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Sample records for ss aisi-348 h2o

  1. Assessment of XM-19 as a Substitute for AISI 348 in ATR Service

    SciTech Connect

    F. A. Garner; L. R. Greenwood; R. E. Mizia; C. R. Tyler

    2007-11-01

    It has been proposed that XM-19 alloy be considered as a possible replacement steel for AISI 348 in the construction of Advanced Test Reactor (ATR) capsules. AISI 348 works well, but is currently very difficult to obtain commercially. The superior and desirable mechanical properties of XM-19 alloy have been proven in non-nuclear applications, but no data are available regarding its use in radiation environments. While most 300 series alloys will meet the conditions required in ATR , it cannot be confidently assumed that XM-19 can be substituted without prior qualification in a radiation test. Compared to AISI 348, XM-19 will have an enhanced tendency for phase instabilities due to its higher levels of Ni and, especially, Si. However, transmutation of important elemental components in the highly thermalized ATR spectrum may have a very pronounced effect on its performance during irradiation. Not only will strong transmutation of Mn to Fe reduce the ductility and strength advantages provided by the higher initial Mn content of XM-19, but the extensive loss of Mn will also release from solution much of the N upon which the higher strength of XM-19 depends. In addition, the combined influence of transmutation and Inverse Kirkendall processes may lead to gas-bubble-covered grain boundaries, producing a very fragile alloy after significant irradiation has accumulated. At present, there are no radiation data available to substantiate this possible scenario. An alternate proposal is therefore advanced. Since the response of AISI 348 and 347 to radiation are expected to be relatively indistinguishable, the AISI 347 might serve as an acceptable replacement. While AISI 348 is usually chosen for nuclear service in order to reduce the overall radioactivity arising from relatively small amounts of highly transmutable elements such as cobalt, these elements have very little effect on the radiation performance of the steel. In the proposed application, however, the activity

  2. Stratospheric H2O

    NASA Technical Reports Server (NTRS)

    Ellsaesser, H. W.; Harries, J. E.; Kley, D.; Penndorf, R.

    1980-01-01

    The present state of our knowledge and understanding of H2O in the stratosphere is reviewed. This reveals continuing discrepancies between observations and expectations following from the Brewer-Dobson hypothesis of stratospheric circulation. In particular, available observations indicate unexplained upward and poleward directed H2O gradients immediately downstream from the tropical tropopause and variable vertical gradients above 20 km which generally disagree with those expected from oxidation of CH4.

  3. Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

    NASA Technical Reports Server (NTRS)

    Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

    2013-01-01

    We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

  4. Electron ionization of H2O

    NASA Astrophysics Data System (ADS)

    King, Simon J.; Price, Stephen D.

    2008-11-01

    Relative partial ionization cross-sections and precursor-specific relative partial ionization cross-sections for fragment ions formed by electron ionization of H2O have been measured using time-of-flight mass spectrometry coupled with a 2D ion coincidence technique. We report data for the formation of H+, H2+, O2+, O+ and OH+ relative to the formation of H2O+, as a function of ionizing electron energy from 30 to 200 eV. This data includes, for the first time, measurements on the formation all positive ion pairs and ion triples by dissociative multiple electron ionization of H2O. Through determinations of the kinetic energy release involved in ion pair formation we provide further evidence that indirect processes contribute significantly to the yield of H+ + OH+ ion pairs below the vertical double ionization threshold.

  5. H2O Adsorption Kinetics on Smectites

    NASA Technical Reports Server (NTRS)

    Zent, Aaron P.; Howard, J.; Quinn, R. C.

    2000-01-01

    The adsorptive equilibration of H2O with montomorillonite has been measured. At low temperatures and pressures equilibration can require many hours, effectively preventing smectites at the martian surface from responding to diurnal pressure and temperature variations.

  6. H2O Adsorption Kinetics on Smectites

    NASA Technical Reports Server (NTRS)

    Zent, Aaron P.; Quinn, Richard C.; Howard, Jeanie; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    The adsorptive equilibration of H2O a with montomorillonite, a smectite clay has been measured. At low temperatures and pressures, equilibration can require many hours, effectively preventing smectites at the martian surface from responding rapidly to diurnal pressure and temperature variations.

  7. EPA H2O Software Tool

    EPA Science Inventory

    EPA H2O allows user to: Understand the significance of EGS in Tampa Bay watershed; visually analyze spatial distribution of the EGS in Tampa Bay watershed; obtain map and summary statistics of EGS values in Tampa Bay watershed; analyze and compare potential impacts of development...

  8. EPA H2O User Manual

    EPA Science Inventory

    EPA H2O is a software tool designed to support research being conducted in the Tampa Bay watershed to provide information, data, and approaches and guidance that communities can use to examine alternatives when making strategic decisions to support a prosperous and environmentall...

  9. The Successive H2O Binding Energies for Fe(H2O)n(+)

    NASA Technical Reports Server (NTRS)

    Ricca, Alessandra; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

    1994-01-01

    The binding energy, computed using density functional theory (DFT), are in good agreement with experiment. The bonding is electrostatic (charge-dipole) in origin for all systems. The structures are therefore determined mostly by metal-ligand and ligand-ligand repulsion. The computed structure for FeH2O(+) is C(2v) where sp hybridization is important in reducing the Fe-H2O repulsion. Fe(H2O)2(+) has D2d symmetry where sdo hybridization is the primary factor leading to the linear O-Fe-O geometry. The bonding in Fe(H2O)3(+) and Fe(H2O)4(+) are very complex because ligand-ligand and metal-ligand repulsion, both for the in-plane and out-of-plane water lone-pair orbitals, are important.

  10. Ion survival probabilities for 3 keV Ar + scattering from La, Yb, and chemisorbed H 2, O 2, and H 2O on La surfaces

    NASA Astrophysics Data System (ADS)

    Kumar, Ranjit; Mintz, Moshe H.; Rabalais, J. Wayne

    1984-11-01

    TOF spectra of scattered primary and surface recoiled neutrals and ions for 3 keV Ar + bombardment of clean La and Yb and H 2, O 2, and H 2O saturated La surfaces are presented. The spectra are analyzed in terms of single (SS) and multiple (MS) scattering of the primary ions and surface recoiling (SR) of adsorbate atoms. Measurement of spectra of neutrals + ions and neutrals alone allows determination of scattered ion fractions Y. The Y values for the SS event are high for clean La (37%) and lower for adsorbate covered La (32% for H 2, 13% for O 2, and 8% for H 2O); Yb exhibits a similar behavior, i.e. 16% for clean Yb and 5% for O 2 + H 2O covered Yb. Photon emission accompanying the scattering collision has been observed from clean La and Yb and adsorbate covered La. A preferential inelastic energy loss of 15 ± 3 eV for the SS event has been observed for scattered neutrals as opposed to ions for La and H 2 saturated La at 135°. These results are interpreted within the models for Auger and resonant electronic charge exchange transitions during approach or departure of an ion with a surface and the electron promotions occuring during close atomic encounters where the electron shells are interpenetrating.

  11. The H2O2-H2O Hypothesis: Extremophiles Adapted to Conditions on Mars?

    NASA Astrophysics Data System (ADS)

    Houtkooper, Joop M.; Schulze-Makuch, Dirk

    2007-08-01

    The discovery of extremophiles on Earth is a sequence of discoveries of life in environments where it had been deemed impossible a few decades ago. The next frontier may be the Martian surface environment: could life have adapted to this harsh environment? What we learned from terrestrial extremophiles is that life adapts to every available niche where energy, liquid water and organic materials are available so that in principle metabolism and propagation are possible. A feasible adaptation mechanism to the Martian surface environment would be the incorporation of a high concentration of hydrogen peroxide in the intracellular fluid of organisms. The H2O2-H2O hypothesis suggests the existence of Martian organisms that have a mixture of H2O2 and H2O instead of salty water as their intracellular liquid (Houtkooper and Schulze-Makuch, 2007). The advantages are that the freezing point is low (the eutectic freezes at 56.5°C) and that the mixture is hygroscopic. This would enable the organisms to scavenge water from the atmosphere or from the adsorbed layers of water molecules on mineral grains, with H2O2 being also a source of oxygen. Moreover, below its freezing point the H2O2-H2O mixture has the tendency to supercool. Hydrogen peroxide is not unknown to biochemistry on Earth. There are organisms for which H2O2 plays a significant role: the bombardier beetle, Brachinus crepitans, produces a 25% H2O2 solution and, when attacked by a predator, mixes it with a fluid containing hydroquinone and a catalyst, which produces an audible steam explosion and noxious fumes. Another example is Acetobacter peroxidans, which uses H2O2 in its metabolism. H2O2 plays various other roles, such as the mediation of physiological responses such as cell proliferation, differentiation, and migration. Moreover, most eukaryotic cells contain an organelle, the peroxisome, which mediates the reactions involving H2O2. Therefore it is feasible that in the course of evolution, water-based organisms

  12. Water in Basaltic Melts: an Experimental and Thermodynamic Study of the Effect of H2O on Liquidus Temperatures.

    NASA Astrophysics Data System (ADS)

    Medard, E.; Grove, T. L.

    2006-12-01

    We present a thermodynamic model for the influence of H2O on liquidus temperatures of olivine-saturated primitive basaltic and andesitic melts. The thermodynamic model has been fitted to a suite of H2O-saturated liquidus experiments carried out on a primitive high-alumina basalt from Medicine Lake Volcano (82-72f) over a pressure range of 10 to 1000 MPa. The model of Silver and Stolper (S+S, 1985, J.Geol. 93:161) has been applied to the experimental data. This model uses the assumption of simple ideal mixing between water species and the anionic matrix in the melt. Water in the melt dissolves as molecular H2O, or dissociates to hydroxyl groups and an oxygen atomic network. For 82-72f, the liquidus olivine shows little compositional variability (Fo87.4 to Fo88.4) over the broad range of pressures and temperatures investigated that is not correlated with H2O content of the melt. This observation supports our assumption that major effect of H2O is on the anionic species in the melt and not on the cation equilibria (e.g. Mg and Si). The model reproduces the experimental data well. We find that there is a large influence of H2O addition on melting point for small amounts of H2O, resulting in a concave-down curvature when liquidus depression is plotted against the amount of H2O added. For addition of 0.8 and 5 wt% H2O to 82-72f, the liquidus is depressed by 35 K and 130 K, respectively. The best fits are obtained by assuming partial water dissociation to OH and H2O species, using the equilibrium constant measured by Stolper (1982). S+S applied their model to simple systems (diopside/H2O, albite/H2O, silica/H2O), and recovered the melting behavior extremely well. They also suggested that melt structure/composition influences the amount of liquidus depression caused by H2O addition. We have investigated the influence of bulk composition by performing complementary experiments on a high-magnesian andesite from Mount Shasta, and on a K, Na, and P rich alkali basalt from

  13. H2O2 space shuttle APU

    NASA Technical Reports Server (NTRS)

    1975-01-01

    A cryogenic H2-O2 auxiliary power unit (APU) was developed and successfully demonstrated. It has potential application as a minimum weight alternate to the space shuttle baseline APU because of its (1) low specific propellant consumption and (2) heat sink capabilities that reduce the amount of expendable evaporants. A reference system was designed with the necessary heat exchangers, combustor, turbine-gearbox, valves, and electronic controls to provide 400 shp to two aircraft hydraulic pumps. Development testing was carried out first on the combustor and control valves. This was followed by development of the control subsystem including the controller, the hydrogen and oxygen control valves, the combustor, and a turbine simulator. The complete APU system was hot tested for 10 hr with ambient and cryogenic propellants. Demonstrated at 95 percent of design power was 2.25 lb/hp-hr. At 10 percent design power, specific propellant consumption was 4 lb/hp-hr with space simulated exhaust and 5.2 lb/hp-hr with ambient exhaust. A 10 percent specific propellant consumption improvement is possible with some seal modifications. It was demonstrated that APU power levels could be changed by several hundred horsepower in less than 100 msec without exceeding allowable turbine inlet temperatures or turbine speed.

  14. A shock tube study of OH + H(2)O(2) --> H(2)O + HO(2) and H(2)O(2) + M --> 2OH + M using laser absorption of H(2)O and OH.

    PubMed

    Hong, Zekai; Cook, Robert D; Davidson, David F; Hanson, Ronald K

    2010-05-13

    The rate constants of the reactions: (1) H2O2+M-->2OH+M, (2) OH+H2O2-->H2O+HO2 were measured in shock-heated H(2)O(2)/Ar mixtures using laser absorption diagnostics for H(2)O and OH. Time-histories of H(2)O were monitored using tunable diode laser absorption at 2550.96 nm, and time-histories of OH were achieved using ring dye laser absorption at 306 nm. Initial H(2)O(2) concentrations were also determined utilizing the H(2)O diagnostic. On the basis of simultaneous time-history measurements of OH and H(2)O, k(2) was found to be 4.6 x 10(13) exp(-2630 K/T) [cm(3) mol(-1) s(-1)] over the temperature range 1020-1460 K at 1.8 atm; additional measurements of k(2) near 1 atm showed no significant pressure dependence. Similarly, k(1) was found to be 9.5 x 10(15) exp(-21 250 K/T) [cm(3) mol(-1) s(-1)] over the same temperature and pressure range.

  15. Tuning the conductance of H2O@C60 by position of the encapsulated H2O

    PubMed Central

    Zhu, Chengbo; Wang, Xiaolin

    2015-01-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green’s function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors. PMID:26643873

  16. Effect of H2O, and combined effects of H2O + F, H2O + CO2, and H2O + F + CO2 on the viscosity of a natural basalt from Fuego volcano, Guatemala

    NASA Astrophysics Data System (ADS)

    Robert, G.; Whittington, A. G.; Knipping, J.; Scherbarth, S.; Stechern, A.; Behrens, H.

    2012-12-01

    We measured the viscosity of 5 series of remelted natural basalt from Fuego volcano, Guatemala. These series include single and multiple volatile species: H2O, F, H2O-F, H2O-CO2, and H2O-CO2-F. The hydrous glasses were synthesized at 3 kbar and 1250°C in Internally Heated Pressure Vessels. The multiple volatile series were synthesized at 5 kbar and 1250°C. CO2 was added as Ag2C2O4, F as AlF3, and H2O as distilled water. The anhydrous, F-bearing series was synthesized at 1 atm by simply remelting the Fuego basalt and adding F as CaF2.The natural, dry, remelted Fuego basalt has an NBO/T of 0.64. The following comparisons are based on parallel-plate viscosity measurements in the range ~108 to 1012 Pa s. The temperature at which the viscosity is 1012 Pa s (T12) is taken to be the viscosimetric glass transition temperature (Tg). The addition of 2 wt.% H2O results in a decrease of T12 of ~150°C for basalt. Fluorine on its own has a measurable, but much smaller effect, than the equivalent amount of water. Indeed, ~2 wt.% F results in a T12 depression of only ~30°C. When H2O and F are both present, their effects are approximately additive. For example, the viscosity of a basalt with 1.44 wt.% H2O is very similar to the viscosity of a basalt with ~1 wt.% H2O and ~1.25 wt.% F, and the viscosities of a basalt with 2.29 wt.% H2O and a basalt with ~1.65 wt.% H2O and ~1.3 wt.% F are also very similar. The effect of CO2 is somewhat ambiguous. The viscosity of a basalt with ~1.7 wt.% H2O, ~1.3 wt.% F and ~0.2 wt.% CO2 is essentially the same as the viscosity of a basalt with 2.29 wt.% H2O, so CO2 seems to have a negligible or even viscosity-increasing effect when F and H2O are also present. However, a basalt with ~0.84 wt.% H2O and ~0.09 wt.% CO2 has about the same viscosity as a basalt with 1.34 wt.% H2O, which could suggest a strong (viscosity-decreasing) effect of very small amounts of CO2. These results suggest that the effects on viscosity of F in basaltic systems are

  17. Scavenging of H2O2 by mouse brain mitochondria

    PubMed Central

    Starkov, Anatoly A.; Andreyev, Alexander Yu; Zhang, Steven F.; Starkova, Natalia N.; Korneeva, Maria; Syromyatnikov, Mikhail; Popov, Vasily N.

    2015-01-01

    Mitochondrial reactive oxygen species (ROS) metabolism is unique in that mitochondria both generate and scavenge ROS. Recent estimates of ROS scavenging capacity of brain mitochondria are surprisingly high, ca. 9-12 nmol H2O2/min/mg, which is ~100 times higher than the rate of ROS generation. This raises a question whether brain mitochondria are a source or a sink of ROS. We studied the interaction between ROS generation and scavenging in mouse brain mitochondria by measuring the rate of removal of H2O2 added at a concentration of 0.4 μM, which is close to the reported physiological H2O2 concentrations in tissues, under conditions of low and high levels of mitochondrial H2O2 generation. With NAD-linked substrates, the rate of H2O2 generation by mitochondria was ~50–70 pmol/min/mg. The H2O2 scavenging dynamics was best approximated by the first order reaction equation. H2O2 scavenging was not affected by the uncoupling of mitochondria, phosphorylation of added ADP, or the genetic ablation of glutathione peroxidase 1, but decreased in the absence of respiratory substrates, in the presence of thioredoxin reductase inhibitor auranofin, or in partially disrupted mitochondria. With succinate, the rate of H2O2 generation was ~2,200–2,900 pmol/min/mg; the scavenging of added H2O2 was masked by a significant accumulation of generated H2O2 in the assay medium. The obtained data were fitted into a simple model that reasonably well described the interaction between H2O2 scavenging and production. It showed that mitochondria are neither a sink nor a source of H2O2, but can function as both at the same time, efficiently stabilizing exogenous H2O2 concentration at a level directly proportional to the ratio of the H2O2 generation rate to the rate constant of the first order scavenging reaction. PMID:25248416

  18. Measurements of H2O2 during WATOX-86

    NASA Astrophysics Data System (ADS)

    Heikes, Brian G.; Walega, James G.; Kok, Gregory L.; Lind, John A.; Lazrus, Allan L.

    1988-03-01

    Measurements of gas phase H2O2 were made on all Western Atlantic Ocean Experiment 1986 (WATOX-86) flights aboard the National Oceanic and Atmospheric Administration (NOAA) WP-3D aircraft. These were some of the first airborne real-time H2O2 measurements made in winter. Operation of the instru- ment was limited to altitude < 3.1 km with a detection limit, determined by interference considerations, of 0.05 parts per billion by volume (ppbv), 10% calibration accuracy and 0.03-ppbv precision. Experimental measurements showed the mean H2O2 to be 0.12 ppbv (standard deviation = 0.07, maximum = 1.2 ppbv). Vertical structure was observed with maximum H2O2 above the cloud-capped marine boundary layer. Boundary layer H2O2 was typically at or below the detection limit.

  19. Infrared spectroscopy of V2+(H2O) complexes

    NASA Astrophysics Data System (ADS)

    Bandyopadhyay, B.; Duncan, M. A.

    2012-03-01

    Doubly charged vanadium-water complexes are produced by laser vaporization in a pulsed supersonic expansion. Size-selected ions are studied with infrared photodissociation spectroscopy in the O-H stretch region using argon complex predissociation. Density functional theory calculations provide structures and vibrational spectra of these ions. The O-H stretches of V2+(H2O) appear at lower frequencies than those of the free water molecule or V+(H2O). The symmetric stretch is more intense than the asymmetric stretch in both V+(H2O) and V2+(H2O) complexes. Spectra of V2+(H2O)Arn (n = 2-7) show that the coordination of the V2+ is filled with six ligands, i.e. one water and five argon atoms.

  20. Pyruvate protects pathogenic spirochetes from H2O2 killing.

    PubMed

    Troxell, Bryan; Zhang, Jun-Jie; Bourret, Travis J; Zeng, Melody Yue; Blum, Janice; Gherardini, Frank; Hassan, Hosni M; Yang, X Frank

    2014-01-01

    Pathogenic spirochetes cause clinically relevant diseases in humans and animals, such as Lyme disease and leptospirosis. The causative agent of Lyme disease, Borrelia burgdorferi, and the causative agent of leptospirosis, Leptospria interrogans, encounter reactive oxygen species (ROS) during their enzootic cycles. This report demonstrated that physiologically relevant concentrations of pyruvate, a potent H2O2 scavenger, and provided passive protection to B. burgdorferi and L. interrogans against H2O2. When extracellular pyruvate was absent, both spirochetes were sensitive to a low dose of H2O2 (≈0.6 µM per h) generated by glucose oxidase (GOX). Despite encoding a functional catalase, L. interrogans was more sensitive than B. burgdorferi to H2O2 generated by GOX, which may be due to the inherent resistance of B. burgdorferi because of the virtual absence of intracellular iron. In B. burgdorferi, the nucleotide excision repair (NER) and the DNA mismatch repair (MMR) pathways were important for survival during H2O2 challenge since deletion of the uvrB or the mutS genes enhanced its sensitivity to H2O2 killing; however, the presence of pyruvate fully protected ΔuvrB and ΔmutS from H2O2 killing further demonstrating the importance of pyruvate in protection. These findings demonstrated that pyruvate, in addition to its classical role in central carbon metabolism, serves as an important H2O2 scavenger for pathogenic spirochetes. Furthermore, pyruvate reduced ROS generated by human neutrophils in response to the Toll-like receptor 2 (TLR2) agonist zymosan. In addition, pyruvate reduced neutrophil-derived ROS in response to B. burgdorferi, which also activates host expression through TLR2 signaling. Thus, pathogenic spirochetes may exploit the metabolite pyruvate, present in blood and tissues, to survive H2O2 generated by the host antibacterial response generated during infection.

  1. Pyruvate Protects Pathogenic Spirochetes from H2O2 Killing

    PubMed Central

    Troxell, Bryan; Zhang, Jun-Jie; Bourret, Travis J.; Zeng, Melody Yue; Blum, Janice; Gherardini, Frank; Hassan, Hosni M.; Yang, X. Frank

    2014-01-01

    Pathogenic spirochetes cause clinically relevant diseases in humans and animals, such as Lyme disease and leptospirosis. The causative agent of Lyme disease, Borrelia burgdorferi, and the causative agent of leptospirosis, Leptospria interrogans, encounter reactive oxygen species (ROS) during their enzootic cycles. This report demonstrated that physiologically relevant concentrations of pyruvate, a potent H2O2 scavenger, and provided passive protection to B. burgdorferi and L. interrogans against H2O2. When extracellular pyruvate was absent, both spirochetes were sensitive to a low dose of H2O2 (≈0.6 µM per h) generated by glucose oxidase (GOX). Despite encoding a functional catalase, L. interrogans was more sensitive than B. burgdorferi to H2O2 generated by GOX, which may be due to the inherent resistance of B. burgdorferi because of the virtual absence of intracellular iron. In B. burgdorferi, the nucleotide excision repair (NER) and the DNA mismatch repair (MMR) pathways were important for survival during H2O2 challenge since deletion of the uvrB or the mutS genes enhanced its sensitivity to H2O2 killing; however, the presence of pyruvate fully protected ΔuvrB and ΔmutS from H2O2 killing further demonstrating the importance of pyruvate in protection. These findings demonstrated that pyruvate, in addition to its classical role in central carbon metabolism, serves as an important H2O2 scavenger for pathogenic spirochetes. Furthermore, pyruvate reduced ROS generated by human neutrophils in response to the Toll-like receptor 2 (TLR2) agonist zymosan. In addition, pyruvate reduced neutrophil-derived ROS in response to B. burgdorferi, which also activates host expression through TLR2 signaling. Thus, pathogenic spirochetes may exploit the metabolite pyruvate, present in blood and tissues, to survive H2O2 generated by the host antibacterial response generated during infection. PMID:24392147

  2. Outbursts of H2O in Comet P/Halley

    NASA Astrophysics Data System (ADS)

    Larson, H. P.; Hu, H.-Y.; Mumma, M. J.; Weaver, H. A.

    1990-07-01

    Comet Halley gas-production monitoring efforts in March 1986 with the NASA Kuiper Airborne Observatory's Fourier transform spectrometer have indicated rapid temporal variations in H2O emissions; a continuous record of an H2O outburst was thus obtained. The event, in which H2O brightness increased by a factor of 2.2 in less than 10 min, is ascribable to an energetic process in the nucleus whose character may have been that of amorphous H2O ice crystallization, chemical explosion, thermal stress, or a compressed gas pocket. The timing and energy of the event appear to require an internal energy source; amorphous ice crystallization is held to be most consistent with compositional and thermal models of cometary nuclei as well as the observations.

  3. Phonon-mediated nuclear spin relaxation in H2O

    NASA Astrophysics Data System (ADS)

    Yamakawa, Koichiro; Azami, Shinya; Arakawa, Ichiro

    2017-03-01

    A theoretical model of the phonon-mediated nuclear spin relaxation in H2O trapped by cryomatrices has been established for the first time. In order to test the validity of this model, we measured infrared spectra of H2O trapped in solid Ar, which showed absorption peaks due to rovibrational transitions of ortho- and para-H2O in the spectral region of the bending vibration. We monitored the time evolution of the spectra and analyzed the rotational relaxation associated with the nuclear spin flip to obtain the relaxation rates of H2O at temperatures of 5-15 K. Temperature dependence of the rate is discussed in terms of the devised model.

  4. Interaction energy and the shift in OH stretch frequency on hydrogen bonding for the H2O --> H2O, CH3OH --> H2O, and H2O --> CH3OH dimers.

    PubMed

    Campen, Richard Kramer; Kubicki, James D

    2010-04-15

    The ability to use calculated OH frequencies to assign experimentally observed peaks in hydrogen bonded systems hinges on the accuracy of the calculation. Here we test the ability of several commonly employed model chemistries--HF, MP2, and several density functionals paired with the 6-31+G(d) and 6-311++G(d,p) basis sets--to calculate the interaction energy (D(e)) and shift in OH stretch fundamental frequency on dimerization (delta(nu)) for the H(2)O --> H(2)O, CH(3)OH --> H(2)O, and H(2)O --> CH(3)OH dimers (where for X --> Y, X is the hydrogen bond donor and Y the acceptor). We quantify the error in D(e) and delta(nu) by comparison to experiment and high level calculation and, using a simple model, evaluate how error in D(e) propagates to delta(nu). We find that B3LYP and MPWB1K perform best of the density functional methods studied, that their accuracy in calculating delta(nu) is approximately 30-50 cm(-1) and that correcting for error in D(e) does little to heighten agreement between the calculated and experimental delta(nu). Accuracy of calculated delta(nu) is also shown to vary as a function of hydrogen bond donor: while the PBE and TPSS functionals perform best in the calculation of delta(nu) for the CH(3)OH --> H(2)O dimer their performance is relatively poor in describing H(2)O --> H(2)O and H(2)O --> CH(3)OH.

  5. The role of H2O in the Saturn ionosphere

    NASA Astrophysics Data System (ADS)

    Shemansky, Donald; Liu, Xianming

    2010-05-01

    Stellar occultations in the Cassini Ultraviolet Imaging Spectrograph Experiment observation program have provided measurements of the vertical profiles of H2 and and minor components of the atmosphere. The minor species identified and measured in the extinction spectra to date are CH4, C2H2, and C2H4. Measurements of abundance profiles are reported here, with limits on H2O content. The focus of this paper is on H2O because of the importance of this species to the understanding of upper atmospheric physical chemistry with significant consequences for ionospheric properties and energy budget. Ionospheric theory published in several papers beginning as early as 1984 have a common critical dependence on a sufficiently large H2O mixing ratio to control the lifetime of the assumed dominant ion, H+. The vertical extinction profiles, which extend down to an impact parameter of 300 km above the 1 bar pressure level, show no evidence of H2O in the spectrum at mid and low latitudes, establishing a mixing ratio [H2O]/[H2] ≤ 4 × 10-8, compatible with earlier global average measurements. The upper limit on H2O abundance at mid latitude establishes a mixing ratio more an order of magnitude too low to influence the ionosphere population in competition with calculated H+ + H2 X(v:J) charge capture reaction rates. The analysis of the extinction spectra produces densities and mixing ratios of the observed species and these results are reported and discussed.

  6. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT ETERNAL Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Wignall, J.; Lyons, Marv; Ertl, G.; Alefeld, Georg; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

    2013-03-01

    ''H2O H2O everywhere; ne'er a drop to drink''[Coleridge(1798)] now: ''H2 H2 everywhere; STILL ne'er a drop to drink'': ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): { ∖{}O/H2O{ ∖}} =[16]/[18] ∖sim 90{ ∖%} O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [ ∖underline {3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9 /2007)] crucial geomorphology which ONLY maximal-buoyancy H2 can exploit, to again make ''Mountains into Fountains'', ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': ''terraforming''(and ocean-rebasificaton!!!) ONLY VIA Siegel[APS March MTGS.:1960s-2000ss) DIFFUSIVE-MAGNETORESISTANCE (DMR) proprietary MAGNETIC-HYDROGEN-VALVE(MHV) ALL-IMPORTANT PRECLUDED RADIAL-diffusion, permitting ONLY AXIAL-H2-BALLISTIC-flow (``G.A''.''/DoE''/''Terrapower''/''Intellectual-Ventures''/ ''Gileland''/ ''Myhrvold''/''Gates'' ``ARCHIMEDES'') in ALREADY IN-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/ famine)

  7. Na(H2O)[Mn(H2O)2(BP2O8)]: Crystal structure refinement

    NASA Astrophysics Data System (ADS)

    Yakubovich, O. V.; Steele, I.; Dimitrova, O. V.

    2009-01-01

    The crystal structure of synthetic manganese sodium borophosphate hydrate Na(H2O)[Mn(H2O)2(BP2O8)] was refined based on X-ray diffraction data. The compound was prepared by soft hydrothermal synthesis in the MnCl2-Na3PO4-B2O3-H2O system. The unit-cell parameters are a= 9.602(1) Å, c= 16.037(3) Å, sp. gr. P6522, Z= 6, D x = 2.57 g/cm3. The water molecules were found to be statistically distributed in the channels of the mixed anionic paraframework consisting of (BO4) and (PO4) tetrahedra and [MnO4(H2O)2] octahedra. The hydrogen atoms of the water molecules coordinated to the Mn2+ cations were located and their positional and thermal parameters were refined. The crystal-chemical features of borophosphates of the general formula A x M(H2O)2(BP2O8)(H2O) are considered.

  8. Destruction and Sequestration of H2O on Mars

    NASA Astrophysics Data System (ADS)

    Clark, Benton

    2016-07-01

    The availability of water in biologically useable form on any planet is a quintessential resource, even if the planet is in a zone habitable with temperature regimes required for growth of organisms (above -18 °C). Mars and most other planetary objects in the solar system do not have sufficient liquid water at their surfaces that photosynthesis or chemolithoautotrophic metabolism could occur. Given clear evidence of hydrous mineral alteration and geomorphological constructs requiring abundant supplies of liquid water in the past, the question arises whether this H2O only became trapped physically as ice, or whether there could be other, more or less accessible reservoirs that it has evolved into. Salts containing S or Cl appear to be ubiquitous on Mars, having been measured in soils by all six Mars landed missions, and detected in additional areas by orbital investigations. Volcanoes emit gaseous H2S, S, SO2, HCl and Cl2. A variety of evidence indicates the geochemical fate of these gases is to be transformed into sulfates, chlorides, chlorates and perchlorates. Depending on the gas, the net reaction causes the destruction of between one and up to eight molecules of H2O per atom of S or Cl (although hydrogen atoms are also released, they are lost relatively rapidly to atmospheric escape). Furthermore, the salt minerals formed often incorporate H2O into their crystalline structures, and can result in the sequestration of up to yet another six (sometimes, more) molecules of H2O. In addition, if the salts are microcrystalline or amorphous, they are potent adsorbents for H2O. In certain cases, they are even deliquescent under martian conditions. Finally, the high solubility of the vast majority of these salts (with notable exception of CaSO4) can result in dense brines with low water activity, aH, as well as cations which can be inimical to microbial metabolism, effectively "poisoning the well." The original geologic materials on Mars, igneous rocks, also provide some

  9. Electrochemical, H2O2-Boosted Catalytic Oxidation System

    NASA Technical Reports Server (NTRS)

    Akse, James R.; Thompson, John O.; Schussel, Leonard J.

    2004-01-01

    An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

  10. Role of Metabolic H2O2 Generation

    PubMed Central

    Sies, Helmut

    2014-01-01

    Hydrogen peroxide, the nonradical 2-electron reduction product of oxygen, is a normal aerobic metabolite occurring at about 10 nm intracellular concentration. In liver, it is produced at 50 nmol/min/g of tissue, which is about 2% of total oxygen uptake at steady state. Metabolically generated H2O2 emerged from recent research as a central hub in redox signaling and oxidative stress. Upon generation by major sources, the NADPH oxidases or Complex III of the mitochondrial respiratory chain, H2O2 is under sophisticated fine control of peroxiredoxins and glutathione peroxidases with their backup systems as well as by catalase. Of note, H2O2 is a second messenger in insulin signaling and in several growth factor-induced signaling cascades. H2O2 transport across membranes is facilitated by aquaporins, denoted as peroxiporins. Specialized protein cysteines operate as redox switches using H2O2 as thiol oxidant, making this reactive oxygen species essential for poising the set point of the redox proteome. Major processes including proliferation, differentiation, tissue repair, inflammation, circadian rhythm, and aging use this low molecular weight oxygen metabolite as signaling compound. PMID:24515117

  11. Vibrational predissociation of ArH2O

    NASA Astrophysics Data System (ADS)

    Bissonnette, C.; Clary, D. C.

    1992-12-01

    Accurate close-coupling calculations are used to investigate the vibrational predissociation of ArH2O as a function of the overall rotation J of the van der Waals complex. A full vibrational and rotational basis of H2O states is used in the calculation. The potential energy surface is of a form due to Cohen and Saykally and derived from far-infrared spectra, with an additional term to introduce the dependence on the vibrations of H2O. The linewidths calculated in this work show a maximum at J=6 and it is found that Fermi resonances affect dramatically the magnitude of the calculated linewidths. Good agreement with experimentally measured linewidths of Nesbitt and Lascola is achieved and the calculations provide a simple picture for the J dependence of the linewidths.

  12. A Global PLASIMO Model for H2O Chemistry

    NASA Astrophysics Data System (ADS)

    Tadayon Mousavi, Samaneh; Koelman, Peter; Graef, Wouter; Mihailova, Diana; van Dijk, Jan; EPG/ Applied Physics/ Eindhoven University of Technology Team; Plasma Matters B. V. Team

    2016-09-01

    Global warming is one of the critical contemporary problems for mankind. Transformation of CO2 into fuels, like CH4, that are transportable with the current infrastructure seems a promising idea to solve this threatening issue. The final aim of this research is to produce CH4 by using microwave plasma in CO2 -H2 O mixture and follow-up catalytic processes. In this contribution we present a global model for H2 O chemistry that is based on the PLASIMO plasma modeling toolkit. The time variation of the electron energy and the species' densities are calculated based on the source and loss terms in plasma due to chemical reactions. The short simulation times of such models allow an efficient assessment and chemical reduction of the H2O chemistry, which is required for full spatially resolved simulations.

  13. H2O2_COD_EPA; MEC_acclimation

    EPA Pesticide Factsheets

    H2O2_COD_EPA: Measurements of hydrogen peroxide and COD concentrations for water samples from the MEC reactors.MEC_acclimation: raw data for current and voltage of the anode in the MEC reactor.This dataset is associated with the following publication:Sim, J., J. An, E. Elbeshbishy, R. Hodon, and H. Lee. Characterization and optimization of cathodic conditions for H2O2 synthesis in microbial electrochemical cells. Bioresource Technology. Elsevier Online, New York, NY, USA, 195: 31-36, (2015).

  14. Global Flux Balance in the Terrestrial H2O Cycle: Reconsidering the Post-Arc Subducted H2O Flux

    NASA Astrophysics Data System (ADS)

    Parai, R.; Mukhopadhyay, S.

    2010-12-01

    Quantitative estimates of H2O fluxes between the mantle and the exosphere (i.e., the atmosphere, oceans and crust) are critical to our understanding of the chemistry and dynamics of the solid Earth: the abundance and distribution of water in the mantle has dramatic impacts upon mantle melting, degassing history, structure and style of convection. Water is outgassed from the mantle is association with volcanism at mid-ocean ridges, ocean islands and convergent margins. H2O is removed from the exosphere at subduction zones, and some fraction of the subducted flux may be recycled past the arc into the Earth’s deep interior. Estimates of the post-arc subducted H2O flux are primarily based on the stability of hydrous phases at subduction zone pressures and temperatures (e.g. Schmidt and Poli, 1998; Rüpke et al., 2004; Hacker, 2008). However, the post-arc H2O flux remains poorly quantified, in part due to large uncertainties in the water content of the subducting slab. Here we evaluate estimated post-arc subducted fluxes in the context of mantle-exosphere water cycling, using a Monte Carlo simulation of the global H2O cycle. Literature estimates of primary magmatic H2O abundances and magmatic production rates at different tectonic settings are used with estimates of the total subducted H2O flux to establish the parameter space under consideration. Random sampling of the allowed parameter space affords insight into which input and output fluxes satisfy basic constraints on global flux balance, such as a limit on sea-level change over time. The net flux of H2O between mantle and exosphere is determined by the total mantle output flux (via ridges and ocean islands, with a small contribution from mantle-derived arc output) and the input flux subducted beyond the arc. Arc and back-arc output is derived mainly from the slab, and therefore cancels out a fraction of the trench intake in an H2O subcycle. Limits on sea-level change since the end of the Archaean place

  15. New Optical Constants for Amorphous and Crystalline H2O-ice and H2O-mixtures.

    NASA Technical Reports Server (NTRS)

    Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

    2006-01-01

    We will present the products of new laboratory measurements of ices relevant to Trans-Neptunian Objects. We have calculated the real and imaginary indices of refraction for amorphous and crystalline H2O-ice and also H2O-rich ices containing other molecular species. We create ice samples by condensing gases onto a cold substrate. We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows. We then collect transmission spectra of the samples in the wavelength range from 0.7-22 micrometers. Using the thickness and the transmission spectra of the ice we calculate the imaginary part of the index of refraction. We then use a Kramers-Kronig calculation to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can then be used to create model spectra for comparison to spectra from Solar System objects, including TNOs. We will summarize the difference between the amorphous and crystalline H2O-ice spectra. These changes include weakening of features and shifting of features to shorter wavelength. One important result is that the 2 pm feature is stronger in amorphous H2O ice than it is in crystalline H2O-ice. We will also discuss the changes seen when H2O is mixed with other components, including CO2, CH4, HCN, and NH3 (Bernstein et al. 2005; Bernstein et al. 2006).

  16. Influence of salicylic acid on H2O2 production, oxidative stress, and H2O2-metabolizing enzymes. Salicylic acid-mediated oxidative damage requires H2O2.

    PubMed Central

    Rao, M V; Paliyath, G; Ormrod, D P; Murr, D P; Watkins, C B

    1997-01-01

    We investigated how salicylic acid (SA) enhances H2O2 and the relative significance of SA-enhanced H2O2 in Arabidopsis thaliana. SA treatments enhanced H2O2 production, lipid peroxidation, and oxidative damage to proteins, and resulted in the formation of chlorophyll and carotene isomers. SA-enhanced H2O2 levels were related to increased activities of Cu,Zn-superoxide dismutase and were independent of changes in catalase and ascorbate peroxidase activities. Prolonging SA treatments inactivated catalase and ascorbate peroxidase and resulted in phytotoxic symptoms, suggesting that inactivation of H2O2-degrading enzymes serves as an indicator of hypersensitive cell death. Treatment of leaves with H2O2 alone failed to invoke SA-mediated events. Although leaves treated with H2O2 accumulated in vivo H2O2 by 2-fold compared with leaves treated with SA, the damage to membranes and proteins was significantly less, indicating that SA can cause greater damage than H2O2. However, pretreatment of leaves with dimethylthiourea, a trap for H2O2, reduced SA-induced lipid peroxidation, indicating that SA requires H2O2 to initiate oxidative damage. The relative significance of the interaction among SA, H2O2, and H2O2-metabolizing enzymes with oxidative damage and cell death is discussed. PMID:9306697

  17. A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

    1981-01-01

    Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

  18. H 2O + ions in comets: models and observations

    NASA Astrophysics Data System (ADS)

    Wegmann, R.; Jockers, K.; Bonev, T.

    1999-06-01

    An improved magnetohydrodynamic (MHD) model with chemistry is presented. The analysis of the source and sink terms for H 2O + shows that for small comets up to 11% of water molecules are finally ionized. For large comets (such as Halley) this fraction decreases to less than 3%. From the MHD scaling laws a similarity law for the individual ion densities is deduced which takes into account that the mother molecules are depleted by dissociation. This is applied to H 2O + ions. Radial density profiles from model calculations, observations by Giotto near comet Halley, and ground based observations of three comets confirm this scaling law for H 2O + ions. From the similarity law for the density a scaling law for the column density is derived which is more convenient to apply for ground based observations. From these scaling laws methods are derived which allow the determination of the water production rate from the ground based images of the H 2O + ions. Finally, the two dimensional images of model column densities are compared with observations.

  19. Preformance Analysis of NH3-H2O Absorption Cycle

    NASA Astrophysics Data System (ADS)

    Tsujimori, Atsushi; Ozaki, Eiichi

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

  20. Multidimentional Normal Mode Calculations for the OH Vibrational Spectra of (H_2O)_3^+, (H_2O)_3^+Ar, H^+(H_2O)_3, and H^+(H_2O)_3Ar

    NASA Astrophysics Data System (ADS)

    Li, Ying-Cheng; Chuang, Hsiao-Han; Tan, Jake Acedera; Takahashi, Kaito; Kuo, Jer-Lai

    2014-06-01

    Recent experimental observations of (H_2O)_3^+, (H_2O)_3^+Ar, H^+(H_2O)_3, and H^+(H_2O)_3Ar clusters in the region 1400-3800 wn show that the OH stretching vibration has distinct characteristics. Multidimensional normal mode calculations were carried out for OH stretching vibrations in the 1200-4000 wn photon energy range. The potential energy and dipole surfaces were evaluated by using first-principles methods. By comparing the calculated frequencies and intensities of OH stretching vibration with experimental spectra, we found that the assignment of OH strecthing of H_3O^+ moiety and free OH strectching vibration have resonable agreement with experimental data. Jeffrey M. Headrick, Eric G. Diken, Richard S. Walters, Nathan I. Hammer, Richard A. Christie, Jun Cui, Evgeniy M. Myshakin, Michael A. Duncan, Mark A. Johnson, Kenneth D. Jordan, Science, 2005, 17, 1765. Kenta Mizuse, Jer-Lai Kuo and Asuka Fujii, Chem. Sci., 2011, 2, 868 Kenta Mizuse and Asuka Fujii, J. Phys. Chem. A, 2013, 117, 929.

  1. The H2O Content of Granite Embryos

    NASA Astrophysics Data System (ADS)

    Bartoli, O.; Cesare, B.; Remusat, L.; Acosta-Vigil, A.; Poli, S.

    2014-12-01

    Quantification of H2O contents of natural granites has been an on-going challenge owing to the extremely fugitive character of H2O during cooling and ascent of melts and magmas. Here we approach this problem by studying granites in their source region (i.e. the partially melted continental crust) and we present the first NanoSIMS analyses of anatectic melt inclusions (MI) hosted in peritectic phases of migmatites and granulites. These MI which totally crystallized upon slow cooling represent the embryos of the upper-crustal granites. The approach based on the combination of MI and NanoSIMS has been here tested on amphibolite-facies migmatites at Ronda (S Spain) that underwent fluid-present to fluid-absent melting at ~700 °C and ~5 kbar. Small (≤ 5 µm) crystallized MI trapped in garnet have been remelted using a piston-cylinder apparatus and they show leucogranitic compositions. We measure high and variable H2O contents (mean of 6.5±1.4 wt%) in these low-temperature, low-pressure granitic melts. We demonstrate that, when the entire population from the same host is considered, MI reveal the H2O content of melt in the specific volume of rock where the host garnet grew. Mean H2O values for the MI in different host crystals range from 5.4 to 9.1 wt%. This range is in rather good agreement with experimental models for granitic melts at the inferred P-T conditions. Our study documents for the first time the occurrence of H2O heterogeneities in natural granitic melts at the source region. These heterogeneities are interpreted to reflect the birth of granitic melts under conditions of "mosaic" equilibrium, where the distinct fractions of melt experience different buffering assemblages at the micro-scale, with concomitant differences in melt H2O content. These results confirm the need for small-scale geochemical studies on natural samples to improve our quantitative understanding of crustal melting and granite formation. The same approach adopted here can be applied to

  2. The H2O content of granite embryos

    NASA Astrophysics Data System (ADS)

    Bartoli, Omar; Cesare, Bernardo; Remusat, Laurent; Acosta-Vigil, Antonio; Poli, Stefano

    2015-04-01

    Quantification of H2O contents of natural granites has been an on-going challenge owing to the extremely fugitive character of H2O during cooling and ascent of melts and magmas. Here we approach this problem by studying granites in their source region (i.e. the partially melted continental crust) and we present the first NanoSIMS analyses of anatectic melt inclusions (MI) hosted in peritectic phases of migmatites and granulites. These MI which totally crystallized upon slow cooling represent the embryos of the upper-crustal granites [1, 2, 3]. The approach based on the combination of MI and NanoSIMS has been here tested on amphibolite-facies migmatites at Ronda (S Spain) that underwent fluid-present to fluid-absent melting at ~700 °C and ~5 kbar. Small (≤ 5 µm) crystallized MI trapped in garnet have been remelted using a piston-cylinder apparatus and they show leucogranitic compositions. We measure high and variable H2O contents (mean of 6.5±1.4 wt%) in these low-temperature, low-pressure granitic melts. We demonstrate that, when the entire population from the same host is considered, MI reveal the H2O content of melt in the specific volume of rock where the host garnet grew. Mean H2O values for the MI in different host crystals range from 5.4 to 9.1 wt%. This range is in rather good agreement with experimental models for granitic melts at the inferred P-T conditions. Our study documents for the first time the occurrence of H2O heterogeneities in natural granitic melts at the source region [3]. These heterogeneities are interpreted to reflect the birth of granitic melts under conditions of "mosaic" equilibrium, where the distinct fractions of melt experience different buffering assemblages at the micro-scale, with concomitant differences in melt H2O content. These results confirm the need for small-scale geochemical studies on natural samples to improve our quantitative understanding of crustal melting and granite formation. The same approach adopted here can

  3. Oxidative degradation of endotoxin by advanced oxidation process (O3/H2O2 & UV/H2O2).

    PubMed

    Oh, Byung-Taek; Seo, Young-Suk; Sudhakar, Dega; Choe, Ji-Hyun; Lee, Sang-Myeong; Park, Youn-Jong; Cho, Min

    2014-08-30

    The presence of endotoxin in water environments may pose a serious public health hazard. We investigated the effectiveness of advanced oxidative processes (AOP: O3/H2O2 and UV/H2O2) in the oxidative degradation of endotoxin. In addition, we measured the release of endotoxin from Escherichia coli following typical disinfection methods, such as chlorine, ozone alone and UV, and compared it with the use of AOPs. Finally, we tested the AOP-treated samples in their ability to induce tumor necrosis factor alpha (TNF-α) in mouse peritoneal macrophages. The production of hydroxyl radical in AOPs showed superior ability to degrade endotoxin in buffered solution, as well as water samples from Korean water treatment facilities, with the ozone/H2O2 being more efficient compared to UV/H2O2. In addition, the AOPs proved effective not only in eliminating E. coli in the samples, but also in endotoxin degradation, while the standard disinfection methods lead to the release of endotoxin following the bacteria destruction. Furthermore, in the experiments with macrophages, the AOPs-deactivated endotoxin lead to the smallest induction of TNF-α, which shows the loss of inflammation activity, compared to ozone treatment alone. In conclusion, these results suggest that AOPs offer an effective and mild method for endotoxin degradation in the water systems.

  4. Vibrational investigations of CO2-H2O, CO2-(H2O)2, and (CO2)2-H2O complexes isolated in solid neon.

    PubMed

    Soulard, P; Tremblay, B

    2015-12-14

    The van der Waals complex of H2O with CO2 has attracted considerable theoretical interest as a typical example of a weak binding complex with a dissociation energy less than 3 kcal/mol. Up to now, experimental vibrational data are sparse. We have studied by FTIR the complexes involving CO2 and water molecules in solid neon. Many new absorption bands close to the well known monomers fundamentals give evidence for at least three (CO2)n-(H2O)m complexes, noted n:m. Concentration effects combined with a detailed vibrational analysis allow for the identification of sixteen, twelve, and five transitions for the 1:1, 1:2, and 2:1 complexes, respectively. Careful examination of the far infrared spectral region allows the assignment of several 1:1 and 1:2 intermolecular modes, confirmed by the observation of combinations of intra + intermolecular transitions, and anharmonic coupling constants have been derived. Our results demonstrate the high sensibility of the solid neon isolation to investigate the hydrogen-bonded complexes in contrast with the gas phase experiments for which two quanta transitions cannot be easily observed.

  5. Silicate-H2O Systems at High Pressure Conditions

    NASA Astrophysics Data System (ADS)

    Tailby, N.; Mavrogenes, J. A.; Hermann, J.; O'Neill, H. S.

    2008-12-01

    Since the discovery of the second critical endpoint (CP2) in the albite-water system, numerous attempts have been made to determine the pressure and temperature of this CP2 and the mutual solubilities within more complex systems. The P-T position of the CP2 has been estimated for many systems: SiO2 (<10 kb/900 °C, Newton and Manning, 2008); NaAlSi3O8 (15 kb/800 °C, Burnham and Davis, 1974; Shen and Keppler, 1997); Pelite (50 kb/1,000 °C, Schmidt et al., 2004), basalt (50 kb/ 1000 °C, Kessel et al., 2004), Peridotite (38 kb/1000 °C, Mibe et al., 2007). A number of experimental techniques have been used to determine phase relations and H2O solubility in experiments. These include in-situ experimental techniques (e.g., HYDAC; Shen and Keppler, 1997), fluid trap techniques (e.g., diamond traps; Stalder et al., 2000), and single crystal weight-loss techniques (e.g., SiO2-H2O techniques employed by Newton and Manning, 2008). None of these techniques is without difficulties, as H2O rich experiments need to overcome huge retrograde fluid solubilities upon quench in order to determine mutual solubilities at experimental conditions. We have developed a new technique to determine "rock"-H2O relationships at high-P conditions, with particular focus on the shape and locus of solvi in pressure temperature space. In this series of experiments, an oxygen fugacity buffer (Re-ReO2) and a sliding H-fugacity sensor (NiO-Ni-Pd mixture) are combined to monitor H2O activity over the entire range of pressure and temperature. Unlike other techniques, the use of sensor capsules does not require textural interpretation of experiments. H2O activity is related to oxygen and hydrogen fugacity by the reaction: H2O = H2 + ½O2 NiO-Ni-Pd mixtures were placed within a ZrO2 jacket and sealed within a welded 2.3 mm Pt capsule. This 2.3 mm Pt sensor capsule was then encased within a larger, thick walled 6 mm diameter Ag capsule. Pelite-H2O mixtures and oxygen buffers were held within this larger

  6. Optimization of H2O2 dosage in microwave-H2O2 process for sludge pretreatment with uniform design method.

    PubMed

    Xiao, Qingcong; Yan, Hong; Wei, Yuansong; Wang, Yawei; Zeng, Fangang; Zheng, Xiang

    2012-01-01

    A microwave-H2O2 process for sludge pretreatment exhibited high efficiencies of releasing organics, nitrogen, and phosphorus, but large quantities of H2O2 residues were detected. A uniform design method was thus employed in this study to further optimize H2O2 dosage by investigating effects of pH and H2O2 dosage on the amount of H2O2 residue and releases of organics, nitrogen, and phosphorus. A regression model was established with pH and H2O2 dosage as the independent variables, and H2O2 residue and releases of organics, nitrogen, and phosphorus as the dependent variables. In the optimized microwave-H2O2 process, the pH value of the sludge was firstly adjusted to 11.0, then the sludge was heated to 80 degrees C and H2O2 was dosed at a H2O2:mixed liquor suspended solids (MLSS) ratio of 0.2, and the sludge was finally heated to 100 degrees C by microwave irradiation. Compared to the microwave-H2O2 process without optimization, the H2O2 dosage and the utilization rate of H2O2 in the optimized microwave-H2O2 process were reduced by 80% and greatly improved by 3.87 times, respectively, when the H2O2:MLSS dosage ratio was decreased from 1.0 to 0.2, resulting in nearly the same release rate of soluble chemical oxygen demand in the microwave-H2O2 process without optimization at H2O2:MLSS ratio of 0.5.

  7. Keggin polyoxoanion supported organic-inorganic trinuclear lutetium cluster, {Na(H2O)3[Lu(pydc)(H2O)3]3}[SiW12O40]·26.5H2O.

    PubMed

    Li, Suzhi; Zhang, Dongdi; Guo, Yuan Yuan; Ma, Pengtao; Qiu, Xiaoyang; Wang, Jingping; Niu, Jingyang

    2012-09-07

    A novel strawberry-like organic-inorganic hybrid, {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}[SiW(12)O(40)]·26.5H(2)O (H(2)pydc = pyridine-2,6-dicarboxylate) containing an intriguing trinuclear lutetium cluster {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}(4+) has been synthesized and its luminescent properties, IR, UV, TG, PXRD analyses and single crystal X-ray diffraction were investigated.

  8. The EUV spectrum of H2O by electron impact

    NASA Technical Reports Server (NTRS)

    Ajello, J. M.

    1984-01-01

    The vacuum ultraviolet (VUV) spectrum of H2O produced by electron impact at 200 eV is presented. A total of 25 spectral features are identified at a resolution of 0.5 nm over the wavelength range from 40 to 280 nm. Absolute emission cross-sections were obtained for each of the features. The differences of the features are all attributed to the various excited states of the dissociation products, H, O and O(+). The Lyman-alpha feature is the brightest for electron-induced fluorescence of H2O from the UV to the near-IR, and had a cross-section of 6.3 (+ or - 1.0 x 10 to the -18th) sq cm at 200 eV. The Lyman-alpha feature contributed 74 percent of the total measured emission cross-section in the EUV.

  9. The Target: H2O on the Moon

    NASA Technical Reports Server (NTRS)

    Green, J.; Wys, J. Negusde; Zuppero, A.

    1992-01-01

    The importance of H2O on the lunar surface has long been identified as a high priority for the existence of a human colony for mining activities and, more recently, for space fuel. Using the Earth as an analog, volcanic activity would suggest the generation of water during lunar history. Evidence of volcanism is found not only in present lunar morphology, but in over 400 locations of lunar transient events cataloged by Middlehurst and Kuiper in the 1960's. These events consisted of sightings since early history of vapor emissions and bright spots or flares. Later infrared scanning by Saari and Shorthill showed 'hot spots', many of which coincided with transient event sites. Many of the locations of Middlehurst and Kuiper were the sites of repeat events, leading to the conclusion that these were possibly volcanic in nature. The detection and use of H2O from the lunar surface is discussed.

  10. Antiferromagnetism of UO2⋅2H2O

    USGS Publications Warehouse

    Pankey, T.; Senftle, F.E.; Cuttitta, F.

    1963-01-01

    Magnetic susceptibility measurements have been made on UO2⋅xH2O for x=1.78 to x=2.13, and from 77° to 375°K. As the value of x decreased the susceptibility increased. Both these data and structural arguments imply that the formula of this compound is U(OH)4 rather than the dihydrate form. Based on this concept the data have been corrected for diamagnetism and also small amounts of UO2 and H2O which were present. The molar susceptibility of U4+ in U(OH)4 is nearly an order of magnitude less than in other uranium compounds, and it is suggested that this is probably due to superexchange between adjacent uranium atoms through intervening oxygen atoms.

  11. Antiproton stopping in H2 and H2O

    NASA Astrophysics Data System (ADS)

    Bailey, J. J.; Kadyrov, A. S.; Abdurakhmanov, I. B.; Fursa, D. V.; Bray, I.

    2015-11-01

    Stopping powers of antiprotons in H2 and H2O targets are calculated using a semiclassical time-dependent convergent close-coupling method. In our approach the H2 target is treated using a two-center molecular multiconfiguration approximation, which fully accounts for the electron-electron correlation. Double-ionization and dissociative ionization channels are taken into account using an independent-event model. The vibrational excitation and nuclear scattering contributions are also included. The H2O target is treated using a neonization method proposed by C. C. Montanari and J. E. Miraglia [J. Phys. B 47, 015201 (2014), 10.1088/0953-4075/47/1/015201], whereby the ten-electron water molecule is described as a dressed Ne-like atom in a pseudospherical potential. Despite being the most comprehensive approach to date, the results obtained for H2 only qualitatively agree with the available experimental measurements.

  12. Role of H2O in Generating Subduction Zone Earthquakes

    NASA Astrophysics Data System (ADS)

    Hasegawa, A.

    2017-03-01

    A dense nationwide seismic network and high seismic activity in Japan have provided a large volume of high-quality data, enabling high-resolution imaging of the seismic structures defining the Japanese subduction zones. Here, the role of H2O in generating earthquakes in subduction zones is discussed based mainly on recent seismic studies in Japan using these high-quality data. Locations of intermediate-depth intraslab earthquakes and seismic velocity and attenuation structures within the subducted slab provide evidence that strongly supports intermediate-depth intraslab earthquakes, although the details leading to the earthquake rupture are still poorly understood. Coseismic rotations of the principal stress axes observed after great megathrust earthquakes demonstrate that the plate interface is very weak, which is probably caused by overpressured fluids. Detailed tomographic imaging of the seismic velocity structure in and around plate boundary zones suggests that interplate coupling is affected by local fluid overpressure. Seismic tomography studies also show the presence of inclined sheet-like seismic low-velocity, high-attenuation zones in the mantle wedge. These may correspond to the upwelling flow portion of subduction-induced secondary convection in the mantle wedge. The upwelling flows reach the arc Moho directly beneath the volcanic areas, suggesting a direct relationship. H2O originally liberated from the subducted slab is transported by this upwelling flow to the arc crust. The H2O that reaches the crust is overpressured above hydrostatic values, weakening the surrounding crustal rocks and decreasing the shear strength of faults, thereby inducing shallow inland earthquakes. These observations suggest that H2O expelled from the subducting slab plays an important role in generating subduction zone earthquakes both within the subduction zone itself and within the magmatic arc occupying its hanging wall.

  13. Near Infrared Spectra of H2O/HCN Mixtures

    NASA Technical Reports Server (NTRS)

    Mastrapa, R. M.; Bernstein, M. P.; Sanford, S. A.

    2006-01-01

    Cassini's VIMS has already returned exciting results interpreting spectra of Saturn's icy satellites. The discovery of unidentified features possibly due to CN compounds inspired the work reported here. We wanted to test HCN as a possibility for explaining these features, and also explore how the features of HCN change when mixed with H2O. We have previously noted that mixing H20 and CO2 produces new spectral features and that those features change with temperature and mixing ratio.

  14. Thermodynamic Properties of LiBr/H2O Solution

    NASA Astrophysics Data System (ADS)

    Murakami, Kazuhiko; Sato, Haruki; Watanabe, Koichi

    Although most of the absorption refrigeration/heat pump systems use LiBr/H2O solution for absorbent/refrigerant pair, there exist only a limited number of reliable sets of data on the bubble-point pressures of LiBr/H2O solution. The objective of the present study is to reveal the concentration and temperature dependence of bubble-point pressures of LiBr/H2O solution over a wide range of parameters so as to provide more precise set of thermodynamic property data for advanced design of the absorption refrigeration/heat pump equipments. A total of 44 bubble-point pressures have been measured along seven concentration isopleths of 20, 30, 40, 45, 50, 58 and 60 wt%LiBr solution which cover the range of temperatures 283-413 K and of pressures up to 300 kPa. The experimental uncertainties of temperature, pressure and concentration measurements were not greater than ±20mK, ±0.1 kPa and ±0.1wt%, respectively.

  15. Early Determinants of H2O2-Induced Endothelial Dysfunction

    PubMed Central

    Boulden, Beth M.; Widder, Julian D.; Allen, Jon C.; Smith, Debra A.; Al-Baldawi, Ruaa N.; Harrison, David G.; Dikalov, Sergey I.; Jo, Hanjoong; Dudley, Samuel C.

    2006-01-01

    Reactive oxygen species (ROS) can stimulate nitric oxide (NO•) production from the endothelium by transient activation of endothelial nitric oxide synthase (eNOS). With continued or repeated exposure, NO• production is reduced, however. We investigated the early determinants of this decrease in NO• production. Following an initial H2O2 exposure, endothelial cells responded by increasing NO• production measured electrochemically. NO• concentrations peaked by 10 min with a slow reduction over 30 min. The decrease in NO• at 30 min was associated with a 2.7 fold increase O2•− production (p<0.05) and a 14 fold reduction of the eNOS cofactor, tetrahydrobiopterin (BH4, p<0.05). Used as a probe for endothelial dysfunction, the integrated NO• production over 30 min upon repeat H2O2 exposure was attenuated by 2.1 fold (p=0.03). Endothelial dysfunction could be prevented by BH4 cofactor supplementation, by scavenging O2•− or peroxynitrite (ONOO−), or by inhibiting the NADPH oxidase. Hydroxyl radical (•OH) scavenging did not have an effect. In summary, early H2O2-induced endothelial dysfunction was associated with a decreased BH4 level and increased O2•− production. Dysfunction required O2•−, ONOO−, or a functional NADPH oxidase. Repeated activation of the NADPH oxidase by ROS may act as a feed forward system to promote endothelial dysfunction. PMID:16895801

  16. A shock origin for interstellar H2O masers

    NASA Technical Reports Server (NTRS)

    Hollenbach, David; Elitzur, Moshe; Mckee, Christopher F.

    1993-01-01

    We present a comprehensive model for the powerful H2O masers observed in starforming regions. In this model the masers occur behind dissociative shocks propagating in dense regions. This paper focuses on high-velocity dissociative shocks in which the heat of H2 reformation on dust grains maintains a large column of 300 - 400 K gas, where the chemistry drives a considerable fraction of the oxygen not in CO to form H2O. The H2O column densities, the hydrogen densities, and the warm temperatures produced by these shocks are sufficiently high to enable powerful maser action, where the maser is excited by thermal collisions with H atoms and H2 molecules. A critical ingredient in determining the shock structure is the magnetic pressure, and the fields required by our models are in agreement with recent observations. The observed brightness temperatures are the result of coherent velocity regions which have dimensions in the shock plane that are five to 50 times the postshock thickness.

  17. Water Oxidation by [(tpy)(H(2)O)(2)Ru(III)ORu(III)(H(2)O)(2)(tpy)](4+).

    PubMed

    Lebeau, Estelle L.; Adeyemi, S. Ajao; Meyer, Thomas J.

    1998-12-14

    The complex [(tpy)(C(2)O(4))Ru(III)ORu(III)(C(2)O(4))(tpy)].8H(2)O (1.8H(2)O) (tpy is 2,2':6',2"-terpyridine) has been prepared and characterized by X-ray crystallography and FTIR, resonance Raman, and (1)H NMR spectroscopies. From the results of the X-ray analysis, angleRuORu is 148.5 degrees with a torsional angle (O(22)-Ru(2)-O(1)-Ru(1)-O(12)) of 22.7 degrees and there is a short Ru-O bridge distance of 1.843 Å. 1 undergoes a chemically reversible one-electron, pH-independent oxidation at 0.73 V vs NHE (0.49 V vs SCE) from pH = 4-8 and a pH-dependent, two-electron, chemically irreversible reduction at -0.35 V below pH = 4.0. Addition of 1.8H(2)O to strong acid generates [(tpy)(H(2)O)(2)Ru(III)ORu(III)(H(2)O)(2)(tpy)](4+) (2), which has been characterized by UV-visible, resonance Raman, and (1)H NMR measurements. In pH-dependent cyclic voltammograms there is evidence for a series of redox couples interrelating oxidation states from Ru(II)ORu(II) to Ru(V)ORu(V). In contrast to the "blue dimer", cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+), oxidation state Ru(IV)ORu(IV) (Ru(V)ORu(III)?) does appear as a stable oxidation state. Oxidation of Ru(IV)ORu(IV) by Ce(IV) in 0.1 M HClO(4) is followed by rapid O(2) production and appearance of an anated form of Ru(IV)ORu(IV). O(2) formation is in competition with oxidative cleavage of Ru(V)ORu(V) by Ce(IV) to give [Ru(VI)(tpy)(O)(2)(OH(2))](2+). Anation and oxidative cleavage prevent this complex from being a true catalyst for water oxidation.

  18. [{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20]36-: a molecular quantum spin icosidodecahedron.

    PubMed

    Botar, Bogdan; Kögerler, Paul; Hill, Craig L

    2005-07-07

    Self-assembly of aqueous solutions of molybdate and vanadate under reducing, mildly acidic conditions results in a polyoxomolybdate-based {Mo72V30} cluster compound Na8K16(VO)(H2O)5[K10 subset{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20].150H2O, 1, a quantum spin-based Keplerate structure.

  19. H2O Adsorption on Smectites: Application to the Diurnal Variation of H2O in the Martian Atmosphere

    NASA Technical Reports Server (NTRS)

    Zent, Aaron P.; Howard, J.; Quinn, R. C.

