase of nitrate concentration was higher in winter (ΔNO3 = 3.6 μg m−3 than in summer (ΔNO3 = 0.7 μg m−3. The variation in particulate nitrate was inherently linked to the gas-to-particle-phase equilibrium of ammonium nitrate and the dynamics of the atmosphere during day. The results of this study suggest that during summer nights, the condensation of HNO3 and NH3 on pre-existing particles represents the most prevalent source of nitrate, whereas during winter, nighttime chemistry is the predominant source of nitrate. During the summer 2008's campaign, a clear diurnal evolution in the oxidation state of the organic matter became evident (Organic Mass to Organic Carbon ratio (OM/OC ranging from 1.65 during night to 1.80 during day and carbon oxidation state (OSc from −0.66 to −0.4, which could be correlated to hydroxyl radical (OH and ozone

  19. Effects of sleeve gastrectomy on the composition and diurnal oscillation of gut microbiota related to the metabolic improvements.

    Science.gov (United States)

    Shao, Yikai; Shen, Qiwei; Hua, Rong; Evers, Simon S; He, Kai; Yao, Qiyuan

    2018-03-07

    Disruptions of the composition and diurnal oscillation of gut microbiota are involved in metabolic disorders. To identify alterations in both the composition and diurnal oscillation of gut microbiota after high-fat diet (HFD) feeding and sleeve gastrectomy (SG) related to host metabolic status. University laboratories. Twenty-one 6-week-old male C57 BL/6 J mice were randomized on an HFD (n = 14) or normal chow (NC, n = 7). After 14 weeks of feeding, HFD-induced obese mice were randomized to receive either SG or sham surgery (n = 7 in each group). Fecal samples were collected every 6 hours over a 24-hour period at 14 weeks of NC or HFD feeding and subsequently 8 weeks after surgery. The composition and diurnal oscillation of gut microbiota were characterized using next-generation Illumina sequencing of 16 S rDNA. HFD feeding led to adiposity, disrupted composition, and impaired diurnal oscillation of gut microbiota relative to NC. After surgery, SG mice had considerable weight loss, improved glucose tolerance, and insulin sensitivity compared with sham mice. SG restored the reduced richness and disruptions in the composition of gut microbiota. The diminished diurnal oscillation of gut microbiota was improved after SG. SG not only changed the disrupted composition of gut microbiota toward that of NC feeding, but also improved the dampened diurnal oscillation of gut microbiota due to HFD feeding. Copyright © 2018 American Society for Bariatric Surgery. Published by Elsevier Inc. All rights reserved.

  20. Diurnal Variation in the Basal Emission Rate of Isoprene

    Science.gov (United States)

    Jennifer Funk; Clive G. Jones; Christine J. Baker; Heather M. Fuller; Christian P. Giardina; Manuel T. Lerdua

    2003-01-01

    Isoprene is emitted from numerous plant species and profoundly influences tropospheric chemistry. Due to the short lifetime of isoprene in the atmosphere, developing an understanding of emission patterns at small time scales is essential for modeling regional atmospheric chemistry processes. Previous studies suggest that diurnal fluctuations in isoprene emission may be...

  1. Radical constructivism: Between realism and solipsism

    Science.gov (United States)

    Martínez-Delgado, Alberto

    2002-11-01

    This paper criticizes radical constructivism of the Glasersfeld type, pointing out some contradictions between the declared radical principles and their theoretical and practical development. These contradictions manifest themselves in a frequent oscillation between solipsism and realism, despite constructivist claims to be an anti-realist theory. The paper also points out the contradiction between the relativism of the radical constructivist principles and the constructivist exclusion of other epistemological or educational paradigms. It also disputes the originality and importance of the radical constructivist paradigm, suggesting the idea of an isomorphism between radical constructivist theory and contemplative realism. In addition, some pedagogical and scientific methodological aspects of the radical constructivist model are examined. Although radical constructivism claims to be a rational theory and advocates deductive thinking, it is argued that there is no logical deductive connection between the radical principles of constructivism and the radical constructivist ideas about scientific research and learning. The paper suggests the possibility of an ideological substratum in the construction and hegemonic success of subjective constructivism and, finally, briefly advances an alternative realist model to epistemological and educational radical constructivism.

  2. Fluorinated cellular polypropylene films with time-invariant excellent surface electret properties by post-treatments

    International Nuclear Information System (INIS)

    An Zhenlian; Mao Mingjun; Yao Junlan; Zhang Yewen; Xia Zhongfu

    2010-01-01

    In this work, to improve the electret properties of cellular polypropylene films, they were fluorinated and post-treated with nitrous oxide and by isothermal crystallization. Surface electret properties of the samples were investigated by thermally stimulated discharge current measurements, and their compositions and structures were analysed by attenuated total reflection infrared spectroscopy and wide angle x-ray diffraction, respectively. Time-dependent deterioration of surface electret properties was observed for the fluorinated samples without the nitrous oxide post-treatment. However, deterioration did not occur for the fluorinated samples post-treated with nitrous oxide, and time-invariant excellent surface electret properties or deep surface charge traps were obtained by the combined post-treatments of the fluorinated samples with nitrous oxide and by isothermal crystallization. Based on the analyses of composition and structure of the treated samples, the deterioration was clarified to be due to a trace of oxygen in the reactive mixture, which led to the formation of peroxy RO 2 . radicals in the fluorinated surface layer. The time invariability of surface electret properties was owing to the rapid termination of the peroxy RO 2 . radicals by nitrous oxide. And the deep surface charge traps resulted from the isothermal crystallization treatment which led to an increase in the efficient charging interface between the crystallite and amorphous region and its property change.

  3. Spectroscopic studies of neutral and chemically oxidized species of β-carotene, lycopene and norbixin in CH{sub 2}Cl{sub 2}: Fluorescence from intermediate compounds

    Energy Technology Data Exchange (ETDEWEB)

    Alwis, D.D.D.H [Department of Chemistry, The Open University of Sri Lanka, Nawala (Sri Lanka); Department of Chemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka); Chandrika, U.G. [Department of Biochemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka); Jayaweera, P.M., E-mail: pradeep@sjp.ac.lk [Department of Chemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka)

    2015-02-15

    Radical cations, dications and oxidized intermediate species of three carotenoids, namely, β-carotene, lycopene and norbixin, were generated in CH{sub 2}Cl{sub 2} solutions via chemical oxidation using anhydrous FeCl{sub 3}. UV–vis, fluorescence and fluorescence-excitation spectroscopic studies were performed to understand and compare the nature of intermediate species generated during the chemical oxidation process and subsequent degradation. The intense emission observed at 550 nm can be assigned to the S{sub 2}→S{sub 0} (1{sup 1}B{sub u}→1{sup 1}A{sub g}) transition of the carotenoid molecules. The 350 nm excitation during the oxidation process for β-carotene, lycopene and norbixin exhibit intense fluorescence peaks at 492 nm, 493 nm and 500 nm, respectively. These peaks are assigned to intermediate peroxy/epoxy compounds of the three molecules that are formed with molecular oxygen prior to the formation of oxidized short-chain stable compounds. - Highlights: • Fluorescence and UV–vis studies on β-carotene, lycopene and norbixin. • Oxidation, induced by FeCl{sub 3} in CH{sub 2}Cl{sub 2} shows blue shifted fluorescence peaks. • Fluorescence peaks were assigned to intermediate peroxy/epoxy forms of carotenoids. • The D0→D3 transition of radical cations are observed in the near IR region.

  4. Simulated precipitation diurnal cycles over East Asia using different CAPE-based convective closure schemes in WRF model

    Science.gov (United States)

    Yang, Ben; Zhou, Yang; Zhang, Yaocun; Huang, Anning; Qian, Yun; Zhang, Lujun

    2018-03-01

    Closure assumption in convection parameterization is critical for reasonably modeling the precipitation diurnal variation in climate models. This study evaluates the precipitation diurnal cycles over East Asia during the summer of 2008 simulated with three convective available potential energy (CAPE) based closure assumptions, i.e. CAPE-relaxing (CR), quasi-equilibrium (QE), and free-troposphere QE (FTQE) and investigates the impacts of planetary boundary layer (PBL) mixing, advection, and radiation on the simulation by using the weather research and forecasting model. The sensitivity of precipitation diurnal cycle to PBL vertical resolution is also examined. Results show that the precipitation diurnal cycles simulated with different closures all exhibit large biases over land and the simulation with FTQE closure agrees best with observation. In the simulation with QE closure, the intensified PBL mixing after sunrise is responsible for the late-morning peak of convective precipitation, while in the simulation with FTQE closure, convective precipitation is mainly controlled by advection cooling. The relative contributions of different processes to precipitation formation are functions of rainfall intensity. In the simulation with CR closure, the dynamical equilibrium in the free troposphere still can be reached, implying the complex cause-effect relationship between atmospheric motion and convection. For simulations in which total CAPE is consumed for the closures, daytime precipitation decreases with increased PBL resolution because thinner model layer produces lower convection starting layer, leading to stronger downdraft cooling and CAPE consumption. The sensitivity of the diurnal peak time of precipitation to closure assumption can also be modulated by changes in PBL vertical resolution. The results of this study help us better understand the impacts of various processes on the precipitation diurnal cycle simulation.

  5. Diurnal changes in flavonoids

    International Nuclear Information System (INIS)

    Veit, M.; Bilger, W.; Mühlbauer, T.; Brummet, W.; Winter, K.

    1996-01-01

    Field studies of a tropical tree, Anacardium excelsum, and a northern hemisphere high altitude fern, Cryptogramma crispa, revealed marked diurnal changes in soluble flavonoid content of leaves and fronds, respectively. The flavonoid content increased during the morning and decreased during the afternoon. In plants of C. crispa covered with UV-B absorbing filters, the flavonoid content remained at a constant level throughout the day/night cycle. Upon removal of UV-B absorbing filters (at night), the flavonoid content increased the next morning in a fashion similar to that observed in control plants maintained without filters. Decreases in photosystem II photochemical efficiency upon exposure of C. crispa to natural daylight were similar in plants previously covered with UV-B absorbing filters and in control plants, probably owing to the observed ability of plants to rapidly accumulate UV-B protective flavonoids. (author)

  6. Radiation balance at the surface in the city of São Paulo, Brazil: diurnal and seasonal variations

    NARCIS (Netherlands)

    Ferreira, M.J.; Oliveira, de A.P.; Soares, J.; Codato, G.; Wilde Barbaro, E.; Escobedo, J.F.

    2012-01-01

    The main goal of this work is to describe the diurnal and seasonal variations of the radiation balance components at the surface in the city of São Paulo based on observations carried out during 2004. Monthly average hourly values indicate that the amplitudes of the diurnal cycles of net radiation

  7. Combined diurnal variations of discharge and hydrochemistry of the Isunnguata Sermia outlet, Greenland Ice Sheet

    Science.gov (United States)

    Graly, Joseph; Harrington, Joel; Humphrey, Neil

    2017-05-01

    In order to examine daily cycles in meltwater routing and storage in the Isunnguata Sermia outlet of the Greenland Ice Sheet, variations in outlet stream discharge and in major element hydrochemistry were assessed over a 6-day period in July 2013. Over 4 days, discharge was assessed from hourly photography of the outlet from multiple vantages, including where midstream naled ice provided a natural gauge. pH, electrical conductivity, suspended sediment, and major element and anion chemistry were measured in samples of stream water collected every 3 h.Photography and stream observations reveal that although river width and stage have only slight diurnal variation, there are large diurnal changes in discharge shown by the doubling in width of what we term the active channel, which is characterized by large standing waves and fast flow. The concentration of dissolved solutes follows a sinusoidal diurnal cycle, except for large and variable increases in dissolved solutes during the stream's waning flow. Solute concentrations vary by ˜ 30 % between diurnal minima and maxima. Discharge maxima and minima lag temperature and surface melt by 3-7 h; diurnal solute concentration minima and maxima lag discharge by 3-6 h.This phase shift between discharge and solute concentration suggests that during high flow, water is either encountering more rock material or is stored in longer contact with rock material. We suggest that expansion of a distributed subglacial hydrologic network into seldom accessed regions during high flow could account for these phenomena, and for a spike of partial silicate reaction products during waning flow, which itself suggests a pressure threshold-triggered release of stored water.

  8. Differential arousal regulation by prokineticin 2 signaling in the nocturnal mouse and the diurnal monkey.

    Science.gov (United States)

    Zhou, Qun-Yong; Burton, Katherine J; Neal, Matthew L; Qiao, Yu; Kanthasamy, Anumantha G; Sun, Yanjun; Xu, Xiangmin; Ma, Yuanye; Li, Xiaohan

    2016-08-18

    The temporal organization of activity/rest or sleep/wake rhythms for mammals is regulated by the interaction of light/dark cycle and circadian clocks. The neural and molecular mechanisms that confine the active phase to either day or night period for the diurnal and the nocturnal mammals are unclear. Here we report that prokineticin 2, previously shown as a circadian clock output molecule, is expressed in the intrinsically photosensitive retinal ganglion cells, and the expression of prokineticin 2 in the intrinsically photosensitive retinal ganglion cells is oscillatory in a clock-dependent manner. We further show that the prokineticin 2 signaling is required for the activity and arousal suppression by light in the mouse. Between the nocturnal mouse and the diurnal monkey, a signaling receptor for prokineticin 2 is differentially expressed in the retinorecipient suprachiasmatic nucleus and the superior colliculus, brain projection targets of the intrinsically photosensitive retinal ganglion cells. Blockade with a selective antagonist reveals the respectively inhibitory and stimulatory effect of prokineticin 2 signaling on the arousal levels for the nocturnal mouse and the diurnal monkey. Thus, the mammalian diurnality or nocturnality is likely determined by the differential signaling of prokineticin 2 from the intrinsically photosensitive retinal ganglion cells onto their retinorecipient brain targets.

  9. Salvage robotic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Samuel D Kaffenberger

    2014-01-01

    Full Text Available Failure of non-surgical primary treatment for localized prostate cancer is a common occurrence, with rates of disease recurrence ranging from 20% to 60%. In a large proportion of patients, disease recurrence is clinically localized and therefore potentially curable. Unfortunately, due to the complex and potentially morbid nature of salvage treatment, radical salvage surgery is uncommonly performed. In an attempt to decrease the morbidity of salvage therapy without sacrificing oncologic efficacy, a number of experienced centers have utilized robotic assistance to perform minimally invasive salvage radical prostatectomy. Herein, we critically evaluate the existing literature on salvage robotic radical prostatectomy with a focus on patient selection, perioperative complications and functional and early oncologic outcomes. These results are compared with contemporary and historical open salvage radical prostatectomy series and supplemented with insights we have gained from our experience with salvage robotic radical prostatectomy. The body of evidence by which conclusions regarding the efficacy and safety of robotic salvage radical prostatectomy can be drawn comprises fewer than 200 patients with limited follow-up. Preliminary results are promising and some outcomes have been favorable when compared with contemporary open salvage prostatectomy series. Advantages of the robotic platform in the performance of salvage radical prostatectomy include decreased blood loss, short length of stay and improved visualization. Greater experience is required to confirm the long-term oncologic efficacy and functional outcomes as well as the generalizability of results achieved at experienced centers.

  10. Study of a Functional Polymorphism in the PER3 Gene and Diurnal Preference in a Colombian Sample

    Science.gov (United States)

    Perea, Claudia S; Niño, Carmen L; López-León, Sandra; Gutiérrez, Rafael; Ojeda, Diego; Arboleda, Humberto; Camargo, Andrés; Adan, Ana; Forero, Diego A

    2014-01-01

    Polymorphisms in human clock genes have been evaluated as potential factors influencing circadian phenotypes in several populations. There are conflicting results for the association of a VNTR in the PER3 gene and diurnal preference in different studies. The objective of this study was to investigate the association between diurnal preference and daytime somnolence with the PER3 VNTR polymorphism (rs57875989) in healthy subjects from Colombia, a Latin American population.A total of 294 undergraduate university students from Bogotá, Colombia participated in this study. Two validated self-report questionnaires, the Composite Scale of Morningness (CSM) and the Epworth Sleep Scale (ESS) were used to assess diurnal preference and daytime somnolence, respectively. Individuals were genotyped for the PER3 VNTR using conventional PCR. Statistical comparisons were carried out with PLINK and SNPStats programs. The PER3 VNTR polymorphism was not associated with either diurnal preference or daytime somnolence in this population. No significant differences in mean scores for those scales were found between PER3 VNTR genotypes. In addition, there were no differences in allelic or genotypic frequencies between chronotype categories. This is consistent with several negative findings in other populations, indicating that the proposed influence of this polymorphism in diurnal preference, and related endophenotypes of neuropsychiatric importance, needs further clarification. This is the first report of molecular genetics of human circadian phenotypes in a Spanish-speaking population. PMID:24860629

  11. Diurnal and annual variations of meteor rates at the arctic circle

    Directory of Open Access Journals (Sweden)

    W. Singer

    2004-01-01

    Full Text Available Meteors are an important source for (a the metal atoms of the upper atmosphere metal layers and (b for condensation nuclei, the existence of which are a prerequisite for the formation of noctilucent cloud particles in the polar mesopause region. For a better understanding of these phenomena, it would be helpful to know accurately the annual and diurnal variations of meteor rates. So far, these rates have been little studied at polar latitudes. Therefore we have used the 33 MHz meteor radar of the ALOMAR observatory at 69° N to measure the meteor rates at this location for two full annual cycles. This site, being within 3° of the Arctic circle, offers in addition an interesting capability: The axis of its antenna field points (almost towards the North ecliptic pole once each day of the year. In this particular viewing direction, the radar monitors the meteoroid influx from (almost the entire ecliptic Northern hemisphere. We report on the observed diurnal variations (averaged over one month of meteor rates and their significant alterations throughout the year. The ratio of maximum over minimum meteor rates throughout one diurnal cycle is in January and February about 5, from April through December 2.3±0.3. If compared with similar measurements at mid-latitudes, our expectation, that the amplitude of the diurnal variation is to decrease towards the North pole, is not really borne out. Observations with the antenna axis pointing towards the North ecliptic pole showed that the rate of deposition of meteoric dust is substantially larger during the Arctic NLC season than the annual mean deposition rate. The daylight meteor showers of the Arietids, Zeta Perseids, and Beta Taurids supposedly contribute considerably to the June maximum of meteor rates. We note, though, that with the radar antenna pointing as described above, all three meteor radiants are close to the local horizon but all three radiants were detected.

  12. Diurnal Transcriptome and Gene Network Represented through Sparse Modeling in Brachypodium distachyon

    Directory of Open Access Journals (Sweden)

    Satoru Koda

    2017-11-01

    Full Text Available We report the comprehensive identification of periodic genes and their network inference, based on a gene co-expression analysis and an Auto-Regressive eXogenous (ARX model with a group smoothly clipped absolute deviation (SCAD method using a time-series transcriptome dataset in a model grass, Brachypodium distachyon. To reveal the diurnal changes in the transcriptome in B. distachyon, we performed RNA-seq analysis of its leaves sampled through a diurnal cycle of over 48 h at 4 h intervals using three biological replications, and identified 3,621 periodic genes through our wavelet analysis. The expression data are feasible to infer network sparsity based on ARX models. We found that genes involved in biological processes such as transcriptional regulation, protein degradation, and post-transcriptional modification and photosynthesis are significantly enriched in the periodic genes, suggesting that these processes might be regulated by circadian rhythm in B. distachyon. On the basis of the time-series expression patterns of the periodic genes, we constructed a chronological gene co-expression network and identified putative transcription factors encoding genes that might be involved in the time-specific regulatory transcriptional network. Moreover, we inferred a transcriptional network composed of the periodic genes in B. distachyon, aiming to identify genes associated with other genes through variable selection by grouping time points for each gene. Based on the ARX model with the group SCAD regularization using our time-series expression datasets of the periodic genes, we constructed gene networks and found that the networks represent typical scale-free structure. Our findings demonstrate that the diurnal changes in the transcriptome in B. distachyon leaves have a sparse network structure, demonstrating the spatiotemporal gene regulatory network over the cyclic phase transitions in B. distachyon diurnal growth.

  13. Muoniated acyl and thioacyl radicals

    International Nuclear Information System (INIS)

    McKenzie, Iain; Brodovitch, Jean-Claude; Ghandi, Khashayar; Percival, Paul W.

    2006-01-01

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and 14 N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and 14 N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy

  14. Muoniated acyl and thioacyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, Iain [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Brodovitch, Jean-Claude [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Ghandi, Khashayar [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Percival, Paul W. [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada)]. E-mail: percival@sfu.ca

    2006-03-31

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and {sup 14}N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and {sup 14}N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy.

  15. Muonium and muonic radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Geeson, D.; Symons, M.C.R.

    1985-01-01

    An energetic positive muon which is injected in a liquid sample of substrate molecules (S) creates an ionization track consisting of substrate cations (S + ) and electrons. Near the end of this track the muon may combine with an electron to form muonium (Mu) which is observable in inert liquids, but which reacts by addition to form a radical. Alternatively, the electron can add to S to form S - , which then combines with the muon to form the radical. Furthermore, instead of ending up in Mu or in a radical the muon may stay in a diamagnetic environment as a solvated muon, or as a muon substituting a proton in a molecule. Of interest in these schemes are the mechanisms and rates of formation of muonated radicals and in particular the rate constants for their reactions to products. Investigations are based on the observation of Mu and the radical by means of the μSR technique in transverse magnetic fields. (Auth.)

  16. High-resolution magnetic resonance imaging of diurnal variations in rheumatoid arthritis

    International Nuclear Information System (INIS)

    Nicholas, R.S.

    2000-09-01

    This thesis describes work that uses high-resolution magnetic resonance imaging (MRI) to give an insight into the aetiology of rheumatoid arthritis (RA) with particular reference to characterising diurnal changes in joint stiffness in the metacarpophalangeal (MCP) joints. The study was performed on a targeted 1.1 T MRI scanner using specialised sequences, including 3-dimensional gradient-echo, magnetisation transfer (MT) and multiple gradient-echo. These enabled tissue-dependent parameters such as MT ratio, effective transverse relaxation time (T 2 *) and proton density (ρ) to be made. Preliminary reproducibility studies of the MRI measurements showed that MT ratio could be measured in vivo to an accuracy of better than 8%. This variation is due to repositioning errors and physiological changes. Equivalent variations in T 2 * and p were 23% and 16% respectively; these poorer figures were contributed to errors in fitting the data to an exponential curve. An MRI study monitoring the diurnal variation of stiffness in RA demonstrated better characterisation of the disease state using MT and T 2 * maps compared to standard gradient-echo imaging. Features associated with arthritis such as bone erosions and cysts were found in the control group and an MT age dependence was measured in the soft tissue on the superior margin of the joint. This region also exhibited a diurnal variation in MT ratio for the patient group. The interaction between this region of tissue and other structures (e.g. the sheath of extensor tendon) within the joint could be a possible cause of joint stiffness. An incidental finding of this study was that Ritchie joint score also showed a diurnal variation. This study has demonstrated that MRI can be used to make reproducible measurements of the diurnal variations in RA. The indication is that the soft tissues in the superior aspect of the joint may be responsible for the symptom of joint stiffness in the MCP joints and future studies should be

  17. diurnal climatic pressure on haematology and blood biochemistry of ...

    African Journals Online (AJOL)

    Twelve 2.5-year-old West African Dward (WAD) sheep consisting of eight (8) ewes and four (4) rams with mean body weight 19.4kg were used to study the effects of diurnal (morning and afternoon) climatic variations on the haematological and biochemical responses in WAD sheep. The animals were randomly assigned to ...

  18. Diurnal modulation and sources of variation affecting ventricular repolarization in Warmblood horses

    DEFF Research Database (Denmark)

    Pedersen, Philip Juul; Moeller, Sine B.; Madsen, Mette Flethøj

    2014-01-01

    Te) are used as repolarization markers. To support the use of these markers in horses, we sought to describe the possible influence of the environment, time of day, day-to-day effects, T wave conformation, age, body weight (BW), and horse-to-horse variation on repolarization measurements. ANIMALS: 12 Warmblood...... affecting these intervals. RESULTS: Differences between individual horses were the largest source of repolarization variability although the environment had a significant effect on repolarization as well. Diurnal variation affected both the RR interval and the repolarization markers. The QT, QTc and Tp......, diurnal variation, the environment, and T wave conformation. These factors must be considered if markers of equine repolarization are used diagnostically....

  19. Leghemoglobin-derived radicals. Evidence for multiple protein-derived radicals and the initiation of peribacteroid membrane damage

    DEFF Research Database (Denmark)

    Moreau, S; Davies, Michael Jonathan; Mathieu, C

    1996-01-01

    , with the consequent generation of lipid-derived radicals. The formation of such radicals may result in the depletion of membrane antioxidants and the initiation of lipid peroxidation. This transfer of damage from the heme center via the protein surface to neighboring membranes may be of considerable biological......-derived phenoxyl radical present at Tyr-133 in the soybean protein and Tyr-138 in the lupin protein. To obtain further information on these protein radicals and their potential interaction with the physiologically important peribacteroid membrane (which surrounds the microsymbiont in vivo), EPR spin trapping......); these radicals may be side chain- or alpha-carbon-derived, their exact sites have not been determined. Some of these radicals are on the protein surface and may be key intermediates in the formation of protein dimers. These radicals have been shown to be capable of reacting with peribacteroid membrane fractions...

  20. Studies of radiation-produced radicals and radical ions. Progress report, June 1, 1981-August 31, 1982

    International Nuclear Information System (INIS)

    Williams, T.F.

    1982-01-01

    The discovery and characterization of novel radical ions produced by the γ irradiation of solids continues to be a fertile field for investigation. This Progress Report describes the generation and ESR identification of several new paramagnetic species, some of which have long been sought as important intermediates in radiation chemistry. We have also contributed to a general theoretical problem in ESR spectroscopy. Solid-state studies of electron attachment reactions, both non-dissociative and dissociative, reveal interesting structural and chemical information about the molecular nature of these processes for simple compounds. In particular, ESR measurements of the spin distribution in the products allow a fairly sharp distinction to be drawn between radical anions and radical-anion pairs or adducts. Dimer radical anion formation can also take place but the crystal structure plays a role in this process, as expected. Some radical anions undergo photolysis to give radical-anion pairs which may then revert back to the original radical anion by a thermal reaction. The chemistry of these reversible processes is made more intricate by a competing reaction in which the radical abstracts a hydrogen atom from a neighboring molecule. However, the unraveling of this complication has also served to extend our knowledge of the role of quantum tunneling in chemical reactions. The results of this investigation testify to the potential of solid-state techniques for the study of novel and frangible radical ions. Progress in this field shows no sign of abating, as witness the recent discovery of perfluorocycloalkane radical anions and alkane radical cations

  1. Seasonal and diurnal variability of N{sub 2}O emissions from a full-scale municipal wastewater treatment plant

    Energy Technology Data Exchange (ETDEWEB)

    Daelman, Matthijs R.J., E-mail: m.r.j.daelman@tudelft.nl [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands); Department of Biosystems engineering, Ghent University, Coupure links 653, 9000 Gent (Belgium); Voorthuizen, Ellen M. van [Royal HaskoningDHV, P.O. Box 151, 6500AD Nijmegen (Netherlands); Dongen, Udo G.J.M. van [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands); Volcke, Eveline I.P. [Department of Biosystems engineering, Ghent University, Coupure links 653, 9000 Gent (Belgium); Loosdrecht, Mark C.M. van [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands)

    2015-12-01

    During nitrogen removal in conventional activated sludge processes, nitrous oxide can be emitted. With a global warming potential of 298 CO{sub 2}-equivalents it is an important greenhouse gas that affects the sustainability of wastewater treatment. The present study reports nitrous oxide emission data from a 16 month monitoring campaign on a full-scale municipal wastewater treatment. The emission demonstrated a pronounced diurnal and seasonal variability. This variability was compared with the variability of a number of process variables that are commonly available on a municipal wastewater treatment plant. On a seasonal timescale, the occurrence of peaks in the nitrite concentration correlated strongly with the emission. The diurnal trend of the emission coincided with the diurnal trend of the nitrite and nitrate concentrations in the tank, suggesting that suboptimal oxygen concentrations may induce the production of nitrous oxide during both nitrification and denitrification. This study documents an unprecedented dataset that could serve as a reference for further research. - Highlights: • Unique dataset of long-term nitrous oxide emission from activated sludge tanks • Emission exhibited pronounced diurnal variability, superimposed on seasonal trend • Seasonal nitrous oxide emission trend correlated with daily nitrite peaks • Emission’s diurnal trend suggests suboptimal oxygen concentrations as cause.

  2. Muonium-containing vinyl radicals

    International Nuclear Information System (INIS)

    Rhodes, C.J.; Symons, M.C.R.; Roduner, E.; Heming, M.

