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Sample records for aerosols carbon h2o

  1. 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

  2. Atmospheric lidar research applying to H2O, O2 and aerosols

    NASA Technical Reports Server (NTRS)

    Mcilrath, T. J.; Wilkerson, T. D.

    1977-01-01

    Experimental research on a near infrared tunable dye laser was reported, and theoretical simulations were presented for various lidar configurations. The visible and nearinfrared wavelengths considered were suitable for observations of aerosols, water vapor, molecular oxygen pressure and temperature in the troposphere and above. The first phase of development work was described on a ruby pumped, tunable dye laser for the wavelength region 715 to 740 nanometers. Lidar simulations were summarized for measurements of H2O and for two color lidar observations of aerosols in the atmosphere.

  3. Constraining Aerosol Properties Using H2O Retrievals from the California Laboratory for Atmospheric Remote Sensing (CLARS)

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Zeng, Z.; Natraj, V.; Shia, R. L.; Sander, S. P.; Wennberg, P. O.; Yung, Y. L.

    2015-12-01

    H2O has absorption features across the electromagnetic spectrum, from the ultraviolet to the infrared. The California Laboratory for Atmospheric Remote Sensing (CLARS) on the top of Mt Wilson, California, offers continuous high-resolution spectral measurements from 4000 to 8000 cm-1. We retrieve H2O slant column densities (SCDs) at different wavelengths using CLARS data. In particular, we compare retrievals from the spectralon, which is above the planetary boundary layer and relatively immune to aerosol scattering, with those from West Pasadena, a location in the Los Angeles basin that is influenced by aerosol scattering. SCD retrievals for West Pasadena show significantly larger variance across different wavelengths. The retrieval error in West Pasadena is much larger than can be attributed to spectroscopic uncertainties, and reflects the wavelength dependence of aerosol scattering. Using a two-stream enhanced single scattering (2S-ESS) radiative transfer (RT) model, we simulated the effect of aerosol scattering on H2O SCD retrievals at different wavelengths. We found the effects are sensitive to the surface albedo, aerosol phase function and single scattering albedo. Using an empirical relationship derived from the radiative transfer model simulations, we relate the H2O retrieval variance to the aerosol optical depth Angstrom coefficient and compare the results with AERONET observations. The additional information gained from H2O retrieval variance within a large range of wavelengths could be used to improve OCO-2 type CO2 retrievals in the presence of aerosols.

  4. A New Parameterization of H2SO4/H2O Aerosol Composition: Atmospheric Implications

    NASA Technical Reports Server (NTRS)

    Tabazadeh, Azadeh; Toon, Owen B.; Clegg, Simon L.; Hamill, Patrick

    1997-01-01

    Recent results from a thermodynamic model of aqueous sulfuric acid are used to derive a new parameterization for the variation of sulfuric acid aerosol composition with temperature and relative humidity. This formulation is valid for relative humidities above 1 % in the temperature range of 185 to 260 K. An expression for calculating the vapor pressure of supercooled liquid water, consistent with the sulfuric acid model, is also presented. We show that the Steele and Hamill [1981] formulation underestimates the water partial pressure over aqueous H2SOI solutions by up to 12% at low temperatures. This difference results in a corresponding underestimate of the H2SO4 concentration in the aerosol by about 6 % of the weight percent at approximately 190 K. In addition, the relation commonly used for estimating the vapor pressure of H2O over supercooled liquid water differs by up to 10 % from our derived expression. The combined error can result in a 20 % underestimation of water activity over a H2SO4 solution droplet in the stratosphere, which has implications for the parameterization of heterogeneous reaction rates in stratospheric sulfuric acid aerosols. The influence of aerosol composition on the rate of homogeneous ice nucleation from a H2SO4 solution droplet is also discussed. This parameterization can also be used for homogeneous gas phase nucleation calculations of H2SO4 solution droplets under various environmental conditions such as in aircraft exhaust or in volcanic plumes.

  5. Composition-dependent freezing nucleation rates for HNO3/H2O aerosols resembling gravity-wave-perturbed stratospheric particles

    NASA Astrophysics Data System (ADS)

    Prenni, Anthony J.; Onasch, Timothy B.; Tisdale, Robert T.; Siefert, Ronald L.; Tolbert, Margaret A.

    1998-11-01

    Laboratory measurements are presented for the freezing kinetics of H2O/HNO3 aerosols over the temperature range of 188-204 K. For 2:1 H2O:HNO3 aerosols crystallizing to NAD we observed a maximum nucleation rate of J = 9.3×109 cm-3 s-1 at 194 K. This temperature is between the glass point of 161 K [Ji et al., 1993] and the melting point of 235.5 K [Ji et al., 1996]. This can be compared to a previous measurement of J = 6.7×109 cm-3 s-1 at 193 K [Disselkamp et al., 1996] and lower temperature measurements of J ≈ 1010-1012 cm-3 s-1 at 178.8 - 175.8 K [Bertram and Sloan, 1998a]. Measured nucleation rates decrease as the aerosol becomes dilute, but NAD formation is still observable for 2.5:1 H2O:HNO3 at temperatures near 195 K. In contrast, freezing of 3:1 H2O:HNO3 aerosol was not observed for constant temperature experiments throughout this temperature range, yielding an upper limit of J<1.5×109 cm-3 s-1. This is the lowest experimental value determined for 3:1 H2O:HNO3 freezing rates at these temperatures. From the measured freezing rates and knowledge of the free energy of diffusion the average interfacial free energy for NAD in a 2:1 H2O:HNO3 solution was determined to be σ = 25.2 ergs cm-2. A limit for the interfacial free energy was placed on 3:1 H2O:HNO3 particles, for which freezing was not observed. These data imply that if aerosols reach compositions more concentrated than 3:1 H2O:HNO3 in the atmosphere, NAD may play a role in polar stratospheric cloud formation.

  6. Quartz Crystal Microbalance: Aerosol Viscoelastic Measurement Calibration and Subsiquent H2O Uptake

    NASA Astrophysics Data System (ADS)

    Farland, D. R., Jr.; Gilles, M. K.; Harder, T.; Weis, J.; Mueller, S.

    2015-12-01

    Aerosol particles exposed to various atmospheric relative humidity (RH) levels exhibit hygroscopic properties which are not fully understood. Water adsorption or diffusion depends on particle viscosity in semi-solid to liquid states. This relationship between particle viscosity as a function of RH and the corresponding hygroscopic behavioral response is the purpose of this study. However, reliable techniques for viscosity quantification have been limited. A Quartz Crystal Microbalance with Dissipation (QCM-D) was used for viscosity measurements and to determine phase changes. Prior to studies on field samples, microscope immersion/viscosity standard oils, salt crystals, sugars and alpha-pinene secondary organic aerosol (SOA) surrogates are used for viscosity, RH calibrations, water uptake and phase change measurements. RH was controlled by flowing N2 gas saturated with H2O for RH's between 0-75% RH. For higher RH values, (75-100% RH range) saturated salt solutions were flowed over a gore membrane to protect the QCM sensor from direct contact with the solutions. The viscosity calibration constructed via QTools fitting software illustrates the limitations as well as the ranges of reliability of the QCM viscosity measurements. Deliquescing salt crystals of differing deliquescence relative humidity's (DRH), sugars and alpha-pinene SOA's provided insight into the detection of various phase change behaviors. Water uptake experiments performed on alpha-pinene SOA and sucrose sugar yielded significantly different frequency and dissipation responses than the deliquescing salts. Future work will apply these experimental methods and analysis on aerosol particles collected during the GoAmazon field campaign.

  7. 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.

  8. 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

  9. Coincident Aerosol and H2O Retrievals versus HSI Imager Field Campaign ReportH2O Retrievals versus HSI Imager Field Campaign Report

    SciTech Connect

    Anderson, Gail P.; Cipar, John; Armstrong, Peter S.; van den Bosch, J.