    2000-01-01

    Observations of the Martian planetary boundary layer lead to interpretations that are baffling and contradictory. In this paper, we specifically address the question of whether or not water vapor finds a substantial diurnal reservoir in the Martian regolith. To address this issue, we have measured H2O adsorption kinetics on SWy-1, a Na-rich montmorillonite from Wyoming. The highest-temperature (273 K) data equilibrates rapidly. Data gathered at realistic H2O partial pressures and temperatures appropriate to early morning show two phenomena that preclude a significant role for smectites in diurnally exchanging a large column abundance. First, the equilibration timescale is longer than a sol. Second, the equilibrium abundances are a small fraction of that predicted by earlier adsorption isotherms. The explanation for this phenomenon is that smectite clay actually increases its surface area as a function of adsorptive coverage. At Mars-like conditions, we show that the interlayer sites of smectites are likely to be unavailable.

  20. Mesospheric H2O and H2O2 densities inferred from in situ positive ion composition measurement

    NASA Technical Reports Server (NTRS)

    Kopp, E.

    1984-01-01

    A model for production and loss of oxonium ions in the high-latitude D-region is developed, based on the observed excess of 34(+) which has been interpreted as H2O2(+). The loss mechanism suggested in the study is the attachment of N2 and/or CO2 in three-body reactions. Furthermore, mesospheric water vapor and H2O2 densities are inferred from measurements of four high-latitude ion compositions, based on the oxonium model. Mixing ratios of hydrogen peroxide of up to two orders of magnitude higher than previous values were obtained. A number of reactions, reaction constants, and a block diagram of the oxonium ion chemistry in the D-region are given.

  1. An ab initio study of the (H2O)20H+ and (H2O)21H+ water clusters

    NASA Astrophysics Data System (ADS)

    Kuś, Tomasz; Lotrich, Victor F.; Perera, Ajith; Bartlett, Rodney J.

    2009-09-01

    The study of the minimum Born-Oppenheimer structures of the protonated water clusters, (H2O)nH+, is performed for n =20 and 21. The structures belonging to four basic morphologies are optimized at the Hartree-Fock, second-order many-body perturbation theory and coupled cluster level, with the 6-31G, 6-31G∗, and 6-311G∗∗ basis sets, using the parallel ACES III program. The lowest energy structure for each n is found to be the cagelike form filled with H2O, with the proton located on the surface. The cage is the distorted dodecahedron for the 21-mer case, and partially rearranged dodecahedral structure for the 20-mer. The results confirm that the lowest energy structure of the magic number n =21 clusters corresponds to a more stable form than that of the 20-mer clusters.

  2. Kinetics of HO2 + HO2 -> H2O2 + O2: Implications for Stratospheric H2O2

    NASA Astrophysics Data System (ADS)

    Christensen, L. E.; Okumura, M.; Sander, S. P.; Salawitch, R. J.; Toon, G. C.; Sen, B.; Blavier, J.-F.; Jucks, K. W.

    2002-05-01

    The reaction HO2 + HO2 -> H2O2 + O2(1) has been studied at 100 Torr and 222 K to 295 K. Experiments employing photolysis of Cl2/CH3OH/O2/N2 and F2/H2/O2/N2 gas mixtures to produce HO2 confirmed that methanol enhanced the observed reaction rate. At 100 Torr, zero methanol, k1 = (8.8 +/- 0.9) 10-13 × exp[(210 +/- 26)/T] cm3 molecule-1 s-1 (2σ uncertainties), which agrees with current recommendations at 295 K but is nearly 2 times slower at 231 K. The general expression for k1, which includes the dependence on bath gas density, is k1 = (1.5 +/- 0.2) × 10-12 × exp[(19 +/- 31)/T] + 1.7 × 10-33 × [M] × exp[1000/T], where the second term is taken from the JPL00-3 recommendation. The revised rate largely accounts for a discrepancy between modeled and measured [H2O2] in the lower to middle stratosphere.

  3. Reconstructing Final H2O Contents of Hydrated Rhyolitic Glasses: Insights into H2O Degassing and Eruptive Style of Silicic Submarine Volcanoes

    NASA Astrophysics Data System (ADS)

    McIntosh, I. M.; Nichols, A. R.; Tani, K.; Llewellin, E. W.

    2015-12-01

    H2O degassing influences the evolution of magma viscosity and vesicularity during ascent through the crust, and ultimately the eruptive style. Investigating H2O degassing requires data on both initial and final H2O contents. Initial H2O contents are revealed by melt inclusion data, while final H2O contents are found from dissolved H2O contents of volcanic glass. However volcanic glasses, particularly of silicic composition, are susceptible to secondary hydration i.e. the addition of H2O from the surrounding environment at ambient temperature during the time following pyroclast deposition. Obtaining meaningful final H2O data therefore requires distinguishing between the original final dissolved H2O content and the H2O added subsequently during hydration. Since H2O added during hydration is added as molecular H2O (H2Om), and the species interconversion between H2Om and hydroxyl (OH) species is negligible at ambient temperature, the final OH content of the glass remains unaltered during hydration. By using H2O speciation models to find the original H2Om content that would correspond to the measured OH content of the glass, the original total H2O (H2Ot) content of the glass prior to hydration can be reconstructed. These H2O speciation data are obtained using FTIR spectroscopy. In many cases, particularly where vesicular glasses necessitate thin wafers, OH cannot be measured directly and instead is calculated indirectly as OH = H2Ot - H2Om. Here we demonstrate the importance of using a speciation-dependent H2Ot molar absorptivity coefficient to obtain accurate H2Ot and H2O speciation data and outline a methodology for calculating such a coefficient for rhyolite glasses, with application to hydrated silicic pumice from submarine volcanoes in the Japanese Izu-Bonin Arc. Although hydrated pumice from Kurose Nishi and Oomurodashi now contain ~1.0 - 2.5 wt% H2Ot, their pre-hydration final H2O contents were typically ~0.3 - 0.4 wt% H2Ot. Furthermore, we show that pre

  4. Thermal decomposition of (UO2)O2(H2O)2·2H2O: Influence on structure, microstructure and hydrofluorination

    NASA Astrophysics Data System (ADS)

    Thomas, R.; Rivenet, M.; Berrier, E.; de Waele, I.; Arab, M.; Amaraggi, D.; Morel, B.; Abraham, F.

    2017-01-01

    The thermal decomposition of uranyl peroxide tetrahydrate, (UO2)O2(H2O)2.2H2O, was studied by combining high temperature powder X-ray diffraction, scanning electron microscopy, thermal analyses and spectroscopic techniques (Raman, IR and 1H NMR). In situ analyses reveal that intermediates and final uranium oxides obtained upon heating are different from that obtained after cooling at room temperature and that the uranyl precursor used to synthesize (UO2)O2(H2O)2·2H2O, sulfate or nitrate, has a strong influence on the peroxide thermal behavior and morphology. The decomposition of (UO2)O2(H2O)2·2H2O ex sulfate is pseudomorphic and leads to needle-like shaped particles of metastudtite, (UO2)O2(H2O)2, and UO3-x(OH)2x·zH2O, an amorphous phase found in air in the following of (UO2)O2(H2O)2 dehydration. (UO2)O2(H2O)2·2H2O and the compounds resulting from its thermal decomposition are very reactive towards hydrofluorination as long as their needle-like morphology is kept.

  5. Observation of the visible absorption spectrum of H2O(+)

    NASA Technical Reports Server (NTRS)

    Das, Biman; Farley, John W.

    1991-01-01

    The water cation, H2O(+), has been studied, using laser absorption spectroscopy in a velocity-modulated discharge. It is shown that it is possible to observe the absorption spectrum of an ion that is not a terminal ion, despite the weak absorption oscillator strength, and despite the use of a relatively noisy dye laser. The relative intensities of the absorption lines have been measured to an accuracy of 13 percent. It is concluded that if the absorption cross section of a single transition can be measured absolutely, then the entire manifold will be known absolutely.

  6. H2O and HCl trace gas kinetics on crystalline HCl hydrates and amorphous HCl / H2O in the range 170 to 205 K: the HCl / H2O phase diagram revisited

    NASA Astrophysics Data System (ADS)

    Iannarelli, R.; Rossi, M. J.

    2014-05-01

    In this laboratory study, H2O ice films of 1 to 2 μm thickness have been used as surrogates for ice particles at atmospherically relevant conditions in a stirred flow reactor (SFR) to measure the kinetics of evaporation and condensation of HCl and H2O on crystalline and amorphous HCl hydrates. A multidiagnostic approach has been employed using Fourier transform infrared spectroscopy (FTIR) absorption in transmission to monitor the condensed phase and residual gas mass spectrometry (MS) for the gas phase. An average stoichiometric ratio of H2O : HCl = 5.8 ± 0.7 has been measured for HCl . 6H2O, and a mass balance ratio between HCl adsorbed onto ice and the quantity of HCl measured using FTIR absorption (Nin - Nesc - Nads) / NFTIR = 1.18 ± 0.12 has been obtained. The rate of evaporation Rev(HCl) for crystalline HCl hexahydrate (HCl . 6H2O) films and amorphous HCl / H2O mixtures has been found to be lower by a factor of 10 to 250 compared to Rev(H2O) in the overlapping temperature range 175 to 190 K. Variations of the accommodation coefficient α(HCl) on pure HCl . 6H2O up to a factor of 10 at nominally identical conditions have been observed. The kinetics (α, Rev) are thermochemically consistent with the corresponding equilibrium vapour pressure. In addition, we propose an extension of the HCl / H2O phase diagram of crystalline HCl . 6H2O based on the analysis of deconvoluted FTIR spectra of samples outside its known existence area. A brief evaluation of the atmospheric importance of both condensed phases - amorphous HCl / H2O and crystalline HCl . 6H2O - is performed in favour of the amorphous phase.

  7. The Influence of Salts on the Stability of Dense H2O Ices (Invited)

    NASA Astrophysics Data System (ADS)

    Manning, C. E.; Daniel, I.

    2009-12-01

    Dense ices in the interiors of icy satellites likely grow from salty water; however, the effect of salts on these ices is poorly understood. We studied phase relations in the system H2O-NaCl at 1 molal (5.5 wt%) NaCl to assess the role of salt on ice VI and ice VII stability. Experiments were conducted in an externally heated, gas-membrane diamond-anvil cell at 22-150°C and 1-5 GPa. Phases were characterized and identified by Raman spectroscopy and optical microscopy. The melting curve of ice VI was observed from 22 to 80°C, yielding Pm = 0.00415exp(0.0190Tm), where Pm is melting pressure (in GPa), Tm is melting temperature (in Kelvins) and R = 0.999; the melting curve for ice VII, observed from 35-150°C, is described by Pm = 0.234exp(0.00700Tm) (R = 0.997). Both melting curves are steeper than the NaCl-free curves, indicating that the freezing-point depression at this bulk composition increases with pressure. The intersection of the liquidus curves indicates that the VI-VII-liquid triple point is shifted toward lower T and higher P relative to pure H2O, requiring that both ices form H2O-NaCl solid solutions. This is consistent with the observation that the 1 molal NaCl solution crystallized to a single ice VIss or ice VIIss at all solidus T ('ss' indicates solid solution). Large single crystals of ice VIss or ice VIIss could be grown by slow compression of the cell from near-liquidus to solidus conditions. Raman spectra revealed zoning of these crystals, and persistence of the zoning (days at 22°C) implies relatively slow Na+ and Cl- diffusivity. The large depression of the freezing point in a 1 molal NaCl solution has important implications for the oceans and interiors of the icy satellites of Jupiter and Saturn. Salty fluids may remain stable to much greater depth than predicted for pure H2O ices. This would promote more extensive water-rock interaction in the silicate interiors. If not limited to ice VI and VII, this behavior may suppress formation of ices

  8. Interaction of Peroxynitric Acid with Solid H2O Ice

    NASA Technical Reports Server (NTRS)

    Li, Zhuangjie; Friedl, Randall R.; Moore, Steven B.; Sander, Stanley P.

    1996-01-01

    The uptake of peroxynitric acid (PNA), HO2NO2 or HNO4, on solid H2O ice at 193 K (-80 C) was studied using a fast flow-mass spectrometric technique. An uptake coefficient of 0.15 +/- 0.10 was measured, where the quoted uncertainty denotes 2 standard deviations. The uptake process did not result in the production of gas phase products. The composition of the condensed phase was investigated using programmed heating (3 K/min) of the substrate coupled with mass spectrometric detection of desorbed species. Significant quantities of HNO, and HNO3 desorbed from the substrates at temperatures above 225 K and 246 K, respectively. The desorbed HNO3, which was less than 9% of the desorbed HNO, and remained unchanged upon incubation of the substrate, was likely due to impurities in the HNO4 samples rather than reaction of HNO, on the substrate. The onset temperatures for HNO4 desorption increased with increasing H2O to HNO4 ratios, indicating that HNO4, like HNO3, tends to be hydrated in the presence of water. These observations suggest possible mechanisms for removal of HNO4 or repartitioning of total odd nitrogen species in the Earth's upper troposphere and stratosphere.

  9. Infrared absorption of H_2_O toward massive young stars.

    NASA Astrophysics Data System (ADS)

    van Dishoeck, E. F.; Helmich, F. P.

    1996-11-01

    We present ISO-SWS observations of absorption lines of gas-phase water within its bending vibrational mode at 6μm toward four massive young stars, which cover a range in physical parameters. Hot water with an excitation temperature >200K is detected toward GL 2136 and GL 4176, in addition to GL 2591 discussed by Helmich et al. (1996A&A...315L.173H). The abundance of water with respect to H_2_ is high in these regions, ~(2-3)x10^-5^, and comparable to the solid H_2_O abundance. In contrast, no gas-phase water absorption lines are seen toward NGC 7538 IRS9. The amount of gas-phase water is correlated with the column density of warm gas along the line of sight. Infrared observations of a larger variety of sources may provide insight into the relative importance of evaporation of grain mantles vs. high temperature gas-phase chemistry in producing the observed high abundance of H_2_O.

  10. Effect of H2O2 dosing strategy on sludge pretreatment by microwave-H2O2 advanced oxidation process.

    PubMed

    Wang, Yawei; Wei, Yuansong; Liu, Junxin

    2009-09-30

    Considering characteristics of breaking down H(2)O(2) into water and molecular oxygen by catalase in waste activated sludge (WAS), the effect of H(2)O(2) dosing strategy on sludge pretreatment by the advanced oxidation process (AOP) of microwave-H(2)O(2) was investigated by batch experiments for optimizing H(2)O(2) dosage. Results showed that the catalase in sludge was active at the low temperature range between 15 degrees C and 45 degrees C, and gradually lost activity from 60 degrees C to 80 degrees C. Therefore, the H(2)O(2) was dosed at 80 degrees C, to which the waste activated sludge was first heated by the microwave (MW), and then the sludge dosed with H(2)O(2) was continuously heated till 100 degrees C by the microwave. Results at different H(2)O(2) dosages showed that the higher the H(2)O(2) dosing ratio was, the more the SCOD and total organic carbon (TOC) were released into the supernatant, and the optimum range of H(2)O(2)/TCOD ratio should be between 0.1 and 1.0. The percentages of consumed H(2)O(2) in the AOP of microwave and H(2)O(2) treating the WAS were 25.38%, 22.53%, 14.82%, 13.61% and 19.63% at different H(2)O(2)/TCOD dosing ratios of 0.1, 0.5, 1, 2, 4, respectively. Along with the increasing H(2)O(2)/TCOD ratio, the contents of TCOD on particles, soluble substances and mineralization increased and the TCOD distribution on solids decreased.

  11. Catalase activity is stimulated by H(2)O(2) in rich culture medium and is required for H(2)O(2) resistance and adaptation in yeast.

    PubMed

    Martins, Dorival; English, Ann M

    2014-01-01

    Catalases are efficient scavengers of H2O2 and protect cells against H2O2 stress. Examination of the H2O2 stimulon in Saccharomyces cerevisiae revealed that the cytosolic catalase T (Ctt1) protein level increases 15-fold on H2O2 challenge in synthetic complete media although previous work revealed that deletion of the CCT1 or CTA1 genes (encoding peroxisomal/mitochondrial catalase A) does not increase the H2O2 sensitivity of yeast challenged in phosphate buffer (pH 7.4). This we attributed to our observation that catalase activity is depressed when yeast are challenged with H2O2 in nutrient-poor media. Hence, we performed a systematic comparison of catalase activity and cell viability of wild-type yeast and of the single catalase knockouts, ctt1∆ and cta1∆, following H2O2 challenge in nutrient-rich medium (YPD) and in phosphate buffer (pH 7.4). Ctt1 but not Cta1 activity is strongly induced by H2O2 when cells are challenged in YPD but suppressed when cells are challenged in buffer. Consistent with the activity results, exponentially growing ctt1∆ cells in YPD are more sensitive to H2O2 than wild-type or cta1∆ cells, whereas in buffer all three strains exhibit comparable H2O2 hypersensitivity. Furthermore, catalase activity is increased during adaptation to sublethal H2O2 concentrations in YPD but not in buffer. We conclude that induction of cytosolic Ctt1 activity is vital in protecting yeast against exogenous H2O2 but this activity is inhibited by H2O2 when cells are challenged in nutrient-free media.

  12. Responsive mechanism of a newly synthesized fluorescent probe for sensing H2O2, NO and H2O2/NO

    NASA Astrophysics Data System (ADS)

    Zhang, Yu-Jin; Wang, Xin; Zhou, Yong; Zhao, Ke; Wang, Chuan-Kui

    2016-10-01

    Optical properties of a newly synthesized fluorescent probe for H2O2, NO and H2O2/NO are investigated by employing time-dependent density functional theory. Three different sets of fluorescence signals are obtained when the probe reacts with H2O2, NO and H2O2/NO. Analysis of molecular orbitals is presented to explore responsive mechanism of the probe for the detected objects, where the fluorescent resonance energy transfer process is for H2O2 (H2O2/NO) and the intramolecular charge transfer process is for NO. Our results provide theoretical explanation of the experimental results, and importantly, suggest possibility of the probe as a two-photon fluorescent sensor.

  13. First Principle Predictions of Isotopic Shifts in H2O

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Kwak, Dochan (Technical Monitor)

    2002-01-01

    We compute isotope independent first and second order corrections to the Born-Oppenheimer approximation for water and use them to predict isotopic shifts. For the diagonal correction, we use icMRCI wavefunctions and derivatives with respect to mass dependent, internal coordinates to generate the mass independent correction functions. For the non-adiabatic correction, we use scaled SCF/CIS wave functions and a generalization of the Handy method to obtain mass independent correction functions. We find that including the non-adiabatic correction gives significantly improved results compared to just including the diagonal correction when the Born-Oppenheimer potential energy surface is optimized for H2O-16. The agreement with experimental results for deuterium and tritium containing isotopes is nearly as good as our best empirical correction, however, the present correction is expected to be more reliable for higher, uncharacterized levels.

  14. Fabry-Perot observations of Comet Halley H2O(+)

    NASA Technical Reports Server (NTRS)

    Scherb, F.; Roesler, F. L. D.; Harlander, J.; Magee-Sauer, K.

    1990-01-01

    Fabry-Perot scanning spectrometer observations of Comet Halley's H2O(+) emissions have yielded 6158.64 and 6158.85 A spin doublet data at distances in the range of 0 to 2 million km from the comet heat in the antisunward direction. Cometary plasma outflow velocities were ascertained on the basis of the emissions' Doppler shifts, yielding results that were mostly but not exclusively consistent with the plasma's constant antisunward acceleration; the acceleration varied from night to night of observations over a 30-300 cm/sec range. The unusual plasma kinematics of December 14-15, 1985, and January 10, 1986, may be associated with the tail-disconnection activity observed by others.

  15. Intermolecular potential for thermal H2O-He collisions

    NASA Technical Reports Server (NTRS)

    Palma, Amedeo; Green, Sheldon; Defrees, D. J.; Mclean, A. D.

    1988-01-01

    Theoretical potentials for rotational excitation of H2O by He were constructed via several methods, all of which start with a large basis set SCF interaction. The semiempirical Hartree-Fock with damped dispersion model adds a damped long-range attraction with parameters adjusted to fit experimental total differential cross sections. Purely ab initio potentials add correlation energies obtained via perturbation theory (MP2 and MP4) or a variational method (ICF1). Scattering calculations were performed on all surfaces to compare wih available beam scattering and pressure broadening data and to assess sensitivity of state-to-state rates to uncertainties in the potential. From comparison with the limited experimental data, the ICF1 surface appears to be marginally better than the MP4 surface. Thermal rates calculated from this surface should be accurate to better than 50 percent, at least for the larger, more important rates.

  16. Ferroelectricity in high-density H2O ice

    DOE PAGES

    Caracas, Razvan; Hemley, Russell J.

    2015-04-01

    The origin of longstanding anomalies in experimental studies of the dense solid phases of H2O ices VII, VIII, and X is examined using a combination of first-principles theoretical methods. We find that a ferroelectric variant of ice VIII is energetically competitive with the established antiferroelectric form under pressure. The existence of domains of the ferroelectric form within anti-ferroelectric ice can explain previously observed splittings in x-ray diffraction data. The ferroelectric form is stabilized by density and is accompanied by the onset of spontaneous polarization. Here, the presence of local electric fields triggers the preferential parallel orientation of the water moleculesmore » in the structure, which could be stabilized in bulk using new high-pressure techniques.« less

  17. Utilization of membranes for H2O recycle system

    NASA Technical Reports Server (NTRS)

    Ohya, H.; Oguchi, M.

    1986-01-01

    Conceptual studies of closed ecological life support systems (CELSS) carried out at NAL in Japan for a water recycle system using membranes are reviewed. The system will treat water from shower room, urine, impure condensation from gas recycle system, and so on. The H2O recycle system is composed of prefilter, ultrafiltration membrane, reverse osmosis membrane, and distillator. Some results are shown for a bullet train of toilet-flushing water recycle equipment with an ultraviltration membrane module. The constant value of the permeation rate with a 4.7 square meters of module is about 70 1/h after 500th of operation. Thermovaporization with porous polytetrafluorocarbon membrane is also proposed to replce the distillator.

  18. Ferroelectricity in high-density H2O ice.

    PubMed

    Caracas, Razvan; Hemley, Russell J

    2015-04-07

    The origin of longstanding anomalies in experimental studies of the dense solid phases of H2O ices VII, VIII, and X is examined using a combination of first-principles theoretical methods. We find that a ferroelectric variant of ice VIII is energetically competitive with the established antiferroelectric form under pressure. The existence of domains of the ferroelectric form within anti-ferroelectric ice can explain previously observed splittings in x-ray diffraction data. The ferroelectric form is stabilized by density and is accompanied by the onset of spontaneous polarization. The presence of local electric fields triggers the preferential parallel orientation of the water molecules in the structure, which could be stabilized in bulk using new high-pressure techniques.

  19. Planar H2O masers in star-forming regions

    NASA Technical Reports Server (NTRS)

    Elitzur, Moshe; Hollenbach, David J.; Mckee, Christopher F.

    1992-01-01

    The paper examines the planar geometry of shocked material, which is the key property in enabling the high brightness temperatures of H2O masers in star-forming regions. The brightness temperature, beaming angle, and the maser spot size are determined for thin, saturated planar masers under the assumption that the velocity change across the maser due to ordered motions is small compared with the thermal or microturbulent line width. For a given set of physical parameters, the brightness temperature is essentially fully determined by the length of the velocity-coherent region in the shocked plane along the line of sight. Effective aspect ratios (about 5-50) are found that are in agreement with values previously inferred from observed brightness temperatures.

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

    NASA Astrophysics Data System (ADS)

    Dey, C. C.

    2014-09-01

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

  1. The H 2O ++ Ground State Potential Energy Surface

    NASA Astrophysics Data System (ADS)

    Bunker, P. R.; Bludsky, Ota; Jensen, Per; Wesolowski, S. S.; Van Huis, T. J.; Yamaguchi, Y.; Schaefer, H. F.

    1999-12-01

    At the correlation-consistent polarized-valence quadruple-zeta complete active space self-consistent field second-order configuration interaction level of ab initio theory (cc-pVQZ CASSCF-SOCI), we calculated 129 points on the ground electronic state potential energy surface of the water dication H2O++; this calculation includes the energy of X3Σ- OH+ at equilibrium and the energy of the triplet oxygen atom. We determined the parameters in an analytical function that represents this surface out to the (OH+ + H+) and (O + 2H+) dissociation limits, for bending angles from 70 to 180°. There is a metastable minimum in this surface, at an energy of 43 600 cm-1 above the H+ + OH+ dissociation energy, and the geometry at this minimum is linear (D∞h), with an OH bond length of 1.195 Å. On the path to dissociation to H+ + OH+, there is a saddle point at an energy of 530 cm-1 above the minimum, and the geometry at the saddle point is linear (C∞ Kv) with OH bond lengths of 1.121 and 1.489 Å. Using the stabilization method, we calculated the lowest resonance on this surface. Relative to the metastable local minimum on the potential energy surface, the position of the lowest resonance for H2O++, D2O++, and T2O++ is 1977(85), 1473(25), and 1249(10) cm-1, respectively, where the width of each resonance (in cm-1) is given in parentheses.

  2. Observations of H2O in Titan's atmosphere with Herschel

    NASA Astrophysics Data System (ADS)

    Moreno, R.; Lellouch, E.; Lara, L. M.; Courtin, R.; Hartogh, P.; Rengel, M.

    2012-04-01

    Disk averaged observations of several H2O far infrared lines in Titan’s atmosphere were performed with the Herschel Space Observatory, as part of the guaranteed time key program "Water and related chemistry in the Solar System" (HssO, see Hartogh et al 2011). Two instruments were used: (i) HIFI, a heterodyne instrument (R~ 106 ) in the sub-millimeter, which measured the H2O(110-101) rotational transition at 557 GHz on June 10 and Dec. 31, 2010 (ii) PACS, a photoconductor spectrometer (R~103) which measured three water lines at 108.1, 75.4 and 66.4 microns on June 22, 2010. Additional PACS measurements at 66.4 microns on Dec. 15 and 22, 2010 and on July 09, 2011, do not show any significant line intensity variation with time, nor between the leading/trailing sides (i.e. longitude). Spectra were analyzed with a line-by-line radiative transfer code accounting for spherical geometry (Moreno et al. 2011). This model considers the H2O molecular opacity from JPL catalog (Pickett et al. 1998) and also includes collision-induced opacities N2-N2, N2-CH4 and CH4-CH4 (Borysow and Frommhold 1986, 1987, Borysow and Tang 1993). Far infrared aerosol opacities derived by CIRS were included, following Anderson and Samuelson (2011) for their vertical distribution and spectral dependencies. Analysis of the 557 GHz narrow line (FWHM ~ 2 MHz) indicates that it originates at altitudes above 300 km, while lines measured with PACS probe mainly deeper levels (80-150 km). The HIFI and PACS observations are fitted simultaneously, considering a vertical distribution of H2O mixing ratio which follows a power law dependency q=q0(P/P0)n, where q0 is the mixing ratio at some reference pressure level P0, taken near the expected condensation level. Model fits will be presented, and compared with previously proposed H2O vertical distributions. We show in particular that both the steep profile proposed by Lara et al. (1996) (and adopted by Coustenis et al. (1998) to model the first detection of H2O

  3. Study of the transient "free" OH radical generated in H2O-H2O2 mixtures by stimulated Raman scattering

    NASA Astrophysics Data System (ADS)

    Li, Fangfang; Ma, Zhiwei; Wang, Shenghan; Li, Tianyu; Sun, Chenglin; Li, Zhanlong; Men, Zhiwei

    2017-03-01

    Forward and backward stimulated Raman scattering (SRS) were studied in the H2O2-H2O mixtures by a strong excitation laser with 532 nm. Only the backward SRS (BSRS) of the H2O2-H2O system shows an unexpected SRS shoulder peak at around 3600 cm- 1, which is similar to the characteristic peak of "free" OH radical. The generation of the "free" OH radical is mainly attributed to the dissociation of hydrogen peroxide (HP) molecules. Simultaneously, the ionization of HP-water clusters generates a part of "free" OH radical under the Laser-induced breakdown (LIB). The interaction of water and HP is also discussed.

  4. Simultaneous mapping of H 2O and H 2O 2 on Mars from infrared high-resolution imaging spectroscopy

    NASA Astrophysics Data System (ADS)

    Encrenaz, T.; Greathouse, T. K.; Richter, M. J.; Bézard, B.; Fouchet, T.; Lefèvre, F.; Montmessin, F.; Forget, F.; Lebonnois, S.; Atreya, S. K.

    2008-06-01

    New maps of martian water vapor and hydrogen peroxide have been obtained in November-December 2005, using the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infra Red Telescope facility (IRTF) at Mauna Kea Observatory. The solar longitude L was 332° (end of southern summer). Data have been obtained at 1235-1243 cm -1, with a spectral resolution of 0.016 cm -1 ( R=8×10). The mean water vapor mixing ratio in the region [0°-55° S; 345°-45° W], at the evening limb, is 150±50 ppm (corresponding to a column density of 8.3±2.8 pr-μm). The mean water vapor abundance derived from our measurements is in global overall agreement with the TES and Mars Express results, as well as the GCM models, however its spatial distribution looks different from the GCM predictions, with evidence for an enhancement at low latitudes toward the evening side. The inferred mean H 2O 2 abundance is 15±10 ppb, which is significantly lower than the June 2003 result [Encrenaz, T., Bézard, B., Greathouse, T.K., Richter, M.J., Lacy, J.H., Atreya, S.K., Wong, A.S., Lebonnois, S., Lefèvre, F., Forget, F., 2004. Icarus 170, 424-429] and lower than expected from the photochemical models, taking in account the change in season. Its spatial distribution shows some similarities with the map predicted by the GCM but the discrepancy in the H 2O 2 abundance remains to be understood and modeled.

  5. I + (H2O)2 → HI + (H2O)OH Forward and Reverse Reactions. CCSD(T) Studies Including Spin-Orbit Coupling.

    PubMed

    Wang, Hui; Li, Guoliang; Li, Qian-Shu; Xie, Yaoming; Schaefer, Henry F

    2016-03-03

    The potential energy profile for the atomic iodine plus water dimer reaction I + (H2O)2 → HI + (H2O)OH has been explored using the "Gold Standard" CCSD(T) method with quadruple-ζ correlation-consistent basis sets. The corresponding information for the reverse reaction HI + (H2O)OH → I + (H2O)2 is also derived. Both zero-point vibrational energies (ZPVEs) and spin-orbit (SO) coupling are considered, and these notably alter the classical energetics. On the basis of the CCSD(T)/cc-pVQZ-PP results, including ZPVE and SO coupling, the forward reaction is found to be endothermic by 47.4 kcal/mol, implying a significant exothermicity for the reverse reaction. The entrance complex I···(H2O)2 is bound by 1.8 kcal/mol, and this dissociation energy is significantly affected by SO coupling. The reaction barrier lies 45.1 kcal/mol higher than the reactants. The exit complex HI···(H2O)OH is bound by 3.0 kcal/mol relative to the asymptotic limit. At every level of theory, the reverse reaction HI + (H2O)OH → I + (H2O)2 proceeds without a barrier. Compared with the analogous water monomer reaction I + H2O → HI + OH, the additional water molecule reduces the relative energies of the entrance stationary point, transition state, and exit complex by 3-5 kcal/mol. The I + (H2O)2 reaction is related to the valence isoelectronic bromine and chlorine reactions but is distinctly different from the F + (H2O)2 system.

  6. Comprehensive copper ion hydration: experimental and theoretical investigation of Cu2+(H2O)n, Cu+(H2O)n, CuOH+(H2O)n

    NASA Astrophysics Data System (ADS)

    Sweeney, Andrew

    Guided ion beam tandem mass spectrometry is used to probe the kinetic energy dependence of both Cu2+(H2O)n, where n = 5--10, and CuOH+(H2O)n, where n = 0--4 colliding with Xe. The resulting cross sections are analyzed using statistical models to yield 0 K bond dissociation energies (BDEs). The primary dissociation pathway for Cu2+(H2O)n consists of water loss followed by the sequential loss of additional waters at higher energies until n = 7, at which point charge separation to form CuOH+(H2O) m + H+(H2O)n-m-2 is energetically favored. The primary dissociation pathway for CuOH+(H 2O)n is also water loss and is followed by the sequential loss of additional waters at higher energies until n = 1, at which point OH loss become competitive. The BDEs for loss of water and OH from CuOH +(H2O) are combined in a thermodynamic cycle with literature values to derive BDEs for the loss of OH from CuOH+(H 2O)n, where n = 0, 2--4. Infrared multiple photon dissociation (IRPD) spectroscopy is performed on CuOH+(H2O)n, where n = 2--9. These spectra are characterized through comparison to theoretical spectra of low energy isomers. It is found that CuOH+(H2O) n prefers a 4-coordinate inner shell, although contributions from 5-coordinate geometries cannot be ruled out in most cases and are clearly present for n = 7. This preference is found in the Cu2+(H2O) n system as well and differs from the Cu+(H2O) n system, which prefers a 2-coordinate inner shell. Electronic structure calculations are further employed to yield BDEs which agree reasonably well with experimental values. A method for modeling kinetic energy release distributions (KERD) on a guided ion beam tandem mass spectrometer is proposed. This method achieves reasonable agreement with dissociations occurring over loose transition states when reactants have little energy in excess of the dissociation threshold. Current limitations and future possibilities of this method are discussed in detail.

  7. A dynamical study of the Si(+) + H(2)O reaction.

    PubMed

    Flores, Jesús R

    2007-11-01

    A dynamical study of the Si(+) + H(2)O reaction has been carried out by means of a quasiclassical trajectory method that decomposes the reaction into a capture step, for which an accurate analytical potential is employed, and an unimolecular step, in which the evolution of the collision complex is studied through a direct dynamics BHandHLYP/6-31G(d,p) method. The capture rate coefficient has been computed for thermal conditions corresponding to temperatures ranging from 50 to 1000 K. It is concluded that the main reason why the reaction rate is about 10 times smaller than the capture rate (at T = 298 K) is the topology of the potential energy surface of the ground state. It is also concluded that the ratio between the rates of product and reactant generation from the collision complex decreases quite steeply with increasing temperature, and therefore, the reaction rate decreases even more sharply. Exciting the stretching normal modes of water substantially increases that ratio, and moderate rotational excitation does not appear to have a relevant effect. The collision complex is always initially SiOH(2)(+), but in some trajectories, it becomes HSiOH(+), which generates the products, although the former species is the main intermediate.

  8. Electron Impact Vibrational Excitation of H2O Molecules

    NASA Astrophysics Data System (ADS)

    Kato, Hidetoshi; Kajita, Rina; Tanaka, Takahiro; Makochekanwa, Casten; Kimura, Mineo; Cho, Hyuck; Kitajima, Masashi; Tanaka, Hiroshi

    2004-09-01

    Electron impact interaction studies with water have invited a lot experimental and theoretical attention for more than half century because it falls into the unique group of polar molecules whose dipole moments are above the critical dipole moments, thus enabling studies of dipole-related threshold peaks [1]. However, because of the experimental difficulties encountered in separating the three fundamental modes of vibration, for instance, there remained controversies about the existence of resonance effects in the vibrational excitation. In this report, the H2O vibrational exciation into modes (100) and (001) investigated at energy losses of 0.43, 0.46, 0.49 and 0.51 eV, where peaks for these two modes closely overlap, while sweeping the impact energies from 1.6 to 10 eV, at angles 60º and 90º, using a cross-beam method [2]. The continuum multiple scattering (CMS) [4] calculations have also been performed for the theoretical analysis of the experimental results. We have observed distinct resonance enhancement only in the symmetric stretching (100) mode, but not in the antisymmetric (001) and bending (010) modes. The theoretical interpretation is provided. [1] K. Rohr and F. Linder, J. Phys. B 9, 2521 (1976). [2] H. Tanaka, L. Boesten, D. Matsunaga and T. Kudo, J. Phys. B 21, 1255 (1988). [3] M. Kimura and H. Sato, Comments At. Mol. Phys. 26, 333 (1991).

  9. An Accurate Potential Energy Surface for H2O

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

  10. H2O2 levels in rainwater collected in south Florida and the Bahama Islands

    NASA Technical Reports Server (NTRS)

    Zika, R.; Saltzman, E.; Chameides, W. L.; Davis, D. D.

    1982-01-01

    Measurements of H2O2 in rainwater collected in Miami, Florida, and the Bahama Islands area indicate the presence of H2O2 concentration levels ranging from 100,000 to 700,000 M. No systematic trends in H2O2 concentration were observed during an individual storm, in marked contrast to the behavior of other anions for example, NO3(-), SO4(-2), and Cl(-). The data suggest that a substantial fraction of the H2O2 found in precipitation is generated by aqueous-phase reactions within the cloudwater rather than via rainout and washout of gaseous H2O2.

  11. Differential regulation of TRPV1 channels by H2O2: implications for diabetic microvascular dysfunction.

    PubMed

    DelloStritto, Daniel J; Connell, Patrick J; Dick, Gregory M; Fancher, Ibra S; Klarich, Brittany; Fahmy, Joseph N; Kang, Patrick T; Chen, Yeong-Renn; Damron, Derek S; Thodeti, Charles K; Bratz, Ian N

    2016-03-01

    We demonstrated previously that TRPV1-dependent coupling of coronary blood flow (CBF) to metabolism is disrupted in diabetes. A critical amount of H2O2 contributes to CBF regulation; however, excessive H2O2 impairs responses. We sought to determine the extent to which differential regulation of TRPV1 by H2O2 modulates CBF and vascular reactivity in diabetes. We used contrast echocardiography to study TRPV1 knockout (V1KO), db/db diabetic, and wild type C57BKS/J (WT) mice. H2O2 dose-dependently increased CBF in WT mice, a response blocked by the TRPV1 antagonist SB366791. H2O2-induced vasodilation was significantly inhibited in db/db and V1KO mice. H2O2 caused robust SB366791-sensitive dilation in WT coronary microvessels; however, this response was attenuated in vessels from db/db and V1KO mice, suggesting H2O2-induced vasodilation occurs, in part, via TRPV1. Acute H2O2 exposure potentiated capsaicin-induced CBF responses and capsaicin-mediated vasodilation in WT mice, whereas prolonged luminal H2O2 exposure blunted capsaicin-induced vasodilation. Electrophysiology studies re-confirms acute H2O2 exposure activated TRPV1 in HEK293A and bovine aortic endothelial cells while establishing that H2O2 potentiate capsaicin-activated TRPV1 currents, whereas prolonged H2O2 exposure attenuated TRPV1 currents. Verification of H2O2-mediated activation of intrinsic TRPV1 specific currents were found in isolated mouse coronary endothelial cells from WT mice and decreased in endothelial cells from V1KO mice. These data suggest prolonged H2O2 exposure impairs TRPV1-dependent coronary vascular signaling. This may contribute to microvascular dysfunction and tissue perfusion deficits characteristic of diabetes.

  12. The enthalpies of formation of nesquehonite, MgCO3 * 3H2O, and hydromagnesite, 5MgO * 4CO2 * 5H2O

    USGS Publications Warehouse

    Hemingway, Bruce S.; Robie, Richard A.

    1973-01-01

    The enthalpies of formation, ΔH°f, of nesquehonite, MgCO3 * 3H2O, and hydromagnesite, 5MgO * 4CO2 * 5H2O, have been determined by HCl solution calorimetry. For the reaction MgO(c) + CO2(g) + 3H2O(l) = MgCO2 * 3H2O(c), the enthalpy change at 298.15 K is -29,781*40 cal mor' . For the reaction 5MgO(c) + 4CO2 + 5H2O = 5MgO * 4CO2 * 5H2O, the enthalpy change at 298.15 K is -120,310±120 cal. For MgCO3 * 3H2O the standard molar enthalpy and standard Gibbs free energy of formation, ΔH°f,298 and ΔG°f,298 are -472,576+110 and 412,040±120 cal. ΔH°f,298 and ΔG°f,298 for 5MgO * 4CO2 * 5H2O are -1,557,090±250 and -1,401,71 0±250 cal.

  13. Cutin monomers and surface wax constituents elicit H2O2 in conditioned cucumber hypocotyl segments and enhance the activity of other H2O2 elicitors

    PubMed

    Fauth; Schweizer; Buchala; Markstadter; Riederer; Kato; Kauss

    1998-08-01

    Hypocotyls from etiolated cucumber (Cucumis sativus L.) seedlings were gently abraded at their epidermal surface and cut segments were conditioned to develop competence for H2O2 elicitation. Alkaline hydrolysates of cutin from cucumber, tomato, and apple elicited H2O2 in such conditioned segments. The most active constituent of cucumber cutin was identified as dodecan-1-ol, a novel cutin monomer capable of forming hydrophobic terminal chains. Additionally, the cutin hydrolysates enhanced the activity of a fungal H2O2 elicitor, similar to cucumber surface wax, which contained newly identified alkan-1,3-diols. The specificity of elicitor and enhancement activity was further elaborated using some pure model compounds. Certain saturated hydroxy fatty acids were potent H2O2 elicitors as well as enhancers. Some unsaturated epoxy and hydroxy fatty acids were also excellent H2O2 elicitors but inhibited the fungal elicitor activity. Short-chain alkanols exhibited good elicitor and enhancer activity, whereas longer-chain alkan-1-ols were barely active. The enhancement effect was also observed for H2O2 elicitation by ergosterol and chitosan. The physiological significance of these observations might be that once the cuticle is degraded by fungal cutinase, the cutin monomers may act as H2O2 elicitors. Corrosion of cutin may also bring surface wax constituents in contact with protoplasts and enhance elicitation.

  14. Degradation of crystal violet by an FeGAC/H2O2 process.

    PubMed

    Chen, Chiing-Chang; Chen, Wen-Ching; Chiou, Mei-Rung; Chen, Sheng-Wei; Chen, Yao Yin; Fan, Huan-Jung

    2011-11-30

    Because of the growing concern over highly contaminated crystal violet (CV) wastewater, an FeGAC/H(2)O(2) process was employed in this research to treat CV-contaminated wastewater. The experimental results indicated that the presence of iron oxide-coated granular activated carbon (FeGAC) greatly improved the oxidative ability of H(2)O(2) for the removal of CV. For instance, the removal efficiencies of H(2)O(2), GAC, FeGAC, GAC/H(2)O(2) and FeGAC/H(2)O(2) processes were 10%, 44%, 40%, 43% and 71%, respectively, at test conditions of pH 3 and 7.4mM H(2)O(2). FeGAC/H(2)O(2) combined both the advantages of FeGAC and H(2)O(2). FeGAC had a good CV adsorption ability and could effectively catalyze the hydrogen peroxide oxidation reaction. Factors (including pH, FeGAC dosage and H(2)O(2) dosage) affecting the removal of CV by FeGAC/H(2)O(2) were investigated in this research as well. In addition, the reaction intermediates were separated and identified using HPLC-ESI-MS. The N-demethylation step might be the main reaction pathway for the removal of CV. The reaction mechanisms for the process proposed in this research might be useful for future application of this technology to the removal of triphenylmethane (TPM) dyes.

  15. Thermal Reactions of H2O2 on Icy Satellites and Small Bodies: Descent with Modification?

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie L.; Loeffler, Mark J.

    2012-01-01

    Magnetospheric radiation drives surface and near-surface chemistry on Europa, but below a few meters Europa's chemistry is hidden from direct observation . As an example, surface radiation chemistry converts H2O and SO2 into H2O2 and (SO4)(sup 2-), respectively, and these species will be transported downward for possible thermally-driven reactions. However, while the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, this molecule's thermally-induced solid-phase chemistry has seldom been studied. Here we report new results on thermal reactions in H2O + H2O2 + SO2 ices at 50 - 130 K. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to (SO4)(sup 2-). These results have implications for the survival of H2O2 as it descends, with modification, towards a subsurface ocean on Europa. We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto.

  16. Submillimeter H2O and H2O+emission in lensed ultra- and hyper-luminous infrared galaxies at z 2-4

    NASA Astrophysics Data System (ADS)

    Yang, C.; Omont, A.; Beelen, A.; González-Alfonso, E.; Neri, R.; Gao, Y.; van der Werf, P.; Weiß, A.; Gavazzi, R.; Falstad, N.; Baker, A. J.; Bussmann, R. S.; Cooray, A.; Cox, P.; Dannerbauer, H.; Dye, S.; Guélin, M.; Ivison, R.; Krips, M.; Lehnert, M.; Michałowski, M. J.; Riechers, D. A.; Spaans, M.; Valiante, E.

    2016-11-01

    We report rest-frame submillimeter H2O emission line observations of 11 ultra- or hyper-luminous infrared galaxies (ULIRGs or HyLIRGs) at z 2-4 selected among the brightest lensed galaxies discovered in the Herschel-Astrophysical Terahertz Large Area Survey (H-ATLAS). Using the IRAM NOrthern Extended Millimeter Array (NOEMA), we have detected 14 new H2O emission lines. These include five 321-312ortho-H2O lines (Eup/k = 305 K) and nine J = 2 para-H2O lines, either 202-111(Eup/k = 101 K) or 211-202(Eup/k = 137 K). The apparent luminosities of the H2O emission lines are μLH2O 6-21 × 108 L⊙ (3 <μ< 15, where μ is the lens magnification factor), with velocity-integrated line fluxes ranging from 4-15 Jy km s-1. We have also observed CO emission lines using EMIR on the IRAM 30 m telescope in seven sources (most of those have not yet had their CO emission lines observed). The velocity widths for CO and H2O lines are found to be similar, generally within 1σ errors in the same source. With almost comparable integrated flux densities to those of the high-J CO line (ratios range from 0.4 to 1.1), H2O is found to be among the strongest molecular emitters in high-redshift Hy/ULIRGs. We also confirm our previously found correlation between luminosity of H2O (LH2O) and infrared (LIR) that LH2O LIR1.1-1.2, with ournew detections. This correlation could be explained by a dominant role of far-infrared pumping in the H2O excitation. Modelling reveals that the far-infrared radiation fields have warm dust temperature Twarm 45-75 K, H2O column density per unit velocity interval NH2O /ΔV ≳ 0.3 × 1015 cm-2 km-1 s and 100 μm continuum opacity τ100> 1 (optically thick), indicating that H2O is likely to trace highly obscured warm dense gas. However, further observations of J ≥ 4 H2O lines are needed to better constrain the continuum optical depth and other physical conditions of the molecular gas and dust. We have also detected H2O+ emission in three sources. A tight correlation

  17. H(2)O(2)-assisted photolysis of reactive dye BES golden yellow simulated wastewater.

    PubMed

    Jian-Xiao, Lv; Guo-Hong, Xie; Qing-Ling, Yue; Li, Zhang; Jian-Min, Li; Ying, Cui

    2009-01-01

    Reactive dye BES golden yellow simulated wastewater was treated with H(2)O(2)-assisted photolysis method. Influences of factors such as reaction time, initial pH and H(2)O(2) dosage were investigated, and the reaction kinetics of the process were explored. Results showed that, the degradation of 200 mg/L BES golden yellow solution happened only in the presence of both conditions: UV irradiation and H(2)O(2) addition. Initial pH and H(2)O(2) dosage had remarkable influence on the removal efficiency of the dye. Through several groups of univariate experiments, the optimum pH and H(2)O(2) dosage of the photolysis process were found to be 6-7 and 0.0375 mL 30% H(2)O(2) per milligram of BES golden yellow, respectively. The photolysis process was approximately in accordance with the second-order kinetic equation.

  18. The Paradox of a Wet (High H2O) and Dry (Low H2O/Ce) Mantle: High Water Concentrations in Mantle Garnet Pyroxenites from Hawaii

    NASA Technical Reports Server (NTRS)

    Peslier, Anne H.; Bizimis, Michael

    2013-01-01

    Water dissolved as trace amounts in anhydrous minerals has a large influence on the melting behavior and physical properties of the mantle. The water concentration of the oceanic mantle is inferred from the analyses of Mid-Ocean Ridge Basalt (MORB) and Oceanic Island Basalt (OIB). but there is little data from actual mantle samples. Moreover, enriched mineralogies (pyroxenites, eclogites) are thought as important sources of heterogeneity in the mantle, but their water concentrations and their effect on the water budget and cycling in the mantle are virtually unknown. Here, we analyzed by FTIR water in garnet clinopyroxenite xenoliths from Salt Lake Crater, Oahu, Hawaii. These pyroxenites are high-pressure (>20kb) crystal fractionates from alkalic melts. The clinopyroxenes (cpx) have 260 to 576 ppm wt H2O, with the least differentiated samples (Mg#>0.8) in the 400-500 ppm range. Orthopyroxene (opx) contain 117-265 ppm H2O, about half of that of cpx, consistent with other natural sample studies, but lower than cpx/opx equilibrium from experimental data. The pyroxenite cpx and opx H2O concentrations are at the high-end of on-and off-craton peridotite xenolith concentrations and those of Hawaiian spinel peridotites. In contrast, garnet has extremely low water contents (<5ppm H2O). There is no correlation between H2O in cpx and lithophile element concentrations. Phlogopite is present in some samples, and its modal abundance shows a positive correlation in Mg# with cpx, implying equilibrium. However, there is no correlation between H2O concentrations and or the presence of phlogopite. These data imply that cpx and opx may be at water saturation, far lower than experimental data suggest. Reconstructed bulk rock pyroxenite H2O ranges from 200-460 ppm (average 331 +/- 75 ppm), 2 to 8 times higher than H2O estimates for the MORB source (50-200 ppm), but in the range of E-MORB, OIB and the source of rejuvenated Hawaiian magmas. The average bulk rock pyroxenite H2O/Ce is 69

  19. Quasiclassical trajectory calculations of photodissociation of Ar-H2O(X˜-Ã) and H2O(X˜-Ã)

    NASA Astrophysics Data System (ADS)

    Christoffel, Kurt M.; Bowman, Joel M.

    1996-06-01

    We present results of full-dimensional quasiclassical trajectory calculations of the photodissociation of H2O(3νOH,X˜-Ã) and Ar-H2O(3νOH,X˜-Ã) at 243 and 218 nm, and compare the resulting OH rotational distributions, and also relate them to recent experiments of Nesbitt and co-workers [D. F. Plusquellic, O. Votava, and D. J. Nesbitt, J. Chem. Phys. 101, 6356 (1994)]. The dynamics calculations make use of a new six degree-of-freedom potential for Ar-H2O(Ã), which is reported here. The potential is based on a previously reported ab initio H2O Östate potential, a semiempirical Ar-OH(2Π) potential, and a semiempirical Ar-H potential, together with an appropriate switching function to ensure permutation symmetry with respect to the two H atoms. Initial conditions for the trajectories are obtained from a product of a Husimi phase-space density for the Ar-H2O(X˜) intermolecular modes and a Wigner/classical phase-space density for the H2O(X˜) intramolecular modes. The Husimi phase-space density is derived from the ground-state wave function for Ar-H2O(X˜), using a previous spectroscopically empirical potential. To assess the accuracy of the trajectory approach, trajectory calculations are also reported for X˜-Ã photodissociation of H2O in the ground vibrational state at 166 nm and compared with the corresponding full-dimensional quantum wave packet calculations of von Dirke and Schinke. To further assess the accuracy of the Östate potential surface for H2O, calculations for H2O(4νOH,X˜-Ã) are also reported at 218 nm and compared with experiment. Rotation/vibration distributions of the OH fragment are also calculated for photodissociation of Ar-H2O(4νOH,X˜-Ã) at 218 nm.

  20. Unexpected size distribution of Ba(H2O)n clusters: why is the intensity of the Ba(H2O)1 cluster anomalously low?

    PubMed

    Cabanillas-Vidosa, Iván; Rossa, Maximiliano; Pino, Gustavo A; Ferrero, Juan C

    2011-08-07

    An experimental and theoretical study on the reactivity of neutral Ba atoms with water clusters has been conducted to unravel the origin of the irregular intensity pattern observed in one-photon ionization mass spectra of a Ba(H(2)O)(n)/BaOH(H(2)O)(n-1) (n = 1-4) cluster distribution, which was generated in a laser vaporization-supersonic expansion source. The most remarkable irregular feature is the finding for n = 1 of a lower intensity for the Ba(+)(H(2)O)(n) peak with respect to that of BaOH(+)(H(2)O)(n-1), which is opposite to the trend for n = 2-4. Rationalization of the data required consideration of a distinct behavior of ground-state and electronically excited state Ba atoms in inelastic and reactive Ba + (H(2)O)(n) encounters that can occur in the cluster source. Within this picture, the generation of Ba(H(2)O)(n) (n > 1) association products results from stabilizing collisions with atoms of the carrier gas, which are favored by intramolecular vibrational redistribution that operates on the corresponding collision intermediates prior to stabilization; the latter is unlikely to occur for Ba + (H(2)O) encounters. Overall, this interpretation is consistent with additional in-source laser excitation and quenching experiments, which aimed to explore qualitatively the effect of perturbing the Ba atom electronic state population distribution on the observed intensity pattern, as well as with the energetics of various possible reactions for the Ba + H(2)O system that derive from high level ab initio calculations.

  1. Intermolecular potential and rovibrational states of the H2O-D2 complex

    NASA Astrophysics Data System (ADS)

    van der Avoird, Ad; Scribano, Yohann; Faure, Alexandre; Weida, Miles J.; Fair, Joanna R.; Nesbitt, David J.

    2012-05-01

    A five-dimensional intermolecular potential for H2O-D2 was obtained from the full nine-dimensional ab initio potential surface of Valiron et al. [P. Valiron, M. Wernli, A. Faure, L. Wiesenfeld, C. Rist, S. Kedžuch, J. Noga, J. Chem. Phys. 129 (2008) 134306] by averaging over the ground state vibrational wave functions of H2O and D2. On this five-dimensional potential with a well depth De of 232.12 cm-1 we calculated the bound rovibrational levels of H2O-D2 for total angular momentum J = 0-3. The method used to compute the rovibrational levels is similar to a scattering approach—it involves a basis of coupled free rotor wave functions for the hindered internal rotations and the overall rotation of the dimer—while it uses a discrete variable representation of the intermolecular distance coordinate R. The basis was adapted to the permutation symmetry associated with the para/ortho (p/o) nature of both H2O and D2, as well as to inversion symmetry. As expected, the H2O-D2 dimer is more strongly bound than its H2O-H2 isotopologue [cf. A. van der Avoird, D.J. Nesbitt, J. Chem. Phys. 134 (2011) 044314], with dissociation energies D0 of 46.10, 50.59, 67.43, and 73.53 cm-1 for pH2O-oD2, oH2O-oD2, pH2O-pD2, and oH2O-pD2. A rotationally resolved infrared spectrum of H2O-D2 was measured in the frequency region of the H2O bend mode. The ab initio calculated values of the rotational and distortion constants agree well with the values extracted from this spectrum.

  2. Hydrothermal synthesis, crystal structure, conductivity, and thermal decomposition of [Cu(4,4'-bipy)(H2O)(Mo3O10)].H2O.

    PubMed

    Kong, Zuping; Weng, Linhong; Tan, Dejun; He, Heyong; Zhang, Biao; Kong, Jilie; Yue, Bin

    2004-09-06

    The hydrothermal reaction of (NH(4))(6)Mo(7)O(24).4H(2)O, CuCl(2).2H(2)O, and 4,4'-bipyridine yields bipyridine-ligated copper-trimolybdate monohydrate [Cu(4,4'-bipy)(H(2)O)(Mo(3)O(10))].H(2)O in the monoclinic system with space group of C(2/c) and cell parameters of a = 15.335(2) A, b = 15.535(2) A, c = 15.106(2) A, beta = 101.162(2) degrees, V = 3530.7(9) A(3), and Z = 8. Its structure consists of one-dimensional infinite ([Mo3O10]2-)( infinity ) chains linked through [Cu2(H2O)2(4,4'-bipy)] units. The Mo-O chain contains distorted [MoO(6)] octahedra connected through corner-sharing oxygen atoms into infinite chains along the c direction and each chain is located in the channel formed by four adjacent crossing chains of [Cu(4,4'-bipy)(H2O)](n)(2n+). The crystal shows weak conductivity through Mo-O chain along the c direction and insulating property along either a or b direction. Furthermore, a crystalline bimetallic oxide, CuMo3O10, forms when the title compound undergoes thermal treatment in N(2) atmosphere after the complete removal of the ligands.

  3. Ro-vibrational spectrum of H2O-Ne in the ν2 H2O bending region: A combined ab initio and experimental investigation

    NASA Astrophysics Data System (ADS)

    Liu, Xunchen; Hou, Dan; Thomas, Javix; Li, Hui; Xu, Yunjie

    2016-12-01

    High resolution ro-vibrational transitions of the H2O-Ne complex in the ν2 bending region of H2O at 6 μm have been measured using a rapid scan infrared spectrometer based on an external cavity quantum cascade laser and an astigmatic multipass optical cell. To aid the spectral assignment, a four-dimension potential energy surface of H2O-Ne which depends on the intramolecular bending coordinate of the H2O monomer and the three intermolecular vibrational coordinates has been constructed and the rovibrational transitions have been calculated. Three ortho and two para H2O-20Ne bands have been identified from the experimental spectra. Some weaker transitions belonging to H2O-22Ne have also been identified experimentally. Spectroscopic fits have been performed for both the experimental and theoretical transition frequencies using a simple pseudo-diatomic Hamiltonian including both Coriolis coupling and Fermi resonance terms. The experimental and theoretical spectroscopic constants thus obtained have been compared. Further improvements needed in the potential energy surface and the related spectral simulation have been discussed.

  4. Heterogeneous degradation of precipitated hexamine from wastewater by catalytic function of silicotungstic acid in the presence of H2O2 and H2O2/Fe2+.

    PubMed

    Taghdiri, Mehdi; Saadatjou, Naghi; Zamani, Navid; Farrokhi, Reyhaneh

    2013-02-15

    The industrial wastewater produced by hexamine plants is considered as a major environmental polluting factor due to resistance to biodegradation. So the treatment of such wastewater is required. In this work, the removal of hexamine from wastewater and its degradation have been studied. Hexamine was precipitated through formation of an insoluble and stable compound with silicotungstic acid. The oxidative heterogeneous degradation of precipitated hexamine was carried out with hydrogen peroxide (H(2)O(2)) aqueous solution and H(2)O(2)/Fe(2+) under the catalysis of silicotungstic acid. The operating conditions including amount of precipitate, hydrogen peroxide and ferrous ion dosage, temperature, time and pH were optimized by evaluating the removal of total organic carbon from system. A total organic carbon conversion higher than 70% was achieved in the presence of H(2)O(2)/Fe(2+). The experimental results showed that hexamine can be effectively degraded with H(2)O(2) and H(2)O(2)/Fe(2+) under the catalysis of silicotungstic acid. It was interesting that the solution of dissolved precipitate with H(2)O(2) can re-react with hexamine after the removal of excess hydrogen peroxide. This observation indicates the catalysis role of silicotungstic acid in the degradation of hexamine. A kinetic analysis based on total organic carbon reduction was carried out. The two steps mechanism was proposed for the degradation of hexamine.

  5. Mesospheric H2O Concentrations Retrieved from SABER/TIMED Measurements

    NASA Technical Reports Server (NTRS)

    Feofilov, A. G.; Marshall, B. T.; Garcia-Comas, M.; Kutepov, A. A.; Lopez-Puertas, M.; Manuilova, R. O.; Yankovsky, V.A.; Goldberg, R. A.; Gordley, L. L.; Petelin, S.; Russell, J. M., III

    2008-01-01

    The SABER instrument on board the TIMED Satellite is a limb scanning infrared radiometer designed to measure temperature and minor constituent vertical profiles and energetics parameters in the mesosphere and lower thermosphere (MLT). The H2O concentrations are retrieved from 6.3 micron band radiances. The populations of H2O(v2) vibrational levels are in non-Local Thermodynamic Equilibrium (non-LTE) above approximately 55 km altitude and the interpretation of 6.3 micron radiance requires utilizing non-LTE H2O model that includes various energy exchange processes in the system of H2O vibrational levels coupled with O2, N2, and CO2 vibrational levels. We incorporated these processes including kinetics of O2/O3 photolysis products to our research non-LTE H2O model and applied it for the development and optimization of SABER operational model. The latter has been validated using simultaneous SCISAT1/ACE occultation measurements. This helped us to estimate CO2(020)-O2(X,v=I), O2(X,v=I)- H2O(010), and O2(X,v=1) O rates at mesopause temperatures that is critical for an adequate interpretation of non-LTE H2O radiances in the MLT. The first distributions of seasonal and meridional H2O concentrations retrieved from SABER 6.3 micron radiances applying an updated non-LTE H2O model are demonstrated and discussed.

  6. The reaction of H2O2 with NO2 and NO

    NASA Technical Reports Server (NTRS)

    Gray, D.; Lissi, E.; Heicklen, J.

    1972-01-01

    The reactions of NO and NO2 with H2O2 have been examined at 25 C. Reaction mixtures were monitored by continuously bleeding through a pinhole into a monopole mass spectrometer. NO2 was also monitored by its optical absorption in the visible part of the spectrum. Reaction mixtures containing initially 1.5 - 2.5 torr of NO2 and 0.8 - 1.4 torr of H2O2 or 1 - 12 torr of NO and 0.5 - 1.5 torr of H2O2 were studied. The H2O2 - NO reaction was complex. There was an induction period followed by a marked acceleration in reactant removal. The final products of the reaction, NO2, probably H2O, and possibly HONO2 were produced mainly after all the H2O2 was removed. The HONO intermediate was shown to disproportionate to NO2 + NO + H2O in a relatively slow first order reaction. The acceleration in H2O2 removal after the NO - H2O2 reaction is started is caused by NO2 catalysis.

  7. Nuclear Magnetic Resonance as a Probe of Meso-timescale Dynamics: Ion and H2O Behavior at Mineral-H2O Interfaces

    NASA Astrophysics Data System (ADS)

    Bowers, G. M.; Kirkpatrick, R. J.; Singer, J. W.

    2012-12-01

    One of the important meso-scales in geochemistry is the meso-timescale that is characteristic of processes too slow to probe with light spectroscopy but too fast to probe macroscopically. Nuclear magnetic resonance (NMR) spectroscopy is one of the only analytical methods with dynamic sensitivity to motions with correlation times on the 10-9 to 1 s timescales and is thus a uniquely powerful probe of meso-timescale dynamic behavior. Here, we describe the results of several studies exploring the meso-timescale motion of ions and H2O at the mineral-H2O interface of hectorite, a smectite clay mineral.1-3 2H, 23Na, 39K and 43Ca NMR results show that H2O molecules associated with the interface undergo anisotropic reorientation due to proximity to the surface and surface-associated cations. This motion can be described by rotational diffusion of the H2O molecule about its C2 symmetry axis at GHz frequencies combined with hopping of the H2O molecule about the normal to the smectite surface at ~>200 kHz. This model describes well the observed 2H NMR spectra of Na+, K+, and Ca2+ hectorites over a range temperatures between -80°C and 50°C, with the specific range dependent only on the total system H2O content. At temperatures above -20°C, systems with excess H2O with respect to a two-layer hydrate (low-H2O pastes through dilute aqueous suspensions) experience additional dynamic averaging due to H2O exchange between cation hydration shells, surface-sorbed species, and bulk inter-particle water. The extent of 2H averaging due to this exchange mechanism is strongly affected by the total H2O content in the system, the identity of the charge balancing cation, and the temperature. The dynamic averaging mechanisms affecting the cationic NMR resonances in these systems become dominated by diffusional processes at progressively lower temperatures as the hydration energy of the cation increases. These interfacial cation dynamics and binding sites are strongly affected by surface

  8. TLR agonists downregulate H2-O in CD8alpha- dendritic cells.

    PubMed

    Porter, Gavin W; Yi, Woelsung; Denzin, Lisa K

    2011-10-15

    Peptide loading of MHC class II (MHCII) molecules is catalyzed by the nonclassical MHCII-related molecule H2-M. H2-O, another MHCII-like molecule, associates with H2-M and modulates H2-M function. The MHCII presentation pathway is tightly regulated in dendritic cells (DCs), yet how the key modulators of MHCII presentation, H2-M and H2-O, are affected in different DC subsets in response to maturation is unknown. In this study, we show that H2-O is markedly downregulated in vivo in mouse CD8α(-) DCs in response to a broad array of TLR agonists. In contrast, CD8α(+) DCs only modestly downregulated H2-O in response to TLR agonists. H2-M levels were slightly downmodulated in both CD8α(-) and CD8α(+) DCs. As a consequence, H2-M/H2-O ratios significantly increased for CD8α(-) but not for CD8α(+) DCs. The TLR-mediated downregulation was DC specific, as B cells did not show significant H2-O and H2-M downregulation. TLR4 signaling was required to mediate DC H2-O downregulation in response to LPS. Finally, our studies showed that the mechanism of H2-O downregulation was likely due to direct protein degradation of H2-O as well as downregulation of H2-O mRNA levels. The differential H2-O and H2-M modulation after DC maturation supports the proposed roles of CD8α(-) DCs in initiating CD4-restricted immune responses by optimal MHCII presentation and of CD8α(+) DCs in promoting immune tolerance via presentation of low levels of MHCII-peptide.

  9. A Search for Submillimeter H2O Masers in Active Galaxies: The Detection of 321 GHZ H2O Maser Emission in NGC 4945

    NASA Astrophysics Data System (ADS)

    Hagiwara, Yoshiaki; Horiuchi, Shinji; Doi, Akihiro; Miyoshi, Makoto; Edwards, Philip G.