    1987-01-01

    Exposure of trimethylsilylacetylene and bis(trimethylsilyl)acetylene to positive muons gave radicals whose muon-electron hyperfine coupling constants establish that the corresponding vinyl radicals were formed. (author)

  3. Radicals in arithmetic

    NARCIS (Netherlands)

    W.J. Palenstijn (Willem Jan)

    2014-01-01

    htmlabstractLet K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement

  4. The Role of Nitric Oxide in Memory is Modulated by Diurnal Time

    Directory of Open Access Journals (Sweden)

    Stephanie L. Gage

    2014-04-01

    Full Text Available Nitric oxide (NO is thought to play an important neuromodulatory role in the olfactory system. This modulation has been suggested to be particularly important for olfactory learning and memory in the antennal lobe (the primary olfactory network in invertebrates. We are using the hawkmoth, Manduca sexta, to further investigate the role of NO in olfactory memory. Recent findings suggest that NO affects short-term memory traces and that NO concentration fluctuates with the light cycle. This gives rise to the hypothesis that NO may be involved in the connection between memory and circadian rhythms. In this study, we explore the role of diurnal time and NO in memory by altering the time of day when associative-olfactory conditioning is performed. We find a strong effect of NO on short-term memory, and two surprising effects of diurnal time. We find that (1 at certain time points, NO affects longer traces of memory in addition to short-term memory, and (2 when conditioning is performed close to the light cycle switches—both from light to dark and dark to light—NO does not significantly affect memory at all. These findings suggest an intriguing functional role for NO in olfactory conditioning that is modulated as a function of diurnal time.

  5. Diurnal variations of summertime precipitation over the Tibetan Plateau in relation to orographically-induced regional circulations

    International Nuclear Information System (INIS)

    Liu Xiaodong; Bai Aijuan; Liu Changhai

    2009-01-01

    The diurnal patterns of variation of summertime precipitation over the Tibetan Plateau were first investigated using the TRMM multi-satellite precipitation analysis product for five summer seasons (i.e. June to August for 2002-2006). Both hourly precipitation amount and precipitation frequency exhibit pronounced daily variability with an overall late-afternoon-evening maximum and a dominant morning minimum. A notable exception is the prevalent nocturnal maximum around the periphery of the Plateau. In terms of the normalized harmonic amplitude, the diurnal signal shows significant regional contrast with the strongest manifestation over the central Plateau and the weakest near the periphery. This remarkable spatial dependence in daily rainfall cycles is clear evidence of orographic and heterogeneous land-surface impacts on convective development. Using six-hourly NCEP FNL data, we then examined the diurnal variability in the atmospheric circulation and thermodynamics in this region. The results show that the Plateau heats (cools) the overlying atmosphere during the day (night) more than the surrounding areas, and as a consequence a relatively stronger confluent circulation in this region occurs during the day than during the night, consistent with the diurnal rainfall cycles. Moreover, the regions with large low-level convergence and upper-level divergence correspond to the strong diurnal rainfall variations. The reversed daily alterations of convergence-divergence patterns in the vicinity of the Plateau edges are in agreement with the observed nighttime rainfall peak therein. This study further demonstrates the importance of the Tibetan Plateau in regulating regional circulation and precipitation.

  6. Solar flare location effect on the spectral characteristics of the diurnal anisotropy of cosmic ray intensity

    Energy Technology Data Exchange (ETDEWEB)

    Yadava, R S; Kumar, S; Naqvi, T N [Aligarh Muslim Univ. (India)

    1977-01-01

    The spectral parameters of the diurnal anisotropy of cosmic ray intensity are studied separately for days where the solar flares have occurred on the western limb as well as on the eastern limb of the solar disc for both nucleonic as well as mesonic components of the cosmic rays. It is observed that the diurnal amplitude of the cosmic ray intensity in space is larger for days where solar flares have occurred on the western limb of the solar disc as compared to the days where solar flares have occurred on the eartern limb of the solar disc. This is true in both nucleonic as well as mesonic components of the cosmic ray intensity. The average value of the direction in space of diurnal anisotropy in local asymptotic time for various stations is almost same and is observed at around the same hours for flares which occur on the western as well as eastern limb of the solar disc. When these results are compared with the direction of the diurnal anisotropy in space on quiet days, it is found that the direction of the diurnal anisotropy on days where solar flares have occurred on the western limb as well as eastern limb of the solar disc is earlier in comparison to quiet days. This phase shift towards earlier hours is about three hours for nucleonic as well as mesonic components of the cosmic rays intensity. The variation of the rigidity exponent observed on different types of days for the nucleonic component has also been discussed.

  7. Factors affecting diurnal stem contraction in young Douglas-fir

    Science.gov (United States)

    Warren D. Devine; Constance Harrington

    2011-01-01

    Diurnal fluctuation in a tree's stem diameter is a function of daily growth and of the tree's water balance, as water is temporarily stored in the relatively elastic outer cambial and phloem tissues. On a very productive site in southwestern Washington, U.S.A we used recording dendrometers to monitor stem diameter fluctuations of Douglas-fir at plantation...

  8. Multiple free-radical scavenging capacity in serum

    Science.gov (United States)

    Oowada, Shigeru; Endo, Nobuyuki; Kameya, Hiromi; Shimmei, Masashi; Kotake, Yashige

    2012-01-01

    We have developed a method to determine serum scavenging-capacity profile against multiple free radical species, namely hydroxyl radical, superoxide radical, alkoxyl radical, alkylperoxyl radical, alkyl radical, and singlet oxygen. This method was applied to a cohort of chronic kidney disease patients. Each free radical species was produced with a common experimental procedure; i.e., uv/visible-light photolysis of free-radical precursor/sensitizer. The decrease in free-radical concentration by the presence of serum was quantified with electron spin resonance spin trapping method, from which the scavenging capacity was calculated. There was a significant capacity change in the disease group (n = 45) as compared with the healthy control group (n = 30). The percent values of disease’s scavenging capacity with respect to control group indicated statistically significant differences in all free-radical species except alkylperoxyl radical, i.e., hydroxyl radical, 73 ± 12% (p = 0.001); superoxide radical, 158 ± 50% (p = 0.001); alkoxyl radical, 121 ± 30% (p = 0.005); alkylperoxyl radical, 123 ± 32% (p>0.1); alkyl radical, 26 ± 14% (p = 0.001); and singlet oxygen, 57 ± 18% (p = 0.001). The scavenging capacity profile was illustrated using a radar chart, clearly demonstrating the characteristic change in the disease group. Although the cause of the scavenging capacity change by the disease state is not completely understood, the profile of multiple radical scavenging capacities may become a useful diagnostic tool. PMID:22962529

  9. Preoperative radiochemotherapy and radical surgery in comparison with radical surgery alone

    International Nuclear Information System (INIS)

    Mohr, C.; Schettler, D.; Bohndorf, W.

    1994-01-01

    A multicentric, randomized study of squamous cell carcinoma (SCC) of the oral cavity and the oropharynx has been undertaken by DOeSAK. The results after radical surgery alone have been compared with the results of combined preoperative radiochemotherapy followed by radical surgery. Patients with primary (biopsy proven) SCC of the oral cavity or the oropharynx with tumor nodes metastasis (TNM) stages T2-4, N0-3, M0 were included in the study. A total of 141 patients were treated by radical surgery alone, whereas 127 patients were treated by radical surgery preceded by preoperative radiochemotherapy. The pre-operative treatment consisted of conventionally fractioned irradiation on the primary and the regional lymph nodes with a total dose of 36 Gy (5 x 2 Gy per week) and low-dose cisplatin chemotherapy with 5 x 12.5 mg cisplatin per m 2 of body surface during the first week of treatment. Radical surgery according to be DOeSAK definitions (DOeSAK, 1982) was performed after a delay of 10-14 days. During the follow-up period, 28.2% of all patients suffered from locoregional recurrence, and 27.2% of the patients died. The percentages were higher after radical surgery alone for locoregional recurrence (31% and 15.6%) and for death (28% and 18.6%). The life-table analysis showed improved survival rates of 4.5% after 1 year and 8.3% after 2 years in the group of patients treated with combined therapy. The demonstrated improvement appeared to be significant with the Gehan-Wilcoxon test as well as with the log rank test below a P value of 5%. (au) (29 refs.)

  10. Radicals in arithmetic

    NARCIS (Netherlands)

    Palenstijn, Willem Jan

    2014-01-01

    Let K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement group. We give

  11. Radicalization as a Vector: Exploring Non-Violent and Benevolent Processes of Radicalization.

    Directory of Open Access Journals (Sweden)

    Ken Reidy

    2018-03-01

    Full Text Available Successful radicalization posits three outcomes: extremism, terrorism or both. As these are undesirable, radicalization is understood as wholly malevolent and governments work to prevent and/or stop it. Nonetheless, a handful of scholars have recognized that the same radicalization process which results in either outcome may, theoretically at least, also have beneficial outcomes such as environmental awareness or human rights. This article explores one such outcome. Based on interviews with British Muslim aid workers (n=6 operating in Jihadist conflict zones post Arab spring and using constructivist grounded theory, it illustrates how the research participants radicalized to humanitarianism which resulted in them assisting the most plighted of Muslims by deploying to the most wanton of areas: ones commonly referred to as Jihadist conflict zones. Evidently, these destinations are shared with Jihadists and given the array of other observable similarities (socio-demographics and [pre-]mobilization behaviours, these morally opposed groups become conflated by the security services. This is further compounded by the fact that Jihadists manipulate and/or impersonate aid workers so as to funnel people and funds. To distinguish both, this article documents the benevolent pathway of the research participants and juxtaposes it to scholarly knowledge on Jihadist pathways. Socialization was revealed to be the key distinguishing feature rather than descriptive risk factors (such as ideology or moral outrage because the process of radicalization was not found to be the start of the radicalized pathway. It concludes that benevolently radicalized Islamic groups constitute an effective means of pathway divergence for particular typologies by offering an attractive and prosocial alternative to Jihadism. This strengths-based preventative approach (“what’s right” takes the form of a community-centric market competitor to Jihadism rather than a problem

  12. The Influence of Roof Material on Diurnal Urban Canyon Breathing

    Science.gov (United States)

    Abuhegazy, Mohamed; Yaghoobian, Neda

    2017-11-01

    Improvements in building energy use, air quality in urban canyons and in general urban microclimates require understanding the complex interaction between urban morphology, materials, climate, and inflow conditions. Review of the literature indicates that despite a long history of valuable urban microclimate studies, more comprehensive approaches are needed to address energy, and heat and flow transport in urban areas. In this study, a more comprehensive simulation of the diurnally varying street canyon flow and associated heat transport is numerically investigated, using Large-eddy Simulation (LES). We use computational modeling to examine the impact of diurnal variation of the heat fluxes from urban surfaces on the air flow and temperature distribution in street canyons with a focus on the role of roof materials and their temperature footprints. A detailed building energy model with a three-dimensional raster-type geometry provides urban surface heat fluxes as thermal boundary conditions for the LES to determine the key aero-thermodynamic factors that affect urban street ventilation.

  13. Diurnal variations of serum erythropoietin at sea level and altitude

    DEFF Research Database (Denmark)

    Klausen, T; Poulsen, T D; Fogh-Andersen, N

    1996-01-01

    in 2, 3 diphosphoglycerate. After 64 h at altitude, six of the nine subjects had down-regulated their serum-EPO concentrations so that median values were three times above those at sea level. These six subjects had significant diurnal variations of serum-EPO concentration at sea level; the nadir......This study tested the hypothesis that the diurnal variations of serum-erythropoietin concentration (serum-EPO) observed in normoxia also exist in hypoxia. The study also attempted to investigate the regulation of EPO production during sustained hypoxia. Nine subjects were investigated at sea level...... and during 4 days at an altitude of 4350 m. Median sea level serum-EPO concentration was 6 (range 6-13) U.l-1. Serum-EPO concentration increased after 18 and 42 h at altitude, [58 (range 39-240) and 54 (range 36-340) U.l-1, respectively], and then decreased after 64 and 88 h at altitude [34 (range 18...

  14. SMLTM simulations of the diurnal tide: comparison with UARS observations

    Directory of Open Access Journals (Sweden)

    R. A. Akmaev

    1997-09-01

    Full Text Available Wind and temperature observations in the mesosphere and lower thermosphere (MLT from the Upper Atmosphere Research Satellite (UARS reveal strong seasonal variations of tides, a dominant component of the MLT dynamics. Simulations with the Spectral mesosphere/lower thermosphere model (SMLTM for equinox and solstice conditions are presented and compared with the observations. The diurnal tide is generated by forcing specified at the model lower boundary and by in situ absorption of solar radiation. The model incorporates realistic parameterizations of physical processes including various dissipation processes important for propagation of tidal waves in the MLT. A discrete multi-component gravity-wave parameterization has been modified to account for seasonal variations of the background temperature. Eddy diffusion is calculated depending on the gravity-wave energy deposition rate and stability of the background flow. It is shown that seasonal variations of the diurnal-tide amplitudes are consistent with observed variations of gravity-wave sources in the lower atmosphere.

  15. Diurnal variation in rates of calcification and carbonate sediment dissolution in Florida Bay

    Science.gov (United States)

    Yates, K.K.; Halley, R.B.

    2006-01-01

    Water quality and circulation in Florida Bay (a shallow, subtropical estuary in south Florida) are highly dependent upon the development and evolution of carbonate mud banks distributed throughout the Bay. Predicting the effect of natural and anthropogenic perturbations on carbonate sedimentation requires an understanding of annual, seasonal, and daily variations in the biogenic and inorganic processes affecting carbonate sediment precipitation and dissolution. In this study, net calcification rates were measured over diurnal cycles on 27 d during summer and winter from 1999 to 2003 on mud banks and four representative substrate types located within basins between mud banks. Substrate types that were measured in basins include seagrass beds of sparse and intermediate density Thalassia sp., mud bottom, and hard bottom communities. Changes in total alkalinity were used as a proxy for calcification and dissolution. On 22 d (81%), diurnal variation in rates of net calcification was observed. The highest rates of net carbonate sediment production (or lowest rates of net dissolution) generally occurred during daylight hours and ranged from 2.900 to -0.410 g CaCO3 m-2 d-1. The lowest rates of carbonate sediment production (or net sediment dissolution) occurred at night and ranged from 0.210 to -1.900 g CaCO3 m -2 night-1. During typical diurnal cycles, dissolution during the night consumed an average of 29% of sediment produced during the day on banks and 68% of sediment produced during the day in basins. Net sediment dissolution also occurred during daylight, but only when there was total cloud cover, high turbidity, or hypersalinity. Diurnal variation in calcification and dissolution in surface waters and surface sediments of Florida Bay is linked to cycling of carbon dioxide through photosynthesis and respiration. Estimation of long-term sediment accumulation rates from diurnal rates of carbonate sediment production measured in this study indicates an overall average

  16. Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

    International Nuclear Information System (INIS)

    Barnabas, M.V.; Trifunac, A.D.

    1994-01-01

    Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

  17. Does the diurnal pattern of enteric methane emissions from dairy cows change over time?

    Science.gov (United States)

    Bell, M J; Craigon, J; Saunders, N; Goodman, J R; Garnsworthy, P C

    2018-02-22

    Diet manipulation and genetic selection are two important mitigation strategies for reducing enteric methane (CH4) emissions from ruminant livestock. The aim of this study was to assess whether the diurnal pattern of CH4 emissions from individual dairy cows changes over time when cows are fed on diets varying in forage composition. Emissions of CH4 from 36 cows were measured during milking in an automatic (robotic) milking station in three consecutive feeding periods, for a total of 84 days. In Periods 1 and 2, the 36 cows were fed a high-forage partial mixed ration (PMR) containing 75% forage, with either a high grass silage or high maize silage content. In Period 3, cows were fed a commercial PMR containing 69% forage. Cows were offered PMR ad libitum plus concentrates during milking and CH4 emitted by individual cows was sampled during 8662 milkings. A linear mixed model was used to assess differences among cows, feeding periods and time of day. Considerable variation was observed among cows in daily mean and diurnal patterns of CH4 emissions. On average, cows produced less CH4 when fed on the commercial PMR in feeding Period 3 than when the same cows were fed on high-forage diets in feeding Periods 1 and 2. The average diurnal pattern for CH4 emissions did not significantly change between feeding periods and as lactation progressed. Emissions of CH4 were positively associated with dry matter (DM) intake and forage DM intake. It is concluded that if the management of feed allocation remains constant then the diurnal pattern of CH4 emissions from dairy cows will not necessarily alter over time. A change in diet composition may bring about an increase or decrease in absolute emissions over a 24-h period without significantly changing the diurnal pattern unless management of feed allocation changes. These findings are important for CH4 monitoring techniques that involve taking measurements over short periods within a day rather than complete 24-h observations.

  18. Shift work parameters and disruption of diurnal cortisol production in female hospital employees.

    Science.gov (United States)

    Hung, Eleanor Wai Man; Aronson, Kristan J; Leung, Michael; Day, Andrew; Tranmer, Joan

    2016-01-01

    Shift work is associated with an increased risk of cardiovascular diseases (CVD). Disruption of cortisol production is a potential underlying mechanism. This study explored the associations of diurnal quantity and pattern of cortisol production in relation to (1) current shift work status (exclusive day versus rotating days and nights), (2) years of past shift work and (3) parameters of rotating shift work (timing, length and intensity). Female hospital employees (160 day workers and 168 rotating shift workers) from southeastern Ontario, Canada, participated in a cross-sectional study. Participants completed a baseline questionnaire and measures of body height, weight, and waist circumference were taken. Midstream urine samples were collected over two separate 24-hour periods to measure creatinine-adjusted cortisol. Total diurnal cortisol production and pattern were described with two measures of the area under the curve. The effect of shift work on cortisol was modeled using multivariable linear regression analyses. Cortisol production in day workers and shift workers on their day shift were similar; however, shift workers on the night shift had flatter diurnal cortisol curves and produced less cortisol. This suggests that night work is associated with an acute attenuation of cortisol production.

  19. Diurnal cycle of the dust instantaneous direct radiative forcing over the Arabian Peninsula

    KAUST Repository

    Osipov, Sergey

    2015-08-27

    In this study we attempted to better quantify radiative effects of dust over the Arabian Peninsula and their dependence on input parameters. For this purpose we have developed a stand-alone column radiation transport model coupled with the Mie, T-matrix and geometric optics calculations and driven by reanalysis meteorological fields and atmospheric composition. Numerical experiments were carried out for a wide range of aerosol optical depths, including extreme values developed during the dust storm on 18–20 March 2012. Comprehensive ground-based observations and satellite retrievals were used to estimate aerosol optical properties, validate calculations and carry out radiation closure. The broadband surface albedo, fluxes at the bottom and top of the atmosphere as well as instantaneous dust radiative forcing were estimated both from the model and observations. Diurnal cycle of the shortwave instantaneous dust direct radiative forcing was studied for a range of aerosol and surface characteristics representative of the Arabian Peninsula. Mechanisms and parameters responsible for diurnal variability of the radiative forcing were evaluated. We found that intrinsic variability of the surface albedo and its dependence on atmospheric conditions, along with anisotropic aerosol scattering, are mostly responsible for diurnal effects.

  20. The diurnal order of the image in Dracula

    Directory of Open Access Journals (Sweden)

    Claudio Vescia Zanini

    2015-02-01

    Full Text Available the article analyses images from Bram Stoker’s novel Dracula having as a main theoretical frame the Diurnal regime of the Image, proposed by Gilbert Durand in The Anthropological Structures of the Imaginary and presented by Durand himself as the “order of antithesis”. By presenting the main kinds of images proposed by Durand in binary pairs (theriomorphic and diæretic, nyctomorphic and spectacular, catamorphic and ascensional, the analysis proposed here aims at staying in tune with both the theoretical approach and the context of production of the novel. Victorian England at the end of the nineteenth century was a time of anxieties, fears and doubts, recurrent in the Victorian cultural production as a whole and well-depicted in Dracula, a work where binary oppositions also seem to be recurrent: life and death, good and evil, moral and desire, among others. The focus is on how the main character is perceived by the other characters, which ultimately affects our perception as readers. Images related to animals, colors, weapons and movements are also included in the analysis. The conclusion points out that the Diurnal Order is a prolific and coherent approach towards an understanding of Bram Stoker’s vampire novel.

  1. Termite mounds harness diurnal temperature oscillations for ventilation.

    Science.gov (United States)

    King, Hunter; Ocko, Samuel; Mahadevan, L

    2015-09-15

    Many species of millimetric fungus-harvesting termites collectively build uninhabited, massive mound structures enclosing a network of broad tunnels that protrude from the ground meters above their subterranean nests. It is widely accepted that the purpose of these mounds is to give the colony a controlled microclimate in which to raise fungus and brood by managing heat, humidity, and respiratory gas exchange. Although different hypotheses such as steady and fluctuating external wind and internal metabolic heating have been proposed for ventilating the mound, the absence of direct in situ measurement of internal air flows has precluded a definitive mechanism for this critical physiological function. By measuring diurnal variations in flow through the surface conduits of the mounds of the species Odontotermes obesus, we show that a simple combination of geometry, heterogeneous thermal mass, and porosity allows the mounds to use diurnal ambient temperature oscillations for ventilation. In particular, the thin outer flutelike conduits heat up rapidly during the day relative to the deeper chimneys, pushing air up the flutes and down the chimney in a closed convection cell, with the converse situation at night. These cyclic flows in the mound flush out CO2 from the nest and ventilate the colony, in an unusual example of deriving useful work from thermal oscillations.

  2. Using diurnal temperature signals to infer vertical groundwater-surface water exchange

    Science.gov (United States)

    Irvine, Dylan J.; Briggs, Martin A.; Lautz, Laura K.; Gordon, Ryan P.; McKenzie, Jeffrey M.; Cartwright, Ian

    2017-01-01

    Heat is a powerful tracer to quantify fluid exchange between surface water and groundwater. Temperature time series can be used to estimate pore water fluid flux, and techniques can be employed to extend these estimates to produce detailed plan-view flux maps. Key advantages of heat tracing include cost-effective sensors and ease of data collection and interpretation, without the need for expensive and time-consuming laboratory analyses or induced tracers. While the collection of temperature data in saturated sediments is relatively straightforward, several factors influence the reliability of flux estimates that are based on time series analysis (diurnal signals) of recorded temperatures. Sensor resolution and deployment are particularly important in obtaining robust flux estimates in upwelling conditions. Also, processing temperature time series data involves a sequence of complex steps, including filtering temperature signals, selection of appropriate thermal parameters, and selection of the optimal analytical solution for modeling. This review provides a synthesis of heat tracing using diurnal temperature oscillations, including details on optimal sensor selection and deployment, data processing, model parameterization, and an overview of computing tools available. Recent advances in diurnal temperature methods also provide the opportunity to determine local saturated thermal diffusivity, which can improve the accuracy of fluid flux modeling and sensor spacing, which is related to streambed scour and deposition. These parameters can also be used to determine the reliability of flux estimates from the use of heat as a tracer.

  3. Youth De-Radicalization: A Canadian Framework

    Directory of Open Access Journals (Sweden)

    Hafal (Haval Ahmad

    2017-09-01

    Full Text Available Youth radicalization leading to violence has become a growing fear among Canadians, as terrorist attacks are carried out in Western states. Although Canada has suffered relatively fewer acts of violence, this fear has intensified and a de-radicalization strategy is needed in the Canadian context. In a qualitative case study methodology, interviews were conducted with school counsellors, religious leaders, and academics to explore solutions to youth radicalization. Youth de-radicalization approaches from the United Kingdom were analyzed and found that community-based initiatives were missing from programming. Social identity theory is used to explain that youth join radicalized groups to feel a sense of belonging and have to be provided an alternative and moderate group identity to de-radicalize. This study found youth de-radicalization in Canada is best served through a community collaboration approach.

  4. Daytime passerine migrants over the Sahara — are these diurnal ...

    African Journals Online (AJOL)

    The landing tendency (sink rate) correlated negatively with the tail wind component. Transect counts on the ground revealed very low proportions of diurnal migrants, not matching the relatively high densities of passerine migration during the day, and a high correlation between transect density of nocturnal migrants and ...

  5. Diurnal variations of serum erythropoietin at sea level and altitude

    DEFF Research Database (Denmark)

    Klausen, T; Poulsen, T D; Fogh-Andersen, N

    1996-01-01

    in 2, 3 diphosphoglycerate. After 64 h at altitude, six of the nine subjects had down-regulated their serum-EPO concentrations so that median values were three times above those at sea level. These six subjects had significant diurnal variations of serum-EPO concentration at sea level; the nadir...

  6. Effects of light on NO3 uptake in small forested streams: diurnal and day-to-day variations

    Energy Technology Data Exchange (ETDEWEB)

    Mulholland, Patrick J [ORNL

    2006-08-01

    We investigated the effects of autotrophy on short-term variations in nutrient dynamics by measuring diurnal and day-to-day variations in light level, primary productivity, and NO{sub 3}{sup -} uptake during early and late spring in 2 forested streams, the East and West Forks of Walker Branch in eastern Tennessee, USA. We predicted that diurnal and day-to-day variations in NO{sub 3}{sup -} uptake rate would be larger in the West Fork than in the East Fork in early spring because of higher rates of primary productivity resulting from a more stable substratum in the West Fork. We also predicted minimal diurnal variations in both streams in late spring after forest leaf emergence when light levels and primary productivity are uniformly low. Reach-scale rates of gross primary production (GPP) were determined using the diurnal dissolved O{sub 2} change technique, and reach-scale rates of NO{sub 3}{sup -} uptake were determined by tracer {sup 15}N-NO{sub 3}{sup -} additions. In the West Fork, significant diurnal and day-to-day variations in NO{sub 3}{sup -} uptake were related to variations in light level and primary productivity in early spring but not in late spring, consistent with our predictions. In early spring, West Fork NO{sub 3}{sup -} uptake rates were 2 to 3x higher at midday than during predawn hours and 50% higher on 2 clear days than on an overcast day several days earlier. In the East Fork, early spring rates of GPP were 4 to 5x lower than in the West Fork and diurnal and day-to-day variations in NO{sub 3}{sup -} uptake rates were <30%, considerably lower than in the West Fork. However, diurnal variations in NO{sub 3}{sup -} uptake rates were greater in late spring in the East Fork, possibly because of diurnal variation in water temperature. Our results indicate the important role of autotrophs in nutrient uptake in some forested streams, particularly during seasons when forest vegetation is dormant and light levels are relatively high. Our results also

  7. Concerted diurnal patterns in riverine nutrient concentrations and physical conditions

    International Nuclear Information System (INIS)

    Scholefield, David; Le Goff, Thierry; Braven, Jim; Ebdon, Les; Long, Terry; Butler, Mark

    2005-01-01

    Several long-term sets of hourly nitrate concentration data were obtained through deployment of a nitrate sensor in an upper reach of the River Taw, a small moorland-fed river in the South West of the UK. Examination of the data obtained during periods of low flow and the absence of rainfall in the catchment revealed the presence of marked diurnal cycles, which were in concert and negatively correlated with diurnal cycles in water temperature. After verifying that these cycles were natural, an intensive 90-h field monitoring campaign was conducted, in which river water was sampled hourly and immediately analysed in the laboratory for molybdate-reactive phosphorus (P), nitrate, nitrite, ammonium, and pH. Coincident measurements of water temperature, river discharge and solar energy were also taken at, or close to, the site. All measurements revealed diurnal patterns and all patterns were concerted. The cycles of P, nitrate, nitrite, and discharge had two maxima and minima per 24 h, while the cycle of water temperature had one, with a maximum at 20.00 and a minimum at 08.00. The amplitudes of the cycles of P and nitrate were each about 30% of the mean values, while the amplitude of the nitrite cycle was as great as 80% of the mean value on occasions. Both biological and physical mechanisms for the cycling could operate through water temperature and/or incident radiation to account for the observed phenomenon, but there remains uncertainty of which is the more important. The observations have important implications for both the accuracy of pollution assessment in rivers and the physiological rhythms of riverine organisms

  8. Concerted diurnal patterns in riverine nutrient concentrations and physical conditions.

    Science.gov (United States)

    Scholefield, David; Le Goff, Thierry; Braven, Jim; Ebdon, Les; Long, Terry; Butler, Mark

    2005-05-15

    Several long-term sets of hourly nitrate concentration data were obtained through deployment of a nitrate sensor in an upper reach of the River Taw, a small moorland-fed river in the South West of the UK. Examination of the data obtained during periods of low flow and the absence of rainfall in the catchment revealed the presence of marked diurnal cycles, which were in concert and negatively correlated with diurnal cycles in water temperature. After verifying that these cycles were natural, an intensive 90-h field monitoring campaign was conducted, in which river water was sampled hourly and immediately analysed in the laboratory for molybdate-reactive phosphorus (P), nitrate, nitrite, ammonium, and pH. Coincident measurements of water temperature, river discharge and solar energy were also taken at, or close to, the site. All measurements revealed diurnal patterns and all patterns were concerted. The cycles of P, nitrate, nitrite, and discharge had two maxima and minima per 24 h, while the cycle of water temperature had one, with a maximum at 20.00 and a minimum at 08.00. The amplitudes of the cycles of P and nitrate were each about 30% of the mean values, while the amplitude of the nitrite cycle was as great as 80% of the mean value on occasions. Both biological and physical mechanisms for the cycling could operate through water temperature and/or incident radiation to account for the observed phenomenon, but there remains uncertainty of which is the more important. The observations have important implications for both the accuracy of pollution assessment in rivers and the physiological rhythms of riverine organisms.