    2016-05-01

    Two spectrally calibrated tarpaulins (tarps) were co-located at a fixed Global Positioning System (GPS) position on the gravel antenna field at the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility’s Southern Great Plains (SGP) site. Their placement was timed to coincide with the overflight of a new hyperspectral imaging satellite. The intention was to provide an analysis of the data obtained, including the measured and retrieved spectral albedos for the calibration tarps. Subsequently, a full suite of retrieved values of H2O column, and the aerosol overburden, were to be compared to those determined by alternate SGP ground truth assets. To the extent possible, the down-looking cloud images would be assessed against the all-sky images. Because cloud contamination above a certain level precludes the inversion processing of the satellite data, coupled with infrequent targeting opportunities, clear-sky conditions were imposed. The SGP site was chosen not only as a target of opportunity for satellite validation, but as perhaps the best coincident field measurement site, as established by DOE’s ARM Facility. The satellite team had every expectation of using the information obtained from the SGP to improve the inversion products for all subsequent satellite images, including the cloud and radiative models and parameterizations and, thereby, the performance assessment for subsequent and historic image collections. Coordinating with the SGP onsite team, four visits, all in 2009, to the Central Facility occurred: • June 6-8 (successful exploratory visit to plan tarp placements, etc.) • July 18-24 (canceled because of forecast for heavy clouds) • Sep 9-12 (ground tarps placed, onset of clouds) • Nov 7-9 (visit ultimately canceled because of weather predictions). As noted, in each instance, any significant overcast prediction precluded image collection from the satellite. Given the long task-scheduling procedures

  10. 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.

  11. Soda-fuel metallurgy: Metal ions for carbon neutral CO2 and H2O reduction

    NASA Astrophysics Data System (ADS)

    Neelameggham, Neale R.

    2009-04-01

    The role of minerals in biomass formation is understood only to a limited extent. When the term “photosynthesis—CO2 and H2O reduction of sugars, using solar energy”—is used, one normally thinks of chlorophyll as a compound containing magnesium. Alkali and alkaline earth metals present in leaf cells in the form of ions are equally essential in this solar energy bioconversion coupled with nitrogen fixation. Application of some of these principles can lead to artificial carbon-neutral processes on an industrial scale close to the concentrated CO2 emission sources.

  12. Carbonate-H2O2 Leaching for Sequestering Uranium from Seawater

    SciTech Connect

    Pan, Horng-Bin; Weisheng, Liao; Wai, Chien; Oyola, Yatsandra; Janke, Christopher James; Tian, Guoxin; Rao, Linfeng

    2014-01-01

    Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with little loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

  13. The activation characteristics of the decomposition of H2O2 on palladium-carbon catalysts

    NASA Astrophysics Data System (ADS)

    Lapko, V. F.; Gerasimyuk, I. P.; Kuts', V. S.; Tarasenko, Yu. A.

    2010-06-01

    The kinetics of catalytic decomposition of H2O2 on palladium-carbon catalysts with various deposited metal distributions in carrier (active carbon) porous granules was studied. The activation parameters ( E a and A 0) of the process were calculated by the Arrhenius equation. A determining factor for the catalytic process was found to be the entropy factor ( A 0), which characterized the formation and dissociation of activated transition complexes. A quantum-chemical study of the electronic structure of palladium-carbon catalysts showed the occurrence of electron density transfer from the carbon matrix to metal clusters and collectivization of their electronic systems. This increased the donor-acceptor ability of the synthesized materials and, as a consequence, their catalytic activity.

  14. The Role of H2O in the Carbonation of Forsterite in Supercritical CO2

    SciTech Connect

    Kwak, Ja Hun; Hu, Jian Z.; Turcu, Romulus VF; Rosso, Kevin M.; Ilton, Eugene S.; Wang, Chong M.; Sears, Jesse A.; Engelhard, Mark H.; Felmy, Andrew R.; Hoyt, David W.

    2011-07-01

    The water concentration dependence of forsterite carbonation in supercritical CO2 (scCO2) at 80°C and 76 bars was investigated by a combination of NMR, XRD, TEM and XPS. Reaction products were not detected using scCO2 alone without added H2O. When trace amounts of water were included, limited reaction was observed. Below saturation, reaction products were a mixture of partially hydrated/hydroxylated magnesium carbonates and hydroxylated silica species that were mainly in an amorphous state, forming a non-resolved layer on the forsterite surface. At water concentrations above saturation, where forsterite was in contact with both a CO2-saturated aqueous fluid and a water-saturated scCO2 fluid, solid reaction products were magnesite (MgCO3) and an amorphous polymerized SiO2 dominated by Q4, and to a lesser extent by Q3 silica coordination. Formation of these phases implies H2O initially bound in precursor hydrated/hydroxylated reaction products was liberated, inducing further reaction. Hence, for a given fluid/mineral ratio there is a water threshold above which a significant portion of the water serves in a catalytic role where more extensive carbonation reaction occurs. Defining the role of water, even in low water content environments, is therefore critical to determining the long term impact of CO2 reactivity in the subsurface.

  15. Modified graphitized carbon black as transducing material for reagentless H2O2 and enzyme sensors.

    PubMed

    Razumiene, Julija; Barkauskas, Jurgis; Kubilius, Virgaudas; Meskys, Rolandas; Laurinavicius, Valdas

    2005-10-15

    Direct electron transfer between redox enzymes and electrodes is the basis for the third generation biosensors. We established direct electron transfer between quinohemoprotein alcohol dehydrogenase (PQQ-ADH) and modified carbon black (CBs) electrodes. Furthermore, for the first time, this phenomenon was observed for pyrroloquinoline quinone (PQQ)-dependent glucose dehydrogenase (PQQ-GDH). Reagentless enzyme biosensors suitable for the determination of ethanol, glucose and sensors for hydrogen peroxide were designed using CB electrodes and screen-printing technique. Aiming to create an optimal transducing material for biosensors, a set of CB batches was synthesized using the matrix of Plackett-Burman experimental design. Depending on the obtained surface functional groups as well as the nano-scale carbon structures in CBs batches, the maximal direct electron transfer current of glucose and ethanol biosensors can vary from 20 to 300 nA and from 30 to 6300 nA for glucose and ethanol, respectively. Using modified CB electrodes, an electrocatalytic oxidation of H(2)O(2) takes place at more negative potentials (0.1-0.4V versus Ag/AgCl). Moreover, H(2)O(2) oxidation efficiency depends on the amount and morphology of fine fraction in the modified CBs.

  16. VLA survey of 22 GHz H2O masers toward ten silicate carbon stars

    NASA Astrophysics Data System (ADS)

    Ohnaka, K.; Boboltz, D. A.; Mulitz-Schimel, G.; Izumiura, H.; Wittkowski, M.

    2013-11-01

    Context. Despite their carbon-rich photospheres, silicate carbon stars show evidence of oxygen-rich circumstellar material, which is thought to exist in disks. Silicate carbon stars represent interesting cases that allow us to study the possible effects of binarity on stellar evolution and mass loss accompanied by the formation of disks. Aims: We present a small survey of 22 GHz H2O masers toward ten silicate carbon stars with much better sensitivity than is the case for previous observations. Methods: We observed our sample with the Karl G. Jansky Very Large Array (VLA) using the most expanded configuration (A-configuration) with a maximum baseline of 36 km. For some of our program stars with noisy Infrared Astronomical Satellite (IRAS) Low Resolution Spectra (LRS), we present new mid-IR spectra obtained with the Very Large Telescope Interferometer and the Spitzer Space Telescope. Results: We detected H2O masers toward five out of ten silicate carbon stars (EU And, V778 Cyg, IRAS 06017+1011, V1415 Cyg, and NC83 = V1945 Cyg), with NC83 being a new detection. No H2O masers were detected toward BM Gem, IRAS 07221-0431, IRAS 08002-3803, IRAS 18006-3213, and HD 189605. The velocity separation between the most blue- and red-shifted maser features is 10-14 km s-1. If we assume that the masers originate in circum-companion disks, the measured velocity separations translate into a lower limit of the rotational velocity of 5-7 km s-1, and the upper limit of the radius of the maser emitting region is estimated to be 10-68 AU for a companion mass of 0.5-1.7 M⊙. The new mid-IR spectra of NC83, IRAS 06017+1011, and HD 189605 confirm the 10 μm silicate emission. The latter two stars show a bump at ~11.5 μm, which is presumably due to SiC originating in the ongoing mass loss from the carbon-rich primary star, not due to crystalline silicate. We also report on the detection of the UV flux at 2271 Å toward HD 189605. Based on MIDI observations made with the Very Large

  17. Catalytic performance of carbon nanotubes in H2O2 decomposition: experimental and quantum chemical study.

    PubMed

    Voitko, Katerina; Tóth, Ajna; Demianenko, Evgenij; Dobos, Gábor; Berke, Barbara; Bakalinska, Olga; Grebenyuk, Anatolij; Tombácz, Etelka; Kuts, Volodymyr; Tarasenko, Yurij; Kartel, Mykola; László, Krisztina

    2015-01-01

    The catalytic performance of multi-walled carbon nanotubes (MWCNTs) with different surface chemistry was studied in the decomposition reaction of H2O2 at various values of pH and temperature. A comparative analysis of experimental and quantum chemical calculation results is given. It has been shown that both the lowest calculated activation energy (∼18.9 kJ/mol) and the highest rate constant correspond to the N-containing CNT. The calculated chemisorption energy values correlate with the operation stability of MWCNTs. Based on the proposed quantum chemical model it was found that the catalytic activity of carbon materials in electron transfer reactions is controlled by their electron donor capability.