    2016-08-01

    We present further results of a search for extragalactic submillimeter H2O masers using the Atacama Large Millimeter/submillimeter Array (ALMA). The detection of a 321 GHz H2O maser in the nearby type 2 Seyfert galaxy, the Circinus galaxy, has previously been reported, and here the spectral analysis of four other galaxies is described. We have discovered H2O maser emission at 321 GHz toward the center of NGC 4945, a nearby type 2 Seyfert. The maser emission shows Doppler-shifted velocity features with velocity ranges similar to those of the previously reported 22 GHz H2O masers however, the non-contemporaneous observations also show differences in velocity offsets. The subparsec-scale distribution of the 22 GHz H2O masers revealed by earlier very long baseline interferometry observations suggests that the submillimeter masers could arise in an edge-on rotating disk. The maser features remain unresolved by the synthesized beam of ˜0.″54 (˜30 pc) and are located toward the 321 GHz continuum peak within errors. A marginally detected (3σ) high-velocity feature is redshifted by 579 km {{{s}}}-1 with respect to the systemic velocity of the galaxy. Assuming that this feature is real and arises from a Keplerian rotating disk in this galaxy, it is located at a radius of ˜0.020 pc (˜1.5 × 105 Schwarzschild radii), which would enable molecular material closer to the central engine to be probed than the 22 GHz H2O masers. This detection confirms that submillimeter H2O masers are a potential tracer of the circumnuclear regions of active galaxies, which will benefit from higher angular resolution studies with ALMA.

  10. Crystal structures of hydrates of simple inorganic salts. III. Water-rich aluminium halide hydrates: AlCl3 · 15H2O, AlBr3 · 15H2O, AlI3 · 15H2O, AlI3 · 17H2O and AlBr3 · 9H2O.

    PubMed

    Schmidt, Horst; Hennings, Erik; Voigt, Wolfgang

    2014-09-01

    Water-rich aluminium halide hydrate structures are not known in the literature. The highest known water content per Al atom is nine for the perchlorate and fluoride. The nonahydrate of aluminium bromide, stable pentadecahydrates of aluminium chloride, bromide and iodide, and a metastable heptadecahydrate of the iodide have now been crystallized from low-temperature solutions. The structures of these hydrates were determined and are discussed in terms of the development of cation hydration spheres. The pentadecahydrate of the chloride and bromide are isostructural. In AlI(3) · 15H2O, half of the Al(3+) cations are surrounded by two complete hydration spheres, with six H2O in the primary and 12 in the secondary. For the heptadecahydrate of aluminium iodide, this hydration was found for every Al(3+).

  11. Probing active galactic nuclei with H2O megamasers.

    PubMed Central

    Moran, J; Greenhill, L; Herrnstein, J; Diamond, P; Miyoshi, M; Nakai, N; Inque, M

    1995-01-01

    the disk must be <1000 K and the toroidal magnetic field component must be <250 mG. If the molecular mass density in the disk is 10(10) cm-3, then the disk mass is approximately 10(4) M[symbol: see text], and the disk is marginally stable as defined by the Toomre stability parameter Q (Q = 6 at the inner edge and 1 at the outer edge). The inward drift velocity is predicted to be <0.007 km.s-1, for a viscosity parameter of 0.1, and the accretion rate is <7 x 10(-5) M[symbol: see text].yr-1. At this value the accretion would be sufficient to power the nuclear x-ray source of 4 x 10(40) ergs-1 (1 erg = 0.1 microJ). The volume of individual maser components may be as large as 10(46) cm3, based on the velocity gradients, which is sufficient to supply the observed luminosity. The pump power undoubtedly comes from the nucleus, perhaps in the form of x-rays. The warp may allow the pump radiation to penetrate the disk obliquely [Neufeld, D. A. & Maloney, P. R. (1995) Astrophys. J. Lett. 447, L17-L19]. A total of 15 H2O megamasers have been identified out of >250 galaxies searched. Galaxy NGC4258 may be the only case where conditions are optimal to reveal a well-defined nuclear disk. Future measurement of proper motions and accelerations for NGC4258 will yield an accurate distance and a more precise definition of the dynamics of the disk Images Fig. 6 PMID:11607612

  12. TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OL)

    Atmospheric Science Data Center

    2016-10-25

    TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OL) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  27 x 23 km Limb ... Access: OPeNDAP Parameters:  H2O Water Volume Mixing Radio Precision Vertical Resolution Order ...

  13. Flexible H2O2 in water: electronic structure from photoelectron spectroscopy and ab initio calculations.

    PubMed

    Thürmer, Stephan; Seidel, Robert; Winter, Bernd; Ončák, Milan; Slavíček, Petr

    2011-06-16

    The effect of hydration on the electronic structure of H(2)O(2) is investigated by liquid-jet photoelectron spectroscopy measurements and ab initio calculations. Experimental valence electron binding energies of the H(2)O(2) orbitals in water are, on average, 1.9 eV red-shifted with respect to the gas-phase molecule. A smaller width of the first peak was observed in the photoelectron spectrum from the solution. Our experiment is complemented by simulated photoelectron spectra, calculated at the ab initio level of theory (with EOM-IP-CCSD and DFT methods), and using path-integral sampling of the ground-state density. The observed shift in ionization energy upon solvation is attributed to a combination of nonspecific electrostatic effects (long-range polarization) and of the specific interactions between H(2)O(2) and H(2)O molecules in the first solvation shell. Changes in peak widths are found to result from merging of the two lowest ionized states of H(2)O(2) in water due to conformational changes upon solvation. Hydration effects on H(2)O(2) are stronger than on the H(2)O molecule. In addition to valence spectra, we report oxygen 1s core-level photoelectron spectra from H(2)O(2)(aq), and observed energies and spectral intensities are discussed qualitatively.

  14. [Degradation of MC-LR by combination of UV/H2O2 process].

    PubMed

    Guo, Jian-Wei; Gao, Nai-Yun; Yin, Di-Di; Li, Lei; Dong, Bing-Zhi; Zhang, Ke-Jia

    2009-02-15

    The degradation of MC-LR in water by UV/H2O2 process was investigated. The effects of intensity of UV radiation, initial concentration of MC-LR, dosages of H2O2, initial pH value and anions on degradation of MC-LR by UV/H2O2 process were studied. The results show that the removal of MC-LR only by H2O2 is nearly zero, and UV process can degrade MC-LR to a certain extent. However, the degradation efficiency of UV/H2O2 process is much higher than UV and H2O2 process due to the synergetic effect between UV and H2O2. The removal of MC-LR increases with the enhancement of intensity of UV radiation, but decreases gradually with the increase of initial concentration of MC-LR. When the dosages of H2O2 change from 1 mmol/L to 3 mmol/L, the constant of degradation rate rises from 0.0844 to 0.1664. The optimum pH value is 3.13. The added anions have adverse effect on the degradation of MC-LR, especially carbonate and nitrate ions have the biggest influence among the studied anions.

  15. 40 CFR 1065.372 - NDUV analyzer HC and H2O interference verification.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calibrations and Verifications Nox and N2o Measurements § 1065.372 NDUV analyzer HC and H2O interference verification. (a) Scope and frequency. If you... analyzer installation and after major maintenance. (b) Measurement principles. Hydrocarbons and H2O...

  16. 40 CFR 1065.372 - NDUV analyzer HC and H2O interference verification.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calibrations and Verifications Nox and N2o Measurements § 1065.372 NDUV analyzer HC and H2O interference verification. (a) Scope and frequency. If you... analyzer installation and after major maintenance. (b) Measurement principles. Hydrocarbons and H2O...

  17. Characterization and optimization of cathodic conditions for H2O2 synthesis in microbial electrochemical cells.

    PubMed

    Sim, Junyoung; An, Junyeong; Elbeshbishy, Elsayed; Ryu, Hodon; Lee, Hyung-Sool

    2015-11-01

    Cathode potential and O2 supply methods were investigated to improve H2O2 synthesis in an electrochemical cell, and optimal cathode conditions were applied for microbial electrochemical cells (MECs). Using aqueous O2 for the cathode significantly improved current density, but H2O2 conversion efficiency was negligible at 0.3-12%. Current density decreased for passive O2 diffusion to the cathode, but H2O2 conversion efficiency increased by 65%. An MEC equipped with a gas diffusion cathode was operated with acetate medium and domestic wastewater, which presented relatively high H2O2 conversion efficiency from 36% to 47%, although cathode overpotential was fluctuated. Due to different current densities, the maximum H2O2 production rate was 141 mg H2O2/L-h in the MEC fed with acetate medium, but it became low at 6 mg H2O2/L-h in the MEC fed with the wastewater. Our study clearly indicates that improving anodic current density and mitigating membrane fouling would be key parameters for large-scale H2O2-MECs.

  18. Application of H2O and UV/H2O2 processes for enhancing the biodegradability of reactive black 5 dye.

    PubMed

    Kalpana, S Divya; Kalyanaraman, Chitra; Gandhi, N Nagendra

    2011-07-01

    Leather processing is a traditional activity in India during which many organic and inorganic chemicals are added while part of it is absorbed by the leather, the remaining chemicals are discharged along with the effluent. The effluent contains both easily biodegradable and not easily biodegradable synthetic organics like dyes, syntans. Easily biodegradable organics are removed in the existing biological treatment units whereas synthetic organics present in the wastewater are mostly adsorbed over the microbes. As the tannery effluent contains complex chemicals, it is difficult to ascertain the degradation of specific pollutants. To determine the increase in the biodegradability, one of the complex and synthetic organic chemical like dye used in the tanning operation was selected for Advanced Oxidation Process (AOPs) treatment for cleaving complex organics and its subsequent treatment in aerobic process. In the present study, Reactive Black 5 Dye used in the tanning operation was selected for Hydrogen Peroxide (H2O2) and UV/H2O2 pre-treatment for different operating conditions like pH, contact time and different volume of H2O2. A comparison was made between the untreated, Hydrogen Peroxide (H2O2) and UV/H2O2 treated effluent in order to ascertain the influence of AOP on the improvement of biodegradability of effluent. An increase in the BOD5/COD ratio from 0.21 to 0.435 was achieved in the UV/H2O2 pre-treatment process. This pre-treated effluent was further subjected to aerobic process. Biochemical Oxygen Demand (BOD5) and Chemical Oxygen Demand (COD) removal efficiency of the UV/H2O2 pre-treated dye solution in the aerobic process was found to be 86.39% and 77.82% when compared to 52.43% of BOD5 and 51.55% of COD removal efficiency without any pre-treatment. Hence from these results, to increase the biodegradability of Reactive Black 5 dye pre-treatment methods like H2O2 and UV/H2O2 can be used prior to biological treatment process.

  19. UV and VUV photolysis vs. UV/H2O2 and VUV/H2O2, treatment for removal of clofibric acid from aqueous solution.

    PubMed

    Li, Wenzhen; Lu, Shuguang; Qiu, Zhaofu; Lin, Kuangfei

    2011-07-01

    Clofibric acid (CA), a metabolite of lipid regulators, was investigated in ultra-pure water and sewage treatment plant (STP) effluent at 10 degrees C under UV, vacuum UV (VUV), UV/H2O2 and VUV/H2O2 processes. The influences of NO3-, HCO3- and humic acid (HA) on CA photolysis in all processes were examined. The results showed that all the experimental data well fitted the pseudo-first-order kinetic model, and the apparent rate constant (k(ap)) and half-life time (t(1/2)) were calculated accordingly. Direct photolysis of CA through UV irradiation was the main process, compared with the indirect oxidation of CA due to the slight generation of hydroxyl radicals dissociated from water molecules under UV irradiation below 200 nm monochromatic wavelength emission. In contrast, indirect oxidation was the main CA degradation mechanism in UV/H2O2 and VUV/H2O2, and VUV/H2O2 was the most effective process for CA degradation. The addition of 20 mg L(-1) HA could significantly inhibit CA degradation, whereas, except for UV irradiation, the inhibitive effects of NO3- and HCO3- (1.0 x 10(-3) and 0.1 mol L(-1), respectively) on CA degradation were observed in all processes, and their adverse effects were more significant in UV/H2O2 and VUV/H2O2 processes, particularly at the high NO3- and HCO3- concentrations. The degradation rate decreased 1.8-4.9-fold when these processes were applied to a real STP effluent owing to the presence of complex constituents. Of the four processes, VUV/H2O2 was the most effective, and the CA removal efficiency reached over 99% after 40 min in contrast to 80 min in both the UV/H2O2 and VUV processes and 240 min in the UV process.

  20. Experimental Determination of the H2O-undersaturated Peridotite Solidus

    NASA Astrophysics Data System (ADS)

    Sarafian, E. K.; Gaetani, G. A.; Hauri, E.; Sarafian, A.

    2015-12-01

    Knowledge of the H2O-undersaturated lherzolite solidus places important constraints on the process of melt generation beneath oceanic spreading centers. While it is generally accepted that the small concentration of H2O (~50-200 ug/g) dissolved in the oceanic upper mantle has a strong influence on the peridotite solidus, but this effect has not been directly determined through experiments. This is because (1) precisely controlling low concentrations of H2O in high-pressure melting experiments is thought to be difficult, (2) small amounts of melt are difficult to identify, and (3) the size of mineral grains that grow in near-solidus experiments is too small to be analyzed for H2O by either Fourier transform infrared (FTIR) spectroscopy or secondary ion mass spectrometry (SIMS). We have developed an experimental approach for determining the peridotite solidus as a function of H2O content that overcomes these difficulties. Our approach utilizes large (~300 um diameter) spheres of San Carlos olivine to monitor the concentration and behavior of H2O in our experiments.. The spheres are mixed in 5:95 proportions with a synthetic peridotite that has the composition of the depleted MORB mantle of Workman and Hart (2005). Partial melting experiments are conducted in is a piston cylinder device using pre-conditioned Au80Pd20 capsules. During an experiment, the H2O content of the San Carlos olivine spheres diffusively equilibrates with the peridotite matrix. After each experiment, the concentration of H2O dissolved in the olivine spheres is determined by secondary ion mass spectrometry. By analyzing the H2O content of the San Carlos olivine spheres and performing a simple mass balance, we can then calculate the amount of H2O in the capsule. The spheres also provides a means to determine the solidus temperature due to the strong partitioning of H2O into silicate melt compared to olivine, pyroxene, and spinel. When a small amount of melt is present the H2O partitions into the

  1. Three-dimensional WS2 nanosheet networks for H2O2 produced for cell signaling

    NASA Astrophysics Data System (ADS)

    Tang, Jing; Quan, Yingzhou; Zhang, Yueyu; Jiang, Min; Al-Enizi, Abdullah M.; Kong, Biao; An, Tiance; Wang, Wenshuo; Xia, Limin; Gong, Xingao; Zheng, Gengfeng

    2016-03-01

    Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in living RAW 264.7 macrophage cells and neurons. First-principles calculations further demonstrate that the enhanced sensitivity of probing H2O2 is attributed to the efficient and spontaneous H2O2 adsorption on WS2 nanosheet edge sites. The combined features of 3D WS2 nanosheet networks suggest attractive new opportunities for exploring the physiological roles of reactive oxygen species like H2O2 in living systems.Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in

  2. Reaction kinetics of waste sulfuric acid using H2O2 catalytic oxidation.

    PubMed

    Wang, Jiade; Hong, Binxun; Tong, Xinyang; Qiu, Shufeng

    2016-12-01

    The process of recovering waste sulfuric acids using H2O2 catalytic oxidation is studied in this paper. Activated carbon was used as catalyst. Main operating parameters, such as temperature, feed rate of H2O2, and catalyst dosage, have effects on the removal of impurities from waste sulfuric acids. The reaction kinetics of H2O2 catalytic oxidation on impurities are discussed. At a temperature of 90°C, H2O2 feeding rate of 50 g (kg waste acid)(-1) per hour, and catalyst dosage of 0.2 wt% (waste acid weight), the removal efficiencies of COD and chrominance were both more than 99%, the recovery ratio of sulfuric acid was more than 95%, and the utilization ratio of H2O2 was 88.57%.

  3. Hydrogen-bond-directed assemblies of [La(18-crown-6)(H2O)4](BiCl6)·3H2O and [Nd(18-crown-6)(H2O)4](BiCl6)·3.5H2O regulated by different symmetries

    NASA Astrophysics Data System (ADS)

    Zhang, Shi-Yong; Li, Jian; Zeng, Ying; Wen, He-Rui; Du, Zi-Yi

    2016-12-01

    The reactions of La2O3 or Nd2O3 with BiCl3 and 18-crown-6 in the presence of excessive hydrochloric acid afforded two ion-pair compounds, namely [La(18-crown-6)(H2O)4](BiCl6)·3H2O (1) and [Nd(18-crown-6)(H2O)4](BiCl6)·3.5H2O (2). Although these two compounds contain similar building blocks, they exhibit two distinct hydrogen-bonded networks, which are mainly induced by the slightly different geometries of their large-sized cationic [Ln(18-crown-6)(H2O)4]3+ components.

  4. The effect of H2O and CO2 on planetary mantles

    NASA Technical Reports Server (NTRS)

    Wyllie, P. J.

    1978-01-01

    The peridotite-H2O-CO2 system is discussed, and it is shown that even traces of H2O and CO2, in minerals or vapor, lower mantle solidus temperatures through hundreds of degrees in comparison with the volatile-free solidus. The solidus for peridotite-H2O-CO2 is a divariant surface traversed by univariant lines that locate the intersections of subsolidus divariant surfaces for carbonation or hydration reactions occurring in the presence of H2O-CO2 mixtures. Vapor phase compositions are normally buffered to these lines, and near the buffered curve for the solidus of partly carbonated peridotite there is a temperature maximum on the peridotite-vapor solidus. Characteristics on the CO2 side of the maximum and on the H2O side of the maximum are described.

  5. Detection of local H2O exposed at the surface of Ceres.

    PubMed

    Combe, Jean-Philippe; McCord, Thomas B; Tosi, Federico; Ammannito, Eleonora; Carrozzo, Filippo Giacomo; De Sanctis, Maria Cristina; Raponi, Andrea; Byrne, Shane; Landis, Margaret E; Hughson, Kynan H G; Raymond, Carol A; Russell, Christopher T

    2016-09-02

    The surface of dwarf planet Ceres contains hydroxyl-rich materials. Theories predict a water ice-rich mantle, and water vapor emissions have been observed, yet no water (H2O) has been previously identified. The Visible and InfraRed (VIR) mapping spectrometer onboard the Dawn spacecraft has now detected water absorption features within a low-illumination, highly reflective zone in Oxo, a 10-kilometer, geologically fresh crater, on five occasions over a period of 1 month. Candidate materials are H2O ice and mineral hydrates. Exposed H2O ice would become optically undetectable within tens of years under current Ceres temperatures; consequently, only a relatively recent exposure or formation of H2O would explain Dawn's findings. Some mineral hydrates are stable on geological time scales, but their formation would imply extended contact with ice or liquid H2O.

  6. Infrared spectra and radiation stability of H2O2 ices relevant to Europa.

    PubMed

    Hudson, Reggie L; Moore, Marla H

    2006-06-01

    In this paper we present spectra of H2O2-containing ices in the near- and mid-infrared (IR) regions. Spectral changes on warming are shown, as is a comparison of near-IR bands of H2O and H2O2-containing ices. An estimate of the A-value (absolute intensity) for the largest near- IR feature of H2O2 is given. Radiation-decay half-lives are reported for 19 K and 80 K, and are related to the surface radiation doses on Europa. The radiation data show that H2O2 destruction is slower at 80 K than 19 K, and are consistent with the claim that icy material in the outermost micrometer of Europa's surface has been heavily processed by radiation.

  7. Copernicus observational searches for OH and H2O in diffuse clouds

    NASA Technical Reports Server (NTRS)

    Smith, W. H.; Snow, T. P., Jr.

    1983-01-01

    An intensive search for OH and H2O in the directions of sigma Sco, alpha Cam, and micron Per was undertaken with the Copernicus satellite. Multiple scans were carried out over the wavelength region for the expected absorption features due to the OH D-X and H2O C-X transitions. The feature due to OH was detected marginally towards sigma Sco, and only an upper limit can be given towards alpha Cam. H2O was not detected in any of the stars at the signal level accumulated. The OH abundance towards sigma Sco and the respective lower limits for the OH/H2O ratios are discussed with regard to the extant models for the steady state abundances of OH and H2O, and shown not to be inconsistent with ion-molecule schemes.

  8. Detection of local H2O exposed at the surface of Ceres

    NASA Astrophysics Data System (ADS)

    Combe, Jean-Philippe; McCord, Thomas B.; Tosi, Federico; Ammannito, Eleonora; Carrozzo, Filippo Giacomo; De Sanctis, Maria Cristina; Raponi, Andrea; Byrne, Shane; Landis, Margaret E.; Hughson, Kynan H. G.; Raymond, Carol A.; Russell, Christopher T.

    2016-09-01

    The surface of dwarf planet Ceres contains hydroxyl-rich materials. Theories predict a water ice-rich mantle, and water vapor emissions have been observed, yet no water (H2O) has been previously identified. The Visible and InfraRed (VIR) mapping spectrometer onboard the Dawn spacecraft has now detected water absorption features within a low-illumination, highly reflective zone in Oxo, a 10-kilometer, geologically fresh crater, on five occasions over a period of 1 month. Candidate materials are H2O ice and mineral hydrates. Exposed H2O ice would become optically undetectable within tens of years under current Ceres temperatures; consequently, only a relatively recent exposure or formation of H2O would explain Dawn’s findings. Some mineral hydrates are stable on geological time scales, but their formation would imply extended contact with ice or liquid H2O.

  9. An H2O Maser survey towards BGPS sources in the Outer Galaxy

    NASA Astrophysics Data System (ADS)

    Xi, Hong-Wei; Zhou, Jian-Jun; Esimbek, Jarken; Wu, Gang; He, Yu-Xin; Ji, Wei-Guang; Tang, Xiao-Ke; Yuan, Ye

    2016-06-01

    We performed an H2O maser survey towards 274 Bolocam Galactic Plane Survey (BGPS) sources with 85° < l < 193° using the Nanshan 25 m radio telescope. We detected 25 H2O masers, and five of them are new detections. The detection rate of H2O masers in our sample is 9% which is very low. The detection rate of H2O masers increases as the 1.1 mm flux density of BGPS sources increases, and both the peak flux density and luminosity of H2O masers increase as the sources evolve. The detection rate of H2O masers toward BGPS sources without HCO+ emission is low. The BGPS sources associated with both H2O and CH3OH masers seem to be more compact than those only associated with H2O masers. This indicates that the sources with both masers may be in a relatively later evolutionary stage. The strongest H2O maser source G133.715+01.217, also well known as W3 IRS 5 which has a flux density of 2.9×103 Jy, was detected at eight different nearby positions. By measuring the correlation between the flux densities of these H2O masers and their angular distance from the true source location, we get the influence radius r = \\frac{1}{{0.8}}log ≤ft({\\frac{{F_0}}{{3\\text{rms}}}}\\right). For our observations, strong sources can be detected anywhere within this radius. It is helpful to determine whether or not a weak maser nearby the strong maser is a true detection.

  10. Sequential hydration energies of the sulfate ion, from determinations of the equilibrium constants for the gas-phase reactions: SO4(H2O)(n)2- = SO4(H2O)(n-1)2- + H2O.

    PubMed

    Blades, Arthur T; Kebarle, Paul

    2005-09-22

    Sequential hydration energies of SO4(H2O)(n)2- were obtained from determinations of the equilibrium constants of the following reactions: SO4(H2O)(n)2- = SO4(H2O)(n-1)2- + H2O. The SO4(2-) ions were produced by electrospray and the equilibrium constants Kn,n-1 were determined with a reaction chamber attached to a mass spectrometer. Determinations of Kn,n-1 at different temperatures were used to obtain DeltaG0n,n-1, DeltaH0 n,n-1, and DeltaS0n,n-1 for n = 7 to 19. Interference of the charge separation reaction SO4(H2O)(n)2- = HSO4(H2O)(n-k)- + OH(H2O)(k-1)- at higher temperatures prevented determinations for n < 7. The DeltaS0n,n-1 values obtained are unusually low and this indicates very loose, disordered structures for the n > or = 7 hydrates. The DeltaH0n,n-1 values are compared with theoretical values DeltaEn,n-1, obtained by Wang, Nicholas, and Wang. Rate constant determinations of the dissociation reactions n,n - 1, obtained with the BIRD method by Wong and Williams, showed relatively lower rates for n = 6 and 12, which indicate that these hydrates are more stable. No discontinuities of the DeltaG0n,n-1 values indicating an unusually stable n = 12 hydrate were observed in the present work. Rate constants evaluated from the DeltaG0n,n-1 results also fail to indicate a lower rate for n = 12. An analysis of the conditions used in the two types of experiments indicates that the different results reflect the different energy distributions expected at the dissociation threshold. Higher internal energies prevail in the equilibrium measurements and allow the participation of more disordered transition states in the reaction.

  11. Hydrogen constituents of the mesosphere inferred from positive ions - H2O, CH4, H2CO, H2O2, and HCN

    NASA Technical Reports Server (NTRS)

    Kopp, E.

    1990-01-01

    The concentrations in the mesosphere of H2O, CH4, H2CO, H2O2, and HCN were inferred from data on positive ion compositions, obtained from one mid-latitude and four high-latitude rocket flights. The inferred concentrations were found to agree only partially with the ground-based microwave measurements and/or model prediction by Garcia and Solomon (1985). The CH4 concentration was found to vary between 70 and 4 ppb in daytime and 900 and 100 ppbv at night, respectively. Unexpectedly high H2CO concentrations were obtained, with H2CO/H2O ratios between 0.0006 and 0.1, and a mean HCN volume mixing ratio of 6 x 10 to the -10th was inferred.

  12. One-dimensional decavanadate chains in the crystal structure of Rb4[Na(H2O)6][HV10O28]·4H2O.

    PubMed

    Yakubovich, Olga V; Steele, Ian M; Yakovleva, Ekaterina V; Dimitrova, Olga V

    2015-06-01

    New decavanadate minerals, the products of the leaching or metasomatic processes, are possible in nature via Na/Rb removal/inclusion reactions. As part of our search for novel vanadate phases with varying functionalities, a new phase, tetrarubidium hexaaquasodium hydrogen decavanadate tetrahydrate, Rb4[Na(H2O)6][HV10O28]·4H2O, has been synthesized by the hydrothermal technique at 553 K. Ten shared edges of V-centred octahedra form monoprotonated decavanadate cages, which are joined together via hydrogen bonds into one-dimensional chains parallel to the [101] direction. Within these chains, H atoms are sandwiched between neighbouring polyanions. Na and Rb atoms and H2O molecules occupy interstices flanked by the anionic chains providing additional crosslinking in the structure. This compound is the second decavanadate with P2/n symmetry. Structural relationships among protonated and deprotonated decavanadates with inorganic cations, including minerals of the pascoite group, are discussed.

  13. Generation of H2, O2, and H2O2 from water by the use of intense femtosecond laser pulses and the possibility of laser sterilization

    NASA Astrophysics Data System (ADS)

    Chin, S. L.; Lagacé, S.

    1996-02-01

    An intense femtosecond Ti-sapphire laser pulse was focused into water, leading to self-focusing. Apart from generating a white light (supercontinuum), the intense laser field in the self-focusing regions of the laser pulse dissociated the water molecules, giving rise to hydrogen and oxygen gas as well as hydrogen peroxide. Our analysis shows that the formation of free radicals O, H, and OH preceded the formation of the stable products of H2, O2, and H2O2. Because O radicals and H2O2 are strong oxydizing agents, one can take advantage of this phenomenon to design a laser scheme for sterilization in medical and biological applications.

  14. Relaxation of H2O from its |04>- vibrational state in collisions with H2O, Ar, H2, N2, and O2

    NASA Astrophysics Data System (ADS)

    Barnes, Peter W.; Sims, Ian R.; Smith, Ian W. M.

    2004-03-01

    We report rate coefficients at 293 K for the collisional relaxation of H2O molecules from the highly excited |04>± vibrational states in collisions with H2O, Ar, H2, N2, and O2. In our experiments, the |04>- state is populated by direct absorption of radiation from a pulsed dye laser tuned to ˜719 nm. Evolution of the population in the (|04>±) levels is observed using the combination of a frequency-quadrupled Nd:YAG laser, which selectively photolyses H2O(|04>±), and a frequency-doubled dye laser, which observes the OH(v=0) produced by photodissociation via laser-induced fluorescence. The delay between the pulse from the pump laser and those from the photolysis and probe lasers was systematically varied to generate kinetic decays. The rate coefficients for relaxation of H2O(|04>±) obtained from these experiments, in units of cm3 molecule-1 s-1, are: k(H2O)=(4.1±1.2)×10-10, k(Ar)=(4.9±1.1)×10-12, k(H2)=(6.8±1.1)×10-12, k(N2)=(7.7±1.5)×10-12, k(O2)=(6.7±1.4)×10-12. The implications of these results for our previous reports of rate constants for the removal of H2O molecules in selected vibrational states by collisions with H atoms (P. W. Barnes et al., Faraday Discuss. Chem. Soc. 113, 167 (1999) and P. W. Barnes et al., J. Chem. Phys. 115, 4586 (2001).) are fully discussed.

  15. Relaxation of H2O from its /04>- vibrational state in collisions with H2O, Ar, H2, N2, and O2.

    PubMed

    Barnes, Peter W; Sims, Ian R; Smith, Ian W M

    2004-03-22

    We report rate coefficients at 293 K for the collisional relaxation of H2O molecules from the highly excited /04>(+/-) vibrational states in collisions with H2O, Ar, H2, N2, and O2. In our experiments, the mid R:04(-) state is populated by direct absorption of radiation from a pulsed dye laser tuned to approximately 719 nm. Evolution of the population in the (/04>(+/-)) levels is observed using the combination of a frequency-quadrupled Nd:YAG laser, which selectively photolyses H2O(/04>(+/-)), and a frequency-doubled dye laser, which observes the OH(v=0) produced by photodissociation via laser-induced fluorescence. The delay between the pulse from the pump laser and those from the photolysis and probe lasers was systematically varied to generate kinetic decays. The rate coefficients for relaxation of H2O(/04>(+/-)) obtained from these experiments, in units of cm3 molecule(-1) s(-1), are: k(H2O)=(4.1+/-1.2) x 10(-10), k(Ar)=(4.9+/-1.1) x 10(-12), k(H2)=(6.8+/-1.1) x 10(-12), k(N2)=(7.7+/-1.5) x 10(-12), k(O2)=(6.7+/-1.4) x 10(-12). The implications of these results for our previous reports of rate constants for the removal of H2O molecules in selected vibrational states by collisions with H atoms (P. W. Barnes et al., Faraday Discuss. Chem. Soc. 113, 167 (1999) and P. W. Barnes et al., J. Chem. Phys. 115, 4586 (2001).) are fully discussed.

  16. Spectroscopic properties of morin in various CH3OH-H2O and CH3CN-H2O mixed solvents.

    PubMed

    Park, Hyoung-Ryun; Im, Seo-Eun; Seo, Jung-Ja; Kim, Bong-Gon; Yoon, Jin Ah; Bark, Ki-Min

    2015-01-01

    The specific fluorescence properties of morin (3,2',4',5,7-pentahydroxyflavone) were studied in various CH3OH-H2O and CH3CN-H2O mixed solvents. Although the dihedral angle is large in the S0 state, morin has an almost planar molecular structure in the S1 state owing to the very low rotational energy barrier around the interring bond between B and the A, C ring. The excited state intramolecular proton transfer (ESIPT) at the S1 state cannot occur immediately after excitation, S1 → S0 fluorescence can be observed. Two conformers, Morin A and B have been known. At the CH3OH-H2O, Morin B will be the principal species but at the CH3CN-H2O, Morin A is the principal species. At the CH3OH-H2O, owing to the large Franck-Condon (FC) factor for S2 → S1 internal convernal (IC) and flexible molecular structure, only S1 → S0 fluorescence was exhibited. At the CH3CN-H2O, as the FC factor for S2 → S1 IC is small and molecular structure is rigid, S2 → S0 and S1 → S0 dual fluorescence was observed. This abnormal fluorescence property was further supported by the small pK1 value, effective delocalization of the lone pair electrons of C(2')-OH to the A, C ring, and a theoretical calculation.

  17. Heterogeneous distribution of H2O in the Martian interior: Implications for the abundance of H2O in depleted and enriched mantle sources

    NASA Astrophysics Data System (ADS)

    McCubbin, Francis M.; Boyce, Jeremy W.; Srinivasan, Poorna; Santos, Alison R.; Elardo, Stephen M.; Filiberto, Justin; Steele, Andrew; Shearer, Charles K.

    2016-11-01

    We conducted a petrologic study of apatite within 12 Martian meteorites, including 11 shergottites and one basaltic regolith breccia. These data were combined with previously published data to gain a better understanding of the abundance and distribution of volatiles in the Martian interior. Apatites in individual Martian meteorites span a wide range of compositions, indicating they did not form by equilibrium crystallization. In fact, the intrasample variation in apatite is best described by either fractional crystallization or crustal contamination with a Cl-rich crustal component. We determined that most Martian meteorites investigated here have been affected by crustal contamination and hence cannot be used to estimate volatile abundances of the Martian mantle. Using the subset of samples that did not exhibit crustal contamination, we determined that the enriched shergottite source has 36-73 ppm H2O and the depleted source has 14-23 ppm H2O. This result is consistent with other observed geochemical differences between enriched and depleted shergottites and supports the idea that there are at least two geochemically distinct reservoirs in the Martian mantle. We also estimated the H2O, Cl, and F content of the Martian crust using known crust-mantle distributions for incompatible lithophile elements. We determined that the bulk Martian crust has 1410 ppm H2O, 450 ppm Cl, and 106 ppm F, and Cl and H2O are preferentially distributed toward the Martian surface. The estimate of crustal H2O results in a global equivalent surface layer (GEL) of 229 m, which can account for at least some of the surface features on Mars attributed to flowing water and may be sufficient to support the past presence of a shallow sea on Mars' surface.

  18. Analysis of a remarkable perpendicular band in Krsbnd H2O with origin close to the ν1 + ν3R(0) line in H2O

    NASA Astrophysics Data System (ADS)

    Vanfleteren; Földes, T.; Vander Auwera, J.; Herman, M.

    2015-01-01

    We have used continuous-wave cavity ring-down spectroscopy to record a band with origin close to 7273.5 cm-1 in a Kr supersonic expansion seeded with H2O. It is assigned to ν1 + ν3 ← GS, ∏(101) ← Σ(000) in Krsbnd H2O. Several lines of the four most abundant Kr isotopic forms are resolved. The rotational structure (Trot = 18 K) is analyzed and the lines fitted (σ < 0.0004 cm-1) together with literature microwave data. The mean upper state predissociation lifetime is estimated to 4 ns.

  19. Experimental constraints on H2O activity in high-pressure metamorphic brines

    NASA Astrophysics Data System (ADS)

    Tropper, P.; Manning, C. E.

    2004-12-01

    Subduction of crustal materials is accompanied by metamorphic reactions liberating fluids. Fluid inclusions in eclogite minerals range from dilute solutions to chloride-rich brines; however, the effect of salinity variations on the stability of hydrous phases in subduction zones is poorly understood. To address this problem, we carried out reversed piston-cylinder experiments on the equilibrium (1) paragonite = jadeite + kyanite + H2O at 700° C, 1.5-2.5 GPa, in the presence of H2O-NaCl fluids. The experiments were conducted using fluids with nominal starting compositions: X(H2O)=1.0, 0.90, 0.75 and 0.62. At X(H2O) = 1.0, the equilibrium lies between 2.25 and 2.30 GPa. Lowering X(H2O) decreases the pressure of paragonite breakdown to 2.10 - 2.20 GPa at X(H2O) = 0.90 and 1.85-1.90 GPa at X(H2O) = 0.75. The experiments at X(H2O) = 0.62 yielded albite + corundum at ≤1.60 GPa, and jadeite + kyanite at ≥1.70 GPa. The shift in the equilibrium pressure constrains a-X relations in the sytem H2O-NaCl and indicates that a(H2O) varies as nearly the square of its mole fraction. The results are consistent with the extrapolated non-ideal activity model of Aranovich and Newton (1996, CMP, 125, 200). Our results permit use of appropriate paragonite-bearing or -absent assemblages to quantify a(H2O) in high-P metamorphic environments, such as the Austroalpine units in the Western Alps. For example, jadeite and kyanite in a metapelite from Val Savenca in the Sesia Lanzo Zone formed during the Eo-Alpine high-P metamorphic event at 1.7-2.0 GPa, 550-650° C. The absence of paragonite requires a fluid with low a(H2O) of 0.3-0.6, which could be due to the presence of saline brines. Petrologic investigations of Sesia Lanzo eclogites from Val Ianca show that paragonite occurs as inclusions in garnet cores but gives way to omphacite + kyanite toward rims, suggesting a decrease in a(H2O) from ˜1.0 to <0.81 (Tropper and Essene, 2002, SMPM, 82, 487-514). During the subsequent hydration in

  20. Potential role of H2O2 in chemoreception in the cat carotid body.

    PubMed

    Osanai, S; Mokashi, A; Rozanov, C; Buerk, D G; Lahiri, S

    1997-03-19

    The hypothesis that H2O2 plays a critical role in hypoxic chemoreception in the cat carotid body (CB) was tested using a perfused-superfused preparation in vitro, measuring chemosensory discharge and CB tissue PO2 (PtiO2). According to the hypothesis NADPH mediated, PO2 dependent increase in H2O2 production would hyperpolarize the glomus cell, decreasing the chemosensory discharge. Thus, lactate and aminotriazole which would increase H2O2 concentration, would decrease the chemosensory discharge during hypoxia. However, 2.5-5.0 mM lactate and 25 mM aminotriazole did not diminish the hypoxic response. But, 2.5 mM lactate decreased the chemosensory discharge during normoxia which can be explained by an increase of CB PtiO2. Diethyldithiocarbamic acid (5 mM), which blocks the conversion of superoxide to H2O2, also diminished the chemosensory discharge, presumably due to an increased CB PtiO2. Menadione (increasing H2O2) and t-butyl hydroperoxide irreversibly decreased the chemosensory discharge, and the data are not useful. H2O2 increased the PO2 of the perfusate, and therefore could not be tested against PO2. Thus, perturbation of endogenous or exogenous H2O2 did not provide any evidence for its critical role in O2 chemoreception.

  1. Decoloration Kinetics of Waste Cooking Oil by 60Co γ-ray/H2O2

    NASA Astrophysics Data System (ADS)

    Xiang, Yulin; Xiang, Yuxiu; Wang, Lipeng

    2016-03-01

    In order to decolorize, waste cooking oil, a dark red close to black solution from homes and restaurants, was subjected to 60Co γ-ray/H2O2 treatment. By virtue of UV/Vis spectrophotometric method, the influence of Gamma irradiation to decoloration kinetics and rate constants of the waste cooking oil in the presence of H2O2 was researched. In addition, the influence of different factors such as H2O2 concentration and irradiation dose on the decoloration rate of waste cooking oil was investigated. Results indicated that the decoloration kinetics of waste cooking oil conformed to the first-order reaction. The decoloration rate increased with the increase of irradiation dose and H2O2 concentration. Saponification analysis and sensory evaluation showed that the sample by 60Co γ-ray/H2O2 treatment presented better saponification performance and sensory score. Furthermore, according to cost estimate, the cost of the 60Co γ-ray/H2O2 was lower and more feasible than the H2O2 alone for decoloration of waste cooking oil.

  2. H2O2 dynamics in the malaria parasite Plasmodium falciparum

    PubMed Central

    Rahbari, Mahsa; Bogeski, Ivan

    2017-01-01

    Hydrogen peroxide is an important antimicrobial agent but is also crucially involved in redox signaling and pathogen-host cell interactions. As a basis for systematically investigating intracellular H2O2 dynamics and regulation in living malaria parasites, we established the genetically encoded fluorescent H2O2 sensors roGFP2-Orp1 and HyPer-3 in Plasmodium falciparum. Both ratiometric redox probes as well as the pH control SypHer were expressed in the cytosol of blood-stage parasites. Both redox sensors showed reproducible sensitivity towards H2O2 in the lower micromolar range in vitro and in the parasites. Due to the pH sensitivity of HyPer-3, we used parasites expressing roGFP2-Orp1 for evaluation of short-, medium-, and long-term effects of antimalarial drugs on H2O2 levels and detoxification in Plasmodium. None of the quinolines or artemisinins tested had detectable direct effects on the H2O2 homeostasis at pharmacologically relevant concentrations. However, pre-treatment of the cells with antimalarial drugs or heat shock led to a higher tolerance towards exogenous H2O2. The systematic evaluation and comparison of the two genetically encoded cytosolic H2O2 probes in malaria parasites provides a basis for studying parasite-host cell interactions or drug effects with spatio-temporal resolution while preserving cell integrity. PMID:28369083

  3. EDTA and electricity synergetic catalyzed Fe(3+)/H2O2 process for amoxicillin oxidation.

    PubMed

    Shen, Ting-Ting; Li, Xiao-Ming; Tang, Yu-Fang; Wang, Juan; Yue, Xiu; Cao, Jian-Bin; Zheng, Wei; Wang, Dong-Bo; Zeng, Guang-Ming

    2009-01-01

    Three oxidation processes for amoxicillin wastewater pretreatment such as Electro-Fe(3+)(EDTA)/H2O2 (EDTA: ethylenediaminetetraacetic acid), Fe(3+)(EDTA)/H2O2 and Electro-Fe(3+)/H2O2 were simultaneously discussed at pH of 7.0 (+/-0.1). It was found that the above processes could achieve 78%, 64%, 33% chemical oxygen demand (COD(cr)) removal, and 86%, 70%, 47% amoxicillin degradation respectively. Moreover, the results of biodegradability (biological oxygen demand (BOD(5))/COD(cr) ratio) showed that the Electro-Fe(3+)(EDTA)/H2O2 process was a promising way to pretreat antibiotic wastewater due to the biodegradability of the effluent improved to 0.48 compared with the cases of Fe(3+)(EDTA)/H2O2 (0.40) and Electro-Fe(3+)/H2O2 process (0.12). Therefore, it was reasonable to note that EDTA and electricity showed synergetic effect on the oxidation process. Additionally, infrared spectra (IR) were applied to concisely propose a potential degradation way of amoxicillin. The characteristic changes of H2O2 and EDTA in the oxidation process were also investigated in detail.

  4. Peroxiredoxin-2 and STAT3 form a redox relay for H2O2 signaling.

    PubMed

    Sobotta, Mirko C; Liou, Willy; Stöcker, Sarah; Talwar, Deepti; Oehler, Michael; Ruppert, Thomas; Scharf, Annette N D; Dick, Tobias P

    2015-01-01

    Hydrogen peroxide (H(2)O(2)) acts as a signaling messenger by oxidatively modifying distinct cysteinyl thiols in distinct target proteins. However, it remains unclear how redox-regulated proteins, which often have low intrinsic reactivity towards H(2)O(2) (k(app) ∼1-10 M(-1) s(-1)), can be specifically and efficiently oxidized by H(2)O(2). Moreover, cellular thiol peroxidases, which are highly abundant and efficient H(2)O(2) scavengers, should effectively eliminate virtually all of the H(2)O(2) produced in the cell. Here, we show that the thiol peroxidase peroxiredoxin-2 (Prx2), one of the most H(2)O(2)-reactive proteins in the cell (k(app) ∼10(7)-10(8) M(-1) s(-1)), acts as a H(2)O(2) signal receptor and transmitter in transcription factor redox regulation. Prx2 forms a redox relay with the transcription factor STAT3 in which oxidative equivalents flow from Prx2 to STAT3. The redox relay generates disulfide-linked STAT3 oligomers with attenuated transcriptional activity. Cytokine-induced STAT3 signaling is accompanied by Prx2 and STAT3 oxidation and is modulated by Prx2 expression levels.

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

    PubMed

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

    2015-10-05

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

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

    DOE PAGES

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

    2015-09-17

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

  7. Optical Absorption and Photo-Thermal Conversion Properties of CuO/H2O Nanofluids.

    PubMed

    Wang, Liangang; Wu, Mingyan; Wu, Daxiong; Zhang, Canying; Zhu, Qunzhi; Zhu, Haitao

    2015-04-01

    Stable CuO/H2O nanofluids were synthesized in a wet chemical method. Optical absorption property of CuO/H2O nanofluids was investigated with hemispheric transmission spectrum in the wavelength range from 200 nm to 2500 nm. Photo-thermal conversion property of the CuO/H2O nanofluids was studied with an evaluation system equipped with an AUT-FSL semiconductor/solid state laser. The results indicate that CuO/H2O nanofluids have strong absorption in visible light region where water has little absorption. Under the irradiation of laser beam with a wavelength of 635 nm and a power of 0.015 W, the temperature of CuO/H2O nanofluids with 1.0% mass fraction increased by 5.6 °C within 40 seconds. Furthermore, the temperature elevation of CuO/H2O nanofluids was proved to increase with increasing mass fractions. On the contrast, water showed little temperature elevation under the identical conditions. The present work shows that the CuO/H2O nanofluids have high potential in the application as working fluids for solar utilization purpose.

  8. Tyrosine Kinase Signal Modulation: A Matter of H2O2 Membrane Permeability?

    PubMed Central

    Bertolotti, Milena; Bestetti, Stefano; García-Manteiga, Jose M.; Medraño-Fernandez, Iria; Dal Mas, Andrea; Malosio, Maria Luisa

    2013-01-01

    Abstract H2O2 produced by extracellular NADPH oxidases regulates tyrosine kinase signaling inhibiting phosphatases. How does it cross the membrane to reach its cytosolic targets? Silencing aquaporin-8 (AQP8), but not AQP3 or AQP4, inhibited H2O2 entry into HeLa cells. Re-expression of AQP8 with silencing-resistant vectors rescued H2O2 transport, whereas a C173A-AQP8 mutant failed to do so. Lowering AQP8 levels affected H2O2 entry into the endoplasmic reticulum, but not into mitochondria. AQP8 silencing also inhibited the H2O2 spikes and phosphorylation of downstream proteins induced by epidermal growth factor. These observations lead to the hypothesis that H2O2 does not freely diffuse across the plasma membrane and AQP8 and other H2O2 transporters are potential targets for manipulating key signaling pathways in cancer and degenerative diseases. Antioxid. Redox Signal. 19, 1447–1451. PMID:23541115

  9. Post-treatment of palm oil mill effluent (POME) using combined persulphate with hydrogen peroxide (S2O8(2-)/H2O2) oxidation.

    PubMed

    Lin, Chia Ken; Bashir, Mohammed J K; Abu Amr, Salem S; Sim, Lan Ching

    2016-12-01

    The aim of the current study is to evaluate the effectiveness of combined persulphate with hydrogen peroxide (S2O8(2-)/H2O2) oxidation as a post-treatment of biologically treated palm oil mill effluent (POME) for the first time in the literature. The removal efficiencies of chemical oxygen demand (COD), ammoniacal nitrogen (NH3-N), and suspended solids (SS) were 36.8%, 47.6%, and 90.6%, respectively, by S2O8(2-) oxidation alone under certain operation conditions (i.e., S2O8(2-) = 0.82 g, pH 11, and contact time 20 min). Nevertheless, the combined process (S2O8(2-)/H2O2) achieved 75.8% and 87.1% removals of NH3-N and SS, respectively, under 2.45/1.63 g/g H2O2/S2O8(2-), pH 11, and 20 min oxidation. Moreover, 56.9% of COD was removed at pH 8.4.

  10. Stability and prospect of UV/H2O2 activated titania films for biomedical use

    NASA Astrophysics Data System (ADS)

    Unosson, Erik; Welch, Ken; Persson, Cecilia; Engqvist, Håkan

    2013-11-01

    Biomedical implants and devices that penetrate soft tissue are highly susceptible to infection, but also accessible for UV induced decontamination through photocatalysis if coated with suitable surfaces. As an on-demand antibacterial strategy, photocatalytic surfaces should be able to maintain their antibacterial properties over repeated activation. This study evaluates the surface properties and photocatalytic performance of titania films obtained by H2O2-oxidation and heat treatment of Ti and Ti-6Al-4V substrates, as well as the prospect of assisting photocatalytic reactions with H2O2 for improved efficiency. H2O2-oxidation generated a nanoporous coating, and subsequent heat treatment above 500 °C resulted in anatase formation. Tests using photo-assisted degradation of rhodamine B showed that prior to heat treatment, an initially high photocatalytic activity (PCA) of H2O2-oxidized substrates decayed significantly with repeated testing. Heat treating the samples at 600 °C resulted in stable yet lower PCA. Addition of 3% H2O2 during the photo-assisted reaction led to a substantial increase in PCA due to synergetic effects at the surface and H2O2 photolysis, the effect being most notable for non-heat treated samples. Both heat treated and non-heat treated samples showed stable PCA through repeated tests with H2O2-assisted photocatalysis, indicating that the combination of H2O2-oxidized titania films, UV light and added H2O2 can improve efficiency of these photocatalytic surfaces.

  11. H2O content of nominally anhydrous mineral inclusions in diamonds from the Udachnaya kimberlite

    NASA Astrophysics Data System (ADS)

    Novella, D.; Bolfan-Casanova, N.; Nestola, F.; Harris, J. W.

    2015-12-01

    Nominally anhydrous minerals (such as olivine, pyroxene and garnet) present in mantle xenoliths have been found to contain up to hundreds of ppm wt H2O, bonded as H to their mineral structure. However, it is not well understood whether these H2O contents are representative for the hydrous state of the deep mantle where they formed, or if they are the result of interactions between the xenoliths and metasomatic fluids or magmas during their travel to the surface. Given the fact that trace amounts of H2O can alter the physical and chemical properties of mantle materials and therefore affect Earth's dynamics, it is important to accurately determine the H2O content of deep mantle minerals. Natural diamonds can contain mineral inclusions that formed at high depths (>5 GPa) and are representative for the deep and inaccessible portions of the mantle where they originated. This is because the strong and inert diamond prevents the inclusions to react with any fluid or melt that get in contact with it. Therefore, valuable information regarding the H2O content of the deep mantle can be obtained by studying these minerals trapped in diamonds. In this study we measured the H2O contents of 10 olivine and garnet inclusions in diamonds from the Udachnaya kimberlite (Siberian craton) by Fourier Transform Infrared spectroscopy. Olivine crystals contain 1-5 ppm wt H2O while garnets do not show absorption bands indicating the presence of detectable H in their structure and are therefore considered dry. The H2O contents of olivine and garnet inclusions in diamonds presented here are considerably lower than those found in xenoliths or xenocrists from the same locality. Based on these new results, we discuss the presence of H2O in the cratonic mantle and its importance in stabilizing these areas during geological time, as well as the volatile signature of diamond forming melts in the Siberian craton.

  12. Production of superoxide/H2O2 by dihydroorotate dehydrogenase in rat skeletal muscle mitochondria.

    PubMed

    Hey-Mogensen, Martin; Goncalves, Renata L S; Orr, Adam L; Brand, Martin D

    2014-07-01

    Dehydrogenases that use ubiquinone as an electron acceptor, including complex I of the respiratory chain, complex II, and glycerol-3-phosphate dehydrogenase, are known to be direct generators of superoxide and/or H2O2. Dihydroorotate dehydrogenase oxidizes dihydroorotate to orotate and reduces ubiquinone to ubiquinol during pyrimidine metabolism, but it is unclear whether it produces superoxide and/or H2O2 directly or does so only indirectly from other sites in the electron transport chain. Using mitochondria isolated from rat skeletal muscle we establish that dihydroorotate oxidation leads to superoxide/H2O2 production at a fairly high rate of about 300pmol H2O2·min(-1)·mg protein(-1) when oxidation of ubiquinol is prevented and complex II is uninhibited. This H2O2 production is abolished by brequinar or leflunomide, known inhibitors of dihydroorotate dehydrogenase. Eighty percent of this rate is indirect, originating from site IIF of complex II, because it can be prevented by malonate or atpenin A5, inhibitors of complex II. In the presence of inhibitors of all known sites of superoxide/H2O2 production (rotenone to inhibit sites in complex I (site IQ and, indirectly, site IF), myxothiazol to inhibit site IIIQo in complex III, and malonate plus atpenin A5 to inhibit site IIF in complex II), dihydroorotate dehydrogenase generates superoxide/H2O2, at a small but significant rate (23pmol H2O2·min(-1)·mg protein(-1)), from the ubiquinone-binding site. We conclude that dihydroorotate dehydrogenase can generate superoxide and/or H2O2 directly at low rates and is also capable of indirect production at higher rates from other sites through its ability to reduce the ubiquinone pool.

  13. Quantum/classical studies of vibrationally mediated photodissociation of Ar x H2O.

    PubMed

    Chen, Feng; McCoy, Anne B

    2008-10-02

    Results of multiple configuration quantum/classical simulations of the dynamics of Ar x H2O photodissociation are reported. In agreement with experimental studies of Nesbitt and co-workers [J. Chem. Phys. 2000, 112, 7449], we find that the OH products emerge rotationally excited, compared to the dissociation of bare H2O. The wavelength dependence of the total cross section and the energy transfer to the argon atom are also investigated. The trends are interpreted in terms of features in the Ar x H2O A state potential surface.

  14. Confinement Effects on the Nuclear Spin Isomer Conversion of H2O.

    PubMed

    Turgeon, Pierre-Alexandre; Vermette, Jonathan; Alexandrowicz, Gil; Peperstraete, Yoann; Philippe, Laurent; Bertin, Mathieu; Fillion, Jean-Hugues; Michaut, Xavier; Ayotte, Patrick

    2017-03-02

    The mechanism for interconversion between the nuclear spin isomers (NSI) of H2O remains shrouded in uncertainties. The temperature dependence displayed by NSI interconversion rates for H2O isolated in an argon matrix provides evidence that confinement effects are responsible for the dramatic increase in their kinetics with respect to the gas phase, providing new pathways for o-H2O↔p-H2O conversion in endohedral compounds. This reveals intramolecular aspects of the interconversion mechanism which may improve methodologies for the separation and storage of NSI en route to applications ranging from magnetic resonance spectroscopy and imaging to interpretations of spin temperatures in the interstellar medium.

  15. H2O and CO2 in magmas from the Mariana arc and back arc systems

    NASA Astrophysics Data System (ADS)

    Newman, Sally; Stolper, Edward; Stern, Robert

    2000-05-01

    We examined the H2O and CO2 contents of glasses from lavas and xenoliths from the Mariana arc system, an intraoceanic convergent margin in the western Pacific, which contains an active volcanic arc, an actively spreading back arc basin, and active behind-the-arc cross-chain volcanoes. Samples include (1) glass rims from Mariana arc, Mariana trough, and cross-chain submarine lavas; (2) glass inclusions in arc and trough phenocrysts; and (3) glass inclusions from a gabbro + anorthosite xenolith from Agrigan (Mariana arc). Glass rims of submarine arc lavas contain 0.3-1.9 wt % H2O, and CO2 is below detection limits. Where they could be compared, glass inclusions in arc phenocrysts contain more H2O than their host glasses; most arc glasses and phenocryst inclusions contain no detectable CO2, with the exception of those from a North Hiyoshi shoshonite, which contains 400-600 ppm. The glass inclusions from the Agrigan xenolith contain 4-6% H2O, and CO2 is below the detection limit. Glasses from the cross-chain lavas are similar to those from the arc: H2O contents are 1.4-1.7 wt %, and CO2 is below detection limits. Volatile contents in Mariana trough lava glass rims are variable: 0.2-2.8 wt % H2O and 0-300 ppm CO2. Glass inclusions from trough phenocrysts have water contents similar to the host glass, but they can contain up to 875 ppm CO2. Volatile contents of melt inclusions from trough and arc lavas and from the xenolith imply minimum depths of crystallization of ~1-8 km. H2O and CO2 contents of Mariana trough glasses are negatively correlated, indicating saturation of the erupting magma with a CO2-H2O vapor at the pressure of eruption (~400 bars for these samples), with the vapor ranging from nearly pure CO2 at the CO2-rich end of the glass array to nearly pure H2O at the H2O-rich end. Degassing of these magmas on ascent and eruption leads to significant loss of CO2 (thereby masking preeruptive CO2 contents) but minimal disturbance of preeruptive H2O contents. For

  16. Do aerosols influence the diurnal variation of H2O2 in the atmosphere?

    NASA Astrophysics Data System (ADS)

    Liang, H.; Chen, Z.; Wu, Q.; Huang, D.; Zhao, Y.

    2013-12-01

    Hydrogen peroxide (H2O2) and organic peroxides are crucial reactive species that are involved in the cycling of HOx (OH and HO2) radicals and the formation of secondary inorganic and organic aerosols in the atmosphere. Despite the importance of peroxides, their formation and removal mechanisms with the coexistence of aerosols are as yet less well known. From June 10 to July 15 2013, summertime surface measurements for atmospheric peroxides were simultaneously obtained in urban Beijing (UB) and Gucheng (GC). The UB site is located in the northern downtown of Beijing city, while the GC site is a rural site located in the North China Plain and ~100 km southwest of Beijing. In both sites, the major peroxides were determined to be H2O2, methyl hydroperoxide (MHP), peroxyformic acid (PFA) and peroxyacetic acid (PAA). By comparing the concentrations of PFA and PAA in the gas phase and rainwater, for the first time, we estimated the Henry's law constant for PFA as ~210 M atm-1 at 298 K, a quarter of that for PAA. Interestingly, we observed different H2O2 profiles in the two sites as follows: (i) the average concentration of H2O2 in UB was 50% higher than that in GC; (ii) H2O2 in GC reached its peak concentration at around 15:30, whereas the peak concentration in UB appeared at as late as 21:00; and (iii) the daily variation of H2O2 in GC generally kept consistent with that of O3 and organic peroxides while it was not always the case in UB. These differences indicate a hitherto unrecognized storage-release mechanism for H2O2 in UB, that is, an extra sink in the noontime and an extra source in the early evening. The extra source of H2O2 would enhance the aerosol phase OH radical in the early evening by the Fenton reaction. A box model analysis shows that the impacts of aerosols were majorly responsible to this unrecognized mechanism, although NOx, regional transport and planet boundary layer height also contributed a minor part. Aerosols participated in the storage

  17. Distribution, structure, and dynamics of cesium and iodide ions at the H2O-CCl4 and H2O-vapor interfaces.

    PubMed

    Wick, Collin D; Dang, Liem X

    2006-04-06

    Molecular dynamics simulations utilizing many-body potentials of H2O-CCl4 and H2O-vapor interfaces were carried out at different cesium and iodide ion concentrations to compare ion distribution, interfacial orientational and structural properties, and dynamics. It was found that cesium was repelled by both interfaces, and iodide was active at both interfaces, but to a much greater degree at the H2O-vapor interface. At the interface, the iodide dipole was strongly induced, orienting perpendicular to the interface for both systems, leading to stronger hydrogen bonds with water. For the H2O-CCl4 interface, though, there was a compensation between these strong hydrogen bonds and short to moderate ranged repulsion between iodide and CCl4. Hydrogen bond distance and angular distributions showed weaker water-water hydrogen bonds at both interfaces, but generally stronger water-iodide hydrogen bonds. Both translational and rotational dynamics of water were faster at the interface, while for CCl4, its translational dynamics was slower, but rotational dynamics faster at the interface. For many of the studied systems and species, translational diffusion was found to be anisotropic at both interfacial and bulk regions.

  18. An Investigation of Armenite, BaCa2Al6Si9O302H2O.H2O Molecules and H Bonding in Microporous Silicates

    NASA Astrophysics Data System (ADS)

    Geiger, C. A.; Gatta, G.; Xue, X.; McIntyre, G.

    2012-12-01

    The crystal chemistry of armenite, ideally BaCa2Al6Si9O30.2H2O, a double-ring structure belonging to the milarite group, was studied to better understand the nature of extra-framework "Ca-oxygen-anion-H2O-molecule quasi-clusters" and H bonding behavior in microporous silicates. Neutron and X-ray single-crystal diffraction and IR powder and 1H NMR spectroscopic measurements were made. Four crystallographically independent Ca and H2O molecule sites were refined from the diffraction data, whereby both sites appear to have partial occupancies such that locally a Ca atom can have only a single H2O molecule bonded to it through an ion-dipole interaction. The Ca cation is further bonded to six O atoms of the framework forming a quasi cluster around it. The neutron results give the first static description of the protons in armenite, allowing bond distances and angles relating to the H2O molecules and H bonds to be determined. The IR spectrum of armenite is characterized in the OH-stretching region at RT by two broad bands at roughly 3470 and 3410 cm-1 and by a single H2O bending mode at 1654 cm-1. At 10 K four intense OH bands are located at 3479, 3454, 3401 and 3384 cm-1 and two H2O bending modes at 1650 and 1606 cm-1. The 1H MAS NMR spectrum shows a single strong resonance near 5.3 ppm and a smaller one near 2.7 ppm. The former can be assigned to H2O molecules bonded to Ca and the latter to weakly bonded H2O located at a site at the center of the structural double ring and it is partially occupied. The nature of H bonding in the microporous Ca-bearing zeolites scolecite, wairakite and epistilbite are also analyzed. The average OH stretching wavenumber shown by the IR spectra of armenite (~3435 cm-1) and scolecite (~3430 cm-1) are similar, while the average OH wavenumbers for wairakite (~3475 cm-1) and epistilbite (~3500 cm-1) are greater. In all cases the average OH stretching wavenumber is more similar to that of liquid water (~3400 cm-1) than of ice (~3220 cm-1). The

  19. Phase relations of phlogopite and pyroxene with magnesite from 4 to 8 GPa: KCMAS-H2O and KCMAS-H2O-CO2

    NASA Astrophysics Data System (ADS)

    Enggist, Andreas; Luth, Robert W.

    2016-11-01

    To constrain the melting phase relationships of phlogopite and magnesite in the presence of clino- and orthopyroxene, we performed experiments in the K2O-CaO-MgO-Al2O3-SiO2-H2O (KCMAS-H2O) and K2O-CaO-MgO-Al2O3-SiO2-H2O-CO2 (KCMAS-H2O-CO2) systems at pressures of 4-8 GPa and temperatures from 1100 to 1600 °C. We bracketed the carbonate-free solidus between 1250 and 1300 °C at 4 and 5 GPa, and between 1300 and 1350 °C at 6, 7 and 8 GPa. The carbonate-bearing solidus was bracketed between 1150 and 1200 °C at 4, 5 and 6 GPa, and between 1100 and 1150 °C at 7 and 8 GPa. Below the solidus in both systems at 4-6 GPa, phlogopite is in equilibrium with enstatite, diopside, garnet (plus magnesite in the carbonate-bearing system) and a fluid. At 7 GPa, phlogopite coexists with KK-richterite, enstatite, diopside, garnet (plus magnesite in the carbonate-bearing system) and a fluid. KK-richterite is the only stable K-bearing phase at 8 GPa and coexists with enstatite, diopside, garnet (plus magnesite in the carbonate-bearing system) and a fluid. In KCMAS-H2O, phlogopite is present to 100 °C above the solidus. Olivine forms at the solidus and coexists with enstatite, diopside, garnet and melt. At depth in a subcontinental lithospheric mantle keel, phlogopite would be stable with orthopyroxene, clinopyroxene and magnesite to 5 GPa along a 40 mW/m2 geotherm. A hydrous, potassic and CO2-bearing melt that intrudes the subcontinental mantle can react with olivine, enstatite and garnet, crystallizing phlogopite, magnesite and potentially liberating a hydrous fluid.

  20. KCo(H2O)2BP2O8·0.48H2O and K0.17Ca0.42Co(H2O)2BP2O8·H2O: two cobalt borophosphates with helical ribbons and disordered (K,Ca)/H2O schemes.

    PubMed

    Guesmi, Abderrahmen; Driss, Ahmed

    2012-08-01

    The two title compounds, potassium diaquacobalt(II) borodiphosphate 0.48-hydrate and potassium-calcium(0.172/0.418) diaquacobalt(II) borodiphosphate monohydrate, were synthesized hydrothermally. They are new members of the borophosphate family characterized by (∞)[BP(2)O(8)](3-) helices running along [001] and constructed of boron (Wyckoff position 6b, twofold axis) and phosphorus tetrahedra. The [CoBP(2)O(8)](-) anionic frameworks in the two materials are structurally similar and result from a connection in the ab plane between the CoO(4)(H(2)O)(2) coordination octahedra (6b position) and the helical ribbons. Nevertheless, the two structures differ in the disorder schemes of the K,Ca and H(2)O species. The alkali cations in the structure of the pure potassium compound are disordered over three independent positions, one of them located on a 6b site. Its framework is characterized by double occupation of the tunnels by water molecules located on twofold rotation axes (6b) and a fraction of alkali cations; its cell parameters, compared with those for the mixed K,Ca compound, show abnormal changes, presumably due to the disorder. For the K,Ca compound, the K and Ca cations are on twofold axes (6b) and the channels are occupied only by disordered solvent water molecules. This shows that it is possible, due to the flexibility of the helices, to replace the alkali and alkaline earth cations while retaining the crystal framework.

  1. 40 CFR 1065.370 - CLD CO2 and H2O quench verification.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... analyzer uses quench compensation algorithms that utilize H2O and/or CO2 measurement instruments, evaluate quench with these instruments active and evaluate quench with the compensation algorithms applied....

  2. Study of the K2Ni(SO4)2 • 6H2O-K2Co(SO4)2 • 6H2O-H2O diagram and determination of the conditions for growing K2(Ni,Co)(SO4)2 • 6H2O mixed crystals

    NASA Astrophysics Data System (ADS)

    Zhokhov, A. A.; Masalov, V. M.; Zverkova, I. I.; Emelchenko, G. A.; Manomenova, V. L.; Rudneva, E. B.; Vasilieva, N. A.; Voloshin, A. E.