  9. Diurnal and seasonal occurrence of polar patches

    Directory of Open Access Journals (Sweden)

    A. S. Rodger

    1996-05-01

    Full Text Available Analysis of the diurnal and seasonal variation of polar patches, as identified in two years of HF-radar data from Halley, Antarctica during a period near sunspot maximum, shows that there is a broad maximum in occurrence centred about magnetic noon, not local noon. There are minima in occurrence near midsummer and midwinter, with maxima in occurrence between equinox and winter. There are no significant correlations between the occurrence of polar patches and the corresponding hourly averages of the solar wind and IMF parameters, except that patches usually occur when the interplanetary magnetic field has a southward component. The results can be understood in terms of UT and seasonal differences in the plasma concentration being convected from the dayside ionosphere into the polar cap. In summer and winter the electron concentrations in the polar cap are high and low, respectively, but relatively unstructured. About equinox, a tongue of enhanced ionisation is convected into the polar cap; this tongue is then structured by the effects of the interplanetary magnetic field, but these Halley data cannot be used to separate the various competing mechanisms for patch formation. The observed diurnal and seasonal variation in the occurrence of polar patches are largely consistent with predictions of Sojka et al. (1994 when their results are translated into the southern hemisphere. However, the ionospheric effects of flux transfer events are still considered essential in their formation, a feature not yet included in the Sojka et al. model.

  10. Global Electric Circuit Diurnal Variation Derived from Storm Overflight and Satellite Optical Lightning Datasets

    Science.gov (United States)

    Mach, Douglas M.; Blakeslee, R. J.; Bateman, M. J.; Bailey, J. C.

    2011-01-01

    We have combined analyses of over 1000 high altitude aircraft observations of electrified clouds with diurnal lightning statistics from the Lightning Imaging Sensor (LIS) and Optical Transient Detector (OTD) to produce an estimate of the diurnal variation in the global electric circuit. Using basic assumptions about the mean storm currents as a function of flash rate and location, and the global electric circuit, our estimate of the current in the global electric circuit matches the Carnegie curve diurnal variation to within 4% for all but two short periods of time. The agreement with the Carnegie curve was obtained without any tuning or adjustment of the satellite or aircraft data. Mean contributions to the global electric circuit from land and ocean thunderstorms are 1.1 kA (land) and 0.7 kA (ocean). Contributions to the global electric circuit from ESCs are 0.22 kA for ocean storms and 0.04 kA for land storms. Using our analysis, the mean total conduction current for the global electric circuit is 2.0 kA.

  11. Chronotype, sleep loss, and diurnal pattern of salivary cortisol in a simulated daylong driving.

    Science.gov (United States)

    Oginska, Halszka; Fafrowicz, Magdalena; Golonka, Krystyna; Marek, Tadeusz; Mojsa-Kaja, Justyna; Tucholska, Kinga

    2010-07-01

    The study focused on chronotype-related differences in subjective load assessment, sleepiness, and salivary cortisol pattern in subjects performing daylong simulated driving. Individual differences in work stress appraisal and psychobiological cost of prolonged load seem to be of importance in view of expanding compressed working time schedules. Twenty-one healthy, male volunteers (mean +/- SD: 27.9 +/- 4.9 yrs) were required to stay in semiconstant routine conditions. They performed four sessions (each lasting approximately 2.5 h) of simulated driving, i.e., completed chosen tasks from computer driving games. Saliva samples were collected after each driving session, i.e., at 10:00-11:00, 14:00-15:00, 18:00-19:00, and 22:00-23:00 h as well as 10-30 min after waking (between 05:00 and 06:00 h) and at bedtime (after 00:00 h). Two subgroups of subjects were distinguished on the basis of the Chronotype Questionnaire: morning (M)- and evening (E)-oriented types. Subjective data on sleep need, sleeping time preferences, sleeping problems, and the details of the preceding night were investigated by questionnaire. Subjective measures of task load (NASA Task Load Index [NASA-TLX]), activation (Thayer's Activation-Deactivation Adjective Check List [AD ACL]), and sleepiness (Karolinska Sleepiness Scale [KSS]) were applied at times of saliva samples collection. M- and E-oriented types differed significantly as to their ideal sleep length (6 h 54 min +/- 44 versus 8 h 13 min +/- 50 min), preferred sleep timing (midpoint at 03:19 versus 04:26), and sleep index, i.e., 'real-to-ideal' sleep ratio, before the experimental day (0.88 versus 0.67). Sleep deficit proved to be integrated with eveningness. M and E types exhibited similar diurnal profiles of energy, tiredness, tension, and calmness assessed by AD ACL, but E types estimated higher their workload (NASA-TLX) and sleepiness (KSS). M types exhibited a trend of higher mean cortisol levels than E types (F = 4.192, p < .056) and

  12. Viscosity changes of riparian water controls diurnal fluctuations of stream-flow and DOC concentration

    Science.gov (United States)

    Schwab, Michael; Klaus, Julian; Pfister, Laurent; Weiler, Markus

    2015-04-01

    Diurnal fluctuations in stream-flow are commonly explained as being triggered by the daily evapotranspiration cycle in the riparian zone, leading to stream flow minima in the afternoon. While this trigger effect must necessarily be constrained by the extent of the growing season of vegetation, we here show evidence of daily stream flow maxima in the afternoon in a small headwater stream during the dormant season. We hypothesize that the afternoon maxima in stream flow are induced by viscosity changes of riparian water that is caused by diurnal temperature variations of the near surface groundwater in the riparian zone. The patterns were observed in the Weierbach headwater catchment in Luxembourg. The catchment is covering an area of 0.45 km2, is entirely covered by forest and is dominated by a schistous substratum. DOC concentration at the outlet of the catchment was measured with the field deployable UV-Vis spectrometer spectro::lyser (scan Messtechnik GmbH) with a high frequency of 15 minutes over several months. Discharge was measured with an ISCO 4120 Flow Logger. During the growing season, stream flow shows a frequently observed diurnal pattern with discharge minima in the afternoon. During the dormant season, a long dry period with daily air temperature amplitudes of around 10 ° C occurred in March and April 2014, with discharge maxima in the afternoon. The daily air temperature amplitude led to diurnal variations in the water temperature of the upper 10 cm of the riparian zone. Higher riparian water temperatures cause a decrease in water viscosity and according to the Hagen-Poiseuille equation, the volumetric flow rate is inversely proportional to viscosity. Based on the Hagen-Poiseuille equation and the viscosity changes of water, we calculated higher flow rates of near surface groundwater through the riparian zone into the stream in the afternoon which explains the stream flow maxima in the afternoon. With the start of the growing season, the viscosity

  13. Effects of diurnal adjustment on biases and trends derived from inter-sensor calibrated AMSU-A data

    Science.gov (United States)

    Chen, H.; Zou, X.; Qin, Z.

    2018-03-01

    Measurements of brightness temperatures from Advanced Microwave Sounding Unit-A (AMSU-A) temperature sounding instruments onboard NOAA Polarorbiting Operational Environmental Satellites (POES) have been extensively used for studying atmospheric temperature trends over the past several decades. Intersensor biases, orbital drifts and diurnal variations of atmospheric and surface temperatures must be considered before using a merged long-term time series of AMSU-A measurements from NOAA-15, -18, -19 and MetOp-A.We study the impacts of the orbital drift and orbital differences of local equator crossing times (LECTs) on temperature trends derivable from AMSU-A using near-nadir observations from NOAA-15, NOAA-18, NOAA-19, and MetOp-A during 1998-2014 over the Amazon rainforest. The double difference method is firstly applied to estimation of inter-sensor biases between any two satellites during their overlapping time period. The inter-calibrated observations are then used to generate a monthly mean diurnal cycle of brightness temperature for each AMSU-A channel. A diurnal correction is finally applied each channel to obtain AMSU-A data valid at the same local time. Impacts of the inter-sensor bias correction and diurnal correction on the AMSU-A derived long-term atmospheric temperature trends are separately quantified and compared with those derived from original data. It is shown that the orbital drift and differences of LECTamong different POESs induce a large uncertainty in AMSU-A derived long-term warming/cooling trends. After applying an inter-sensor bias correction and a diurnal correction, the warming trends at different local times, which are approximately the same, are smaller by half than the trends derived without applying these corrections.

  14. Solar diurnal anisotropy measured using muons in GRAPES-3 ...

    Indian Academy of Sciences (India)

    The mean energy of muons at sea level is ∼4 GeV with a rel- .... of decays of mesons and muons work against each other resulting in temperature coef- ..... The mean muon rate of 16 modules measured every 15 min for one week interval from .... 4. 8. 12. 16. 20. 24. Hours. Figure 12. Solar diurnal anisotropy measured in ...

  15. Peroxyl radical reactions with carotenoids in microemulsions: Influence of microemulsion composition and the nature of peroxyl radical precursor.

    Science.gov (United States)

    El-Agamey, Ali; McGarvey, David J

    2016-01-01

    The reactions of acetylperoxyl radicals with different carotenoids (7,7'-dihydro-β-carotene and ζ-carotene) in SDS and CTAC microemulsions of different compositions were investigated using laser flash photolysis (LFP) coupled with kinetic absorption spectroscopy. The primary objective of this study was to explore the influence of microemulsion composition and the type of surfactant used on the yields and kinetics of various transients formed from the reaction of acetylperoxyl radicals with carotenoids. Also, the influence of the site (hydrocarbon phases or aqueous phase) of generation of the peroxyl radical precursor was examined by using 4-acetyl-4-phenylpiperidine hydrochloride (APPHCl) and 1,1-diphenylacetone (11DPA) as water-soluble and lipid-soluble peroxyl radical precursors, respectively. LFP of peroxyl radical precursors with 7,7'-dihydro-β-carotene (77DH) in different microemulsions gives rise to the formation of three distinct transients namely addition radical (λmax=460 nm), near infrared transient1 (NIR, λmax=700 nm) and 7,7'-dihydro-β-carotene radical cation (77DH(•+), λmax=770 nm). In addition, for ζ-carotene (ZETA) two transients (near infrared transient1 (NIR1, λmax=660 nm) and ζ-carotene radical cation (ZETA(•+), λmax=730-740 nm)) are generated following LFP of peroxyl radical precursors in the presence of ζ-carotene (ZETA) in different microemulsions. The results show that the composition of the microemulsion strongly influences the observed yield and kinetics of the transients formed from the reactions of peroxyl radicals (acetylperoxyl radicals) with carotenoids (77DH and ZETA). Also, the type of surfactant used in the microemulsions influences the yield of the transients formed. The dependence of the transient yields and kinetics on microemulsion composition (or the type of surfactant used in the microemulsion) can be attributed to the change of the polarity of the microenvironment of the carotenoid. Furthermore, the nature of

  16. Glutathione as a radical scavenger and the biological consequences of thiyl radical production

    International Nuclear Information System (INIS)

    Winterbourn, C.C.

    1996-01-01

    A large number of compounds that have toxic effects can be metabolised to free radicals and secondary reactive oxygen species. These may be directly damaging or affect cell function by altering regulatory mechanisms through changing redox status. Protection is provided by an integrated system of antioxidant defenses. This includes reduced glutathione (GSH), one of the functions of which is as a free radical scavenger. For GSH to be an effective radical scavenging antioxidant, therefore, it must act in concert with superoxide dismutase to remove the superoxide so generated. Superoxide is produced in a variety of metabolic processes. It is also a secondary product of radicals reacting with oxygen either directly or through GSH. The biological reactivity of superoxide has been the subject of much debate ever since the discovery of superoxide dismutase in 1968. It has more recently become apparent that its rapid reaction with nitric oxide to give peroxynitrite, and its ability to reversibly oxidise and inactivate iron sulphur enzymes, contribute to the toxicity of superoxide. Another mechanism that could be important involves addition reactions of superoxide with other radicals to give organic peroxides. This reaction, to form a tyrosine peroxide, has come to authors attention through the study of the scavenging of tyrosyl radicals by GSH. It is also shown that a tyrosine peroxide is a major product of the oxidation of tyrosine by neutrophils

  17. Taking a radical position: Evidence for position specific radical representations in Chinese character recognition using masked priming ERP

    Directory of Open Access Journals (Sweden)

    I-Fan eSu

    2012-09-01

    Full Text Available In the investigation of orthographic representation of Chinese characters, one question that has stimulated much research is whether radicals (character components are specified for spatial position in a character (e.g. Ding, Peng, & Taft, 2004; Tsang & Chen, 2009. Differing from previous work, component or radical position information in this study is conceived in terms of relative frequency across different positions of characters containing it. A lexical decision task in a masked priming paradigm focusing on radicals with preferred position of occurrence was conducted. A radical position that encompasses more characters than other positions was identified to be the preferred position of a particular radical. The prime that was exposed for 96ms might share a radical with the target in the same or different positions. Moreover, the shared radical appeared either in its preferred or non-preferred position in the target. While response latencies only revealed the effect of graphical similarity, both effects of graphical similarity and radical position preference were found in the ERP results. The former effect was reflected in greater positivity in occipital P1 and greater negativity in N400 for radicals in different positions in prime and target characters. The latter effect manifested as greater negativity in occipital N170 and greater positivity in frontal P200 in the same time window elicited by radicals in their non-preferred position. Equally interesting was the reversal of the effect of radical position preference in N400 with greater negativity associated with radicals in preferred position. These findings identify the early ERP components associated with activation of position-specific radical representations in the orthographic lexicon, and reveal the change in the nature of competition from processing at the radical level to the lexical level.

  18. ESA STSE Project “Sea Surface Temperature Diurnal Variability: Regional Extend – Implications in Atmospheric Modelling”

    DEFF Research Database (Denmark)

    Karagali, Ioanna

    of the vertical extend of diurnal signals. Drifting buoys provide measurements close to the surface but are not always available. Moored buoys are generally not able to resolve the daily SST signal, which strongly weakens with depth within the upper water column. For such reasons, the General Ocean Turbulence......, atmospheric and oceanic modelling, bio-chemical processes and oceanic CO2 studies. The diurnal variability of SST, driven by the coincident occurrence of low enough wind and solar heating, is currently not properly understood. Atmospheric, oceanic and climate models are currently not adequately resolving...... the daily SST variability, resulting in biases of the total heat budget estimates and therefore, demised model accuracies. The ESA STSE funded project SSTDV:R.EX.-IM.A.M. aimed at characterising the regional extend of diurnal SST signals and their impact in atmospheric modelling. This study will briefly...

  19. Radical production in biological systems

    International Nuclear Information System (INIS)

    Johnson, J.R.; Akabani, G.

    1994-10-01

    This paper describes our effort to develop a metric for radiation exposure that is more fundamental than adsorbed dose and upon which a metric for exposure to chemicals could be based. This metric is based on the production of radicals by the two agents. Radicals produced by radiation in biological systems commonly assumed to be the same as those produced in water despite the presence of a variety of complex molecules. This may explain why the extensive efforts to describe the relationship between energy deposition (track structure) and molecular damage to DNA, based on the spectrum of radicals produced, have not been successful in explaining simple biological effects such as cell killing. Current models assume that DNA and its basic elements are immersed in water-like media and only model the production and diffusion of water-based radicals and their interaction with DNA structures; these models lack the cross sections associated with each macro-component of DNA and only treat water-based radicals. It has been found that such models are not realistic because DNA is not immersed in pure water. A computer code capable of simulating electron tracks, low-energy electrons, energy deposition in small molecules, and radical production and diffusion in water like media has been developed. This code is still in at a primitive stage and development is continuing. It is being used to study radical production by radiation, and radical diffusion and interactions in simple molecular systems following their production. We are extending the code to radical production by chemicals to complement our PBPK modeling efforts. It therefore has been developed primarily for use with radionuclides that are in biological materials, and not for radiation fields

  20. Kinetics and mechanism of elementary chemical processes of importance in combustion. Periodic report 2 for the period October 1986 - April 1987

    International Nuclear Information System (INIS)

    Munk, J.; Pagsberg, P.; Ratajczak, E.; Sillesen, A.

    1987-04-01

    UV-spectra of vinyl and propargyl radicals have been recorded employing the technique of pulse radiolysis combined with time resolved UV-absorption spectroscoppy. The kinetics of vinyl radiocals was studied by monitoring the transient absorption signals in the range of 215-230 nm. In the presence of oxygen we observed the build-up of strong transient absorption signals at 230nm. Based on analysis of the spectral and kinetic features we have tentatively assigned the new absorption band to the vinyl peroxy radical. Propargyl radicals were produced by the argon sensitized radiolysis of propargyl bromide. In addition to the well-known absorption band at 332 nm we have observed a much stronger band with a maximum at 250 nm. The observed second order decay kinetics is accounted for by the combination reactions 2 C x H x -> products and C 3 H 3 + Br -> C 3 H 3 Br. (EG)

  1. The impact of diurnal variations of air traffic on contrail radiative forcing

    Directory of Open Access Journals (Sweden)

    N. Stuber

    2007-06-01

    Full Text Available We combined high resolution aircraft flight data from the EU Fifth Framework Programme project AERO2k with analysis data from the ECMWF's integrated forecast system to calculate diurnally resolved 3-D contrail cover. We scaled the contrail cover in order to match observational data for the Bakan area (eastern-Atlantic/western-Europe.

    We found that less than 40% of the global distance travelled by aircraft is due to flights during local night time. Yet, due to the cancellation of shortwave and longwave effects during daytime, night time flights contribute a disproportional 60% to the global annual mean forcing. Under clear sky conditions the night flights contribute even more disproportionally at 76%. There are pronounced regional variations in night flying and the associated radiative forcing. Over parts of the North Atlantic flight corridor 75% of air traffic and 84% of the forcing occurs during local night, whereas only 35% of flights are during local night in South-East Asia, yet these contribute 68% of the radiative forcing. In general, regions with a significant local contrail radiative forcing are also regions for which night time flights amount to less than half of the daily total of flights. Therefore, neglecting diurnal variations in air traffic/contrail cover by assuming a diurnal mean contrail cover can over-estimate the global mean radiative forcing by up to 30%.

  2. Diurnal and seasonal DOC and POC variability in the land-locked sea

    Directory of Open Access Journals (Sweden)

    Beata Szymczycha

    2017-07-01

    Full Text Available Organic matter is a minor yet important component of the marine environment. The aim of this study was to investigate the diurnal and seasonal changes in dissolved and particulate organic carbon (DOC and POC, respectively. Thus, DOC and POC as well as chlorophyll a (Chl a, δ13C, NO3−, NO2−, NH4+, PO43−, salinity, pH, and temperature were regularly measured in samples collected for 24 h (2-h resolution in the Gdańsk Deep (54°44.730′N, 19°08.531′E at three water depths (1, 10, and 40 m during sampling campaigns in 2011 (May, 2014 (May, and 2015 (January, March, May, July, September, November. Seasonal variations in DOC and POC followed the seasonality of Chl a (proportional trend and nutrients (reverse trend concentrations. Diurnal oscillations were detected in six out of the eight measurement series. The strongest diurnal variability in both POC and DOC occurred in May 2011 and March 2015, when phytoplankton activity was highest (high Chl a. The surprisingly low δ13C values (range: −28‰ to −24‰ measured over the course of the study revealed the gaps in our knowledge of the isotopic characteristics of terrestrial- vs. marine-derived particulate organic matter.

  3. Chemical repair of trypsin-histidinyl radical

    International Nuclear Information System (INIS)

    Jovanovic, S.V.; Ruvarac, I.; Jankovic, I.; Josimovic, L.

    1991-01-01

    Oxyl radicals, such as hydroxyl, alkoxyl and peroxyl, react with biomolecules to produce bioradicals. Unless chemically repaired by suitable antioxidants, these bioradicals form stable products. This leads to loss of biological function of parent biomolecules with deleterious biological results, such as mutagenesis and cancer. Consequently, the understanding of the mechanisms of oxyl radical damage to biomolecules and chemical repair of such damage is crucial for the development of strategies for anticarcinogenesis and radioprotection. In this study the chemical repair of the histidinyl radical generated upon the trichloromethylperoxyl radical reaction with trypsin vas investigated by gamma radiolysis. The trypsin histidinyl radical is a resonance-stabilized heterocyclic free radical which was found to be unreactive with oxygen. The efficacy of the chemical repair of the trypsin-histidinyl radical by endogenous antioxidants which are electron donors (e.g. 5-hydroxytryptophan, uric acid) is compared to that of antioxidants which are H-atom donors (e. g. glutathione). 9 refs., 2 figs., 1 tab

  4. A stochastic differential equation model of diurnal cortisol patterns

    Science.gov (United States)

    Brown, E. N.; Meehan, P. M.; Dempster, A. P.

    2001-01-01

    Circadian modulation of episodic bursts is recognized as the normal physiological pattern of diurnal variation in plasma cortisol levels. The primary physiological factors underlying these diurnal patterns are the ultradian timing of secretory events, circadian modulation of the amplitude of secretory events, infusion of the hormone from the adrenal gland into the plasma, and clearance of the hormone from the plasma by the liver. Each measured plasma cortisol level has an error arising from the cortisol immunoassay. We demonstrate that all of these three physiological principles can be succinctly summarized in a single stochastic differential equation plus measurement error model and show that physiologically consistent ranges of the model parameters can be determined from published reports. We summarize the model parameters in terms of the multivariate Gaussian probability density and establish the plausibility of the model with a series of simulation studies. Our framework makes possible a sensitivity analysis in which all model parameters are allowed to vary simultaneously. The model offers an approach for simultaneously representing cortisol's ultradian, circadian, and kinetic properties. Our modeling paradigm provides a framework for simulation studies and data analysis that should be readily adaptable to the analysis of other endocrine hormone systems.

  5. Gnosticism and Radical Feminism

    DEFF Research Database (Denmark)

    Cahana, Jonathan

    2016-01-01

    and radical feminism would easily fall under this definition. There is, however, one major difference: since radical feminism is a relatively recent phenomenon which also benefited from modern modes of text production and preservation, almost all of the sources are still with us. This, in turn, may allow us...... to use radical feminism to make certain aspects of ancient Gnosticism re-emerge from their long submersion, provided that enough similarities can be independently drawn between the two phenomena to merit such a comparison. This paper therefore presents a comparison between concepts and positions...

  6. Radical's view of sciences

    International Nuclear Information System (INIS)

    Mittal, J.P.

    2004-01-01

    Full text: General concept in radiation biology is that free radicals are highly reactive and they can damage vital cellular molecules leading to injurious effects. However, in this talk, evidence will be presented through the techniques of electron paramagnetic resonance ( EPR ) and pulse radiolysis that free radicals can be highly selective in their reaction with the target molecules. In addition, attempts will be made to present a brief account of emerging scenario of free radical generation, identification and their involvement in radiation damage mechanisms in chemical and biological systems

  7. The effect of the number of consecutive night shifts on diurnal rhythms in cortisol, melatonin and heart rate variability (HRV)

    DEFF Research Database (Denmark)

    Jensen, Marie Aarrebo; Garde, Anne Helene; Kristiansen, Jesper

    2016-01-01

    PURPOSE: The purpose of this review is to summarize the current knowledge from field studies on how many consecutive night shifts are required for adaptation of diurnal rhythms in cortisol, melatonin and heart rate variability (HRV) to night work. METHODS: A systematic search of the databases Pub...... recordings for HRV. Most of the studies in the review were small studies with less than 30 participants, and most studies evaluated diurnal rhythms after only two consecutive night shifts whereas only six studies used seven or more consecutive night shifts. The majority of studies found that adaptation...... to night work had not occurred after two consecutive night shifts, whereas a small number found evidence for full adaptation after seven consecutive night shifts based on diurnal rhythms in cortisol and melatonin. CONCLUSION: There are methodological differences in the field studies analyzing diurnal...

  8. Diurnal Variation of Tropical Ice Cloud Microphysics inferred from Global Precipitation Measurement Microwave Imager (GPM-GMI)'s Polarimetric Measurement

    Science.gov (United States)

    Gong, J.; Zeng, X.; Wu, D. L.; Li, X.

    2017-12-01

    Diurnal variation of tropical ice cloud has been well observed and examined in terms of the area of coverage, occurring frequency, and total mass, but rarely on ice microphysical parameters (habit, size, orientation, etc.) because of lack of direct measurements of ice microphysics on a high temporal and spatial resolutions. This accounts for a great portion of the uncertainty in evaluating ice cloud's role on global radiation and hydrological budgets. The design of Global Precipitation Measurement (GPM) mission's procession orbit gives us an unprecedented opportunity to study the diurnal variation of ice microphysics on the global scale for the first time. Dominated by cloud ice scattering, high-frequency microwave polarimetric difference (PD, namely the brightness temperature difference between vertically- and horizontally-polarized paired channel measurements) from the GPM Microwave Imager (GMI) has been proven by our previous study to be very valuable to infer cloud ice microphysical properties. Using one year of PD measurements at 166 GHz, we found that cloud PD exhibits a strong diurnal cycle in the tropics (25S-25N). The peak PD amplitude varies as much as 35% over land, compared to only 6% over ocean. The diurnal cycle of the peak PD value is strongly anti-correlated with local ice cloud occurring frequency and the total ice mass with a leading period of 3 hours for the maximum correlation. The observed PD diurnal cycle can be explained by the change of ice crystal axial ratio. Using a radiative transfer model, we can simulate the observed 166 GHz PD-brightness temperature curve as well as its diurnal variation using different axial ratio values, which can be caused by the diurnal variation of ice microphysical properties including particle size, percentage of horizontally-aligned non-spherical particles, and ice habit. The leading of the change of PD ahead of ice cloud mass and occurring frequency implies the important role microphysics play in the

  9. Ten-Year Climatology of Summertime Diurnal Rainfall Rate Over the Conterminous U.S.

    Science.gov (United States)

    Matsui, Toshihisa; Mocko, David; Lee, Myong-In; Tao, Wei-Kuo; Suarez, Max J.; Pielke, Roger A., Sr.

    2010-01-01

    Diurnal cycles of summertime rainfall rates are examined over the conterminous United States, using radar-gauge assimilated hourly rainfall data. As in earlier studies, rainfall diurnal composites show a well-defined region of rainfall propagation over the Great Plains and an afternoon maximum area over the south and eastern portion of the United States. Zonal phase speeds of rainfall in three different small domains are estimated, and rainfall propagation speeds are compared with background zonal wind speeds. Unique rainfall propagation speeds in three different regions can be explained by the evolution of latent-heat theory linked to the convective available potential energy, than by gust-front induced or gravity wave propagation mechanisms.

  10. EPR spin trapping of protein radicals

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan; Hawkins, Clare Louise

    2004-01-01

    Electron paramagnetic resonance (EPR) spin trapping was originally developed to aid the detection of low-molecular-mass radicals formed in chemical systems. It has subsequently found widespread use in biology and medicine for the direct detection of radical species formed during oxidative stress...... tumbling radicals are often broad and relatively poor in distinctive features, a number of techniques have been developed that allow a wealth of information to be obtained about the nature, site, and reactions of such radicals. This article summarizes recent developments in this area and reviews selected...... examples of radical formation on proteins....

  11. The diurnal variation in urine acidification differs between normal individuals and uric acid stone formers

    Science.gov (United States)

    Cameron, Mary Ann; Maalouf, Naim M.; Poindexter, John; Adams-Huet, Beverley; Sakhaee, Khashayar; Moe, Orson W.

    2012-01-01

    Many biologic functions follow circadian rhythms driven by internal and external cues that synchronize and coordinate organ physiology to diurnal changes in the environment and behavior. Urinary acid-base parameters follow diurnal patterns and it is thought these changes are due to periodic surges in gastric acid secretion. Abnormal urine pH is a risk factor for specific types of nephrolithiasis and uric acid stones are typical of excessively low urine pH. Here we placed 9 healthy volunteers and 10 uric acid stone formers on fixed metabolic diets to study the diurnal pattern of urinary acidification. All showed clear diurnal trends in urinary acidification but none of the patterns were affected by inhibitors of the gastric proton pump. Uric acid stone formers had similar patterns of change through the day but their urine pH was always lower compared to healthy volunteers. Uric acid stone formers excreted more acid (normalized to acid ingestion) with the excess excreted primarily as titratable acid rather than ammonium. Urine base excretion was also lower in uric acid stone formers (normalized to base ingestion) along with lower plasma bicarbonate concentrations during part of the day. Thus, increased net acid presentation to the kidney and the preferential use of buffers, other than ammonium, result in much higher concentrations of un-dissociated uric acid throughout the day and consequently an increased risk of uric acid stones. PMID:22297671

  12. Sleep Deprivation and Caffeine Treatment Potentiate Photic Resetting of the Master Circadian Clock in a Diurnal Rodent.