  18. Synthesis of carbon doped WO3·0.33H2O hierarchical photocatalyst with improved photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Zheng, Yi; Chen, Gang; Yu, Yaoguang; Zhou, Yansong; He, Fang

    2016-01-01

    A carbon doping method is developed to overcome the drawback of conventional carbon doping method. The carbon dopant is synthesized by treating carbon with dilute nitric acid through hydrothermal process. Carbon-doped WO3·0.33H2O (Csbnd WO3·0.33H2O) is obtained by adding the carbon dopant solution, and then through an additional hydrothermal process. Based on XRD, Raman and XPS, carbon have been incorporated into the interstitial position of WO3·0.33H2O unit cell rather than substitution of oxygen in lattice of WO3·0.33H2O, which induces distortion of WO6 octahedron and lattice defect. In addition, carbon doping also induces the emergence of new level above the valence band. The new level increases the migration pathway of photo-generated carriers, which reduces the recombination rate of photo-generated carriers. The changes of band structure, distortion of WO6 octahedron and lattice defect are beneficial to improve the photocatalytic performance of WO3·0.33H2O. Compared with pristine WO3·0.33H2O, Csbnd WO3·0.33H2O display better photocatalytic performance on degradation of rhodamine B (RhB), which include the faster de-ethylation process and cycloreversion process. Moreover, the experiments of radical quenchers confirmed that the h+ display the main influence on degradation of RhB. This study implies that carbon can be doped into some metal oxide hydrates through a mild preparation process, which provides a possible way for the synthesis of carbon doped thermal unstable materials.

  19. Constraints on the H2O formation mechanism in the wind of carbon-rich AGB stars

    NASA Astrophysics Data System (ADS)

    Lombaert, R.; Decin, L.; Royer, P.; de Koter, A.; Cox, N. L. J.; González-Alfonso, E.; Neufeld, D.; De Ridder, J.; Agúndez, M.; Blommaert, J. A. D. L.; Khouri, T.; Groenewegen, M. A. T.; Kerschbaum, F.; Cernicharo, J.; Vandenbussche, B.; Waelkens, C.

    2016-04-01

    Context. The recent detection of warm H2O vapor emission from the outflows of carbon-rich asymptotic giant branch (AGB) stars challenges the current understanding of circumstellar chemistry. Two mechanisms have been invoked to explain warm H2O vapor formation. In the first, periodic shocks passing through the medium immediately above the stellar surface lead to H2O formation. In the second, penetration of ultraviolet interstellar radiation through a clumpy circumstellar medium leads to the formation of H2O molecules in the intermediate wind. Aims: We aim to determine the properties of H2O emission for a sample of 18 carbon-rich AGB stars and subsequently constrain which of the above mechanisms provides the most likely warm H2O formation pathway. Methods: Using far-infrared spectra taken with the PACS instrument onboard the Herschel telescope, we combined two methods to identify H2O emission trends and interpreted these in terms of theoretically expected patterns in the H2O abundance. Through the use of line-strength ratios, we analyzed the correlation between the strength of H2O emission and the mass-loss rate of the objects, as well as the radial dependence of the H2O abundance in the circumstellar outflow per individual source. We computed a model grid to account for radiative-transfer effects in the line strengths. Results: We detect warm H2O emission close to or inside the wind acceleration zone of all sample stars, irrespective of their stellar or circumstellar properties. The predicted H2O abundances in carbon-rich environments are in the range of 10-6 up to 10-4 for Miras and semiregular-a objects, and cluster around 10-6 for semiregular-b objects. These predictions are up to three orders of magnitude greater than what is predicted by state-of-the-art chemical models. We find a negative correlation between the H2O/CO line-strength ratio and gas mass-loss rate for Ṁg> 5 × 10-7 M⊙ yr-1, regardless of the upper-level energy of the relevant transitions

  20. Graphitic Carbon Nitride Nanosheets-Based Ratiometric Fluorescent Probe for Highly Sensitive Detection of H2O2 and Glucose.

    PubMed

    Liu, Jin-Wen; Luo, Ying; Wang, Yu-Min; Duan, Lu-Ying; Jiang, Jian-Hui; Yu, Ru-Qin

    2016-12-14

    Graphitic carbon nitride (g-C3N4) nanosheets, an emerging graphene-like carbon-based nanomaterial with high fluorescence and large specific surface areas, hold great potential for biosensor applications. Current g-C3N4 nanosheets based fluorescent biosensors majorly rely on single fluorescent intensity reading through fluorescence quenching interactions between the nanosheets and metal ions. Here we report for the first time the development of a novel g-C3N4 nanosheets-based ratiometric fluorescence sensing strategy for highly sensitive detection of H2O2 and glucose. With o-phenylenediamine (OPD) oxidized by H2O2 in the presence of horseradish peroxidase (HRP), the oxidization product can assemble on the g-C3N4 nanosheets through hydrogen bonding and π-π stacking, which effectively quenches the fluorescence of g-C3N4 while delivering a new emission peak. The ratiometric signal variations enable robust and sensitive detection of H2O2. On the basis of the glucose converting into H2O2 through the catalysis of glucose oxidase, the g-C3N4-based ratiometric fluorescence sensing platform is also exploited for glucose assay. The developed strategy is demonstrated to give a detection limit of 50 nM for H2O2 and 0.4 μM for glucose, at the same time, it has been successfully used for glucose levels detection in human serum. This strategy may provide a cost-efficient, robust, and high-throughput platform for detecting various species involving H2O2-generation reactions for biomedical applications.

  1. Detection of Free Tropospheric Air Masses With High So2 and Aerosol Concentrations: Evidence For New Aerosol Particle Formation By H2so4/h2o Nucleation

    NASA Astrophysics Data System (ADS)

    Katragkou, E.; Wilhelm, S.; Kiendler, A.; Arnold, F.; Minikin, A.; Schlager, H.; van Velthoven, P.

    Sulfur dioxide and aerosol measurements were performed in the free troposphere (FT) and the Planetary Boundary Layer (PBL) above continental Europe. The measure- ments took place on board of the German research aircraft "Falcon" in 18 April 2001 as a part of the SCAVEX campaign. A novel aircraft based CIMS (Chemical Ion- ization Mass Spectrometry) instrument equipped with an ion trap mass spectrometer (ITMS) with a low detection limit (50pptv) and a high time resolution (1.3s) operated by MPI-K was used to perform the SO2 measurements. For the aerosol measurements DLR-IPA operated a Condensation Particle Size Analyzer, detecting particles with diameters d > 4, 7, 9 and 20nm and a PCASP-100X aerosol spectrometer probe (d > 100nm). In the measurements made mostly around 5000m altitude SO2 rich air masses were occasionally observed with SO2 VMR of up to 2900pptv. The strong SO2 pollu- tion was due to fast vertical transport of polluted continental PBL air and small-scale deep convection, as indicated by the 5-day backward 3D trajectories. These observa- tions of strong SO2 pollution have interesting implications for aerosol processes, in- cluding efficient formation of gaseous sulfuric acid (GSA) and new aerosol particles. They also imply fast growth of freshly nucleated aerosol particles, which increases the chance for new particles to grow to the size of a CCN. Our analysis indicates the occurrence of new particle formation by H2SO4/H2O nucleation and fast new particle growth by H2SO4/H2O condensation and self-coagulation in the different air masses encountered during the flight.