    2016-11-01

    The phase diagram of the K2Ni(SO4)2 · 6H2O-K2Co(SO4)2 · 6H2O-H2O ternary system is investigated in the temperature range of 30-70°C, and a relationship between the compositions of the equilibrium phases of the K2Co x Ni(1- x)(SO4)2 · 6H2O (KCNSH) solid solution and the growth solution is established. It is shown how the salt compositions of the liquid and solid phases change during crystal growth upon slow cooling of solution. A dependence of the lattice parameters of the KCNSH solid solution on the concentration of isomorphic components is experimentally found.

  3. Detection of label-free H2O2 based on sensitive Au nanorods as sensor.

    PubMed

    Shan, Guiye; Zheng, Shujing; Chen, Shaopeng; Chen, Yanwei; Liu, Yichun

    2013-02-01

    A rapid, reproducible, cost-effective approaches for the detection of hydrogen peroxide has been developed based on the change of localized surface plasmon resonance (LSPR) peak of Au nanorods (NRs). Au NRs were prepared by silver ion-assisted seed-mediated method, which are characterized by UV-vis spectroscopy and transmission electron microscopy. The longitudinal plasmon band of Au nanorods is highly sensitive to their aspect ratios so that LSPR peak of Au NRs was shift with change of their aspect ratios. Hydrogen peroxide (H(2)O(2)) with high oxidation potential can decompose Au NRs. As a result, Au NRs can be shortened through an oxidation reaction by H(2)O(2). After shortening Au NRs, the LSPR peaks show blue shift. The LSPR peak of Au NRs displays the dependence of spectral shift on concentration of H(2)O(2). It provides a more simple and sensitive method for detecting H(2)O(2).

  4. The condensation and vaporization behavior of H2O:CO ices and implications for interstellar grains and cometary activity

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Allamandola, Louis J.

    1988-01-01

    IR spectroscopy has been used to ascertain several parameters associated with CO, H2O, and H2O:CO ices' physical behavior. Since CO is noted to be capable of condensing into H2O-rich ices at temperatures that are twice as high as those required for condensation in pure CO, CO is able to condense onto H2O-rich ice grains at temperatures of up to 50 K. CO's presence in H2O ice modestly enhances the effective volatility of the H2O. Attention is given to the implications of these results for cometary models generally and the question of cometary formation specifically.

  5. Prediction of Arc Magma Water Contents via Measurement of H2O in Clinopyroxene

    NASA Astrophysics Data System (ADS)

    Wade, J. A.; Plank, T.; Hauri, E.; Roggensack, K.; Kelley, K.

    2006-12-01

    Water is fundamental to arc magma genesis, evolution, and eruption, but most models make predictions that have yet to be tested against actual pre-eruptive H2O measurements. This is because few direct measurements of H2O have been made in arc volcanoes, as rocks found at the surface have extensively degassed upon eruption. We present here a new method for calculating pre-eruptive magmatic H2O, which corresponds closely to water contents measured directly in olivine-hosted melt inclusions. We picked clinopyroxene (cpx) phenocrysts from ash/lapilli samples from 4 volcanoes whose magmatic H2O contents span the global range: Galunggung (Java), Irazu (Costa Rica), Arenal (Costa Rica), and Cerro Negro (Nicaragua). Nominally anhydrous minerals (NAM's) such as pyroxene and olivine can incorporate non-trivial amounts of water into their crystal structures, and water contents in these arc cpx range from ~ 40 - 900 ppm (measured by SIMS ion microprobe). Transects across several grains reveal high H2O in the cores, which decreases towards the rim along with Mg#, Al, and Ca. For example, Irazu cpx range from > 300 ppm H2O at Mg# 88 to < 150 ppm wt% H2O at Mg# 72. These features are most likely the result of growth zoning that develops during degassing and fractionation, giving insight into magmatic evolution during ascent that neither whole rocks nor melt inclusions typically yield. In order to quantify water concentrations of liquids in equilibrium with the cpx, we have used the Al(IV)-dependent partitioning relationship described by Hauri et al. (2006). In all 4 volcanoes, calculated maximum magmatic H2O contents agree remarkably well with melt inclusion data from the same samples: 0.45, 3.4, 4.3, and 6.5 wt% H2O in Galunggung, Irazu, Arenal, and Cerro Negro, respectively. In the Central American samples, water contents also correlate with Sr/Nd in the cpx (measured by LA-ICP-MS), as predicted by models for slab fluid compositions. The H2O-Sr/Nd trend preserved in the cpx

  6. TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OLS)

    Atmospheric Science Data Center

    2016-10-25

    TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OLS) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  27 x 23 km Limb ... Access:  OPeNDAP Parameters:  H2O Water Volume Mixing Radio Precision Vertical Resolution Order ...

  7. Radiolysis of H2O:CO2 ices by heavy energetic cosmic ray analogs

    NASA Astrophysics Data System (ADS)

    Pilling, S.; Seperuelo Duarte, E.; Domaracka, A.; Rothard, H.; Boduch, P.; da Silveira, E. F.

    2010-11-01

    An experimental study of the interaction of heavy, highly charged, and energetic ions (52 MeV 58Ni13+) with pure H2O, pure CO2 and mixed H2O:CO2 astrophysical ice analogs is presented. This analysis aims to simulate the chemical and the physicochemical interactions induced by heavy cosmic rays inside dense and cold astrophysical environments, such as molecular clouds or protostellar clouds. The measurements were performed at the heavy ion accelerator GANIL (Grand Accélérateur National d'Ions Lourds in Caen, France). The gas samples were deposited onto a CsI substrate at 13 K. In-situ analysis was performed by a Fourier transform infrared (FTIR) spectrometer at different fluences. Radiolysis yields of the produced species were quantified. The dissociation cross sections of pure H2O and CO2 ices are 1.1 and 1.9 × 10-13 cm2, respectively. For mixed H2O:CO2 (10:1), the dissociation cross sections of both species are about 1 × 10-13 cm2. The measured sputtering yield of pure CO2 ice is 2.2 × 104 molec ion-1. After a fluence of 2-3 × 1012 ions cm-2, the CO2/CO ratio becomes roughly constant (~0.1), independent of the initial CO2/H2O ratio. A similar behavior is observed for the H2O2/H2O ratio, which stabilizes at 0.01, independent of the initial H2O column density or relative abundance.

  8. Drosophila TRPA1 isoforms detect UV light via photochemical production of H2O2

    PubMed Central

    Guntur, Ananya R.; Gu, Pengyu; Takle, Kendra; Chen, Jingyi; Xiang, Yang; Yang, Chung-Hui

    2015-01-01

    The transient receptor potential A1 (TRPA1) channel is an evolutionarily conserved detector of temperature and irritant chemicals. Here, we show that two specific isoforms of TRPA1 in Drosophila are H2O2 sensitive and that they can detect strong UV light via sensing light-induced production of H2O2. We found that ectopic expression of these H2O2-sensitive Drosophila TRPA1 (dTRPA1) isoforms conferred UV sensitivity to light-insensitive HEK293 cells and Drosophila neurons, whereas expressing the H2O2-insensitive isoform did not. Curiously, when expressed in one specific group of motor neurons in adult flies, the H2O2-sensitive dTRPA1 isoforms were as competent as the blue light-gated channelrhodopsin-2 in triggering motor output in response to light. We found that the corpus cardiacum (CC) cells, a group of neuroendocrine cells that produce the adipokinetic hormone (AKH) in the larval ring gland endogenously express these H2O2-sensitive dTRPA1 isoforms and that they are UV sensitive. Sensitivity of CC cells required dTRPA1 and H2O2 production but not conventional phototransduction molecules. Our results suggest that specific isoforms of dTRPA1 can sense UV light via photochemical production of H2O2. We speculate that UV sensitivity conferred by these isoforms in CC cells may allow young larvae to activate stress response—a function of CC cells—when they encounter strong UV, an aversive stimulus for young larvae. PMID:26443856

  9. H2O2-dependent substrate oxidation by an engineered diiron site in a bacterial hemerythrin.

    PubMed

    Okamoto, Yasunori; Onoda, Akira; Sugimoto, Hiroshi; Takano, Yu; Hirota, Shun; Kurtz, Donald M; Shiro, Yoshitsugu; Hayashi, Takashi

    2014-04-04

    The O2-binding carboxylate-bridged diiron site in DcrH-Hr was engineered in an effort to perform the H2O2-dependent oxidation of external substrates. A His residue was introduced near the diiron site in place of a conserved residue, Ile119. The I119H variant promotes the oxidation of guaiacol and 1,4-cyclohexadiene upon addition of H2O2.

  10. Accumulation of 2H2O in plasma and eccrine sweat during exercise-heat stress.

    PubMed

    Armstrong, Lawrence E; Klau, Jennifer F; Ganio, Matthew S; McDermott, Brendon P; Yeargin, Susan W; Lee, Elaine C; Maresh, Carl M

    2010-02-01

    The purpose of this research was to characterize the movement of ingested water through body fluids, during exercise-heat stress. Deuterium oxide ((2)H(2)O) accumulation in plasma and eccrine sweat was measured at two sites (back and forehead). The exercise of 14 males was controlled via cycle ergometry in a warm environment (60 min; 28.7 degrees C, 51%rh). Subjects consumed (2)H(2)O (0.15 mg kg(-1), 99.9% purity) mixed in flavored, non-caloric, colored water before exercise, then consumed 3.0 ml kg(-1) containing no (2)H(2)O every 15 min during exercise. We hypothesized that water transit from mouth to skin would occur before 15 min. (2)H(2)O appeared rapidly in both plasma and sweat (P < 0.05), within 10 min of water consumption. The ratio (2)H(2)O/H(2)O (D:H) was 47.3-55.0 times greater in plasma than in back sweat at minutes 10, 20, and 30 (DeltaD:H relative to baseline). At elapsed minute 20, the mean rate of deuterium accumulation (DeltaD:H min(-1)) in plasma was 14.9 and 23.7 times greater than in forehead and back sweat samples, respectively. Mean (+/-SE) whole-body sweat rate was 1.04 +/- 0.05 L h(-1) and subjects with the greatest whole-body sweat rate exhibited the greatest peak deuterium enrichment in sweat (r(2) = 0.87, exponential function); the peak (2)H(2)O enrichment in sweat was not proportional (P > 0.05) to body mass, volume of the deuterium dose, or total volume of fluid consumed. These findings clarify the time course of fluid movement from mouth to eccrine sweat glands, and demonstrate considerable differences of (2)H(2)O enrichment in plasma versus sweat.

  11. Drosophila TRPA1 isoforms detect UV light via photochemical production of H2O2.

    PubMed

    Guntur, Ananya R; Gu, Pengyu; Takle, Kendra; Chen, Jingyi; Xiang, Yang; Yang, Chung-Hui

    2015-10-20

    The transient receptor potential A1 (TRPA1) channel is an evolutionarily conserved detector of temperature and irritant chemicals. Here, we show that two specific isoforms of TRPA1 in Drosophila are H2O2 sensitive and that they can detect strong UV light via sensing light-induced production of H2O2. We found that ectopic expression of these H2O2-sensitive Drosophila TRPA1 (dTRPA1) isoforms conferred UV sensitivity to light-insensitive HEK293 cells and Drosophila neurons, whereas expressing the H2O2-insensitive isoform did not. Curiously, when expressed in one specific group of motor neurons in adult flies, the H2O2-sensitive dTRPA1 isoforms were as competent as the blue light-gated channelrhodopsin-2 in triggering motor output in response to light. We found that the corpus cardiacum (CC) cells, a group of neuroendocrine cells that produce the adipokinetic hormone (AKH) in the larval ring gland endogenously express these H2O2-sensitive dTRPA1 isoforms and that they are UV sensitive. Sensitivity of CC cells required dTRPA1 and H2O2 production but not conventional phototransduction molecules. Our results suggest that specific isoforms of dTRPA1 can sense UV light via photochemical production of H2O2. We speculate that UV sensitivity conferred by these isoforms in CC cells may allow young larvae to activate stress response--a function of CC cells--when they encounter strong UV, an aversive stimulus for young larvae.

  12. Detection of hydrogen peroxide (H2O2) in the Martian atmosphere with MEX / PFS

    NASA Astrophysics Data System (ADS)

    Aoki, S.; Kasaba, Y.; Giuranna, M.; Geminale, A.; Sindoni, G.; Nakagawa, H.; Kasai, Y.; Murata, I.; Grassi, D.; Formisano, V.

    2011-10-01

    We first derived the long-term averaged abundance of hydrogen peroxide (H2O2) in the Martian atmosphere with data sets of Planetary Fourier Spectroscopy (PFS) onboard Mars Express (MEX). The total averaged amounts of H2O2 at three Martian years were 45 ± 21 ppb and 25 ± 18 ppb in the forward/reverse pendulum direction, respectively. It could not explain the observed short lifetime of CH4 in the Martian atmosphere.

  13. Ferric and cupric ions requirement for DNA single-strand breakage by H2O2.

    PubMed

    Tachon, P

    1989-01-01

    Hydrogen peroxide (H2O2), was able to nick the replicative form of the phage fd, without the addition of a reducing agent or of a metal. This DNA single-strand breakage decreased with an increase of the ionic strength, suggesting that H2O2 reacted with traces of metal bound to DNA. When cupric of ferric ions were added, the rate of DNA single-strand breakage by H2O2 greatly increased and it was 20-30 times faster with cupric than with ferric ions. The addition of EDTA at an equimolar ratio or in excess of metal prevented partially DNA single-strand cleavage by H2O2 in the presence of ferric ions and completely when cupric ions were used. Superoxide dismutase prevented DNA single-strand breakage by H2O2 and ferric ions. On the contrary, with cupric ions and H2O2, the addition of superoxide dismutase increased the rate of DNA single-strand breakage. That superoxide dismutase was acting catalytically was shown by the loss of its effects after heat inactivation of the enzyme. The results of the present study show that besides its involvement in the Fenton reaction, H2O2 is able to reduce the metal bound to DNA, generating the superoxide anion radical or/and its protonated form, the perhydroxyl radical involved in DNA nicking. On the other hand, the ability of cuprous ions unlike ferrous ions to dismutate the superoxide radical may explain some differences observed between iron and copper in the DNA single-strand breakage by H2O2.

  14. Catalase evolved to concentrate H2O2 at its active site.

    PubMed

    Domínguez, Laura; Sosa-Peinado, Alejandro; Hansberg, Wilhelm

    2010-08-01

    Catalase is a homo-tetrameric enzyme that has its heme active site deeply buried inside the protein. Its only substrate, hydrogen peroxide (H2O2), reaches the heme through a 45 A-long channel. Large-subunit catalases, but not small-subunit catalases, have a loop (gate loop) that interrupts the major channel. Two accesses lead to a gate that opens the final section of the channel to the heme; gates from the R-related subunits are interconnected. Using molecular dynamic simulations of the Neurospora crassa catalase-1 tetramer in a box of water (48,600 molecules) or 6M H2O2, it is shown that the number of H2O2 molecules augments at the surface of the protein and in the accesses to the gate and the final section of the channel. Increase in H2O2 is due to the prevalence and distribution of amino acids that have an increased residency for H2O2 (mainly histidine, proline and charged residues), which are localized at the protein surface and the accesses to the gate. In the section of the channel from the heme to the gate, turnover rate of water molecules was faster than for H2O2 and increased residence sites for water and H2O2 were determined. In the presence of H2O2, the exclusion of water molecules from a specific site suggests a mechanism that could contend with the competing activity of water, allowing for catalase high kinetic efficiency.

  15. Main species and chemical pathways in cold atmospheric-pressure Ar + H2O plasmas

    NASA Astrophysics Data System (ADS)

    Liu, Dingxin; Sun, Bowen; Iza, Felipe; Xu, Dehui; Wang, Xiaohua; Rong, Mingzhe; Kong, Michael G.

    2017-04-01

    Cold atmospheric-pressure plasmas in Ar + H2O gas mixtures are a promising alternative to He + H2O plasmas as both can produce reactive oxygen species of relevance for many applications and argon is cheaper than helium. Although He + H2O plasmas have been the subject of multiple experimental and computational studies, Ar + H2O plasmas have received less attention. In this work we investigate the composition and chemical pathways in Ar + H2O plasmas by means of a global model that incorporates 57 species and 1228 chemical reactions. Water vapor concentrations from 1 ppm to saturation (32 000 ppm) are considered in the study and abrupt transitions in power dissipation channels, species densities and chemical pathways are found when the water concentration increases from 100 to 1000 ppm. In this region the plasma transitions from an electropositive discharge in which most power is coupled to electrons into an electronegative one in which most power is coupled to ions. While increasing electronegativity is also observed in He + H2O plasmas, in Ar + H2O plasmas the transition is more abrupt because Penning processes do not contribute to gas ionization and the changes in the electron energy distribution function and mean electron energy caused by the increasing water concentration result in electron-neutral excitation and ionization rates changing by many orders of magnitude in a relatively small range of water concentrations. Insights into the main chemical species and pathways governing the production and loss of electrons, O, OH, OH(A) and H2O2 are provided as part of the study.

  16. Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

    PubMed Central

    Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

    2017-01-01

    Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32−, SO42−) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments. PMID:28262831

  17. Fluorescent gold nanoclusters based photoelectrochemical sensors for detection of H2O2 and glucose.

    PubMed

    Zhang, Jianxiu; Tu, Liping; Zhao, Shuang; Liu, Guohua; Wang, Yangyun; Wang, Yong; Yue, Zhao

    2015-05-15

    In this work, low-toxicity fluorescent gold nanoclusters (AuNCs) based photoelectrochemical sensors were developed for H2O2 and glucose detection. Herein, the processes used to fabricate the sensors and the photoelectrochemical performances of the sensors under different conditions were presented. Based on the energy band levels of the AuNCs and electron tunneling processes, a detailed photoelectrochemical sensing model was given. The designed sensors were then used for H2O2 and glucose detection without any extra modification of the AuNCs or complex enzyme immobilization. The results demonstrate that the AuNCs allow for H2O2 sensing based on their capacity for both fluorescence and catalysis. Indeed, it was observed that H2O2 was catalyzed by the AuNCs and reduced by photoinduced electrons derived from excited AuNCs. Furthermore, an enhancement in photocurrent amplitude followed the increase in the concentrations of H2O2 and glucose. The effects of the types of ligands surrounding the AuNCs and the applied potential on the output photocurrent were well studied to optimize the measurement conditions. The sensitivity and LOD of MUA-AuNCs at -500 mV were 4.33 nA/mM and 35 μM, respectively. All experimental results indicated that AuNCs could not only serve as a promising photoelectrical material for building the photoelectrochemical biosensors but as catalysts for H2O2 sensing.

  18. Proximity-based protein thiol oxidation by H2O2-scavenging peroxidases.

    PubMed

    Gutscher, Marcus; Sobotta, Mirko C; Wabnitz, Guido H; Ballikaya, Seda; Meyer, Andreas J; Samstag, Yvonne; Dick, Tobias P

    2009-11-13

    H(2)O(2) acts as a signaling molecule by oxidizing critical thiol groups on redox-regulated target proteins. To explain the efficiency and selectivity of H(2)O(2)-based signaling, it has been proposed that oxidation of target proteins may be facilitated by H(2)O(2)-scavenging peroxidases. Recently, a peroxidase-based protein oxidation relay has been identified in yeast, namely the oxidation of the transcription factor Yap1 by the peroxidase Orp1. It has remained unclear whether the protein oxidase function of Orp1 is a singular adaptation or whether it may represent a more general principle. Here we show that Orp1 is in fact not restricted to oxidizing Yap1 but can also form a highly efficient redox relay with the oxidant target protein roGFP (redox-sensitive green fluorescent protein) in mammalian cells. Orp1 mediates near quantitative oxidation of roGFP2 by H(2)O(2), and the Orp1-roGFP2 redox relay effectively converts physiological H(2)O(2) signals into measurable fluorescent signals in living cells. Furthermore, the oxidant relay phenomenon is not restricted to Orp1 as the mammalian peroxidase Gpx4 also mediates oxidation of proximal roGFP2 in living cells. Together, these findings support the concept that certain peroxidases harbor an intrinsic and powerful capacity to act as H(2)O(2)-dependent protein thiol oxidases when they are recruited into proximity of oxidizable target proteins.

  19. Proximity-based Protein Thiol Oxidation by H2O2-scavenging Peroxidases*♦

    PubMed Central

    Gutscher, Marcus; Sobotta, Mirko C.; Wabnitz, Guido H.; Ballikaya, Seda; Meyer, Andreas J.; Samstag, Yvonne; Dick, Tobias P.

    2009-01-01

    H2O2 acts as a signaling molecule by oxidizing critical thiol groups on redox-regulated target proteins. To explain the efficiency and selectivity of H2O2-based signaling, it has been proposed that oxidation of target proteins may be facilitated by H2O2-scavenging peroxidases. Recently, a peroxidase-based protein oxidation relay has been identified in yeast, namely the oxidation of the transcription factor Yap1 by the peroxidase Orp1. It has remained unclear whether the protein oxidase function of Orp1 is a singular adaptation or whether it may represent a more general principle. Here we show that Orp1 is in fact not restricted to oxidizing Yap1 but can also form a highly efficient redox relay with the oxidant target protein roGFP (redox-sensitive green fluorescent protein) in mammalian cells. Orp1 mediates near quantitative oxidation of roGFP2 by H2O2, and the Orp1-roGFP2 redox relay effectively converts physiological H2O2 signals into measurable fluorescent signals in living cells. Furthermore, the oxidant relay phenomenon is not restricted to Orp1 as the mammalian peroxidase Gpx4 also mediates oxidation of proximal roGFP2 in living cells. Together, these findings support the concept that certain peroxidases harbor an intrinsic and powerful capacity to act as H2O2-dependent protein thiol oxidases when they are recruited into proximity of oxidizable target proteins. PMID:19755417

  20. Activation of Host Defense Mechanisms by Elevated Production of H2O2 in Transgenic Plants.

    PubMed Central

    Wu, G.; Shortt, B. J.; Lawrence, E. B.; Leon, J.; Fitzsimmons, K. C.; Levine, E. B.; Raskin, I.; Shah, D. M.

    1997-01-01

    Active oxygen species have been postulated to perform multiple functions in plant defense, but their exact role in plant resistance to diseases is not fully understood. We have recently demonstrated H2O2-mediated disease resistance in transgenic potato (Solanum tuberosum) plants expressing a foreign gene encoding glucose oxidase. In this study we provide further evidence that the H2O2-mediated disease resistance in potato is effective against a broad range of plant pathogens. We have investigated mechanisms underlying the H2O2-mediated disease resistance in transgenic potato plants. The constitutively elevated levels of H2O2 induced the accumulation of total salicylic acid severalfold in the leaf tissue of transgenic plants, although no significant change was detected in the level of free salicylic acid. The mRNAs of two defense-related genes encoding the anionic peroxidase and acidic chitinase were also induced. In addition, an increased accumulation of several isoforms of extracellular peroxidase, including a newly induced one, was observed. This was accompanied by a significant increase in the lignin content of stem and root tissues of the transgenic plants. The results suggest that constitutively elevated sublethal levels of H2O2 are sufficient to activate an array of host defense mechanisms, and these defense mechanisms may be a major contributing factor to the H2O2-mediated disease resistance in transgenic plants. PMID:12223817

  1. Photometric Measurements of H2O Ice Crystallinity on Trans-Neptunian Objects

    NASA Astrophysics Data System (ADS)

    Terai, Tsuyoshi; Itoh, Yoichi; Oasa, Yumiko; Furusho, Reiko; Watanabe, Junichi

    2016-08-01

    We present a measurement of H2O ice crystallinity on the surface of trans-neptunian objects with near-infrared narrow-band imaging. The newly developed photometric technique allows us to efficiently determine the strength of a 1.65 μm absorption feature in crystalline H2O ice. Our data for three large objects—Haumea, Quaoar, and Orcus—which are known to contain crystalline H2O ice on the surfaces, show a reasonable result with high fractions of the crystalline phase. It can also be pointed out that if the grain size of H2O ice is larger than ˜20 μm, the crystallinities of these objects are obviously below 1.0, which suggests the presence of the amorphous phase. In particular, Orcus exhibits a high abundance of amorphous H2O ice compared to Haumea and Quaoar, possibly indicating a correlation between the bulk density of the bodies and the degree of surface crystallization. We also found the presence of crystalline H2O ice on Typhon and 2008 AP129, both of which are smaller than the minimum size limit for inducing cryovolcanism as well as a transition from amorphous to crystalline phase through thermal evolution due to the decay of long-lived isotopes. Based on data collected at Subaru Telescope, which is operated by the National Astronomical Observatory of Japan (NAOJ).

  2. Addition of H2O and O-2 to Acetone and Dimethylsulfoxide Ligated Uranyl (V) Dioxocations

    SciTech Connect

    C. M. Leavitt; V. S. Bryantsev; W. A. deJong; M. S. Diallo; W. A. Goddard III; G. S. Groenewold; M. J. Van Stipdonk

    2009-03-01

    Gas-phase complexes of the formula [UO2(lig)]+ (lig = acetone (aco) or dimethylsulfoxide (dmso)) were generated by electrospray ionization (ESI) and studied by tandem ion-trap mass spectrometry to determine the general effect of ligand charge donation on the reactivity of UO2+ with respect to water and dioxygen. The original hypothesis that addition of O2 is enhanced by strong s-donor ligands bound to UO2+ is supported by results from competitive collision-induced dissociation (CID) experiments, which show near exclusive loss of H2O from [UO2(dmso)(H2O)(O2)]+, whereas both H2O and O2 are eliminated from the corresponding [UO2(aco)(H2O)(O2)]+ species. Ligand-addition reaction rates were investigated by monitoring precursor and product ion intensities as a function of ion storage time in the ion-trap mass spectrometer: these experiments suggest that the association of dioxygen to the UO2+ complex is enhanced when the more basic dmso ligand was coordinated to the metal complex. Conversely, addition of H2O is favored for the analogous complex ion that contains an aco ligand. Experimental rate measurements are supported by density function theory calculations of relative energies, which show stronger bonds between UO2+ and O2 when dmso is the coordinating ligand, whereas bonds to H2O are stronger for the aco complex.

  3. Cross Talk between H2O2 and Interacting Signal Molecules under Plant Stress Response

    PubMed Central

    Saxena, Ina; Srikanth, Sandhya; Chen, Zhong

    2016-01-01

    It is well established that oxidative stress is an important cause of cellular damage. During stress conditions, plants have evolved regulatory mechanisms to adapt to various environmental stresses. One of the consequences of stress is an increase in the cellular concentration of reactive oxygen species, which is subsequently converted to H2O2. H2O2 is continuously produced as the byproduct of oxidative plant aerobic metabolism. Organelles with a high oxidizing metabolic activity or with an intense rate of electron flow, such as chloroplasts, mitochondria, or peroxisomes are major sources of H2O2 production. H2O2 acts as a versatile molecule because of its dual role in cells. Under normal conditions, H2O2 immerges as an important factor during many biological processes. It has been established that it acts as a secondary messenger in signal transduction networks. In this review, we discuss potential roles of H2O2 and other signaling molecules during various stress responses. PMID:27200043

  4. Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

    NASA Astrophysics Data System (ADS)

    Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

    2017-03-01

    Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32‑, SO42‑) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.

  5. Efficiency and energy requirements for the transformation of organic micropollutants by ozone, O3/H2O2 and UV/H2O2.

    PubMed

    Katsoyiannis, Ioannis A; Canonica, Silvio; von Gunten, Urs

    2011-07-01

    The energy consumptions of conventional ozonation and the AOPs O(3)/H(2)O(2) and UV/H(2)O(2) for transformation of organic micropollutants, namely atrazine (ATR), sulfamethoxazole (SMX) and N-nitrosodimethylamine (NDMA) were compared. Three lake waters and a wastewater were assessed. With p-chlorobenzoic acid (pCBA) as a hydroxyl radical ((•)OH) probe compound, we experimentally determined the rate constants of organic matter of the selected waters for their reaction with (•)OH (k(OH,DOM)), which varied from 2.0 × 10(4) to 3.5 × 10(4) L mgC(-1) s(-1). Based on these data we calculated (•)OH scavenging rates of the various water matrices, which were in the range 6.1-20 × 10(4) s(-1). The varying scavenging rates influenced the required oxidant dose for the same degree of micropollutant transformation. In ozonation, for 90% pCBA transformation in the water with the lowest scavenging rate (lake Zürich water) the required O(3) dose was roughly 2.3 mg/L, and in the water with the highest scavenging rate (Dübendorf wastewater) it was 13.2 mg/L, corresponding to an energy consumption of 0.035 and 0.2 kWh/m(3), respectively. The use of O(3)/H(2)O(2) increased the rate of micropollutant transformation and reduced bromate formation by 70%, but the H(2)O(2) production increased the energy requirements by 20-25%. UV/H(2)O(2) efficiently oxidized all examined micropollutants but energy requirements were substantially higher (For 90% pCBA conversion in lake Zürich water, 0.17-0.75 kWh/m(3) were required, depending on the optical path length). Energy requirements between ozonation and UV/H(2)O(2) were similar only in the case of NDMA, a compound that reacts slowly with ozone and (•)OH but is transformed efficiently by direct photolysis.

  6. Vibrational relaxation of H2O(|04> ) in collisions with H2O, Ar, H2, N2 and O2: dynamical and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Barnes, P. W.; Sims, I. R.; Smith, I. W.

    2003-04-01

    It has been suggested that sequential two-photon dissociation of water might provide a mechanism for the atmospheric production of OH radical. ^1 This mechanism requires that photodissociation of vibrationally excited molecules must occur at a rate competitive with their relaxation by collisions with atmospheric gases. In this paper, we shall describe new experiments on the collisional relaxation of H_2O molecules from the highly excited mid04>± vibrational state in collisions with H_2O, Ar, H_2, N_2 and O_2. In our experiments, the mid04>^- state is populated by direct absorption of radiation from a pulsed dye laser tuned to ca. 719 nm. Evolution of the population in the (mid04>±) levels is observed using the combination of a frequency-quadrupled Nd:YAG laser, which selectively photolyses H_2O(mid04>±), and a frequency-doubled dye laser, which observes the OH(v = 0) produced via laser-induced fluorescence (LIF). The delay between the pulse from the pump laser and those from the photolysis and probe lasers was systematically varied to generate kinetic decays. The rate coefficients for relaxation obtained from these experiments, in units of cm^3 molecule-1 s-1, are: k(H_2O) = (4.1 ± 1.2) x 10-10, k(Ar) = (4.9 ± 1.1) x 10-12, k(H_2) = (6.8 ± 1.1) x 10-12, k(N_2) = (7.7 ± 1.5) x 10-12, k(O_2) = (6.7 ± 1.4) x 10-12. The results will be discussed in two contexts. First, we shall consider the implications of our new results for the interpretation of our previous experiments on the reactions of vibrationally excited H_2O with H atoms.^2 Second, we shall consider the proposal of Goss et al.1 in the light of our finding that the collisional relaxation of H_2O(mid04>±) by N_2 and O_2 is rather rapid. ^1 L. M Goss, V. Vaida, J. W. Brault and R. T. Skodje, J. Phys. Chem. A, 05, 70 (2001). ^2 (a) G. Hawthorne, P. Sharkey and I. W. M. Smith, J. Chem. Phys., 108, 4693(1998); (b) P. W. Barnes, P. Sharkey, I. R. Sims and I. W. M. Smith, Faraday Discuss. Chem. Soc., 13, 167

  7. Microchannel Reactor System Design & Demonstration For On-Site H2O2 Production by Controlled H2/O2 Reaction

    SciTech Connect

    Adeniyi Lawal

    2008-12-09

    We successfully demonstrated an innovative hydrogen peroxide (H2O2) production concept which involved the development of flame- and explosion-resistant microchannel reactor system for energy efficient, cost-saving, on-site H2O2 production. We designed, fabricated, evaluated, and optimized a laboratory-scale microchannel reactor system for controlled direct combination of H2 and O2 in all proportions including explosive regime, at a low pressure and a low temperature to produce about 1.5 wt% H2O2 as proposed. In the second phase of the program, as a prelude to full-scale commercialization, we demonstrated our H2O2 production approach by ‘numbering up’ the channels in a multi-channel microreactor-based pilot plant to produce 1 kg/h of H2O2 at 1.5 wt% as demanded by end-users of the developed technology. To our knowledge, we are the first group to accomplish this significant milestone. We identified the reaction pathways that comprise the process, and implemented rigorous mechanistic kinetic studies to obtain the kinetics of the three main dominant reactions. We are not aware of any such comprehensive kinetic studies for the direct combination process, either in a microreactor or any other reactor system. We showed that the mass transfer parameter in our microreactor system is several orders of magnitude higher than what obtains in the macroreactor, attesting to the superior performance of microreactor. A one-dimensional reactor model incorporating the kinetics information enabled us to clarify certain important aspects of the chemistry of the direct combination process as detailed in section 5 of this report. Also, through mathematical modeling and simulation using sophisticated and robust commercial software packages, we were able to elucidate the hydrodynamics of the complex multiphase flows that take place in the microchannel. In conjunction with the kinetics information, we were able to validate the experimental data. If fully implemented across the whole

  8. Homogeneous bubble nucleation in H2O- and H2O-CO2-bearing basaltic melts: Results of high temperature decompression experiments

    NASA Astrophysics Data System (ADS)

    Le Gall, Nolwenn; Pichavant, Michel

    2016-11-01

    High pressure and temperature decompression experiments were conducted to provide experimental information on the conditions of homogeneous bubble nucleation in basaltic melts. Experiments were performed on H2O- and H2O-CO2-bearing natural melts from Stromboli. Three starting volatile compositions were investigated: series #1 (4.91 wt% H2O, no CO2), series #2 (2.37-2.45 wt% H2O, 901-1011 ppm CO2) and series #3 (0.80-1.09 wt% H2O, 840-923 ppm CO2). The volatile-bearing glasses were first synthesized at 1200 °C and 200 MPa, and second continuously decompressed in the pressure range 150-25 MPa and rapidly quenched. A fast decompression rate of 78 kPa/s (or 3 m/s) was applied to limit the water loss from the glass cylinder and the formation of a H2O-depleted rim. Post-decompression glasses were characterized texturally by X-ray microtomography. The results demonstrate that homogenous bubble nucleation requires supersaturation pressures (difference between saturation pressure and pressure at which homogeneous bubble nucleation is observed, ∆ PHoN) ≤ 50-100 MPa. ∆ PHoN varies with the dissolved CO2 concentration, from ≪ 50 MPa (no CO2, series #1) to ≤ 50 MPa (872 ± 45 ppm CO2, series #3) to < 100 MPa (973 ± 63 ppm CO2, series #2). In series #1 melts, homogeneous bubble nucleation occurs as two distinct events, the first at high pressure (200 < P < 150 MPa) and the second at low pressure (50 < P < 25 MPa), just below the fragmentation level. In contrast, homogenous nucleation in series #2 and #3 melts is a continuous process. As well, chemical near-equilibrium degassing occurs in the series #1 melts, unlike in the series #2 and #3 melts which retain high CO2 concentrations even for higher vesicularities (up to 23% at 25 MPa). Thus, our experimental observations underline a significant effect of CO2 on the physical mechanisms of bubble vesiculation in basaltic melts. Our experimental decompression textures either reproduce or approach the characteristics of

  9. Neuroprotective and antioxidant activities of bamboo salt soy sauce against H2O2-induced oxidative stress in rat cortical neurons

    PubMed Central

    JEONG, JONG HEE; NOH, MIN-YOUNG; CHOI, JAE-HYEOK; LEE, HAIWON; KIM, SEUNG HYUN

    2016-01-01

    Bamboo salt (BS) and soy sauce (SS) are traditional foods in Asia, which contain antioxidants that have cytoprotective effects on the body. The majority of SS products contain high levels of common salt, consumption of which has been associated with numerous detrimental effects on the body. However, BS may be considered a healthier substitute to common salt. The present study hypothesized that SS made from BS, known as bamboo salt soy sauce (BSSS), may possess enhanced cytoprotective properties; this was evaluated using a hydrogen peroxide (H2O2)-induced neuronal cell death rat model. Rat neuronal cells were pretreated with various concentrations (0.001, 0.01, 0.1, 1 and 10%) of BSSS, traditional soy sauce (TRSS) and brewed soy sauce (BRSS), and were subsequently exposed to H2O2 (100 µM). The viability of neuronal cells, and the occurrence of DNA fragmentation, was subsequently examined. Pretreatment of neuronal cells with TRSS and BRSS reduced cell viability in a concentration-dependent manner, whereas neuronal cells pretreated with BSSS exhibited increased cell viability, as compared with non-treated neuronal cells. Furthermore, neuronal cells pretreated with 0.01% BSSS exhibited the greatest increase in viability. Exposure of neuronal cells to H2O2 significantly increased the levels of reactive oxygen species (ROS), B-cell lymphoma 2-associated X protein, poly (ADP-ribose), cleaved poly (ADP-ribose) polymerase, cytochrome c, apoptosis-inducing factor, cleaved caspase-9 and cleaved caspase-3, in all cases. Pretreatment of neuronal cells with BSSS significantly reduced the levels of ROS generated by H2O2, and increased the levels of phosphorylated AKT and phosphorylated glycogen synthase kinase-3β. Furthermore, the observed effects of BSSS could be blocked by administration of 10 µM LY294002, a phosphatidylinositol 3-kinase inhibitor. The results of the present study suggested that BSSS may exert positive neuroprotective effects against H2O2-induced cell death

  10. Experimental determination of the H2O-undersaturated peridotite solidus

    NASA Astrophysics Data System (ADS)

    Sarafian, E. K.; Gaetani, G. A.; Hauri, E. H.; Sarafian, A. R.

    2014-12-01

    Knowledge of the H2O-undersaturated lherzolite solidus places important constraints on the process of melt generation and mantle potential temperatures beneath oceanic spreading centers. The small concentration of H2O (~50-200 μg/g) dissolved in the oceanic mantle is thought to exert a strong influence on the peridotite solidus, but this effect has not been directly determined. The utility of existing experimental data is limited by a lack of information on the concentration of H2O dissolved in the peridotite and uncertainties involved with identifying small amounts of partial melt. We have developed an experimental approach for determining the peridotite solidus as a function of H2O content that overcomes these difficulties. Our initial results demonstrate that the solidus temperature for spinel lherzolite containing 150 μg/g H2O is higher than existing estimates for the anhydrous solidus. Our approach to determining the H2O-undersaturated lherzolite solidus is as follows. First, a small proportion (~5 %) of San Carlos olivine spheres, ~300 μm in diameter, are added to a peridotite synthesized from high-purity oxides and carbonates. Melting experiments are then conducted in pre-conditioned Au80Pd20 capsules over a range of temperatures at a single pressure using a piston-cylinder device. Water diffuses rapidly in olivine resulting in thorough equilibration between the olivine spheres and the surrounding fine-grained peridotite, and allowing the spheres to be used as hygrometers. After the experiment, the concentration of H2O dissolved in the olivine spheres is determined by secondary ion mass spectrometry. Melting experiments, spaced 20°C apart, were performed from 1250 to 1430°C at 1.5 GPa. The starting material has the composition of the depleted MORB mantle of Workman and Hart (2005) containing 0.13 wt% Na2O and 150 µg/g H2O. The concentration of H2O in the olivine spheres remains constant up to 1350°C, and then decreases systematically with increasing

  11. High pressure experimental study of eclogite with varying H2O contents

    NASA Astrophysics Data System (ADS)

    Rosenthal, A.; Frost, D. J.; Petitgirard, S.; Yaxley, G. M.; Berry, A.; Woodland, A. B.; Pinter, Z.; Vasilyev, P.; Ionov, D. A.; Jacob, D. E.; Pearson, G. D.; Kovacs, I.; Padron-Navarta, A.

    2014-12-01

    Given the strong influence of volatiles on mantle melting processes, it is critical to understand the behaviour of volatiles (such as H2O) in subducted oceanic crustal material (eclogite) during subduction and subsequent recycling and mantle melting processes, and their impacts on volcanism. As natural samples from subduction zones from the deep Earth's interior are largely inaccessible, the only way to determine the H2O content of eclogite is to simulate high pressure (P) and temperature (T) conditions equivalent to conditions of the Earth's interior using high-P experimental facilities. A particular interest is to determine the H2O content of eclogitic nominally anhydrous minerals (NAMs; such as garnet, clinopyroxene) at the conditions where hydrous phases (such as phengite) are breaking down to release H2O that would then leave the slab. As a starting material, we use average oceanic basalt (GA1, representative of recycled oceanic crust [1]) with varying bulk %H2O (≤7 wt.%). We conducted experiments using GA1 at different P's (6-10 GPa), T's (850-1500°C) and bulk %H2O (up to 7 wt.%) using multi anvil apparatuses. The run products at each P, T, and bulk H2O contents show well-equilibrated eclogitic phase assemblages of garnet ± clinopyroxene ± coesite/stishovite ± rutile ± phengite ± melt ± vapour. Runs (>0.5 wt.% H2O) at 6 GPa and up to ~950°C, and at 8-9 GPa and up to ~1050°C are subsolidus, while towards higher T small melt fractions appear. Similar to previous studies [e.g. 2-6], the stability of phengite varies as a function of P, T, buffering mineral paragenesis and bulk H2O concentration. Phengite breaks down >9 GPa. Eclogitic NAMs and phengite also break down at subsolidus conditions in the presence of excess of hydrous fluids. For instance, K2O in phengite and clinopyroxene decrease with increasing bulk H2O content at subsolidus conditions at given P, T, suggesting a leaching role of K2O by a vapour-rich fluid. [1] Yaxley, G. M. & Green, D. H

  12. Rate constants of atomic hydrogen formation in H3O+(H2O) n + e → H + (H2O) n gas-phase processes

    NASA Astrophysics Data System (ADS)

    Stepanov, N. F.; Novakovskaya, Yu. V.

    2009-09-01

    Using the Maxwellian electron velocity distribution and the Breit-Wigner approximation of the reaction cross section, the kinetic parameters of the hydrogen atom formation upon the electron capture by positively charged hydronium-water clusters are estimated. Calculations of the cross sections and rate constants are based on the data of quantum chemical studies of H3O+(H2O) n and H3O(H2O) n clusters, particularly on the detailed analysis of the spacing of high-lying states of the radicals and the character of the unpaired electron density distribution, as well as on the general trend in the electron affinity change of the cations depending on the number of water molecules. The lifetimes of the radicals before the dissociation are taken from the classical nonempirical molecular dynamics runs. The results are compared to available experimental data.

  13. Analysis of a perpendicular band in Ar-H2O with origin close to the ν1 + ν3, R(0) line in H2O

    NASA Astrophysics Data System (ADS)

    Vanfleteren, T.; Földes, T.; Herman, M.

    2015-05-01

    We have used continuous-wave cavity ring-down spectroscopy to record a band with origin close to 7275.1 cm-1 in an Ar supersonic expansion seeded with H2O. It is assigned to ν1 + ν3 ← GS, Π(101) ← Σ(000) in Ar-H2O. The rotational structure (Trot = 12 K) is analyzed and the lines fitted (σ = 0.0008 cm-1) together with literature microwave data. The fit includes strongly perturbed Q lines, from interaction with a Π state with origin determined to be close to 7274.5 cm-1. The mean upper state predissociation lifetime is determined to be 3 ns for all reported e and f upper levels.

  14. Base fluid and temperature effects on the heat transfer characteristics of SiC in ethylene glycol/H2O and H2O nanofluids

    NASA Astrophysics Data System (ADS)

    Timofeeva, Elena V.; Yu, Wenhua; France, David M.; Singh, Dileep; Routbort, Jules L.

    2011-01-01

    Experimental data are presented for the thermal conductivity, viscosity, and turbulent flow heat transfer coefficient of nanofluids with SiC particles suspended in ethylene glycol (EG)/water (H2O) mixture with a 50/50 volume ratio. The results are compared to the analogous suspensions in water for four sizes of SiC particles (16-90 nm). It is demonstrated that the heat transfer efficiency is a function of both the average particle size and the system temperature. The results show that adding SiC nanoparticles to an EG/H2O mixture can significantly improve the cooling efficiency while water-based nanofluids are typically less efficient than the base fluids. This is one of the few times that substantial nanofluid heat transfer enhancement has been reported in the literature based on a realistic comparison basis of constant velocity or pumping power. The trends important for engineering efficient heat transfer nanofluids are summarized.

  15. Low H2O/Ce in Icelandic basalts as evidence for crustal recycling

    NASA Astrophysics Data System (ADS)

    Neave, David; Shorttle, Oliver; Hartley, Margaret; Maclennan, John

    2016-04-01

    The generation of new crust at mid-ocean ridges is balanced by the subduction of partially hydrothermally altered basaltic material back into the mantle. This subducted material may then be recycled and returned via mantle plumes to the Earth's surface at hot spots. Long-identified isotopic and trace element signatures of oceanic crust recycling in ocean island basalts (OIBs) have been recently supplemented by evidence of major element, i.e. lithological, heterogeneity in the melting region. For example, combined major and trace element systematics from Iceland suggest that the mantle source contains at least 5% recycled basalt. Observations of high water (H2O) contents in subglacially quenched basalts from Iceland have previously been attributed to the incorporation of wet recycled material into the mantle source. However, when combined with trace element analyses, recent volatile analyses from the Laki-Grímsvötn and Bárðarbunga-Veiðivötn systems in the Eastern Volcanic Zone (EVZ) of Iceland suggest that the underlying mantle is comparatively depleted in H2O for its degree of major and trace element enrichment. Correlations between H2O and cerium (Ce) within individual mid-ocean ridge basalt (MORB) suites reveal that these elements partition similarly prior to H2O degassing at low pressures; H2O/Ce remains constant during melting and fractionation, and hence reflects the average H2O/Ce of the melting region. MORBs from the Mid-Atlantic Ridge south of Iceland have a mean H2O/Ce value of 304±48 at a mean La/Yb of 2.1±1.5. In contrast, basalts from the EVZ have a lower mean H2O/Ce of 180±20 at a higher mean La/Yb of 3.1±0.5. Thus, despite coming from an enriched section of the Mid-Atlantic ridge in terms of trace element content, basalts from the EVZ have the lowest H2O/Ce values known from the ridge, and are hence comparatively depleted in H2O. Given that H2O/Ce from un-degassed basalts is considered to represent mantle source values, we suggest that low H

  16. Influence of H2O Rich Fluid Inclusions on Quartz Deformation

    NASA Astrophysics Data System (ADS)

    Thust, Anja; Heilbronner, Renée.; Stünitz, Holger; Tarantola, Alexandre; Behrens, Harald

    2010-05-01

    The effect of H2O on the strength of quartz is well known and has been discussed many times in the literature (e.g. Griggs & Blacic 1965, Kronenberg 1994). In this project we study the H2O interactions between natural dry quartz and H2O rich fluid inclusions during deformation in the solid medium Griggs apparatus. High pressure and temperature experiments were carried out using a quartz single crystal containing a large number of H2O-rich fluid inclusions. Adjacent to the fluid inclusions the crystal is essentially dry (< 100 H/106Si, as determined by FTIR). Two sample orientations where used: (1) ⊥{m} orientation: normal to one of the prism planes, (2) O+ orientation: 45° to and 45° to [c]. Confining pressures were 700 MPa, 1000 MPa and 1500 MPa, with a constant displacement rate of 10-6 s-1 and a constant temperature of 900° C. Additionally, experiments where carried out at lower temperatures (800° C, 700° C) and faster strain rate ( 10-5 s-1). During increasing pressure and temperature we remained close to the fluid inclusion isochore and exceeded the α - β transition as late as possible. The strengths of the majority of the samples are between 150 and 250 MPa (the weakest is 84 MPa, the strongest 414 MPa). Low strength can be explained by dynamic recrystallization and deformation by dislocation creep, higher strength correlates with a lower H2O content and absence of dislocation creep. In the undeformed material, the H2O rich fluid inclusions contain different chlorides like antarticite (CaCl2×6H2O) and hydrohalite (NaCl×2H2O), as measured with micro thermometry. They show a large range in size from 50 μm to 700 μm and their spatial distribution is extremely heterogeneous. After deformation the inclusions are more homogeneously distributed throughout the sample and dramatically reduced in size (< 0.1μm). Regions with a high density of very small fluid inclusions are the regions with the highest concentration of deformation and yield an H2O content

  17. Iron weathering products in a CO 2 + (H 2O or H 2O 2) atmosphere: Implications for weathering processes on the surface of Mars

    NASA Astrophysics Data System (ADS)

    Chevrier, V.; Mathé, P.-E.; Rochette, P.; Grauby, O.; Bourrié, G.; Trolard, F.

    2006-08-01

    Various iron-bearing primary phases and rocks have been weathered experimentally to simulate possible present and past weathering processes occurring on Mars. We used magnetite, monoclinic and hexagonal pyrrhotites, and metallic iron as it is suggested that meteoritic input to the martian surface may account for an important source of reduced iron. The phases were weathered in two different atmospheres: one composed of CO 2 + H 2O, to model the present and primary martian atmosphere, and a CO 2 + H 2O + H 2O 2 atmosphere to simulate the effect of strong oxidizing agents. Experiments were conducted at room temperature and a pressure of 0.75 atm. Magnetite is the only stable phase in the experiments and is thus likely to be released on the surface of Mars from primary rocks during weathering processes. Siderite, elemental sulfur, ferrous sulfates and ferric (oxy)hydroxides (goethite and lepidocrocite) are the main products in a water-bearing atmosphere, depending on the substrate. In the peroxide atmosphere, weathering products are dominated by ferric sulfates and goethite. A kinetic model was then developed for iron weathering in a water atmosphere, using the shrinking core model (SCM). This model includes competition between chemical reaction and diffusion of reactants through porous layers of secondary products. The results indicate that for short time scales, the mechanism is dominated by a chemical reaction with second order kinetics ( k = 7.75 × 10 -5 g -1/h), whereas for longer time scales, the mechanism is diffusion-controlled (De A = 2.71 × 10 -10 m 2/h). The results indicate that a primary CO 2- and H 2O-rich atmosphere should favour sulfur, ferrous phases such as siderite or Fe 2+-sulfates, associated with ferric (oxy)hydroxides (goethite and lepidocrocite). Further evolution to more oxidizing conditions may have forced these precursors to evolve into ferric sulfates and goethite/hematite.

  18. Expression patterns of H2-O in mouse B cells and dendritic cells correlate with cell function.

    PubMed

    Fallas, Jennifer L; Yi, Woelsung; Draghi, Nicole A; O'Rourke, Helen M; Denzin, Lisa K

    2007-02-01

    In the endosomes of APCs, the MHC class II-like molecule H2-M catalyzes the exchange of class II-associated invariant chain peptides (CLIP) for antigenic peptides. H2-O is another class II-like molecule that modulates the peptide exchange activity of H2-M. Although the expression pattern of H2-O in mice has not been fully evaluated, H2-O is expressed by thymic epithelial cells, B cells, and dendritic cells (DCs). In this study, we investigated H2-O, H2-M, and I-A(b)-CLIP expression patterns in B cell subsets during B cell development and activation. H2-O was first detected in the transitional 1 B cell subset and high levels were maintained in marginal zone and follicular B cells. H2-O levels were down-regulated specifically in germinal center B cells. Unexpectedly, we found that mouse B cells may have a pool of H2-O that is not associated with H2-M. Additionally, we further evaluate H2-O and H2-M interactions in mouse DCs, as well as H2-O expression in bone marrow-derived DCs. We also evaluated H2-O, H2-M, I-A(b), and I-A(b)-CLIP expression in splenic DC subsets, in which H2-O expression levels varied among the splenic DC subsets. Although it has previously been shown that H2-O modifies the peptide repertoire, H2-O expression did not alter DC presentation of a number of endogenous and exogenous Ags. Our further characterization of H2-O expression in DCs, as well as the identification of a potential free pool of H2-O in mouse splenic B cells, suggest that H2-O may have a yet to be elucidated role in immune responses.

  19. H2O concentration in the middle atmosphere: Processing of LIMS radiance measurements with a research algorithm

    NASA Astrophysics Data System (ADS)

    Fischer, H.

    Transmittance functions as well as inversion algorithms have been developed for deriving H2O profiles from radiometer measurements. These computer programs have been applied to evaluate own stratospheric balloon occultation measurements and LIMS (Limb Infrared Monitor of the Stratosphere) radiance measurements in the H2O channel. The results are compared with the H2O profiles in the LIMS data archive. The differences between corresponding H2O profiles are discussed in dependence of altitude and latitude.

  20. Rovibrational states of the H2O-H2 complex: An ab initio calculation

    NASA Astrophysics Data System (ADS)

    van der Avoird, Ad; Nesbitt, David J.

    2011-01-01

    All bound rovibrational levels of the H2O-H2 dimer are calculated for total angular momentum J = 0-5 on two recent intermolecular potential surfaces reported by Valiron et al. [J. Chem. Phys. 129, 134306 (2008)] and Hodges et al. [J. Chem. Phys. 120, 710 (2004)] obtained through ab initio calculations. The method used handles correctly the large amplitude internal motions in this complex; it involves a discrete variable representation of the intermolecular distance coordinate R and a basis of coupled free rotor wave functions for the hindered internal rotations and the overall rotation of the dimer. The basis is adapted to the permutation symmetry associated with the para/ortho (p/o) nature of both H2O and H2 as well as to inversion symmetry. Dimers containing oH2 are more strongly bound than dimers with pH2, as expected, with dissociation energies D_0 of 33.57, 36.63, 53.60, and 59.04 cm^{-1}for pH2O-pH2, oH2O-pH2, pH2O-oH2, and oH2O-oH2, respectively, on the potential of Valiron et al. that corresponds to a binding energy D_e of 235.14 cm^{-1}. Rovibrational wave functions are computed as well and the nature of the bound states in the four different dimer species is discussed. Converged rovibrational levels on both potentials agree well with the high-resolution spectrum reported by Weida and Nesbitt [J. Chem. Phys. 110, 156 (1999)]; the hindered internal rotor model that was used to interpret this spectrum is qualitatively correct.

  1. Sources of superoxide/H2O2 during mitochondrial proline oxidation.

    PubMed

    Goncalves, Renata L S; Rothschild, Daniel E; Quinlan, Casey L; Scott, Gary K; Benz, Christopher C; Brand, Martin D

    2014-01-01

    p53 Inducible gene 6 (PIG6) encodes mitochondrial proline dehydrogenase (PRODH) and is up-regulated several fold upon p53 activation. Proline dehydrogenase is proposed to generate radicals that contribute to cancer cell apoptosis. However, there are at least 10 mitochondrial sites that can produce superoxide and/or H2O2, and it is unclear whether proline dehydrogenase generates these species directly, or instead drives production by other sites. Amongst six cancer cell lines, ZR75-30 human breast cancer cells had the highest basal proline dehydrogenase levels, and mitochondria isolated from ZR75-30 cells consumed oxygen and produced H2O2 with proline as sole substrate. Insects use proline oxidation to fuel flight, and mitochondria isolated from Drosophila melanogaster were even more active with proline as sole substrate than ZR75-30 mitochondria. Using mitochondria from these two models we identified the sites involved in formation of superoxide/H2O2 during proline oxidation. In mitochondria from Drosophila the main sites were respiratory complexes I and II. In mitochondria from ZR75-30 breast cancer cells the main sites were complex I and the oxoglutarate dehydrogenase complex. Even with combinations of substrates and respiratory chain inhibitors designed to minimize the contributions of other sites and maximize any superoxide/H2O2 production from proline dehydrogenase itself, there was no significant direct contribution of proline dehydrogenase to the observed H2O2 production. Thus proline oxidation by proline dehydrogenase drives superoxide/H2O2 production, but it does so mainly or exclusively by providing anaplerotic carbon for other mitochondrial dehydrogenases and not by producing superoxide/H2O2 directly.

  2. Rovibrational states of the H2O-H2 complex: an ab initio calculation.

    PubMed

    van der Avoird, Ad; Nesbitt, David J

    2011-01-28

    All bound rovibrational levels of the H(2)O-H(2) dimer are calculated for total angular momentum J = 0-5 on two recent intermolecular potential surfaces reported by Valiron et al. [J. Chem. Phys. 129, 134306 (2008)] and Hodges et al. [J. Chem. Phys. 120, 710 (2004)] obtained through ab initio calculations. The method used handles correctly the large amplitude internal motions in this complex; it involves a discrete variable representation of the intermolecular distance coordinate R and a basis of coupled free rotor wave functions for the hindered internal rotations and the overall rotation of the dimer. The basis is adapted to the permutation symmetry associated with the para/ortho (p/o) nature of both H(2)O and H(2) as well as to inversion symmetry. Dimers containing oH(2) are more strongly bound than dimers with pH(2), as expected, with dissociation energies D(0) of 33.57, 36.63, 53.60, and 59.04 cm(-1)for pH(2)O-pH(2), oH(2)O-pH(2), pH(2)O-oH(2), and oH(2)O-oH(2), respectively, on the potential of Valiron et al. that corresponds to a binding energy D(e) of 235.14 cm(-1). Rovibrational wave functions are computed as well and the nature of the bound states in the four different dimer species is discussed. Converged rovibrational levels on both potentials agree well with the high-resolution spectrum reported by Weida and Nesbitt [J. Chem. Phys. 110, 156 (1999)]; the hindered internal rotor model that was used to interpret this spectrum is qualitatively correct.

  3. H2O2 Synthesis Induced by Irradiation of H2O with Energetic H(+) and Ar(+) Ions at Various Temperatures

    NASA Technical Reports Server (NTRS)

    Baragiola, R. A.; Loeffler, M. J.; Raut, U.; Vidal, R. A.; Carlson, R. W.

    2004-01-01

    The detection of H2O2 on Jupiter's icy satellite Europa by the Galileo NIMS instrument presented a strong evidence for the importance of radiation effects on icy surfaces. A few experiments have investigated whether solar flux of protons incident on Europa ice could cause a significant if any H2O2 production. These published results differ as to whether H2O2 can be formed by ions impacting water at temperatures near 80 K, which are appropriate to Europa. This discrepancy may be a result of the use of different incident ion energies, different vacuum conditions, or different ways of processing the data. The latter possibility comes about from the difficulty of identifying the 3.5 m peroxide OH band on the long wavelength wing of the much stronger water 3.1 m band. The problem is aggravated by using straight line baselines to represent the water OH band with a curvature, in the region of the peroxide band, that increases with temperature. To overcome this problem, we use polynomial baselines that provide good fits to the water band and its derivative.

  4. Differentiating between apparent and actual rates of H2O2 metabolism by isolated rat muscle mitochondria to test a simple model of mitochondria as regulators of H2O2 concentration.

    PubMed

    Treberg, Jason R; Munro, Daniel; Banh, Sheena; Zacharias, Pamela; Sotiri, Emianka

    2015-08-01

    Mitochondria are often regarded as a major source of reactive oxygen species (ROS) in animal cells, with H2O2 being the predominant ROS released from mitochondria; however, it has been recently demonstrated that energized brain mitochondria may act as stabilizers of H2O2 concentration (Starkov et al. [1]) based on the balance between production and the consumption of H2O2, the later of which is a function of [H2O2] and follows first order kinetics. Here we test the hypothesis that isolated skeletal muscle mitochondria, from the rat, are able to modulate [H2O2] based upon the interaction between the production of ROS, as superoxide/H2O2, and the H2O2 decomposition capacity. The compartmentalization of detection systems for H2O2 and the intramitochondrial metabolism of H2O2 leads to spacial separation between these two components of the assay system. This results in an underestimation of rates when relying solely on extramitochondrial H2O2 detection. We find that differentiating between these apparent rates found when using extramitochondrial H2O2 detection and the actual rates of metabolism is important to determining the rate constant for H2O2 consumption by mitochondria in kinetic experiments. Using the high rate of ROS production by mitochondria respiring on succinate, we demonstrate that net H2O2 metabolism by mitochondria can approach a stable steady-state of extramitochondrial [H2O2]. Importantly, the rate constant determined by extrapolation of kinetic experiments is similar to the rate constant determined as the [H2O2] approaches a steady state.

  5. 40 CFR 1065.369 - H2O, CO, and CO2 interference verification for photoacoustic alcohol analyzers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 33 2014-07-01 2014-07-01 false H2O, CO, and CO2 interference... Verifications Hydrocarbon Measurements § 1065.369 H2O, CO, and CO2 interference verification for photoacoustic... analyzer, verify the amount of H2O, CO, and CO2 interference after initial analyzer installation and...

  6. Effects of a single water molecule on the OH + H2O2 reaction.

    PubMed

    Buszek, Robert J; Torrent-Sucarrat, Miquel; Anglada, Josep M; Francisco, Joseph S

    2012-06-21

    The effect of a single water molecule on the reaction between H(2)O(2) and HO has been investigated by employing MP2 and CCSD(T) theoretical approaches in connection with the aug-cc-PVDZ, aug-cc-PVTZ, and aug-cc-PVQZ basis sets and extrapolation to an ∞ basis set. The reaction without water has two elementary reaction paths that differ from each other in the orientation of the hydrogen atom of the hydroxyl radical moiety. Our computed rate constant, at 298 K, is 1.56 × 10(-12) cm(3) molecule(-1) s(-1), in excellent agreement with the suggested value by the NASA/JPL evaluation. The influence of water vapor has been investigated by considering either that H(2)O(2) first forms a complex with water that reacts with hydroxyl radical or that H(2)O(2) reacts with a previously formed H(2)O·OH complex. With the addition of water, the reaction mechanism becomes much more complex, yielding four different reaction paths. Two pathways do not undergo the oxidation reaction but an exchange reaction where there is an interchange between H(2)O(2)·H(2)O and H(2)O·OH complexes. The other two pathways oxidize H(2)O(2), with a computed total rate constant of 4.09 × 10(-12) cm(3) molecule(-1) s(-1) at 298 K, 2.6 times the value of the rate constant of the unassisted reaction. However, the true effect of water vapor requires taking into account the concentration of the prereactive bimolecular complex, namely, H(2)O(2)·H(2)O. With this consideration, water can actually slow down the oxidation of H(2)O(2) by OH between 1840 and 20.5 times in the 240-425 K temperature range. This is an example that demonstrates how water could be a catalyst in an atmospheric reaction in the laboratory but is slow under atmospheric conditions.

  7. Carboxylesterase converts Amplex red to resorufin: Implications for mitochondrial H2O2 release assays

    PubMed Central

    Miwa, Satomi; Treumann, Achim; Bell, Amy; Vistoli, Giulio; Nelson, Glyn; Hay, Sam; von Zglinicki, Thomas

    2016-01-01

    Amplex Red is a fluorescent probe that is widely used to detect hydrogen peroxide (H2O2) in a reaction where it is oxidised to resorufin by horseradish peroxidase (HRP) as a catalyst. This assay is highly rated amongst other similar probes thanks to its superior sensitivity and stability. However, we report here that Amplex Red is readily converted to resorufin by a carboxylesterase without requiring H2O2, horseradish peroxidase or oxygen: this reaction is seen in various tissue samples such as liver and kidney as well as in cultured cells, causing a serious distortion of H2O2 measurements. The reaction can be inhibited by Phenylmethyl sulfonyl fluoride (PMSF) at concentrations which do not disturb mitochondrial function nor the ability of the Amplex Red-HRP system to detect H2O2.In vitro experiments and in silico docking simulations indicate that carboxylesterases 1 and 2 recognise Amplex Red with the same kinetics as carboxylesterase-containing mitochondria. We propose two different approaches to correct for this problem and re-evaluate the commonly performed experimental procedure for the detection of H2O2 release from isolated liver mitochondria. Our results call for a serious re-examination of previous data. PMID:26577176

  8. Multiple myeloma cells' capacity to decompose H2O2 determines lenalidomide sensitivity.

    PubMed

    Sebastian, Sinto; Zhu, Yuan X; Braggio, Esteban; Shi, Chang-Xin; Panchabhai, Sonali C; Van Wier, Scott A; Ahmann, Greg J; Chesi, Marta; Bergsagel, P Leif; Stewart, A Keith; Fonseca, Rafael

    2017-02-23

    Lenalidomide is an immunomodulatory drug (IMiDs) with clinical efficacy in multiple myeloma (MM) and other late B-cell neoplasms. Although cereblon (CRBN) is an essential requirement for IMiD action, the complete molecular and biochemical mechanisms responsible for lenalidomide-mediated sensitivity or resistance remain unknown. Here, we report that IMiDs work primarily via inhibition of peroxidase-mediated intracellular H2O2 decomposition in MM cells. MM cells with lower H2O2-decomposition capacity were more vulnerable to lenalidomide-induced H2O2 accumulation and associated cytotoxicity. CRBN-dependent degradation of IKZF1 and IKZF3 was a consequence of H2O2-mediated oxidative stress. Lenalidomide increased intracellular H2O2 levels by inhibiting thioredoxin reductase (TrxR) in cells expressing CRBN, causing accumulation of immunoglobulin light-chain dimers, significantly increasing endoplasmic reticulum stress and inducing cytotoxicity by activation of BH3-only protein Bim in MM. Other direct inhibitors of TrxR and thioredoxin (Trx) caused similar cytotoxicity, but in a CRBN-independent fashion. Our findings could help identify patients most likely to benefit from IMiDs and suggest direct TrxR or Trx inhibitors for MM therapy.

  9. Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method

    NASA Technical Reports Server (NTRS)

    Sakugawa, H.; Kaplan, I. R.

    1987-01-01

    Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater.