    Science.gov (United States)

    Jha, Pawan Kumar; Bouâouda, Hanan; Gourmelen, Sylviane; Dumont, Stephanie; Fuchs, Fanny; Goumon, Yannick; Bourgin, Patrice; Kalsbeek, Andries; Challet, Etienne

    2017-04-19

    Circadian rhythms in nocturnal and diurnal mammals are primarily synchronized to local time by the light/dark cycle. However, nonphotic factors, such as behavioral arousal and metabolic cues, can also phase shift the master clock in the suprachiasmatic nuclei (SCNs) and/or reduce the synchronizing effects of light in nocturnal rodents. In diurnal rodents, the role of arousal or insufficient sleep in these functions is still poorly understood. In the present study, diurnal Sudanian grass rats, Arvicanthis ansorgei , were aroused at night by sleep deprivation (gentle handling) or caffeine treatment that both prevented sleep. Phase shifts of locomotor activity were analyzed in grass rats transferred from a light/dark cycle to constant darkness and aroused in early night or late night. Early night, but not late night, sleep deprivation induced a significant phase shift. Caffeine on its own induced no phase shifts. Both sleep deprivation and caffeine treatment potentiated light-induced phase delays and phase advances in response to a 30 min light pulse, respectively. Sleep deprivation in early night, but not late night, potentiated light-induced c-Fos expression in the ventral SCN. Caffeine treatment in midnight triggered c-Fos expression in dorsal SCN. Both sleep deprivation and caffeine treatment potentiated light-induced c-Fos expression in calbindin-containing cells of the ventral SCN in early and late night. These findings indicate that, in contrast to nocturnal rodents, behavioral arousal induced either by sleep deprivation or caffeine during the sleeping period potentiates light resetting of the master circadian clock in diurnal rodents, and activation of calbindin-containing suprachiasmatic cells may be involved in this effect. SIGNIFICANCE STATEMENT Arousing stimuli have the ability to regulate circadian rhythms in mammals. Behavioral arousal in the sleeping period phase shifts the master clock in the suprachiasmatic nuclei and/or slows down the photic

  13. Diurnal adjustment in ultraviolet sunscreen protection is widespread among higher plants.

    Science.gov (United States)

    Barnes, Paul W; Flint, Stephan D; Tobler, Mark A; Ryel, Ronald J

    2016-05-01

    The accumulation of ultraviolet (UV)-absorbing compounds (flavonoids and related phenylpropanoids) in the epidermis of higher plants reduces the penetration of solar UV radiation to underlying tissues and is a primary mechanism of acclimation to changing UV conditions resulting from ozone depletion and climate change. Previously we reported that several herbaceous plant species were capable of rapid, diurnal adjustments in epidermal UV transmittance (T UV), but how widespread this phenomenon is among plants has been unknown. In the present study, we tested the generality of this response by screening 37 species of various cultivated and wild plants growing in four locations spanning a gradient of ambient solar UV and climate (Hawaii, Utah, Idaho and Louisiana). Non-destructive measurements of adaxial T UV indicated that statistically significant midday decreases in T UV occurred in 49 % of the species tested, including both herbaceous and woody growth forms, and there was substantial interspecific variation in the magnitude of these changes. In general, plants in Louisiana exhibited larger diurnal changes in T UV than those in the other locations. Moreover, across all taxa, the magnitude of these changes was positively correlated with minimum daily air temperatures but not daily UV irradiances. Results indicate that diurnal changes in UV shielding are widespread among higher plants, vary both within and among species and tend to be greatest in herbaceous plants growing in warm environments. These findings suggest that plant species differ in their UV protection "strategies" though the functional and ecological significance of this variation in UV sunscreen protection remains unclear at present.

  14. Tidal influences on vertical diffusion and diurnal variability of ozone in the mesosphere

    Science.gov (United States)

    Bjarnason, Gudmundur G.; Solomon, Susan; Garcia, Rolando R.

    1987-01-01

    Possible dynamical influences on the diurnal behavior of ozone are investigated. A time dependent one-dimensional photochemical model is developed for this purpose; all model calculations are made at 70 deg N during summer. It is shown that the vertical diffusion can vary as much as 1 order of magnitude within a day as a result of large changes in the zonal wind induced by atmospheric thermal tides. It is found that by introducing a dissipation time scale for turbulence produced by breaking gravity waves, the agreement with Poker Flat echo data is improved. Comparisons of results from photochemical model calculations, where the vertical diffusion is a function of height only, with those in which the vertical diffusion coefficient is changing in time show large differences in the diurnal behavior of ozone between 70 and 90 km. By including the dynamical effect, much better agreement with the Solar Mesosphere Explorers data is obtained. The results are, however, sensitive to the background zonally averaged wind. The influence of including time-varying vertical diffusion coefficient on the OH densities is also large, especially between 80 and 90 km. This suggests that dynamical effects are important in determining the diurnal behavior of the airglow emission from the Meinel bands.

  15. [Effects of diurnal warming on soil N2O emission in soybean field].

    Science.gov (United States)

    Hu, Zheng-Hua; Zhou, Ying-Ping; Cui, Hai-Ling; Chen, Shu-Tao; Xiao, Qi-Tao; Liu, Yan

    2013-08-01

    To investigate the impact of experimental warming on N2O emission from soil of soybean field, outdoor experiments with simulating diurnal warming were conducted, and static dark chamber-gas chromatograph method was used to measure N2O emission fluxes. Results indicated that: the diurnal warming did not change the seasonal pattern of N2O emissions from soil. In the whole growing season, comparing to the control treatment (CK), the warming treatment (T) significantly enhanced the N2O flux and the cumulative amount of N2O by 17.31% (P = 0.019), and 20.27% (P = 0.005), respectively. The significant correlations were found between soil N2O emission and soil temperature, moisture. The temperature sensitivity values of soil N2O emission under CK and T treatments were 3.75 and 4.10, respectively. In whole growing stage, T treatment significantly increased the crop aboveground and total biomass, the nitrate reductase activity, and total nitrogen in leaves, while significantly decreased NO3(-) -N content in leaves. T treatment significantly increased soil NO3(-) -N content, but had no significant effect on soil organic carbon and total nitrogen contents. The results of this study suggested that diurnal warming enhanced N2O emission from soil in soybean field.

  16. Fragmentation characteristics of the unstable [CH3 CO][radical sign] radicals generated by neutralization of [CH3CO]+ cations

    Science.gov (United States)

    Hop, C. E. C. A.; Holmes, J. L.

    1991-03-01

    The stability and fragmentation characteristics of [CH3 CO][radical sign] radicals, generated by vertical charge exchange between acetyl cations and permanent gases or metal vapours (He, Xe, NO, Cd, Na and K), were examined mass spectrometrically. Two dissociation reactions were observed, the losses of CH[radical sign]3 and H[radical sign]. The H[radical sign] loss reaction, the higher energy dissociation, became of greater importance as the exothermicity of the charge exchange was increased. Based on the analysis of the kinetic energy releases it was concluded that these decompositions arose from the population of two excited states of the [CH3 CO][radical sign] radical.

  17. MicroRNA mir-16 is anti-proliferative in enterocytes and exhibits diurnal rhythmicity in intestinal crypts

    Energy Technology Data Exchange (ETDEWEB)

    Balakrishnan, Anita, E-mail: anita.balakrishnan@doctors.org.uk [Department of Surgery, Brigham and Women' s Hospital, Boston, MA 02115 (United States); Department of Surgery, Harvard Medical School, Boston, MA 02115 (United States); School of Clinical Sciences, Division of Gastroenterology, University of Liverpool, Liverpool L69 3GE (United Kingdom); Stearns, Adam T. [Department of Surgery, Brigham and Women' s Hospital, Boston, MA 02115 (United States); Department of Surgery, Harvard Medical School, Boston, MA 02115 (United States); Department of Physiology, Anatomy and Genetics, University of Oxford, Oxford OX1 2JD (United Kingdom); Park, Peter J. [Department of Medicine, Brigham and Women' s Hospital, Boston, MA 02115 (United States); Harvard Medical School, Center for Biomedical Informatics, Boston, MA 02115 (United States); Dreyfuss, Jonathan M. [Department of Medicine, Brigham and Women' s Hospital, Boston, MA 02115 (United States); Ashley, Stanley W. [Department of Surgery, Brigham and Women' s Hospital, Boston, MA 02115 (United States); Department of Surgery, Harvard Medical School, Boston, MA 02115 (United States); Rhoads, David B. [Department of Surgery, Harvard Medical School, Boston, MA 02115 (United States); Pediatric Endocrine Unit, MassGeneral Hospital for Children, Boston, MA 02114 (United States); Tavakkolizadeh, Ali, E-mail: atavakkoli@partners.org [Department of Surgery, Brigham and Women' s Hospital, Boston, MA 02115 (United States); Department of Surgery, Harvard Medical School, Boston, MA 02115 (United States)

    2010-12-10

    Background and aims: The intestine exhibits profound diurnal rhythms in function and morphology, in part due to changes in enterocyte proliferation. The regulatory mechanisms behind these rhythms remain largely unknown. We hypothesized that microRNAs are involved in mediating these rhythms, and studied the role of microRNAs specifically in modulating intestinal proliferation. Methods: Diurnal rhythmicity of microRNAs in rat jejunum was analyzed by microarrays and validated by qPCR. Temporal expression of diurnally rhythmic mir-16 was further quantified in intestinal crypts, villi, and smooth muscle using laser capture microdissection and qPCR. Morphological changes in rat jejunum were assessed by histology and proliferation by immunostaining for bromodeoxyuridine. In IEC-6 cells stably overexpressing mir-16, proliferation was assessed by cell counting and MTS assay, cell cycle progression and apoptosis by flow cytometry, and cell cycle gene expression by qPCR and immunoblotting. Results: mir-16 peaked 6 hours after light onset (HALO 6) with diurnal changes restricted to crypts. Crypt depth and villus height peaked at HALO 13-14 in antiphase to mir-16. Overexpression of mir-16 in IEC-6 cells suppressed specific G1/S regulators (cyclins D1-3, cyclin E1 and cyclin-dependent kinase 6) and produced G1 arrest. Protein expression of these genes exhibited diurnal rhythmicity in rat jejunum, peaking between HALO 11 and 17 in antiphase to mir-16. Conclusions: This is the first report of circadian rhythmicity of specific microRNAs in rat jejunum. Our data provide a link between anti-proliferative mir-16 and the intestinal proliferation rhythm and point to mir-16 as an important regulator of proliferation in jejunal crypts. This function may be essential to match proliferation and absorptive capacity with nutrient availability.

  18. MicroRNA mir-16 is anti-proliferative in enterocytes and exhibits diurnal rhythmicity in intestinal crypts

    International Nuclear Information System (INIS)

    Balakrishnan, Anita; Stearns, Adam T.; Park, Peter J.; Dreyfuss, Jonathan M.; Ashley, Stanley W.; Rhoads, David B.; Tavakkolizadeh, Ali

    2010-01-01

    Background and aims: The intestine exhibits profound diurnal rhythms in function and morphology, in part due to changes in enterocyte proliferation. The regulatory mechanisms behind these rhythms remain largely unknown. We hypothesized that microRNAs are involved in mediating these rhythms, and studied the role of microRNAs specifically in modulating intestinal proliferation. Methods: Diurnal rhythmicity of microRNAs in rat jejunum was analyzed by microarrays and validated by qPCR. Temporal expression of diurnally rhythmic mir-16 was further quantified in intestinal crypts, villi, and smooth muscle using laser capture microdissection and qPCR. Morphological changes in rat jejunum were assessed by histology and proliferation by immunostaining for bromodeoxyuridine. In IEC-6 cells stably overexpressing mir-16, proliferation was assessed by cell counting and MTS assay, cell cycle progression and apoptosis by flow cytometry, and cell cycle gene expression by qPCR and immunoblotting. Results: mir-16 peaked 6 hours after light onset (HALO 6) with diurnal changes restricted to crypts. Crypt depth and villus height peaked at HALO 13-14 in antiphase to mir-16. Overexpression of mir-16 in IEC-6 cells suppressed specific G1/S regulators (cyclins D1-3, cyclin E1 and cyclin-dependent kinase 6) and produced G1 arrest. Protein expression of these genes exhibited diurnal rhythmicity in rat jejunum, peaking between HALO 11 and 17 in antiphase to mir-16. Conclusions: This is the first report of circadian rhythmicity of specific microRNAs in rat jejunum. Our data provide a link between anti-proliferative mir-16 and the intestinal proliferation rhythm and point to mir-16 as an important regulator of proliferation in jejunal crypts. This function may be essential to match proliferation and absorptive capacity with nutrient availability.

  19. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    Science.gov (United States)

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  20. Genetic architecture of local adaptation in lunar and diurnal emergence times of the marine midge Clunio marinus (Chironomidae, Diptera).

    Science.gov (United States)

    Kaiser, Tobias S; Heckel, David G

    2012-01-01

    Circadian rhythms pre-adapt the physiology of most organisms to predictable daily changes in the environment. Some marine organisms also show endogenous circalunar rhythms. The genetic basis of the circalunar clock and its interaction with the circadian clock is unknown. Both clocks can be studied in the marine midge Clunio marinus (Chironomidae, Diptera), as different populations have different local adaptations in their lunar and diurnal rhythms of adult emergence, which can be analyzed by crossing experiments. We investigated the genetic basis of population variation in clock properties by constructing the first genetic linkage map for this species, and performing quantitative trait locus (QTL) analysis on variation in both lunar and diurnal timing. The genome has a genetic length of 167-193 centimorgans based on a linkage map using 344 markers, and a physical size of 95-140 megabases estimated by flow cytometry. Mapping the sex determining locus shows that females are the heterogametic sex, unlike most other Chironomidae. We identified two QTL each for lunar emergence time and diurnal emergence time. The distribution of QTL confirms a previously hypothesized genetic basis to a correlation of lunar and diurnal emergence times in natural populations. Mapping of clock genes and light receptors identified ciliary opsin 2 (cOps2) as a candidate to be involved in both lunar and diurnal timing; cryptochrome 1 (cry1) as a candidate gene for lunar timing; and two timeless (tim2, tim3) genes as candidate genes for diurnal timing. This QTL analysis of lunar rhythmicity, the first in any species, provides a unique entree into the molecular analysis of the lunar clock.

  1. Is the diurnal pattern sufficient to explain the intraday variation in volatility? A nonparametric assessment

    DEFF Research Database (Denmark)

    Christensen, Kim; Hounyo, Ulrich; Podolskij, Mark

    In this paper, we propose a nonparametric way to test the hypothesis that time-variation in intraday volatility is caused solely by a deterministic and recurrent diurnal pattern. We assume that noisy high-frequency data from a discretely sampled jump-diffusion process are available. The test...... inference, we propose a new bootstrap approach, which leads to almost correctly sized tests of the null hypothesis. We apply the developed framework to a large cross-section of equity high-frequency data and find that the diurnal pattern accounts for a rather significant fraction of intraday variation...

  2. Modelled and Observed Diurnal SST Signals: "SSTDV:R.EX.-IM.A.M." Project Preliminary Results

    DEFF Research Database (Denmark)

    Karagali, Ioanna; Høyer, Jacob; LeBorgne, Pierre

    2013-01-01

    This study presents some of the preliminary results from the ESA Support To Science Element (STSE) funded project on the Diurnal Variability of the Sea Surface Temperature, regarding its Regional Extend and Implications in Atmospheric Modelling (SSTDV:R.EX.–IM.A.M.). During this phase of the proj......This study presents some of the preliminary results from the ESA Support To Science Element (STSE) funded project on the Diurnal Variability of the Sea Surface Temperature, regarding its Regional Extend and Implications in Atmospheric Modelling (SSTDV:R.EX.–IM.A.M.). During this phase...

  3. Reaction between protein radicals and other biomolecules

    DEFF Research Database (Denmark)

    Østdal, H.; Davies, M.J.; Andersen, Henrik Jørgen

    2002-01-01

    The present study investigates the reactivity of bovine serum albumin (BSA) radicals towards different biomolecules (urate, linoleic acid, and a polypeptide, poly(Glu-Ala-Tyr)). The BSA radical was formed at room temperature through a direct protein-to-protein radical transfer from H(2)O(2....... Subsequent analysis showed a decrease in the concentration of urate upon reaction with the BSA radical, while the BSA radical in the presence of poly(Glu-Ala-Tyr) resulted in increased formation of the characteristic protein oxidation product, dityrosine. Reaction between the BSA radical and a linoleic acid...

  4. Formation of long-lived radicals on proteins by radical transfer from heme enzymes--a common process?

    DEFF Research Database (Denmark)

    Ostdal, H; Andersen, H J; Davies, Michael Jonathan

    1999-01-01

    concentrations were observed after limited digestion, although this effect was less marked with the HRP/H2O2/BSA system than with Fe(III)Mb/H2O2/BSA, consistent with different modes of radical transfer. More extensive digestion of BSA decreased the radical concentration to levels below those detected with native...... investigated using horseradish peroxidase (HRP)/H2O2, in the presence and absence of added tyrosine. Incubation of HRP with H2O2 and bovine or human serum albumins, in the presence and absence of tyrosine, gave long-lived albumin-derived radicals as detected by EPR spectroscopy. Evidence has been obtained...... for these albumin radicals being located on buried tyrosine residues on the basis of blocking experiments. The effect of protein conformation on radical transfer has been investigated using partial proteolytic digestion prior to protein oxidation. With HRP/H2O2/BSA and Fe(III)Mb/H2O2/BSA increased radical...

  5. Diurnal Variation of Radon Concentration in the Postojna Cave

    International Nuclear Information System (INIS)

    Gregoric, A.; Vaupotic, J.

    2011-01-01

    Postojna Cave, with 20 km of galleries, is the longest known cave system and also the largest of about 20 show caves in Slovenia and one of the most visited show caves in the world. It is well known that high concentrations of radon are common in karstic caves, although quantities of uranium (238U) in limestone are rather low. The reason for this is low natural ventilation of the underground cavities. Tectonic faults constitute an additional source of radon. Variations of radon concentration in cave air arise from a balance of the emission from cave surfaces and drip waters, decay in cave air, and exchange with the outside atmosphere. Because of its elevated radon concentrations, Postojna Cave has been under permanent radon survey since 1995. The influence of meteorological conditions on the radon levels and their temporal variations depends mostly on the shape of the cave, and the number and directions of cracks, corridors and fissures connecting the cave rooms with the outside atmosphere. The driving force for air movement in horizontal caves, and thus the inflow of fresh air and release of the cave air to the atmosphere, is the temperature difference between the cave air and outdoors, which causes seasonal pattern of radon concentration in the cave with high levels in summer and low in winter. However, on a daily scale different behaviour of radon can be observed at different locations in the cave. In this paper diurnal variation of radon concentration at two locations is presented and discussed. Postojna Cave is a horizontal cave with a stable yearly temperature around 10 degrees of @C. Continuous measurements of radon concentration were carried out from 2005 to 2010 at two locations along the guided tourist trail. Radon concentration was measured with Radim 5 WP monitors (SMM Company, Prague, Czech Republic) with sampling frequency once an hour. The evaluation of five-year radon monitoring at two sites in the Postojna Cave reveals significant diurnal and

  6. ANALYSIS THE DIURNAL VARIATIONS ON SELECTED PHYSICAL AND PHYSIOLOGICAL PARAMETERS

    Directory of Open Access Journals (Sweden)

    A. MAHABOOBJAN

    2010-12-01

    Full Text Available The purpose of the study was to analyze the diurnal variations on selected physical and physiological parameters such as speed, explosive power, resting heart rate and breath holding time among college students. To achieve the purpose of this study, a total of twenty players (n=20 from Government Arts College, Salem were selected as subjects To study the diurnal variation of the players on selected physiological and performance variables, the data were collected 4 times a day with every four hours in between the times it from 6.00 to 18.00 hours were selected as another categorical variable. One way repeated measures (ANOVA was used to analyze the data. If the obtained F-ratio was significant, Seheffe’s post-hoc test was used to find out the significant difference if anyamong the paired means. The level of significance was fixed at.05 level. It has concluded that both physical and physiological parameters were significantly deferred with reference to change of temperature in a day

  7. Influence of observed diurnal cycles of aerosol optical depth on aerosol direct radiative effect

    Directory of Open Access Journals (Sweden)

    A. Arola

    2013-08-01

    Full Text Available The diurnal variability of aerosol optical depth (AOD can be significant, depending on location and dominant aerosol type. However, these diurnal cycles have rarely been taken into account in measurement-based estimates of aerosol direct radiative forcing (ADRF or aerosol direct radiative effect (ADRE. The objective of our study was to estimate the influence of diurnal aerosol variability at the top of the atmosphere ADRE estimates. By including all the possible AERONET sites, we wanted to assess the influence on global ADRE estimates. While focusing also in more detail on some selected sites of strongest impact, our goal was to also see the possible impact regionally. We calculated ADRE with different assumptions about the daily AOD variability: taking the observed daily AOD cycle into account and assuming diurnally constant AOD. Moreover, we estimated the corresponding differences in ADREs, if the single AOD value for the daily mean was taken from the the Moderate Resolution Imaging Spectroradiometer (MODIS Terra or Aqua overpass times, instead of accounting for the true observed daily variability. The mean impact of diurnal AOD variability on 24 h ADRE estimates, averaged over all AERONET sites, was rather small and it was relatively small even for the cases when AOD was chosen to correspond to the Terra or Aqua overpass time. This was true on average over all AERONET sites, while clearly there can be much stronger impact in individual sites. Examples of some selected sites demonstrated that the strongest observed AOD variability (the strongest morning afternoon contrast does not typically result in a significant impact on 24 h ADRE. In those cases, the morning and afternoon AOD patterns are opposite and thus the impact on 24 h ADRE, when integrated over all solar zenith angles, is reduced. The most significant effect on daily ADRE was induced by AOD cycles with either maximum or minimum AOD close to local noon. In these cases, the impact on

  8. On the Diurnal Periodicity of Representative Earthquakes in Greece: Comparison of Data from Different Observation Systems

    Science.gov (United States)

    Desherevskii, A. V.; Sidorin, A. Ya.

    2017-12-01

    Due to the initiation of the Hellenic Unified Seismic Network (HUSN) in late 2007, the quality of observation significantly improved by 2011. For example, the representative magnitude level considerably has decreased and the number of annually recorded events has increased. The new observational system highly expanded the possibilities for studying regularities in seismicity. In view of this, the authors revisited their studies of the diurnal periodicity of representative earthquakes in Greece that was revealed earlier in the earthquake catalog before 2011. We use 18 samples of earthquakes of different magnitudes taken from the catalog of Greek earthquakes from 2011 to June 2016 to derive a series of the number of earthquakes for each of them and calculate its average diurnal course. To increase the reliability of the results, we compared the data for two regions. With a high degree of statistical significance, we have obtained that no diurnal periodicity can be found for strongly representative earthquakes. This finding differs from the estimates obtained earlier from an analysis of the catalog of earthquakes at the same area for 1995-2004 and 2005-2010, i.e., before the initiation of the Hellenic Unified Seismic Network. The new results are consistent with the hypothesis of noise discrimination (observational selection) explaining the cause of the diurnal variation of earthquakes with different sensitivity of the seismic network in daytime and nighttime periods.

  9. Diurnal changes of remote sensing reflectance over Chesapeake Bay: Observations from the Airborne Compact Atmospheric Mapper

    Science.gov (United States)

    Zhang, Minwei; Hu, Chuanmin; Cannizzaro, Jennifer; Kowalewski, Matthew G.; Janz, Scott J.

    2018-01-01

    Using hyperspectral data collected by the Airborne Compact Atmospheric Mapper (ACAM) and a shipborne radiometer in Chesapeake Bay in July-August 2011, this study investigates diurnal changes of surface remote sensing reflectance (Rrs). Atmospheric correction of ACAM data is performed using the traditional "black pixel" approach through radiative transfer based look-up-tables (LUTs) with non-zero Rrs in the near-infrared (NIR) accounted for by iterations. The ACAM-derived Rrs was firstly evaluated through comparison with Rrs derived from the Moderate Resolution Imaging Spectroradiometer satellite measurements, and then validated against in situ Rrs using a time window of ±1 h or ±3 h. Results suggest that the uncertainties in ACAM-derived Rrs are generally comparable to those from MODIS satellite measurements over coastal waters, and therefore may be used to assess whether Rrs diurnal changes observed by ACAM are realistic (i.e., with changes > 2 × uncertainties). Diurnal changes observed by repeated ACAM measurements reaches up to 66.8% depending on wavelength and location and are consistent with those from the repeated in situ Rrs measurements. These findings suggest that once airborne data are processed using proper algorithms and validated using in situ data, they are suitable for assessing diurnal changes in moderately turbid estuaries such as Chesapeake Bay. The findings also support future geostationary satellite missions that are particularly useful to assess short-term changes.

  10. Diurnal and circadian rhythms in the tomato transcriptome and their modulation by cryptochrome photoreceptors.

    Directory of Open Access Journals (Sweden)

    Paolo Facella

    Full Text Available BACKGROUND: Circadian clocks are internal molecular time-keeping mechanisms that provide living organisms with the ability to adjust their growth and physiology and to anticipate diurnal environmental changes. Circadian clocks, without exception, respond to light and, in plants, light is the most potent and best characterized entraining stimulus. The capacity of plants to respond to light is achieved through a number of photo-perceptive proteins including cryptochromes and phytochromes. There is considerable experimental evidence demonstrating the roles of photoreceptors in providing light input to the clock. METHODOLOGY: In order to identify genes regulated by diurnal and circadian rhythms, and to establish possible functional relations between photoreceptors and the circadian clock in tomato, we monitored the temporal transcription pattern in plants entrained to long-day conditions, either by large scale comparative profiling, or using a focused approach over a number of photosensory and clock-related genes by QRT-PCR. In parallel, focused transcription analyses were performed in cry1a- and in CRY2-OX tomato genotypes. CONCLUSIONS: We report a large series of transcript oscillations that shed light on the complex network of interactions among tomato photoreceptors and clock-related genes. Alteration of cryptochrome gene expression induced major changes in the rhythmic oscillations of several other gene transcripts. In particular, over-expression of CRY2 had an impact not only on day/night fluctuations but also on rhythmicity under constant light conditions. Evidence was found for widespread diurnal oscillations of transcripts encoding specific enzyme classes (e.g. carotenoid biosynthesis enzymes as well as for post-transcriptional diurnal and circadian regulation of the CRY2 transcript.

  11. Dim nighttime light impairs cognition and provokes depressive-like responses in a diurnal rodent.

    Science.gov (United States)

    Fonken, Laura K; Kitsmiller, Emily; Smale, Laura; Nelson, Randy J

    2012-08-01

    Circadian disruption is a common by-product of modern life. Although jet lag and shift work are well-documented challenges to circadian organization, many more subtle environmental changes cause circadian disruption. For example, frequent fluctuations in the timing of the sleep/wake schedule, as well as exposure to nighttime lighting, likely affect the circadian system. Most studies of these effects have focused on nocturnal rodents, which are very different from diurnal species with respect to their patterns of light exposure and the effects that light can have on their activity. Thus, the authors investigated the effect of nighttime light on behavior and the brain of a diurnal rodent, the Nile grass rat. Following 3 weeks of exposure to standard light/dark (LD; 14:10 light [~150 lux] /dark [0 lux]) or dim light at night (dLAN; 14:10 light [~150 lux] /dim [5 lux]), rats underwent behavioral testing, and hippocampal neurons within CA1, CA3, and the dentate gyrus (DG) were examined. Three behavioral effects of dLAN were observed: (1) decreased preference for a sucrose solution, (2) increased latency to float in a forced swim test, and (3) impaired learning and memory in the Barnes maze. Light at night also reduced dendritic length in DG and basilar CA1 dendrites. Dendritic length in the DG positively correlated with sucrose consumption in the sucrose anhedonia task. Nighttime light exposure did not disrupt the pattern of circadian locomotor activity, and all grass rats maintained a diurnal activity pattern. Together, these data suggest that exposure to dLAN can alter affective responses and impair cognition in a diurnal animal.

  12. Radical surgery compared with intracavitary cesium followed by radical surgery in cervical carcinoma stage IB

    Energy Technology Data Exchange (ETDEWEB)

    Tinga, D.J.; Bouma, J.; Aalders, J.G. (Dept. of Obstetrics and Gynaecology, State Univ. Hospital, Groningen (Netherlands)); Hollema, H. (Dept. of Pathology, State Univ. Hospital, Groningen (Netherlands))

    1990-01-01

    Forty-nine patients aged {le} 45 years, with cervical carcinoma stage IB ({le} 3 cm) were treated with either primary radical surgery (n = 26), or intracavitary irradiation followed by radical surgery (n = 23). With primary surgery, ovarian function had been preserved in 15 of the 25 patients, who were alive and well. Seven of the primary surgery patients were irradiated postoperatively and 2 others with a central recurrence were cured by irradiation. One other patient, who was not irradiated postoperatively, had an intestinal metastasis and died of the disease. If any of the adverse prognostic factors (as reported in the literature) had been considered as an indication for postoperative irradiation, 17 patients instead of 7 would have been irradiated after primary radical surgery. In the comparable group of 23 patients treated by intracavitary irradiation and radical surgery (and in 4 cases postoperative irradiation as well) there was no recurrence. There was no significant statistical difference between the treatment results in the cesium + surgery group and those who underwent primary radical surgery. Young patients with early cervical carcinoma without prognostic indicators for postoperative irradiation can benefit from primary radical surgery, because their ovarian function can be preserved. (authors).