  2. Nanoporous Carbon Nanofibers Decorated with Platinum Nanoparticles for Non-Enzymatic Electrochemical Sensing of H2O2

    PubMed Central

    Li, Yang; Zhang, Mingfa; Zhang, Xiaopeng; Xie, Guocheng; Su, Zhiqiang; Wei, Gang

    2015-01-01

    We describe the preparation of nanoporous carbon nanofibers (CNFs) decorated with platinum nanoparticles (PtNPs) in this work by electrospining polyacrylonitrile (PAN) nanofibers and subsequent carbonization and binding of PtNPs. The fabricated nanoporous CNF-PtNP hybrids were further utilized to modify glass carbon electrodes and used for the non-enzymatic amperometric biosensor for the highly sensitive detection of hydrogen peroxide (H2O2). The morphologies of the fabricated nanoporous CNF-PtNP hybrids were observed by scanning electron microscopy, transmission electron microscopy, and their structure was further investigated with Brunauer–Emmett–Teller (BET) surface area analysis, X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectrum. The cyclic voltammetry experiments indicate that CNF-PtNP modified electrodes have high electrocatalytic activity toward H2O2 and the chronoamperometry measurements illustrate that the fabricated biosensor has a high sensitivity for detecting H2O2. We anticipate that the strategies utilized in this work will not only guide the further design and fabrication of functional nanofiber-based biomaterials and nanodevices, but also extend the potential applications in energy storage, cytology, and tissue engineering.

  3. Atmospheric aerosol models for systems including the ions H+, NH4+, Na+, SO42-, NO3-, Cl-, Br-, and H2O

    NASA Astrophysics Data System (ADS)

    Wexler, Anthony S.; Clegg, Simon L.

    2002-07-01

    Mole fraction based equations for aqueous phase activities, together with equilibrium constants for the formation of gases and solids, have been combined with a Gibbs free energy minimization algorithm to create equilibrium phase partitioning models of inorganic atmospheric aerosols. The water content, phase state (solid or liquid), and gas/aerosol partitioning are predicted for known ionic composition, relative humidity, and temperature. The models are valid from <200 to 328 K for the subsystems (H+-SO42--NO3--Cl--Br--H2O) and (H+-NH4+-SO42--NO3--H2O), and 298.15 K only for (H+-NH4+-Na+-SO42--NO3--Cl--H2O). The models involve no simplifying assumptions and include all solid phases identified in bulk experiments, including hydrated and double salt forms not treated in most other studies. The Henry's law constant of H2SO4 is derived as a function of temperature, based upon available data, and the model treatment of the solubility of HBr in aqueous H2SO4 is revised. Phase diagrams are calculated for the (NH4)2SO4/H2SO4/H2O system to low temperature. The models are also used to explore the importance of the double salts in urban inorganic aerosols. These Aerosol Inorganics Model (AIM) models can be run on the Web for a variety of problem types at http://mae.ucdavis.edu/wexler/aim.html and http://www.uea.ac.uk/~e770/aim.html, and their use is summarized here.

  4. H2O and CO2 devolatilization in subduction zones: implications for the global water and carbon cycles (Invited)

    NASA Astrophysics Data System (ADS)

    van Keken, P. E.; Hacker, B. R.; Syracuse, E. M.; Abers, G. A.

    2010-12-01

    Subduction of sediments and altered oceanic crust functions as a major carbon sink. Upon subduction the carbon may be released by progressive metamorphic reactions, which can be strongly enhanced by free fluids. Quantification of the CO2 release from subducting slabs is important to determine the provenance of CO2 that is released by the volcanic arc and to constrain the flux of carbon to the deeper mantle. In recent work we used a global set of high resolution thermal models of subduction zones to predict the flux of H2O from the subducting slab (van Keken, Hacker, Syracuse, Abers, Subduction factory 4: Depth-dependent flux of H2O from subducting slabs worldwide, J. Geophys. Res., under review) which provides a new estimate of the dehydration efficiency of the global subducting system. It was found that mineralogically bound water can pass efficiently through old and fast subduction zones (such as in the western Pacific) but that warm subduction zones (such as Cascadia) see nearly complete dehydration of the subducting slab. The top of the slab is sufficiently hot in all subduction zones that the upper crust dehydrates significantly. The degree and depth of dehydration is highly diverse and strongly depends on (p,T) and bulk rock composition. On average about one third of subducted H2O reaches 240 km depth, carried principally and roughly equally in the gabbro and peridotite sections. The present-day global flux of H2O to the deep mantle translates to an addition of about one ocean mass over the age of the Earth. We extend the slab devolatilization work to carbon by providing an update to Gorman et al. (Geochem. Geophys. Geosyst, 2006), who quantified the effects of free fluids on CO2 release. The thermal conditions were based on three end-member subduction zones with linear interpolation to provide a global CO2 flux. We use the new high resolution and global set of models to provide higher resolution predictions for the provenance and pathways of CO2 release to

  5. Corrosion of low carbon steel weldments at 600-800 °C in N2/H2S/H2O gases

    NASA Astrophysics Data System (ADS)

    Lee, Dong Bok

    2014-03-01

    A low carbon steel was arc-welded, and corroded at 600, 700 and 800 °C for up to 20 h in 1 atm of either N2/H2S-mixed gases or N2/H2S/H2O-mixed gases to characterize the effects of H2S and H2O gases on the high-temperature corrosion of welded joints. Corrosion proceeded fast and almost linearly. It increased with the increases in the corrosion temperature and with the addition of H2S and H2O. H2S formed FeS, while H2O formed iron oxides such as Fe3O4. Hydrogen and sulfur that were released from H2S and H2O made the scales fragile and nonadherent. Weld metals corroded faster than base metals because the former had coarser grains than the latter.

  6. Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O

    USGS Publications Warehouse

    Chen, S.G.; Yang, R.T.

    1997-01-01

    From molecular orbital calculations, a unified mechanism is proposed for the gasification reactions of graphite by CO2 and H2O, both uncatalyzed and catalyzed by alkali and alkaline earth catalysts. In this mechanism, there are two types of oxygen intermediates that are bonded to the active edge carbon atoms: an in-plane semiquinone type, Cf(O), and an off-plane oxygen bonded to two saturated carbon atoms that are adjacent to the semiquinone species, C(O)Cf(O). The rate-limiting step is the decomposition of these intermediates by breaking the C-C bonds that are connected to Cf(O). A new rate equation is derived for the uncatalyzed reactions, and that for the catalyzed reactions is readily available from the proposed mechanism. The proposed mechanism can account for several unresolved experimental observations: TPD and TK (transient kinetics) desorption results of the catalyzed systems, the similar activation energies for the uncatalyzed and catalyzed reactions, and the relative activities of the alkali and alkaline earth elements. The net charge of the edge carbon active site is substantially changed by gaining electron density from the alkali or alkaline earth element (by forming C-O-M, where M stands for metal). The relative catalytic activities of these elements can be correlated with their abilities of donating electrons and changing the net charge of the edge carbon atom. As shown previously (Chen, S. G.; Yang, R. T. J. Catal. 1993, 141, 102), only clusters of the alkali compounds are active. This derives from the ability of the clusters to dissociate CO2 and H2O to form O atoms and the mobility of the dissociated O atoms facilitated by the clusters.

  7. Partitioning of H2O between olivine and carbonate-silicate melts at 6.3 GPa and 1400 °C: Implications for kimberlite formation

    NASA Astrophysics Data System (ADS)

    Sokol, Alexander G.; Kupriyanov, Igor N.; Palyanov, Yuri N.