  10. Effect of H2O2 concentrations on copper removal using the modified hydrothermal biochar.

    PubMed

    Zuo, XiaoJun; Liu, Zhengang; Chen, MinDong

    2016-05-01

    This study investigated effect of H2O2 concentrations on copper removal using H2O2 modified hydrothermal carbonization Cymbopogon schoenanthus L. Spreng (HLG). Sorption behaviors of Cu (II) on the modified HLG by 20% H2O2 (mHLG2) could be the most desirable. Based on Langmuir isotherm, the maximum amount of Cu (II) uptake was in the sequence of mHLG2 (53.8mgg(-1))>mHLG1 (44.2mgg(-1))>mHLG3 (42.0mgg(-1))>mHLG0 (35.8mgg(-1)), which was higher than the results from majority of previous studies, suggesting that H2O2 modification advanced sorption capacity of hydrothermal biochars evidently. Effect mechanisms exploration indicated that the difference of Cu (II) removal by biochars before and after the modification was mainly related to functional groups. Carboxylic group was responsible for the best sorption property of Cu (II) by mHLG2, which was attributed to its significant relationships with H2O2 modification and Cu (II) removal.

  11. Photoluminescence Probing of Complex H2O Adsorption on InGaN/GaN Nanowires.

    PubMed

    Maier, Konrad; Helwig, Andreas; Müller, Gerhard; Hille, Pascal; Teubert, Jörg; Eickhoff, Martin

    2017-02-08

    We demonstrate that the complex adsorption behavior of H2O on InGaN/GaN nanowire arrays is directly revealed by their ambient-dependent photoluminescence properties. Under low-humidity, ambient-temperature, and low-excitation-light conditions, H2O adsorbates cause a quenching of the photoluminescence. In contrast, for high humidity levels, elevated temperature, and high excitation intensity, H2O adsorbates act as efficient photoluminescence enhancers. We show that this behavior, which can only be detected due to the low operation temperature of the InGaN/GaN nanowires, can be explained on the basis of single H2O adsorbates forming surface recombination centers and multiple H2O adsorbates forming surface passivation layers. Reversible creation of such passivation layers is induced by the photoelectrochemical splitting of adsorbed water molecules and by the interaction of reactive H3O(+) and OH(-) ions with photoactivated InGaN surfaces. Due to electronic coupling of adsorbing molecules with photoactivated surfaces, InGaN/GaN nanowires act as sensitive nanooptical probes for the analysis of photoelectrochemical surface processes.

  12. Starvation-induced cross protection against heat or H2O2 challenge in Escherichia coli.

    PubMed

    Jenkins, D E; Schultz, J E; Matin, A

    1988-09-01

    Glucose- or nitrogen-starved cultures of Escherichia coli exhibited enhanced resistance to heat (57 degrees C) or H2O2 (15 mM) challenge, compared with their exponentially growing counterparts. The degree of resistance increased with the time for which the cells were starved prior to the challenge, with 4 h of starvation providing the maximal protection. Protein synthesis during starvation was essential for these cross protections, since chloramphenicol addition at the onset of starvation prevented the development of thermal or oxidative resistance. Starved cultures also demonstrated stronger thermal and oxidative resistance than did growing cultures adapted to heat, H2O2, or ethanol prior to the heat or H2O2 challenge. Two-dimensional gel electrophoresis of 35S-pulse-labeled proteins showed that subsets of the 30 glucose starvation proteins were also synthesized during heat or H2O2 adaptation; three proteins were common to all three stresses. Most of the common proteins were among the previously identified Pex proteins (J.E. Schultz, G. I. Latter, and A. Matin, J. Bacteriol. 170:3903-3909, 1988), which are independent of cyclic AMP positive control for their induction during starvation. Induction of starvation proteins dependent on cyclic AMP was not important in these cross protections, since a delta cya strain of E. coli K-12 exhibited the same degree of resistance to heat or H2O2 as the wild-type parent did during both growth and starvation.

  13. Degradation of 40 selected pharmaceuticals by UV/H2O2.

    PubMed

    Wols, B A; Hofman-Caris, C H M; Harmsen, D J H; Beerendonk, E F

    2013-10-01

    The occurrence of pharmaceuticals in source waters is increasing. Although UV advanced oxidation is known to be an effective barrier against micropollutants, degradation rates are only available for limited amounts of pharmaceuticals. Therefore, the degradation of a large group of pharmaceuticals has been studied in this research for the UV/H2O2 process under different conditions, including pharmaceuticals of which the degradation by UV/H2O2 was never reported before (e.g., metformin, paroxetine, pindolol, sotalol, venlafaxine, etc.). Monochromatic low pressure (LP) and polychromatic medium pressure (MP) lamps were used for three different water matrices. In order to have well defined hydraulic conditions, all experiments were conducted in a collimated beam apparatus. Degradation rates for the pharmaceuticals were determined. For those compounds used in this research that are also reported in literature, measured degradation results are in good agreement with literature data. Pharmaceutical degradation for only photolysis with LP lamps is small, which is increased by using a MP lamp. Most of the pharmaceuticals are well removed when applying both UV (either LP or MP) and H2O2. However, differences in degradation rates between pharmaceuticals can be large. For example, ketoprofen, prednisolone, pindolol are very well removed by UV/H2O2, whereas metformin, cyclophosphamide, ifosfamide are very little removed by UV/H2O2.

  14. Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

    NASA Technical Reports Server (NTRS)

    Santee, M. L.; Read, W. G.; Waters, J. W.; Froidevaux, L.; Manney, G. L.; Flower, D. A.; Jarnot, R. F.; Harwood, R. S.; Peckham, G. E.

    1995-01-01

    Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone 'hole' is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

  15. Phase Separation Kinetics in Isopycnic Mixtures of H2O/CO2/Ethoxylated Alcohol Surfactants

    NASA Technical Reports Server (NTRS)

    Lesemann, Markus; Paulaitis, Michael E.; Kaler, Eric W.

    1999-01-01

    Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(sub i)E(sub j)) surfactants form three coexisting liquid phases at conditions where two of the phases have equal densities (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing C8E5, C10E6, and C12E6 surfactants, but not for those mixtures containing either C4E1 or C8E3 surfactants. Pressure-temperature (PT) projections for this three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. Measurements of the microstructure in H2O/CO2/C12E6 mixtures as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%) have also been carried out to show that while micellar structure remains essentially un-changed, critical concentration fluctuations increase as the phase boundary and plait point are approached. In this report, we present our first measurements of the kinetics of isopycnic phase separation for ternary mixtures of H2O/CO2/C8E5.

  16. Catalase and ascorbate peroxidase-representative H2O2-detoxifying heme enzymes in plants.

    PubMed

    Anjum, Naser A; Sharma, Pallavi; Gill, Sarvajeet S; Hasanuzzaman, Mirza; Khan, Ekhlaque A; Kachhap, Kiran; Mohamed, Amal A; Thangavel, Palaniswamy; Devi, Gurumayum Devmanjuri; Vasudhevan, Palanisamy; Sofo, Adriano; Khan, Nafees A; Misra, Amarendra Narayan; Lukatkin, Alexander S; Singh, Harminder Pal; Pereira, Eduarda; Tuteja, Narendra

    2016-10-01

    Plants have to counteract unavoidable stress-caused anomalies such as oxidative stress to sustain their lives and serve heterotrophic organisms including humans. Among major enzymatic antioxidants, catalase (CAT; EC 1.11.1.6) and ascorbate peroxidase (APX; EC 1.11.1.11) are representative heme enzymes meant for metabolizing stress-provoked reactive oxygen species (ROS; such as H2O2) and controlling their potential impacts on cellular metabolism and functions. CAT mainly occurs in peroxisomes and catalyzes the dismutation reaction without requiring any reductant; whereas, APX has a higher affinity for H2O2 and utilizes ascorbate (AsA) as specific electron donor for the reduction of H2O2 into H2O in organelles including chloroplasts, cytosol, mitochondria, and peroxisomes. Literature is extensive on the glutathione-associated H2O2-metabolizing systems in plants. However, discussion is meager or scattered in the literature available on the biochemical and genomic characterization as well as techniques for the assays of CAT and APX and their modulation in plants under abiotic stresses. This paper aims (a) to introduce oxidative stress-causative factors and highlights their relationship with abiotic stresses in plants; (b) to overview structure, occurrence, and significance of CAT and APX in plants;

  17. H2O2-responsive molecularly engineered polymer nanoparticles as ischemia/reperfusion-targeted nanotherapeutic agents

    NASA Astrophysics Data System (ADS)

    Lee, Dongwon; Bae, Soochan; Hong, Donghyun; Lim, Hyungsuk; Yoon, Joo Heung; Hwang, On; Park, Seunggyu; Ke, Qingen; Khang, Gilson; Kang, Peter M.

    2013-07-01

    The main culprit in the pathogenesis of ischemia/reperfusion (I/R) injury is the overproduction of reactive oxygen species (ROS). Hydrogen peroxide (H2O2), the most abundant form of ROS produced during I/R, causes inflammation, apoptosis and subsequent tissue damages. Here, we report H2O2-responsive antioxidant nanoparticles formulated from copolyoxalate containing vanillyl alcohol (VA) (PVAX) as a novel I/R-targeted nanotherapeutic agent. PVAX was designed to incorporate VA and H2O2-responsive peroxalate ester linkages covalently in its backbone. PVAX nanoparticles therefore degrade and release VA, which is able to reduce the generation of ROS, and exert anti-inflammatory and anti-apoptotic activity. In hind-limb I/R and liver I/R models in mice, PVAX nanoparticles specifically reacted with overproduced H2O2 and exerted highly potent anti-inflammatory and anti-apoptotic activities that reduced cellular damages. Therefore, PVAX nanoparticles have tremendous potential as nanotherapeutic agents for I/R injury and H2O2-associated diseases.

  18. Cordierite-garnet-H2O equilibrium: A geological thermometer, barometer and water fugacity indicator

    NASA Astrophysics Data System (ADS)

    Martignole, Jacques; Sisi, Jean-Charles

    1981-03-01

    The high-grade assemblage Cd-Ga-Si-Qz can be thermodynamically modelled from available calorimetric data on the metastable reaction: (I) 410_2005_Article_BF01161500_TeX2GIFE1.gif 3 MgCd rightleftarrows 2 Py + 4 Si + 5 Qz natural K {D/Fe-Mg} between garnet and cordierite and experimental results on cordierite hydration. In the system SiO2-Al2O3-MgO-H2O, reaction (I) becomes (II) 410_2005_Article_BF01161500_TeX2GIFE2.gif 3 MgCd \\cdot nH_2 O rightleftarrows 2 Py + 4 Si + 5 Qz + 3 nH_2 O . However, hydrous cordierite is neither a hydrate nor a solid solution between water and anhydrous cordierite and when nH2O (number of moles of H2O in Cd) is plotted againstP_{H_2 O} , the resulting isotherms are similar to adsorption isotherms characteristic of zeolitic minerals. Reaction (II) can thus be considered as a combination of reaction (I) with a physical equilibrium of the type nH2O (in Cd)⇆nH2O (in vapor phase). Starting from a point on equilibrium (I), introduction of H2O into anhydrous Mg-cordierite lowers the chemical potential of MgCd and hence stabilizes this mineral to higher pressure relative to the right-hand assemblage in reaction (I). The pressure increment of stabilization, ΔP, above the pressure limit of anhydrous cordierite stability at constant T, has been calculated using the standard thermodynamics of adsorption isotherms. Cordierite is regarded as a mixture of Mg2Al4Si5O18 and H2O. The activity of H2O in the cordierite is evaluated relative to an hypothetical standard state extrapolated from infinite H2O dilution, by using measured hydration data. The activity of Mg2Al4Si5O18 in the cordierite is then obtained by integration of the Gibbs-Duhem equation, and the pressure stabilization increment, ΔP, computed by means of the relation: 410_2005_Article_BF01161500_TeX2GIFE3.gif Δ V_s Δ P \\cong - RTln a_{MgCd}^{MgCd \\cdot nH2O} left( {Δ V indepentdent of P and T} right) . Thus, one may contour the P-T plane in isopleths of nH2O=constant within the

  19. Synergistic effect of proanthocyanidin on the bactericidal action of the photolysis of H2O2.

    PubMed

    Ikai, Hiroyo; Nakamura, Keisuke; Kanno, Taro; Shirato, Midori; Meirelles, Luiz; Sasaki, Keiichi; Niwano, Yoshimi

    2013-01-01

    The in vitro antibacterial activity of the hydroxyl radical generation system by the photolysis of H2O2 in combination with proanthocyanidin, which refers to a group of polyphenolic compounds, was examined. Bactericidal activity of photo-irradiated H2O2 at 405 nm against Streptococcus mutans, a major pathogen of dental caries, was augmented in the presence of proanthocyanidin, whose bactericidal effect by itself was very poor, in a concentration-dependent manner. This combination was also proven effective against Porphyromonas gingivalis, a major pathogen of periodontitis. It is speculated that H2O2, generated from photo-irradiated proanthocyanidin around the bacterial cells, is photolyzed to the hydroxyl radical, which would in turn affect the membrane structure and function of the bacterial cells, resulting in augmented sensitivity of bacterial cells to the disinfection system utilizing the photolysis of H2O2. The present study suggests that the combination of H2O2 and proanthocyanidin works synergistically to kill bacteria when photo-irradiated.

  20. Competitive sorption of CO2 and H2O in 2:1 layer phyllosilicates

    NASA Astrophysics Data System (ADS)

    Schaef, Herbert T.; Loring, John S.; Glezakou, Vassiliki-Alexandra; Miller, Quin R. S.; Chen, Jeffrey; Owen, Antoinette T.; Lee, Mal-Soon; Ilton, Eugene S.; Felmy, Andrew R.; McGrail, B. Pete; Thompson, Christopher J.

    2015-07-01

    Expandable clays such as montmorillonite have interlayer exchange sites whose hydration state can be systematically varied from near anhydrous to almost bulk-like water conditions. This phenomenon has new significance with the simultaneous implementation of geological sequestration and secondary utilization of CO2 to both mitigate climate warming and enhance extraction of methane from hydrated clay-rich formations. In this study, the partitioning of CO2 and H2O between Na-, Ca-, and Mg-exchanged montmorillonite and variably hydrated supercritical CO2 (scCO2) was investigated using in situ X-ray diffraction (HXRD), infrared (IR) spectroscopic titrations, and quartz crystal microbalance (QCM) measurements. Density functional theory calculations provided mechanistic insights. Structural volumetric changes were correlated to quantified changes in sorbed H2O and CO2 concentrations as a function of percent H2O saturation in scCO2. Intercalation of CO2 is inhibited when the clay is fully collapsed (dehydrated interlayer), peaks sharply with the introduction of some H2O and partial expansion of the interlayer region, and then decreases systematically with further hydration of the clay. This behavior is discussed in the context of recent theoretical calculations of the montmorillonite H2O-CO2 system.

  1. Active sites and mechanisms for H2O2 decomposition over Pd catalysts

    PubMed Central

    Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

    2016-01-01

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

  2. Correction of Doppler-broadened Rayleigh backscattering effects in H2O dial measurements

    NASA Technical Reports Server (NTRS)

    Ansmann, A.; Bosenberg, J.

    1986-01-01

    A general method of solutions for treating effects of Doppler-broadened Rayleigh backscattering in H2O Differential Absorption Lidar (DIAL) measurements are described and discussed. Errors in vertical DIAL measuremtns caused by this laser line broadening effect can be very large and, therfore, this effect has to be accounted for accurately. To analyze and correct effects of Doppler-broadened Rayleigh backscattering in DIAL experiments, a generalized DIAL approximation was derived starting from a lidar equation, which includes Doppler broadening. To evaluate the accuracy of H2O DIAL measurements, computer simulations were performed. It was concluded that correction of Doppler broadened Rayleigh backscattering is possible with good accuracy in most cases of tropospheric H2O DIAL measurements, but great care has to be taken when layers with steep gradients of Mie backscattering like clouds or inversion layers are present.

  3. Production of vibrationally excited H(2)O from charge exchange of H(3)O(+) with cesium.

    PubMed

    Mann, Jennifer E; Xie, Zhen; Savee, John D; Bowman, Joel M; Continetti, Robert E

    2009-01-28

    The center-of-mass kinetic energy release for the dissociation of H(3)O following charge exchange of H(3)O(+) with cesium has been studied experimentally and modeled using quasiclassical trajectory calculations based on an ab initio potential energy surface for H(3)O(+) and "direct dynamics" for H(3)O. Branching fractions for the H(2)O+H and OH+H(2) dissociation channels have been measured and compared to the calculations. The dominant channel is found to be H(2)O+H and the experimental kinetic energy release spectrum reveals that H(2)O is formed with a vibrational inversion in stretching vibrations, coupled with low bending and rotational excitation.

  4. Excitations from dissociative fragments produced in H++H2O collisions

    NASA Astrophysics Data System (ADS)

    Monce, Michael N.; Pan, Sihui; Radeva, Nadezhda L.; Pepper, Jaime L.

    2009-01-01

    We report on photon emissions in the 200 800nm region resulting from collisions of 200keV protons with H2O . The most prominent features observed in the spectrum are the Balmer series of hydrogen and two OH molecular bands. Several less intense O+ as well as neutral O lines are also observed. The absolute photon emission cross sections of the major lines and bands were measured. The results indicate that a primary dissociation pathway involves the formation of H2O+ by removing a 1b2 electron. The unstable H2O+ ion further dissociates into H++OH or OH++H . The dominant presence of neutral hydrogen lines and O+ lines leads to the conclusion that the subsequent dissociation of OH+ into H+O+ prevails over the other possible dissociation pathway leading to H+ and neutral oxygen fragments.

  5. Optical spectrophotometry of Comet P/Giacobini-Zinner and emission profiles of H2O+

    NASA Technical Reports Server (NTRS)

    Strauss, M. A.; Mccarthy, P. J.; Spinrad, H.

    1986-01-01

    Two-dimensional CCD spectrograms were obtained of Comet P/Giacobini-Zinner (1984e) on five occasions between July and October 1985. Spatial emission profiles of H2O+ were extracted at 6198 angstroms (the strongest ionic line in the visible spectrum). This emission line traces the extent of the ion, or plasma, tail. The spectrographic slit was placed approximately along the trajectory of the ICE spacecraft on September 11, 1985; the resulting H2O+ profile has a full-width-half-maximum of about 5700 km, about three times that of the plasma density profile measured by ICE, and has a full-width-zero-intensity of about 30,000 km, very similar to the ICE values. H2O production rates for the comet are derived and compared with those of Comet P/Halley (1982i).

  6. Possible sources of H2 to H2O enrichment at evaporation of parent chondritic material

    NASA Technical Reports Server (NTRS)

    Makalkin, A. B.; Dorofeyeva, V. A.; Vityazev, A. V.

    1993-01-01

    One of the results obtained from thermodynamic simulation of recondensation of the source chondritic material is that at 1500-1800 K it's possible to form iron-rich olivine by reaction between enstatite, metallic iron and water vapor in the case of (H2O)/(H2) approximately equal to 0.1. This could be reached if the gas depletion in hydrogen is 200-300 times relative to solar abundance. To get this range of depletion one needs some source material more rich in hydrogen than the carbonaceous CI material which is the richest in volatiles among chondrites. In the case of recondensation at impact heating and evaporation of colliding planetesimals composed of CI material, we obtain insufficiently high value of (H2)/(H2O) ratio. In the present paper we consider some possible source materials and physical conditions necessary to reach gas composition with (H2)/(H2O) approximately 10 at high temperature.

  7. Rheologies of H2O ices Ih, II, and III at high pressures - A progress report

    NASA Astrophysics Data System (ADS)

    Kirby, S. H.; Durham, W. B.; Heard, H. C.

    Ordinary hexagonal ice (ice Ih) represents the stable crystalline form of H2O on the earth's surface. It is known that ice exists elsewhere in the solar system. Thus, several of the moons of Saturn and Jupiter are composed predominately of H2O and their surface temperatures are about 75 and 100 K. The pressures in the interior of some of the larger of the moons may be as high as 3 GPa. The involved pressures and temperatures extend far beyond the conditions over which the rheological laws for ice Ih can be confidently extrapolated. It is, therefore, necessary to obtain information regarding the rheologies of H2O ices in pressure and temperature ranges which had not yet been previously considered. Since 1981, over 100 triaxial compression tests have been conducted over a wide range of temperatures (77 to 258 K) and pressures (0.1 to 350 MPa). The present paper provides a progress report of these experiments.

  8. VUV photoionization cross sections of HO2, H2O2, and H2CO.

    PubMed

    Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

    2015-02-26

    The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.

  9. NaBH4/H2O2 Fuel Cells for Lunar and Mars Exploration

    NASA Astrophysics Data System (ADS)

    Luo, Nie; Miley, George H.; Mather, Joseph; Burton, Rodney; Hawkins, Glenn; Gimlin, Richard; Rusek, John; Valdez, Tom I.; Narayanan, Sekharipuram R.

    2006-01-01

    The properties of direct hydrogen peroxide (H2O2) fuel cells are studied in this research. Different catalysts and diffusion electrodes are tested to optimize the cell performance. Initial results indicate: 1) conversion efficiency over 60% at a practical current density of 250mA/cm2; 2) power density over 0.6 W/cm2, at room temperature and ambient pressure, better than that of any traditional fuel cell. Further, the unique combination of NaBH4 and H2O2, both of which are in an aqueous form, paves the way for a convenient unitized regeneration, which is inherently compact compared to other cells that use gas phase reactants, such as the conventional H2 and O2. These excellent properties make the NaBH4/H2O2 fuel cell a very promising candidate for future space power systems. A conceptual design to power Lunar and Mars missions is discussed.

  10. Variability of the OH and H2O maser emission toward AS 501

    NASA Astrophysics Data System (ADS)

    Ashimbaeva, N. T.; Colom, P.; Krasnov, V. V.; Lekht, E. E.; Pashchenko, M. I.; Rudnitskii, G. M.; Tolmachev, A. M.

    2017-01-01

    The results of observations of OH (λ = 18 cm) and H2O (λ = 1.35 cm) masers toward AS 501 obtained with the Nançay Observatory Radio Telescope (France) and the 22-m radio telescope of the Pushchino Radio Astronomy Observatory (Russia), respectively, are presented. Nine cycles of H2O maser activity ranging from 2.8 to 6.0 years were detected, identifying AS 501 as an irregular variable star. Zeeman splitting was found only in the 1612-MHz satellite line at -59.2 km/s. The splitting is 0.11 km/s, corresponding to a line-of-sight magnetic field strength of 0.48 mG. The field is directed toward the observer. The detected radial-velocity drift of the H2O emission features can be explained in a model with elongated filaments with radial-velocity gradients.

  11. Theoretical study of the rovibrational spectrum of H2O-H2

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-Gang; Carrington, Tucker

    2011-01-01

    In this paper we report transition frequencies and line strengths computed for H_2O-H_2 and compare with the experimental observations of [M. J. Weida and D. J. Nesbitt, J. Chem. Phys. 110, 156 (1999)]. To compute the spectra we use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. Our results corroborate the assignments of Weida and Nesbitt and there is good agreement between calculated and observed transitions. Possible candidates for lines that Weida and Nesbitt were not able to assign are presented. Several other bands that may be observable are also discovered. Although all the observed bands are associated with states localized near the global potential minimum, at which H_2O acts as proton acceptor, a state with significant amplitude near the T-shape secondary potential minimum at which H_2O acts as proton donor is identified by examining many different probability density plots.

  12. Influence of Rayleigh-Doppler broadening on the selection of H2O dial system parameters

    NASA Technical Reports Server (NTRS)

    Ismail, S.; Browell, E. V.

    1986-01-01

    Computer simulations have enabled the performance of a H2O Differential Absorption Lidar (DIAL) system to be studied by spectrally analyzing the forward propagating and backscattered laser energy. The simulations were done for a high altitude (21 km) DIAL system operating in a nadir-viewing mode. The influence of Rayleigh Doppler broadening on DIAL measurement accuracies were evaluated and show that the Rayleigh broadening influence, which can be corrected to first order in regions free of large aerosol gradients, reduces the sensitivity of DIAL H2O measurement errors in the upper tropospheric region. The ability to correct the Rayleigh broadening and the selection of H2O DIAL parameters when all the systematic effects are combined, were discussed.

  13. Palladium-tin catalysts for the direct synthesis of H2O2 with high selectivity

    DOE PAGES

    Freakley, Simon J.; He, Qian; Harrhy, Jonathan H.; ...

    2016-02-25

    The direct synthesis of hydrogen peroxide (H2O2 ) from H2 and O2 represents a potentially atom-efficient alternative to the current industrial indirect process. We show that the addition of tin to palladium catalysts coupled with an appropriate heat treatment cycle switches off the sequential hydrogenation and decomposition reactions, enabling selectivities of >95% toward H2O2 . This effect arises from a tin oxide surface layer that encapsulates small Pd-rich particles while leaving larger Pd-Sn alloy particles exposed. In conclusion, we show that this effect is a general feature for oxide-supported Pd catalysts containing an appropriate second metal oxide component, and wemore » set out the design principles for producing high-selectivity Pd-based catalysts for direct H2O2 production that do not contain gold.« less

  14. Sailuotong Prevents Hydrogen Peroxide (H2O2)-Induced Injury in EA.hy926 Cells

    PubMed Central

    Seto, Sai Wang; Chang, Dennis; Ko, Wai Man; Zhou, Xian; Kiat, Hosen; Bensoussan, Alan; Lee, Simon M. Y.; Hoi, Maggie P. M.; Steiner, Genevieve Z.; Liu, Jianxun

    2017-01-01

    Sailuotong (SLT) is a standardised three-herb formulation consisting of Panax ginseng, Ginkgo biloba, and Crocus sativus designed for the management of vascular dementia. While the latest clinical trials have demonstrated beneficial effects of SLT in vascular dementia, the underlying cellular mechanisms have not been fully explored. The aim of this study was to assess the ability and mechanisms of SLT to act against hydrogen peroxide (H2O2)-induced oxidative damage in cultured human vascular endothelial cells (EAhy926). SLT (1–50 µg/mL) significantly suppressed the H2O2-induced cell death and abolished the H2O2-induced reactive oxygen species (ROS) generation in a concentration-dependent manner. Similarly, H2O2 (0.5 mM; 24 h) caused a ~2-fold increase in lactate dehydrogenase (LDH) release from the EA.hy926 cells which were significantly suppressed by SLT (1–50 µg/mL) in a concentration-dependent manner. Incubation of SLT (50 µg/mL) increased superoxide dismutase (SOD) activity and suppressed the H2O2-enhanced Bax/Bcl-2 ratio and cleaved caspase-3 expression. In conclusion, our results suggest that SLT protects EA.hy916 cells against H2O2-mediated injury via direct reduction of intracellular ROS generation and an increase in SOD activity. These protective effects are closely associated with the inhibition of the apoptotic death cascade via the suppression of caspase-3 activation and reduction of Bax/Bcl-2 ratio, thereby indicating a potential mechanism of action for the clinical effects observed. PMID:28067784

  15. Hydrogen isotope systematics of H2-H2O-CH4 during hydrogenotrophic methanogenesis

    NASA Astrophysics Data System (ADS)

    Kobayashi, M.; Kawagucci, S.; Hattori, S.; Yamada, K.; Ueno, Y.; Takai, K.; Yoshida, N.

    2011-12-01

    Hydrogen and carbon isotopes of CH4 have been utilized to trace microbial processes. The isotope fractionations during hydrogenotrophic methanogenesis, one of the major processes of environmental CH4, have been studied by several laboratory incubations. For the carbon isotope, H2 concentration is thought to be the major parameter controlling the carbon isotope fractionation by hydrogenotrophic methanogenesis. For the hydrogen, on the other hand, factors controlling isotope fractionation remain poorly understood, although H2 concentration is suggested to be important. This uncertainty prevents us to utilize δD-CH4 value as the tracer. The most important and principal question is whether all hydrogen atoms in microbially-generated CH4 come from environmental H2O or not. To answer the question, we investigated the D/H systematics of H2-H2O-CH4 during hydrogenotrophic methanogenesis by pure culture incubation with softly deuterium-enriched H2 and/or H2O. Our results demonstrate that δD-CH4 value produced by hydrogenotrophic methanogens depends not only on δD-H2O value but also on δD-H2 value. We observed constant correlation between δD-H2 and δD-CH4 values as well as between δD-H2O and δD-CH4 values, which suggests that hydrogen (/deuterium) atom of substrate H2 is also transferred to the product CH4. This implies that the range of δD-CH4 value produced by hydrogenotrophic methanogenesis should be re-evaluated considering the distribution of δD-H2 and δD-H2O values in natural environments.

  16. [Study on UV and H2O2 combined inactivation of E. coli in drinking water].

    PubMed

    Zhang, Yi-Qing; Zhou, Ling-Ling; Zhang, Yong-Ji

    2013-06-01

    The inactivation effect of E. coli with both UV irradiation and hydrogen peroxide disinfection individually and in different combination modes was investigated. The results showed that hydrogen peroxide alone caused hardly any inactivation of E. coli. Only 0.02 lg inactivation was achieved by hydrogen peroxide with concentration of 20 mg x L(-1) and contact time of 30 min. UV irradiation was able to inactivate E. coli to a certain extent. The inactivation reached 4.51 lg at a UV dose of 10 mJ x cm(-2). The combination of UV and H2O2 could significantly improve the inactivation effect and the different combination modes affected the inactivation effect. The inactivation effect of UV-H2O2 was better than that of H2O2 -UV. The inactivation was increased by 0.09, 0.35, 0.38, 0.68 lg and 0.01, 0.07, 0.14, 0.53 lg when compared to the treatment with solely UV irradiation, respectively, at UV dose of 5 mJ x cm(-2) with hydrogen peroxide at contact time of 2.5, 5, 10, 20 minutes. UV/H2O2 achieved better results than sequential disinfection. The inactivation was enhanced by 0.43 lg and 0.58 lg when compared to UV-H2O2 and H2O2-UV, respectively, at UV dose of 5 mJ x cm(-2) with hydrogen peroxide at contact time of 20 minutes. The inactivation of E. coli increased with the enhancement of UV radiation intensity.

  17. H2O2: a Ca(2+) or Mg(2+)-sensing function in statin passive diffusion.

    PubMed

    Guillaume, Yves Claude; Lethier, Lydie; André, Claire

    2015-09-01

    In a previous paper Guillaume's group demonstrated that magnesium (Mg(2+) concentration range 0.00-2.60 mm) increased the passive diffusion of statins and thus played a role in their potential toxicity. In order to confirm an increase in this passive diffusion by divalent salt cations, the role of calcium chloride (CaCl2) on the statin-immobilized artificial membrane (IAM) association was studied. It was demonstrated that calcium supplementation (Ca(2+) concentration range 0.00-3.25 mm) increases the statin passive diffusion. In addition, it was shown that the Ca(2+) effect on the statin-IAM association is higher than that of Mg(2+). These results show that Ca(2+) enhances the passive diffusion of drugs into biological membranes and thus their potential toxicity. Also, addition of H2O2 to the medium showed a hyperbolic response for the statin passive diffusion and this effect was enhanced for the highest Ca(2+) or Mg(2+) concentrations in the medium. H2O2 is likely to interact with the polar head groups of the IAM through dipole-dipole interactions. The conformational changes in H2O2-IAM result in a higher degree of exposure of hydrophobic areas, thus explaining why the binding of pravastatin, which showed the lowest logP value, was less affected by H2O2. This result shows the significant contribution of H2O2 and thus the oxidative stress on the statin passive diffusion. Much of the sensitivity derives from the action of Ca(2+) or Mg(2+), in turn supported the idea that H2O2 may serve a Ca(2+) or Mg(2+) sensing function in statin passive diffusion.

  18. Ortho-para mixing hyperfine interaction in the H2O+ ion and nuclear spin equilibration.

    PubMed

    Tanaka, Keiichi; Harada, Kensuke; Oka, Takeshi

    2013-10-03

    The ortho to para conversion of water ion, H2O(+), due to the interaction between the magnetic moments of the unpaired electron and protons has been theoretically studied to calculate the spontaneous emission lifetime between the ortho- and para-levels. The electron spin-nuclear spin interaction term, Tab(SaΔIb + SbΔIa) mixes ortho (I = 1) and para (I = 0) levels to cause the "forbidden" ortho to para |ΔI| = 1 transition. The mixing term with Tab = 72.0 MHz is 4 orders of magnitude higher for H2O(+) than for its neutral counterpart H2O where the magnetic field interacting with proton spins is by molecular rotation rather than the free electron. The resultant 10(8) increase of ortho to para conversion rate possibly makes the effect of conversion in H2O(+) measurable in laboratories and possibly explains the anomalous ortho to para ratio recently reported by Herschel heterodyne instrument for the far-infrared (HIFI) observation. Results of our calculations show that the ortho ↔ para mixings involving near-degenerate ortho and para levels are high (∼10(-3)), but they tend to occur at high energy levels, ∼300 K. Because of the rapid spontaneous emission, such high levels are not populated in diffuse clouds unless the radiative temperature of the environment is very high. The low-lying 101 (para) and 111 (ortho) levels of H2O(+) are mixed by ∼10(-4) making the spontaneous emission lifetime for the para 101 → ortho 000 transition 520 years and 5200 years depending on the F value of the hyperfine structure. Thus the ortho ↔ para conversion due to the unpaired electron is not likely to seriously affect thermalization of interstellar H2O(+) unless either the radiative temperature is very high or number density of the cloud is very low.

  19. Tanshinone IIA Protects Endothelial Cells from H2O2-Induced Injuries via PXR Activation.

    PubMed

    Zhu, Haiyan; Chen, Zhiwu; Ma, Zengchun; Tan, Hongling; Xiao, Chengrong; Tang, Xianglin; Zhang, Boli; Wang, Yuguang; Gao, Yue

    2017-02-06

    Tanshinone IIA (Tan IIA) is a pharmacologically active substance extracted from the rhizome of Salvia miltiorrhiza Bunge (also known as the Chinese herb Danshen), and is widely used to treat atherosclerosis. The pregnane X receptor (PXR) is a nuclear receptor that is a key regulator of xenobiotic and endobiotic detoxification. Tan IIA is an efficacious PXR agonist that has a potential protective effect on endothelial injuries induced by xenobiotics and endobiotics via PXR activation. Previously numerous studies have demonstrated the possible effects of Tan IIA on human umbilical vein endothelial cells, but the further mechanism for its exerts the protective effect is not well established. To study the protective effects of Tan IIA against hydrogen peroxide (H2O2) in human umbilical vein endothelial cells (HUVECs), we pretreated cells with or without different concentrations of Tan IIA for 24 h, then exposed the cells to 400 μM H2O2 for another 3 h. Therefore, our data strongly suggests that Tan IIA may lead to increased regeneration of glutathione (GSH) from the glutathione disulfide (GSSG) produced during the GSH peroxidase-catalyzed decomposition of H2O2 in HUVECs, and the PXR plays a significant role in this process. Tan IIA may also exert protective effects against H2O2-induced apoptosis through the mitochondrial apoptosis pathway associated with the participation of PXR. Tan IIA protected HUVECs from inflammatory mediators triggered by H2O2 via PXR activation. In conclusion, Tan IIA protected HUVECs against H2O2-induced cell injury through PXR-dependent mechanisms.

  20. Competitive Sorption of CO2 and H2O in 2:1 Layer Phyllosilicates

    SciTech Connect

    Schaef, Herbert T.; Loring, John S.; Glezakou, Vassiliki Alexandra; Miller, Quin R.; Chen, Jeffrey; Owen, Antionette T.; Lee, Mal Soon; Ilton, Eugene S.; Felmy, Andrew R.; McGrail, B. Peter; Thompson, Christopher J.

    2015-07-01

    The salting out effect, where increasing the ionic strength of aqueous solutions decreases the solubility of dissolved gases is a well-known phenomenon. Less explored is the opposite process where an initially anhydrous system containing a volatile, relatively non-polar component and inorganic ions is systematically hydrated. Expandable clays such as montmorillonite are ideal systems for exploring this scenario as they have readily accessible exchange sites containing cations that can be systematically dehydrated or hydrated, from near anhydrous to almost bulk-like water conditions. This phenomenon has new significance with the simultaneous implementation of geological sequestration and secondary utilization of CO2 to both mitigate climate warming and enhance extraction of methane from hydrated clay-rich formations. Here, the partitioning of CO2 and H2O between Na-, Ca-, and Mg-exchanged montmorillonite and variably hydrated supercritical CO2 (scCO2) was investigated using in situ X-ray diffraction, infrared (IR)spectroscopic titrations, and quartz crystal microbalance (QCM) measurements. Density functional theory calculations provided mechanistic insights. Structural volumetric changes were correlated to quantified changes in sorbed H2O and CO2 concentrations as a function of %H2O saturated in scCO2. Intercalation of CO2 is favored at low H2O/CO2 ratios in the interlayer region, where CO2 can solvate the interlayer cation. As the clay becomes more hydrated and the H2O/CO2 ratio increases, H2O displaces CO2 from the solvation shell of the cation and CO2 tends to segregate. This transition decreases both the entropic and enthalpic driving force for CO2 intercalation, consistent with experimentally observed loss of intercalated CO2.

  1. Mixing schemes in a urea-H2O system: a differential approach in solution thermodynamics.

    PubMed

    Koga, Yoshikata; Miyazaki, Yuji; Nagano, Yatsuhisa; Inaba, Akira

    2008-09-11

    The excess partial molar enthalpies of urea (UR), H U R (E ), were experimentally determined in UR-H 2O at 25 degrees C. The H U R (E ) data were determined accurately and in small increments in the mole fraction of UR, x U R , up to x U R approximately 0.22. Hence it was possible to evaluate one more x U R -derivative graphically without resorting to any fitting function, and the model-free UR-UR enthalpic interaction, H U R- U R (E ), was calculated. Using previous data for the excess chemical potential, mu U R (E ), the entropy analogue, S U R- U R (E ), was also calculated. The x U R -dependences of both H U R- U R (E ) and S U R- U R (E ) indicate that there is a boundary at x U R approximately 0.09 at which the aggregation nature of urea changes. From the results of our earlier works, we suggest that a few UR molecules aggregate at x U R approximately 0.09, while the integrity of H 2O is retained at least up to x U R approximately 0.20. Together with the findings from our previous studies, we suggest that in the concentration range x U R < 0.22, UR or its aggregate form hydrogen bonds to the H 2O network, reducing the degree of fluctuation characteristic to liquid H 2O. However, up to at least x U R = 0.20 the hydrogen bond network remains intact. Above x U R approximately 0.22, the integrity of H 2O is likely be lost. Thus, in discussing the effect of urea on H 2O and in relating it to the structure and function of biopolymers in aqueous solutions, the concentration region in question must be specified.

  2. Oxygen isotope partitioning between immiscible silicate melts with H2O, P and S

    NASA Astrophysics Data System (ADS)

    Lester, Gregory W.; Kyser, T. K.; Clark, Alan H.

    2013-05-01

    Differences between the δ18O values of immiscible Si- and Fe-rich melts in the systems Fe2SiO4-Fe3O4-KAlSi2O6-SiO2, Fe3O4-KAlSi2O6-SiO2, and Fe3O4-Fe2O3-KAlSi2O6-SiO2, with H2O, H2O + P or H2O + S have been determined in isothermal, isobaric experiments at 1100 and 1200 °C and 200 MPa. The Δ18O values for conjugate Fe2SiO4-Fe3O4-KAlSi2O6-SiO2 + H2O and, Fe3O4-KAlSi2O6-SiO2·KAlSi2O6-SiO2 + H2O melts are only 0.4-0.6‰ and do not differ significantly from those for anhydrous melts of similar composition. The Δ18O values for melts with added H2O + P or S are more variable, ranging from 0.0 to 0.8‰. Partitioning of 18O between the immiscible melts is 0.6-1‰ less than the partitioning reported for melt-mineral and mineral-mineral pairs. The partitioning of 18O in the network modifier-bearing immiscible melts is not controlled by the relative degree of polymerization in the melts or fO2. The upper limit of the range of Δ18O values (<1‰), and the variation in the δ18O values of conjugate melts that occurs with the inclusion of network modifying constituents, suggest that in some cases, oxygen isotope ratios might be useful to distinguish lithologies evolved from coexisting immiscible silicate melts, from lithologies that have evolved by crystal fractionation only.

  3. No effect of H2O degassing on the oxidation state of magmatic liquids

    NASA Astrophysics Data System (ADS)

    Waters, Laura E.; Lange, Rebecca A.

    2016-08-01

    The underlying cause for why subduction-zone magmas are systematically more oxidized than those formed at mid-ocean spreading ridges is a topic of vigorous debate. It is either a primary feature inherited from the subduction of oxidized oceanic crust into the mantle or a secondary feature that develops because of H2O degassing and/or magma differentiation. Low total iron contents and high melt H2O contents render rhyolites sensitive to any effect of H2O degassing on ferric-ferrous ratios. Here, pre-eruptive magmatic Fe2+ concentrations, measured using Fe-Ti oxides that co-crystallized with silicate phenocrysts under hydrous conditions, are compared with Fe2+ post-eruptive concentrations in ten crystal-poor, fully-degassed obsidian samples; five are microlite free. No effect of H2O degassing on the ferric-ferrous ratio is found. In addition, Fe-Ti oxide data from this study and the literature show that arc magmas are systematically more oxidized than both basalts and hydrous silicic melts from Iceland and Yellowstone prior to extensive degassing. Nor is there any evidence that differentiation (i.e., crystal fractionation, crustal assimilation) is the cause of the higher redox state of arc magmas relative to those of Iceland/Yellowstone rhyolites. Instead, the evidence points to subduction of oxidized crust and the release of an H2O-rich fluid and/or melt with a high oxygen fugacity (fO2), which plays a role during H2O-flux melting of the mantle in creating basalts that are relatively oxidized.

  4. Partial phase diagram for the system NH3-H2O - The water-rich region

    NASA Technical Reports Server (NTRS)

    Johnson, M. L.; Schwake, A.; Nicol, M.

    1984-01-01

    Phase boundaries of the H2O-NH3 system for (NH3)/x/(H2O)/1-x/ have been determined with diamond-anvil cells for mixtures in two composition ranges: (1) for x in the range from 0 to 0.3, at pressures up to 4 GPa at 21 C, and (2) for x in the range from 0.46 to 0.50, at pressures up to 5 GPa from 150 to 400 K. Phases were identified visually with a microscope and polarized optics. The NH3.2(H2O) phase is strongly anisotropic with a much smaller refractive index than that of ice VII and cracks in two nonperpendicular networks. NH3.H2O has a refractive index closer to that of Ice VII and does not appear to form cracks. Both phases are colorless. Phase boundaries were determined on both increasing and decreasing pressures, and compositions of the ammonia ices were determined by estimating relative amounts of water and ammonia ices at known overall compositions. For low-ammonia compositions (x equal to or less than 0.15), the following assemblages succedd one another as pressure increases: liquid; liquid and Ice VI (at 1.0 + GPa); liquid and Ice VII (at 2.1 GPa); Ice VII and NH3.H2O (at 3.5 GPa). For x in the range from 0.15 to 0.30, the water ice and liquid fields are replaced by the NH3.2(H2O) and liquid field at pressures down to 1.0 GPa and lower.

  5. H2O2 Improves Quality of Radix scutellariae Through Anti-oxidant Effect

    PubMed Central

    Qi, Song; Wu-lin, Cao; Hua, Jiang; Ai-hua, Zhang; Xiang-cai, Meng

    2016-01-01

    Introduction: The correlation between the quality and geographical origin of herbal medicine was traced back to Tang Dynasty in China, more than 1200 years, and the effects of ecological environments on the secondary metabolites such as flavonoids have been confirmed. However, little is known about how the adversity impacts on the quality. Reactive oxygen species (ROS) may be medium between the ecological environment and the secondary metabolism. Materials and Methods: The fresh roots of Scutellaria baicalensis Georgi were treated with 0.002 μmol/L, 0.2 μmol/L, and 20 μmol/L H2O2, respectively. A stress model was established to elucidate the change of secondary metabolism, anti-oxidant enzyme system, and enzymes relating to flavonoids. Results: The activities of superoxide dismutase, catalase and peroxidase decreased. Too much H2O2, firstly, boosted transformation of flavonoids glycoside into aglucon with the most remarkable activities through UDP-glucuronate baicalein 7-O-glucuronosyltransferase (UBGAT), and β-glucuronidase (GUS), then regulated the gene expression of phenylalanine ammonialyase, GUS, and UBGAT, and increased the contents of flavones, motivated the flavonoid glycoside converting into aglucon. With this action, the flavones displaced the anti-oxidant enzymes. The higher the dosage, the more baicalein and wogonin increased, the later they took action. Conclusion: The plant secondary metabolites to keep ROS constant are identical to the effective materials in clinic. They are closely linked. H2O2 can improve flavones, especially the aglucon, and further increased the quality of herbal medicine, which possesses very important value in medical practice. SUMMARY H2O2 decreasing the activities of CAT and POD lead to accumulation of more H2O2. Excess of H2O2 up-regulated PAL, BUG, promote biosynthesis of flavones, and enhance the nonenzyme system. “↑” and “↓” represent activity or content “up” and “down” respectively. PMID:27019566

  6. Thyroid Ca2+/NADPH-dependent H2O2 generation is partially inhibited by propylthiouracil and methimazole.

    PubMed

    Ferreira, Andrea C Freitas; de Carvalho Cardoso, Luciene; Rosenthal, Doris; de Carvalho, Denise Pires

    2003-06-01

    H2O2 generation is a limiting step in thyroid hormone biosynthesis. Biochemical studies have confirmed that H2O2 is generated by a thyroid Ca2+/NADPH-dependent oxidase. Decreased H2O2 availability may be another mechanism of inhibition of thyroperoxidase activity produced by thioureylene compounds, as propylthiouracil (PTU) and methimazole (MMI) are antioxidant agents. Therefore, we analyzed whether PTU or MMI could scavenge H2O2 or inhibit thyroid NADPH oxidase activity in vitro. Our results show that PTU and thiourea did not significantly scavenge H2O2. However, MMI significantly scavenged H2O2 at high concentrations. Only MMI was able to decrease the amount of H2O2 generated by the glucose-glucose oxidase system. On the other hand, both PTU and MMI were able to partially inhibit thyroid NADPH oxidase activity in vitro. As PTU did not scavenge H2O2 under the conditions used here, we presume that this drug may directly inhibit thyroid NADPH oxidase. Also, at the concentration necessary to inhibit NADPH oxidase activity, MMI did not scavenge H2O2, also suggesting a direct effect of MMI on thyroid NADPH oxidase. In conclusion, this study shows that MMI, but not PTU, is able to scavenge H2O2 in the micromolar range and that both PTU and MMI can impair thyroid H2O2 generation in addition to their potent thyroperoxidase inhibitory effects.

  7. Exploring external time-dependent sources of H2O into Titan's atmosphere

    NASA Astrophysics Data System (ADS)

    Lara, Luisa-Maria; Lellouch, Emmanuel; González, Marta; Moreno, Raphael; Rengel, Miriam

    2014-05-01

    Recent observations (Cottini et al., 2012, and Moreno et al., 2012) and steady-state photochemical modelling (Moreno et al., 2012; Dobrijevic et al., 2014) indicate that the amounts of CO2 and H2O in Titan's stratosphere imply relatively inconsistent values of the OH/H2O input flux. Moreno et al. (2012) proposed that the oxygen source is time-variable, whereas Dobrijevic et al. (2014) arrived to the same conclusion of Moreno et al. (2012) that the HSO (Herschel Space Observatory) measured H2O profile is'inconsistent" with the CO2 abundance. Furthermore, Dobrijevic et al. (2014) also found that reconciliation was possible if abundances reported by Cottini et al. (2012) are correct instead, though in this situation and for an Enceladus source, their model tended to overpredict the thermospheric abundance of H2O , compared to the upper limit by Cui et al. (2009). We attempt to reconcile the H2O and CO2 observed profiles in Titan's atmosphere by considering several time-dependent scenarios for the infux/evolution of oxygen species. To explore this, we use a time-dependent photochemical model of Titan's atmosphere to calculate effective lifetimes and the response of Titan's oxygen compounds to changes in the oxygen input flux. We consider a time-variable Enceladus source, as well as the evolution of material delivered by a cometary impact. We will show results on effective H2O and CO2 effective lifetimes, on the feasibility of time-variable Enceladus source, and on an additional H2O loss-to-the-haze. Regarding CO2, we will analyse its production following a cometary impact. A summary on viable scenarios to explain the H2O / CO2 puzzle will be given. References Moreno, R., Lellouch, E., Lara, L. M., et al. 2012, Icarus, 221, 753. Cottini, V., Nixon, C. A., Jennings, D. E., et al. 2012, Icarus, 220, 855. Cui, J., Yelle, R. V., Vuitton, V., et al. 2009, Icarus, 200, 581. Dobrijevic, M., Hébrard, E., Loison, J., and Hickson, K. 2014, Icarus, 228, 324.

  8. Using HDO/H2O dynamics to constrain GCM convective processes during the MJO

    NASA Astrophysics Data System (ADS)

    Tuinenburg, Obbe; Risi, Camille; Lacour, Jean-Lionel; Schneider, Matthias

    2014-05-01

    This research aims to improve the convective processes during the MJO and other modes of intra-seasonal variability in the LMDZ atmospheric models, by making use of joint HDO and H2O (vapor) measurements. The joint use of HDO/H2O yields additional information compared to sole humidity measurements. In addition to atmospheric drying and wetting derived from the humidity measurements, the HDO measurements provide enrichment and depletion information. This information is used to distinguish between different moistening and drying processes. For example, a separation can be made between atmospheric moistening due to ocean surface evaporation and due to rain re-evaporation, as the re-evaporating moisture is more depleted in HDO than the surface evaporation. We use IASI and TES satellite HDO and H2O measurements and determine their evolution in the troposphere (700 to 400 hPa) during the MJO. Moreover, these evolutions are compared to the isotope enabled LMDZ GCM, which is forced with reanalysis wind fields. In this nudged mode, sensitivity tests of key parameters (cold pool representation, entrainment rate, precipitation efficiency, droplet size and fall speed, etc.) in the convection scheme are performed and compared with the measurements. Initial results suggest that over the Indian ocean, there is a difference between the lower- and mid-tropospheric HDO-H2O dynamics for MJO events. In the lower troposphere (at 700 hPa), the dynamics of HDO and H2O are exactly out of phase, following a curve which indicates surface moistening by surface evaporation throughout the MJO event. At 500 hPa, the measurements indicate the main moisture source is surface evaporation before the MJO peak and rain re-evaporation during the 10 days after the MJO peak. Over the maritime continent, the dynamics are the same in the lower and mid-troposphere. The predominant source is surface evaporation before the event, and re-evaporation during the 10 days after the event. The model captures the

  9. The influence of H2O line blanketing on the spectra of cool dwarf stars

    NASA Technical Reports Server (NTRS)

    Allard, F.; Hauschildt, P. H.; Miller, S.; Tennyson, J.

    1994-01-01

    We present our initial results of model atmosphere calculations for cool M dwarfs using an opacity sampling method and a new list of H2O lines. We obtain significantly improved fits to the infrared spectrum of the M dwarf VB10 when compared to earlier models. H2O is by far the dominant opacity source in cool stars. To illustrate this, we show the Rosseland mean of the total extinction under various assumptions. Our calculations demonstrate the importance of a good treatment of the water opacities in cool stars and the improvements possible by using up-to-date data for the water line absorption.

  10. Cardiovascular effects of resveratrol and atorvastatin treatments in an H2O2-induced stress model

    PubMed Central

    SONER, BURAK CEM; ŞAHIN, AYŞE SAIDE

    2014-01-01

    Oxidative stress has been implicated in the pathophysiology of several types of cardiovascular disease (CVD). Statins are widely used to inhibit the progression of atherosclerosis and reduce the incidence of CVD. Certain over-the-counter products, including resveratrol, show similar effects to statins and may thus be used in conjunction with statins for the treatment of the majority of patients with CVD. The aim of the present study was to evaluate the effects of atorvastatin, resveratrol and resveratrol + atorvastatin (R+A) pretreatment on myocardial contractions and vascular endothelial functions in the presence of H2O2 as an experimental model of oxidative stress in rats. Four groups were established and referred to as the control, atorvastatin, resveratrol and R+A groups. Atorvastatin (40 mg/kg, per oral) and/or resveratrol (30 mg/kg, intraperitoneal) treatments were administered for 14 days. On the 15th day, the thoracic aortas and hearts of the rats were dissected and placed into isolated organ baths. Vascular responses to cumulative doses of H2O2 (1×10−8–1×10−4 M H2O2) with and without N (G)-nitro-L-arginine methyl ester (L-NAME) incubation were measured. In addition, myocardial electrical stimulation (ES) responses to various H2O2 concentrations (1×10−7–1×10−5 M H2O2) were evaluated. In the control and atorvastatin groups, H2O2 application caused a significant dose-dependent decrease in the ES-induced contractions in the myocardial tissue of rats. In the resveratrol and R+A groups, H2O2 application did not significantly affect myocardial contraction at any dose. In all groups, incubation with L-NAME caused a significant augmentation in the H2O2 response, revealing that this effect was mediated via the vascular endothelium. In conclusion, pretreatment with R+A for CVD appears to be superior to pretreatment with either agent alone. PMID:25289077

  11. One- or Two-Electron Water Oxidation, Hydroxyl Radical, or H2O2 Evolution.

    PubMed

    Siahrostami, Samira; Li, Guo-Ling; Viswanathan, Venkatasubramanian; Nørskov, Jens K

    2017-02-27

    Electrochemical or photoelectrochemcial oxidation of water to form hydrogen peroxide (H2O2) or hydroxyl radicals ((•)OH) offers a very attractive route to water disinfection, and the first process could be the basis for a clean way to produce hydrogen peroxide. A major obstacle in the development of effective catalysts for these reactions is that the electrocatalyst must suppress the thermodynamically favored four-electron pathway leading to O2 evolution. We develop a thermochemical picture of the catalyst properties that determine selectivity toward the one, two, and four electron processes leading to (•)OH, H2O2, and O2.

  12. Critical behavior of dilute NaCl in H2O

    USGS Publications Warehouse

    Pitzer, Kenneth S.; Bischoff, J.L.; Rosenbauer, R.J.

    1987-01-01

    The compositions of the saturated vapor and liquid phases are measured for the system NaCl-H2O at 380??C, which is close to the critical point of pure water. The shape of the phase equilibrium curve is classical, which confirms a conclusion reached earlier on the basis of less accurate data. This implies that the long-range forces introduced by the NaCl suppress the non-classical effects present in pure H2O. An empirical equation of a classical type fits these data. ?? 1987.

  13. Effect of plant extracts on H2O2-induced inflammatory gene expression in macrophages

    PubMed Central

    Pomari, Elena; Stefanon, Bruno; Colitti, Monica

    2014-01-01

    Background Arctium lappa (AL), Camellia sinensis (CS), Echinacea angustifolia, Eleutherococcus senticosus, Panax ginseng (PG), and Vaccinium myrtillus (VM) are plants traditionally used in many herbal formulations for the treatment of various conditions. Although they are well known and already studied for their anti-inflammatory properties, their effects on H2O2-stimulated macrophages are a novel area of study. Materials and methods Cell viability was tested after treatment with increasing doses of H2O2 and/or plant extracts at different times of incubation to identify the optimal experimental conditions. The messenger (m)RNA expression of TNFα, COX2, IL1β, NFκB1, NFκB2, NOS2, NFE2L2, and PPARγ was analyzed in macrophages under H2O2 stimulation. The same genes were also quantified after plant extract treatment on cells pre-stimulated with H2O2. Results A noncytotoxic dose (200 μM) of H2O2 induced active mRNA expression of COX2, IL1β, NFE2L2, NFκB1, NFκB2, NOS2, and TNFα, while PPARγ was depressed. The expression of all genes tested was significantly (P<0.001) regulated by plant extracts after pre-stimulation with H2O2. COX2 was downregulated by AL, PG, and VM. All extracts depressed IL1β expression, but upregulated NFE2L2. NFκB1, NFκB2, and TNFα were downregulated by AL, CS, PG, and VM. NOS2 was inhibited by CS, PG, and VM. PPARγ was decreased only after treatment with E. angustifolia and E. senticosus. Conclusion The results of the present study indicate that the stimulation of H2O2 on RAW267.4 cells induced the transcription of proinflammatory mediators, showing that this could be an applicable system by which to activate macrophages. Plant extracts from AL, CS, PG, and VM possess in vitro anti-inflammatory activity on H2O2-stimulated macrophages by modulating key inflammation mediators. Further in vitro and in vivo investigation into molecular mechanisms modulated by herbal extracts should be undertaken to shed light on the development of novel

  14. One- or two-electron water oxidation, hydroxyl radical, or H2O2 evolution

    DOE PAGES

    Siahrostami, Samira; Li, Guo -Ling; Viswanathan, Venkatasubramanian; ...

    2017-02-23

    Electrochemical or photoelectrochemcial oxidation of water to form hydrogen peroxide (H2O2) or hydroxyl radicals (•OH) offers a very attractive route to water disinfection, and the first process could be the basis for a clean way to produce hydrogen peroxide. A major obstacle in the development of effective catalysts for these reactions is that the electrocatalyst must suppress the thermodynamically favored four-electron pathway leading to O2 evolution. Here, we develop a thermochemical picture of the catalyst properties that determine selectivity toward the one, two, and four electron processes leading to •OH, H2O2, and O2.

  15. Application of multiwalled carbon nanotubes-graphene hybrid nanocomposite for nonenzymatic H2O2 biosensor

    NASA Astrophysics Data System (ADS)

    Nayak, Pranati; Santhosh, P. N.; Ramaprabhu, S.

    2013-02-01

    In the present work, we report the fabrication of nonenzymatic hydrogen peroxide (H2O2) biosensor using multiwalled carbon nanotubes-solar exfoliated graphene hybrid nanocomposite (MWCNTs-sG) as a transducer candidate. The hybrid material has been synthesized by solar reduction technique from a mixture of MWCNTs and graphite oxide (GO). The fabricated MWCNTs-sG based biosensor shows a high catalytic response towards H2O2 reduction at a low potential of -0.4 V and good linearity over a wide range of concentration from 2 mM to 344 mM.

  16. The paradox of a wet (high H2O) and dry (low H2O/Ce) mantle: High water concentrations in mantle garnet pyroxenites from Hawaii

    NASA Astrophysics Data System (ADS)

    Bizimis, M.; Peslier, A. H.

    2013-12-01

    Water dissolved as trace amounts in anhydrous minerals has a large influence on the melting behavior and physical properties of the mantle. The water concentration of the oceanic mantle is inferred from the analyses of MORB and OIB [1], but there is little data from actual mantle samples. Moreover, enriched mineralogies (pyroxenites, eclogites) are thought as important sources of heterogeneity in the mantle, but their water concentrations and their effect on the water budget and cycling in the mantle are virtually unknown. We analyzed by FTIR water concentrations in garnet clinopyroxenite xenoliths from Salt Lake Crater, Oahu, Hawaii. These pyroxenites are high-pressure (>20kb) crystal fractionates from alkalic melts. The clinopyroxenes (cpx) have 260 to 576 ppm wt. H2O, with the least differentiated samples (Mg#>0.8) in the 400-500 ppm range. Orthopyroxene (opx) contain 117-265 ppm H2O, about half of that of cpx, consistent with other natural sample studies, but lower than experimental cpx/opx equilibrium data. These pyroxenite cpx and opx water concentrations are at the high-end of on-and off-craton peridotite xenolith concentrations and megacrysts from kimberites [2] and those of Hawaiian spinel peridotites. In contrast, garnet has extremely low water contents (<5ppm H2O). There is no correlation between water in cpx and lithophile element concentrations. Phlogopite is present in some samples, and its modal abundance shows a positive correlation in Mg# with cpx, implying equilibrium. However, there is no correlation between water concentrations and the presence of phlogopite. These data imply that cpx and opx water concentrations may be buffered by phlogopite crystallization. Reconstructed bulk rock pyroxenite water concentrations (not including phlogopite, i.e. minimum) range from 200-460 ppm (average 331× 75 ppm), significantly higher than water estimates for the MORB source (50-200 ppm), but in the range of E-MORB, OIB and the source of rejuvenated Hawaiian

  17. Fluorescent property of the Gd3+-doped terbium complexes and crystal structure of [Tb(TPTZ)(H2O)6]Cl3.3H2O.

    PubMed

    Zhao, Yan-Fang; Zhao, Yong-Liang; Bai, Feng; Wei, Xiao-yan; Zhou, Yong-sheng; Shan, Mei-na; Li, Huan-huan; Ma, Rui-jun; Fu, Xiao-tao; Du, Yan

    2010-05-01

    The complex of Tb(TPTZ)Cl(3).3H(2)O was synthesized by adding the ethyl alcohol solution of TbCl(3) (1 mmol) to the solution of 2,4,6-tris-(2-pyridyl)-s-triazine(TPTZ, 1 mmol) with constant stirring. The solution which had been filtered was kept at the room temperature for 4 weeks, and then a kind of transparent crystal was formed. Besides, nine kinds of solid complexes in the different molar proportion of terbium to gadolinium had been synthesized by adopting the similar method mentioned above. It was inferred from the elemental analysis and rare earth complexometry that the composition of these complexes is (Tb(x)Gd(y))(TPTZ)Cl(3).3H(2)O (x : y = 0.9 : 0.1, 0.8 : 0.2, 0.7 : 0.3, 0.6 : 0.4, 0.5 : 0.5, 0.4 : 0.6, 0.3 : 0.7, 0.2 : 0.8, 0.1 : 0.9). The absorption spectra and photoluminescence of the complexes were determined in dimethylsulfoxide (DMF), which showed that the excitation of the complexes is mostly ligand based. The triplet state energy level of TPTZ was measured, indicating that the lowest excitation state energy level of Tb(III) and the triplet state energy level of TPTZ match well each other. The fluorescent data indicated that the fluorescent emission intensity of Tb(3+) ions would be enhanced in the complexes after terbium was doped with Gd(3+) ion. When x : y was 0.5 : 0.5, the fluorescent emission intensity was the largest. The result obtained by testing the X-ray diffraction of the monocrystal revealed that the molecular formula of the mono-crystal complex is [Tb(TPTZ)(H(2)O)(6)]Cl(3).3H(2)O. The number of metal ion coordinates is nine, and the tridentate TPTZ and six water molecules are bonded with terbium respectively. Besides, it also revealed that the monocrystal belongs to the monoclinic system, and space group Cc with the following unit cell parameters is a = 1.4785 (3) nm, b = 1.0547 (2) nm, c = 1.7385 (4) nm, beta = 94.42 (3) degrees, V = 2.7028 (9) nm(3) and Z = 4.

  18. Hydrous albite magmas at lower crustal pressure: new results on liquidus H2O content, solubility, and H2O activity in the system NaAlSi3O8-H2O-NaCl at 1.0 GPa

    NASA Astrophysics Data System (ADS)

    Makhluf, A. R.; Newton, R. C.; Manning, C. E.

    2016-09-01

    The system albite-H2O serves as an important model for the generation of granitic magmas, yet relatively few experimental investigations have focused on phase relations at high pressure. This study reports new experimental results, at 1.0 GPa and 690-1050 °C, on the temperature and liquid composition at vapor-saturated melting, the H2O content of undersaturated silicate liquids in equilibrium with albite, the solubility of albite in H2O-NaCl fluids immediately below the solidus, and the activity of H2O in hydrous NaAlSi3O8 liquids along the liquidus. Albite melts and dissolves congruently at all temperatures and salinities. In the NaCl-absent system, the temperature of vapor-saturated melting of low albite, confirmed by X-ray diffraction, is 695 ± 5 °C and the liquid composition is 18.14 ± 1.35 wt% H2O. The temperature dependence of the fluid-undersaturated liquidus curve in the system NaAlSi3O8-H2O varies with H2O wt% (w_{{{{H}}2 {{O}}}}) according to T = - 2.0331 × 10^{ - 3} w_{{{{H}}2 {{O}}}}3 + 1.6497w_{{{{H}}2 {{O}}}}2 {-} 58.963w_{{{{H}}2 {{O}}}} + 1235.5°C} indicating positive curvature in temperature-composition coordinates and a dry melting temperature of 1235 °C. At 690 °C, immediately below the solidus, albite solubility decreases drastically with NaCl content of the fluid phase, from 8.8 ± 0.6 wt% in the NaCl-free fluid to ˂2 % at NaCl concentration of only 10 mol%. Experiments determining the activity of H2O (a_{{{{H}}2 {{O}}}}) in liquids at vapor-saturated melting exploited low Cl solubility in liquids and low albite solubility in the presence of H2O-NaCl fluids. The maximum Cl content of quenched glasses, only 0.95 wt%, and very low albite solubility together make possible H2O activity measurement in melts equilibrated with NaCl-H2O solutions. When combined with activity data for H2O-NaCl fluids, experimentally determined a_{{{{H}}2 {{O}}}} along the liquidus is described by T = - {469.16a_{{H2 O}}L}^{{1/2}} {-} 93.382a_{{H2 O}}L + 1235.5

  19. 40 CFR 1065.350 - H2O interference verification for CO2 NDIR analyzers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 34 2013-07-01 2013-07-01 false H2O interference verification for CO2 NDIR analyzers. 1065.350 Section 1065.350 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calibrations and Verifications Co and...

  20. 40 CFR 1065.350 - H2O interference verification for CO2 NDIR analyzers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 33 2014-07-01 2014-07-01 false H2O interference verification for CO2 NDIR analyzers. 1065.350 Section 1065.350 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calibrations and Verifications Co and...

  1. 40 CFR 1065.350 - H2O interference verification for CO2 NDIR analyzers.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 33 2011-07-01 2011-07-01 false H2O interference verification for CO2 NDIR analyzers. 1065.350 Section 1065.350 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calibrations and Verifications Co and...