  13. Radical surgery compared with intracavitary cesium followed by radical surgery in cervical carcinoma stage IB

    International Nuclear Information System (INIS)

    Tinga, D.J.; Bouma, J.; Aalders, J.G.; Hollema, H.

    1990-01-01

    Forty-nine patients aged ≤ 45 years, with cervical carcinoma stage IB (≤ 3 cm) were treated with either primary radical surgery (n = 26), or intracavitary irradiation followed by radical surgery (n = 23). With primary surgery, ovarian function had been preserved in 15 of the 25 patients, who were alive and well. Seven of the primary surgery patients were irradiated postoperatively and 2 others with a central recurrence were cured by irradiation. One other patient, who was not irradiated postoperatively, had an intestinal metastasis and died of the disease. If any of the adverse prognostic factors (as reported in the literature) had been considered as an indication for postoperative irradiation, 17 patients instead of 7 would have been irradiated after primary radical surgery. In the comparable group of 23 patients treated by intracavitary irradiation and radical surgery (and in 4 cases postoperative irradiation as well) there was no recurrence. There was no significant statistical difference between the treatment results in the cesium + surgery group and those who underwent primary radical surgery. Young patients with early cervical carcinoma without prognostic indicators for postoperative irradiation can benefit from primary radical surgery, because their ovarian function can be preserved. (authors)

  14. Circadian clock-dependent and -independent rhythmic proteomes implement distinct diurnal functions in mouse liver.

    Science.gov (United States)

    Mauvoisin, Daniel; Wang, Jingkui; Jouffe, Céline; Martin, Eva; Atger, Florian; Waridel, Patrice; Quadroni, Manfredo; Gachon, Frédéric; Naef, Felix

    2014-01-07

    Diurnal oscillations of gene expression controlled by the circadian clock underlie rhythmic physiology across most living organisms. Although such rhythms have been extensively studied at the level of transcription and mRNA accumulation, little is known about the accumulation patterns of proteins. Here, we quantified temporal profiles in the murine hepatic proteome under physiological light-dark conditions using stable isotope labeling by amino acids quantitative MS. Our analysis identified over 5,000 proteins, of which several hundred showed robust diurnal oscillations with peak phases enriched in the morning and during the night and related to core hepatic physiological functions. Combined mathematical modeling of temporal protein and mRNA profiles indicated that proteins accumulate with reduced amplitudes and significant delays, consistent with protein half-life data. Moreover, a group comprising about one-half of the rhythmic proteins showed no corresponding rhythmic mRNAs, indicating significant translational or posttranslational diurnal control. Such rhythms were highly enriched in secreted proteins accumulating tightly during the night. Also, these rhythms persisted in clock-deficient animals subjected to rhythmic feeding, suggesting that food-related entrainment signals influence rhythms in circulating plasma factors.

  15. Observed diurnal variations in Mars Science Laboratory Dynamic Albedo of Neutrons passive mode data

    Science.gov (United States)

    Tate, C. G.; Moersch, J.; Jun, I.; Mitrofanov, I.; Litvak, M.; Boynton, W. V.; Drake, D.; Fedosov, F.; Golovin, D.; Hardgrove, C.; Harshman, K.; Kozyrev, A. S.; Kuzmin, R.; Lisov, D.; Maclennan, E.; Malakhov, A.; Mischna, M.; Mokrousov, M.; Nikiforov, S.; Sanin, A. B.; Starr, R.; Vostrukhin, A.

    2018-06-01

    The Mars Science Laboratory Dynamic Albedo of Neutrons (DAN) experiment measures the martian neutron leakage flux in order to estimate the amount of water equivalent hydrogen present in the shallow regolith. When DAN is operating in passive mode, it is sensitive to neutrons produced through the interactions of galactic cosmic rays (GCR) with the regolith and atmosphere and neutrons produced by the rover's Multi-Mission Radioisotope Thermoelectric Generator (MMRTG). During the mission, DAN passive mode data were collected over the full diurnal cycle at the locations known as Rocknest (sols 60-100) and John Klein (sols 166-272). A weak, but unexpected, diurnal variation was observed in the neutron count rates reported at these locations. We investigate different hypotheses that could be causing these observed variations. These hypotheses are variations in subsurface temperature, atmospheric pressure, the exchange of water vapor between the atmosphere and regolith, and instrumental effects on the neutron count rates. Our investigation suggests the most likely factors contributing to the observed diurnal variations in DAN passive data are instrumental effects and time-variable preferential shielding of alpha particles, with other environmental effects only having small contributions.

  16. Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN above a Ponderosa pine forest

    Directory of Open Access Journals (Sweden)

    G. M. Wolfe

    2009-01-01

    Full Text Available During the Biosphere Effects on AeRosols and Photochemistry EXperiment 2007 (BEARPEX-2007, we observed eddy covariance (EC fluxes of speciated acyl peroxy nitrates (APNs, including peroxyacetyl nitrate (PAN, peroxypropionyl nitrate (PPN and peroxymethacryloyl nitrate (MPAN, above a Ponderosa pine forest in the western Sierra Nevada. All APN fluxes are net downward during the day, with a median midday PAN exchange velocity of −0.3 cm s−1; nighttime storage-corrected APN EC fluxes are smaller than daytime fluxes but still downward. Analysis with a standard resistance model shows that loss of PAN to the canopy is not controlled by turbulent or molecular diffusion. Stomatal uptake can account for 25 to 50% of the observed downward PAN flux. Vertical gradients in the PAN thermal decomposition (TD rate explain a similar fraction of the flux, suggesting that a significant portion of the PAN flux into the forest results from chemical processes in the canopy. The remaining "unidentified" portion of the net PAN flux (~15% is ascribed to deposition or reactive uptake on non-stomatal surfaces (e.g. leaf cuticles or soil. Shifts in temperature, moisture and ecosystem activity during the summer – fall transition alter the relative contribution of stomatal uptake, non-stomatal uptake and thermochemical gradients to the net PAN flux. Daytime PAN and MPAN exchange velocities are a factor of 3 smaller than those of PPN during the first two weeks of the measurement period, consistent with strong intra-canopy chemical production of PAN and MPAN during this period. Depositional loss of APNs can be 3–21% of the gross gas-phase TD loss depending on temperature. As a source of nitrogen to the biosphere, PAN deposition represents approximately 4–19% of that due to dry deposition of nitric acid at this site.

  17. Free radicals in an Adamantane matrix. XI. Electron paramagnetic resonance study of conformations in the β-halo-tert-butyl radicals

    International Nuclear Information System (INIS)

    Lloyd, R.V.; Wood, D.E.

    1975-01-01

    The β-halo-tert-butyl radicals were prepared by x-irradiation of the corresponding isobutyl halides in an adamantane matrix at 77 0 K and their conformations were determined by analysis of their EPR spectra. The radicals are nonplanar at the radical site, the fluoro and chloro radicals trans eclipsed and the bromo and iodo radicals gauche staggered with respect to the relative orientation of the carbon halogen bond and the direction of the singly occupied orbital. Vibration-rotation motions about the favored conformation are much larger for the fluoro radical than for the others. The rate of interconversion of the inequivalent methylene protons is approximately 1.5 x 10 9 sec -1 for the bromo radical at 202 0 K while it is too slow to measure for the iodo radical at the same temperature. The barrier to interconversion has a lower limit of 3 kcal/mol for the bromo radical and higher than that for the iodo radical. The halogen and proton hfsc in gauss and the g values for the XCH 2 C(CH 3 ) 2 radicals are: 19 F = 103.7, CH 2 = 10.4, CH 3 = 23.3, g = 2.0030 at 214 K; 35 Cl = 19.5, CH 2 = 6.3, CH 3 = 21.1, g = 2.0042 at 215 K; 81 Br = 6.7, CH 2 = 21.4, 42.7, CH 3 = 21.4, g = 2.0010 at 202 K; 127 I = 7.0, CH 2 = 21.9, 43.8, CH 3 = 21.9, g = 2.0009 at 208 K. The fluoro radical decays to nonradical products above 318 0 K, the chloro radical converts to 2-methyl allyl radical above 306 0 K, the bromo radical converts to tert-butyl radical by exchange with a matrix proton (or deuteron) at 209 0 K as does the iodo radical above 225 0 K. Photolysis with a Xe lamp converts the bromo and iodo radicals to nonradical products in less than the experimental time constant of 0.3 sec. The hypothesis is put forward that the nonplanarity and high barrier to rotation observed explain the retention of stereochemical configuration in reactions involving β-chloro, β-bromo, and β-iodo alkyl radicals. (auth)

  18. The role of mesoscale convective systems in the diurnal cycle of rainfall and its seasonality over sub-Saharan Northern Africa

    Science.gov (United States)

    Liu, Weiran; Cook, Kerry H.; Vizy, Edward K.

    2018-03-01

    This study evaluates the role of MCSs in the total rainfall distribution as a function of season from a climatological perspective (1998-2014) over sub-Saharan northern Africa and examines how the diurnal cycle of rainfall changes with season. Tropical Rainfall Measuring Mission (TRMM) 3B42V7 rainfall estimates and European Centre for Medium-Range Weather Forecasts ERA-Interim reanalysis are used to evaluate the climatology. The percentages of the full TRMM precipitation delivered by MCSs have meridional structures in spring, fall and winter, ranging from 0 to 80% across sub-Saharan northern Africa, while the percentages are homogenous in summer (> 80%). The diurnal cycles of MCS-associated precipitation coincide with the full TRMM rainfall. Attributes of MCSs, including size, count, and intensity, vary synchronously with the diurnal cycle of rainfall. The diurnal peaks are classified into three categories: single afternoon peak, continuous afternoon peak, and nocturnal peak. Single afternoon peaks dominate in spring and fall while continuous afternoon and nocturnal peaks are more common in summer, indicating the seasonality of the diurnal cycle. The continuous afternoon peak combines rainfall from two system types—one locally-generated and one propagating. The seasonality of the diurnal cycle is related to the seasonality of MCS lifetimes, and propagation speeds and directions. The moisture component of the MSE profile contributes to the instability most in summer when convection is more frequent. Low-level temperature, which is related to surface warming and sensible heat fluxes, influences the instability more during winter and spring.

  19. 17.9.3 Radical cations of diazo compounds

    Science.gov (United States)

    Davies, A. G.

    This document is part of Subvolume E2 `Phosphorus-Centered Radicals, Radicals Centered on Other Heteroatoms, Organic Radical Ions' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  20. Inhibition of radiation-induced DNA strand breaks by hoechst 33258: OH-radical scavenging and DNA radical quenching

    International Nuclear Information System (INIS)

    Adhikary, A.; Bothe, E.; Von Sonntag, C.; Adhikary, A.

    1997-01-01

    The minor-groove-binding dye Hoechst 33258 has been found to protect pBR322 DNA in aqueous solution against radiation-induced single-strand breaks (ssb). This protective effect has been assumed to be largely due to the scavenging of the strand-break-generating OH radicals by Hoechst. From D 37 values for ssb at different Hoechst concentrations the value of the OH radical scavenging constant of DNA-bound Hoechst has been estimated at k Ho/DNA = 2.7 * 10 11 dm 3 mol -1 . This unexpectedly high value has led us to study the reactions of OH radicals with Hoechst in the absence and in the presence of double-stranded calf thymus DNA (ds DNA) by pulse radiolysis, and the formation of radiation-induced ssb by low angle laser light scattering. The D 37 /D 37 0 values at different Hoechst concentrations agree with the values obtained by Martin and al. and demonstrate the protection. However, this protection cannot be explained on the basis of OH radical scavenging alone using the above rate constants. There must, in addition, be some quenching of DNA radicals. Hoechst radicals are formed in the later ms time range, i.e a long time after the disappearance of the OH radicals. This delayed Hoechst radical formation has been assigned to a a reaction of DNA radicals with Hoechst, thereby inhibiting strand breakage. In confirmation, pulse radiolysis of aqueous solution of nucleotides in the presence of Hoechst yields a similar delayed Hoechst radical formation. The data indicate that in DNA the cross-section of this quenching has a diameter of 3 to 4 base pairs per Hoechst molecule. (N.C.)

  1. Radical-Local Teaching and Learning

    DEFF Research Database (Denmark)

    Hedegaard, Mariane; Chaiklin, Seth

    Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded in the l......Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded...... radical-local teaching and learning approach. The first half of the book introduces the idea of radical-local teaching and learning and develops the theoretical background for this perspective, drawing on the cultural-historical research tradition, particularly from Vygotsky, El'konin, Davydov......, and Aidarova. The second half of the book addresses the central concern of radical-local teaching and learning - how to relate educational practices to children's specific historical and cultural conditions. The experiment was conducted for an academic year in an afterschool programme in the East Harlem...

  2. Electronic structure of Co islands grown on the {radical}3 x {radical}3-Ag/Ge(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Xiao-Lan; Chou, Chi-Hao; Lin, Chun-Liang; Tomaszewska, Agnieszka; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

    2011-09-30

    By means of room temperature scanning tunneling spectroscopy (RT STS), we have studied the electronic structure of two different Ag/Ge(111) phases as well as Co islands grown on the {radical}3 x {radical}3-Ag/Ge (111) forming either {radical}13 x {radical}13 or 2 x 2 patterns. The spectrum obtained from 4 x 4-Ag/Ge(111) structure shows the existence of a shoulder at 0.7 V which is also present in the electronic structure of the Ge(111)-c2 x 8 and indicates donation of Ge electrons to electronic states of the Ag-driven phase. However, this fact is not supported by the electronic spectrum taken from the {radical}3 x {radical}3-Ag/Ge (111). The complexity of the Co-{radical}13 x {radical}13 islands bonding with the substrate is mirrored by a large number of peaks in their electronic spectra. The spectra obtained from the Co-2 x 2 islands which had grown on the step differ from those taken from Co-2 x 2 islands located along the edge of the terrace by a number of peaks at negative sample bias. This discrepancy is elucidated in terms of dissimilarities of Co-substrate interaction accompanying Co islands growth on different areas of the stepped surface.

  3. Understanding political radicalization: The two-pyramids model.

    Science.gov (United States)

    McCauley, Clark; Moskalenko, Sophia

    2017-04-01

    This article reviews some of the milestones of thinking about political radicalization, as scholars and security officials struggled after 9/11 to discern the precursors of terrorist violence. Recent criticism of the concept of radicalization has been recognized, leading to a 2-pyramids model that responds to the criticism by separating radicalization of opinion from radicalization of action. Security and research implications of the 2-pyramids model are briefly described, ending with a call for more attention to emotional experience in understanding both radicalization of opinion and radicalization of action. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

  4. Orgasm after radical prostatectomy

    NARCIS (Netherlands)

    Koeman, M; VanDriel, MF; Schultz, WCMW; Mensink, HJA

    Objective To evaluate the ability to obtain and the quality of orgasm after radical prostatectomy, Patients and methods The orgasms experienced after undergoing radical prostatectomy were evaluated in 20 men (median age 65 years, range 56-76) using a semi-structured interview and a self-administered

  5. The diurnal vertical dynamics of cape hake and their potential prey ...

    African Journals Online (AJOL)

    cephalopods. Together with their cohabitant potential prey, hake are known to undertake diurnal vertical migrations, aggregating near the bottom during daylight, but migrating off the bottom at night. An attempt to determine the ... predation dominating. This may indicate a feeding strategy where vision is not important.

  6. Global evaluation of ammonia bidirectional exchange and livestock diurnal variation schemes

    Science.gov (United States)

    Bidirectional air–surface exchange of ammonia (NH3) has been neglected in many air quality models. In this study, we implement the bidirectional exchange of NH3 in the GEOS-Chem global chemical transport model. We also introduce an updated diurnal variability scheme for NH3...

  7. O Behaviorismo Radical como filosofia da mente Radical Behaviorism as philosophy of mind

    Directory of Open Access Journals (Sweden)

    Carlos Eduardo Lopes

    2003-01-01

    Full Text Available O Behaviorismo Radical de B. F. Skinner é constantemente acusado de eliminar a mente de sua explicação do comportamento humano. Uma análise do livro The Concept of Mind, de Gilbert Ryle, sugere a possibilidade de defender a existência de uma mente relacional, diferente da categoria de existência da mente defendida em interpretações cartesianas (mente substancial. A análise de alguns textos de Skinner sugere que o conceito de uma mente relacional também pode ser defendido no Behaviorismo Radical. Esse fato, culminaria na possibilidade de que, além de filosofia da Ciência do Comportamento, o Behaviorismo Radical, também pode ser uma filosofia da mente, o que traria conseqüências ao estudo e à aplicação da Análise do Comportamento.B. F. Skinner's Radical Behaviorism has been repeatedly accused of eliminating the mind from its explanation of human behavior. An analysis of Gilbert Ryle's book, The Concept of Mind, suggests the possibility of defending the existence of a relational mind, different from the category of existence of mind defended in Cartesian interpretations (substantial mind. The analysis of some texts of Skinner suggests that the concept of a relational mind can also be defended in Radical Behaviorism. This fact would lead to the possibility that, beyond a philosophy of Behavior Science, Radical Behaviorism may also be a philosophy of mind, which would bring consequences to the study and application of Analysis of Behavior.

  8. Muonium radicals in benzene-styrene mixtures

    International Nuclear Information System (INIS)

    Ng, B.W.; Stadlbauer, J.W.; Walker, D.C.

    1984-01-01

    Muonium radicals were observed through their μ + SR precession frequencies in high transverse magnetic fields in pure benzene, pure styrene and their mixtures, all as liquids at room temperature. In benzene-styrene mixtures, the radicals obtained in each pure liquid are both present, so no slow (10 -9 -10 -5 s) intermolecular exchange occurs; but strong selectivity was found with the formation of the radical from styrene being about eight-times more probable than the radical from benzene. (Auth.)

  9. Nocturnal to Diurnal Switches with Spontaneous Suppression of Wheel-Running Behavior in a Subterranean Rodent.

    Directory of Open Access Journals (Sweden)

    Patricia Tachinardi

    Full Text Available Several rodent species that are diurnal in the field become nocturnal in the lab. It has been suggested that the use of running-wheels in the lab might contribute to this timing switch. This proposition is based on studies that indicate feed-back of vigorous wheel-running on the period and phase of circadian clocks that time daily activity rhythms. Tuco-tucos (Ctenomys aff. knighti are subterranean rodents that are diurnal in the field but are robustly nocturnal in laboratory, with or without access to running wheels. We assessed their energy metabolism by continuously and simultaneously monitoring rates of oxygen consumption, body temperature, general motor and wheel running activity for several days in the presence and absence of wheels. Surprisingly, some individuals spontaneously suppressed running-wheel activity and switched to diurnality in the respirometry chamber, whereas the remaining animals continued to be nocturnal even after wheel removal. This is the first report of timing switches that occur with spontaneous wheel-running suppression and which are not replicated by removal of the wheel.

  10. Nocturnal to Diurnal Switches with Spontaneous Suppression of Wheel-Running Behavior in a Subterranean Rodent

    Science.gov (United States)

    Tachinardi, Patricia; Tøien, Øivind; Valentinuzzi, Veronica S.; Buck, C. Loren; Oda, Gisele A.

    2015-01-01

    Several rodent species that are diurnal in the field become nocturnal in the lab. It has been suggested that the use of running-wheels in the lab might contribute to this timing switch. This proposition is based on studies that indicate feed-back of vigorous wheel-running on the period and phase of circadian clocks that time daily activity rhythms. Tuco-tucos (Ctenomys aff. knighti) are subterranean rodents that are diurnal in the field but are robustly nocturnal in laboratory, with or without access to running wheels. We assessed their energy metabolism by continuously and simultaneously monitoring rates of oxygen consumption, body temperature, general motor and wheel running activity for several days in the presence and absence of wheels. Surprisingly, some individuals spontaneously suppressed running-wheel activity and switched to diurnality in the respirometry chamber, whereas the remaining animals continued to be nocturnal even after wheel removal. This is the first report of timing switches that occur with spontaneous wheel-running suppression and which are not replicated by removal of the wheel. PMID:26460828

  11. Diurnal Dynamics of Standard Deviations of Three Wind Velocity Components in the Atmospheric Boundary Layer

    Science.gov (United States)

    Shamanaeva, L. G.; Krasnenko, N. P.; Kapegesheva, O. F.

    2018-04-01

    Diurnal dynamics of the standard deviation (SD) of three wind velocity components measured with a minisodar in the atmospheric boundary layer is analyzed. Statistical analysis of measurement data demonstrates that the SDs for x- and y-components σx and σy lie in the range from 0.2 to 4 m/s, and σz = 0.1-1.2 m/s. The increase of σx and σy with the altitude is described sufficiently well by a power law with exponent changing from 0.22 to 1.3 depending on time of day, and σz increases by a linear law. Approximation constants are determined and errors of their application are estimated. It is found that the maximal diurnal spread of SD values is 56% for σx and σy and 94% for σz. The established physical laws and the obtained approximation constants allow the diurnal dynamics of the SDs for three wind velocity components in the atmospheric boundary layer to be determined and can be recommended for application in models of the atmospheric boundary layer.

  12. On the influence of cloud fraction diurnal cycle and sub-grid cloud optical thickness variability on all-sky direct aerosol radiative forcing

    International Nuclear Information System (INIS)

    Min, Min; Zhang, Zhibo

    2014-01-01

    The objective of this study is to understand how cloud fraction diurnal cycle and sub-grid cloud optical thickness variability influence the all-sky direct aerosol radiative forcing (DARF). We focus on the southeast Atlantic region where transported smoke is often observed above low-level water clouds during burning seasons. We use the CALIOP observations to derive the optical properties of aerosols. We developed two diurnal cloud fraction variation models. One is based on sinusoidal fitting of MODIS observations from Terra and Aqua satellites. The other is based on high-temporal frequency diurnal cloud fraction observations from SEVIRI on board of geostationary satellite. Both models indicate a strong cloud fraction diurnal cycle over the southeast Atlantic region. Sensitivity studies indicate that using a constant cloud fraction corresponding to Aqua local equatorial crossing time (1:30 PM) generally leads to an underestimated (less positive) diurnal mean DARF even if solar diurnal variation is considered. Using cloud fraction corresponding to Terra local equatorial crossing time (10:30 AM) generally leads overestimation. The biases are a typically around 10–20%, but up to more than 50%. The influence of sub-grid cloud optical thickness variability on DARF is studied utilizing the cloud optical thickness histogram available in MODIS Level-3 daily data. Similar to previous studies, we found the above-cloud smoke in the southeast Atlantic region has a strong warming effect at the top of the atmosphere. However, because of the plane-parallel albedo bias the warming effect of above-cloud smoke could be significantly overestimated if the grid-mean, instead of the full histogram, of cloud optical thickness is used in the computation. This bias generally increases with increasing above-cloud aerosol optical thickness and sub-grid cloud optical thickness inhomogeneity. Our results suggest that the cloud diurnal cycle and sub-grid cloud variability are important factors

  13. Laparoscopic radical cystectomy: key points

    Directory of Open Access Journals (Sweden)

    D. V. Perlin

    2018-01-01

    Full Text Available Background. Radical cystectomy remains the golden standard for treatment of muscle invasive bladder cancer. Objective: to duplicate with highest accuracy the open radical cystectomy procedure, which we successfully utilized earlier in our clinic, in the of laparoscopic conditions in order to preserve the advantages of minimally invasive procedures and retain the reliability of the tried and tested open surgery.Materials and methods. In the report were included 35 patients (27 men and 8 women with bladder cancer, who underwent laparoscopic radical cystectomy in Volgograd Regional Center of Urology and Nephrology between April 2013 and March 2016. Only the patients who had been submitted to full intracorporal ileal conduits were included.Results. The mean operative time was 378 minutes, the mean blood loss was 285 millilitres, the mean length of hospital stay was 12.4 days, only 20 % of patients required the narcotic anesthetics. The postoperative complication rate was 11.4 %. However, the majority of the patients were successfully treated with minimally invasive procedures. Generally, our results were similar to other reported studies.Conclusion. Laparoscopic radical cystectomy is a safe and efficient modality of treatment of bladder cancer. However, it needs more procedures and longer observation period to establish laparoscopic radical cystectomy as an alternative to open radical cystectomy.

  14. Seasonal variations of the semi-diurnal and diurnal tides in the MLT: multi-year MF radar observations from 2 to 70°N, and the GSWM tidal model

    Science.gov (United States)

    Manson, A.; Meek, C.; Hagan, M.; Hall, C.; Hocking, W.; MacDougall, J.; Franke, S.; Riggin, D.; Fritts, D.; Vincent, R.; Burrage, M.

    1999-07-01

    Continuous observations of the wind field have been made by six Medium Frequency Radars (MFRs), located between the equator and high northern latitudes: Christmas Islands (2°N), Hawaii (22°N), Urbana (40°N), London (43°N), Saskatoon (52°N) and Tromsø (70°N). Data have been sought for the time interval 1990-1997, and typically 5 years of data have become available from each station, to demonstrate the level of annual consistency and variability. Common harmonic analysis is applied so that the monthly amplitudes and phases of the semi-diurnal (SD) and diurnal (D) wind oscillations are available in the height range of (typically) 75-95 km in the upper Middle Atmosphere. Comparisons are made with tides from the Global Scale Wave Model (GSWM), which are available for 3-month seasons. The emphasis is upon the monthly climatologies at each location based upon comparisons of profiles, and also latitudinal plots of amplitudes and phases at particular heights. For the diurnal tide, the agreement between observations and model is now quite excellent with modelled values frequently lying within the range of yearly values. Both observations and model demonstrate strong seasonal changes. This result is a striking improvement over the comparisons of 1989 (JATP, Special issue). In particular, the phases and phase-gradients for the non-winter months at mid- to high-latitudes are now in excellent agreement. Some of the low latitude discrepancies are attributed to the existence of non-migrating tidal components associated with tropospheric latent heat release. For the semi-diurnal tide, the observed strong transitions between clear solstitial states are less well captured by the model. There is little evidence for improvement over the promising comparisons of 1989. In particular, the late-summer/autumnal tidal maximum of mid-latitudes is observed to be larger, and with strong monthly variability. Also the summer modelled tide has unobserved short (20 km) wavelengths at high

  15. Effects of Molecular Iodine and 4-tert-Butylcatechol Radical Inhibitor on the Radical Polymerization of Styrene

    Directory of Open Access Journals (Sweden)

    Mojtaba Bozorg

    2017-05-01

    Full Text Available The presence of molecular iodine was studied in relation the molecular weight and molecular weight distribution of polystyrene, produced by radical poly merization. Radical polymerization of styrene initiated by 2,2׳-azobisisobutyronitrile (AIBN was performed at 70°C in the presence of molecular iodine. The synthesized polymers were characterized by gel permeation chromatography (GPC and proton- nuclear magnetic resonance (1H NMR techniques. The results of these reactions including conversion data, number-average molecular weight and molecular weight distribution were compared with those obtained for styrene radical polymerization initiated by AIBN at the same temperature in the absence of molecular iodine. It was found that the presence of iodine had a profound effect on the molecular weight and its distribution in the produced polystyrene. This was attributed to the ability of iodine to control the polymerization of styrene initiated by AIBN via reverse iodine transfer polymerization (RITP mechanism. The polymer produced by this method had a molecular weight of 10600 g/mol with a molecular weight polydispersity index of 1.3. Due to the importance of induction period in reverse iodine transfer radical polymerization, increasing the temperature to 120°C during the induction period resulted in shorter induction periods and the produced species led to better control of the molecular weight. Also, due to the role of iodine molecules as a radical inhibitor, the presence of a secondary radical inhibitor, i.e. 4-tert-butylcatechol, along with the iodine was investigated in radical polymerization of polystyrene initiated by AIBN. It was observed that the secondary radical inhibitor prevented the consumption of the iodine molecules by the radicals produced from decomposition of the AIBN initiator; therefore, alkyl halides were not produced during the induction period.

  16. Diurnal circulations and their multi-scale interaction leading to rainfall over the South China Sea upstream of the Philippines during intraseasonal monsoon westerly wind bursts

    Energy Technology Data Exchange (ETDEWEB)

    Park, Myung-Sook; Elsberry, Russell L. [Naval Postgraduate School, Department of Meteorology, Monterey, CA (United States); Ho, Chang-Hoi [Seoul National University, School of Earth and Environmental Sciences, Seoul (Korea, Republic of); Kim, Jinwon [University of California in Los Angeles, Department of Meteorology, Berkeley, CA (United States)

    2011-10-15

    The morning diurnal precipitation maximum over the coastal sea upstream of the Philippines during intraseasonal westerly wind bursts is examined from observations and numerical model simulations. A well-defined case of precipitation and large-scale circulation over the coastal sea west of the Philippines during 17-27 June 2004 is selected as a representative case. The hypothesis is that the mesoscale diurnal circulation over the Philippines and a large-scale diurnal circulation that is induced by large-scale differential heating over Asian continent and the surrounding ocean interact to produce the offshore precipitation maximum during the morning. Three-hourly combined satellite microwave and infrared rainfall retrievals define the morning rainfall peak during this period, and then later the stratiform rain area extends toward the open sea. A control numerical simulation in which a grid-nudging four-dimensional data assimilation (FDDA) is applied to force the large-scale diurnal circulation represents reasonably well the morning rainfall maximum. An enhanced low-level convergence similar to observations is simulated due to the interaction of the local- and large-scale diurnal circulations. The essential role of the local-scale diurnal circulation is illustrated in a sensitivity test in which the solar zenith angle is fixed at 7 am to suppress this diurnal circulation. The implication for climate diagnosis or modeling of such upstream coastal sea precipitation maxima is that the diurnal variations of both the local- and the large-scale circulations must be taken into consideration. (orig.)