    2013-12-01

    Partitioning of H2O between olivine and carbonate-silicate melts has been studied at 6.3 GPa and 1400 °C using a split-sphere multianvil apparatus. Olivine was synthesized in equilibrium with hydrous silicate and hydrous carbonate-silicate±chloride melts saturated with respect to one of Opx, Grt, Ms or a harzburgitic (Ol+Opx+Grt) residue and had CO2/(CO2+SiO2) molar ratios from 0 to 0.8. The concentration of H2O in olivine was determined using FTIR spectroscopy. We found that depending on the melt carbonation and saturation in equilibrium silicate phases the H2O content in olivine varied from 100 to 1500 ppm. The obtained results and data reported in Sokol et al. (2013) indicate that H2O content in olivine becomes approximately two times lower as CO2/(CO2+SiO2) molar ratios in the equilibrium melt increases from 0 to 0.4-0.8 and the crystallization media transform from hydrous silicate to hydrous carbonate-silicate (kimberlite like) melt. The estimated water partitioning between carbonate-silicate melt and nominally anhydrous mantle minerals indicates that carbonatitic melt can effectively extract water once it invades H2O-poore the peridotite. We suggest that extraction of H2O owing to the freezing point depression may provide the necessary melting degree of metasomatized peridotite source and formation of kimberlitic magma.

  8. Basalt-CO2-H2O Interactions and Variability in Carbonate Mineralization Rates

    SciTech Connect

    Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.

    2009-02-01

    Flood basalts are receiving increasing attention as possible host formations for geologic sequestration of anthropogenic CO2, with studies underway in the U.S., India, Iceland, and Canada. Our previous laboratory studies with Columbia River basalts showed relative quick precipitation of carbonate minerals compared to other siliclastic rocks when batch reacted with water and supercritical CO2. In this study, our prior work with Columbia River basalt was extended to tests with basalts from the eastern U.S., India, and Africa. The basalts are all similar in bulk chemistry and share common minerals such as plagioclase, augite, and a glassy mesostasis. Single pass flow through dissolution experiments under dilute solution and mildly acidic conditions indicate similar cation release behavior among the basalt samples tested. Despite similar bulk chemistry and apparent dissolution kinetics, long-term static experiments with CO2 saturated water show significant differences in rates of mineralization as well as precipitate chemistry and morphology. For example, basalt from the Newark Basin in the U.S. is by far the most reactive of any basalt tested to date. Carbonate reaction products for the Newark Basin basalt were globular in form and contained significantly more Fe than the secondary carbonates that precipitated on the other basalt samples. Calcite grains with classic “dogtooth spar” morphology and trace cation substitution (Mg and Mn) were observed in post-reacted samples associated with the Columbia River basalts. Other basalts produced solid precipitates with compositions that varied chemically throughout the entire testing period. Polished cross sections of the reacted grains show precipitate overgrowths with irregular regions outlined by dark and bright layers indicative of zonations of different compositions. For example, SEM-EDX analysis across carbonate precipitates, which resulted from 854 days of reaction of the Central Atlantic Mafic Province (CAMP

  9. Impact of coagulation as a pre-treatment for UVC/H2O2-biological activated carbon treatment of a municipal wastewater reverse osmosis concentrate.

    PubMed

    Umar, Muhammad; Roddick, Felicity; Fan, Linhua

    2016-01-01

    After coagulation of high salinity reverse osmosis concentrate (ROC) with either alum or ferric chloride followed by UVC/H2O2 treatment, biological activated carbon (BAC) was investigated for the removal of DOC. BAC treatment mainly removed low molecular weight (LMW) neutral molecules indicating that biodegradation was the predominant mechanism of organic matter removal. Coagulation with ferric chloride gave greater DOC reductions than alum both as a stand-alone treatment and after the sequence of UVC/H2O2 and BAC treatment. However, overall reduction after the sequence of coagulation, UVC/H2O2 and BAC treatment was only marginally greater for ferric chloride (68%) than for alum (62%). Trihalomethane formation potential and N-Nitrosodimethylamine concentration decreased markedly after UVC/H2O2 treatment. UVC/H2O2 treatment of the ROC led to the generation of extreme toxicity according to the Microtox assay, but no toxicity was observed after BAC, demonstrating its advantage for enabling safe disposal of the treated ROC. Implementation of coagulation as a pre-treatment and BAC as a post-treatment markedly reduced (6-8 times) the electrical energy dose (EED) required for the UVC/H2O2 process. The sequence of coagulation, UVC/H2O2 and BAC treatment was demonstrated as a potential process for the removal of organic matter from high salinity municipal ROC.

  10. A fundamental study on carbon composites of FeF3.0.33H2O as open-framework cathode materials for calcium-ion batteries

    NASA Astrophysics Data System (ADS)

    Murata, Yoshiaki; Minami, Ryoji; Takada, Shoki; Aoyanagi, Kengo; Tojo, Tomohiro; Inada, Ryoji; Sakurai, Yoji

    2017-01-01

    Carbon composites of open-framework iron fluoride (FeF3.0.33H2O/C) was investigated as a new cathode material for calcium ion batteries for the first time. FeF3.0.33H2O/C delivers a relatively large capacity of ca. 110mAhg-1. Its reversible capacity was greatly improved over non-composite FeF3.0.33H2O. During the first discharge and discharge-charge, insertion/extraction of Ca2+ into/from FeF3.0.33H2O/C were confirmed by an ex-situ X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) analysis. From the ex-situ analysis results, it was confirmed that Ca2+ was inserted and extracted with redox of Fe.

  11. Development of a reactor with carbon catalysts for modular-scale, low-cost electrochemical generation of H 2 O 2

    DOE PAGES

    Chen, Zhihua; Chen, Shucheng; Siahrostami, Samira; ...

    2017-03-01

    The development of small-scale, decentralized reactors for H2O2 production that can couple to renewable energy sources would be of great benefit, particularly for water purification in the developing world. Herein, we describe our efforts to develop electrochemical reactors for H2O2 generation with high Faradaic efficiencies of >90%, requiring cell voltages of only ~1.6 V. The reactor employs a carbon-based catalyst that demonstrates excellent performance for H2O2 production under alkaline conditions, as demonstrated by fundamental studies involving rotating-ring disk electrode methods. The low-cost, membrane-free reactor design represents a step towards a continuous, modular-scale, de-centralized production of H2O2.

  12. Voltammetric Determination of Cocaine in Confiscated Samples Using a Carbon Paste Electrode Modified with Different [UO2(X-MeOsalen)(H2O)] · H2O Complexes

    PubMed Central

    de Oliveira, Laura Siqueira; dos Santos Poles, Ana Paula; Balbino, Marco Antonio; Teles de Menezes, Matheus Manoel; de Andrade, José Fernando; Dockal, Edward Ralph; Tristão, Heloísa Maria; de Oliveira, Marcelo Firmino

    2013-01-01

    A fast and non-destructive voltammetric method to detect cocaine in confiscated samples based on carbon paste electrode modified with methoxy-substituted N,N'-ethylene-bis(salcylideneiminato)uranyl(VI)complexes, [UO2(X-MeOSalen)(H2O)].H2O, where X corresponds to the positions 3, 4 or 5 of the methoxy group on the aromatic ring, is described. The electrochemical behavior of the modified electrode and the electrochemical detection of cocaine were investigated using cyclic voltammetry. Using 0.1 mol·L−1 KCl as supporting-electrolyte, a concentration-dependent, well-defined peak current for cocaine at 0.62 V, with an amperometric sensitivity of 6.25 × 104 μA·mol·L−1 for cocaine concentrations ranging between 1.0 × 10−7 and 1.3 × 10−6 mol·L−1 was obtained. Chemical interference studies using lidocaine and procaine were performed. The position of the methoxy group affects the results, with the 3-methoxy derivative being the most sensitive. PMID:23771156

  13. Voltammetric determination of cocaine in confiscated samples using a carbon paste electrode modified with different [UO2(X-MeOsalen)(H2O)] · H2O complexes.