  2. 40 CFR 1065.350 - H2O interference verification for CO2 NDIR analyzers.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 34 2012-07-01 2012-07-01 false H2O interference verification for CO2 NDIR analyzers. 1065.350 Section 1065.350 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calibrations and Verifications Co and...

  3. 40 CFR 1065.370 - CLD CO2 and H2O quench verification.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... quench with these instruments active and evaluate quench with the compensation algorithms applied. (c... calculate quench as described in § 1065.675. (e) H 2O quench verification procedure. Use the following..., and valves from the point where x H2Omeas is measured to the analyzer are at least 5 °C above...

  4. Indonesian low rank coal oxidation: The effect of H2O2 concentration and oxidation temperature

    NASA Astrophysics Data System (ADS)

    Rahayu, S. S.; Findiati, F.; Aprilia, F.

    2016-11-01

    Extraction of Indonesian low rank coals by alkaline solution has been performed to isolate the humic substances. Pretreatments of the coals by oxidation using H2O2 prior to extraction are required to have higher yield of humic substances. In the previous research, only the extraction process was considered. Therefore, the effects of reaction temperature and residence time on coal oxidation and composition of extract residues are also investigated in this research. The oxidation temperatures studied were 40°C, 50°C, and 70°C and the H2O2 concentrations studied were 5%, 15%, 20 %, and 30 %. All the oxidation variables were studied for 90 minutes. The results show that the higher the concentration of H2O2 used, the less oxidized coal produced. The same trend was obtained by using higher oxidation temperature. The effect of H2O2 concentration, oxidation temperature and reaction time to the yield of humic substances extraction have positive trends.

  5. Electron collisions with the CH2O-H2O complex

    NASA Astrophysics Data System (ADS)

    Freitas, T. C.; Bettega, M. H. F.; Lima, M. A. P.; Canuto, S.

    2009-11-01

    In this conference we will present cross sections for elastic electron collisions with the CH2O-H2O complex bonded through hydrogen bond. We will investigate electron collisions with different structures of this complex which were obtained by Classical Monte Carlo simulations. This work would help in understanding the hole of water in the dissociative electron attachment in biological molecules.

  6. Morroniside protects SK-N-SH human neuroblastoma cells against H2O2-induced damage

    PubMed Central

    Zhang, Jing-Xing; Wang, Rui; Xi, Jin; Shen, Lin; Zhu, An-You; Qi, Qi; Wang, Qi-Yi; Zhang, Lun-Jun; Wang, Feng-Chao; Lü, He-Zuo; Hu, Jian-Guo

    2017-01-01

    Oxidative stress-induced cell injury has been linked to the pathogenesis of neurodegenerative disorders such as spinal cord injury, Parkinson's disease, and multiple sclerosis. Morroniside is an antioxidant derived from the Chinese herb Shan-Zhu-Yu. The present study investigated the neuroprotective effect of morroniside against hydrogen peroxide (H2O2)-induced cell death in SK-N-SH human neuroblastoma cells. H2O2 increased cell apoptosis, as determined by flow cytometry and Hoechst 33342 staining. This effect was reversed by pretreatment with morroniside at concentrations of 1–100 µM. The increase in intracellular reactive oxygen species (ROS) generation and lipid peroxidation induced by H2O2 was also abrogated by morroniside. H2O2 induced a reduction in mitochondrial membrane potential, increased caspase-3 activity, and caused downregulation of B cell lymphoma-2 (Bcl-2) and upregulation of Bcl-2-associated X protein (Bax) expression. These effects were blocked by morroniside pretreatment. Thus, morroniside protects human neuroblastoma cells against oxidative damage by inhibiting ROS production while suppressing Bax and stimulating Bcl-2 expression, thereby blocking mitochondrial-mediated apoptosis. These results indicate that morroniside has therapeutic potential for the prevention and treatment of neurodegenerative diseases. PMID:28204825

  7. Mussel oligopeptides protect human fibroblasts from hydrogen peroxide (H2O2)-induced premature senescence.

    PubMed

    Zhou, Yue; Dong, Ying; Xu, Qing-Gang; Zhu, Shu-Yun; Tian, Shi-Lei; Huo, Jing-jing; Hao, Ting-Ting; Zhu, Bei-Wei

    2014-01-01

    Mussel bioactive peptides have been viewed as mediators to maximize the high quality of life. In this study, the anti-aging activities of mussel oligopeptides were evaluated using H2O2-induced prematurely senescent MRC-5 fibroblasts. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and flow cytometry displayed that exposure to H2O2 led to the loss of cell viability and cell cycle arrest. In addition, H2O2 caused the elevation of senescence-associated-β-galactosidase (SA-β-gal) activity and formation of senescence-associated heterochromatin foci (SAHF). It was found that pretreatment with mussel oligopeptides could significantly attenuate these properties associated with cellular senescence. Mussel oligopeptides also led to the increase of glutathione (GSH) level and mitochondrial transmembrane potential (Δψm) recovery. In addition, mussel oligopeptides resulted in an improvement in transcriptional activity of peroxiredoxin 1 (Prx1), nicotinamide phosphoribosyltransferase (NAMPT) and sirtuin 1 (SIRT1). This study revealed that mussel oligopeptides could protect against cellular senescence induced by H2O2, and the effects were closely associated with redox cycle modulating and potentiating the SIRT1 pathway. These findings provide new insights into the beneficial role of mussel bioactive peptides on retarding senescence process.

  8. Mars: Long Term Changes in the State and Distribution of H2O

    NASA Technical Reports Server (NTRS)

    Fanale, F. P.; Salvail, J. R.; Zent, A. P.; Postawko, S. E.

    1985-01-01

    A model for H2O distribution and migration on Mars was formulated which takes into account: (1) thermal variations at all depths in the regolith due to variations in obliquity, eccentricity and the solar constant; (2) variations in atmospheric PH2O caused by corresponding changes in polar surface insolation; and (3) the finite kinetics of H2O migration in both the regolith and atmosphere. Results suggest that regolith H2O transport rates are more strongly influenced by polar-controlled atmospheric PH2O variations than variations in pore gas PH2O brought about by thermal variations at the buried ice interface. The configuration of the ice interface as a function of assumed soil parameter and time is derived. Withdrawal of ice proceeds to various depths at latitudes less than 50 deg and is accompanied by filling of regolith pores at latitudes greater than 50 deg and transfer of H2O to the polar cap. The transfer has a somewhat oscillatory character, but only less than 1g/sq cm is shifted into and out the regolith during each obliquity cycle. It is concluded that this process combined with periodic thermal cycles played a major role in development of the fretted terrain, deflationary features in general, patterned ground, the north polar cap and the layered terrain.

  9. Reaction of N2O5 with H2O on carbonaceous surfaces

    NASA Technical Reports Server (NTRS)

    Brouwer, L.; Rossi, M. J.; Golden, D. M.

    1986-01-01

    The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

  10. Factors affecting UV/H2O2 inactivation of Bacillus atrophaeus spores in drinking water.

    PubMed

    Zhang, Yongji; Zhang, Yiqing; Zhou, Lingling; Tan, Chaoqun

    2014-05-05

    This study aims at estimating the performance of the Bacillus atrophaeus spores inactivation by the UV treatment with addition of H2O2. The effect of factors affecting the inactivation was investigated, including initial H2O2 dose, UV irradiance, initial cell density, initial solution pH and various inorganic anions. Under the experimental conditions, the B. atrophaeus spores inactivation followed both the modified Hom Model and the Chick's Model. The results revealed that the H2O2 played dual roles in the reactions, while the optimum reduction of 5.88lg was received at 0.5mM H2O2 for 10min. The inactivation effect was affected by the UV irradiance, while better inactivation effect was achieved at higher irradiance. An increase in the initial cell density slowed down the inactivation process. A slight acid condition at pH 5 was considered as the optimal pH value. The inactivation effect within 10min followed the order of pH 5>pH 7>pH 9>pH 3>pH 11. The effects of three added inorganic anions were investigated and compared, including sulfate (SO4(2)(-)), nitrate (NO3(-)) and carbonate (CO3(2)(-)). The sequence of inactivation effect within 10min followed the order of control group>SO4(2)(-)>NO3(-)>CO3(2)(-).

  11. New Optical Constants for Amorphous and Crystalline H2O-ice

    NASA Technical Reports Server (NTRS)

    Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

    2006-01-01

    We have used the infrared spectra of laboratory ices to calculate the real and imaginary indices of refraction for amorphous and crystalline H2O-ice. We create H2O-ice samples in vacuum (approx. 10(exp ^-8)Torr). We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows and then collect transmission spectra of the samples in the wavelength range 1.25-22 micrometers. Using the ice thickness and transmission spectrum we calculate the imaginary part of the index of refraction. A Kramers-Kronig calculation is then used to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can be used to create model spectra for comparison to spectra from Solar System objects. We will summarize the differences between the amorphous and crystalline H2O-ice spectra. These include weakening of features and shifting of features to shorter wavelength in amorphous H,O-ice spectra. We will also discuss methods of using band area ratios to quickly estimate the fraction of amorphous to crystalline H2O-ice. We acknowledge financial support from the NASA Origins of the Solar System Program, the NASA Planetary Geology and Geophysics Program, and the NASA Postdoctoral Program.

  12. High Concentrations of H2O2 Make Aerobic Glycolysis Energetically More Favorable for Cellular Respiration

    PubMed Central

    Molavian, Hamid R.; Kohandel, Mohammad; Sivaloganathan, Sivabal

    2016-01-01

    Since the original observation of the Warburg Effect in cancer cells, over 8 decades ago, the major question of why aerobic glycolysis is favored over oxidative phosphorylation has remained unresolved. An understanding of this phenomenon may well be the key to the development of more effective cancer therapies. In this paper, we use a semi-empirical method to throw light on this puzzle. We show that aerobic glycolysis is in fact energetically more favorable than oxidative phosphorylation for concentrations of peroxide (H2O2) above some critical threshold value. The fundamental reason for this is the activation and high engagement of the pentose phosphate pathway (PPP) in response to the production of reactive oxygen species (ROS) H2O2 by mitochondria and the high concentration of H2O2 (produced by mitochondria and other sources). This makes oxidative phosphorylation an inefficient source of energy since it leads (despite high levels of ATP production) to a concomitant high energy consumption in order to respond to the hazardous waste products resulting from cellular processes associated with this metabolic pathway. We also demonstrate that the high concentration of H2O2 results in an increased glucose consumption, and also increases the lactate production in the case of glycolysis. PMID:27601999

  13. X-ray irradiation activates K+ channels via H2O2 signaling.

    PubMed

    Gibhardt, Christine S; Roth, Bastian; Schroeder, Indra; Fuck, Sebastian; Becker, Patrick; Jakob, Burkhard; Fournier, Claudia; Moroni, Anna; Thiel, Gerhard

    2015-09-09

    Ionizing radiation is a universal tool in tumor therapy but may also cause secondary cancers or cell invasiveness. These negative side effects could be causally related to the human-intermediate-conductance Ca2+-activated-K+-channel (hIK), which is activated by X-ray irradiation and affects cell proliferation and migration. To analyze the signaling cascade downstream of ionizing radiation we use genetically encoded reporters for H2O2 (HyPer) and for the dominant redox-buffer glutathione (Grx1-roGFP2) to monitor with high spatial and temporal resolution, radiation-triggered excursions of H2O2 in A549 and HEK293 cells. The data show that challenging cells with ≥1 Gy X-rays or with UV-A laser micro-irradiation causes a rapid rise of H2O2 in the nucleus and in the cytosol. This rise, which is determined by the rate of H2O2 production and glutathione-buffering, is sufficient for triggering a signaling cascade that involves an elevation of cytosolic Ca2+ and eventually an activation of hIK channels.

  14. Coupling UV-H2O2 to accelerate dimethyl phthalate (DMP) biodegradation and oxidation.

    PubMed

    Chen, Bin; Song, Jiaxiu; Yang, Lihui; Bai, Qi; Li, Rongjie; Zhang, Yongming; Rittmann, Bruce E

    2015-11-01

    Dimethyl phthalate (DMP), an important industrial raw material, is an endocrine disruptor of concern for human and environmental health. DMP exhibits slow biodegradation, and its coupled treatment by means of advanced oxidation may enhance its biotransformation and mineralization. We evaluated two ways of coupling UV-H2O2 advanced oxidation to biodegradation: sequential coupling and intimate coupling in an internal circulation baffled biofilm reactor (ICBBR). During sequential coupling, UV-H2O2 pretreatment generated carboxylic acids that depressed the pH, and subsequent biodegradation generated phthalic acid; both factors inhibited DMP biodegradation. During intimately coupled UV-H2O2 with biodegradation, carboxylic acids and phthalic acid (PA) did not accumulate, and the biodegradation rate was 13 % faster than with biodegradation alone and 78 % faster than with biodegradation after UV-H2O2 pretreatment. Similarly, DMP oxidation with intimate coupling increased by 5 and 39 %, respectively, compared with biodegradation alone and sequential coupling. The enhancement effects during intimate coupling can be attributed to the rapid catabolism of carboxylic acids, which generated intracellular electron carriers that directly accelerated di-oxygenation of PA and relieved the inhibition effect of PA and low pH. Thus, intimate coupling optimized the impacts of energy input from UV irradiation used together with biodegradation.

  15. Effect of acute vs chronic H2O2-induced oxidative stress on antioxidant enzyme activities.

    PubMed

    Miguel, Fernanda; Augusto, Amanda C; Gurgueira, Sonia A

    2009-04-01

    H2O2 can freely crosses membranes and in the presence of Fe2+ (or Cu+) it is prone to participate in Fenton reaction. This study evaluated the concentration and time-dependent effects of H2O2-induced oxidative stress on MnSOD, Se:GPx and catalase and on aconitase. Acute and chronic H2O2 treatments were able to induce oxidative stress in HeLa cells as they significantly decreased aconitase activity and also caused a very significant decrease on antioxidant enzyme activities. The inhibition of enzyme activities was time- and concentration-dependent. Chronic treatment with 5 microM H2O2/h after 24 h was able to decrease all enzyme activities almost at the same level as the acute treatment. Acute and chronic treatments on antioxidant enzyme activities were prevented by cell treatment with ascorbic acid or N-acetylcysteine. These results indicate that antioxidant enzymes can also be affected by the same ROS they produce or neutralize if the time of exposure is long enough.

  16. Effective Reuse of Electroplating Rinse Wastewater by Combining PAC with H2O2/UV Process.

    PubMed

    Yen, Hsing Yuan; Kang, Shyh-Fang; Lin, Chen Pei

    2015-04-01

    This study evaluated the performance of treating electroplating rinse wastewater by powder activated carbon (PAC) adsorption, H2O2/UV oxidation, and their combination to remove organic compounds and heavy metals. The results showed that neither the process of PAC adsorption nor H2O2/UV oxidation could reduce COD to 100 mg/L, as enforced by the Taiwan Environmental Protection Agency. On the other hand, the water sample treated by the combined approach of using PAC (5 g/L) pre-adsorption and H2O2/UV post-oxidation (UV of 64 W, H2O2 of 100 mg/L, oxidation time of 90 min), COD and DOC were reduced to 8.2 mg/L and 3.8 mg/L, respectively. Also, the combined approach reduced heavy metals to meet the effluent standards and to satisfy the in-house water reuse criteria for the electroplating factory. The reaction constant analysis indicated that the reaction proceeded much more rapidly for the combined process. Hence, it is a more efficient, economic and environmentally friendly process.

  17. [Comparison of H2O2 and UV processes on the inactivation efficiency of Microcystic aeruginosa].

    PubMed

    Guo, Jian-wei; Zhang, Yong-ji; Zeng, Guo; Zhou, Ling-ling; Gao, Nai-yun

    2010-08-01

    Setting Microcystic aeruginosa as study subject, the inactivation efficiency and its effect on photosynthetic activity by H2O2 and UV processes were investigated. The results showed that the inactivating efficiency increased with H2O2 dosage in the range of 0-2 mmol x L(-1), and the photosynthetic activity decreased with it gradually, but the efficiency wasn't enhanced when the dosage exceeded 2 mmoL x L(-1). The inactivation by UV process was high. Under the algae concentration of 35 x 10(8) cells/L, UV dosage of 91.8 mJ/cm2 was enough to inhibit its growth by 7d; UV process was superior to H2O2 in terms of photosynthetic activity, also the parameters could be fitted exponentially well; To guarantee high removal of algae, H2O2 must be dosed excessively, so UV254 of algae solution would be higher than that of UV process.

  18. NO Removal in High Pressure Plasmas of N_2/H_2O/NO Mixtures

    NASA Astrophysics Data System (ADS)

    Fresnet, F.; Baravian, G.; Magne, L.; Pasquiers, S.; Postel, C.; Puech, V.; Rousseau, A.

    2001-10-01

    Influence of H_2O on NO removal has been studied using a homogeneous photo-triggered discharge with a time resolved LIF measurement of the NO density, in N_2/H_2O/NO mixtures at 460 mbar. The H_2O maximum concentration was 2.5 was between 70 and 160 J/l. Measurement of NO density has been performed up to 180 µs after the current pulse excitation of short duration, 50 ns. Kinetic analysis has been made using a self-consistent 0D-discharge model. NO is in great part dissociated, in N_2/NO, through collisions with the excited singlet states of N_2. We have previously shown that addition of ethene induces de-excitation of these states, leading to a decrease of the NO removal ( F. Fresnet, G. Baravian, L. Magne, S. Pasquiers, C. Postel, V. Puech, A. Rousseau, Appl. Phys. Lett., 77 (2000) 4118.). Similar processes take place when C_2H4 is replaced by H_2O. The value of the rate constant for collision of singlet states with water, 3.10-10 cm^3 s-1, is obtained from our study.

  19. Formation of low-temperature cirrus from H2SO4/H2O aerosol droplets.

    PubMed

    Bogdan, A; Molina, M J; Sassen, K; Kulmala, M

    2006-11-23

    We present experimental results obtained with a differential scanning calorimeter (DSC) that indicate the small ice particles in low-temperature cirrus clouds are not completely solid but rather coated with an unfrozen H2SO4/H2O overlayer. Our results provide a new look on the formation, development, and microphysical properties of low-temperature cirrus clouds.

  20. X-ray irradiation activates K+ channels via H2O2 signaling

    PubMed Central

    Gibhardt, Christine S.; Roth, Bastian; Schroeder, Indra; Fuck, Sebastian; Becker, Patrick; Jakob, Burkhard; Fournier, Claudia; Moroni, Anna; Thiel, Gerhard

    2015-01-01

    Ionizing radiation is a universal tool in tumor therapy but may also cause secondary cancers or cell invasiveness. These negative side effects could be causally related to the human-intermediate-conductance Ca2+-activated-K+-channel (hIK), which is activated by X-ray irradiation and affects cell proliferation and migration. To analyze the signaling cascade downstream of ionizing radiation we use genetically encoded reporters for H2O2 (HyPer) and for the dominant redox-buffer glutathione (Grx1-roGFP2) to monitor with high spatial and temporal resolution, radiation-triggered excursions of H2O2 in A549 and HEK293 cells. The data show that challenging cells with ≥1 Gy X-rays or with UV-A laser micro-irradiation causes a rapid rise of H2O2 in the nucleus and in the cytosol. This rise, which is determined by the rate of H2O2 production and glutathione-buffering, is sufficient for triggering a signaling cascade that involves an elevation of cytosolic Ca2+ and eventually an activation of hIK channels. PMID:26350345

  1. Crystal Structures and Thermal Properties of Two Transition-Metal Compounds {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O and Pb(DNI)2(H2O)4 (DNI = 2,4-Dinitroimidazolate)

    PubMed Central

    Zhang, Guo-Fang; Cai, Mei-Yu; Jing, Ping; He, Chong; Li, Ping; Zhao, Feng-Qi; Li, Ji-Zhen; Fan, Xue-Zhong; Ng, Seik Weng

    2010-01-01

    Two transition-metal compounds derived from 2,4-dinitroimidazole, {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O, 1, and Pb(DNI)2(H2O)4, 2, were characterized by elemental analysis, FT-IR, TG-DSC and X-ray single-crystal diffraction analysis. Crystal data for 1: monoclinic, space group C2/c, a = 26.826(3), b = 7.7199(10), c = 18.579(2) Å, β = 111.241(2)° and Z = 4; 2: monoclinic, space group C2/c, a = 6.5347(6), b = 17.1727(17), c = 14.1011(14) Å, β = 97.7248(10) and Z = 4. Compound 1 contains two isolated nickel centers in its structure, one being six-coordinate and another five-coordinate. The structure of 2 contains a lead (II) center surrounded by two chelating DNI ligands and four water molecules in distorted square-antiprism geometry. The abundant hydrogen bonds in two compounds link the molecules into three-dimensional network and stabilize the molecules. The TG-DSC analysis reveals that the first step is the loss of water molecules and the final residue is the corresponding metal oxides and carbon. PMID:20526419

  2. Water Planetary and Cometary Atmospheres: H2O/HDO Transmittance and Fluorescence Models

    NASA Technical Reports Server (NTRS)

    Villanueva, G. L.; Mumma, M. J.; Bonev, B. P.; Novak, R. E.; Barber, R. J.; DiSanti, M. A.

    2012-01-01

    We developed a modern methodology to retrieve water (H2O) and deuterated water (HDO) in planetary and cometary atmospheres, and constructed an accurate spectral database that combines theoretical and empirical results. Based on a greatly expanded set of spectroscopic parameters, we built a full non-resonance cascade fluorescence model and computed fluorescence efficiencies for H2O (500 million lines) and HDO (700 million lines). The new line list was also integrated into an advanced terrestrial radiative transfer code (LBLRTM) and adapted to the CO2 rich atmosphere of Mars, for which we adopted the complex Robert-Bonamy formalism for line shapes. We then retrieved water and D/H in the atmospheres of Mars, comet C/2007 WI, and Earth by applying the new formalism to spectra obtained with the high-resolution spectrograph NIRSPEC/Keck II atop Mauna Kea (Hawaii). The new model accurately describes the complex morphology of the water bands and greatly increases the accuracy of the retrieved abundances (and the D/H ratio in water) with respect to previously available models. The new model provides improved agreement of predicted and measured intensities for many H2O lines already identified in comets, and it identifies several unassigned cometary emission lines as new emission lines of H2O. The improved spectral accuracy permits retrieval of more accurate rotational temperatures and production rates for cometary water.

  3. SO2:H2O surface complex found at the vapor/water interface.

    PubMed

    Tarbuck, Teresa L; Richmond, Geraldine L

    2005-12-07

    A weakly bonded SO2:H2O surface complex is found at the vapor/water interface prior to the reaction and dissolution of SO2 into the aqueous phase. The results have important implications for understanding the formation of atmospheric aerosols and understanding the atmospheric sulfur cycle.

  4. 40 CFR 1065.370 - CLD CO2 and H2O quench verification.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... mole fraction of H2O and the maximum CO2 concentration expected during emission testing. If the CLD... operating mode. (4) Use a CO2 span gas that meets the specifications of § 1065.750 and a concentration that is approximately twice the maximum CO2 concentration expected during emission testing. (5) Use an...

  5. Dysregulated autophagy increased melanocyte sensitivity to H2O2-induced oxidative stress in vitiligo

    PubMed Central

    He, Yuanmin; Li, Shuli; Zhang, Weigang; Dai, Wei; Cui, Tingting; Wang, Gang; Gao, Tianwen; Li, Chunying

    2017-01-01

    In vitiligo, melanocytes are particularly vulnerable to oxidative stress owing to the pro-oxidant state generated during melanin synthesis and to the genetic antioxidant defects. Autophagy is a controlled self-digestion process which can protect cells against oxidative damage. However, the exact role of autophagy in vitiligo melanocytes in response to oxidative stress and the mechanism involved are still not clear. To determine the implications of autophagy for melanocyte survival in response to oxidative stress, we first detected the autophagic flux in normal melanocytes exposure to H2O2, and found that autophagy was significantly enhanced in normal melanocytes, for protecting cells against H2O2-induced oxidative damage. Nevertheless, vitiligo melanocytes exhibited dysregulated autophagy and hypersensitivity to H2O2-induced oxidative injury. In addition, we confirmed that the impairment of Nrf2-p62 pathway is responsible for the defects of autophagy in vitiligo melanocytes. Noteworthily, upregulation of the Nrf2-p62 pathway or p62 reduced H2O2-induced oxidative damage of vitiligo melanocytes. Therefore, our data demonstrated that dysregulated autophagy owing to the impairment of Nrf2-p62 pathway increase the sensitivity of vitiligo melanocytes to oxidative stress, thus promote the development of vitiligo. Upregulation of p62-dependent autophagy may be applied to vitiligo treatment in the future. PMID:28186139

  6. Characterization and optimization of cathodic conditions for H2O2 synthesis in microbial electrochemical cells

    EPA Science Inventory

    Cathode potential and O2 supply methods were investigated to improve H2O2 synthesis in an electrochemical cell, and optimal cathode conditions were applied for microbial electrochemical cells (MECs). Using aqueous O2 for the cathode significantly improved current density, but H2...

  7. Morroniside protects SK-N-SH human neuroblastoma cells against H2O2-induced damage.

    PubMed

    Zhang, Jing-Xing; Wang, Rui; Xi, Jin; Shen, Lin; Zhu, An-You; Qi, Qi; Wang, Qi-Yi; Zhang, Lun-Jun; Wang, Feng-Chao; Lü, He-Zuo; Hu, Jian-Guo

    2017-03-01

    Oxidative stress-induced cell injury has been linked to the pathogenesis of neurodegenerative disorders such as spinal cord injury, Parkinson's disease, and multiple sclerosis. Morroniside is an antioxidant derived from the Chinese herb Shan-Zhu-Yu. The present study investigated the neuroprotective effect of morroniside against hydrogen peroxide (H2O2)-induced cell death in SK-N-SH human neuroblastoma cells. H2O2 increased cell apoptosis, as determined by flow cytometry and Hoechst 33342 staining. This effect was reversed by pretreatment with morroniside at concentrations of 1-100 µM. The increase in intracellular reactive oxygen species (ROS) generation and lipid peroxidation induced by H2O2 was also abrogated by morroniside. H2O2 induced a reduction in mitochondrial membrane potential, increased caspase-3 activity, and caused downregulation of B cell lymphoma-2 (Bcl-2) and upregulation of Bcl-2-associated X protein (Bax) expression. These effects were blocked by morroniside pretreatment. Thus, morroniside protects human neuroblastoma cells against oxidative damage by inhibiting ROS production while suppressing Bax and stimulating Bcl-2 expression, thereby blocking mitochondrial-mediated apoptosis. These results indicate that morroniside has therapeutic potential for the prevention and treatment of neurodegenerative diseases.

  8. Atomistic molecular dynamics simulations of H2O diffusivity in liquid and supercritical CO2

    NASA Astrophysics Data System (ADS)

    Moultos, Othonas A.; Orozco, Gustavo A.; Tsimpanogiannis, Ioannis N.; Panagiotopoulos, Athanassios Z.; Economou, Ioannis G.

    2015-09-01

    Molecular dynamics simulations were employed for the calculation of diffusion coefficients of pure CO2 and of H2O in CO2 over a wide range of temperatures (298.15 K < T < 523.15 K) and pressures (5.0 MPa < P < 100.0 MPa), that are of interest to CO2 capture-and-sequestration processes. Various combinations of existing fixed-point-charge force-fields for H2O (TIP4P/2005 and Exponential-6) and CO2 (elementary physical model 2 [EPM2], transferable potentials for phase equilibria [TraPPE], and Exponential-6) were tested. All force-field combinations qualitatively reproduce the trends of the experimental data for infinitely diluted H2O in CO2; however, TIP4P/2005-EPM2, TIP4P/2005-TraPPE and Exponential-6-Exponential-6 were found to be the most consistent. Additionally, for H2O compositions ranging from infinite dilution to ?, the Maxwell-Stefan diffusion coefficient is shown to have a weak non-linear composition dependence.

  9. Conductivity measurements on H2O-bearing CO2-rich fluids

    DOE PAGES

    Capobianco, Ryan M.; Miroslaw S. Gruszkiewicz; Bodnar, Robert J.; ...

    2014-09-10

    Recent studies report rapid corrosion of metals and carbonation of minerals in contact with carbon dioxide containing trace amounts of dissolved water. One explanation for this behavior is that addition of small amounts of H2O to CO2 leads to significant ionization within the fluid, thus promoting reactions at the fluid-solid interface analogous to corrosion associated with aqueous fluids. The extent of ionization in the bulk CO2 fluid was determined using a flow-through conductivity cell capable of detecting very low conductivities. Experiments were conducted from 298 to 473 K and 7.39 to 20 MPa with H2O concentrations up to ~1600 ppmwmore » (xH2O ≈ 3.9 x 10-3), corresponding to the H2O solubility limit in liquid CO2 at ambient temperature. All solutions showed conductivities <10 nS/cm, indicating that the solutions were essentially ion-free. Furthermore, this observation suggests that the observed corrosion and carbonation reactions are not the result of ionization in CO2-rich bulk phase, but does not preclude ionization in the fluid at the fluid-solid interface.« less

  10. Particle-in-Cell Simulations of Atmospheric Pressure He/2%H2O Discharges

    NASA Astrophysics Data System (ADS)

    Kawamura, E.; Lieberman, M. A.; Lichtenberg, A. J.; Graves, D. B.; Gopalakrishnan, R.

    2015-09-01

    Atmospheric pressure micro-discharges in contact with liquid surfaces are of increasing interest, especially in the bio-medical field. We conduct 1D3v particle-in-cell (PIC) simulations of a voltage-driven 1 mm width atmospheric pressure He/2% H2O plasma discharge in series with an 0.5 mm width liquid H2O layer and a 1mm width quartz dielectric layer. A previously developed two-temperature hybrid global model of atmospheric pressure He/H2O discharges was used to determine the most important species and collisional reactions to use in the PIC simulations. We found that H13O6+, H5O3-, and electrons were the most prominent charged species, while most of the metastable helium He* was quenched via Penning ionization. The ion-induced secondary emission coefficient γi was assumed to be 0.15 at all surfaces. A series of simulations were conducted at 27.12 MHz with Jrf ~ 800-2200 A/m2. The H2O rotational and vibrational excitation losses were so high that electrons reached the walls at thermal temperatures. We also simulated a much lower frequency case of 50 kHz with Vrf = 10 kV. In this case, the discharge ran in a pure time-varying γ-mode. This work was supported by the Department of Energy Office of Fusion Energy Science Contract DE-SC0001939.

  11. UV/H(2)O(2) treatment of drinking water increases post-chlorination DBP formation.

    PubMed

    Dotson, Aaron D; Keen, Volha Olya S; Metz, Debbie; Linden, Karl G

    2010-06-01

    Ultraviolet (UV) irradiation has become popular as a primary disinfectant because it is very effective against Cryptosporidium and does not directly form regulated disinfection by-products. Higher UV doses and UV advanced oxidation (UV/H2O2) processes are under consideration for the treatment of trace organic pollutants (e.g. pharmaceuticals, personal care products). Despite the disinfection effectiveness of UV light, a secondary disinfectant capable of maintaining a distribution system residual is required to meet current U.S. regulation. This study investigated changes in disinfection by-product (DBP) formation attributed to UV or UV/H2O2 followed by application of free chlorine to quench hydrogen peroxide and provide residual disinfectant. At a UV dose of 1000 mJ/cm(2), trihalomethane (THM) yield increased by up to 4 microg/mg-C and 13 microg/mg-C when treated with low and medium pressure UV, respectively. With the addition of hydrogen peroxide, THM yield increased by up to 25 microg/mg-C (5mg-H2O2/L) and 37 microg/mg-C (10 mg-H2O2/L). Although no changes in DBPs are expected during UV disinfection, application of UV advanced oxidation followed by chlorine addition was assessed with regard to impacts on DBP formation.

  12. Production of OH(A) in fast collisions of O with H2O

    NASA Astrophysics Data System (ADS)

    Levin, Debbie; Drakes, James

    1999-10-01

    For spacecraft flying in low-earth orbit of 250 to 250 km altitude, typical vehicle velocities with respect to the ambient atmosphere can exceed 7 km/sec. The atmospheric composition is also almost solely atomic oxygen at translational temperatures near 1000K. When the spacecraft thrusters operate, the effluent can attain speeds over 10 km/sec in the lab frame with respect to the atomic oxygen, depending upon the thruster orientation. Reactions between the fast exhaust effluent species, dominated by H2O, and the atmospheric atomic oxygen can result in the direct generation of product molecules, such as OH, in electronically excited states. A study has been undertaken to examine the product reaction channels for the generation of OH excited states in fast collisions of atomic oxygen with H2O. A potential hypersurface for H2O has been used to compute the branching fractions of the collision exit channels using monte carlo molecular dynamics techniques. The results of the computation are compared to the literature extrapolation of the OH(A) excitation rate. These rates are based upon thermal measurements of the ground state products of O with H2O, with adjustment to the activation energy to accommodate the increased endothermicity of the electronically excited A2PI state. The trajectory calculations presented herein will be used to derive a more appropriate rate expression.

  13. 40 CFR 1065.372 - NDUV analyzer HC and H2O interference verification.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... verification. 1065.372 Section 1065.372 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calibrations and Verifications Nox and N2o Measurements § 1065.372 NDUV analyzer HC and H2O interference verification. (a) Scope and frequency. If...

  14. 40 CFR 1065.372 - NDUV analyzer HC and H2O interference verification.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... verification. 1065.372 Section 1065.372 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calibrations and Verifications Nox and N2o Measurements § 1065.372 NDUV analyzer HC and H2O interference verification. (a) Scope and frequency. If...

  15. The effect of coordinated water on the connectivity of uranium(IV) sulfate x-hydrate: [U(SO4)2(H2O)5]·H2O and [U(SO4)2(H2O)6]·2H2O, and a comparison with other known structures.

    PubMed

    Burns, Alexander D; Patrick, Brian O; Lam, Anita E; Dreisinger, David

    2014-07-01

    Two new solid-state uranium(IV) sulfate x-hydrate complexes (where x is the total number of coordinated plus solvent waters), namely catena-poly[[pentaaquauranium(IV)]-di-μ-sulfato-κ(4)O:O'] monohydrate], {[U(SO4)2(H2O)5]·H2O}n, and hexaaquabis(sulfato-κ(2)O,O')uranium(IV) dihydrate, [U(SO4)2(H2O)6]·2H2O, have been synthesized, structurally characterized by single-crystal X-ray diffraction and analyzed by vibrational (IR and Raman) spectroscopy. By comparing these structures with those of four other known uranium(IV) sulfate x-hydrates, the effect of additional coordinated water molecules on their structures has been elucidated. As the number of coordinated water molecules increases, the sulfate bonds are displaced, thus changing the binding mode of the sulfate ligands to the uranium centre. As a result, uranium(IV) sulfate x-hydrate changes from being fully crosslinked in three dimensions in the anhydrous compound, through sheet and chain linking in the tetra- and hexahydrates, to fully unlinked molecules in the octa- and nonahydrates. It can be concluded that coordinated waters play an important role in determining the structure and connectivity of U(IV) sulfate complexes.

  16. Decolorization of methylene blue in layered manganese oxide suspension with H2O2.

    PubMed

    Zhang, Lili; Nie, Yulun; Hu, Chun; Hu, Xuexiang

    2011-06-15

    Layered birnessite-type manganese oxides (Na-OL-1) were prepared via a redox reaction involving MnO(4)(-) and Mn(2+) under markedly alkaline conditions. According to the XRD analysis, the resulting material exhibited a well-crystallized octahedral layer (OL) structure with several different phases, including β-MnOOH, α-MnOOH and γ-Mn(3)O(4). The catalyst was highly effective for the decolorization and degradation of methylene blue (MB) in the presence of H(2)O(2) at neutral pH. The tested MB was completely decolorized in Na-OL-1 suspension by the fraction dosing of H(2)O(2) (556.5mM at the beginning and then 183.8mM at 40 min). Based on the studies of electron spin resonance and the effect of radical scavengers, the (1)O(2) and O(2)(-) were the main reactive oxygen species (ROS) in the reaction. It was found that both oxygen and ROS were generated from the decomposition of H(2)O(2) in Na-OL-1 suspension, wherein the decomposition pathways were proposed. The generation of H(2)O(2) in Na-OL-1 suspension at air atmosphere indicated that the existence of multivalent manganese oxides greatly enhanced the interfacial electron transfer, leading to the high activity of Na-OL-1.

  17. Advanced NaBH4/H2O2 Fuel Cell for Space Applications

    NASA Astrophysics Data System (ADS)

    Miley, George H.; Kim, Kyu-Jung; Luo, Nie; Shrestha, Prajakti Joshi

    2009-03-01

    Fuel cells have played an important role in NASA's space program starting with the Gemini space program. However, improved fuel cell performance will be needed to enable demanding future missions. An advanced fuel cell (FC) using liquid fuel and oxidizer is being developed by U of IL/NPL team to provide air independence and to achieve higher power densities than normal H2/O2 fuel cells (Lou et al., 2008; Miley, 2007). Hydrogen peroxide (H2O2) is used in this FC directly at the cathode (Lou and Miley, 2004). Either of two types of reactant, namely a gas-phase hydrogen or an aqueous NaBH4 solution, is utilized as fuel at the anode. Experiments with both 10-W single cells and 500-W stacks demonstrate that the direct utilization of H2O2 and NaBH4 at the electrodes result in >30% higher voltage output compared to the ordinary H2/O2 FC (Miley, 2007). Further, the use of this combination of all liquid fuels provides—from an operational point of view—significant advantages (ease of storage, reduced pumping requirements, simplified heat removal). This design is inherently compact compared to other fuel cells that use gas phase reactants. This results in a high overall system (including fuel tanks, pumps and piping, waste heat radiator) power density. Further, work is in progress on a regenerative version which uses an electrical input, e.g. from power lines or a solar panel to regenerate reactants.

  18. Synthesis and biological evaluation of decavanadate Na4Co(H2O)6V10O28.18H2O.

    PubMed

    Zhai, Fengying; Wang, Xiaohong; Li, Dongliu; Zhang, He; Li, Rui; Song, Liansheng

    2009-01-01

    We have reported the synthesis and biological evaluation of a decavanadate Na(4)Co(H(2)O)(6)V(10)O(28).18H(2)O (CoV(10)) designed as a potential antitumoral agent. The human cancer cell lines SMMC-7721 (liver cancer) and SK-OV-3 (ovary cancer) were tested for their viability by the MTT method in vitro, which showed that the compound exhibited a remarkable activity against two cell lines with IC(50) values smaller than 0.24 microg/mL, 0.32 microg/mL, respectively. CoV(10) showed the tumor growth suppression for Hep-A-22 (mice liver cancer) in tumor bearing mice in vivo. In addition, using flow cytometry analysis, the ratio of apoptotic cells was up to 8.33% with treatment of CoV(10) at 1.56 microg/mL after 30 min, suggesting that the antitumoral activity of CoV(10) comes from the activation of the apoptotic pathway.

  19. The Frequency Detuning Correction and the Asymmetry of Line Shapes: The Far Wings of H2O-H2O

    NASA Technical Reports Server (NTRS)

    Ma, Q.; Tipping, R. H.; Hansen, James E. (Technical Monitor)

    2002-01-01

    A far-wing line shape theory which satisfies the detailed balance principle is applied to the H2O-H2O system. Within this formalism, two line shapes are introduced, corresponding to band-averages over the positive and negative resonance lines, respectively. Using the coordinate representation, the two line shapes can be obtained by evaluating 11-dimensional integrations whose integrands are a product of two factors. One depends on the interaction between the two molecules and is easy to evaluate. The other contains the density matrix of the system and is expressed as a product of two 3-dimensional distributions associated with the density matrices of the absorber and the perturber molecule, respectively. If most of the populated states are included in the averaging process, to obtain these distributions requires extensive computer CPU time, but only have to be computed once for a given temperature. The 11-dimensional integrations are evaluated using the Monte Carlo method, and in order to reduce the variance, the integration variables are chosen such that the sensitivity of the integrands on them is clearly distinguished.

  20. OH and H2O maser variations in W33B

    NASA Astrophysics Data System (ADS)

    Colom, P.; Lekht, E. E.; Pashchenko, M. I.; Rudnitskij, G. M.

    2015-03-01

    Context. The active star-forming region W33B is a source of OH and H2O maser emission located in distinct zones around the central object. Aims: The aim was to obtain the complete Stokes pattern of polarised OH maser emission and to trace its variability and to investigate flares and long-term variability of the H2O maser and evolution of individual emission features. Methods: Observations in the OH lines at a wavelength of 18 cm were carried out on the Nançay radio telescope (France) at a number of epochs in 2008-2014; H2O line observations (long-term monitoring) at λ = 1.35 cm were performed on the 22 m radio telescope of the Pushchino Radio Astronomy Observatory (Russia) between 1981 and 2014. Results: We have observed strong variability of the emission features in the main 1665- and 1667 MHz OH lines as well as in the 1612 MHz satellite line. Zeeman splitting has been detected in the 1665 MHz OH line at 62 km s-1 and in the 1667 MHz line at 62 and 64 km s-1. The magnetic field intensity was estimated to be from 2 to 3 mG. The H2O emission features form filaments, chains with radial-velocity gradients, or more complicated structures including large-scale ones. Conclusions: Long-term observations of the hydroxyl maser in the W33B region have revealed narrowband polarised emission in the 1612 MHz line with a double-peak profile characteristic of type IIb circumstellar masers. The 30 year monitoring of the water-vapour maser in W33B showed several strong flares of the H2O line. The observed radial-velocity drift of the H2O emission features suggests propagation of an excitation wave in the masering medium with a gradient of radial velocities. In OH and H2O masers some turbulent motions of material are inferred. The spectra of Fig. 7 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/575/A49 or at http://comet.sai.msu.ru/~gmr/Maser_monitoring/W33B

  1. H2O2-Induced Oxidative Stress Affects SO4= Transport in Human Erythrocytes

    PubMed Central

    Morabito, Rossana; Romano, Orazio; La Spada, Giuseppa; Marino, Angela

    2016-01-01

    The aim of the present investigation was to verify the effect of H2O2-induced oxidative stress on SO4= uptake through Band 3 protein, responsible for Cl-/HCO3- as well as for cell membrane deformability, due to its cross link with cytoskeletal proteins. The role of cytoplasmic proteins binding to Band 3 protein has been also considered by assaying H2O2 effects on hemoglobin-free resealed ghosts of erythrocytes. Oxidative conditions were induced by 30 min exposure of human erythrocytes to different H2O2 concentrations (10 to 300 μM), with or without GSH (glutathione, 2 mM) or curcumin (10 μM), compounds with proved antioxidant properties. Since SO4= influx through Band 3 protein is slower and better controllable than Cl- or HCO3- exchange, the rate constant for SO4= uptake was measured to prove anion transport efficiency, while MDA (malondialdehyde) levels and –SH groups were estimated to quantify the effect of oxidative stress. H2O2 induced a significant decrease in rate constant for SO4= uptake at both 100 and 300 μM H2O2. This reduction, observed in erythrocytes but not in resealed ghosts and associated to increase in neither MDA levels nor in –SH groups, was impaired by both curcumin and GSH, whereas only curcumin effectively restored H2O2-induced changes in erythrocytes shape. Our results show that: i) 30 min exposure to 300 μM H2O2 reduced SO4= uptake in human erythrocytes; ii) oxidative damage was revealed by the reduction in rate constant for SO4= uptake, but not by MDA or –SH groups levels; iii) the damage was produced via cytoplasmic components which cross link with Band 3 protein; iv) the natural antioxidant curcumin may be useful in protecting erythrocytes from oxidative injury; v) SO4= uptake through Band 3 protein may be reasonably suggested as a tool to monitor erythrocytes function under oxidative conditions possibly deriving from alcohol consumption, use of drugs, radiographic contrast media administration, hyperglicemia or

  2. Uptaking of plagioclase xenocryst into H2O-rich rear-arc basaltic magma

    NASA Astrophysics Data System (ADS)

    Hamada, M.

    2015-12-01

    Kuritani et al. (2013, Mineral. Petrol.) and Kuritani et al. (2014, Contrib. Mineral. Petrol.) estimated genetic conditions of primary arc magmas beneath the Iwate volcano (a frontal arc volcano in the northeast Japan arc) and the Sannome-gata volcano (a rear-arc volcano in the northeast Japan arc) based on analyses of volcanic rocks and numerical simulation. They estimated that H2O concentrations of primary melts are 4-5 wt.% beneath the Iwate volcano and 6-7 wt.% beneath the Sannnome-gata volcano, respectively. Their arguments mean that primary melts beneath frontal-arc volcanoes and rear-arc volcanoes are both H2O-rich, yet there has been no direct evidence to support their arguments at the Sannnome-gata volcano because volcanic rocks are either almost aphyric and/or almost no melt inclusions were found. Hydrogen concentration in nominally anhydrous minerals serves as a hygrometer of arc basaltic melts (e.g., Hamada et al. 2013, Earth Planet. Sci. Lett.). In this study, hydrogen concentration of plagioclase as a crustal xenocryst was analyzed to estimate H2O concentration of basaltic melt coexisted with plagioclase before the eruption. Plagioclase xenocrists were separated from crushed scoria which erupted from the Sannome-gata volcano 20,000-24,000 years ago. Composition of the plagioclase core is homogeneous and ranges from An30 through An35. The rim is 150 to 200-μm-thick dusty zone whose composition is around An60, suggesting that the rim crystallized rapidly from degassed basaltic melt. The profiles of infrared absorption area per unit thickness across the plagioclase core were obtained using Fourier Transform InfraRed spectrometer (FTIR). The inner core contains hydrogen of about 60 wt. ppm H2O, and hydrogen concentration elevates at outer core. Hydrogen concentration at the outermost core of plagioclase is >200 wt. ppm H2O, suggesting that plagioclase xenocrists were taken by hydrous melt (H2O>5 wt.%; Hamada et al. 2014, Earth Planet. Sci. Lett.) and

  3. Kinetic Model for UV/H2O2 Degradation of 5-Methoxypsoralen

    NASA Astrophysics Data System (ADS)

    Tchaikovskaya, O. N.; Bryantseva, N. G.; Carrasco, J. L. Gómez; Krayukhina, V. S.; Almagro, M. D. Murcia; Gómez, M. Gómez

    2016-08-01

    The influence of H2O2 on the photodegradataion of 5-methoxypsoralen (5-MOP) in ethanol and in waterethanol solutions upon exposure to KrCl excilamp radiation (λrad = 222 nm) and XeBr excilamp radiation (λrad = 283 nm) is investigated. A kinematic model of photodegradation of the investigated molecule is constructed. The addition of H2O2 resulted in a weak increase of the decay rate of 5-MOP in ethanol exposed to KrCl excilamp radiation. In water-ethanol solutions the addition of H2O2 altered the mechanism of decay of 5-MOP irradiated by the KrCl excilamp in comparison with irradiation by the XeBr excilamp. It has been shown that upon exposure to XeBr excilamp radiation in the presence of H2O2, the primary photoproduct of the transformation of 5-MOP in the reaction corresponding to the first-order kinetic model is formed both in ethanol and in the water-ethanol solutions. Maximum removal of 5-MOP takes place for the ratio of initial concentrations [5-MOP]:[H2O2] = 1:3 after 60 min irradiation. It is found that irradiation by the XeBr excilamp the decay rate of 5-MOP is 5 times higher in the water-ethanol solutions in comparison with ethanol. Upon exposure to KrCl excilamp radiation the mechanism of 5-MOP decay corresponds to a pseudo-firstorder kinetic model. The nature of the dependence of the decay rate of 5-MOP on the irradiation time for the ratio of initial concentrations [5-MOP]:[H2O2] = 1:24 indicates that during decay of the initial compound a photoproduct appears in the system which decays during the irradiation time into secondary compounds. Efficient removal of 5-MOP under this irradiation takes place for the ratio of initial concentrations [5-MOP]:[H2O2] = 1:10 after 60 min irradiation.

  4. The structures of fluorene-(H2O)1,2 determined by rotational coherence spectroscopy

    NASA Astrophysics Data System (ADS)

    Laman, David M.; Joly, Alan G.; Ray, Douglas

    2003-07-01

    Rotational coherence spectroscopy (RCS), via time-correlated single photon counting, and two-color resonant two-photon ionization (R2PI) time-of-flight mass spectrometry, have been used to characterize fluorene-(water)1,2 [FL-(H2O)1,2] van der Waals clusters generated in supersonic jets. Rotational coherence traces have been obtained at excitation energies corresponding to several resonant features in the S1←S0 R2PI spectra of FL-(H2O)1,2. RCS simulations and diagonalization of the moment of inertia tensor have been used to obtain S1 excited state rotational constants and structures of FL-(H2O)1,2 that are consistent with the experimental rotational coherence traces. The RCS results indicate that: (i) the water molecule in FL-H2O resides above the central five member ring and interacts with both aromatic sites; (ii) the water molecules in FL-(H2O)2 form a water dimer that is most likely oriented along the long axis of fluorene and is hydrogen-bonded to both aromatic sites. The S1←S0 R2PI spectra of FL-(D2O)1,2 and FL-HDO have also been obtained. The 000 transition is a doublet in the R2PI spectra of FL-H2O, FL-D2O, and a singlet in the R2PI spectrum of FL-HDO. The presence of this doublet in the FL-H2O/D2O spectra, and the absence of such a splitting in the FL-HDO spectrum, is an indication of internal rotation of the water molecule on a potential energy surface that changes upon electronic excitation. Lastly, the use of RCS and time-resolved fluorescence as a tool for assigning features in R2PI spectra that are of ambiguous origin due to fragmentation of higher mass clusters into lower mass channels is demonstrated.

  5. The infrared spectra of nitriles and related compounds frozen in Ar and H2O

    NASA Technical Reports Server (NTRS)

    Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

    1997-01-01

    We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C triple bond N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C triple bond N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2

  6. The Infrared Spectra of Nitriles and Related Compounds Frozen in Ar and H2O

    NASA Technical Reports Server (NTRS)

    Bernstain, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Witteborn, Fred C. (Technical Monitor)

    1996-01-01

    We present the 2320-2050/cm (4.31-4.88 micron) infrared spectra of 16 solid state nitrites, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C(is congruent to)N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile phenylcyanide) 9-anthracenecarbonitrile, dimethylcyanamide, isopropy1nitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyr-uvonitrile, dicyandiamide, cyanamide, n-butyfisocyanide, methylisocyanoacetate, dilsopropylcarbodiimide, and hydrogen cyanide. The C(is congruent to)N stretching bands of the majority of nitrites fall in the 2300-2200/cm (4.35-4.55 micron) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contest, the isonitriles and a few exceptional nitrites and related species produce bands at lower frequencies spanning the 2200-2080/cm (4.55-4.81 micron) range. These features also have similar positions in both Am and H2O matrices and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C(is congruent to)N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165/cm (4.62 micron) "XCN" interstellar feature and the 4550/cm (2.2 micron) feature of

  7. Degassing of H2O in a phonolitic melt: A closer look at decompression experiments

    NASA Astrophysics Data System (ADS)

    Marxer, Holger; Bellucci, Philipp; Nowak, Marcus

    2015-05-01

    Melt degassing during magma ascent is controlled by the decompression rate and can be simulated in decompression experiments. H2O-bearing phonolitic melts were decompressed at a super-liquidus T of 1323 K in an internally heated argon pressure vessel, applying continuous decompression (CD) as well as to date commonly used step-wise decompression (SD) techniques to investigate the effect of decompression method on melt degassing. The hydrous melts were decompressed from 200 MPa at nominal decompression rates of 0.0028-1.7 MPa·s- 1. At final pressure (Pfinal), the samples were quenched rapidly at isobaric conditions with ~ 150 K·s- 1. The bubbles in the quenched samples are often deformed and dented. Flow textures in the glass indicate melt transport at high viscosity. We suggest that this observation is due to bubble shrinkage during quench. This general problem was mostly overlooked in the interpretation of experimentally degassed samples to date. Bubble shrinkage due to decreasing molar volume (Vm) of the exsolved H2O in the bubbles occurs during isobaric rapid quench until the melt is too viscous too relax. The decrease of Vm(H2O) during cooling at Pfinal of the experiments results in a decrease of the bubble volume by a shrinking factor Bs: At nominal decompression rates > 0.17 MPa·s- 1 and a Pfinal of 75 MPa, the decompression method has only minor influence on melt degassing. SD and CD result in high bubble number densities of 104-105 mm- 3. Fast P drop leads to immediate supersaturation with H2O in the melt. At such high nominal decompression rates, the diffusional transport of H2O is limited and therefore bubble nucleation is the predominant degassing process. The residual H2O contents in the melts decompressed to 75 MPa increase with nominal decompression rate. After homogeneous nucleation is triggered, CD rates ≤ 0.024 MPa·s- 1 facilitate continuous reduction of the supersaturation by H2O diffusion into previously nucleated bubbles. Bubble number

  8. Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

    NASA Astrophysics Data System (ADS)

    Lange, R. A.; Waters, L.

    2014-12-01

    The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ∆NNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels

  9. The Infrared Spectra of Nitriles and Related Compounds Frozen in Ar and H2O

    NASA Astrophysics Data System (ADS)

    Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.

    1997-02-01

    We present the 2320-2050 cm-1 (4.31-4.88 μm) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C≡N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C≡N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 μm) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 μm) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C≡N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 μm) ``XCN'' interstellar feature and the 4550 cm-1 (2.2 μm) feature of various objects in the solar system are

  10. Glutathione/thioredoxin systems modulate mitochondrial H2O2 emission: An experimental-computational study

    PubMed Central

    Aon, Miguel Antonio; Stanley, Brian Alan; Sivakumaran, Vidhya; Kembro, Jackelyn Melissa; O'Rourke, Brian; Paolocci, Nazareno

    2012-01-01

    The net emission of hydrogen peroxide (H2O2) from mitochondria results from the balance between reactive oxygen species (ROS) continuously generated in the respiratory chain and ROS scavenging. The relative contribution of the two major antioxidant systems in the mitochondrial matrix, glutathione (GSH) and thioredoxin (Trx), has not been assessed. In this paper, we examine this key question via combined experimental and theoretical approaches, using isolated heart mitochondria from mouse, rat, and guinea pig. As compared with untreated control mitochondria, selective inhibition of Trx reductase with auranofin along with depletion of GSH with 2,4-dinitrochlorobenzene led to a species-dependent increase in H2O2 emission flux of 17, 11, and 6 fold in state 4 and 15, 7, and 8 fold in state 3 for mouse, rat, and guinea pig mitochondria, respectively. The maximal H2O2 emission as a percentage of the total O2 consumption flux was 11%/2.3% for mouse in states 4 and 3 followed by 2%/0.25% and 0.74%/0.29% in the rat and guinea pig, respectively. A minimal computational model accounting for the kinetics of GSH/Trx systems was developed and was able to simulate increase in H2O2 emission fluxes when both scavenging systems were inhibited separately or together. Model simulations suggest that GSH/Trx systems act in concert. When the scavenging capacity of either one of them saturates during H2O2 overload, they relieve each other until complete saturation, when maximal ROS emission occurs. Quantitatively, these results converge on the idea that GSH/Trx scavenging systems in mitochondria are both essential for keeping minimal levels of H2O2 emission, especially during state 3 respiration, when the energetic output is maximal. This suggests that the very low levels of H2O2 emission observed during forward electron transport in the respiratory chain are a result of the well-orchestrated actions of the two antioxidant systems working continuously to offset ROS production. PMID

  11. H2O2-Induced Oxidative Stress Affects SO4= Transport in Human Erythrocytes.

    PubMed

    Morabito, Rossana; Romano, Orazio; La Spada, Giuseppa; Marino, Angela

    2016-01-01

    The aim of the present investigation was to verify the effect of H2O2-induced oxidative stress on SO4= uptake through Band 3 protein, responsible for Cl-/HCO3- as well as for cell membrane deformability, due to its cross link with cytoskeletal proteins. The role of cytoplasmic proteins binding to Band 3 protein has been also considered by assaying H2O2 effects on hemoglobin-free resealed ghosts of erythrocytes. Oxidative conditions were induced by 30 min exposure of human erythrocytes to different H2O2 concentrations (10 to 300 μM), with or without GSH (glutathione, 2 mM) or curcumin (10 μM), compounds with proved antioxidant properties. Since SO4= influx through Band 3 protein is slower and better controllable than Cl- or HCO3- exchange, the rate constant for SO4= uptake was measured to prove anion transport efficiency, while MDA (malondialdehyde) levels and -SH groups were estimated to quantify the effect of oxidative stress. H2O2 induced a significant decrease in rate constant for SO4= uptake at both 100 and 300 μM H2O2. This reduction, observed in erythrocytes but not in resealed ghosts and associated to increase in neither MDA levels nor in -SH groups, was impaired by both curcumin and GSH, whereas only curcumin effectively restored H2O2-induced changes in erythrocytes shape. Our results show that: i) 30 min exposure to 300 μM H2O2 reduced SO4= uptake in human erythrocytes; ii) oxidative damage was revealed by the reduction in rate constant for SO4= uptake, but not by MDA or -SH groups levels; iii) the damage was produced via cytoplasmic components which cross link with Band 3 protein; iv) the natural antioxidant curcumin may be useful in protecting erythrocytes from oxidative injury; v) SO4= uptake through Band 3 protein may be reasonably suggested as a tool to monitor erythrocytes function under oxidative conditions possibly deriving from alcohol consumption, use of drugs, radiographic contrast media administration, hyperglicemia or neurodegenerative

  12. Ab initio study of H2O and water-chain-induced properties of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Agrawal, B. K.; Singh, V.; Pathak, A.; Srivastava, R.

    2007-05-01

    We perform an ab initio study of the motion of the nano sized water dimer through a single-walled carbon nanotube (SWCNT), the stability of an encapsulated one-dimensional (1D) water chain inside SWCNT, and the H2O -induced structural, energetic, electronic, and optical properties of the SWCNTs. The adsorption of the water molecules is caused by the dispersion forces, i.e., the van der Waals (vdW) interactions. Thus, the role of the vdW interactions in the estimation of the BE for the weakly bound adsorbates cannot be ignored as has been done in several earlier publications. We find that a single H2O molecule or single water dimer or a 1D chain of water dimers is trapped inside the medium-sized (6,6) carbon nanotube placed in vacuum. However, the H2O molecule or water dimer may be transmitted in case the tube is surrounded by water or water vapor at high vapor pressure at high temperatures. On the other hand, a chain of single H2O molecules or more number of the encapsulated H2O molecules is very weakly coupled to the wide (10,10) carbon nanotube and can, thus, easily transmit through the carbon nanotube in agreement with the recent experiments. Further, appreciable adsorption both inside and on the surface of the (10,10) carbon nanotube is predicted in concurrence with the experiments. The small (medium-sized) diameter tubes will adsorb strongly (accommodate) the water molecules outside (inside) the nanotubes. The H2O adsorption converts the conducting small-diameter zigzag (5,0) tube into a semiconductor. Further, the adsorption reduces the band gap of the semiconducting achiral zigzag (10,0) nanotube but increases the band gap of a chiral semiconducting (4,2) tube. The adsorbed H2O molecules increase the electrical conductivity in agreement with the experiment. The overall peak structure in the optical absorption for the pristine tube is not altered significantly by the adsorption except for small alterations in the energy locations and the relative intensities

  13. Monitoring Observatinos of H2O and SiO Masers Toward Post-AGB Stars

    NASA Astrophysics Data System (ADS)

    Kim, Jaeheon; Cho, Se-Hyung; Yoon, Dong-Hwan

    2016-12-01

    We present the results of simultaneous monitoring observations of H_2O 6_{1,6}-5_{2,3} (22 GHz) and SiO J=1-0, 2-1, 3-2 maser lines (43, 86, 129 GHz) toward five post-AGB (candidate) stars, using the 21-m single-dish telescopes of the Korean VLBI Network. Depending on the target objects, 7 - 11 epochs of data were obtained. We detected both H_2O and SiO maser lines from four sources: OH16.1-0.3, OH38.10-0.13, OH65.5+1.3, and IRAS 19312+1950. We could not detect H_2O maser emission toward OH13.1+5.1 between the late OH/IR and post-AGB stage. The detected H_2O masers show typical double-peaked line profiles. The SiO masers from four sources, except IRAS 19312+1950, show the peaks around the stellar velocity as a single peak, whereas the SiO masers from IRAS 19312+1950 occur above the red peak of the H_2O maser. We analyzed the properties of detected maser lines, and investigated their evolutionary state through comparison with the full widths at zero power. The distribution of observed target sources was also investigated in the IRAS two-color diagram in relation with the evolutionary stage of post-AGB stars. From our analyses, the evolutionary sequence of observed sources is suggested as OH65.5+1.3 → OH13.1+5.1 → OH16.1-0.3 → OH38.10-0.13, except for IRAS 19312+1950. In addition, OH13.1+5.1 from which the H_2O maser has not been detected is suggested to be on the gateway toward the post-AGB stage. With respect to the enigmatic object, IRAS 19312+1950, we could not clearly figure out its nature. To properly explain the unusual phenomena of SiO and H_2O masers, it is essential to establish the relative locations and spatial distributions of two masers using VLBI technique. We also include the 1.2 - 160 μm spectral energy distribution using photometric data from the following surveys: 2MASS, WISE, MSX, IRAS, and AKARI (IRC and FIS). In addition, from the IRAS LRS spectra, we found that the depth of silicate absorption features shows significant variations

  14. Mapping of [HDO]/[H2O] in the Martian Atmosphere

    NASA Astrophysics Data System (ADS)

    Novak, R. E.; Mumma, M. J.; Villanueva, G.; Bonev, B.; Disanti, M.

    Observations of the Martian atmosphere were taken for several seasonal dates at NASA's IRTF using CSHELL. Column densities of HDO and H2O were extracted from individual spectral lines near 3.67 ìm and 3.29 ìm. The slit was positioned N-S on Mars centered at the sub-earth point producing spectral/spatial images. Spectra were extracted at 0.6 arc-sec. intervals and analyzed with models created from GENLN2 atmospheric software; the models include solar Fraunhofer lines, a two-way transmission through Mars' atmosphere, thermal emission from Mars' surface and atmosphere, and a one way transmission through the Earth's atmosphere. From these, latitudinal maps of HDO/H2O were constructed across the observable planet. The HDO/H2O ratios have been found to be larger than those on Earth and they vary with both latitude and season. The higher global HDO/H2O value on Mars compared to that of the Earth is attributed to differential Jeans escape of D and H over geologic time. The ratio in the southern Martian hemisphere is found to be larger than that in the north. This difference could be the signature of Rayleigh distillation, a process in which the different mean temperatures of the polar caps causes a different degree of HDO sequestration resulting in different degrees of enrichment in the polar caps. Detailed results for Ls= 357o in 2006 will be presented when both the HDO and the H2O column densities were obtain from CSHELL data. These will be compared to results from other seasons.Observations of the Martian atmosphere were taken for several seasonal dates at NASA's IRTF using CSHELL. Column densities of HDO and H2O were extracted from individual spectral lines near 3.67 ìm and 3.29 ìm. The slit was positioned N-S on Mars centered at the sub-earth point producing spectral/spatial images. Spectra were extracted at 0.6 arc-sec. intervals and analyzed with models created from GENLN2 atmospheric software; the models include solar Fraunhofer lines, a two-way transmission

  15. Descent without Modification? The Thermal Chemistry of H2O2 on Europa and Other Icy Worlds.

    PubMed

    Loeffler, Mark J; Hudson, Reggie L

    2015-06-01

    The strong oxidant H2O2 is known to exist in solid form on Europa and is suspected to exist on several other Solar System worlds at temperatures below 200 K. However, little is known of the thermal chemistry that H2O2 might induce under these conditions. Here, we report new laboratory results on the reactivity of solid H2O2 with eight different compounds in H2O-rich ices. Using infrared spectroscopy, we monitored compositional changes in ice mixtures during warming. The compounds CH4 (methane), C3H4 (propyne), CH3OH (methanol), and CH3CN (acetonitrile) were unaltered by the presence of H2O2 in ices, showing that exposure to either solid H2O2 or frozen H2O+H2O2 at cryogenic temperatures will not oxidize these organics, much less convert them to CO2. This contrasts strongly with the much greater reactivity of organics with H2O2 at higher temperatures, and particularly in the liquid and gas phases. Of the four inorganic compounds studied, CO, H2S, NH3, and SO2, only the last two reacted in ices containing H2O2, NH3 making NH4+ and SO2 making SO(4)2- by H+ and e- transfer, respectively. An important astrobiological conclusion is that formation of surface H2O2 on Europa and that molecule's downward movement with H2O-ice do not necessarily mean that all organics encountered in icy subsurface regions will be destroyed by H2O2 oxidation.

  16. Descent Without Modification? The Thermal Chemistry of H2O2 on Europa and Other Icy Worlds

    NASA Technical Reports Server (NTRS)

    Loeffler, Mark Josiah; Hudson, Reggie Lester

    2015-01-01

    The strong oxidant H2O2 is known to exist in solid form on Europa and is suspected to exist on several other Solar System worlds at temperatures below 200 K. However, little is known of the thermal chemistry that H2O2 might induce under these conditions. Here, we report new laboratory results on the reactivity of solid H2O2 with eight different compounds in H2O-rich ices. Using infrared spectroscopy, we monitored compositional changes in ice mixtures during warming. The compounds CH4 (methane), C3H4 (propyne), CH3OH (methanol), and CH3CN (acetonitrile) were unaltered by the presence of H2O2 in ices, showing that exposure to either solid H2O2 or frozen H2O+H2O2 at cryogenic temperatures will not oxidize these organics, much less convert them to CO2. This contrasts strongly with the much greater reactivity of organics with H2O2 at higher temperatures, and particularly in the liquid and gas phases. Of the four inorganic compounds studied, CO, H2S, NH3, and SO2, only the last two reacted in ices containing H2O2, NH3 making NHþ 4 and SO2 making SO2 4 by H+ and e - transfer, respectively. An important astrobiological conclusion is that formation of surface H2O2 on Europa and that molecule's downward movement with H2O-ice do not necessarily mean that all organics encountered in icy subsurface regions will be destroyed by H2O2 oxidation.