  17. Evaluation of the diurnal intraocular pressure fluctuations and blood pressure under dehydration due to fasting

    Directory of Open Access Journals (Sweden)

    Gonen Baser

    2016-12-01

    Full Text Available Introduction: This study aimed to investigate the diurnal intraocular pressure fluctuations under dehydration conditions and the relationship between the intraocular pressure fluctuations and blood pressure. Methods: The intraocular pressures (IOP, body weights, as well as systolic and diastolic blood pressures (SBP, DBP of 36 fasting healthy volunteers were recorded at 8:00 a.m. and 5:00 p.m. in the Ramadan of 2014 and two weeks after it. The data were analyzed using paired Student’s t-test and Pearson correlation analysis. Results: As the results demonstrated, the mean diurnal IOP differences of IOP, SBP, DBP, and weight were 2.67±1.33 mmHg, 9.44±8.02 mmHg, 3.33±5.94 mmHg, and 0.90±0.46 kg during the fasting period, respectively. In addition, the mean diurnal IOP differences of IOP, SBP, DBP, and weight were -0.33±1.4 mmHg (P=0.001, 0.55±7.25mmHg (P=0.003, -3.33±5.94 mmHg (P=0.001, and 0.12±0.45 kg (P=0.001 during the control period, respectively. There was a moderate correlation between the diurnal IOP and SBP differences (r=0.517, P=0.028. Conclusion: Based on the findings of the current study, the total fluid volume might have a more dominant effect on IOP peaks than the sympathetic system activity. Furthermore, the SBP was found to correlate with the IOP.

  18. Computational study of hydrogen shifts and ring-opening mechanisms in α-pinene ozonolysis products

    DEFF Research Database (Denmark)

    Kurtén, Theo; Rissanen, Matti P.; Mackeprang, Kasper

    2015-01-01

    , sterically unhindered) H-shifts of all four peroxy radicals formed in the ozonolysis of α-pinene using density functional (ωB97XD) and coupled cluster [CCSD(T)-F12] theory. In contrast to the related but chemically simpler cyclohexene ozonolysis system, none of the calculated H-shifts have rate constants...... products in the α-pinene ozonolysis system, additional ring-opening reaction mechanisms breaking the cyclobutyl ring are therefore needed. We further investigate possible uni- and bimolecular pathways for opening the cyclobutyl ring in the α-pinene ozonolysis system....

  19. Sources of HO x and production of ozone in the upper troposphere over the United States

    OpenAIRE

    Jaeglé, L.; Jacob, Daniel James; Brune, W. H.; Tan, D.; Faloona, I. C.; Weinheimer, A. J.; Ridley, B. A.; Campos, T. L.; Sachse, G. W.

    1998-01-01

    The sources of HOx (OH+peroxy radicals) and the associated production of ozone at 8–12 km over the United States are examined by modeling observations of OH, HO2, NO, and other species during the SUCCESS aircraft campaign in April–May 1996. The HOx concentrations measured in SUCCESS are up to a factor of 3 higher than can be calculated from oxidation of water vapor and photolysis of acetone. The highest discrepancy was seen in the outflow of a convective storm. We show that convective injecti...

  20. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2011-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  1. Radical chemistry of artemisinin

    Science.gov (United States)

    Denisov, Evgenii T.; Solodova, S. L.; Denisova, Taisa G.

    2010-12-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  2. Radical chemistry of artemisinin

    International Nuclear Information System (INIS)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G

    2010-01-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  3. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2010-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  4. Oxygen free radicals in rheumatoid arthritis

    NARCIS (Netherlands)

    P. Biemond (Pieter)

    1986-01-01

    textabstractCurrent knowledge strongly suggests that oxygen free radicals are involved in the pathogenesis of RA. Additional information about the mechanism of free radical attack is necessary in order to find out if interaction with the mechanism of free radical damage can be used in the treatment

  5. Free radicals in health and disease

    International Nuclear Information System (INIS)

    Gonet, B.

    1993-01-01

    Free radicals appear in the cells as the result of exogenic factors (ionizing radiation, UV) or reactions naturally occurring in the cell. Free radical reactions may cause destruction of macromolecules (DNA, lipids, proteins). Free radical pathology is important in many diseases and aging processes in organisms

  6. Diurnal Variations of the Flux Imbalance Over Homogeneous and Heterogeneous Landscapes

    Science.gov (United States)

    Zhou, Yanzhao; Li, Dan; Liu, Heping; Li, Xin

    2018-05-01

    It is well known that the sum of the turbulent sensible and latent heat fluxes as measured by the eddy-covariance method is systematically lower than the available energy (i.e., the net radiation minus the ground heat flux). We examine the separate and joint effects of diurnal and spatial variations of surface temperature on this flux imbalance in a dry convective boundary layer using the Weather Research and Forecasting model. Results show that, over homogeneous surfaces, the flux due to turbulent-organized structures is responsible for the imbalance, whereas over heterogeneous surfaces, the flux due to mesoscale or secondary circulations is the main contributor to the imbalance. Over homogeneous surfaces, the flux imbalance in free convective conditions exhibits a clear diurnal cycle, showing that the flux-imbalance magnitude slowly decreases during the morning period and rapidly increases during the afternoon period. However, in shear convective conditions, the flux-imbalance magnitude is much smaller, but slightly increases with time. The flux imbalance over heterogeneous surfaces exhibits a diurnal cycle under both free and shear convective conditions, which is similar to that over homogeneous surfaces in free convective conditions, and is also consistent with the general trend in the global observations. The rapid increase in the flux-imbalance magnitude during the afternoon period is mainly caused by the afternoon decay of the turbulent kinetic energy (TKE). Interestingly, over heterogeneous surfaces, the flux imbalance is linearly related to the TKE and the difference between the potential temperature and surface temperature, ΔT; the larger the TKE and ΔT values, the smaller the flux-imbalance magnitude.

  7. Free radicals in wood induced by γ-radiation

    International Nuclear Information System (INIS)

    Xu Honglin; Zhang Wenhui

    1994-01-01

    The free radicals in wood induced by γ-radiation were studied by electron spin resonance. The fine structure of the ESR signal from sawdust samples irradiated could be resolved into various radicals. These free radicals have a very long lifetime. The major spectrum for the free radicals will exponentially increased along with the radiation dose according to Y 1-Exp(-α a D). The intensity of radiation radicals is dependent on tree species. The stronger the intensity of mechanic free radicals is, the stronger the intensity of radiation free radicals

  8. Diurnal Solar Energy Conversion and Photoprotection in Rice Canopies.

    Science.gov (United States)

    Meacham, Katherine; Sirault, Xavier; Quick, W Paul; von Caemmerer, Susanne; Furbank, Robert

    2017-01-01

    Genetic improvement of photosynthetic performance of cereal crops and increasing the efficiency with which solar radiation is converted into biomass has recently become a major focus for crop physiologists and breeders. The pulse amplitude modulated chlorophyll fluorescence technique (PAM) allows quantitative leaf level monitoring of the utilization of energy for photochemical light conversion and photoprotection in natural environments, potentially over the entire crop lifecycle. Here, the diurnal relationship between electron transport rate (ETR) and irradiance was measured in five cultivars of rice (Oryza sativa) in canopy conditions with PAM fluorescence under natural solar radiation. This relationship differed substantially from that observed for conventional short term light response curves measured under controlled actinic light with the same leaves. This difference was characterized by a reduced curvature factor when curve fitting was used to model this diurnal response. The engagement of photoprotective processes in chloroplast electron transport in leaves under canopy solar radiation was shown to be a major contributor to this difference. Genotypic variation in the irradiance at which energy flux into photoprotective dissipation became greater than ETR was observed. Cultivars capable of higher ETR at midrange light intensities were shown to produce greater leaf area over time, estimated by noninvasive imaging. © 2017 American Society of Plant Biologists. All Rights Reserved.

  9. Nonphotic entrainment in a diurnal mammal, the European ground squirrel (Spermophilus citellus)

    NARCIS (Netherlands)

    Hut, Roelof A.; Mrosovsky, N.; Daan, Serge

    1999-01-01

    Entrainment by nonphotic, activity-inducing stimuli has been investigated in detail in nocturnal rodents, but little is known about nonphotic entrainment in diurnal animals. Comparative studies would offer the opportunity to distinguish between two possibilities. (1) If nonphotic phase shifts depend

  10. Radical-Local Teaching and Learning

    DEFF Research Database (Denmark)

    Hedegaard, Mariane; Chaiklin, Seth

    radical-local teaching and learning approach. The first half of the book introduces the idea of radical-local teaching and learning and develops the theoretical background for this perspective, drawing on the cultural-historical research tradition, particularly from Vygotsky, El'konin, Davydov......, and Aidarova. The second half of the book addresses the central concern of radical-local teaching and learning - how to relate educational practices to children's specific historical and cultural conditions. The experiment was conducted for an academic year in an afterschool programme in the East Harlem......Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded...

  11. What is Radical Behaviorism? A Review of Jay Moore's Conceptual Foundations of Radical Behaviorism

    Science.gov (United States)

    Baum, William M

    2011-01-01

    B. F. Skinner founded both radical behaviorism and behavior analysis. His founding innovations included: a versatile preparation for studying behavior; explicating the generic nature of stimulus and response; a pragmatic criterion for defining behavioral units; response rate as a datum; the concept of stimulus control; the concept of verbal behavior; and explicating the explanatory power of contingencies. Besides these achievements, however, Skinner also made some mistakes. Subsequent developments in radical behaviorist thought have attempted to remedy these mistakes. Moore's book presents a “party line” version of radical behaviorism. It focuses narrowly on a few of Skinner's concepts (mostly mentalism and verbal behavior) and contains no criticism of his mistakes. In fact, Moore adds a few mistakes of his own manufacture; for example, he insists that the mental realm does not exist—an unprovable and distracting assertion. The book's portrayal of behavior analysis would have been current around 1960; it mentions almost none of the developments since then. It also includes almost no developments in radical behaviorism since Skinner. Moore's book would give an unwary reader a highly distorted picture of contemporary behavior analysis and radical behaviorism.

  12. Orthographic Skills Important to Chinese Literacy Development: The Role of Radical Representation and Orthographic Memory of Radicals

    Science.gov (United States)

    Yeung, Pui-sze; Ho, Connie Suk-han; Chan, David Wai-ock; Chung, Kevin Kien-hoa

    2016-01-01

    A 3-year longitudinal study among 239 Chinese students in Grades 2-4 was conducted to investigate the relationships between orthographic skills (including positional and functional knowledge of semantic radicals and phonetic radicals, and orthographic memory of radicals) and Chinese literacy skills (word reading, word spelling, reading…

  13. The Games Radicals Play: Special Issue on Free Radicals and Radical Ions

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2015-02-01

    Full Text Available Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and arrangements appearing on the scene are even more interesting. Some of these are ephemeral and enjoy only a brief appearance, others are retro-types reappearing in new guises, still others are genuinely new and “go viral” in the scientific world. This Special Issue of Molecules contains the observations and reflections of a select group of chemists and physicists fascinated by this spectacle. It contains an eclectic mix reflecting on new modes and advances as well as on permutations and combinations that revive mature themes. [...

  14. Mn-Catalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols.

    Science.gov (United States)

    Sun, Xiang; Li, Xinyao; Song, Song; Zhu, Yuchao; Liang, Yu-Feng; Jiao, Ning

    2015-05-13

    An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.

  15. Bibliographies on radiation chemistry

    International Nuclear Information System (INIS)

    Greenstock, C.L.; Ross, A.B.; Helman, W.P.

    1981-01-01

    This bibliography lists about 400 papers dealing solely with the production and reactivity of superoxide radical anions in irradiated aqueous and organic liquids. Only papers dealing with quantitative mechanistic, spectroscopic or kinetic data have been included. The listing was prepared by searching the RCDC bibliographic data base with SELECT keywords O 2 - or HO 2 and aqueous solution. The key words radicals (oxygen), peroxy radicals, pulse radiolysis, flash radiolysis, esr and gamma rays were also used. Additional relevant references were obtained from inspection of reviews, individual author indexes and cited references. The present bibliography excludes solid and gas phase studies, and also technical, government and in-house reports, theses, patents and some symposia proceedings. Several references prior to 1960 have been added, and the list should be reasonably comprehensive from 1965-1980. The listing is in chronological order, according to year of publication in the categories Photochemistry, Radiation Chemistry, Other, and Reviews. (author)

  16. Mechanisms of diurnal precipitation over the US Great Plains: a cloud resolving model perspective

    Science.gov (United States)

    Lee, Myong-In; Choi, Ildae; Tao, Wei-Kuo; Schubert, Siegfried D.; Kang, In-Sik

    2010-02-01

    The mechanisms of summertime diurnal precipitation in the US Great Plains were examined with the two-dimensional (2D) Goddard Cumulus Ensemble (GCE) cloud-resolving model (CRM). The model was constrained by the observed large-scale background state and surface flux derived from the Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Program’s Intensive Observing Period (IOP) data at the Southern Great Plains (SGP). The model, when continuously-forced by realistic surface flux and large-scale advection, simulates reasonably well the temporal evolution of the observed rainfall episodes, particularly for the strongly forced precipitation events. However, the model exhibits a deficiency for the weakly forced events driven by diurnal convection. Additional tests were run with the GCE model in order to discriminate between the mechanisms that determine daytime and nighttime convection. In these tests, the model was constrained with the same repeating diurnal variation in the large-scale advection and/or surface flux. The results indicate that it is primarily the surface heat and moisture flux that is responsible for the development of deep convection in the afternoon, whereas the large-scale upward motion and associated moisture advection play an important role in preconditioning nocturnal convection. In the nighttime, high clouds are continuously built up through their interaction and feedback with long-wave radiation, eventually initiating deep convection from the boundary layer. Without these upper-level destabilization processes, the model tends to produce only daytime convection in response to boundary layer heating. This study suggests that the correct simulation of the diurnal variation in precipitation requires that the free-atmospheric destabilization mechanisms resolved in the CRM simulation must be adequately parameterized in current general circulation models (GCMs) many of which are overly sensitive to the parameterized boundary layer

  17. Habitual sleep quality and diurnal rhythms of salivary cortisol and dehydroepiandrosterone in postmenopausal women.

    Science.gov (United States)

    Huang, Tianyi; Poole, Elizabeth M; Vetter, Celine; Rexrode, Kathryn M; Kubzansky, Laura D; Schernhammer, Eva; Rohleder, Nicolas; Hu, Frank B; Redline, Susan; Tworoger, Shelley S

    2017-10-01

    Dysregulation of the hypothalamus-pituitary-adrenal (HPA) axis has been suggested as a potential mechanism linking sleep and cardiometabolic disorders. However, the associations of two primary outputs of the HPA axis, cortisol and its antagonist dehydroepiandrosterone (DHEA), with sleep are less well studied. In the Nurses' Health Study II, 233 postmenopausal women provided five timed saliva samples over one day (immediately upon waking, 45min, 4h, and 10h after waking, and prior to going to sleep) to measure cortisol and DHEA. Of these, 209 completed assessment of their habitual sleep patterns using the Pittsburgh Sleep Quality Index (PSQI). We used piecewise linear mixed models to compare cross-sectional associations of slopes reflecting diurnal cortisol and DHEA rhythms with overall sleep quality and with seven sub-components. Overall, we observed no differences in the diurnal patterns of cortisol or DHEA between good versus poor sleepers as assessed by the global PSQI score. However, longer sleep latency was associated with significantly reduced cortisol awakening rise (p=0.02). Poorer subjective sleep quality (p=0.02), shorter sleep duration (p=0.02), and lower sleep efficiency (p=0.03) were associated with slower rate of cortisol decline later in the day. Women reporting daytime dysfunction had a sharper cortisol decline early in the day (p=0.03) but a flattened decline later in the day (p=0.01). The differences in diurnal patterns of DHEA between good versus poor sleepers, though less pronounced, were similar in direction to those of cortisol. Self-reported sleep duration, efficiency, latency and daytime dysfunction were associated with altered diurnal rhythms of cortisol and, to a lesser extent, DHEA. These findings provide support for the interplay between sleep and the HPA axis that may contribute to cardiometabolic disease. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Seasonal variations of the semi-diurnal and diurnal tides in the MLT: multi-year MF radar observations from 2–70° N, modelled tides (GSWM, CMAM

    Directory of Open Access Journals (Sweden)

    A. H. Manson

    2002-05-01

    Full Text Available In an earlier paper (Manson et al., 1999a tidal data (1990–1997 from six Medium Frequency Radars (MFR were compared with the Global Scale Wave Model (GSWM, original 1995 version. The radars are located between the equator and high northern latitudes: Christmas Island (2° N, Hawaii (22° N, Urbana (40° N, London (43° N, Saskatoon (52° N and Tromsø (70° N. Common harmonic analysis was applied, to ensure consistency of amplitudes and phases in the 75–95 km height range. For the diurnal tide, seasonal agreements between observations and model were excellent while for the semi-diurnal tide the seasonal transitions between clear solstitial states were less well captured by the model. Here the data set is increased by the addition of two locations in the Pacific-North American sector: Yamagawa 31° N, and Wakkanai 45° N. The GSWM model has undergone two additional developments (1998, 2000 to include an improved gravity wave (GW stress parameterization, background winds from UARS systems and monthly tidal forcing for better characterization of seasonal change. The other model, the Canadian Middle Atmosphere Model (CMAM which is a General Circulation Model, provides internally generated forcing (due to ozone and water vapour for the tides. The two GSWM versions show distinct differences, with the 2000 version being either closer to, or further away from, the observations than the original 1995 version. CMAM provides results dependent upon the GW parameterization scheme inserted, but one of the schemes provides very useful tides, especially for the semi-diurnal component.Key words. Meteorology and atmospheric dynamics (middle atmosphere dynamics; waves and tides

  19. Radical-pair based avian magnetoreception

    Science.gov (United States)

    Procopio, Maria; Ritz, Thorsten

    2014-03-01

    Behavioural experiments suggest that migratory birds possess a magnetic compass sensor able to detect the direction of the geomagnetic. One hypothesis for the basis of this remarkable sensory ability is that the coherent quantum spin dynamics of photoinduced radical pair reactions transduces directional magnetic information from the geomagnetic field into changes of reaction yields, possibly involving the photoreceptor cryptochrome in the birds retina. The suggested radical-pair based avian magnetoreception has attracted attention in the field of quantum biology as an example of a biological sensor which might exploit quantum coherences for its biological function. Investigations on such a spin-based sensor have focussed on uncovering the design features for the design of a biomimetic magnetic field sensor. We study the effects of slow fluctuations in the nuclear spin environment on the directional signal. We quantitatively evaluate the robustness of signals under fluctuations on a timescale longer than the lifetime of a radical pair, utilizing two models of radical pairs. Our results suggest design principles for building a radical-pair based compass sensor that is both robust and highly directional sensitive.

  20. Amazon forest structure generates diurnal and seasonal variability in light utilization

    Science.gov (United States)

    Douglas C. Morton; Jeremy Rubio; Bruce D. Cook; Jean-Philippe Gastellu-Etchegorry; Marcos Longo; Hyeungu Choi; Maria Hunter; Michael Keller

    2016-01-01

    The complex three-dimensional (3-D) structure of tropical forests generates a diversity of light environments for canopy and understory trees. Understanding diurnal and seasonal changes in light availability is critical for interpreting measurements of net ecosystem exchange and improving ecosystem models. Here, we used the Discrete Anisotropic Radiative Transfer (DART...

  1. Annual and diurnal african biomass burning temporal dynamics

    Directory of Open Access Journals (Sweden)

    G. Roberts

    2009-05-01

    Full Text Available Africa is the single largest continental source of biomass burning emissions. Here we conduct the first analysis of one full year of geostationary active fire detections and fire radiative power data recorded over Africa at 15-min temporal interval and a 3 km sub-satellite spatial resolution by the Spinning Enhanced Visible and Infrared Imager (SEVIRI imaging radiometer onboard the Meteosat-8 satellite. We use these data to provide new insights into the rates and totals of open biomass burning over Africa, particularly into the extremely strong seasonal and diurnal cycles that exist across the continent. We estimate peak daily biomass combustion totals to be 9 and 6 million tonnes of fuel per day in the northern and southern hemispheres respectively, and total fuel consumption between February 2004 and January 2005 is estimated to be at least 855 million tonnes. Analysis is carried out with regard to fire pixel temporal persistence, and we note that the majority of African fires are detected only once in consecutive 15 min imaging slots. An investigation of the variability of the diurnal fire cycle is carried out with respect to 20 different land cover types, and whilst differences are noted between land covers, the fire diurnal cycle characteristics for most land cover type are very similar in both African hemispheres. We compare the Fire Radiative Power (FRP derived biomass combustion estimates to burned-areas, both at the scale of individual fires and over the entire continent at a 1-degree scale. Fuel consumption estimates are found to be less than 2 kg/m2 for all land cover types noted to be subject to significant fire activity, and for savanna grasslands where literature values are commonly reported the FRP-derived median fuel consumption estimate of 300 g/m2 is well within commonly quoted values. Meteosat-derived FRP data of the type presented here is now available freely to interested users continuously and in near

  2. An explanation for the different climate sensitivities of land and ocean surfaces based on the diurnal cycle

    Directory of Open Access Journals (Sweden)

    A. Kleidon

    2017-09-01

    Full Text Available Observations and climate model simulations consistently show a higher climate sensitivity of land surfaces compared to ocean surfaces. Here we show that this difference in temperature sensitivity can be explained by the different means by which the diurnal variation in solar radiation is buffered. While ocean surfaces buffer the diurnal variations by heat storage changes below the surface, land surfaces buffer it mostly by heat storage changes above the surface in the lower atmosphere that are reflected in the diurnal growth of a convective boundary layer. Storage changes below the surface allow the ocean surface–atmosphere system to maintain turbulent fluxes over day and night, while the land surface–atmosphere system maintains turbulent fluxes only during the daytime hours, when the surface is heated by absorption of solar radiation. This shorter duration of turbulent fluxes on land results in a greater sensitivity of the land surface–atmosphere system to changes in the greenhouse forcing because nighttime temperatures are shaped by radiative exchange only, which are more sensitive to changes in greenhouse forcing. We use a simple, analytic energy balance model of the surface–atmosphere system in which turbulent fluxes are constrained by the maximum power limit to estimate the effects of these different means to buffer the diurnal cycle on the resulting temperature sensitivities. The model predicts that land surfaces have a 50 % greater climate sensitivity than ocean surfaces, and that the nighttime temperatures on land increase about twice as much as daytime temperatures because of the absence of turbulent fluxes at night. Both predictions compare very well with observations and CMIP5 climate model simulations. Hence, the greater climate sensitivity of land surfaces can be explained by its buffering of diurnal variations in solar radiation in the lower atmosphere.

  3. Diurnal variations of airborne fungal spores concentration in the town and rural area

    Directory of Open Access Journals (Sweden)

    Idalia Kasprzyk

    2012-12-01

    Full Text Available Airborne fungal spores were monitored in 2001-2002 in Rzeszów (town and its neighborhood. The aim of investigations was to ascertain if there were differences in diurnal variations of airborne fungal spores concentration between town and rural area. The sampling was carried out using volumetric method. Traps were located at the same heights - app. 12 m. Airborne spores were sampled continuously. Microscopical slides were prepared for each day. Analysis was carried out on one longitudinal band of 48 mm long divided into 24 segments corresponding following hours of day. The results were expressed as mean number of fungal spores per cubic meter per 24 hours. For this survey, five geni of allergenic fungi were selected: Alternaria, Botrytis, Cladosporium, Epicoccum, Ganoderma. The concentrations of their airborne spores were high or very high. It was calculated theoretical day, where the hourly count was the percentage mean of number of spores at that time every chosen day without rainfall from 2001 and 2001 years. The diurnal periodicity of Alternaria, Cladosporium, Epicoccum and Ganoderma showed one peak, while Botrytis two. Anamorphic spores peaked in the afternoon, while their minima occurred in the morning. The highest concentrations of Ganoderma basidiospores were at down or at night, but minima during the day. There were no clear differences in the peak values between two studied sites. The results indicate that maximum concentrations of all spores generally occurred a few hour earlier in the rural area than in the town. Probably, in the rural area airborne spores came from many local sources and their diurnal periodicity reflected rhythm of spore liberation. Towns are characterized by specific microclimate with higher temperature and wind blowing to the centre. In Rzeszów fungal spores could be transported outside and carried out by wind from distant sources. This study showed, among others, that habitat conditions are an important factors

  4. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali

    2009-12-17

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  5. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali; Khashab, Niveen M.; Fahrenbach, Albert C.; Friedman, Douglas C.; Colvin, Michael T.; Coti, Karla K.; Bení tez, Diego S.; Tkatchouk, Ekaterina; Olsen, John Carl; Belowich, Matthew E.; Carmieli, Raanan; Khatib, Hussam A.; Goddard, William Andrew III; Wasielewski, Michael R.; Stoddart, Fraser Fraser Raser

    2009-01-01

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  6. Formation and spectroscopy of {alpha}-muoniated radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W

    2003-02-01

    Several novel {alpha}-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In {alpha}-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a {beta}-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison.

  7. Formation and spectroscopy of α-muoniated radicals

    International Nuclear Information System (INIS)

    McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W.

    2003-01-01

    Several novel α-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In α-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a β-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison

  8. Effects of diurnal variations in temperature on non-accidental mortality among the elderly population of Montreal, Québec, 1984-2007.

    Science.gov (United States)

    Vutcovici, Maria; Goldberg, Mark S; Valois, Marie-France

    2014-07-01

    The association between ambient temperature and mortality has been studied extensively. Recent data suggest an independent role of diurnal temperature variations in increasing daily mortality. Elderly adults-a growing subgroup of the population in developed countries-may be more susceptible to the effects of temperature variations. The aim of this study was to determine whether variations in diurnal temperature were associated with daily non-accidental mortality among residents of Montreal, Québec, who were 65 years of age and over during the period between 1984 and 2007. We used distributed lag non-linear Poisson models constrained over a 30-day lag period, adjusted for temporal trends, mean daily temperature, and mean daily concentrations of nitrogen dioxide and ozone to estimate changes in daily mortality with diurnal temperature. We found, over the 30 day lag period, a cumulative increase in daily mortality of 5.12% [95% confidence interval (CI): 0.02-10.49%] for a change from 5.9 °C to 11.1 °C (25th to 75th percentiles) in diurnal temperature, and a 11.27% (95%CI: 2.08-21.29%) increase in mortality associated with an increase of diurnal temperature from 11.1 to 17.5 °C (75th to 99th percentiles). The results were relatively robust to adjustment for daily mean temperature. We found that, in Montreal, diurnal variations in temperature are associated with a small increase in non-accidental mortality among the elderly population. More studies are needed in different geographical locations to confirm this effect.

  9. Estimation of Diurnal Cycle of Land Surface Temperature at High Temporal and Spatial Resolution from Clear-Sky MODIS Data

    Directory of Open Access Journals (Sweden)

    Si-Bo Duan

    2014-04-01

    Full Text Available The diurnal cycle of land surface temperature (LST is an important element of the climate system. Geostationary satellites can provide the diurnal cycle of LST with low spatial resolution and incomplete global coverage, which limits its applications in some studies. In this study, we propose a method to estimate the diurnal cycle of LST at high temporal and spatial resolution from clear-sky MODIS data. This method was evaluated using the MSG-SEVIRI-derived LSTs. The results indicate that this method fits the diurnal cycle of LST well, with root mean square error (RMSE values less than 1 K for most pixels. Because MODIS provides at most four observations per day at a given location, this method was further evaluated using only four MSG-SEVIRI-derived LSTs corresponding to the MODIS overpass times (10:30, 13:30, 22:30, and 01:30 local solar time. The results show that the RMSE values using only four MSG-SEVIRI-derived LSTs are approximately two times larger than those using all LSTs. The spatial distribution of the modeled LSTs at the MODIS pixel scale is presented from 07:00 to 05:00 local solar time of the next day with an increment of 2 hours. The diurnal cycle of the modeled LSTs describes the temporal evolution of the LSTs at the MODIS pixel scale.

  10. The diurnal interaction between convection and peninsular-scale forcing over South Florida

    Science.gov (United States)

    Cooper, H. J.; Simpson, J.; Garstang, M.