    PubMed

    de Oliveira, Laura Siqueira; Poles, Ana Paula dos Santos; Balbino, Marco Antonio; de Menezes, Matheus Manoel Teles; de Andrade, José Fernando; Dockal, Edward Ralph; Tristão, Heloísa Maria; de Oliveira, Marcelo Firmino

    2013-06-14

    A fast and non-destructive voltammetric method to detect cocaine in confiscated samples based on carbon paste electrode modified with methoxy-substituted N,N'-ethylene-bis(salcylideneiminato)uranyl(VI)complexes, [UO2(X-MeOSalen)(H2O)] · H2O, where X corresponds to the positions 3, 4 or 5 of the methoxy group on the aromatic ring, is described. The electrochemical behavior of the modified electrode and the electrochemical detection of cocaine were investigated using cyclic voltammetry. Using 0.1 mol · L(-1) KCl as supporting-electrolyte, a concentration-dependent, well-defined peak current for cocaine at 0.62 V, with an amperometric sensitivity of 6.25 × 104 μA · mol · L(-1) for cocaine concentrations ranging between 1.0 × 10(-7) and 1.3 × 10(-6) mol · L-1 was obtained. Chemical interference studies using lidocaine and procaine were performed. The position of the methoxy group affects the results, with the 3-methoxy derivative being the most sensitive.

  14. The Solubility Product of NaUO2PO4.xH2O Determined in Phosphate and Carbonate Solutions

    SciTech Connect

    Felmy, Andrew R.; Xia, Yuanxian; Wang, Zheming

    2005-07-01

    The solubility product of NaUO2PO4.xH2O was determined in phosphate containing solutions at low pCH+ values in the absence of carbonate and at higher pCH+ values in the presence of carbonate. NaUO2PO4.xH2O exhibited very low solubilities (~10-7 M in U) over a broad range of hydrogen ion concentrations, NaNO3 concentrations and in the absence of added carbonate. Time Resolved Laser Fluorescence Spectroscopy (TRLFS) analysis of non-carbonate solutions outside of the acidic region revealed the presence of complex mixtures of aqueous U(VI) hydroxyl or phosphate species and uranium phosphate nanoparticles. The presence of the nanoparticles made it impossible to accurately calculate a solubility product for NaUO2PO4.xH2O in the absence of carbonate and at higher pCH+ values. Therefore in order to increase the concentration of U(VI) in solution and thereby verify the solubility product calculated from the most acidic samples, we systematically introduced know concentrations of carbonate, which resulted in the formation of U(VI) carbonate complexes. Development of an accurate aqueous thermodynamic model for the aqueous U(VI) carbonate complexes then allowed calculation of a solubility product for NaUO2PO4.xH2O in the higher pH samples which was in good agreement with the values for the more acidic samples.

  15. 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.

  16. Highly sensitive nonenzymatic glucose and H2O2 sensor based on Ni(OH)2/electroreduced graphene oxide--multiwalled carbon nanotube film modified glass carbon electrode.

    PubMed

    Gao, Wei; Tjiu, Weng Weei; Wei, Junchao; Liu, Tianxi

    2014-03-01

    In this article, a nonenzymatic sensor based on Ni(OH)2/electroreduced graphene oxide (ERGO)-multiwalled carbon nanotube (MWNT) nanocomposites is fabricated via convenient electrodeposition of Ni(OH)2 nanoparticles on ERGO-MWNT film modified glass carbon electrode (GCE). Graphene oxide (GO) sheets can serve as surfactants to stabilize the dispersion of pristine MWNTs in aqueous solution, rendering a fine coverage of ERGO-MWNT film on GCE during the fabrication process. MWNTs perform as conducting bridges between ERGO sheets to enhance the electron transfer rate in the substrate. By combining the advantages of ERGO and MWNTs, together with electrocatalytic effect of Ni(OH)2 nanoparticles, the well-designed nanocomposites exhibit excellent sensing behavior towards glucose and hydrogen peroxide (H2O2). The linear detection ranges for glucose and H2O2 are 10-1500 µM and 10 µM-9050 µM while the detection limits are 2.7 µM and 4.0 µM, respectively. Furthermore, a very high sensitivity is achieved with 2042 µAm M(-1) cm(-2) estimated for glucose and 711 µAm M(-1) cm(-2) for H2O2. These results suggest that Ni(OH)2/ERGO-MWNT nanocomposites thus easily prepared through a green electrochemical method are promising electrode materials for biosensing. Additionally, good recoveries of analytes in real samples like urine and milk confirm the reliability of the prepared sensor in practical applications.

  17. Ab Initio Thermodynamic Study of the CO2 Capture Properties of Potassium Carbonate Sesquihydrate, K2CO3·1.5H2O

    SciTech Connect

    Duan, Yuhua; Luebkes,David R.; Pennline, Henry W; Li, Bingyun Li; Janik, Michael J.; Halley, Woods

    2012-01-01

    By combining density functional theory and lattice phonon dynamics, the thermodynamic properties of CO2 absorption/desorption reactions with dehydrated potassium carbonates through K2CO3·1.5H2O + CO2 = 2KHCO3 + 0.5H2O(g) are analyzed. The energy change and the chemical potential of this reaction have been calculated and used to evaluate its thermodynamic properties and phase transitions. The results indicate that the K2CO3·1.5H2O can only be applied for postcombustion CO2 capture technology at temperatures lower than its phase transition temperature, which depends on the CO2 pressure and the steam pressure with the best range being PH2O ≤ 1.0 bar. Above the phase transition temperature, the sorbent will be regenerated into anhydrous K2CO3. If the steam pressure PH2O is much greater than 1.0 bar, it is possible to use the K2CO3·1.5H2O sorbent for precombustion CO2 capture technology. Compared to anhydrous K2CO3, K2CO3·1.5H2O requires less energy for regeneration.

  18. Characterization and Conductivity Behavior of Magnetic Activated Carbon (MAC) from FeCl2.4H2O-Containing Carbon

    NASA Astrophysics Data System (ADS)

    Aripin, Department Of Physics, Faculty Of Mathematics; Natural Science, Haluoleo University, Kampus Bumi Tridharma Anduonohu Kendari 93232 Indonesia

    2007-05-01

    Activated carbons (AC) and magnetic-containing activated carbons (MAC) have been synthesized using coconut shells as carbon sources and FeCl2.4H2O as magnetic precursor. The samples were characterized by nitrogen sorption, XRD, and FTIR. The BET surface area and total pore volume of MAC increase as the temperature increased. AC has XRD peaks, which evidences an amorphous carbon framework and MAC shows that this material consists of an organized carbon with the nanocrystalline magnetite embedded in its structure. The FTIR spectrum of MAC shows that carboxyl groups decreased as the temperature increased. Absorption bands of MAC shows the stretching and torsional vibration modes of the magnetite Fe-O bond in tetrahedral and octahedral sites, respectively. The electrical conductivity studies showed that conductivity of MAC is more than the AC due to structural properties of carbons exists on a framework containing metal structures.

  19. Fabrication of a sensitive amperometric sensor for NADH and H2O2 using palladium nanoparticles-multiwalled carbon nanotube nanohybrid.

    PubMed

    Hamidi, Hassan; Haghighi, Behzad

    2016-05-01

    Palladium nanoparticles decorated multiwalled carbon nanotubes (PdNPs-MWCNTs) were synthesized and simply cast on the surface of a glassy carbon electrode (GCE) to prepare an amperometric sensor. The fabricated sensor (PdNPs-MWCNTs/GCE) showed excellent electrocatalytic activity towards NADH and H2O2 oxidation and H2O2 reduction. A fast, linear and highly sensitive response was observed for NADH in the concentration range between 0.1 and 200 μM with a detection limit (S/N=3) of 32 nM. Also, the sensor exhibited fast and sensitive responses (<2 s) towards H2O2. The sensitivity and detection limit for H2O2 at the operating potential of +0.35 V were 167 nA μM(-1)cm(-2) and 1.2 μM, respectively and better than those obtained at the operating potential of -0.25 V (68 nA μM(-1)cm(-2) and 14 μM). Moreover, further modification of the proposed sensor by glucose oxidase led to the fabrication of a glucose biosensor with satisfactory performance.

  20. UV-H2O2 based AOP and its integration with biological activated carbon treatment for DBP reduction in drinking water.