  17. First outer-sphere 1,3-diethyl-2-thiobarbituric compounds [M(H2O)6](1,3-diethyl-2-thiobarbiturate)2·2H2O (M = Co2+, Ni2+): Crystal structure, spectroscopic and thermal properties

    NASA Astrophysics Data System (ADS)

    Golovnev, Nicolay N.; Molokeev, Maxim S.; Lesnikov, Maxim K.; Atuchin, Victor V.

    2016-06-01

    Two new d-element compounds, [Co(H2O)6](Detba)2·2H2O (1) and [Ni(H2O)6](Detba)2·2H2O (2) (HDetba - 1,3-diethyl-2-thiobarbituric acid) were synthesized and characterized by single-crystal and powder X-ray diffraction analysis, TG-DSC and FT-IR. Structural analysis revealed that (1) and (2) are discrete structures, in which M2+ ion (M = Co, Ni) is six-coordinated by water molecules and it forms an octahedron. The outer-sphere Detba- ions and H2O molecules participate in Osbnd H⋯(O/S) intermolecular hydrogen bonds which form the 2D layer. Thermal decomposition includes the stage of dehydration and the following stage of oxidation of Detba- with a release of CO2, SO2, H2O, NH3 and isocyanate gases.

  18. Abundant gas-phase H2O in absorption toward massive protostars

    NASA Astrophysics Data System (ADS)

    Boonman, A. M. S.; van Dishoeck, E. F.

    2003-06-01

    We present infrared spectra of gas-phase H2O around 6 mu m toward 12 deeply embedded massive protostars obtained with the Short Wavelength Spectrometer on board the Infrared Space Observatory (ISO). The nu2 ro-vibrational band has been detected toward 7 of the sources and the excitation temperatures indicate an origin in the warm gas at Tex>~ 250 K. Typical derived gas-phase H2O abundances are ~ 5*E-6-6*E-5, with the abundances increasing with the temperature of the warm gas. The inferred gas/solid ratios show a similar trend with temperature and suggest that grain-mantle evaporation is important. The increasing gas/solid ratio correlates with other indicators of increased temperatures. If the higher temperatures are due to a larger ratio of source luminosity to envelope mass, this makes gas-phase H2O a good evolutionary tracer. Comparison with chemical models shows that three different chemical processes, ice evaporation, high-T chemistry, and shocks, can reproduce the high inferred gas-phase H2O abundances. In a forthcoming paper each of these processes are investigated in more detail in comparison with data from the Long Wavelength Spectrometer on board ISO and the Submillimeter Wave Astronomy Satellite (SWAS). Comparison with existing SWAS data indicates that a jump in the H2O abundance is present and that the observed nu2 ro-vibrational band traces primarily the warm inner envelope. Based on observations with ISO, an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, the Netherlands and the United Kingdom) and with the participation of ISAS and NASA.

  19. Theoretical study of negatively charged Fe(-)-(H2O)(n ≤ 6) clusters.

    PubMed

    Castro, Miguel

    2012-06-14

    Interactions of a singly negatively charged iron atom with water molecules, Fe(-)-(H(2)O)(n≤6), in the gas phase were studied by means of density functional theory. All-electron calculations were performed using the B3LYP functional and the 6-311++G(2d,2p) basis set for the Fe, O, and H atoms. In the lowest total energy states of Fe(-)-(H(2)O)(n), the metal-hydrogen bonding is stronger than the metal-oxygen one, producing low-symmetry structures because the water molecules are directly attached to the metal by basically one of their hydrogen atoms, whereas the other ones are involved in a network of hydrogen bonds, which together with the Fe(δ-)-H(δ+) bonding accounts for the nascent hydration of the Fe(-) anion. For Fe(-)-(H(2)O)(3≤n), three-, four-, five-, and six-membered rings of water molecules are bonded to the metal, which is located at the surface of the cluster in such a way as to reduce the repulsion with the oxygen atoms. Nevertheless, internal isomers appear also, lying less than 3 or 5 kcal/mol for n = 2-3 or n = 4-6. These results are in contrast with those of classical TM(+)-(H(2)O)(n) complexes, where the direct TM(+)-O bonding usually produces high symmetry structures with the metal defining the center of the complex. They show also that the Fe(-) anions, as the TM(+) ions, have great capability for the adsorption of water molecules, forming Fe(-)-(H(2)O)(n) structures stabilized by Fe(δ-)-H(δ+) and H-bond interactions.

  20. Distillation of H2O from hard-frozen Martian permafrost

    NASA Technical Reports Server (NTRS)

    Zent, A. P.; Gwynne, O.

    1991-01-01

    The authors present a method for distillation of hard-frozen Martian permafrost. A cable-tool is drilled into hard frozem permafrost to a depth of 10 to 20 m. They calculate that a 10 m hole could be drilled in a few days. A 10 m shaft with a diameter equal to the bore is inserted into the hole, and a air tight tent-like structure is erected over the borehole. Photovoltaic cells mounted on the tent supply electrical energy that is dissipated in the shaft. Drilling power can be supplied by other sources. With 1000 watts, the shaft can be heated to near 350 K, producing relatively high temperatures in the vicinity of the borehole. Surrounding H2O is vaporized and diffuses up through the regolith. The authors calculate that a tent of a radius of no more than a few meters would intercept most of the H2O as it diffused to the surface. Calculations suggest that it would require perhaps 30 days to extract H2O from most of the volume drained by this technique. Assuming that the hard frozen regolith is no more than 10 percent ice, the author's calculate that that about 2890 kg of H2O could be extracted in 30 days. Since the nominal requirement for each crew member is about 5 kg/day, one such borehole might be expected to supply enough H2O to maintain a crew of 5 for perhaps 100 days. Additional engineering studies will be done to attempt to improve the capacity or efficiency of this method.

  1. Scavenging property of three cresol isomers against H2O2, hypochlorite, superoxide and hydroxyl radicals.

    PubMed

    Yeung, S Y; Lan, W H; Huang, C S; Lin, C P; Chan, C P; Chang, M C; Jeng, J H

    2002-10-01

    Formocresol has long been used for pulpotomy of primary teeth and as an intracanal medicament. Little is known, however, about the pharmacological effect of tricresols. This study showed that three cresol isomers, o-cresol, m-cresol and p-cresol, are H2O2 scavengers with a 50% inhibitory concentration (IC50) of 502, 6.7 and 10.16 microM, respectively. o-, m- and p-cresol were also shown to be effective scavengers of superoxide radicals generated by xanthine/xanthine oxidase with an IC50 of 282, 153 and > 4000 microM, respectively, as analyzed by luminometer. o-, m- and p-cresol showed protective effects on the DNA breaks generated by H2O2/FeCl2 and FeCl3/ascorbate/H2O2 systems at concentrations ranging from 70 microM to 1.43 mM, o-, m- and p-cresol also showed differential protective effects against DNA breaks induced by 0.17% NaOCl with 100% inhibitory concentration (IC100) of about 10, 1 and 10 mM, respectively. In addition, reaction with 3% H2O2 and 0.17% NaOCl completely prevented NaOCl-induced DNA breaks. The results indicate that the three cresol isomers are effective ROS scavengers and may prevent ROS induced damage when used as pulpotomy agents or as intracanal medicaments. Owing to the difference in the position of the functional hydroxyl group in the three cresol isomers, m-cresol is the most effective ROS scavenger. Concomitant use of H2O2 for root canal irrigation may diminish both the tissue dissolving capacity of NaOCl and NaOCl-induced DNA damage.

  2. H2O2 intensifies CN(-)-induced apoptosis in pea leaves.

    PubMed

    Samuilov, V D; Kiselevsky, D B; Sinitsyn, S V; Shestak, A A; Lagunova, E M; Nesov, A V

    2006-04-01

    H2O2 intensifies CN(-)-induced apoptosis in stoma guard cells and to lesser degree in basic epidermal cells in peels of the lower epidermis isolated from pea leaves. The maximum effect of H2O2 on guard cells was observed at 10(-4) M. By switching on non-cyclic electron transfer in chloroplasts menadione and methyl viologen intensified H2O2 generation in the light, but prevented the CN--induced apoptosis in guard cells. The light stimulation of CN- effect on guard cell apoptosis cannot be caused by disturbance of the ribulose-1,5-bisphosphate carboxylase function and associated OH* generation in chloroplasts with participation of free transition metals in the Fenton or Haber-Weiss type reactions as well as with participation of the FeS clusters of the electron acceptor side of Photosystem I. Menadione and methyl viologen did not suppress the CN(-)-induced apoptosis in epidermal cells that, unlike guard cells, contain mitochondria only, but not chloroplasts. Quinacrine and diphenylene iodonium, inhibitors of NAD(P)H oxidase of cell plasma membrane, had no effect on the respiration and photosynthetic O2 evolution by leaf slices, but prevented the CN(-)-induced guard cell death. The data suggest that NAD(P)H oxidase of guard cell plasma membrane is a source of reactive oxygen species (ROS) needed for execution of CN(-)-induced programmed cell death. Chloroplasts and mitochondria were inefficient as ROS sources in the programmed death of guard cells. When ROS generation is insufficient, exogenous H2O2 exhibits a stimulating effect on programmed cell death. H2O2 decreased the inhibitory effects of DCMU and DNP-INT on the CN(-)-induced apoptosis of guard cells. Quinacrine, DCMU, and DNP-INT had no effect on CN(-)-induced death of epidermal cells.

  3. OH+ and H2O+ absorption toward PKS 1830-211

    NASA Astrophysics Data System (ADS)

    Muller, S.; Müller, H. S. P.; Black, J. H.; Beelen, A.; Combes, F.; Curran, S.; Gérin, M.; Guélin, M.; Henkel, C.; Martín, S.; Aalto, S.; Falgarone, E.; Menten, K. M.; Schilke, P.; Wiklind, T.; Zwaan, M. A.

    2016-11-01

    We report the detection of OH+ and H2O+ in the z = 0.89 absorber toward the lensed quasar PKS 1830-211. The abundance ratio of OH+ and H2O+ is used to quantify the molecular hydrogen fraction (fH2) and the cosmic-ray ionization rate of atomic hydrogen (ζH) along two lines of sight, located at 2 kpc and 4 kpc to either side of the absorber's center. The molecular fraction decreases outward, from 0.04 to 0.02, comparable to values measured in the Milky Way at similar galactocentric radii. For ζH , we find values of 2 × 10-14 s-1 and 3 × 10-15 s-1, respectively, which are slightly higher than in the Milky Way at comparable galactocentric radii, possibly due to a higher average star formation activity in the z = 0.89 absorber. The ALMA observations of OH+, H2O+, and other hydrides toward PKS 1830-211reveal the multi-phase composition of the absorbing gas. Taking the column density ratios along the southwest and northeast lines of sight as a proxy of molecular fraction, we classify the species ArH+, OH+, H2Cl+, H2O+, CH, and HF as tracing gases increasingly more molecular. Incidentally, our data allow us to improve the accuracy of H2O+ rest frequencies and thus refine the spectroscopic parameters. The reduced spectra (FITS files) are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/595/A128

  4. Appearance of high-pressure H2O ice on ice-covered terrestrial planets

    NASA Astrophysics Data System (ADS)

    Ueta, S.; Sasaki, T.

    2014-03-01

    A lot of terrestrial exoplanets and free-floating planets have been discovered. Whether terrestrial planets with liquid water exist is an important question to consider, especially in terms of their habitability. Even in a globally ice-covered state, liquid water could exist beneath the surface ice shell because sufficient geothermal heat flow from the planetary interior is likely to melt the interior ice, so that an internal ocean under the surface ice shell could appear (e.g., Hoffman & Schrag 2002). In this study, we argue the conditions that must be satisfied for ice-covered terrestrial planets to have an internal ocean on the timescale of planetary evolution (Ueta & Sasaki 2013). Geothermal heat flow calculated by a parameterized convection model (e.g., McGovern & Schubert 1989) is considered as the heat source at the origin of the internal ocean. By applying and improving the model of Tajika (2008), we also examine how the amount of radiogenic heat and H2O mass affect these conditions. Moreover, we investigate the structures of surface H2O layers of ice-covered planets by considering the effects of ice under high pressure (high-pressure ice). At 1 AU from the central star, as shown in Fig. 1, a 1M.+ planet with 0.6-25 times H2O mass of the Earth could have an internal ocean. When the planet has an H2O mass over 25 times that of the Earth, high-pressure ice layers may appear between the internal ocean and the rock-part of the planet. The results indicate that planetary size and surface H2O mass strongly ristrict the conditions under which an extrasolar terrestrial planet could have an internal ocean without high-pressure ice existing under the internal ocean. The habitability of a planet might be influenced by the existence of such high-pressure ice layers.

  5. Reducing THMFP by H2O2/UV oxidation for humic acid of small molecular weight.

    PubMed

    Yen, Hsing Yuan; Yen, Li Shuang

    2015-01-01

    In this study, the merits of using H2O2/UV oxidation for reducing trihalomethane formation potential (THMFP), colour, and dissolved organic carbon (DOC) of smaller molecular humic acid were investigated, especially the energy consumption based on EEO. The results show that THMFP decreases by increasing oxidation time, H2O2 dose and UV intensity. The reaction constant in descending order is kColour>kDOC>kTHMFP. Furthermore, EEO shows three trends. First, it decreases as H2O2 dose increases. That is, by increasing the amount of H2O2 dose, the electrical energy efficiency becomes better. Second, EEO,9 W>EEO,13 W, implying that higher UV power would result in a higher electrical energy efficiency. Third, EEO,THMFP>EEO,DOC>EEO,colour. That is, the electric energy efficiency is the best for colour removal, second for DOC removal, and third for THMFP reduction. The operation costs for 90% removal of colour, DOC, and THMFP are from 0.31 to 0.69, from 0.78 to 1.72, and from 1.11 to 2.29 US$/m3, respectively. However, reducing THMs to Taiwan's drinking water standard of 80 µg/L needs only 0.25-0.60 US$/m3. Therefore, the condition with UV of 9 W, H2O2 of 50 mg/L, and oxidation time of 23 min can be applied for THMs reduction as the cost is the smallest of 0.25 US$/m3, even lower than current Taiwan's drinking water price of 0.3 US$/m3.

  6. Bacterial Ice Nucleation in Monodisperse D2O and H2O-in-Oil Emulsions.

    PubMed

    Weng, Lindong; Tessier, Shannon N; Smith, Kyle; Edd, Jon F; Stott, Shannon L; Toner, Mehmet

    2016-09-13

    Ice nucleation is of fundamental significance in many areas, including atmospheric science, food technology, and cryobiology. In this study, we investigated the ice-nucleation characteristics of picoliter-sized drops consisting of different D2O and H2O mixtures with and without the ice-nucleating bacteria Pseudomonas syringae. We also studied the effects of commonly used cryoprotectants such as ethylene glycol, propylene glycol, and trehalose on the nucleation characteristics of D2O and H2O mixtures. The results show that the median freezing temperature of the suspension containing 1 mg/mL of a lyophilized preparation of P. syringae is as high as -4.6 °C for 100% D2O, compared to -8.9 °C for 100% H2O. As the D2O concentration increases every 25% (v/v), the profile of the ice-nucleation kinetics of D2O + H2O mixtures containing 1 mg/mL Snomax shifts by about 1 °C, suggesting an ideal mixing behavior of D2O and H2O. Furthermore, all of the cryoprotectants investigated in this study are found to depress the freezing phenomenon. Both the homogeneous and heterogeneous freezing temperatures of these aqueous solutions depend on the water activity and are independent of the nature of the solute. These findings enrich our fundamental knowledge of D2O-related ice nucleation and suggest that the combination of D2O and ice-nucleating agents could be a potential self-ice-nucleating formulation. The implications of self-nucleation include a higher, precisely controlled ice seeding temperature for slow freezing that would significantly improve the viability of many ice-assisted cryopreservation protocols.

  7. Promotion of CO oxidation on PdO(101) by adsorbed H2O

    NASA Astrophysics Data System (ADS)

    Choi, Juhee; Pan, Li; Mehar, Vikram; Zhang, Feng; Asthagiri, Aravind; Weaver, Jason F.

    2016-08-01

    We investigated the influence of adsorbed H2O on the oxidation of CO on PdO(101) using temperature programmed reaction spectroscopy (TPRS), reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations. We find that water inhibits CO adsorption on PdO(101) by site blocking, but also provides a more facile pathway for CO oxidation compared with the bare oxide surface. In the presence of adsorbed H2O, the oxidation of CO on PdO(101) produces a CO2 TPRS peak that is centered at a temperature 50 K lower than the main CO2 TPRS peak arising from CO oxidation on clean PdO(101) ( 330 vs. 380 K). RAIRS shows that CO continues to adsorb on atop-Pd sites of PdO(101) when H2O is co-adsorbed, and provides no evidence of other reactive intermediates. DFT calculations predict that the CO oxidation mechanism follows the same steps for CO adsorbed on PdO(101) with and without co-adsorbed H2O, wherein an atop-CO species recombines with an oxygen atom from the oxide surface lattice. According to DFT, hydrogen bonding interactions with adsorbed H2O species stabilize the carboxyl-like transition structure and intermediate that result from the initial recombination of CO and O on the PdO(101) surface. This stabilization lowers the energy barrier for CO oxidation on PdO(101) by 10 kJ/mol, in good agreement with our experimental estimate.

  8. H2O release in cold subduction zones: eclogitization vs. lawsonite stability

    NASA Astrophysics Data System (ADS)

    Vitale Brovarone, A.; Groppo, C.; Hetényi, G.; Compagnoni, R.

    2012-04-01

    Transition from blueschist to eclogite facies is considered as a major step of dehydration during subduction of oceanic crust. In cold subduction zones, this critical transitional field is characterized by the stability of lawsonite, which represents the major H2O carrier in HP basaltic rocks. Lawsonite-bearing eclogites are commonly associated with lawsonite-blueschist [1]. This association is commonly referred to prograde (i.e. from blueschist- to eclogite-facies conditions) or retrograde (i.e. from eclogite- to blueschist-facies conditions) incomplete re-equilibration. However, field, microstructural and petrological data indicate that the two assemblages can coexist over a wide PT field. In Alpine Corsica (France), deeply subducted metabasalts are well preserved as lawsonite-bearing eclogite (Law-Ecl) and lawsonite-bearing blueschist (Law-Bs), providing a unique access to these rocks rarely preserved elsewhere. The Corsican Law-Ecl, consisting of omphacite + lawsonite + garnet + phengite + titanite, commonly occur as single undeformed metabasaltic pillows surrounded by Law-Bs. Law-Bs are found as variably deformed metabasaltic pillows locally cross-cut by eclogitic veins and consist of glaucophane + actinolite + lawsonite + garnet + phengite + titanite. Field evidence and microstructures reveal that both Law-Ecl and Law-Bs are stable at the metamorphic peak in the lawsonite-eclogite stability field. Isochemical phase diagrams (pseudosections) calculated in the system MnNKCFMASH for representative Law-Ecl and Law-Bs samples indicate that both lithologies equilibrated at the same conditions of 520 ± 20 °C and 2.3 ± 0.1 GPa, in response of primary differences in the bulk rock compositions, probably acquired during igneous or seafloor metasomatic processes [2]. These PT estimates are comparable with and therefore representative of common PT values registered and preserved by exhumed rocks in HP orogenic belts. Despite the two rocks are omphacite-free (i.e. Law

  9. Nuclear quantum effect and H/D isotope effect on F + (H2O)n → FH + (H2O)n-1OH (n = 1-3) reactions

    NASA Astrophysics Data System (ADS)

    Udagawa, Taro; Tachikawa, Masanori

    2016-10-01

    Potential energy profiles for F + (H2O)n → FH + (H2O)n-1OH (n = 1-3) reactions, which are widely relevant to solvent effects on chemical reactions, have been investigated using the conventional quantum mechanical (QM) methods and our multicomponent QM (MC_QM) methods, which can take account of nuclear quantum effect of light nucleus, such as proton and deuteron. For these reactions, Li and co-workers [G. Li et al., J. Phys. Chem. A 117, 11979 (2013)] reported that (i) for F + H2O → FH + OH reaction, MPW1K density functional gave the best barrier among 49 kinds of density functionals and (ii) the energy of transition state of F + (H2O)2 → FH + (H2O)OH reaction is lower than that of the separated reactant molecules by the contribution of the second water molecule using high-accuracy CCSD(T)/cc-pVQZ calculations. We have found that ω B97XD density functional reasonably reproduces the CCSD(T) geometries well, whereas MPW1K was not suited for analyzing F + (H2O)2 → FH + (H2O)OH reaction. Our MC_QM calculations reveal that nuclear quantum nature of hydrogen nucleus lowers the activation barrier of the reactions. The H/D isotope effect on F + (H2O)n → FH + (H2O)n-1OH (n = 1-3) reactions was also investigated.

  10. The effect of ZnO addition on H2O activation over Co/ZrO2 catalysts

    SciTech Connect

    Davidson, Stephen D.; Sun, Junming; Wang, Yong

    2016-07-01

    The effect of ZnO addition on the dissociation of H2O and subsequent effects on cobalt oxidation state and ethanol reaction pathway were investigated over Co/ZrO2 catalyst during ethanol steam reforming (ESR). Catalyst physical properties were characterized by BET, XRD, and TEM. To characterize the catalysts ability to dissociate H2O, Raman spectroscopy, H2O-TPO, and pulsed H2O oxidation coupled with H2-TPR were used. It was found that the addition of ZnO to cobalt supported on ZrO2 decreased the activity for H2O dissociation, leading to a lower degree of cobalt oxidation. The decreased H2O dissociation was also found to affect the reaction pathway, evidenced by a shift in liquid product selectivity away from acetone and towards acetaldehyde.

  11. Space-Borne H2O Observations in the Arctic Stratosphere and Mesosphere in the Spring of 1992

    NASA Technical Reports Server (NTRS)

    Aellig, C. P.; Bacmeister, J.; Bevilacqua, R. M.; Daehler, M.; Kriebel, D.; Pauls, T.; Siskind, D.; Kaempfer, N.; Langen, J.; Hartmann, G.; Berg, A.; Park, J. H.; Russell, J. M., III

    1996-01-01

    We report on stratospheric and mesospheric water vapor (H2O) observations obtained by the Millimeter wave Atmospheric Sounder (MAS) in the Arctic spring of 1992. In the lower stratosphere, the observations show enhanced H2O inside the vortex between 450 K and 625 K, in agreement with other H2O observations. In the upper stratosphere and lower mesosphere, at potential temperatures between 1850 K and 2200 K, we find regions of depressed H2O volume mixing ratio coincident with remnants of high potential vorticity. The depressed mesospheric H2O, as well as the enhanced lower stratospheric H2O, are consistent with wintertime descent. It also suggests effective containment of air up into the lower mesosphere.

  12. Ground and excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters: Insight into the electronic structure of the [Fe(H2O)6]2+ – [Fe(H2O)6]3+ complex

    SciTech Connect

    Miliordos, Evangelos; Xantheas, Sotiris S.

    2015-04-14

    We report the ground and low lying electronically excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters using multi-configuration electronic structure theory. In particular, we have constructed the Potential Energy Curves (PECs) with respect to the iron-oxygen distance when removing all water ligands at the same time from the cluster minima and established their correlation to the long range dissociation channels. Due to the fact that both the second and third ionization potentials of iron are larger than the one for water, the ground state products asymptotically correlate with dissociation channels that are repulsive in nature at large separations as they contain at least one H2O+ fragment and a positive metal center. The most stable equilibrium structures emanate – via intersections and/or avoided crossings – from the channels consisting of the lowest electronic states of Fe2+(5D; 3d6) or Fe3+(6S; 3d5) and six neutral water molecules. Upon hydration, the ground state of Fe2+(H2O)6 is a triply (5Tg) degenerate one with the doubly (5Eg) degenerate state lying slightly higher in energy. Similarly, Fe3+(H2O)6 has a ground state of 6Ag symmetry under Th symmetry. We furthermore examine a multitude of electronically excited states of many possible spin multiplicities, and report the optimized geometries for several selected states. The PECs for those cases are characterized by a high density of states. Focusing on the ground and the first few excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters, we studied their mutual interaction in the gas phase. We obtained the optimal geometries of the Fe2+(H2O)6 – Fe3+(H2O)6 gas phase complex for different Fe–Fe distances. For distances shorter than 6.0 Å, the water molecules in the respective first solvation shells located between the two metal centers were found to interact via weak hydrogen bonds. We examined a total of ten electronic states for this complex, including those corresponding to the

  13. Use of Enzymatic Biosensors to Quantify Endogenous ATP or H2O2 in the Kidney

    PubMed Central

    Palygin, Oleg; Levchenko, Vladislav; Evans, Louise C.; Blass, Gregory; Cowley, Allen W.; Staruschenko, Alexander

    2015-01-01

    Enzymatic microelectrode biosensors have been widely used to measure extracellular signaling in real-time. Most of their use has been limited to brain slices and neuronal cell cultures. Recently, this technology has been applied to the whole organs. Advances in sensor design have made  possible the measuring of cell signaling in blood-perfused in vivo kidneys. The present protocols list the steps needed to measure ATP and H2O2 signaling in the rat kidney interstitium. Two separate sensor designs are used for the ex vivo and in vivo protocols. Both types of sensor are coated with a thin enzymatic biolayer on top of a permselectivity layer to give fast responding, sensitive and selective biosensors. The permselectivity layer protects the signal from the interferents in biological tissue, and the enzymatic layer utilizes the sequential catalytic reaction of glycerol kinase and glycerol-3-phosphate oxidase in the presence of ATP to produce H2O2. The set of sensors used for the ex vivo studies further detected analyte by oxidation of H2O2 on a platinum/iridium (Pt-Ir) wire electrode. The sensors for the in vivo studies are instead based on the reduction of H2O2 on a mediator coated gold electrode designed for blood-perfused tissue. Final concentration changes are detected by real-time amperometry followed by calibration to known concentrations of analyte. Additionally, the specificity of the amperometric signal can be confirmed by the addition of enzymes such as catalase and apyrase that break down H2O2 and ATP correspondingly. These sensors also rely heavily on accurate calibrations before and after each experiment. The following two protocols establish the study of real-time detection of ATP and H2O2 in kidney tissues, and can be further modified to extend the described method for use in other biological preparations or whole organs. PMID:26485400

  14. Kinetics and mechanisms of degradation of chloroacetonitriles by the UV/H2O2 process.

    PubMed

    Ling, Li; Sun, Jianliang; Fang, Jingyun; Shang, Chii

    2016-08-01

    Haloacetonitriles (HANs) are emerging disinfection by-products (DBPs) that are more toxic than the regulated DBPs and widely found in the chlorinated/chloraminated water. This paper studied kinetics and mechanisms of the degradation of chloroacetonitriles (CANs) by the UV/H2O2 process at pH 6 and 7.5 and H2O2 concentrations of 1 × 10(-3) M, 5 × 10(-3) M and 1 × 10(-2) M. The degradation followed pseudo first-order degradation kinetics. The degradation rate of monochloroacetonitrile (MCAN) remained similar, while those of dichloroacetonitrile (DCAN) and trichloroacetonitrile (TCAN) increased with increasing pH and H2O2 concentrations. The different trends were attributed to the changing contributions of the two major mechanisms: the nucleophilic attack by hydroperoxide ions ( [Formula: see text] ) and the hydroxyl radical (•OH) oxidation. The second-order rate constants of [Formula: see text] towards MCAN, DCAN and TCAN were determined to be 11.8 (±0.62), 4.83 (±0.01) × 10(3), and 2.54 (±0.23) × 10(5) M(-1) s(-1), respectively, while that of •OH were 8.7 × 10(6), 4.4 × 10(6), and < 10(6) M(-1) s(-1), respectively. The degradation of TCAN was mainly attributed to the [Formula: see text] nucleophilic attack, while that of MCAN was dominated by the •OH oxidation. DCAN was degraded by both mechanisms. The nucleophilic attack increased linearly with increasing [Formula: see text] concentration as a result of increasing H2O2 concentration and/or pH, while the •OH oxidation was less dependent on H2O2 concentrations and/or pH. The nucleophilic attack mainly transformed HANs to haloacetamides, while the •OH oxidation dechlorinated HANs. This paper firstly illustrated the importance of the [Formula: see text] nucleophilic attack, in addition to the •OH oxidation, on the CAN degradation in the UV/H2O2 process.

  15. Experimental constraints on differentiation and H 2O abundance of calc-alkaline magmas

    NASA Astrophysics Data System (ADS)

    Kawamoto, Tatsuhiko

    1996-11-01

    Partial melting experiments were conducted on a natural high-alumina basalt from the Higashi-Izu volcanoes (47.4 wt.% SiO2; 8.3 wt.% MgO) with 1 and 2 wt.% total H2O at 0.5 and 1 GPa, 1125-875°C. The partial melts produced segregate by capillary action into crimped parts of the capsule, preventing chemical modification of the melt during quenching. Liquid compositions in 1 wt.% total H2O runs at 0.5 GPa mimic the chemical variations of calc-alkaline andesites and dacites associated with the basalt. The residual phase assemblages from 1 wt.% total H2O experiments are consistent with the observed phenocrysts in two pyroxene andesite and hornblende (hb)-orthopyroxene (opx) dacite. In contrast, a clinopyroxene (cpx)-hb rhyolite assemblage is produced in the 2 wt.% total H2O experiments. Although no such cpx-hb rhyolite is found in either Northeast Japan or the Izu-Mariana arc, this type of rhyolite is found in Central America, which is also characterized by high H2O contents in the associated basaltic melts ([1]). The abundance of SiO2 in residual liquids increased from 49 to 54 wt.% in the 25°C interval between 1125° and 1100°C in the 1 wt.% total H2O system, and from 63 to 71 wt.% in the 50°C interval between 975° and 925°C. The first gap between basalt and andesite is generated by a sudden change in the amount of partial melt, and the second gap between andesite and dacite is produced by the formation of hornblende by the consumption of pyroxene, because the SiO2 abundance of hornblende is less than that of pyroxene. These two reaction relations result in the existence of two compositional gaps, between basalt and andesite, and between andesite and dacite, which are recognized in the Higashi-Izu volcano group and many other calc-alkaline volcanoes.

  16. Solid organic residues produced by irradiation of hydrocarbon-containing H2O and H2O/NH3 ices - Infrared spectroscopy and astronomical implications

    NASA Astrophysics Data System (ADS)

    Khare, B. N.; Thompson, W. R.; Murray, B. G. J. P. T.; Chyba, C. F.; Sagan, C.; Arakawa, E. T.

    1989-06-01

    Plasma-discharge irradiations were conducted for the methane clathrate expected in outer solar system satellites and cometary nuclei; also irradiated were ices prepared from other combinations of H2O with CH4, C2H6, or C2H2. Upon evaporation of the yellowish-to-tan irradiated ices, it is found that a colored solid film adheres to the walls of the reaction vessel at room temperature. These organic films are found to exhibit IR band identifiable with alkane, aldehide, alcohol, and perhaps alkene, as well as substituted aromatic functional groups. These spectra are compared with previous studies of UV- or photon-irradiated nonclathrated hydrocarbon-containing ices.

  17. A potential energy surface for the process H2 + H2O yielding H + H + H2O - Ab initio calculations and analytical representation

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Walch, Stephen P.; Taylor, Peter R.

    1991-01-01

    Extensive ab initio calculations on the ground state potential energy surface of H2 + H2O were performed using a large contracted Gaussian basis set and a high level of correlation treatment. An analytical representation of the potential energy surface was then obtained which reproduces the calculated energies with an overall root-mean-square error of only 0.64 mEh. The analytic representation explicitly includes all nine internal degrees of freedom and is also well behaved as the H2 dissociates; it thus can be used to study collision-induced dissociation or recombination of H2. The strategy used to minimize the number of energy calculations is discussed, as well as other advantages of the present method for determining the analytical representation.

  18. Alleviation of drought stress by mycorrhizas is related to increased root H2O2 efflux in trifoliate orange

    PubMed Central

    Huang, Yong-Ming; Zou, Ying-Ning; Wu, Qiang-Sheng

    2017-01-01

    The Non-invasive Micro-test Technique (NMT) is used to measure dynamic changes of specific ions/molecules non-invasively, but information about hydrogen peroxide (H2O2) fluxes in different classes of roots by mycorrhiza is scarce in terms of NMT. Effects of Funneliformis mosseae on plant growth, H2O2, superoxide radical (O2·−), malondialdehyde (MDA) concentrations, and H2O2 fluxes in the taproot (TR) and lateral roots (LRs) of trifoliate orange seedlings under well-watered (WW) and drought stress (DS) conditions were studied. DS strongly inhibited mycorrhizal colonization in the TR and LRs, whereas mycorrhizal inoculation significantly promoted plant growth and biomass production. H2O2, O2·−, and MDA concentrations in leaves and roots were dramatically lower in mycorrhizal seedlings than in non-mycorrhizal seedlings under DS. Compared with non-mycorrhizal seedlings, mycorrhizal seedlings had relatively higher net root H2O2 effluxes in the TR and LRs especially under WW, as well as significantly higher total root H2O2 effluxes in the TR and LRs under WW and DS. Total root H2O2 effluxes were significantly positively correlated with root colonization but negatively with root H2O2 and MDA concentrations. It suggested that mycorrhizas induces more H2O2 effluxes of the TR and LRs, thus, alleviating oxidative damage of DS in the host plant. PMID:28176859

  19. [Gd(Try-TTDA)(H2O)]2-: a new MRI contrast agent for copper ion sensing.

    PubMed

    Kasala, Dayananda; Lin, Tsung-Sheng; Chen, Chiao-Yun; Liu, Gin-Chung; Kao, Chai-Lin; Cheng, Tian-Lu; Wang, Yun-Ming

    2011-05-14

    In this study, we have developed two new L-tryptophan based contrast agents [Gd(Try-TTDA)(H(2)O)](2-) and [Gd(Try-ac-DOTA)(H(2)O)](-). Upon addition of Cu(II) to [Gd(Try-TTDA)(H(2)O)](2-), significant increases in the relaxivity (r(1)) and hydration number of [Gd(Try-TTDA)(H(2)O)](2-) were observed. However, it only induced a minute increase in the relaxivity (r(1)) in the case of [Gd(Try-ac-DOTA)(H(2)O)](-). Furthermore, the interaction of Cu(II) with the indole ring of Gd(III) complexes was explored by measuring the intrinsic fluorescence of the tryptophan of the Gd(III) complex. With the addition of one equivalent of Cu(II) to [Gd(Try-TTDA)(H(2)O)](2-) the indole fluorescence was completely quenched. Moreover, the [Gd(Try-TTDA)(H(2)O)](2-) complex shows excellent selectivity towards Cu(II) over other metal ions (Cu(II) > La(III) > Mg(II)). Importantly, the significant signal intensity (2073 ± 67) for in vitro MR imaging using [Gd(Try-TTDA)(H(2)O)](2-) in the presence of Cu(II) implicates that this new smart contrast agent ([Gd(Try-TTDA)(H(2)O)](2-)) can serve as a Cu(II) sensor for MR imaging.

  20. Synthesis and comparative study of Co(pym)(VO3)2 and [Co(H2O)2(VO3)2]·2H2O.

    PubMed

    Larrea, Edurne S; Mesa, José L; Pizarro, José L; Fernández de Luis, Roberto; Rodríguez Fernández, Jesús; Rojo, Teófilo; Arriortua, María I

    2012-12-14

    The three-dimensional Co(pym)(VO(3))(2), 1, hybrid compound, where pym is pyrimidine, has been synthesized under mild hydrothermal conditions at 120 °C. The compound has been characterized by FT-IR spectroscopy, elemental analysis, thermogravimetric measurements, thermodiffractometry, UV-Vis spectroscopy, temperature-dependent magnetic susceptibility and magnetization, and finally a study of specific heat has been performed. The crystal structure of 1 was solved using single-crystal X-ray diffraction data, taking into account that the crystals of this compound are twins of two components. It crystallizes in the monoclinic system, space group C2/c, a = 12.899(5) Å, b = 9.859(2) Å, c = 7.051(1) Å, β = 111.41(3)°, Z = 4. The crystal structure is built up from edge sharing VO(5) trigonal bipyramid double chains and [CoO(4)pym](n) chains. This resembles the structure of the [Co(H(2)O)(2)(VO(3))(2)]·2H(2)O compound, 2. For this reason a comparative study of their properties was carried out. Magnetic measurements of 1, performed in the 2.0 to 300 K range, reveal the existence of a weak ferromagnetic order near 3 K. This fact was confirmed with magnetization measurements, which show irreversibility characteristic of soft ferromagnets. Magnetic measurements of 2 show a 3D antiferromagnetic ordering at 2.5 K. The magnetization shows a small change of curvature indicating the occurrence of a metamagnetic transition. Specific heat measurements of both compounds confirm the 3D nature of the magnetic order. The comparative study of the magneto-structural correlations reveals that the pyrimidine molecules are responsible for the different magnetic behaviour between 1 and 2.

  1. Distance-dependent radiation chemistry: Oxidation versus hydrogenation of CO in electron-irradiated H2O/CO/H2O ices

    SciTech Connect

    Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven; Kimmel, Gregory A.

    2014-11-26

    Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflection-absorption spectroscopy (IRAS) as function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than ~ 15 ML, CO oxidation dominates over the sequential hydrogenation of CO to methanol (CH3OH), and CO2 is the major product of CO oxidation, consistent with previous observations. At its highest yield, CO2 accounts for ~45% of all the reacted CO. Another oxidation product is identified as the formate anion (HCO2-). In contrast, for CO buried more than ~ 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate are not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on pre-irradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.

  2. Velocity distributions of H and OH produced through solar photodissociation of H2O

    NASA Technical Reports Server (NTRS)

    Wu, C. Y. Robert; Chen, F. Z.; Judge, D. L.

    1992-01-01

    The calculated velocity distributions of atomic hydrogen and hydroxyl radicals produced through solar photodissociation of gaseous water molecules are presented. Under collisionless conditions, the calculation was carried out using the most recent available data for the production of H and OH through photodissociation of H2O from its dissociation onset throughout the EUV region. Because the lack of data in certain spectral regions, only upper and lower bounds to the velocity distributions can be obtained. The results show that the H atoms and OH radicals produced exhibit multiple velocity groups. Since most of the current cometary modeling uses a single velocity of 20 km/s associated with the photodissociation of H2O, the present results may be useful in interpreting the many peaks observed in the velocity distributions of cometary atomic hydrogen.

  3. Absolute cross sections for dissociative electron attachment to H2O and D2O

    NASA Astrophysics Data System (ADS)

    Rawat, Prashant; Prabhudesai, Vaibhav S.; Aravind, G.; Rahman, M. A.; Krishnakumar, E.

    2007-12-01

    The dissociative electron attachment (DEA) process to water (H2O) and heavy water (D2O) has been studied in the gas phase in a cross beam experiment for electron energies up to 20 eV. The apparatus used eliminates discrimination due to the kinetic energy and angular distribution of the ions. The cross sections are normalized to absolute values using the cross section for production of O- from O2 (Rapp and Briglia 1965 J. Chem. Phys. 43 1480). These are the first exhaustive measurements of absolute cross sections for both the H- and O- from H2O and D- and O- from D2O at all the three resonances. The results are compared with the scarce data available in the literature. Isotope effect is observed at the 12 eV resonance in the H- channel and at all the three resonances in the O- channel.

  4. Fragmentation Pathways of H+(H2O)2 after Extreme Ultraviolet Photoionization

    NASA Astrophysics Data System (ADS)

    Lammich, L.; Domesle, C.; Jordon-Thaden, B.; Förstel, M.; Arion, T.; Lischke, T.; Heber, O.; Klumpp, S.; Martins, M.; Guerassimova, N.; Treusch, R.; Ullrich, J.; Hergenhahn, U.; Pedersen, H. B.; Wolf, A.

    2010-12-01

    Photofragmentation of the protonated water dimer H+(H2O)2, a fundamental system both in aqueous solutions and gas-phase water clusters, has been studied at 13.8 nm using the Free Electron Laser FLASH in Hamburg. In a crossed-beam experiment using time-resolved, single-molecule fragment imaging, the two-body breakup into H2O++H3O+ was found as a prominent fragmentation channel with a kinetic energy release of up to 10 eV. This channel was observed with at least a similar yield as events with stronger fragmentation, producing protons together with neutral fragments and showing an absolute cross section of (0.5±0.2)×10-18cm2.

  5. In situ electrical conductivity measurements of H2O under static pressure up to 28 GPa

    NASA Astrophysics Data System (ADS)

    Liu, Bao; Gao, Yang; Han, Yonghao; Ma, Yanzhang; Gao, Chunxiao

    2016-08-01

    The in situ electrical conductivity measurements on water in both solid state and liquid state were performed under pressure up to 28 GPa and temperature from 77 K to 300 K using a microcircuit fabricated on a diamond anvil cell (DAC). Water chemically ionization mainly contributes to electrical conduction in liquid state, which is in accord with the results obtained under dynamic pressure. Energy band theory of liquid water was used to understand effect of static pressure on electrical conduction of water. The electric conductivity of H2O decreased discontinuously by four orders of magnitude at 0.7-0.96 GPa, indicating water frozen at this P-T condition. Correspondingly, the conduction of H2O in solid state is determined by arrangement and bending of H-bond in ice VI and ice VII. Based on Jaccard theory, we have concluded that the charge carriers of ice are already existing ions and Bjerrum defects.

  6. Theoretical study of the chemiluminescence of the Al + H2O reaction.

    PubMed

    Álvarez-Barcia, Sonia; Flores, Jesús R; Granucci, Giovanni; Persico, Maurizio

    2013-01-10

    We performed surface hopping simulations of Al + H(2)O collisions by a direct semiempirical method, reproducing the conditions of previous beam-gas experiments. We observed the formation of the HAlOH species, that dissociates to AlOH + H after a lifetime of about 0.6 ps. This species undergoes nonadiabatic transitions to its first excited state and is responsible for chemiluminescence in the visible range, while the Al-H(2)O complex emits in the infrared. The computed emission band in the visible is red-shifted with respect to the experimental one, because of slight inaccuracies of the potential energy surfaces. However, collisions with more water molecules and exciplex formation with excited Al((2)S, (4)P) atoms may also contribute to the short wavelength emission, as we show by accurate ab initio calculations.

  7. Photoassisted Oxygen Reduction Reaction in H2 -O2 Fuel Cells.

    PubMed

    Zhang, Bingqing; Wang, Shengyang; Fan, Wenjun; Ma, Weiguang; Liang, Zhenxing; Shi, Jingying; Liao, Shijun; Li, Can

    2016-11-14

    The oxygen reduction reaction (ORR) is a key step in H2 -O2 fuel cells, which, however, suffers from slow kinetics even for state-of-the-art catalysts. In this work, by making use of photocatalysis, the ORR was significantly accelerated with a polymer semiconductor (polyterthiophene). The onset potential underwent a positive shift from 0.66 to 1.34 V, and the current was enhanced by a factor of 44 at 0.6 V. The improvement was further confirmed in a proof-of-concept light-driven H2 -O2 fuel cell, in which the open circuit voltage (Voc ) increased from 0.64 to 1.18 V, and the short circuit current (Jsc ) was doubled. This novel tandem structure combining a polymer solar cell and a fuel cell enables the simultaneous utilization of photo- and electrochemical energy, showing promising potential for applications in energy conversion and storage.

  8. Remedy of dye manufacturing process effluent by UV/H2O2 process.

    PubMed

    Shu, Hung-Yee; Chang, Ming-Chin; Hsieh, Wen-Pin

    2006-01-16

    The effluent from dye manufacturing industry is more difficult to be treated than laboratory synthesized wastewater according to high variability of composition and color intensity. Thus, this study aimed to propose the method for remedying industrial effluent by UV/H2O2 process in a recirculated batch reactor system while considering the effects on hydrogen peroxide dosage, UV power and wastewater intensity for the removal of color and COD. From the experimental results, it was feasibly treated that the distinguished removal of color and COD by increasing the hydrogen peroxide dosage and UV power, but not by the strong intensity of industrial effluent. Therefore, UV/H2O2 process of the developed reactor was a positively superior treatment or pre-treatment for dye manufacturing plant effluent to comply the regulated requirements.

  9. H2-O2 auxiliary power unit for Space Shuttle vehicles - A progress report.

    NASA Technical Reports Server (NTRS)

    Joyce, J. P.; Beremand, D. G.; Cameron, H. M.; Jefferies, K. S.

    1973-01-01

    Description of a program to establish technology readiness of hydrogen-oxygen (H2-O2) auxiliary power units for use on board the Space Shuttle orbiter vehicle. Fundamental objectives include experimentally establishing an acceptable propellant flow control method, verification of combustor stability, and adequate thermal management. An initial auxiliary power unit (APU) configuration with recycled hydrogen flow has been studied and revised toward greater simplicity and scaling ease. The selected APU is a recuperated open-cycle, turbine-driven unit. Series flow of cryogenic hydrogen removes internally-generated heat and heat from the hydraulic system. The revised configuration schematic and its calculated performance are reviewed. A weight comparison is made between the shuttle baseline hydrazine and H2-O2 APU systems, showing that hydrogen-oxygen APUs have the potential of increasing the payload of the Space Shuttle.

  10. Measurements of H2O-broadening coefficients of O2 A-band lines

    NASA Astrophysics Data System (ADS)

    Delahaye, T.; Landsheere, X.; Pangui, E.; Huet, F.; Hartmann, J.-M.; Tran, H.

    2016-11-01

    We report laboratory measurements of H2O-broadening coefficients of O2 absorption lines in the A-band near 13,000 cm-1. For this, four spectra of oxygen gas mixed with water vapor were recorded with a high resolution Fourier transform spectrometer for total pressures ranging from 125 to 175 Torr at 323 K, and a fifth at 175 Torr and 365 K. Broadening coefficients of 39 transitions (up to J″ = 21) were retrieved from the measured spectra through fits using Galatry line profiles. Values at room temperature (296 K) were then extrapolated and compared with previous determinations in the A-band and millimeter waves region. This enables to resolve some controversial issues related to the inconsistencies between these studies. Finally, comparing our results with the line broadening coefficients by dry air confirms that H2O-broadenings of oxygen lines are, on average, 10% larger than those by dry air.

  11. Numerical simulation of detonation reignition in H 2-O 2 mixtures in area expansions

    NASA Astrophysics Data System (ADS)

    Jones, D. A.; Kemister, G.; Tonello, N. A.; Oran, E. S.; Sichel, M.

    Time-dependent, two-dimensional, numerical simulations of a transmitted detonation show reignition occuring by one of two mechanisms. The first mechanism involves the collision of triple points as they expand along a decaying shock front. In the second mechanism ignition results from the coalescence of a number of small, relatively high pressure regions left over from the decay of weakened transverse waves. The simulations were performed using an improved chemical kinetic model for stoichiometric H 2-O 2 mixtures. The initial conditions were a propagating, two-dimensional detonation resolved enough to show transverse wave structure. The calculations provide clarification of the reignition mechanism seen in previous H 2-O 2-Ar simulations, and again demonstrate that the transverse wave structure of the detonation front is critical to the reignition process.

  12. Effect of O3 and O3/H2O2 on algae harvesting using chitosan.

    PubMed

    Pranowo, R; Lee, D J; Liu, J C; Chang, J S

    2013-01-01

    We examined the effects of pre-oxidation using ozone (O3) and a combination of O3 and hydrogen peroxide (O3/H2O2) on algae suspensions and their harvesting. Inactivation of algae cells, release of intracellular organic matter (IOM), mineralization of extracellular organic matter (EOM), and changes in molecular weight distribution of EOM were found after pre-oxidation. Enhanced separation efficiency of turbidity, dissolved organic carbon (DOC), protein, and polysaccharide using chitosan and polyaluminum chloride (PACl) was found after pre-oxidation, especially when algae cells were subject to O3/H2O2. Chitosan showed higher efficiency than PACl. Judging from the remarkable increase in floc size, it was proposed that released IOM formed complexes with cationic chitosan and resulted in enhanced dual flocculation and facilitated algae separation.

  13. Ultraviolet Irradiation of Naphthalene in H2O Ice: Implications for Meteorites and Biogenesis

    NASA Technical Reports Server (NTRS)

    Bernstein, Max P.; Dworkin, Jason; Sandford, Scott A.; Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H2O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H2O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon-rich meteorites and interplanetary dust particles (IDPs), and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life.

  14. In situ observations of a high-pressure phase of H2O ice

    USGS Publications Warehouse

    Chou, I.-Ming; Blank, J.G.; Goncharov, A.F.; Mao, Ho-kwang; Hemley, R.J.

    1998-01-01

    A previously unknown solid phase of H2O has been identified by its peculiar growth patterns, distinct pressure-temperature melting relations, and vibrational Raman spectra. Morphologies of ice crystals and their pressure-temperature melting relations were directly observed in a hydrothermal diamond-anvil cell for H2O bulk densities between 1203 and 1257 kilograms per cubic meter at temperatures between -10??and 50??C. Under these conditions, four different ice forms were observed to melt: two stable phases, ice V and ice VI, and two metastable phases, ice IV and the new ice phase. The Raman spectra and crystal morphology are consistent with a disordered anisotropic structure with some similarities to ice VI.

  15. Inhibition of the alternative oxidase stimulates H2O2 production in plant mitochondria.

    PubMed

    Popov, V N; Simonian, R A; Skulachev, V P; Starkov, A A

    1997-09-22

    The hypothesis that a non-coupled alternative oxidase of plant mitochondria operates as an antioxygen defence mechanism [Purvis, A.C. and Shewfelt, R.L., Physiol. Plant. 88 (1993) 712-718; Skulachev, V.P., Biochemistry (Moscow) 59 (1994) 1433-1434] has been confirmed in experiments on isolated soybean and pea cotyledon mitochondria. It is shown that inhibitors of the alternative oxidase, salicyl hydroxamate and propyl gallate strongly stimulate H2O2 production by these mitochondria oxidizing succinate. Effective concentrations of the inhibitors proved to be the same as those decreasing the cyanide-resistant respiration. The inhibitors proved to be ineffective in stimulating H2O2 formation in rat liver mitochondria lacking the alternative oxidase.

  16. Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria.

    PubMed

    Circone, Susan; Kirby, Stephen H; Stern, Laura A

    2006-04-27

    Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within +/-2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol(-1) K(-1) for 1/nCH4.H2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled.

  17. Ice Grain Collisions in Comparison: CO2, H2O, and Their Mixtures

    NASA Astrophysics Data System (ADS)

    Musiolik, Grzegorz; Teiser, Jens; Jankowski, Tim; Wurm, Gerhard

    2016-08-01

    Collisions of ice particles play an important role in the formation of planetesimals and comets. In recent work, we showed that CO2 ice behaves like silicates in collisions. The resulting assumption was that it should therefore stick less efficiently than H2O ice. Within this paper, a quantification of the latter is presented. We used the same experimental setup to study collisions of pure CO2 ice, pure water ice, and 50% mixtures by mass between CO2 and water at 80 K, 1 mbar, and an average particle size of ˜90 μm. The results show a strong increase of the threshold velocity between sticking and bouncing with increasing water content. This supports the idea that water ice is favorable for early growth phases of planets in a zone within the H2O and the CO2 iceline.

  18. Fragmentation pathways of H+(H2O)2 after extreme ultraviolet photoionization.

    PubMed

    Lammich, L; Domesle, C; Jordon-Thaden, B; Förstel, M; Arion, T; Lischke, T; Heber, O; Klumpp, S; Martins, M; Guerassimova, N; Treusch, R; Ullrich, J; Hergenhahn, U; Pedersen, H B; Wolf, A

    2010-12-17

    Photofragmentation of the protonated water dimer H+(H2O)_{2}, a fundamental system both in aqueous solutions and gas-phase water clusters, has been studied at 13.8 nm using the Free Electron Laser FLASH in Hamburg. In a crossed-beam experiment using time-resolved, single-molecule fragment imaging, the two-body breakup into H2O++H3O+ was found as a prominent fragmentation channel with a kinetic energy release of up to 10 eV. This channel was observed with at least a similar yield as events with stronger fragmentation, producing protons together with neutral fragments and showing an absolute cross section of (0.5 ± 0.2) × 10(-18) cm2.

  19. Ab initio potential energy and dipole moment surfaces of the F(-)(H2O) complex.

    PubMed

    Kamarchik, Eugene; Toffoli, Daniele; Christiansen, Ove; Bowman, Joel M

    2014-02-05

    We present full-dimensional, ab initio potential energy and dipole moment surfaces for the F(-)(H2O) complex. The potential surface is a permutationally invariant fit to 16,114 coupled-cluster single double (triple)/aVTZ energies, while the dipole surface is a covariant fit to 11,395 CCSD(T)/aVTZ dipole moments. Vibrational self-consistent field/vibrational configuration interaction (VSCF/VCI) calculations of energies and the IR-spectrum are presented both for F(-)(H2O) and for the deuterated analog, F(-)(D2O). A one-dimensional calculation of the splitting of the ground state, due to equivalent double-well global minima, is also reported.

  20. Mars - Long term changes in the state and distribution of H2O

    NASA Astrophysics Data System (ADS)

    Fanale, F. P.; Salvail, J. R.; Zent, A. P.; Postawko, S. E.

    Cold climate surface features on Mars suggest that a substantial amount of subsurface water ice may have existed in the porous regolith throughout Martial geologic history. The geologic evidence for the widespread occurrence of subsurface ice is in agreement with theoretical estimates of the global inventory of water on Mars. It is pointed out that Mars has experienced great insolation variations as the results of changes in its obliquity and orbital eccentricity. Changes in the solar constant may also have had an effect. The consequences of these developments for CO2 distribution and climate change appear to be profound. The present paper provides preliminary results of an attempt to examine the possible effects of these changes on the state and distribution of regolith, polar cap H2O, and atmospheric H2O. Conclusions regarding the withdrawal of water from the equatorial zone and a transfer to available regolith pores at higher latitudes and to the polar cap are discussed.

  1. Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

    USGS Publications Warehouse

    Circone, S.; Kirby, S.H.; Stern, L.A.

    2006-01-01

    Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

  2. Transport Parameters For Positive IONS In Pure H2O DC Discharge

    NASA Astrophysics Data System (ADS)

    Petrovic, Zoran; Stojanovic, Vladimir; Jovanovic, Jasmina; Maric, Dragana

    2016-09-01

    Transport properties of positive ions originating from H2O (H2O+, OH+) in DC fields and at the room temperature were calculated by using Monte Carlo simulation technique. Initially, the relevant cross section sets were assessed by using Denpoh-Nanbu theory for resolving between elastic and reactive collision events and then resolving contribution of exothermic processes from available experimental data. Newest experimentally or theoretically determined cross sections were compiled and included wherever possible. We present transport coefficients for low and moderate reduced electric fields E / N (N-gas density) accounting for non-conservative processes. Acknowledgment to Ministry of Education, Science and Technology of Republic Serbia, Projects No. 171037 and 410011.

  3. Stratospheric H2O and HNO3 profiles derived from solar occultation measurements

    NASA Astrophysics Data System (ADS)

    Fischer, H.; Fergg, F.; Rabus, D.; Burkert, P.

    1985-04-01

    Compact two-channel radiometers for solar occultation experiments have been constructed in order to measure stratospheric trace gases. The instruments can be used as filter- or correlation-type radiometers, depending on the trace gas under investigation. Within the LIMS correlative measurement program, balloon flights were performed with a payload of up to four of these two-channel radiometers. From the filter-type measurements, profiles of the trace gases H2O and HNO3 are inferred for the height region between the tropopause and the balloon float level. The data evaluation also includes a comprehensive analysis of the error sources and their effect on the accuracy of the trace gas profiles. The derived H2O and HNO3 profiles are assessed against the observations of other authors and are discussed in the light of the trace gas distributions calcualted from photochemical models.

  4. Timescales of magma ascent recorded by H2O zonation in clinopyroxene

    NASA Astrophysics Data System (ADS)

    Lloyd, A. S.; Plank, T. A.; Ruprecht, P.; Hauri, E. H.; Rose, W. I.

    2013-12-01

    Magma ascent prior to explosive eruptions occurs on timescales of minutes to hours, and so requires exceptionally fast chronometers to quantify. One promising approach involves the diffusion of water in clinopyroxene (cpx), given laboratory measurements of diffusivities on the order of 10-9.5 to 10-11.5 at temperatures appropriate for mafic magmas [1]. Previous studies have observed H2O zonation in cpx grains but this was accompanied by major element zonation, leaving open the possibility for crystal growth zonation instead of diffusive loss of water [2]. We report SIMS and EMP analyses for three cpx phenocrysts from ash samples collected in situ during the Oct 17, 1974 sub-plinian eruption of Volcán de Fuego. Concentration profiles were assessed by 5-6 measurements along ~350-450 μm transects measured perpendicular to glassy rims. The maximum H2O measured in the cores of the cpx ranges from 230-320 ppm; whereas, the measurements closest to the rim range from 80-170 ppm. Importantly, we chose grains with limited major element zonation (i.e., Mg# and Al2O3 remain relatively constant or do not co-vary with H2O concentrations). Based on a temperature-dependent parameterization for the partition coefficient of H2O between cpx and melt that accounts for tetrahedrally coordinated Al3+ [3], cores and rims of these cpx are in equilibrium with a melt containing 2.0-2.7 wt% (core) and 0.7-1.6 wt% (rim). The maximum H2O concentration measured in olivine-hosted melt inclusions (~4.2 wt% H2O) erupted on the same day as the cpx phenocrysts [4] suggests that the cpx are not in equilibrium with the melt inclusions. The Mg# of the cpxs (73-77) fall within the range of that for the olivines (72-78) indicating that cpx and olivine were co-crystalizing and that H+ loss by diffusion has potentially occurred. Utilizing the same melt inclusion data to constrain the degassing path for the ascending magma under Fuego, we used forward models to estimate the decompression rate needed to

  5. H2O Loss From Melt Inclusions During Laboratory Heating: Evidence From UV Raman Microspectroscopy

    NASA Astrophysics Data System (ADS)

    Severs, M.; Azbej, T.; Thomas, J. B.; Mandeville, C. W.; Bodnar, R. J.

    2006-05-01

    Melt inclusions (MI) represent the best technique available to estimate the pre-eruptive volatile content of silicate melts. Application of MI to determine volatile contents assumes that volatiles are not lost (or gained) from the MI after trapping, including during eruption and cooling in nature or during laboratory heating. Some previous authors have suggested that water may be lost from melt inclusions during laboratory heating. Experiments have been conducted to quantify H2O loss from MI based on Raman spectroscopic analysis of MI before and after heating. Quartz-hosted MI from the early-erupted plinian stage of the Bishop Tuff were heated to 800°C and 1 kbar for 4 to 1512 hours (63 days). Previous studies had shown that unheated melt inclusions from this unit of the Bishop Tuff contain 4.8-6.5 wt % H2O. Most of the MI were glassy to partly devitrified before heating and did not contain a bubble. After the experiment, most of the inclusions in samples heated for 24 hours or more contained a visible bubble. Many MI, including those from the Bishop Tuff, fluoresce when analyzed using a visible (514 nm) laser excitation. The fluorescence intensity is often sufficiently high to preclude accurate determination of peak heights and areas required to determine the water content. To minimize fluorescence, the Bishop Tuff MI were analyzed using an UV (244 nm) excitation source. The relationship between Raman peak areas and H2O content was established using silicate glass standards with known H2O contents. The MI show insignificant water loss when heated for less than 12 hours, but approximately 75% of the original water was lost after 1512 hours (63 days) at 800° C and 1 kbar. Calculations suggest that a decrease in water content from 5.0 to 1.0 wt% (i.e., loss of 80% of the original water) should result in a decrease in the melt volume of about 27%. This decrease should be manifested as a "vacuum" bubble in the inclusion. Image analyses indicate that although the

  6. High resolution diode laser spectroscopy of H2O spectra broadened by nitrogen and noble gases

    NASA Astrophysics Data System (ADS)

    Kapitanov, Venedikt A.; Osipov, Konstantin Yu.; Protasevich, Alexander E.; Ponurovskiy, Yakov Ya.

    2014-11-01

    The absorption spectra of pure H2O with mixtures of broadening gases N2, Ar, Xe, He, Ar and air have been measured in 1.39 mμ spectral region by high resolution spectrometer based on diode laser (DFB NEL, Japan). For the processing of pure water spectra and it's mixtures with a different broadening gases in a wide pressure range we used a multispectrum fitting procedure developed at IAO. The program is based on a relatively simple Rautian-Sobel'man line profile and linear pressure dependence of the line profile parameters. H2O measured spectra bulk processing results in the retrieving of such line parameters: zero-pressure line center positions, intensities, self-broadening and self-shift coefficients of pure water, broadening and shift coefficients for other gases which are describes the experiment with the minimum residuals in a wide pressure range.

  7. Diagnosing shock temperature with NH3 and H2O profiles

    NASA Astrophysics Data System (ADS)

    Gómez-Ruiz, A. I.; Codella, C.; Viti, S.; Jiménez-Serra, I.; Navarra, G.; Bachiller, R.; Caselli, P.; Fuente, A.; Gusdorf, A.; Lefloch, B.; Lorenzani, A.; Nisini, B.

    2016-10-01

    In a previous study of the L1157 B1 shocked cavity, a comparison between NH3(10-00) and H2O(110-101) transitions showed a striking difference in the profiles, with H2O emitting at definitely higher velocities. This behaviour was explained as a result of the high-temperature gas-phase chemistry occurring in the post-shock gas in the B1 cavity of this outflow. If the differences in behaviour between ammonia and water are indeed a consequence of the high gas temperatures reached during the passage of a shock, then one should find such differences to be ubiquitous among chemically rich outflows. In order to determine whether the difference in profiles observed between NH3 and H2O is unique to L1157 or a common characteristic of chemically rich outflows, we have performed Herschel-HIFI observations of the NH3(10-00) line at 572.5 GHz in a sample of eight bright low-mass outflow spots already observed in the H2O(110-101) line within the Water In Star-forming regions with Herschel Key Programme. We detected the ammonia emission at high velocities at most of the outflows positions. In all cases, the water emission reaches higher velocities than NH3, proving that this behaviour is not exclusive of the L1157-B1 position. Comparisons with a gas-grain chemical and shock model confirms, for this larger sample, that the behaviour of ammonia is determined principally by the temperature of the gas.

  8. Communication: State-to-state differential cross sections for H2O(tilde B) photodissociation

    NASA Astrophysics Data System (ADS)

    Jiang, Bin; Xie, Daiqian; Guo, Hua

    2011-06-01

    Quantum state-to-state differential cross sections, along with the absorption spectrum and product internal state distributions, have been calculated for the photodissociation of H2O in its B band on a new set of ab initio potential energy surfaces in a diabatic representation. The theoretical attributes are in good agreement with the recent experimental data, shedding light on the non-adiabatic dissociation dynamics.

  9. Thermodynamic modelling of a double-effect LiBr-H2O absorption refrigeration cycle

    NASA Astrophysics Data System (ADS)

    Iranmanesh, A.; Mehrabian, M. A.

    2012-12-01

    The goal of this paper is to estimate the conductance of components required to achieve the approach temperatures, and gain insights into a double-effect absorption chiller using LiBr-H2O solution as the working fluid. An in-house computer program is developed to simulate the cycle. Conductance of all components is evaluated based on the approach temperatures assumed as input parameters. The effect of input data on the cycle performance and the exergetic efficiency are investigated.

  10. Line Intensities in the Far-Infrared Spectrum of H 2O 2

    NASA Astrophysics Data System (ADS)

    Perrin, A.; Flaud, J.-M.; Camy-Peyret, C.; Schermaul, R.; Winnewisser, M.; Mandin, J.-Y.; Dana, V.; Badaoui, M.; Koput, J.

    1996-04-01

    Using high resolution Fourier transform spectra (resolution 0.002 cm -1) recorded at the Instituto Ricerca Onde Electromagnetiche Firenze and at the Justus Liebig University Giessen, it has been possible to measure the relative intensities of lines in the far-infrared spectrum of H 2O 2in the 25-400 cm -1spectral region. These intensities were used as input data in a least-squares fit calculation in order to obtain the expansion parameters of the transition moment operator of the pure torsional-rotational transitions of H 2O 2. For these intensity calculations, the theoretical model takes into account the cos γ-type dependence of the dipole moment due to the large amplitude motion of the H atoms relative to the O-O bond, where 2γ is the torsion angle. The value of the dipole moment obtained from the fit of the observed intensities was then scaled to the value obtained from Stark effect measurements. Finally, a synthetic spectrum of the far infrared band of H 2O 2was generated, using the dipole moment expansion determined in this work for the line intensities and the parameters and the Hamiltonian matrix given in a previous analysis (C. Camy-Peyret, J.-M. Flaud, J. W. C. Johns, and M. Noel, J. Mol. Spectrosc.155,84-104 (1992)) for the line positions. In addition to the (Δ n= ±1, Δ Ka= ∓2) torsional-rotational resonances within the ground vibrational state, which are usually observed for H 2O 2, the Hamiltonian model takes explicitly into account both the vibration-rotation resonances involving the ground state and the v3= 1 vibrational state and the "staggering" effect which is due to the cispotential barrier.