    1982-01-01

    One of the outstanding problems in modern meterology is that of describing in detail the manner in which larger scales of motion interact with, influence and are influenced by successively smaller scales of motion. The present investigation is concerned with a study of the diurnal evolution of convection, the interaction between the peninsular-scale convergence and convection, and the role of the feedback produced by the cloud-scale downdrafts in the maintenance of the convection. Attention is given to the analysis, the diurnal cycle of the network area-averaged divergence, convective-scale divergence, convective mass transports, and the peninsular scale divergence. The links established in the investigation between the large scale (peninsular), the mesoscale (network), and the convective scale (cloud) are found to be of fundamental importance to the understanding of the initiation, maintenance, and decay of deep precipitating convection and to its theoretical parameterization.

  11. Diurnal modulation due to self-interacting mirror and hidden sector dark matter

    International Nuclear Information System (INIS)

    Foot, R.

    2012-01-01

    Mirror and more generic hidden sector dark matter models can simultaneously explain the DAMA, CoGeNT and CRESST-II dark matter signals consistently with the null results of the other experiments. This type of dark matter can be captured by the Earth and shield detectors because it is self-interacting. This effect will lead to a diurnal modulation in dark matter detectors. We estimate the size of this effect for dark matter detectors in various locations. For a detector located in the northern hemisphere, this effect is expected to peak in April and can be detected for optimistic parameter choices. The diurnal variation is expected to be much larger for detectors located in the southern hemisphere. In particular, if the CoGeNT detector were moved to e.g. Sierra Grande, Argentina then a 5σ dark matter discovery would be possible in around 30 days of operation

  12. Influences of diurnal bright or dim light exposure on urine volume in humans.

    Science.gov (United States)

    Hyun, Ki-Ja; Nishimura, Shinya; Tokura, Hiromi

    2006-03-01

    We investigated with eight healthy females if 8 hr diurnal (0700 to 1500 h) bright rather than dim light (5,000 vs. 80 lx) influenced urine volume. Environmental illuminance was made identical at all other times besides 07:00 to 15:00 h. The participants spent time at strictly regulated schedules in a bioclimatic chamber (26 degrees C, relative humidity 60%) for 57 h. Blood was drawn (2 ml) just before lunch in order to calculate Creatinine clearance (Ccr). Urine volume was significantly higher during wakefulness and the 8-h sleep period with bright rather than dim light. Ccr was significantly higher after bright light. The results were discussed in terms of suppression of the sympathetic nerve system under the influence of diurnal bright light exposure. We also discussed these in terms of physiological polymorphisms.

  13. Semantic Radicals Contribute More Than Phonetic Radicals to the Recognition of Chinese Phonograms: Behavioral and ERP Evidence in a Factorial Study

    Directory of Open Access Journals (Sweden)

    Xieshun Wang

    2017-12-01

    Full Text Available The Chinese phonograms consist of a semantic radical and a phonetic radical. The two types of radicals have different functional contributions to their host phonogram. The semantic radical typically signifies the meaning of the phonogram, while the phonetic radical usually contains a phonological clue to the phonogram’s pronunciation. However, it is still unclear how they interplay with each other when we attempt to recognize a phonogram because previous studies rarely manipulated the functionality of the two types of radicals in a single design. Using a full factorial design, the present study aimed to probe this issue by directly manipulating the functional validity of the two types of radicals in a lexical decision task with both behavioral and event-related potential (ERP measurements. The results showed that recognition of phonograms which were related to their semantic radicals in meaning took a shorter reaction time, showed a lower error rate, and elicited a smaller P200 and a larger N400 than did recognition of those which had no semantic relation with their semantic radicals. However, the validity of phonetic radicals did not show any main effect or interaction with that of semantic radicals on either behavioral or ERP measurements. These results indicated that semantic radicals played a dominant role in the recognition of phonograms. Transparent semantic radicals, which provide valid semantic cues to phonograms, can facilitate the recognition of phonograms.

  14. Diurnal Cortisol Profile in Williams Syndrome in Novel and Familiar Settings

    Science.gov (United States)

    Lense, Miriam Diane; Tomarken, Andrew J.; Dykens, Elisabeth M.

    2013-01-01

    Williams syndrome (WS) is a neurodevelopmental genetic disorder associated with high rates of anxiety and social issues. We examined diurnal cortisol, a biomarker of the stress response, in adults with WS in novel and familiar settings, and compared these profiles to typically developing (TD) adults. WS and TD participants had similar profiles in…

  15. Pyrimidine nucleobase radical reactivity in DNA and RNA

    Science.gov (United States)

    Greenberg, Marc M.

    2016-11-01

    Nucleobase radicals are major products of the reactions between nucleic acids and hydroxyl radical, which is produced via the indirect effect of ionizing radiation. The nucleobase radicals also result from hydration of cation radicals that are produced via the direct effect of ionizing radiation. The role that nucleobase radicals play in strand scission has been investigated indirectly using ionizing radiation to generate them. More recently, the reactivity of nucleobase radicals resulting from formal hydrogen atom or hydroxyl radical addition to pyrimidines has been studied by independently generating the reactive intermediates via UV-photolysis of synthetic precursors. This approach has provided control over where the reactive intermediates are produced within biopolymers and facilitated studying their reactivity. The contributions to our understanding of pyrimidine nucleobase radical reactivity by this approach are summarized.

  16. Diurnal variability in carbon and nitrogen pools within Chesapeake Bay and northern Gulf of Mexico: implications for future ocean color satellite sensors

    Science.gov (United States)

    Mannino, A.; Novak, M. G.; Tzortziou, M.; Salisbury, J.

    2016-02-01

    Relative to their areal extent, estuaries and coastal ocean ecosystems contribute disproportionately more to global biogeochemical cycling of carbon, nitrogen and other elements compared to the open ocean. Applying ocean color satellite data to study biological and biogeochemical processes within coastal ecosystems is challenging due to the complex mixtures of aquatic constituents derived from terrestrial, anthropogenic, and marine sources, human-impacted atmospheric properties, presence of clouds during satellite overpass, fine-scale spatial gradients, and time-varying processes on diurnal scales that cannot be resolved with current sensors. On diurnal scales, biological, photochemical, and biogeochemical processes are regulated by the variation in solar radiation. Other physical factors, such as tides, river discharge, estuarine and coastal ocean circulation, wind-driven mixing, etc., impart further variability on biological and biogeochemical processes on diurnal to multi-day time scales. Efforts to determine the temporal frequency required from a NASA GEO-CAPE ocean color satellite sensor to discern diurnal variability C and N stocks, fluxes and productivity culminated in field campaigns in the Chesapeake Bay and northern Gulf of Mexico. Near-surface drogues were released and tracked in quasi-lagrangian space to monitor hourly changes in community production, C and N stocks, and optical properties. While only small diurnal changes were observed in dissolved organic carbon (DOC) and colored dissolved organic matter (CDOM) absorption in Chesapeake Bay, substantial variation in particulate organic carbon (POC) and nitrogen (PN), chlorophyll-a, and inorganic nitrogen (DIN) were measured. Similar or greater diurnal changes in POC, PN, chlorophyll-a and DIN were found in Gulf of Mexico nearshore and offshore sites. These results suggest that satellite observations at hourly frequency are desirable to capture diurnal variability in carbon and nitrogen stocks, fluxes

  17. Quantification of hydroxyl radical produced during phacoemulsification.

    Science.gov (United States)

    Gardner, Jonathan M; Aust, Steven D

    2009-12-01

    To quantitate hydroxyl radicals produced during phacoemulsification with various irrigating solutions and conditions used in cataract surgery. Chemistry and Biochemistry Department, Utah State University, Logan, Utah, USA. All experiments were performed using an Infiniti Vision System phacoemulsifier with irrigation and aspiration. Hydroxyl radicals were quantitated using electron spin resonance spectroscopy and a spectrophotometric assay for malondialdehyde, which is formed by the oxidation of deoxyribose by the hydroxyl radical. Hydroxyl radical production increased during longitudinal-stroking phacoemulsification as power levels were increased in a nonlinear, nonexponential fashion. The detection of hydroxyl radical was reduced in irrigating solutions containing organic molecules (eg, citrate, acetate, glutathione, dextrose) and further reduced in Navstel, an irrigating solution containing a viscosity-modifying agent, hydroxypropyl methylcellulose. Hydroxyl radicals produced in settings representative of those used in phacoemulsification cataract surgery were quantitated using the deoxyribose method. Hydroxyl radical production was dependent on the level of ultrasound power applied and the irrigating solution used. Oxidative stress on the eye during phacoemulsification may be minimized by using irrigating solutions that contain organic molecules, including the viscosity-modifying agent hydroxypropyl methylcellulose, that can compete for reaction with hydroxyl radicals.

  18. Free radicals in biology. Volume II

    International Nuclear Information System (INIS)

    Pryor, W.A.

    1976-01-01

    This volume continues the treatment of topics in free radical biology and free radical pathology from Volume I. In the first chapter, pyridinyl radicals, radicals which are models for those derived from NAD, are discussed. Pyridinyl radicals can be synthesized and isolated and directly studied in a number of chemical systems. The next chapter treats the role of glutathione in the cell. It is becoming even more apparent that this vital thiol controls a large number of important cellular functions. The GSH/GSSG balance has recently been implicated as a control for cellular development; this balance also may be important in relaying the effects of oxidants from one site to another in the body. The next chapter outlines the reactions of singlet oxygen; some of these involve free radicals and some do not. This reactive intermediate appears to be important both in photochemical smog and in cellular chemistry where singlet oxygen is produced by nonphotochemical processes. The production of free radicals from dry tissues, a controversial area with conflicting claims is reviewed. The next chapter outlines the current status of the studies of photochemical smog. The next two chapters treat specific reactive materials which are present in smog. The first discusses the chemistry of nitrogen oxides and ozone. The second chapter treats the chemistry of the peroxyacyl nitrites. These compounds, although present in only small concentration, are among the most toxic components of smog. The last two chapters treat radiation damage to proteins and radiation protection and radical reactions produced by radiation in nucleic acids

  19. Arvicanthis ansorgei, a Novel Model for the Study of Sleep and Waking in Diurnal Rodents

    Science.gov (United States)

    Hubbard, Jeffrey; Ruppert, Elisabeth; Calvel, Laurent; Robin-Choteau, Ludivine; Gropp, Claire-Marie; Allemann, Caroline; Reibel, Sophie; Sage-Ciocca, Dominique; Bourgin, Patrice

    2015-01-01

    Study Objectives: Sleep neurobiology studies use nocturnal species, mainly rats and mice. However, because their daily sleep/wake organization is inverted as compared to humans, a diurnal model for sleep studies is needed. To fill this gap, we phenotyped sleep and waking in Arvicanthis ansorgei, a diurnal rodent widely used for the study of circadian rhythms. Design: Video-electroencephalogram (EEG), electromyogram (EMG), and electrooculogram (EOG) recordings. Setting: Rodent sleep laboratory. Participants: Fourteen male Arvicanthis ansorgei, aged 3 mo. Interventions: 12 h light (L):12 h dark (D) baseline condition, 24-h constant darkness, 6-h sleep deprivation. Measurements and Results: Wake and rapid eye movement (REM) sleep showed similar electrophysiological characteristics as nocturnal rodents. On average, animals spent 12.9 h ± 0.4 awake per 24-h cycle, of which 6.88 h ± 0.3 was during the light period. NREM sleep accounted for 9.63 h ± 0.4, which of 5.13 h ± 0.2 during dark period, and REM sleep for 89.9 min ± 6.7, which of 52.8 min ± 4.4 during dark period. The time-course of sleep and waking across the 12 h light:12 h dark was overall inverted to that observed in rats or mice, though with larger amounts of crepuscular activity at light and dark transitions. A dominant crepuscular regulation of sleep and waking persisted under constant darkness, showing the lack of a strong circadian drive in the absence of clock reinforcement by external cues, such as a running wheel. Conservation of the homeostatic regulation was confirmed with the observation of higher delta power following sustained waking periods and a 6-h sleep deprivation, with subsequent decrease during recovery sleep. Conclusions: Arvicanthis ansorgei is a valid diurnal rodent model for studying the regulatory mechanisms of sleep and so represents a valuable tool for further understanding the nocturnality/diurnality switch. Citation: Hubbard J, Ruppert E, Calvel L, Robin-Choteau L, Gropp CM

  20. O conceito de mal radical The concept of radical evil

    Directory of Open Access Journals (Sweden)

    Adriano Correia

    2005-01-01

    Full Text Available A noção de mal radical aparece em Kant no contexto da discussão da religião nos limites da simples razão e busca dar conta da complexa relação entre o respeito pela lei moral e o amor-próprio na definição do móbil para a ação. Na busca por identificar o fundamento da propensão para o mal no homem, Kant se vê diante da dificuldade de ter de articular natureza e liberdade, e ainda que a noção de mal radical possa conservar algumas ambigüidades, permite conceber uma noção de responsabilidade compatível com uma inata propensão para o mal. Neste texto busco explicitar alguns passos fundamentais na construção do conceito por Kant.The concept of radical evil appears in Kant's theory when he discusses the religion in the limits of the mere reason and aims explain the complex relationship between respect for the moral law and the self-love, for establish the motive of the action. By aiming identify the basis of human inclination to evil, Kant is faced with the trouble of have to put nature and freedom in connection. Despite of the concept of radical evil retain some ambiguity, it allows conceive a notion of responsibility suitable to an inherent inclination to evil. In this paper is my purpose to explain some basic moments of Kantian formulation of that notion.

  1. Diurnal phase of late-night against late-afternoon of stratiform and convective precipitation in summer southern contiguous China

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Rucong [Chinese Academy of Sciences, LASG, Institute of Atmospheric Physics, Beijing (China); China Meteorological Administration, LaSW, Chinese Academy of Meteorological Sciences, Beijing (China); Yuan, Weihua [Chinese Academy of Sciences, LASG, Institute of Atmospheric Physics, Beijing (China); Graduate School of the Chinese Academy of Sciences, Beijing (China); Li, Jian [China Meteorological Administration, LaSW, Chinese Academy of Meteorological Sciences, Beijing (China); Fu, Yunfei [Chinese Academy of Sciences, LASG, Institute of Atmospheric Physics, Beijing (China); University of Science and Technology of China, Laboratory of Satellite Remote Sensing and Climate Environment, Hefei, Anhui (China)

    2010-09-15

    Using the tropical rainfall measuring mission (TRMM) Precipitation Radar (PR) observations combined with the surface rain gauge data during 1998-2006, the robust diurnal features of summer stratiform and convective precipitation over the southern contiguous China are revealed by exploring the diurnal variations of rain rate and precipitation profile. The precipitation over the southern contiguous China exhibits two distinguishing diurnal phases: late-night (2200-0600 LST) and late-afternoon (1400-2200 LST), dependent on the location, precipitation type and duration time. Generally, the maximum rain rate and the highest profile of stratiform precipitation occur in the late-afternoon (late-night) over the southeastern (southwestern) China, while most of the stratiform short-duration rain rate tends to present late-afternoon peaks over the southern China. For convective precipitation, the maximum rain rate and the highest profile occur in the late-afternoon over most of the southern contiguous China, while the convective long-duration rain rate exhibits late-night peaks over the southwestern China. Without regional dependence, the convective precipitation exhibits much larger amplitude of diurnal variations in both near surface rain rate and vertical extension compared with stratiform precipitation and the convective rain top rises most rapidly between noon and afternoon. However, there are two distinctive sub-regions. The diurnal phases of precipitation there are very weakly dependent on precipitation type and duration time. Over the eastern periphery of the Tibetan Plateau, the maximum rain rate and the highest profile of either convective or stratiform precipitation occur in the late-night. Over the southeastern coastal regions, both the near surface rain rate and rain top of convective and stratiform precipitation peak in the late-afternoon. (orig.)

  2. HPLC-ESR techniques for detection of complex trapped radicals

    International Nuclear Information System (INIS)

    Tu Tiecheng; Dong Jirong; Lin Nianyun; Xie Leidong; Liu Rengzhong

    1992-01-01

    High performance liquid chromatography (HPLC) and ESR combined examination of radical species is an advanced techniques for separation and identification of complex radical species. At SRCL, Waters 990 HPLC has been used to separate the complex trapped radicals and Varian E-112 ESR spectrometer to record the spectra of single trapped radicals after HPLC separation. The advantages of the combined techniques are described as bellow: HPLC is used to separate the long-lived complex trapped radicals derived from reaction of short-lived radicals with spin trap. ESR spectra from single trapped radicals, obtained following HPLC separation of complex trapped radicals, are recorded one by one and well resolved. The structures of short-lived radicals can be inferred from the ESR spectra of the long-lived trapped radicals

  3. Biodegradation of Toluene under seasonal and diurnal fluctuations of soil-water temperature

    NARCIS (Netherlands)

    Yadav, B.K.; Shrestha, S.R.; Hassanizadeh, S.M.

    2012-01-01

    An increasing interest in bioremediation of hydrocarbon polluted sites raises the question of the influence of seasonal and diurnal changes on soil-water temperature on biodegradation of BTEX, a widespread group of (sub)-surface contaminants. Therefore, we investigated the impact of a wide range of

  4. Oral Contraceptives and Renal Water Handling; A diurnal study in young women

    DEFF Research Database (Denmark)

    Graugaard-Jensen, Charlotte; Hvistendahl, Gitte M; Frøkiær, Jørgen

    2017-01-01

    To test the hypothesis that use of oral contraceptives (OC) changes diurnal variation in fluid balance mechanisms including blood pressure, secretion of vasopressin and oxytocin, and renal water and electrolyte excretion. Fifteen naturally cycling (NC) women in mid-follicular phase and 11 long-te...

  5. Scavenging of free-radical metabolites of aniline xenobiotics and drugs by amino acid derivatives: toxicological implications of radical-transfer reactions.

    Science.gov (United States)

    Michail, Karim; Baghdasarian, Argishti; Narwaley, Malyaj; Aljuhani, Naif; Siraki, Arno G

    2013-12-16

    We investigated a novel scavenging mechanism of arylamine free radicals by poly- and monoaminocarboxylates. Free radicals of arylamine xenobiotics and drugs did not react with oxygen in peroxidase-catalyzed reactions; however, they showed marked oxygen uptake in the presence of an aminocarboxylate. These free-radical intermediates were identified using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and electron paramagnetic resonance (EPR) spectrometry. Diethylenetriaminepentaacetic acid (DTPA), a polyaminocarboxylate, caused a concentration-dependent attenuation of N-centered radicals produced by the peroxidative metabolism of arylamines with the subsequent formation of secondary aliphatic carbon-centered radicals stemming from the cosubstrate molecule. Analogously, N,N-dimethylglycine (DMG) and N-methyliminodiacetate (MIDA), but not iminodiacetic acid (IDA), demonstrated a similar scavenging effect of arylamine-derived free radicals in a horseradish peroxidase/H2O2 system. Using human promyelocytic leukemia (HL-60) cell lysate as a model of human neutrophils, DTPA, MIDA, and DMG readily reduced anilinium cation radicals derived from the arylamines and gave rise to the corresponding carbon radicals. The rate of peroxidase-triggered polymerization of aniline was studied as a measure of nitrogen-radical scavenging. Although, IDA had no effect on the rate of aniline polymerization, this was almost nullified in the presence of DTPA and MIDA at half of the molar concentration of the aniline substrate, whereas a 20 molar excess of DMPO caused only a partial inhibition. Furthermore, the yield of formaldehyde, a specific reaction endproduct of the oxidation of aminocarboxylates by aniline free-radical metabolites, was quantitatively determined. Azobenzene, a specific reaction product of peroxidase-catalyzed free-radical dimerization of aniline, was fully abrogated in the presence of DTPA, as confirmed by GC/MS. Under aerobic conditions, a radical-transfer reaction

  6. Tracking diurnal changes of photosynthesis and evapotranspiration using fluorescence, gas exchange and hyperspectral remote sensing measurements

    Science.gov (United States)

    Wang, S.; Zhang, L.; Guanter, L.; Huang, C.

    2017-12-01

    Photosynthesis and evapotranspiration (ET) are the two most important activities of vegetation and make a great contribution to carbon, water and energy exchanges. Remote sensing provides opportunities for monitoring these processes across time and space. This study focuses on tracking diurnal changes of photosynthesis and evapotranspiration over soybean using multiple measurement techniques. Diurnal changes of both remote sensing-based indicators, including active and passive chlorophyll fluorescence and biophysical-related parameters, including photosynthesis rate (photo) and leaf stomatal conductance (cond), were observed. Results showed that both leaf-level steady-state fluorescence (Fs) and canopy-level solar-induced chlorophyll fluorescence were linearly correlated to photosynthetically active radiation (PAR) during the daytime. A double-peak diurnal change curve was observed for leaf-level photo and cond but not for Fs or SIF. Photo and cond showed a strong nonlinear (second-order) correlation, indicating that photosynthesis, which might be remotely sensed by SIF, has the opportunity to track short-term changes of ET. Results presented in this report will be helpful for better understanding the relationship between remote-sensing-based indices and vegetation's biophysical processes.

  7. Reactions of carbonate radical with cobalt(II) aminopolycarboxylates

    International Nuclear Information System (INIS)

    Mandal, P.C.; Bardhan, D.K.; Bhattacharyya, S.N.

    1992-01-01

    Reactions of carbonate (CO 3 - radical) and bicarbonate (HCO 3 radical) radicals generated by photolysis of a carbonate or bicarbonate solution at pH 11.2 and 8.5, respectively, with Co(II) complexes of iminodiacetic acid (IDA) and ethylenediaminetetraacetic acid (EDTA) have been studied. The rate constants for the reactions were in the order of 10 6 -10 7 dm 3 mol -1 s -1 . From the time-resolved spectroscopy of the products formed after reaction of CO 3 - radical or HCO 3 radical, it is observed that CO 3 - radical or HCO 3 radical oxidize the metal center to its higher oxidation state. (author) 26 refs.; 2 figs.; 1 tab

  8. Self-Terminating, Oxidative Radical Cyclizations

    Directory of Open Access Journals (Sweden)

    Uta Wille

    2004-05-01

    Full Text Available The recently discovered novel concept of self-terminating, oxidative radical cyclizations, through which alkynes can be converted into carbonyl compounds under very mild reaction conditions using O-centered inorganic and organic radicals as oxidants, is described

  9. Corrigendum: Childhood Adversity, Self-Esteem, and Diurnal Cortisol Profiles Across the Life Span.

    Science.gov (United States)

    2018-01-01

    Original article: Zilioli, S., Slatcher, R. B., Chi, P., Li, X., Zhao, J., & Zhao, G. (2016). Childhood adversity, self-esteem, and diurnal cortisol profiles across the life span. Psychological Science, 27, 1249-1265. doi:10.1177/0956797616658287.

  10. The influence of sea- and land-breeze circulations on the diurnal variability in precipitation over a tropical island

    Directory of Open Access Journals (Sweden)

    L. Zhu

    2017-11-01

    Full Text Available This study examines the diurnal variation in precipitation over Hainan Island in the South China Sea using gauge observations from 1951 to 2012 and Climate Prediction Center MORPHing technique (CMORPH satellite estimates from 2006 to 2015, as well as numerical simulations. The simulations are the first to use climatological mean initial and lateral boundary conditions to study the dynamic and thermodynamic processes (and the impacts of land–sea breeze circulations that control the rainfall distribution and climatology. Precipitation is most significant from April to October and exhibits a strong diurnal cycle resulting from land–sea breeze circulations. More than 60 % of the total annual precipitation over the island is attributable to the diurnal cycle with a significant monthly variability. The CMORPH and gauge datasets agree well, except that the CMORPH data underestimate precipitation and have a 1 h peak delay. The diurnal cycle of the rainfall and the related land–sea breeze circulations during May and June were well captured by convection-permitting numerical simulations with the Weather Research and Forecasting (WRF model, which were initiated from a 10-year average ERA-Interim reanalysis. The simulations have a slight overestimation of rainfall amounts and a 1 h delay in peak rainfall time. The diurnal cycle of precipitation is driven by the occurrence of moist convection around noontime owing to low-level convergence associated with the sea-breeze circulations. The precipitation intensifies rapidly thereafter and peaks in the afternoon with the collisions of sea-breeze fronts from different sides of the island. Cold pools of the convective storms contribute to the inland propagation of the sea breeze. Generally, precipitation dissipates quickly in the evening due to the cooling and stabilization of the lower troposphere and decrease of boundary layer moisture. Interestingly, the rather high island orography is not a

  11. Diurnal temperature variations affect development of a herbivorous arthropod pest and its predators.

    Directory of Open Access Journals (Sweden)

    Dominiek Vangansbeke

    Full Text Available The impact of daily temperature variations on arthropod life history remains woefully understudied compared to the large body of research that has been carried out on the effects of constant temperatures. However, diurnal varying temperature regimes more commonly represent the environment in which most organisms thrive. Such varying temperature regimes have been demonstrated to substantially affect development and reproduction of ectothermic organisms, generally in accordance with Jensen's inequality. In the present study we evaluated the impact of temperature alternations at 4 amplitudes (DTR0, +5, +10 and +15°C on the developmental rate of the predatory mites Phytoseiulus persimilis Athias-Henriot and Neoseiulus californicus McGregor (Acari: Phytoseiidae and their natural prey, the two-spotted spider mite Tetranychus urticae Koch (Acari: Tetranychidae. We have modelled their developmental rates as a function of temperature using both linear and nonlinear models. Diurnally alternating temperatures resulted in a faster development in the lower temperature range as compared to their corresponding mean constant temperatures, whereas the opposite was observed in the higher temperature range. Our results indicate that Jensen's inequality does not suffice to fully explain the differences in developmental rates at constant and alternating temperatures, suggesting additional physiological responses play a role. It is concluded that diurnal temperature range should not be ignored and should be incorporated in predictive models on the phenology of arthropod pests and their natural enemies and their performance in biological control programmes.

  12. Diurnal Temperature Variations Affect Development of a Herbivorous Arthropod Pest and its Predators

    Science.gov (United States)

    Vangansbeke, Dominiek; Audenaert, Joachim; Nguyen, Duc Tung; Verhoeven, Ruth; Gobin, Bruno; Tirry, Luc; De Clercq, Patrick

    2015-01-01

    The impact of daily temperature variations on arthropod life history remains woefully understudied compared to the large body of research that has been carried out on the effects of constant temperatures. However, diurnal varying temperature regimes more commonly represent the environment in which most organisms thrive. Such varying temperature regimes have been demonstrated to substantially affect development and reproduction of ectothermic organisms, generally in accordance with Jensen’s inequality. In the present study we evaluated the impact of temperature alternations at 4 amplitudes (DTR0, +5, +10 and +15°C) on the developmental rate of the predatory mites Phytoseiulus persimilis Athias-Henriot and Neoseiulus californicus McGregor (Acari: Phytoseiidae) and their natural prey, the two-spotted spider mite Tetranychus urticae Koch (Acari: Tetranychidae). We have modelled their developmental rates as a function of temperature using both linear and nonlinear models. Diurnally alternating temperatures resulted in a faster development in the lower temperature range as compared to their corresponding mean constant temperatures, whereas the opposite was observed in the higher temperature range. Our results indicate that Jensen’s inequality does not suffice to fully explain the differences in developmental rates at constant and alternating temperatures, suggesting additional physiological responses play a role. It is concluded that diurnal temperature range should not be ignored and should be incorporated in predictive models on the phenology of arthropod pests and their natural enemies and their performance in biological control programmes. PMID:25874697

  13. Comparison of specific-yield estimates for calculating evapotranspiration from diurnal groundwater-level fluctuations

    Science.gov (United States)

    Gribovszki, Zoltán

    2018-05-01

    Methods that use diurnal groundwater-level fluctuations are commonly used for shallow water-table environments to estimate evapotranspiration (ET) and recharge. The key element needed to obtain reliable estimates is the specific yield (Sy), a soil-water storage parameter that depends on unsaturated soil-moisture and water-table fluxes, among others. Soil-moisture profile measurement down to the water table, along with water-table-depth measurements, can provide a good opportunity to calculate Sy values even on a sub-daily scale. These values were compared with Sy estimates derived by traditional techniques, and it was found that slug-test-based Sy values gave the most similar results in a sandy soil environment. Therefore, slug-test methods, which are relatively cheap and require little time, were most suited to estimate Sy using diurnal fluctuations. The reason for this is that the timeframe of the slug-test measurement is very similar to the dynamic of the diurnal signal. The dynamic characteristic of Sy was also analyzed on a sub-daily scale (depending mostly on the speed of drainage from the soil profile) and a remarkable difference was found in Sy with respect to the rate of change of the water table. When comparing constant and sub-daily (dynamic) Sy values for ET estimation, the sub-daily Sy application yielded higher correlation, but only a slightly smaller deviation from the control ET method, compared with the usage of constant Sy.

  14. Quantifying Diurnal Cloud Radiative Effects by Cloud Type in the Tropical Western Pacific

    Energy Technology Data Exchange (ETDEWEB)

    Burleyson, Casey D.; Long, Charles N.; Comstock, Jennifer M.