    PubMed

    Toor, Ramn; Mohseni, Madjid

    2007-02-01

    The presence of disinfection byproducts (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs) in drinking water is of great concern due to their adverse effects on human health. Emerging regulation limiting the concentration of DBPs in drinking water has increased demands for technologies and processes which reduce the formation of DBPs in drinking water. In this study, UV-H2O2 based advance oxidation process (AOP) was used to treat raw surface water. Experiments were conducted using low pressure mercury vapor UV lamps in collimated beam and flow-through annular photoreactors. The effect of UV fluence (0-3500 mJ cm(-2)) and hydrogen peroxide concentration (0-23 mg l(-1)) in reducing the concentration of THMs and HAAs was examined. The UV-H2O2 AOP was then coupled with a downstream biological activated carbon (BAC) treatment to assess the synergetic benefits of combining the two treatments. It was observed that UV-H2O2 AOP was only effective at reducing DBPs at UV fluences of more than 1000 mJ cm(-2) and initial H2O2 concentrations of about or greater than 23 mg l(-1). However, the combined AOP-BAC treatment showed significant reductions of 43%, 52%, and 59% relative to untreated raw water for DBPs, TOC, and UV254, respectively.

  1. Low-cost preparation of photoluminescent carbon nanodots and application as peroxidase mimetics in colorimetric detection of H2O2 and glucose.

    PubMed

    Wu, Di; Deng, Xiang; Huang, Xiaomei; Wang, Kun; Liu, Qingye

    2013-10-01

    A low-cost and facile preparation of water-soluble photoluminescent carbon nanodots (CDs) with a quantum yield of approximately 12.4% by hydrothermal method utilizing the leaves of Olea Europaea, a large number of planted trees in southwest of China, as a carbon source is developed for the first time. The prepared photoluminescent CDs not only show favorable photoluminescent properties, but also possess intrinsic peroxidase-like activity for colorimetric and UV-Vis absorption detection of hydrogen oxide (H2O2) and glucose. This sensing system exhibits excellent sensitivity toward H2O2 and glucose with the limit of detection as low as 0.6 microM and 5.2 microM. The practical use of this system for glucose determination in serum samples is also demonstrated successfully. The stability and low cost of photoluminescent CDs make them a powerful tool for a wide range of potential applications in biochemical analysis.

  2. Probing Metal Carbonation Reactions of CO2 in a Model System Containing Forsterite and H2O Using Si-29, C-13 Magic Angle Sample Spinning NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Hu, J.; Kwak, J.; Hoyt, D. W.; Sears, J. A.; Rosso, K. M.; Felmy, A. R.

    2009-12-01

    Ex situ solid state NMR have been used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration using a model silicate mineral forsterite (Mg2SiO4)+scCO2 with and without H2O. Run conditions were 80C and 96 bar. Si-29 NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce Mg2+, and mono- and oligomeric hydroxylated silica species. The surface hydrolysis products contain only Q0 (Si(OH)4) and Q1 (Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to less than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. Si-29 NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. C-13 MAS NMR identified a possible reaction intermediates as (MgCO3)4*Mg(OH)2*5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed. This research is part of a broader effort at PNNL to develop experimental tools and fundamental insights into chemical transformations affecting subsurface CO2 reactive transport. Si-29 (left) and C-13 (right) MAS NMR spectra of Mg2SiO4 under various reaction conditions. Si-29 NMR reveals that in scCO2 without H2O, no reaction is

  3. The influence of dissolved H2O content in supercritical carbon dioxide to the inclusion complexes formation of ketoprofen/β-cyclodextrin

    NASA Astrophysics Data System (ADS)

    Goenawan, Joshua; Trisanti, P. N.; Sumarno

    2015-12-01

    This work studies the relation between dissolved H2O content in supercritical carbon dioxide (SC-CO2) with the formation of ketoprofen (KP)/β-cyclodextrin(CD) inclusion complexes. The process involves a physical mixture of these two compounds into contact with the supercritical carbon dioxide which had been previously saturated with H2O over a certain duration. The pressure used for saturation process is 130 bar and saturation temperature was ranged between 30 °C to 50 °C. The inclusion process was achieved by keeping it for 2 hours at 160 bar and 200 bar with inclusion temperature of 50 °C. The results enable us to suggest explanations for the inclusion formation. The inclusion complexes can be formed by contacting the dissolved H2O in SC-CO2 to the physical mixture of KP and CD. An increase in the temperature of saturation process resulted in an increase of dissolved H2O content in the supercritical carbon dioxide. The increasing levels of this water soluble resulted an increase in the inclusion complexes that has been formed. The formation of inclusion complexes includes the water molecules enhancing the emptying of the CD cavities and being replaced by KP, towards a more stable energy state. The drug release used for analyzing the dissolution rate of the KP/CD complexes. The results vary from 79,85% to 99,98% after 45 minutes which is above the rate that has been assigned by Farmakope Indonesia at 70% dissolution rate for KP. The use of SC-CO2 offers a new methods for increasing the rate of dissolution of drugs that are hydrophobic such as KP. CO2 used as a supercritical fluid because of its relatively low cost, easily obtainable supercritical conditions, and lack of toxicity. The material samples were characterized by DSC and Spectrophotometer UV-vis technique.

  4. Metal Carbonation of Forsterite in Supercritical CO2 and H2O Using Solid State 29Si, 13C NMR Spectroscop

    SciTech Connect

    Kwak, Ja Hun; Hu, Jian Z.; Hoyt, David W.; Sears, Jesse A.; Wang, Chong M.; Rosso, Kevin M.; Felmy, Andrew R.

    2010-03-11

    Ex situ solid state NMR was used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration (GCS) using a model silicate mineral forsterite (Mg2SiO4)+supercriticalCO2 with and without H2O. Run conditions were 80 C and 96 atm. 29Si NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce dissolved Mg2+, and mono- and oligomeric hydroxylated silica species. Surface hydrolysis products contain only Q0 (Si(OH)4) and Q1(Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to less than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. 29Si NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. 13C MAS NMR identified a possible reaction intermediate as (MgCO3)4-Mg(OH)2-5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed.

  5. Aerosol chamber study of optical constants and N2O5 uptake on supercooled H2SO4/H2O/HNO3 solution droplets at polar stratospheric cloud temperatures.

    PubMed

    Wagner, Robert; Naumann, Karl-Heinz; Mangold, Alexander; Möhler, Ottmar; Saathoff, Harald; Schurath, Ulrich

    2005-09-15

    The mechanism of the formation of supercooled ternary H(2)SO(4)/H(2)O/HNO(3) solution (STS) droplets in the polar winter stratosphere, i.e., the uptake of nitric acid and water onto background sulfate aerosols at T < 195 K, was successfully mimicked during a simulation experiment at the large coolable aerosol chamber AIDA of Forschungszentrum Karlsruhe. Supercooled sulfuric acid droplets, acting as background aerosol, were added to the cooled AIDA vessel at T = 193.6 K, followed by the addition of ozone and nitrogen dioxide. N(2)O(5), the product of the gas phase reaction between O(3) and NO(2), was then hydrolyzed in the liquid phase with an uptake coefficient gamma(N(2)O(5)). From this experiment, a series of FTIR extinction spectra of STS droplets was obtained, covering a broad range of different STS compositions. This infrared spectra sequence was used for a quantitative test of the accuracy of published infrared optical constants for STS aerosols, needed, for example, as input in remote sensing applications. The present findings indicate that the implementation of a mixing rule approach, i.e., calculating the refractive indices of ternary H(2)SO(4)/H(2)O/HNO(3) solution droplets based on accurate reference data sets for the two binary H(2)SO(4)/H(2)O and HNO(3)/H(2)O systems, is justified. Additional model calculations revealed that the uptake coefficient gamma(N(2)O(5)) on STS aerosols strongly decreases with increasing nitrate concentration in the particles, demonstrating that this so-called nitrate effect, already well-established from uptake experiments conducted at room temperature, is also dominant at stratospheric temperatures.

  6. DFT Calculations with van der Waals Interactions of Hydrated Calcium Carbonate Crystals CaCO3·(H2O, 6H2O): Structural, Electronic, Optical, and Vibrational Properties.