  11. Ionized state of hydroperoxy radical-water hydrogen-bonded complex: (HO2-H2O)+.

    PubMed

    Joshi, Ravi; Ghanty, Tapan K; Naumov, Sergej; Mukherjee, Tulsi

    2007-12-27

    Ab initio molecular orbital calculations have been employed to characterize the structure and bonding of the (HO2-H2O)+ radical cation system. Geometry optimization of this system was carried out using unrestricted density functional theory in conjunction with the BHHLYP functional and 6-311++G(2df,2p) as well as 6-311++G(3df,3p) basis sets, the second-order Møller-Plesset perturbation (MP2) method with the 6-311++G(3df,3p) basis set, and the couple cluster (CCSD) method with the aug-cc-pVTZ basis set. The effect of spin multiplicity on the stability of the (HO2-H2O)+ system has been studied and also compared with that of oxygen. The calculated results suggest a proton-transferred hydrogen bond between HO2 and H2O in H3O3+ wherein a proton is partially transferred to H2O producing the O2...H3O+ structure. The basis set superposition error and zero-point energy corrected results indicate that the H3O3+ system is energetically more stable in the triplet state; however, the singlet state of H3O3+ is more stable with respect to its dissociation into H3O+ and singlet O2. Since the resulting proton-transferred hydrogen-bonded complex (O2...H3O+) consists of weakly bound molecular oxygen, it might have important implications in various chemical processes and aquatic life systems.

  12. Degradation of antibiotics norfloxacin by Fenton, UV and UV/H2O2.

    PubMed

    Santos, Lucilaine Valéria de Souza; Meireles, Alexandre Moreira; Lange, Liséte Celina

    2015-05-01

    This study aimed to evaluate the degradation of the antibiotic norfloxacin, using direct photolysis (UV), photolysis with hydrogen peroxide (UV/H2O2) and Fenton's oxidation processes. Initially, it was evaluated the behavior of the antibiotic norfloxacin on direct photolysis, in order to see if the process could be a pertinent way to eliminate the drug in water treatment stations. The results showed that the use of direct photolysis was not effective in the degradation of the antibiotic, reaching a degradation rate of 85% and a mineralization rate of 2% in 7 h of reaction; leading to the formation of intermediates products. To optimize the UV treatment, it was used the combined UV/H2O2 process. Several concentrations of hydrogen peroxide (0.7, 1.4, 2.1, 2.8, 3.5 and 4.2 mmol/L) at pH 7 were tested. The concentration of 2.1 mmol/L reached a degradation rate of 100% in 100 min of reaction. Based on this result, the speed of the reaction at pH 2, 3, 5, and 10 was evaluated for that same concentration of H2O2. The shortest reaction time (60 min) was verified at pH 2 and 3. For the treatment using Fenton oxidation, a degradation rate of 60% of the compound and a mineralization rate of 55% was obtained in 60 min. The study revealed that the Fenton oxidation and UV/H2O2 can be used for norfloxacin removal, reaching respectively degradation rates of 100% and 60%, and mineralization rates of 55% and 32%.

  13. Reactions of OH/+/ and H2O/+/ ions with some diatomic and simple polyatomic molecules

    NASA Technical Reports Server (NTRS)

    Karpas, Z.; Huntress, W. T., Jr.

    1978-01-01

    The rate constants and product distributions of the reactions of OH(+) and H2O(+) with some diatomic and simple polyatomic molecules were studied by ion cyclotron resonance (ICR) mass spectrometric techniques. Reaction rates with CO, NO, O2, N2, CO2, H2S, N2O, H2CO, CH4 and CD4 were measured. Charge transfer and proton transfer were generally observed in cases for which the reaction channel is exothermic, but processes involving rearrangement were not found.

  14. Verification of the H2O linelists with theoretically developed tools

    NASA Astrophysics Data System (ADS)

    Ma, Q.; Tipping, R. H.; Lavrentieva, N. N.; Dudaryonok, A. S.

    2013-11-01

    Two basic rules (i.e., the pair identity and the smooth variation rules) resulting from the properties of the energy levels and wave functions of H2O states govern how the spectroscopic parameters vary with the H2O lines within the individually defined groups of lines. With these rules, for those lines involving high j states in the same groups, variations of all their spectroscopic parameters (i.e., the transition frequency, intensity, pressure broadened half-width, pressure-induced shift, and temperature exponent) can be well monitored. Thus, the rules can serve as simple and effective tools to screen the H2O spectroscopic data listed in the HITRAN database and verify the latter's accuracies. By checking violations of the rules occurring among the data within the individual groups, possible errors can be picked up and also possible missing lines in the linelist whose intensities are above the threshold can be identified. We have used these rules to check the accuracies of the spectroscopic parameters and the completeness of the linelists for several important H2O vibrational bands. Based on our results, the accuracy of the line frequencies in HITRAN 2008 is consistent. For the line intensity, we have found that there are a substantial number of lines whose intensity values are questionable. With respect to other parameters, many mistakes have been found. The above claims are consistent with a well known fact that values of these parameters in HITRAN contain larger uncertainties. Furthermore, supplements of the missing line list consisting of line assignments and positions can be developed from the screening results.

  15. Copper-catalyzed formic acid synthesis from CO2 with hydrosilanes and H2O.

    PubMed

    Motokura, Ken; Kashiwame, Daiki; Miyaji, Akimitsu; Baba, Toshihide

    2012-05-18

    A copper-catalyzed formic acid synthesis from CO2 with hydrosilanes has been accomplished. The Cu(OAc)2·H2O-1,2-bis(diphenylphosphino)benzene system is highly effective for the formic acid synthesis under 1 atm of CO2. The TON value approached 8100 in 6 h. The reaction pathway was revealed by in situ NMR analysis and isotopic experiments.

  16. Verification of the H2O Linelists with Theoretically Developed Tools

    NASA Technical Reports Server (NTRS)

    Ma, Qiancheng; Tipping, R.; Lavrentieva, N. N.; Dudaryonok, A. S.

    2013-01-01

    Two basic rules (i.e., the pair identity and the smooth variation rules) resulting from the properties of the energy levels and wave functions of H2O states govern how the spectroscopic parameters vary with the H2O lines within the individually defined groups of lines. With these rules, for those lines involving high j states in the same groups, variations of all their spectroscopic parameters (i.e., the transition frequency, intensity, pressure broadened half-width, pressure-induced shift, and temperature exponent) can be well monitored. Thus, the rules can serve as simple and effective tools to screen the H2O spectroscopic data listed in the HITRAN database and verify the latter's accuracies. By checking violations of the rules occurring among the data within the individual groups, possible errors can be picked up and also possible missing lines in the linelist whose intensities are above the threshold can be identified. We have used these rules to check the accuracies of the spectroscopic parameters and the completeness of the linelists for several important H2O vibrational bands. Based on our results, the accuracy of the line frequencies in HITRAN 2008 is consistent. For the line intensity, we have found that there are a substantial number of lines whose intensity values are questionable. With respect to other parameters, many mistakes have been found. The above claims are consistent with a well known fact that values of these parameters in HITRAN contain larger uncertainties. Furthermore, supplements of the missing line list consisting of line assignments and positions can be developed from the screening results.

  17. Leptospira interrogans catalase is required for resistance to H2O2 and for virulence.

    PubMed

    Eshghi, Azad; Lourdault, Kristel; Murray, Gerald L; Bartpho, Thanatchaporn; Sermswan, Rasana W; Picardeau, Mathieu; Adler, Ben; Snarr, Brendan; Zuerner, Richard L; Cameron, Caroline E

    2012-11-01

    Pathogenic Leptospira spp. are likely to encounter higher concentrations of reactive oxygen species induced by the host innate immune response. In this study, we characterized Leptospira interrogans catalase (KatE), the only annotated catalase found within pathogenic Leptospira species, by assessing its role in resistance to H(2)O(2)-induced oxidative stress and during infection in hamsters. Pathogenic L. interrogans bacteria had a 50-fold-higher survival rate under H(2)O(2)-induced oxidative stress than did saprophytic L. biflexa bacteria, and this was predominantly catalase dependent. We also characterized KatE, the only annotated catalase found within pathogenic Leptospira species. Catalase assays performed with recombinant KatE confirmed specific catalase activity, while protein fractionation experiments localized KatE to the bacterial periplasmic space. The insertional inactivation of katE in pathogenic Leptospira bacteria drastically diminished leptospiral viability in the presence of extracellular H(2)O(2) and reduced virulence in an acute-infection model. Combined, these results suggest that L. interrogans KatE confers in vivo resistance to reactive oxygen species induced by the host innate immune response.

  18. Tertiary treatment of slaughterhouse effluent: degradation kinetics applying UV radiation or H2O2/UV.

    PubMed

    Luiz, D B; Genena, A K; José, H J; Moreira, R F P M; Schröder, H Fr

    2009-01-01

    In some Brazilian regions, surface water has become scarce, e.g. semi arid climate areas and densely populated and industrial areas, where water over-exploitation and/or fluvial pollution has been more common. Advanced oxidative processes (AOP) provide treated water as a source of reuse water even with the characteristics of drinking water enabling water reuse practices also in food industries. The secondary wastewater of a slaughterhouse was the water source for a tertiary treatment study evaluating the kinetics of the photo-induced degradation of color and UV254 under UV radiation with and without the addition of H2O2. The proximity of the k' values of color and UV254 degradation by UV indicates that the compounds responsible for color may be the same content measured by UV254. The H2O2/UV treatment was 5.2 times faster than simple UV in removing aromatic compounds. The degradation kinetics of aromatic compounds in both treatments followed a pseudo-first order law. The pseudo-first order constant for H2O2/UV and UV treatments were kUV254'=0.0306 min(-1) and kUV254'=0.0056 min(-1), respectively.

  19. Liquid water on Mars - An energy balance climate model for CO2/H2O atmospheres

    NASA Technical Reports Server (NTRS)

    Hoffert, M. I.; Callegari, A. J.; Hsieh, C. T.; Ziegler, W.

    1981-01-01

    A simple climatic model is developed for a Mars atmosphere containing CO2 and sufficient liquid water to account for the observed hydrologic surface features by the existence of a CO2/H2O greenhouse effect. A latitude-resolved climate model originally devised for terrestrial climate studies is applied to Martian conditions, with the difference between absorbed solar flux and emitted long-wave flux to space per unit area attributed to the divergence of the meridional heat flux and the poleward heat flux assumed to equal the atmospheric eddy heat flux. The global mean energy balance is calculated as a function of atmospheric pressure to assess the CO2/H2O greenhouse liquid water hypothesis, and some latitude-resolved cases are examined in detail in order to clarify the role of atmospheric transport and temperature-albedo feedback. It is shown that the combined CO2/H2O greenhouse at plausible early surface pressures may account for climates hot enough to support a hydrological cycle and running water at present-day insolation and visible albedo levels.

  20. Pyrite-enhanced degradation of chloramphenicol by low concentrations of H2O2.

    PubMed

    Wu, Deli; Liu, Yanxia; Zhang, Zhiyong; Ma, Luming; Zhang, Yalei

    2015-01-01

    A pyrite-catalyzed reaction was used to degrade chloramphenicol. Chloramphenicol could be almost 100% removed within 60 minutes when 1 mM H2O2 and 0.1 g/L pyrite were added at an initial pH=3. During oxidation, intermediates such as nitrobenzaldehyde and dichloroacetamide were identified by gas chromatography/mass spectrometry (GC/MS). The •OH was identified by electron spin-resonance spectroscopy. Pyrite was digested to determine elements by ICP (inductive coupled plasma emission spectrometer). To understand the reaction mechanism and the role of natural pyrite in these processes, techniques including scanning electron microscopy and energy dispersive spectrometry were employed to characterize the solid sample. The results explain that pyrite acts as a 'bond' between Fe3+ and H2O2, and this pathway continues to form •OH and inhibit the quenching reaction. Therefore, pyrite-catalyzed reactions would proceed even in low concentrations of H2O2.

  1. 2Q NMR of 2H2O ordering at solid interfaces

    NASA Astrophysics Data System (ADS)

    Krivokhizhina, Tatiana V.; Wittebort, R. J.

    2014-06-01

    Solvent ordering at an interface can be studied by multiple-quantum NMR. Quantitative studies of 2H2O ordering require clean double-quantum (2Q) filtration and an analysis of 2Q buildup curves that accounts for relaxation and, if randomly oriented samples are used, the distribution of residual couplings. A pulse sequence with absorption mode detection is extended for separating coherences by order and measuring relaxation times such as the 2Q filtered T2. Coherence separation is used to verify 2Q filtration and the 2Q filtered T2 is required to extract the coupling from the 2Q buildup curve when it is unresolved. With our analysis, the coupling extracted from the buildup curve in 2H2O hydrated collagen was equivalent to the resolved coupling measured in the usual 1D experiment and the 2Q to 1Q signal ratio was in accord with theory. Application to buildup curves from 2H2O hydrated elastin, which has an unresolved coupling, revealed a large increase in the 2Q signal upon mechanical stretch that is due to an increase in the ordered water fraction while changes in the residual coupling and T2 are small.

  2. Pilot-scale UV/H2O2 study for emerging organic contaminants decomposition.

    PubMed

    Chu, Xiaona; Xiao, Yan; Hu, Jiangyong; Quek, Elaine; Xie, Rongjin; Pang, Thomas; Xing, Yongjie

    2016-03-01

    Human behaviors including consumption of drugs and use of personal care products, climate change, increased international travel, and the advent of water reclamation for direct potable use have led to the introduction of significant amounts of emerging organic contaminants into the aqueous environment. In addition, the lower detection limits associated with improved scientific methods of chemical analysis have resulted in a recent increase in documented incidences of these contaminants which previously were not routinely monitored in water. Such contaminants may cause known or suspected adverse ecological and/or human health effects at very low concentrations. Conventional drinking water treatment processes may not effectively remove these organic contaminants. Advanced oxidation process (AOP) is a promising treatment process for the removal of most of these emerging organic contaminants, and has been accepted worldwide as a suitable treatment process. In this study, different groups of emerging contaminants were studied for decomposition efficiency using pilot-scale UV/H2O2 oxidation setup, including EDCs, PPCPs, taste and odor (T&O), and perfluorinated compounds. Results found that MP UV/H2O2 AOP was efficient in removing all the selected contaminants except perfluorinated compounds. Study of the kinetics of the process showed that both light absorption and quantum yield of each compound affected the decomposition performance. Analysis of water quality parameters of the treated water indicated that the outcome of both UV photolysis and UV/H2O2 processes can be affected by changes in the feed water quality.

  3. Autophagic lysosomal reformation depends on mTOR reactivation in H2O2-induced autophagy.

    PubMed

    Zhang, Jiqian; Zhou, Wei; Lin, Jun; Wei, Pengfei; Zhang, Yunjiao; Jin, Peipei; Chen, Ming; Man, Na; Wen, Longping

    2016-01-01

    Autophagic lysosomal reformation, a key cellular process for maintaining lysosome homeostasis in elevated autophagy, so far has only been reported for cells under certain forms of starvation. For this reason, it is controversial that whether this phenomenon is starvation-specific and its importance in lysosomal regeneration at the late stage of autophagy is often challenged. Here we show that exogenous hydrogen peroxide (H2O2) induced lysosome depletion and recovery characteristic of autophagic lysosomal reformation, and we confirmed the occurrence of autophagic lysosomal reformation after H2O2 treatment by demonstrating Rab7 dissociation from autolysosomes, recruitment of Phosphatidylinositol 4-phosphate (PI4P) and clathrin to the surface of autolysosomes, and the existence of tubular "pro-lysosome" structures extending from autolysosomes. Similar to starvation, H2O2 caused an initial deactivation and a subsequent reactivation for mTOR, and mTOR reactivation was essential for ALR. Our results provided a first non-starvation example of autophagic lysosomal reformation and provide evidence for its importance for some autophagic processes other than that of starvation.

  4. Characteristics of alpha-glycerophosphate-evoked H2O2 generation in brain mitochondria.

    PubMed

    Tretter, Laszlo; Takacs, Katalin; Hegedus, Vera; Adam-Vizi, Vera

    2007-02-01

    Characteristics of reactive oxygen species (ROS) production in isolated guinea-pig brain mitochondria respiring on alpha-glycerophosphate (alpha-GP) were investigated and compared with those supported by succinate. Mitochondria established a membrane potential (DeltaPsi(m)) and released H(2)O(2) in parallel with an increase in NAD(P)H fluorescence in the presence of alpha-GP (5-40 mm). H(2)O(2) formation and the increase in NAD(P)H level were inhibited by rotenone, ADP or FCCP, respectively, being consistent with a reverse electron transfer (RET). The residual H(2)O(2) formation in the presence of FCCP was stimulated by myxothiazol in mitochondria supported by alpha-GP, but not by succinate. ROS under these conditions are most likely to be derived from alpha-GP-dehydrogenase. In addition, huge ROS formation could be provoked by antimycin in alpha-GP-supported mitochondria, which was prevented by myxothiazol, pointing to the generation of ROS at the quinol-oxidizing center (Q(o)) site of complex III. FCCP further stimulated the production of ROS to the highest rate that we observed in this study. We suggest that the metabolism of alpha-GP leads to ROS generation primarily by complex I in RET, and in addition a significant ROS formation could be ascribed to alpha-GP-dehydrogenase in mammalian brain mitochondria. ROS generation by alpha-GP at complex III is evident only when this complex is inhibited by antimycin.

  5. Density functional study of reactivity and regioselectivity of H2O C60

    NASA Astrophysics Data System (ADS)

    KC, Govinda Bahadur

    The exohedral reactivity of endohedral fullerene has aroused significant interest because of its potential applications in biology, medicine and material science. The encapsulation of a single water molecule without any hydrogen bonding to other compounds, inside the hydrophobic environment of C60 is an intriguing topic to study about. In 2011, Kurotobi and Murata successfully synthesized H2O C60 fullerene. The presence of a polar water molecule inside the cage is expected to cause changes in the exohedral reactivity of C60. In order to find out the impact of an entrapped single water molecule on the reactivity of C60 fullerene, we use density functional theory to study the thermodynamics and kinetics of [4+2] Diels-Alder reaction of 1, 3 cis butadiene at all non-identical bonds of free C60 and H2O C60. Our calculations show that the encapsulation of a single water molecule does not have any significant effect on the exohedral reactivity compared to free C60. Moreover, the obtained reaction energies and activation barriers indicate that [6, 6] bond is more reactive than [5, 6] bond and thus cycloaddition is clearly favored at [6, 6] bond. The dipole moment of the H2O C60 is only 0.48 Debye significantly smaller than that of water molecule. The infrared and Raman spectra of the endohedral fullerene are also computed.

  6. Phosphate buffer effects on thermal stability and H2O2-resistance of horseradish peroxidase.

    PubMed

    Asad, Sedigheh; Torabi, Seyed-Fakhreddin; Fathi-Roudsari, Mehrnoosh; Ghaemi, Nasser; Khajeh, Khosro

    2011-05-01

    Horseradish peroxidase (HRP) has attracted intense research interest due to its potential applications in biotechnological fields. However, inadequate stability under prevalent conditions such as elevated temperatures and H(2)O(2) exposure, has limited its industrial application. In this study, stability of HRP was investigated in the presence of different buffer systems (potassium phosphate and Tris-HCl) and additives. It was shown that the concentration of phosphate buffer severely affects enzyme thermostability in a way that in diluted potassium phosphate buffer (10mM) half-life (from 13 to 35 min at 80 °C) and T(m) (from 73 to 77.5 °C) increased significantly. Among additives tested, trehalose had the most thermostabilizing effect. Exploring the role of glycosylation in stabilizing effect of phosphate buffer, non-glycosylated recombinant HRP was also examined for its thermal and H(2)O(2) stability in both diluted and concentrated phosphate buffers. The recombinant enzyme was more thermally stable in diluted buffer in accordance to glycosylated HRP; but interestingly recombinant HRP showed higher H(2)O(2) tolerance in concentrated buffer.

  7. High pressure-temperature Raman spectroscopy of H2-H2O clathrate.

    NASA Astrophysics Data System (ADS)

    Somayazulu, Maddury; Levedahl, Alexander; Goncharov, Alexander; Mao, Ho-Kwang; Hemley, Russell

    2007-03-01

    The melting curve of the C2 clathrate H2-H2O has been determined by in-situ Raman spectroscopy measurements in an externally heated diamond anvil cell. We have determined the melting curve to a maximum pressure of 27 GPa. These are the first measurements on the melting line in this clathrate. Depending on the stoichiometry of the starting mixture of H2 and H2O, we are able to study either a mixture of C2 and H2O or C2 and H2. In either case, we were able to pinpoint the melting of the clathrate from the measurements of the molecular stretching mode (vibron) in the clathrate. In the case of C2 + Ice VII, we observe the vibron in the clathrate at a frequency higher than in pure H2 at the same pressure. We have cross-calibrated the melting temperatures using the Stokes-anti Stokes ratio of the diamond first order and Raman active TO phonon of cubic Boron Nitride. We find that the clathrate melts well above the H2 melting at all pressures studied indicating that the stabilization of this clathrate at high pressures is indeed due to interactions between the host and guest molecules.

  8. High pressure Raman spectroscopy of H2O-CH3OH mixtures.

    PubMed

    Hsieh, Wen-Pin; Chien, Yu-Hsiang

    2015-02-23

    Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

  9. Experimental constraints on CO2 and H2O in the Martian mantle and primary magmas

    NASA Technical Reports Server (NTRS)

    Holloway, John R.; Domanik, Kenneth J.; Cocheo, Peter A.

    1993-01-01

    We present new data on the stability of hornblende in a Martian mantle composition, on CO2 solubility in iron-rich basaltic magmas, and on the solubility of H2O in an alkalic basaltic magma. These new data are combined with a summary of data from the literature to present a summary of the current state of our estimates of solubilities of H2O and CO2 in probable Martian magmas and the stability of hornblende in a slightly hydrous mantle. The new results suggest that hornblende stability is not sensitive to the Mg/(Mg+Fe) ratio (mg#) of the mantle, that is the results for terrestrial mantle compositions are similar to the more iron-rich Martian composition. Likewise, CO2 solubility in iron-rich tholeiitic basaltic magmas is similar to iron-poor terrestrial compositions. The solubility of H2O has been measured in an alkalic basaltic (basanite) composition for the first time, and it is significantly lower than predicted for models of water solubility in magmas. The lack of mg# dependence observed in hornblende stability and on CO2 solubility that in many cases terrestrial results can be applied to Martian compositions. This conclusion does not apply to other phenomena such as primary magma compositions and major mantle mineral mineralogy.

  10. Normalized fluctuations, H2O vs n-hexane: Site-correlated percolation

    NASA Astrophysics Data System (ADS)

    Koga, Yoshikata; Westh, Peter; Sawamura, Seiji; Taniguchi, Yoshihiro

    1996-08-01

    Entropy, volume and the cross fluctuations were normalized to the average volume of a coarse grain with a fixed number of molecules, within which the local and instantaneous value of interest is evaluated. Comparisons were made between liquid H2O and n-hexane in the range from -10 °C to 120 °C and from 0.1 MPa to 500 MPa. The difference between H2O and n-hexane in temperature and pressure dependencies of these normalized fluctuations was explained in terms of the site-correlated percolation theory for H2O. In particular, the temperature increase was confirmed to reduce the hydrogen bond probability, while the pressure appeared to have little effect on the hydrogen bond probability. According to the Le Chatelier principle, however, the putative formation of ``ice-like'' patches at low temperatures due to the site-correlated percolation requirement is retarded by pressure increases. Thus, only in the limited region of low pressure (<300 MPa) and temperature (<60 °C), the fluctuating ice-like patches are considered to persist.

  11. Prediction of absolute infrared intensities for the fundamental vibrations of H2O2

    NASA Technical Reports Server (NTRS)

    Rogers, J. D.; Hillman, J. J.

    1981-01-01

    Absolute infrared intensities are predicted for the vibrational bands of gas-phase H2O2 by the use of a hydrogen atomic polar tensor transferred from the hydroxyl hydrogen atom of CH3OH. These predicted intensities are compared with intensities predicted by the use of a hydrogen atomic polar tensor transferred from H2O. The predicted relative intensities agree well with published spectra of gas-phase H2O2, and the predicted absolute intensities are expected to be accurate to within at least a factor of two. Among the vibrational degrees of freedom, the antisymmetric O-H bending mode nu(6) is found to be the strongest with a calculated intensity of 60.5 km/mole. The torsional band, a consequence of hindered rotation, is found to be the most intense fundamental with a predicted intensity of 120 km/mole. These results are compared with the recent absolute intensity determinations for the nu(6) band.

  12. H2O Megamasers toward Radio-bright Seyfert 2 Nuclei

    NASA Astrophysics Data System (ADS)

    Zhang, J. S.; Liu, Z. W.; Henkel, C.; Wang, J. Z.; Coldwell, G. V.

    2017-02-01

    Using the Effelsberg-100 m telescope, we perform a successful pilot survey on H2O maser emission toward a small sample of radio-bright Seyfert 2 galaxies with a redshift larger than 0.04. The targets were selected from a large Seyfert 2 sample derived from the spectroscopic Sloan Digital Sky Survey Data Release 7 (SDSS-DR7). One source, SDSS J102802.9+104630.4 (z ∼ 0.0448), was detected four times during our observations, with a typical maser flux density of ∼30 mJy and a corresponding (very large) luminosity of ∼1135 L ⊙. The successful detection of this radio-bright Seyfert 2 and an additional tentative detection support our previous statistical results that H2O megamasers tend to arise from Seyfert 2 galaxies with large radio luminosity. The finding provides further motivation for an upcoming larger H2O megamaser survey toward Seyfert 2s with particularly radio-bright nuclei with the basic goal to improve our understanding of the nuclear environment of active megamaser host galaxies. Based on observations with the 100 m telescope of the MPIfR (Max-Planck-Institut für Radioastronomie) at Effelsberg.

  13. NO fluorescence sensing by europium tetracyclines complexes in the presence of H2O2.

    PubMed

    Simões, Eliana F C; Leitão, João M M; Esteves da Silva, Joaquim C G

    2013-07-01

    The effect on the fluorescence of the europium:tetracycline (Eu:Tc), europium:oxytetracycline (Eu:OxyTc) and europium:chlortetracycline (Eu:ClTc) complexes in approximately 2:1 ratio of nitric oxide (NO), peroxynitrite (ONOO(-)), hydrogen peroxide (H2O2) and superoxide (O2 (·-)) was assessed at three ROS/RNS concentrations levels, 30 °C and pH 6.00, 7.00 and 8.00. Except for the NO, an enhancement of fluorescence intensity was observed at pH 7.00 for all the europium tetracyclines complexes-the high enhancement was observed for H2O2. The quenching of the fluorescence of the Tc complexes, without and with the presence of other ROS/RNS species, provoked by NO constituted the bases for an analytical strategy for NO detection. The quantification capability was evaluated in a NO donor and in a standard solution. Good quantification results were obtained with the Eu:Tc (3:1) and Eu:OxyTc (4:1) complexes in the presence of H2O2 200 μM with a detection limit of about 3 μM (Eu:OxyTc).

  14. Protective effect of pomegranate seed oil against H2O2 -induced oxidative stress in cardiomyocytes

    PubMed Central

    Bihamta, Mehdi; Hosseini, Azar; Ghorbani, Ahmad; Boroushaki, Mohammad Taher

    2017-01-01

    Objective: It has been well documented that oxidative stress is involved in the pathogenesis of cardiac diseases. Previous studies have shown that pomegranate seed oil (PSO) has antioxidant properties. This study was designed to investigate probable protective effects of PSO against hydrogen peroxide (H2O2)-induced damage in H9c2 cardiomyocytes. Materials and Methods: The cells were pretreated 24 hr with PSO 1 hr before exposure to 200 µM H2O2. Cell viability was evaluated using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium (MTT) assay. The level of reactive oxygen species (ROS) and lipid peroxidation were measured by fluorimetric methods. Results: H2O2 significantly decreased cell viability which was accompanied by an increase in ROS production and lipid peroxidation and a decline in superoxide dismutase activity. Pretreatment with PSO increased viability of cardiomyocytes and decrease the elevated ROS production and lipid peroxidation. Also, PSO was able to restore superoxide dismutase activity. Conclusion: PSO has protective effect against oxidative stress-induced damage in cardiomyocytes and can be considered as a natural cardioprotective agent to prevent cardiovascular diseases. PMID:28265546

  15. Infrared spectrum and stability of the H2O-HO complex: experiment and theory.

    PubMed

    Soloveichik, Pesia; O'Donnell, Bridget A; Lester, Marsha I; Francisco, Joseph S; McCoy, Anne B

    2010-01-28

    Infrared action spectroscopy is utilized to characterize the gas-phase, hydrogen-bonded H(2)O-HO complex, a primary interaction in the hydration of the hydroxyl radical. The OH radical stretch of the H(2)O-HO complex is identified at 3490 cm(-1), shifted 78 cm(-1) to lower frequency of the OH monomer transition. The stability of the complex, D(0) < or = 5.14 kcal mol(-1), is derived from the highest observed OH product channel in the associated product state distribution. The assignment is supported by high level ab initio calculations of the spectral shift of the binary complex from free OH and its dissociation energy, D(e)(CBS-infinity) = 5.6 kcal mol(-1). A second weaker feature, appearing 15 cm(-1) to lower frequency at 3475 cm(-1), is attributed to a hot band, the OH radical stretch originating from an out-of-plane H(2)O bending state, based on two-dimensional calculations of frequencies and strengths of transitions involving the coupled vibrational modes.

  16. Improving enzymatic saccharification of bamboo shoot shell by alkalic salt pretreatment with H2O2.

    PubMed

    Qing, Qing; Zhou, Linlin; Huang, Meizi; Guo, Qi; He, Yucai; Wang, Liqun; Zhang, Yue

    2016-02-01

    Pretreatment of bamboo shoot shell (BSS) by a combination of alkalic salts with hydrogen peroxide (H2O2) was evaluated for its delignification effect and for its ability to enhance enzymatic saccharification of pretreated solids. By comparing different alkalic salts, the combination of 9% Na3PO4·12H2O and 0.3g/g H2O2 (ASHP) was identified as an effective system that showed the highest delignification of 87.7% and the total reducing sugar yield of 97.1% when pretreated BSS at a solid to liquid ratio of 1/20 (w/w) at 80°C for 2h. The delignification effect and the disruption of the lignocelluloses structure by this novel pretreatment method were deduced to be the main reasons that led to enhanced enzymatic saccharification as supported by the chemical composition analysis and the results of SEM, FTIR and XRD analyses of the untreated and alkalic salt pretreated BSS.

  17. Isopycnic Phases and Structures in H2O/CO2/Ethoxylated Alcohol Surfactant Mixtures

    NASA Technical Reports Server (NTRS)

    Paulaitis, Michael E.; Zielinski, Richard G.; Kaler, Eric W.

    1996-01-01

    Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(i)E(j)) surfactants can form three coexisting liquid phases at conditions where two of the phases have the same density (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing the surfactants C8E5, C10E6, and C12E6, but not for those mixtures containing either C4E1 or CgE3. Pressure-temperature (PT) projections for this isopycnic three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. As a preliminary to measuring the microstructure in isopycnic three component mixtures, phase behavior and small angle neutron scattering (SANS) experiments were performed on mixtures of D2O/CO2/ n-hexaethyleneglycol monododecyl ether (C12E6) as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%). Parameters extracted from model fits of the SANS spectra indicate that, while micellar structure remains essentially unchanged, critical concentration fluctuations increase as the phase boundary and plait point are approached.

  18. Mars - Remote spectral identification of H2O frost and mineral hydrate

    NASA Technical Reports Server (NTRS)

    Huguenin, R. L.; Clark, R. N.; Mccord, T. B.

    1978-01-01

    A reflectance spectrum (0.62-2.6 microns) of Mars (integral disk) is obtained using a newly developed IR spectrometer at the 2.25 m telescope on Mauna Kea, Hawaii. Details of the instrument, observations, and data reduction are presented. Several distinct absorption features are evident that were apparently caused by H2O, but the positions and intensities of the features are quite unusual. In summary, the regolith is probably not as desiccated and dehydrated as the full disk reflectance spectrum and Viking soil analyses would suggest. The surface materials become desiccated and dehydrated as a result of solar UV effects and because of the relative adsorption and desorption rates during the strong diurnal cycling. There may be significant amounts of H2O at depth, and in the Solis Lacus region the H2O reservoir may extend to within a few centimeters of the surface. The Solis Lacus region may therefore be an important target for future Mars landing or sample return mission.

  19. Direct NaBH 4/H 2O 2 fuel cells

    NASA Astrophysics Data System (ADS)

    Miley, George H.; Luo, Nie; Mather, Joseph; Burton, Rodney; Hawkins, Glenn; Gu, Lifeng; Byrd, Ethan; Gimlin, Richard; Shrestha, Prajakti Joshi; Benavides, Gabriel; Laystrom, Julia; Carroll, David

    A fuel cell (FC) using liquid fuel and oxidizer is under investigation. H 2O 2 is used in this FC directly at the cathode. Either of two types of reactant, namely a gas-phase hydrogen or an aqueous NaBH 4 solution, are utilized as fuel at the anode. Experiments demonstrate that the direct utilization of H 2O 2 and NaBH 4 at the electrodes results in >30% higher voltage output compared to the ordinary H 2/O 2 FC. Further, the use of this combination of all liquid fuels, provides numerous advantages (ease of storage, reduced pumping requirements, simplified heat removal, etc.) from an operational point of view. This design is inherently compact compared to other cells that use gas phase reactants. Further, regeneration is possible using an electrical input, e.g. from power lines or a solar panel. While the peroxide-based FC is ideally suited for applications such as space power where air is not available and a high energy density fuel is essential, other distributed and mobile power uses are of interest.

  20. H2O grain size and the amount of dust in Mars' residual North polar cap

    USGS Publications Warehouse

    Kieffer, H.H.

    1990-01-01

    In Mars' north polar cap the probable composition of material residual from the annual condensation cycle is a mixture of fine dust and H2O grains of comparable size and abundance. However, metamorphism of such material will gradually lower its albedo by increasing the size of the H2O grains only. If the cap is undergoing net annual sublimation (as inferred from water vapor observations), late summer observations should be of old ice with H2O grain sizes of 100 ??m or more. Ice of this granularity containing 30% fine dust has a reflectivity similar to that of dust alone; the observed albedo and computed ice grain size imply dust concentrations of 1 part per 1000 or less. The brightness of the icy areas conflicts with what would be expected for a residual cap deposited by an annual cycle similar to that observed by Viking and aged for thousands of years. The residual cap surface cannot be "old dirty' ice. It could be old, coarse, and clean; or it could be young, fine, and dirty. This brings into question both the source of the late summer water vapor and the formation rate of laminated terrain. -Author

  1. Crystal structure of a new cyclomaltoheptaose hydrate: beta-cyclodextrin.7.5H2O.

    PubMed

    Li, Jian-Ye; Sun, Dao-Feng; Hao, Ai-You; Sun, Hong-Yuan; Shen, Jian

    2010-03-30

    The crystallographic study of a partially hydrated form of cyclomaltoheptaose (beta-cyclodextrin, betaCD) is reported. C(42)H(70)O(35).7.5H(2)O; space group P2(1) with unit cell constants a=15.1667(5), b=10.1850(3), c=20.9694(7)A, beta=110.993(2) degrees ; final discrepancy index R=0.0760 for the 6181 observed reflections and 784 refined parameters. One water molecule is included in the cavity and distributed over two partially occupied positions, the other 6.5 waters distributed over eight positions are located as space-filler between the macrocycles. The crystal structure belongs to the cage-type, like that observed in Form I (betaCD.12H(2)O; Lindner, K; Saenger, W. Carbohydr. Res. 1982, 99, 103-115) and Form II (betaCD.11H(2)O; Betzel, C., et al. J. Am. Chem. Soc., 1984, 106, 7545-7567).

  2. H2O-Silicate Microphysics in Ascending Volcanic Plumes on Mars

    NASA Technical Reports Server (NTRS)

    Zent, A. P.

    2003-01-01

    Physical adsorption of water vapor plays a much more significant role in eruptive plume energetics on Mars than on Earth. The total surface area in martian plumes is likely comparable to terrestrial ash, while the erupting magma and ambient atmosphere are drier. Plumes cool rapidly during ascent, and a limited population of H2O molecules find adsorption sites to be increasingly stable. Release of latent heat of condensation and the onset of moist convection are diminished, delayed, or even prevented by adsorptive interaction We have developed a 5-component numerical model of the behavior of water in eruptive plumes under Mars-like conditions. We have used the model to study the fate of both juvenile and ambient atmospheric water in the eruption column. Here we investigate the adsorptive interaction of water and silicates as they effect plume dynamics and the partitioning and distribution of H2O to the martian environment. Our focus is on the role of adsorption in scavenging H2O from the ascending eruption column, and the possibility that adsorptive scavenging depresses the vapor pressure in the column below the level considered in most eruptive models.

  3. A novel near-infrared fluorescent probe for H2O2 in alkaline environment and the application for H2O2 imaging in vitro and in vivo.

    PubMed

    Liu, Keyin; Shang, Huiming; Kong, Xiuqi; Ren, Mingguang; Wang, Jian-Yong; Liu, Yong; Lin, Weiying

    2016-09-01

    H2O2 as one of the most important ROS (Reactive Oxygen Species) has more attack activity to biomolecules such as DNA, RNA, protein and enzyme in alkaline environment and leads to a series of disease. However, no attention has been paid to the fluorescent detection of H2O2 in alkaline environment in the past. Herein, we reported the first ratiometric near-infrared fluorescent probe based on a boric acid derivative of Changsha near-infrared dye (CSBOH) for H2O2 detection in alkaline condition and the application for H2O2 imaging in vivo. ICT (intra-molecular charge transfer) mechanism was used in CSBOH to modulate the fluorescence change. The photophysical change of CSBOH was investigated by comparison with a phenol derivative of Changsha near-infrared dye (CSOH), a structural analogue bearing phenol group. In the presence of H2O2, CSBOH exhibited remarkably different fluorescence change at 650 nm and 720 nm when excited by 560 nm and 670 nm light respectively in alkaline buffer and showed high selectivity toward H2O2. Cellular experiments demonstrate that CSBOH can image endogenously generated H2O2 in macrophages and A431 cells. In vivo experiment demonstrates that both CSOH and CSBOH can be used for bio-imaging, and CSBOH can image H2O2 in living animal successfully.

  4. Characterization of titanium dioxide nanoparticles modified with polyacrylic acid and H2O2 for use as a novel radiosensitizer.

    PubMed

    Morita, Kenta; Miyazaki, Serika; Numako, Chiya; Ikeno, Shinya; Sasaki, Ryohei; Nishimura, Yuya; Ogino, Chiaki; Kondo, Akihiko

    2016-12-01

    An induction of polyacrylic acid-modified titanium dioxide with hydrogen peroxide nanoparticles (PAA-TiO2/H2O2 NPs) to a tumor exerted a therapeutic enhancement of X-ray irradiation in our previous study. To understand the mechanism of the radiosensitizing effect of PAA-TiO2/H2O2 NPs, analytical observations that included DLS, FE-SEM, FT-IR, XAFS, and Raman spectrometry were performed. In addition, highly reactive oxygen species (hROS) which PAA-TiO2/H2O2 NPs produced with X-ray irradiation were quantified by using a chemiluminescence method and a EPR spin-trapping method. We found that PAA-TiO2/H2O2 NPs have almost the same characteristics as PAA-TiO2. Surprisingly, there were no significant differences in hROS generation. However, the existence of H2O2 was confirmed in PAA-TiO2/H2O2 NPs, because spontaneous hROS production was observed w/o X-ray irradiation. In addition, PAA-TiO2/H2O2 NPs had a curious characteristic whereby they absorbed H2O2 molecules and released them gradually into a liquid phase. Based on these results, the H2O2 was continuously released from PAA-TiO2/H2O2 NPs, and then released H2O2 assumed to be functioned indirectly as a radiosensitizing factor.

  5. Descent with Modification: Thermal Reactions of Subsurface H2O2 of Relevance to Icy Satellites and Other Small Bodies

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie L.; Loefler, Mark J.

    2012-01-01

    Laboratory experiments have demonstrated that magnetospheric radiation in the Jovian system drives reaction chemistry in ices at temperatures relevant to Europa and other icy satellites. Similarly, cosmic radiation (mainly protons) acting on cometary and interstellar ices can promote extensive chemical change. Among the products that have been identified in irradiated H20-ice is hydrogen peroxide (H202), which has been observed on Europa and is suspected on other worlds. Although the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, the thermally-induced solid-phase chemistry of H2O2 is largely unknown. Therefore, in this presentation we report new laboratory results on reactions at 50 - 130 K in ices containing H2O2 and other molecules, both in the presence and absence of H2O. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to SO4(2-). We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto. If other molecules prove to be just as reactive with frozen H2O2 then it may explain why H2O2 has been absent from surfaces of many of the small icy bodies that are known to be exposed to ionizing radiation. Our results also have implications for the survival of H2O2 as it descends towards a subsurface ocean on Europa.

  6. Thermodynamics of Silicon-Hydroxide Formation in H2O Containing Atmospheres

    NASA Technical Reports Server (NTRS)

    Copland, Evan; Myers, Dwight; Opila, Elizabeth J.; Jacobson, Nathan S.

    2001-01-01

    The formation of volatile silicon-hydroxide species from SiO2 in water containing atmospheres has been identified as a potentially important mode of degradation of Si-based ceramics. Availability of thermodynamic data for these species is a major problem. This study is part of an ongoing effort to obtain reliable, experimentally determined thermodynamic data for these species. The transpiration method was used to measure the pressure of Si-containing vapor in equilibrium with SiO2 (cristobalite) and Ar + H2O(g) with various mole fractions of water vapor, X(sub H2O), at temperatures ranging from 1000 to 1780 K. Enthalpies and entropies for the reaction, SiO2(s) + 2H2O(g) = Si(OH)4(g), were obtained, at X(sub H2O) = 0.15 and 0.37, from the variation of lnK with 1/T according to the 'second law method'. The following data were obtained: delta(H)deg = 52.9 +/- 3.7 kJ/mole and delta(S)deg = -68.6 +/- 2.5 J/mole K at an average temperature of 1550 K, and delta(H)deg = 52.5+/-2.0 kJ/mole and delta(S)deg= -69.7 +/- 1.5 J/moleK at an average temperature of 1384 K, for X(sub H2O)= 0.15 and 0.37, respectively. These data agree with results from the literature obtained at an average temperature of 1600 K, and strongly suggest Si(OH)4(g) is the dominant vapor species. Contradictory results were obtained with the determination of the dependence of Si-containing vapor pressure on the partial pressure of water vapor at 1187 and 1722 K. These results suggested the Si-containing vapor could be a mixture of Si(OH)4 + SiO(OH)2. Further pressure dependent studies are in progress to resolve these issues.

  7. Variations in the association of H2O with sulfur on Mars

    NASA Astrophysics Data System (ADS)

    Karunatillake, S.; Wray, J. J.; Gasnault, O.; McLennan, S. M.; Rogers, D.; Boynton, W. V.; Skok, J. R.; Ojha, L.; Button, N. E.

    2014-12-01

    Sulfates may constrain the salinity and acidity of martian paleo-fluids, with consequent impact on the planet's habitability. However, information about sulfate mineralogy, subsurface abundance, and hydration remains unclear owing to shallow sampling and limited ability of infrared spectroscopy to distinguish among some sulfates. We address this with H2O and S chemical maps, derived from the Mars Odyssey Gamma Ray Spectrometer (GRS) spectra, sampling at regional scales and decimeter depths[1]. Resulting chemical constraints apply primarily to bulk soil, which dominates at such spatial scales. We assess trends in the association of H2O and S, with bivariate correlations(r) across 10° wide latitudinal bands, corresponding molar ratios H2O:S denoted as hydration state, and hydration states across compositional extremes. We characterize the hydration state distribution with kernel density estimated frequency histograms (KDE). Twenty seven sulfate minerals confirmed or suggested on Mars, from in situ, orbital, and analog observations, provide 13 reference hydration states. Bivariate correlations across latitudinal bands show consistency with hemispheric results. The strengths of correlations are similar at extreme north and south latitudes, with r values of 0.2 at ±55° centered latitudinal bands. However, most southern latitudinal bands manifest r values no less than 0.60, while northern bands remain below 0.60. Accordingly, at the coarsest hemispheric scale and the finest latitudinal scale, H2O may associate with S in bulk soil of the southern hemisphere. Regions of compositional extremes show that H2O concentration, not S, affects the degree of sulfate hydration. Variable soil thickness, ground ice table depths[2], atmospheric processes[3], and insolation may contribute hemispheric differences in the progression of hydration with latitude. KDE results suggest Fe-sulfates as a possibly key hydrous mineral group[4]. This encourages further modeling of Fe

  8. Detection and monitoring of H2O and CO2 ice clouds on Mars

    USGS Publications Warehouse

    Bell, J.F.; Calvin, W.M.; Ockert-Bell, M. E.; Crisp, D.; Pollack, James B.; Spencer, J.

    1996-01-01

    We have developed an observational scheme for the detection and discrimination of Mars atmospheric H2O and CO2 clouds using ground-based instruments in the near infrared. We report the results of our cloud detection and characterization study using Mars near IR images obtained during the 1990 and 1993 oppositions. We focused on specific wavelengths that have the potential, based on previous laboratory studies of H2O and CO2 ices, of yielding the greatest degree of cloud detectability and compositional discriminability. We have detected and mapped absorption features at some of these wavelengths in both the northern and southern polar regions of Mars. Compositional information on the nature of these absorption features was derived from comparisons with laboratory ice spectra and with a simplified radiative transfer model of a CO2 ice cloud overlying a bright surface. Our results indicate that both H2O and CO2 ices can be detected and distinguished in the polar hood clouds. The region near 3.00 ??m is most useful for the detection of water ice clouds because there is a strong H2O ice absorption at this wavelength but only a weak CO2 ice band. The region near 3.33 ??m is most useful for the detection of CO2 ice clouds because there is a strong, relatively narrow CO2 ice band at this wavelength but only broad "continuum" H2O ice absorption. Weaker features near 2.30 ??m could arise from CO2 ice at coarse grain sizes, or surface/dust minerals. Narrow features near 2.00 ??m, which could potentially be very diagnostic of CO2 ice clouds, suffer from contamination by Mars atmospheric CO2 absorptions and are difficult to interpret because of the rather poor knowledge of surface elevation at high latitudes. These results indicate that future ground-based, Earth-orbital, and spacecraft studies over a more extended span of the seasonal cycle should yield substantial information on the style and timing of volatile transport on Mars, as well as a more detailed understanding of

  9. Radiative Lifetime for Nuclear Spin Conversion of Water-Ion H_2O^+

    NASA Astrophysics Data System (ADS)

    Tanaka, Keiichi; Harada, Kensuke; Oka, Takeshi

    2013-06-01

    Nuclear spin conversion interaction of the water ion, H_2O^+, has been studied to derive the spontaneous emission lifetime between the ortho- and para-levels. The H_2O^+ ion is a radical with ^2 B _1 electronic ground state and the off-diagonal electron spin-nuclear spin interaction term, T_{ab} (S_aΔ I_b + S_bΔ I_a), connects para and ortho levels, because Δ {I} = {I}_1 - {I}_2 has nonvanishing matrix elements between I = 0 and 1. The T_{ab} coupling constant, derived by an ab initio calculation in MRD-CI/Bk level to be 72 MHz, is larger than that of H_2O by 4 orders of magnitude, makes the ortho to para conversion of H_2O^+ faster than that of H_2O by 8 orders of magnitude and possibly competitive with other astrophysical processes. Last year we reported ortho and para coupling channels below 900 cm^{-1} caused by accidental near degeneracy of rotational levels. For example, hyperfine components of the 4_{2,2}(o) and 3_{3,0}(p) levels mix each other by 1.2 x 10^{-3} due to the near degeneracy (Δ E = 0.417 cm^{-1}), but the lower lying 1_{0,1}(p) and 1_{1,1}(o) levels mix only by 8.9 x 10^{-5} because of their large separation (Δ E = 16.27 cm^{-1}). In the present study, we solved the radiative rate equations including all the rotational levels below 900 cm^{-1} to give the o-p conversion lifetime to be 0.451, 3.27, 398 and 910 years for the equilibrium o/p ratio of 3.00, 3.00, 4.52, and 406 when the radiation temperature T_r is 100, 60, 20 and 5 K. These results qualitatively help to understand the observed high o/p ratio of 4.8 ± 0.5 (corresponding to the nuclear spin temperature of 21 K) toward Sgr B2, but they are too slow to compete with the reaction by collision unless the number of density of H_2 in the region is very low (n˜1 cm^{-3}) or the radiative temperature is very high (T_r > 50K). K. Tanaka, K. Harada, and T. Oka, the 67th OSU Symposium MG06, 2012. P. Schilke, et al., A&A 521, L11 (2010). K. Tanaka, K. Harada, and T. Oka, J. Phys. Chem. A

  10. Seasonal Mapping of [HDO]/[H2O] in the Martian Atmosphere

    NASA Astrophysics Data System (ADS)

    Novak, Robert E.; Mumma, M. J.; Villanueva, G.; DiSanti, M. A.; Bonev, B.; Rahon, C. L.; Sanstead, C. C.

    2007-10-01

    We report seasonal changes in isotopic water on Mars, based on observations taken at NASA's IRTF using CSHELL. Column densities of HDO and H2O were extracted from individual spectral lines near 3.67 μm and 3.29 μm. The slit was positioned N-S on Mars' central meridian. Data were acquired in an ABBA sequence and their difference constitutes a spectral/spatial image from which each species was quantified. The frames were rectified by re-sampling in wavelength and spatial dimension, and spectra were then extracted at 0.6 arc-second intervals along the slit. We created atmospheric models for Earth and Mars using GENLN2 atmospheric software. The models include solar continuum (and Fraunhofer lines) with two-way transmission through Mars’ atmosphere, thermal emission from Mars’ surface and atmosphere with one-way transmission through Mars atmosphere, and one-way transmission through Earth's atmosphere for both. Latitudinal maps of [HDO]/[H2O] were constructed. The [HDO]/[H2O] ratios are always higher than terrestrial and they vary with both latitude and season. The ratio in the southern Martian hemisphere is found to be larger than that in the northern. This difference could be the signature of Rayleigh distillation, a process in which the different mean temperatures of the polar caps cause a different degree of HDO sequestration, resulting in different degrees of enrichment in the polar caps. For Ls =155o in 2003 and Ls =357o in 2006, HDO and H2O column densities were both obtained from CSHELL data. They will be compared with results from other seasons (Ls =67o in 1997, Ls =223o in 2005, and Ls =333o in 2004) when HDO was measured with CSHELL and H2O was measured by MGS-TES. This work was partially funded by grants from NASA's Planetary Astronomy Program (RTOP 344-32-51-96) and NSF RUI Program (AST-0505765). We acknowledge the NASA-IRTF for observing time and M. Smith for providing TES results.

  11. Magnetic fields around evolved stars: further observations of H2O maser polarization

    NASA Astrophysics Data System (ADS)

    Leal-Ferreira, M. L.; Vlemmings, W. H. T.; Kemball, A.; Amiri, N.

    2013-06-01

    Context. A low- or intermediate-mass star is believed to maintain a spherical shape throughout the evolution from the main sequence to the asymptotic giant branch (AGB) phase. However, many post-AGB objects and planetary nebulae exhibit non-spherical symmetry. Several candidates have been suggested as factors that can play a role in this change of morphology, but the problem is still not well understood. Magnetic fields are one of these possible agents. Aims: We aim to detect the magnetic field and infer its properties around four AGB stars using H2O maser observations. The sample we observed consists of the following sources: the semi-regular variable RT Vir, and the Mira variables AP Lyn, IK Tau, and IRC+60370. Methods: We observed the 61,6 -52,3 H2O maser rotational transition in full-polarization mode to determine its linear and circular polarization. Based on the Zeeman effect, one can infer the properties of the magnetic field from the maser polarization analysis. Results: We detected a total of 238 maser features in three of the four observed sources. No masers were found toward AP Lyn. The observed masers are all located between 2.4 and 53.0 AU from the stars. Linear and circular polarization was found in 18 and 11 maser features, respectively. Conclusions: We more than doubled the number of AGB stars in which a magnetic field has been detected from H2O maser polarization. Our results confirm the presence of fields around IK Tau, RT Vir, and IRC+60370. The strength of the field along the line of sight is found to be between 47 and 331 mG in the H2O maser region. Extrapolating this result to the surface of the stars, assuming a toroidal field (∝ r-1), we find magnetic fields of 0.3-6.9 G on the stellar surfaces. If, instead of a toroidal field, we assume a poloidal field (∝ r-2), then the extrapolated magnetic field strength on the stellar surfaces are in the range between 2.2 and ~115 G. Finally, if a dipole field (∝ r-3) is assumed, the field

  12. Reactivity of organic complexes at mineral-CO2-H2O interfaces

    NASA Astrophysics Data System (ADS)

    Miller, Q. R.; Schaef, T.; Kaszuba, J. P.; Qiu, L.; Bowden, M. E.; McGrail, B. P.

    2015-12-01

    Understanding the interactions between minerals and organics in H2O-CO2 fluids is important, as they are the two most abundant volatiles in the crust. CO2-rich fluids in natural and anthropogenic environments, such as metamorphic aureoles and carbon storage reservoirs, respectively, produce a complex geochemical setting in which CO2-rich fluids containing dissolved water and organic compounds interact with rocks and minerals. We have undertaken experimental and theoretical studies to evaluate how organics impact carbonate mineralization and to determine the partitioning behavior of organic complexes between CO2, H2O, and mineral interfaces. The first groups of experiments have clarified how the type and concentration of simple organic ligands impact the degree and type of carbonation in interfacial water films. In these experiments, salts of simple organic ligands were equilibrated with wet supercritical CO2, which was reacted with the model mineral forsterite (Mg2SiO4). The forsterite dissolution and coupled carbonate precipitation reactions were followed with time-resolved pressurized X-ray diffraction (XRD) at 50 °C and 90 bar. The extent of carbonation and the relative abundance of anhydrous magnesite (MgCO3) precipitated relative to hydrated nesquehonite (MgCO3·3H2O) was impacted by the type of organic ligand. Magnesite enhancement was observed with the trend of citrate>oxalate≈malonate>acetate>organic-free control. This indicates that the organic ligands complexed Mg2+ in the interfacial water film environment and helped alleviate kinetic barriers to magnesite formation. Additional XRD experiments with varying concentrations of citrate verified the dependence of magnesite enhancement and the degree of overall carbonation on the amount of organic present in the water film. Lastly, our ongoing work concerning the partitioning of organic and metal-organic complexes between CO2, H2O, and interfacial water films will be presented. This experimental work, which

  13. Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

    PubMed

    Srithep, Sirinthip; Phattarapattamawong, Songkeart

    2017-06-01

    The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H2O2, UV/O3, and UV/H2O2/O3) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H2O2/O3 was the most effective process for removing HAN precursors, followed by UV/H2O2, and UV/O3, respectively. For 20min contact time, the UV/H2O2/O3, UV/H2O2, and UV/O3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL(-1) in UV/O3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H2O2, and UV/H2O2/O3), except for the UV/O3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k'DCANFP) by the UV/H2O2/O3, UV/H2O2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k'DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors.

  14. H2O and HCl trace gas kinetics on crystalline and amorphous HCl hydrates in the range 170 to 205 K: the HCl/H2O phase diagram revisited

    NASA Astrophysics Data System (ADS)

    Iannarelli, R.; Rossi, M. J.

    2013-11-01

    In this laboratory study, H2O ice films of 1 to 2 μm thickness have been used as surrogates for ice particles at atmospherically relevant conditions in a stirred flow reactor (SFR) to measure the kinetics of evaporation and condensation of HCl and H2O on crystalline and amorphous HCl hydrates. A multidiagnostic approach has been employed using FTIR absorption spectroscopy in transmission to monitor the condensed phase and residual gas mass spectrometry (MS) for the gas phase. An average mass balance ratio between HCl adsorbed onto ice and the quantity of HCl measured using FTIR absorption, (Nn - Nesc - Nads)/NFTIR = 1.182 ± 0.123 has been obtained. The rate of evaporation Rev(HCl) for crystalline HCl hexahydrate (HCl·6H2O) films and amorphous HCl/H2O mixtures has been found to be lower by a factor of 10 to 250 compared to Rev(H2O) in the overlapping temperature range 175 to 190 K. Variations of the accommodation coefficient α (HCl) on pure HCl·6H2O up to a factor of 10 have been observed. The kinetic parameters are thermochemically consistent with the corresponding equilibrium vapour pressure. In addition, we propose an extension of the HCl/H2O phase diagram of crystalline HCl·6H2O based on the analysis of deconvoluted FTIR spectra of samples outside its known existence area. A brief evaluation of the atmospheric importance of both condensed phases, amorphous HCl/H2O and crystalline HCl·6H2O, is performed in favour of the amorphous phase.

  15. CO and H2O vibrational emission toward Orion Peak 1 and Peak 2

    NASA Astrophysics Data System (ADS)

    González-Alfonso, E.; Wright, C. M.; Cernicharo, J.; Rosenthal, D.; Boonman, A. M. S.; van Dishoeck, E. F.

    2002-05-01

    ISO/SWS observations of Orion Peak 1 and Peak 2 show strong emission in the ro-vibrational lines of CO v=1-0 at 4.45-4.95 μm and of H2O ν2=1-0 at 6.3-7.0 μm. Toward Peak 1 the total flux in both bands is, assuming isotropic emission, ≈2.4 and ≈0.53 Lsun, respectively. This corresponds to ≈14 and ≈3% of the total H2 luminosity in the same beam. Two temperature components are found to contribute to the CO emission from Peak 1/2: a warm component, with TK=200-400 K, and a hot component with Tk~3×103 K. At Peak 2 the CO flux from the warm component is similar to that observed at Peak 1, but the hot component is a factor of ≈2 weaker. The H2O band is ≈25% stronger toward Peak 2, and seems to arise only in the warm component. The P-branch emission of both bands from the warm component is significantly stronger than the R-branch, indicating that the line emission is optically thick. Neither thermal collisions with H2 nor with H I seem capable of explaining the strong emission from the warm component. Although the emission arises in the postshock gas, radiation from the most prominent mid-infrared sources in Orion BN/KL is most likely pumping the excited vibrational states of CO and H2O. CO column densities along the line of sight of N{(CO)}=5-10×1018 cm-2 are required to explain the band shape, the flux, and the P-R-asymmetry, and beam-filling is invoked to reconcile this high N(CO) with the upper limit inferred from the H2 emission. CO is more abundant than H2O by a factor of at least 2. The density of the warm component is estimated from the H2O emission to be ~ 2×107 cm-3. The CO emission from the hot component is neither satisfactorily explained in terms of non-thermal (streaming) collisions, nor by resonant scattering. Vibrational excitation through collisions with H2 for densities of ~3×108 cm-3 or, alternatively, with atomic hydrogen, with a density of at least 107 cm-3, are invoked to explain simultaneously the emission from the hot component

  16. Understanding the role of H(2)O(2) during pea seed germination: a combined proteomic and hormone profiling approach.

    PubMed

    Barba-Espín, Gregorio; Diaz-Vivancos, Pedro; Job, Dominique; Belghazi, Maya; Job, Claudette; Hernández, José Antonio

    2011-11-01

    In a previous publication, we showed that the treatment of pea seeds in the presence of hydrogen peroxide (H(2)O(2)) increased germination performance as well as seedling growth. To gain insight into the mechanisms responsible for this behaviour, we have analysed the effect of treating mature pea seeds in the presence of 20 mm H(2)O(2) on several oxidative features such as protein carbonylation, endogenous H(2)O(2) and lipid peroxidation levels. We report that H(2)O(2) treatment of the pea seeds increased their endogenous H(2)O(2) content and caused carbonylation of storage proteins and of several metabolic enzymes. Under the same conditions, we also monitored the expression of two MAPK genes known to be activated by H(2)O(2) in adult pea plants. The expression of one of them, PsMAPK2, largely increased upon pea seed imbibition in H(2)O(2) , whereas no change could be observed in expression of the other, PsMAPK3. The levels of several phytohormones such as 1-aminocyclopropane carboxylic acid, indole-3-acetic acid and zeatin appeared to correlate with the measured oxidative indicators and with the expression of PsMAPK2. Globally, our results suggest a key role of H(2)O(2) in the coordination of pea seed germination, acting as a priming factor that involves specific changes at the proteome, transcriptome and hormonal levels.

  17. Inhibition of PKR protects against H2O2-induced injury on neonatal cardiac myocytes by attenuating apoptosis and inflammation

    PubMed Central

    Wang, Yongyi; Men, Min; Xie, Bo; Shan, Jianggui; Wang, Chengxi; Liu, Jidong; Zheng, Hui; Yang, Wengang; Xue, Song; Guo, Changfa

    2016-01-01

    Reactive oxygenation species (ROS) generated from reperfusion results in cardiac injury through apoptosis and inflammation, while PKR has the ability to promote apoptosis and inflammation. The aim of the study was to investigate whether PKR is involved in hydrogen peroxide (H2O2) induced neonatal cardiac myocytes (NCM) injury. In our study, NCM, when exposed to H2O2, resulted in persistent activation of PKR due to NCM endogenous RNA. Inhibition of PKR by 2-aminopurine (2-AP) or siRNA protected against H2O2 induced apoptosis and injury. To elucidate the mechanism, we revealed that inhibition of PKR alleviated H2O2 induced apoptosis companied by decreased caspase3/7 activity, BAX and caspase-3 expression. We also revealed that inhibition of PKR suppressed H2O2 induced NFκB pathway and NLRP3 activation. Finally, we found ADAR1 mRNA and protein expression were both induced after H2O2 treatment through STAT-2 dependent pathway. By gain and loss of ADAR1 expression, we confirmed ADAR1 modulated PKR activity. Therefore, we concluded inhibition of PKR protected against H2O2-induced injury by attenuating apoptosis and inflammation. A self-preservation mechanism existed in NCM that ADAR1 expression is induced by H2O2 to limit PKR activation simultaneously. These findings identify a novel role for PKR/ADAR1 in myocardial reperfusion injury. PMID:27929137

  18. Enhancement of photoelectric response of bacteriorhodopsin by multilayered WO3 x H2O nanocrystals/PVA membrane.

    PubMed

    Li, Rui; Hu, Fengping; Bao, Qiaoliang; Bao, Shujuan; Qiao, Yan; Yu, Shucong; Guo, Jun; Li, Chang Ming

    2010-02-07

    For the first time, a multilayered WO(3) x H(2)O/PVA membrane on bacteriorhodopsin (bR) is constructed to significantly enhance the photoelectric response of bR by the spillover effect of WO(3) x H(2)O nanocrystals, providing great potential in its important applications in bioelectronics and proton exchange membrane fuel cells.

  19. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Ertl, G.; Alefeld, G.; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

    2011-03-01

    "H2O H2O everywhere; ne'er a drop to drink"[Coleridge(1798)]; now: "H2 H2 everywhere; STILL ne'er a drop to drink": ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): {O/H2O}=[16]/[18] 90 % ; O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [{3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9/2007)] crucial geomorph-ology which ONLY maximal-buoyancy H2 can exploit, to again make "Mountains into Fountains", ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': "terraforming"(and ocean-rebasificaton!!!) Siegel proprietary magnetic-hydrogen-valve (MHV) permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/famine) Hydrogen-economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!!!

  20. Diel variations of H2O2 in Greenland: A discussion of the cause and effect relationship

    NASA Astrophysics Data System (ADS)

    Bales, Roger C.; McConnell, Joseph R.; Losleben, Mark V.; Conklin, Martha H.; Fuhrer, Katrin; Neftel, Albrecht; Dibb, Jack E.; Kahl, Jonathan D. W.; Stearns, Charles R.

    1995-09-01

    Atmospheric hydrogen peroxide (H2O2) measurements at Summit, Greenland, in May-June, 1993 exhibited a diel variation, with afternoon highs typically 1-2 parts per billion by volume (ppbv) and nighttime lows about 0.5 ppbv lower. This variation closely followed that for temperature; specific humidity exhibited the same general trend. During a 17-day snowfall-free period, surface snow was accumulating H2O2, apparently from nighttime cocondensation of H2O and H2O2. Previous photochemical modeling (Neftel et al., 1995) suggests that daytime H2O2 should be about 1 ppbv, significantly lower than our measured values. Previous equilibrium partitioning measurements between ice and gas phase (Conklin et al., 1993) suggest that air in equilibrium with H2O2 concentrations measured in surface snow (15-18 μM) should have an H2O2 concentration 2-3 times what we measured 0.2-3.5 m above the snow surface. A simple eddy diffusion model, with vertical eddy diffusion coefficients calculated from balloon soundings, suggested that atmospheric H2O2 concentrations should be affected by any H2O2 degassed from surface snow. However, field measurements showed the absence of either high concentrations of H2O2 or a measurable concentration gradient between inlets 0.2 and 3 m above the snow. A surface resistance to degassing, that is, slow release of H2O2 from the ice matrix, is a plausible explanation for the differences between observations and modeled atmospheric profiles. Degassing of H2O2 at a rate below our detection limit would still influence measured atmospheric concentrations and help explain the difference between measurements and photochemical modeling. The cumulative evidence suggests that surface snow adjusts slowly to drops in atmospheric H2O2 concentration, over timescales of at least weeks. The H2O2 losses previously observed in pits sampled over more than 1 year are thought to have occurred later in the summer or fall, after the May-July field season.