    2015-06-01

    Cloud radiative effects are examined using long-term datasets collected at the three Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facilities in the tropical western Pacific. We quantify the surface radiation budget, cloud populations, and cloud radiative effects by partitioning the data by cloud type, time of day, and as a function of large scale modes of variability such as El Niño Southern Oscillation (ENSO) phase and wet/dry seasons at Darwin. The novel facet of our analysis is that we break aggregate cloud radiative effects down by cloud type across the diurnal cycle. The Nauru cloud populations and subsequently the surface radiation budget are strongly impacted by ENSO variability whereas the cloud populations over Manus only shift slightly in response to changes in ENSO phase. The Darwin site exhibits large seasonal monsoon related variations. We show that while deeper convective clouds have a strong conditional influence on the radiation reaching the surface, their limited frequency reduces their aggregate radiative impact. The largest source of shortwave cloud radiative effects at all three sites comes from low clouds. We use the observations to demonstrate that potential model biases in the amplitude of the diurnal cycle and mean cloud frequency would lead to larger errors in the surface energy budget compared to biases in the timing of the diurnal cycle of cloud frequency. Our results provide solid benchmarks to evaluate model simulations of cloud radiative effects in the tropics.

  15. On the diurnal ranges of Sea Surface Temperature (SST) in the ...

    Indian Academy of Sciences (India)

    (Solomon and Jin 2005). The diurnal change in. SST has also been examined to study the possible feedbacks on the atmosphere (Clayson and Chen. 2002; Bernie et al 2007). Solar heating of the sea surface in low-wind conditions can lead to the development of a stable warm layer of a few meters thickness at the surface.

  16. Diurnal variation in the performance of rapid response systems: the role of critical care services-a review article.

    Science.gov (United States)

    Sundararajan, Krishnaswamy; Flabouris, Arthas; Thompson, Campbell

    2016-01-01

    The type of medical review before an adverse event influences patient outcome. Delays in the up-transfer of patients requiring intensive care are associated with higher mortality rates. Timely detection and response to a deteriorating patient constitute an important function of the rapid response system (RRS). The activation of the RRS for at-risk patients constitutes the system's afferent limb. Afferent limb failure (ALF), an important performance measure of rapid response systems, constitutes a failure to activate a rapid response team (RRT) despite criteria for calling an RRT. There are diurnal variations in hospital staffing levels, the performance of rapid response systems and patient outcomes. Fewer ward-based nursing staff at night may contribute to ALF. The diurnal variability in RRS activity is greater in unmonitored units than it is in monitored units for events that should result in a call for an RRT. RRT events include a significant abnormality in either the pulse rate, blood pressure, conscious state or respiratory rate. There is also diurnal variation in RRT summoning rates, with most activations occurring during the day. The reasons for this variation are mostly speculative, but the failure of the afferent limb of RRT activation, particularly at night, may be a factor. The term "circadian variation/rhythm" applies to physiological variations over a 24-h cycle. In contrast, diurnal variation applies more accurately to extrinsic systems. Circadian rhythm has been demonstrated in a multitude of bodily functions and disease states. For example, there is an association between disrupted circadian rhythms and abnormal vital parameters such as anomalous blood pressure, irregular pulse rate, aberrant endothelial function, myocardial infarction, stroke, sleep-disordered breathing and its long-term consequences of hypertension, heart failure and cognitive impairment. Therefore, diurnal variation in patient outcomes may be extrinsic, and more easily modifiable

  17. Oxidation of aromatic amines and diamines by OH radicals. Formation and ionization constants of amine cation radicals in water

    International Nuclear Information System (INIS)

    Hayon, E.; Rao, P.S.

    1975-01-01

    The one-electron oxidation by hydroxyl radicals of aromatic amines and diamines in water was studied using the fast-reaction technique of pulse radiolysis and kinetic absorption spectrophotometry. The following compounds were examined: N,N,N 1 ,N 1 - tetramethyl-p-phenylenediamine (TMPD), p-phenylenediamine (PD), N,N-dimethyl-p-phenylenediamene (DMPD), N,N,N 1 ,N 1 -tetramethylbenzidine (TMB), and diphenylamine (DPA). The main initial reaction of the OH radicals is suggested to be an addition to these compounds to give absorption spectra which absorb strongly in the visible and uv regions. These OH radical adducts decay by first-order kinetics and have lifetimes of approximately 5-50 μsec, dependent on the pH, buffer concentration, and the nature of the aromatic amines and diamines. They decay to give species with somewhat similar absorption spectra and extinction coefficients, which are very long lived in the absence of oxygen. The latter species are assigned to the cation radicals TMPD. + , PD. + , DMPD. + , TMB. + , and DPA. + . The OH radical adducts and the cation radicals have acid-base properties. The pK/sub a/ values of the cation radicals TMPDH. 2+ , PDH. 2+ , DMPDH. 2+ , TMBH. 2+ , and DPAH. 2+ were found to be 5.3, 5.9, 6.1, 5.1, and 4.2, respectively. The results indicate that these aromatic amines and diamines can be oxidized by free radicals to yield the corresponding cation radicals. (U.S.)

  18. Effects of the Relaxation of Upwelling-Favorable Winds on the Diurnal and Semidiurnal Water Temperature Fluctuations in the Santa Barbara Channel, California

    Science.gov (United States)

    Aristizábal, María. F.; Fewings, Melanie R.; Washburn, Libe

    2017-10-01

    In the Santa Barbara Channel, California, and around the Northern Channel Islands, water temperature fluctuations in the diurnal and semidiurnal frequency bands are intermittent, with amplitudes that vary on time scales of days to weeks. The cause of this intermittency is not well understood. We studied the effects of the barotropic tide, vertical stratification, propagation of coastal-trapped waves, regional wind relaxations, and diurnal-band winds on the intermittency of the temperature fluctuations during 1992-2015. We used temperature data from 43 moorings in 10-200 m water depth and wind data from two buoys and one land station. Subtidal-frequency changes in vertical stratification explain 20-40% of the intermittency in diurnal and semidiurnal temperature fluctuations at time scales of days to weeks. Along the mainland north of Point Conception and at the Northern Channel Islands, the relaxation of upwelling-favorable winds substantially increases vertical stratification, accounting for up to 55% of the subtidal-frequency variability in stratification. As a result of the enhanced stratification, wind relaxations enhance the diurnal and semidiurnal temperature fluctuations at those sites, even though the diurnal-band wind forcing decreases during wind relaxation. A linear model where the background stratification is advected vertically explains a substantial fraction of the temperature fluctuations at most sites. The increase of vertical stratification and subsequent increase in diurnal and semidiurnal temperature fluctuations during wind relaxation is a mechanism that can supply nutrients to the euphotic zone and kelp forests in the Channel in summer when upwelling is weak.

  19. Diurnal variation in glycogen phosphorylase activity in rat liver. A quantitative histochemical study

    NARCIS (Netherlands)

    Frederiks, W. M.; Marx, F.; Bosch, K. S.

    1987-01-01

    The diurnal variations of the glycogen content and of glycogen phosphorylase activity in periportal and pericentral areas of rat liver parenchyma have been analyzed in periodic acid Schiff (PAS)-stained cryostat sections using quantitative microdensitometry. Glycogen content and phosphorylase

  20. Near-Infrared Free-Radical and Free-Radical-Promoted Cationic Photopolymerizations by In-Source Lighting Using Upconverting Glass.

    Science.gov (United States)

    Kocaarslan, Azra; Tabanli, Sevcan; Eryurek, Gonul; Yagci, Yusuf

    2017-11-13

    A method is presented for the initiation of free-radical and free-radical-promoted cationic photopolymerizations by in-source lighting in the near-infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron-transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free-radical-promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N-vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Diurnal variation in ruminal pH on the digestibility of highly digestible perennial ryegrass during continuous culture fermentation.

    Science.gov (United States)

    Wales, W J; Kolver, E S; Thorne, P L; Egan, A R

    2004-06-01

    Dairy cows grazing high-digestibility pastures exhibit pronounced diurnal variation in ruminal pH, with pH being below values considered optimal for digestion. Using a dual-flow continuous culture system, the hypothesis that minimizing diurnal variation in pH would improve digestion of pasture when pH was low, but not at a higher pH, was tested. Four treatments were imposed, with pH either allowed to exhibit normal diurnal variation around an average pH of 6.1 or 5.6, or maintained at constant pH. Digesta samples were collected during the last 3 d of each of four, 9-d experimental periods. A constant pH at 5.6 compared with a constant pH of 6.1 reduced the digestibility of organic matter (OM), neutral detergent (NDF), and acid detergent fiber (ADF) by 7, 14, and 21%, respectively. When pH was allowed to vary (averaging 5.6), digestion of OM, NDF, and ADF were reduced by 15,30, and 36%, respectively, compared with pH varying at 6.1. There was little difference in digestion parameters when pH was either constant or varied with an average pH of 6.1. However, when average pH was 5.6, maintaining a constant pH significantly increased digestion of OM, NDF, and ADF by 5, 25, and 24% compared with a pH that exhibited normal diurnal variation. These in vitro results show that gains in digestibility and potential milk production can be made by minimizing diurnal variation in ruminal pH, but only when ruminal pH is low (5.6). However, larger gains in productivity can be achieved by increasing average daily ruminal pH from 5.6 to 6.1.

  2. Cognitive control moderates parenting stress effects on children's diurnal cortisol

    OpenAIRE

    Raffington, Laurel; Schmiedek, Florian; Heim, Christine; Shing, Yee Lee

    2018-01-01

    This study investigated associations between parenting stress in parents and self-reported stress in children with children's diurnal cortisol secretion and whether these associations are moderated by known stress-regulating capacities, namely child cognitive control. Salivary cortisol concentrations were assessed from awakening to evening on two weekend days from 53 6-to-7-year-old children. Children completed a cognitive control task and a self-report stress questionnaire with an experiment...

  3. OH radical induced depolymerization of poly(methacrylic acid)

    Science.gov (United States)

    Ulanski, Piotr; Bothe, Eberhard; von Sonntag, Clemens

    1999-05-01

    Hydroxyl radicals (generated pulse radiolytically in dilute N 2O-saturated aqueous solutions) react with poly(methacrylic acid) producing two kinds of radicals. The primary radical is converted into a secondary one by H-abstraction ( k=3.5 × 10 2 s -1) as monitored by changes in the UV spectrum. Subsequently, the secondary radicals undergo chain scission ( k=1.8 s -1 at pH 7-9). This process has been followed both by spectrophotometry as well as by conductometry. In competition with the bimolecular decay of the radicals the ensuing end-chain radicals undergo efficient depolymerization resulting in the release of monomer. Since the lifetime of the radicals is much longer at high pH, where the polymer attains a rod-like conformation, depolymerization is most efficient in basic solution.

  4. ESA STSE “SST Diurnal Variability: Regional Extend - Implications in Atmospheric Modelling”

    DEFF Research Database (Denmark)

    Karagali, Ioanna

    The diurnal variability of SST, driven by the coincident occurrence of low enough wind and solar heating, has been observed in various regions of the global ocean [4, 5, 6]. Atmospheric, oceanic and climate models are not adequately resolving the daily SST cycle, resulting in biases of the total...

  5. Electron spin resonance study of radicals in irradiated polyethylene

    International Nuclear Information System (INIS)

    Fujimura, Takashi

    1979-02-01

    In order to elucidate radiation effect in polyethylene, the nature and behavior of radicals produced in polyethylene and the model compound of polyethylene irradiated at 77 0 K were studied by using electron spin resonance. The structure of radical pairs, which are composed of two radicals produced very closely each other, was investigated in drawn polyethylene and the single crystal of n-eicosane. The radical pairs of intrachain type and interchain type were found in polyethylene and n-eicosane respectively. It was suggested that these two types of radical pairs are the precursors of double bonds and crosslinks respectively. The thermal decay reactions of radicals themselves produced in irradiated polyethylene were investigated. It was made clear that the short range distances between two radicals play an important role in the decay reaction of alkyl radicals at low temperatures. The trapping regions of radicals were studied and it was clarified that allyl radicals, which are produced by the reaction of alkyl radicals with double bonds, are trapped both in the crystalline and non-crystalline regions. (author)

  6. Redox properties of free radicals

    International Nuclear Information System (INIS)

    Neta, P.

    1981-01-01

    Results of electron transfer reactions observed and monitored by pulse radiolysis are reported. This technique allows determination of the first one-electron reduction or oxidation of a compound rather than the overall two-electron transfer usually reported. Pulse radiolysis allows the determination of absolute rate constants for reactions of free radicals and helps elucidate the mechanisms involved. Studies using this technique to study radicals derived from quinones, nitro compounds, pyridines, phenols, and anilines are reported. Radicals of biochemical interest arising from riboflavin, ascorbic acid, vitamin K 3 , vitamin E, MAD + , porphyrins, etc. have also been studied

  7. Hot wire radicals and reactions

    International Nuclear Information System (INIS)

    Zheng Wengang; Gallagher, Alan

    2006-01-01

    Threshold ionization mass spectroscopy is used to measure radical (and stable gas) densities at the substrate of a tungsten hot wire (HW) reactor. We report measurements of the silane reaction probability on the HW and the probability of Si and H release from the HW. We describe a model for the atomic H release, based on the H 2 dissociation model. We note major variations in silicon-release, with dependence on prior silane exposure. Measured radical densities versus silane pressure yield silicon-silane and H-silane reaction rate coefficients, and the dominant radical fluxes to the substrate

  8. Mechanisms of Diurnal Precipitation over the United States Great Plains: A Cloud-Resolving Model Simulation

    Science.gov (United States)

    Lee, M.-I.; Choi, I.; Tao, W.-K.; Schubert, S. D.; Kang, I.-K.

    2010-01-01

    The mechanisms of summertime diurnal precipitation in the US Great Plains were examined with the two-dimensional (2D) Goddard Cumulus Ensemble (GCE) cloud-resolving model (CRM). The model was constrained by the observed large-scale background state and surface flux derived from the Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Program s Intensive Observing Period (IOP) data at the Southern Great Plains (SGP). The model, when continuously-forced by realistic surface flux and large-scale advection, simulates reasonably well the temporal evolution of the observed rainfall episodes, particularly for the strongly forced precipitation events. However, the model exhibits a deficiency for the weakly forced events driven by diurnal convection. Additional tests were run with the GCE model in order to discriminate between the mechanisms that determine daytime and nighttime convection. In these tests, the model was constrained with the same repeating diurnal variation in the large-scale advection and/or surface flux. The results indicate that it is primarily the surface heat and moisture flux that is responsible for the development of deep convection in the afternoon, whereas the large-scale upward motion and associated moisture advection play an important role in preconditioning nocturnal convection. In the nighttime, high clouds are continuously built up through their interaction and feedback with long-wave radiation, eventually initiating deep convection from the boundary layer. Without these upper-level destabilization processes, the model tends to produce only daytime convection in response to boundary layer heating. This study suggests that the correct simulation of the diurnal variation in precipitation requires that the free-atmospheric destabilization mechanisms resolved in the CRM simulation must be adequately parameterized in current general circulation models (GCMs) many of which are overly sensitive to the parameterized boundary layer heating.

  9. Synthesis and Characterization of Ethylenedithio-MPTTF-PTM Radical Dyad as a Potential Neutral Radical Conductor

    DEFF Research Database (Denmark)

    Souto, Manuel; Bendixen, Dan; Jensen, Morten

    2016-01-01

    During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF...

  10. Predominant role of water in regulating the tree-growth response to diurnal asymmetric warmin

    Science.gov (United States)

    Chen, Z.; Xia, J.; Cui, E.

    2017-12-01

    Growth of the Northern Hemisphere trees is affected by diurnal asymmetric warming, which is generally considered to touch off carbon assimilation and increment of carbon storage. Asymmetric effects of diurnal warming on vegetation greenness were validated in previous researches, however, the effect of diurnal warming on wood tissue which stores most carbon of a whole plant is still unknown. Here, we combined ring-width index (RWI), remote sensing-based normalized difference vegetation index (NDVI) and climate datasets to detect the effects of daytime and night-time warming on vegetation growth, respectively. Our results indicate that daytime warming enhances NDVI but has neutral effect on tree woody growth over the Northern Hemisphere. Response of wood growth to daytime warming is linearly regulated by soil water availability. The underlying mechanism of different response of canopy and wood growth to daytime warming may attribute to the biomass change, that is, allocation to foliage tissues increased at the expense of wood tissue under warming and water-limited conditions. Night-time warming show neutral effects on NDVI and RWI over the Northern Hemisphere, and the neutral Tmin-NDVI correlations result from the non-linear mediation of soil water availability. Our results highlight the current greening trend under daytime warming does not mean higher carbon sink capacity, the warming-drying climate may impair the large carbon sink of global forests.

  11. Diurnal microstructural variations in healthy adult brain revealed by diffusion tensor imaging.

    Directory of Open Access Journals (Sweden)

    Chunxiang Jiang

    Full Text Available Biorhythm is a fundamental property of human physiology. Changes in the extracellular space induced by cell swelling in response to the neural activity enable the in vivo characterization of cerebral microstructure by measuring the water diffusivity using diffusion tensor imaging (DTI. To study the diurnal microstructural alterations of human brain, fifteen right-handed healthy adult subjects were recruited for DTI studies in two repeated sessions (8∶30 AM and 8∶30 PM within a 24-hour interval. Fractional anisotropy (FA, apparent diffusion coefficient (ADC, axial (λ// and radial diffusivity (λ⊥ were compared pixel by pixel between the sessions for each subject. Significant increased morning measurements in FA, ADC, λ// and λ⊥ were seen in a wide range of brain areas involving frontal, parietal, temporal and occipital lobes. Prominent evening dominant λ⊥ (18.58% was detected in the right inferior temporal and ventral fusiform gyri. AM-PM variation of λ⊥ was substantially left side hemisphere dominant (p<0.05, while no hemispheric preference was observed for the same analysis for ADC (p = 0.77, λ// (p = 0.08 or FA (p = 0.25. The percentage change of ADC, λ//, λ⊥, and FA were 1.59%, 2.15%, 1.20% and 2.84%, respectively, for brain areas without diurnal diffusivity contrast. Microstructural variations may function as the substrates of the phasic neural activities in correspondence to the environment adaptation in a light-dark cycle. This research provided a baseline for researches in neuroscience, sleep medicine, psychological and psychiatric disorders, and necessitates that diurnal effect should be taken into account in following up studies using diffusion tensor quantities.

  12. Nighttime Convection, Temperature Inversions, and Diurnal Variations at Low Altitudes in the Martian Tropics

    Science.gov (United States)

    Hinson, D. P.; Haberle, R. M.; Spiga, A.; Tellmann, S.; Paetzold, M.; Asmar, S. W.; Haeusler, B.

    2014-07-01

    We are using radio occultation measurements and numerical simulations to explore the atmospheric structure and diurnal variations in the lowest few scale heights of the martian atmosphere, with emphasis on nighttime convective layers.

  13. Free radicals trapped in polyethylene matrix

    International Nuclear Information System (INIS)

    Shimada, S.; Maeda, M.; Hori, Y.; Kashiwabara, H.

    1977-01-01

    Two types of alkyl radicals were found to be trapped in irradiated crystals grown from polyethylene solution. One of them corresponds to the broad sextet pattern of the e.s.r. spectrum and the other corresponds to the sharp sextet pattern. The free radicals attributed to the broad sextet began to disappear at a lower temperature than the temperature at which the free radicals attributed to the sharp sextet disappeared. When butadiene molecules were brought into contact with the specimen, the decay of the free radicals corresponding to the broad sextet was accelerated. When the specimen was subjected to fuming nitric acid treatment, no broad sextet was observed. The mat of the crystals was aligned so that the c-axes of its crystallites were perpendicular to its surface. The broad sextet showed no anisotropy when the angle between the direction of applied magnetic field and that of the c-axis of the crystallite was varied. On the other hand, the sharp component of the spectrum showed apparent anisotropy. It can be concluded that the broad component comes from the free radicals trapped in the lamellar surface and the sharp component is attributed to the free radicals trapped in the inner part of the crystallite. (author)

  14. The role of melanin as protector against free radicals in skin and its role as free radical indicator in hair

    Science.gov (United States)

    Herrling, Thomas; Jung, Katinka; Fuchs, Jürgen

    2008-05-01

    Throughout the body, melanin is a homogenous biological polymer containing a population of intrinsic, semiquinone-like radicals. Additional extrinsic free radicals are reversibly photo-generated by UV and visible light. Melanin photochemistry, particularly the formation and decay of extrinsic radicals, has been the subject of numerous electron spin resonance (ESR) spectroscopy studies. Several melanin monomers exist, and the predominant monomer in a melanin polymer depends on its location within an organism. In skin and hair, melanin differs in content of eumelanin or pheomelanin. Its bioradical character and its susceptibility to UV irradiation makes melanin an excellent indicator for UV-related processes in both skin and hair. The existence of melanin in skin is strongly correlated with the prevention against free radicals/ROS generated by UV radiation. Especially in the skin melanin (mainly eumelanin) ensures the only natural UV protection by eliminating the generated free radicals/ROS. Melanin in hair can be used as a free radical detector for evaluating the efficacy of hair care products. The aim of this study was to investigate the suitability of melanin as protector of skin against UV generated free radicals and as free radical indicator in hair.

  15. Observing Seasonal and Diurnal Hydrometeorological Variability Within a Tropical Alpine Valley: Implications for Evapotranspiration

    Science.gov (United States)

    Hellstrom, R. A.; Mark, B. G.

    2007-12-01

    Conditions of glacier recession in the seasonally dry tropical Peruvian Andes motivate research to better constrain the hydrological balance in alpine valleys. There is an outstanding need to better understand the impact of the pronounced tropical hygric seasonality on energy and water budgets within pro-glacial valleys that channel glacier runoff to stream flow. This paper presents a novel embedded network installed in the glacierized Llanganuco valley of the Cordillera Blanca (9°S) comprising eight low-cost, discrete temperature and humidity microloggers ranging from 3470 to 4740 masl and an automatic weather station at 3850 masl. Data are aggregated into distinct dry and wet periods sampled from two full annual cycles (2004-2006) to explore patterns of diurnal and seasonal variability. The magnitude of diurnal solar radiation varies little within the valley between the dry and wet periods, while wet season near-surface air temperatures are cooler. Seasonally characteristic diurnal fluctuations in lapse rate partially regulate convection and humidity. Steep lapse rates during the wet season afternoon promote up-slope convection of warm, moist air and nocturnal rainfall events. Standardized grass reference evapotranspiration (ET0) was estimated using the FAO-56 algorithm of the United Nations Food and Agriculture Organization and compared with estimates of actual ET from the process-based BROOK90 model that incorporates more realistic vegetation parameters. Comparisons of composite diurnal cycles of ET for the wet and dry periods suggest about twice the daily ET0 during the dry period, attributed primarily to the 500% higher vapor pressure deficit and 20% higher daily total solar irradiance. Conversely, the near absence of rainfall during the dry season diminishes actual ET below that of the wet season by two orders of magnitude. Nearly cloud-free daylight conditions are critical for ET during the wet season. We found significant variability of ET with elevation

  16. Impact of land convection on temperature diurnal variation in the tropical lower stratosphere inferred from COSMIC GPS radio occultations

    Directory of Open Access Journals (Sweden)

    S. M. Khaykin

    2013-07-01

    Full Text Available Following recent studies evidencing the influence of deep convection on the chemical composition and thermal structure of the tropical lower stratosphere, we explore its impact on the temperature diurnal variation in the upper troposphere and lower stratosphere using the high-resolution COSMIC GPS radio-occultation temperature measurements spanning from 2006 through 2011. The temperature in the lowermost stratosphere over land during summer displays a marked diurnal cycle characterized by an afternoon cooling. This diurnal cycle is shown collocated with most intense land convective areas observed by the Tropical Rainfall Measurement Mission (TRMM precipitation radar and in phase with the maximum overshooting occurrence frequency in late afternoon. Two processes potentially responsible for that are identified: (i non-migrating tides, whose physical nature is internal gravity waves, and (ii local cross-tropopause mass transport of adiabatically cooled air by overshooting turrets. Although both processes can contribute, only the lofting of adiabatically cooled air is well captured by models, making it difficult to characterize the contribution of non-migrating tides. The impact of deep convection on the temperature diurnal cycle is found larger in the southern tropics, suggesting more vigorous convection over clean rain forest continents than desert areas and polluted continents in the northern tropics.

  17. The effects of diurnal Ramadan fasting on energy expenditure and substrate oxidation in healthy men.

    Science.gov (United States)

    Alsubheen, Sana'a A; Ismail, Mohammad; Baker, Alicia; Blair, Jason; Adebayo, Adeboye; Kelly, Liam; Chandurkar, Vikram; Cheema, Sukhinder; Joanisse, Denis R; Basset, Fabien A

    2017-12-01

    The study aimed to examine the effects of diurnal Ramadan fasting (RF) on substrate oxidation, energy production, blood lipids and glucose as well as body composition. Nine healthy Muslim men (fasting (FAST) group) and eight healthy non-practicing men (control (CNT) group) were assessed pre- and post-RF. FAST were additionally assessed at days 10, 20 and 30 of RF in the morning and evening. Body composition was determined by hydrodensitometry, substrate oxidation and energy production by indirect calorimetry, blood metabolic profile by biochemical analyses and energy balance by activity tracker recordings and food log analyses. A significant group×time interaction revealed that chronic RF reduced body mass and adiposity in FAST, without changing lean mass, whereas CNT subjects remained unchanged. In parallel to these findings, a significant main diurnal effect (morning v. evening) of RF on substrate oxidation (a shift towards lipid oxidation) and blood metabolic profile (a decrease in glucose and an increase in total cholesterol and TAG levels, respectively) was observed, which did not vary over the course of the Ramadan. In conclusion, although RF induces diurnal metabolic adjustments (morning v. evening), no carryover effect was observed throughout RF despite the extended daily fasting period (18·0 (sd 0·3) h) and changes in body composition.

  18. Water-stress-induced breakdown of carbon-water relations: indicators from diurnal FLUXNET patterns

    Science.gov (United States)

    Nelson, Jacob A.; Carvalhais, Nuno; Migliavacca, Mirco; Reichstein, Markus; Jung, Martin

    2018-04-01

    Understanding of terrestrial carbon and water cycles is currently hampered by an uncertainty in how to capture the large variety of plant responses to drought. In FLUXNET, the global network of CO2 and H2O flux observations, many sites do not uniformly report the ancillary variables needed to study drought response physiology. To this end, we outline two data-driven indicators based on diurnal energy, water, and carbon flux patterns derived directly from the eddy covariance data and based on theorized physiological responses to hydraulic and non-stomatal limitations. Hydraulic limitations (i.e. intra-plant limitations on water movement) are proxied using the relative diurnal centroid (CET*), which measures the degree to which the flux of evapotranspiration (ET) is shifted toward the morning. Non-stomatal limitations (e.g. inhibitions of biochemical reactions, RuBisCO activity, and/or mesophyll conductance) are characterized by the Diurnal Water-Carbon Index (DWCI), which measures the degree of coupling between ET and gross primary productivity (GPP) within each day. As a proof of concept we show the response of the metrics at six European sites during the 2003 heat wave event, showing a varied response of morning shifts and decoupling. Globally, we found indications of hydraulic limitations in the form of significantly high frequencies of morning-shifted days in dry/Mediterranean climates and savanna/evergreen plant functional types (PFTs), whereas high frequencies of decoupling were dominated by dry climates and grassland/savanna PFTs indicating a prevalence of non-stomatal limitations in these ecosystems. Overall, both the diurnal centroid and DWCI were associated with high net radiation and low latent energy typical of drought. Using three water use efficiency (WUE) models, we found the mean differences between expected and observed WUE to be -0.09 to 0.44 µmol mmol-1 and -0.29 to -0.40 µmol mmol-1 for decoupled and morning-shifted days, respectively, compared

  19. Free radicals generated by radiolysis of aqueous solutions

    International Nuclear Information System (INIS)

    Schwarz, H.A.

    1981-01-01

    The free radicals produced in the radiolysis of aqueous solutions span the range of redox potentials from -2.9 to +2.65 volts. The identity and nature of these radicals were discussed. Most of the discussion was results obtained with low LET radiation sources ( 60 Co gamma radiation or electron accelerators). Water radiolysis provides the synthesis of many radicals and radical ions in aqueous solution. The primary radicals, e/sub aq/ - H, OH, are well characterized. The radical population can be made to be 90% pure OH (or O - ) if N 2 O solutions are irradiated, the remaining 10% being H atoms. 55% of the radicals can be converted to H atoms in acid solution or in neutral phosphate solutions(e/sub aq/ - reacts with H 2 PO 4- to produce H). The remaining 45% (OH radicals) are difficult to convert to H by reaction with H 2 , due to the slow rate of the reaction. About 100 atmospheres of H 2 are required to do the conversion in less than 10 - 6 sec. 3 figures, 3 tables. (DP)

  20. Radical carbonylations using a continuous microflow system

    Directory of Open Access Journals (Sweden)

    Takahide Fukuyama

    2009-07-01

    Full Text Available Radical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.