    PubMed

    Costa, Stefane N; Freire, Valder N; Caetano, Ewerton W S; Maia, Francisco F; Barboza, Carlos A; Fulco, Umberto L; Albuquerque, Eudenilson L

    2016-07-21

    The role of hydration on the structural, electronic, optical, and vibrational properties of monohydrated (CaCO3·H2O, hexagonal, P31, Z = 9) and hexahydrated (CaCO3·6H2O, monoclinic, C2/c, Z = 4) calcite crystals is assessed with the help of published experimental and theoretical data applying density functional theory within the generalized gradient approximation and a dispersion correction scheme. We show that the presence of water increases the main band gap of monohydrocalcite by 0.4 eV relative to the anhydrous structure, although practically not changing the hexahydrocalcite band gap. The gap type, however, is modified from indirect to direct as one switches from the monohydrated to the hexahydrated crystal. A good agreement was obtained between the simulated vibrational infrared and Raman spectra and the experimental data, with an infrared signature of hexahydrocalcite relative to monohydrocalcite being observed at 837 cm(-1). Other important vibrational signatures of the lattice, water molecules, and CO3(2-) were identified as well. Analysis of the phonon dispersion curves shows that, as the hydration level of calcite increases, the longitudinal optical-transverse optical phonon splitting becomes smaller. The thermodynamics properties of hexahydrocalcite as a function of temperature resemble closely those of calcite, while monohydrocalcite exhibits a very distinct behavior.

  7. Metal Carbonation of Forsterite in Wet Supercritical CO2: The Role of H2O Studied by Solid State C-13 and Si-29 NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Hu, J.; Kwak, J.; Turcu, R. V.; Rosso, K. M.; Ilton, E. S.; Wang, C.; Sears, J. A.; Felmy, A. R.; Hoyt, D. W.

    2010-12-01

    Selected as a model mineral carbonation system for geological carbon sequestration in mafic host rocks, chemical mechanisms of forsterite carbonation in supercritical CO2 containing water varied from dry to well above saturation, including at saturation, were investigated by a combination of solid state NMR (C-13 SP-, CP-MAS, Si-29 SP-, CP-MAS), XRD, TEM and XPS. Run conditions were 80 degrees (C) and 75 bars. Major findings are as follows. At high water contents where a bulk aqueous solution coexisted with water-saturated scCO2, forsterite was converted into magnesite and a separate Mg-free amorphous SiO2 reaction product characterized by highly polymerized oligomeric Q4, and to a lesser extent by Q3 silica species. As the amount of added water was reduced, hydrated intermediate reaction products that did not evolve to magnesite could be identified until at zero water no reaction intermediates or magnesite carbonation products were observed. The intermediate reaction products identified were a complex mixture of partially hydrated/hydroxylated magnesium carbonate species and a variety of surface silica species with low polymerization extent. The intermediates were mainly in an amorphous state, forming a thin layer on the surface. Formation of these intermediate species consumes water by hydrolysis of Mg-O-Si linkages at the forsterite surface as well as by incorporation of water in the lattice. If insufficient water is available, the reaction is found not to proceed far enough to form magnesite and amorphous SiO2. Water in excess of this limit appears necessary for the intermediates to evolve to anhydrous magnesite, a process that is expected to liberate water for continued reaction. Hence, for a given fluid/forsterite ratio there appears to be a water threshold (i.e., the formation of H2O film with sufficient thickness estimated to be between 3.2 and 18.4 nm) above which a significant portion of the water is recycled in an apparent quasi-catalytic role for the

  8. Combinative dyebath treatment with activated carbon and UV/H2O2: a case study on Everzol Black-GSP.

    PubMed

    Ince, N H; Hasan, D A; Ustün, B; Tezcanli, G

    2002-01-01

    Treatability of textile dyebath effluents by two simultaneously operated processes comprising adsorption and advanced oxidation was investigated using a reactive dyestuff, Everzol Black-GSP (EBG). The method was comprised of contacting aqueous solutions of the dye with hydrogen peroxide and granules of activated carbon (GAC) during irradiation of the reactor with ultraviolet light (UV). Control experiments were run separately with each individual process (advanced oxidation with UV/H2O2 and adsorption on GAC) to select the operating parameters on the basis of maximum color removal. The effectiveness of the combined scheme was tested by monitoring the rate of decolorization and the degree of carbon mineralization in effluent samples. It was found that in a combined medium of advanced oxidation and adsorption, color was principally removed by oxidative degradation, while adsorption contributed to the longer process of dye mineralization. Economic evaluation of the system based on total color removal and 50% mineralization showed that in the case of Everzol Black-GSP, which adsorbs relatively poorly on GAC, the proposed combination provides 25% and 35% reduction in hydrogen peroxide and energy consumption relative to the UV/H2O2 system. Higher cost reductions are expected in cases with well adsorbing dyes and/or with less costly adsorbents.

  9. Morphology of hydrothermally synthesized ZnO nanoparticles tethered to carbon nanotubes affects electrocatalytic activity for H2O2 detection

    PubMed Central

    Wayu, Mulugeta B.; Spidle, Ryan T.; Devkota, Tuphan; Deb, Anup K.; Delong, Robert K.; Ghosh, Kartik C.; Wanekaya, Adam K.; Chusuei, Charles C.

    2013-01-01

    We describe the synthesis of zinc oxide (ZnO) nanoparticles and demonstrate their attachment to multiwalled carbon tubes, resulting in a composite with a unique synergistic effect. Morphology and size of ZnO nanostructures were controlled using hydrothermal synthesis, varying the hydrothermal treatment temperature, prior to attachment to carboxylic acid functionalized multi-walled carbon nanotubes for sensing applications. A strong dependence of electrocatalytic activity on nanosized ZnO shape was shown. High activity for H2O2 reduction was achieved when nanocomposite precursors with a roughly semi-spherical morphology (no needle-like particles present) formed at 90 °C. A 2.4-fold increase in cyclic voltammetry current accompanied by decrease in overpotential from the composites made from the nanosized, needle-like-free ZnO shapes was observed as compared to those composites produced from needle-like shaped ZnO. Electrocatalytic activity varied with pH, maximizing at pH 7.4. A stable, linear response for H2O2 concentrations was observed in the 1–20 mM concentration range. PMID:25684785

  10. Immobilization of myoglobin on Au nanoparticle-decorated carbon nanotube/polytyramine composite as a mediator-free H2O2 and nitrite biosensor

    NASA Astrophysics Data System (ADS)

    Vilian, A. T. Ezhil; Veeramani, Vediyappan; Chen, Shen-Ming; Madhu, Rajesh; Kwak, Cheol Hwan; Huh, Yun Suk; Han, Young-Kyu

    2015-12-01

    A novel composite film was designed for use as a highly selective mediator-free amperometric biosensor, and a method was created for accomplishing direct electrochemistry of myoglobin on a multi-walled carbon nanotube and tyramine-modified composite decorated with Au nanoparticles on a glassy carbon electrode. The ultraviolet-visible and electrochemical impedance spectroscopy results showed that myoglobin retained its native conformation in the interaction with Au-PTy-f-MWCNT. The surface coverage of Mb-heme-Fe(II)/(III) immobilized on Au-PTy-f-MWCNT and the heterogeneous electron-transfer rate constant were 2.12 × 10-9 mol cm-2 and 4.86 s-1, respectively, indicating a higher loading capacity of the nanocomposite for direct electron transfer of Mb onto the electrode surface. The proposed Mb/Au-PTy-f-MWCNT biofilm exhibited excellent electrocatalytic behavior toward the reduction of H2O2 and the oxidation of nitrite with linear ranges of 2 to 5000 μM and 1 to 8000 μM and lower detection limits of 0.01 μM and 0.002 μM, respectively. An apparent Michaelis-Menten constant of 0.12 mM indicated that the Mb immobilized on the Au-PTy-f-MWCNT film retained its native activity. This biosensor can be successfully applied to detect H2O2 and nitrite in disinfectant cream, eye drops, pickle juice, and milk samples.

  11. Surface analysis and electrochemistry of a robust carbon-nanofiber-based electrode platform H2O2 sensor

    NASA Astrophysics Data System (ADS)

    Suazo-Dávila, D.; Rivera-Meléndez, J.; Koehne, J.; Meyyappan, M.; Cabrera, C. R.

    2016-10-01

    A vertically aligned carbon nanofiber-based (VACNF) electrode platform was developed for an enzymeless hydrogen peroxide sensor. Vertical nanofibers have heights on the order of 2-3 μm, and diameters that vary from 50 to 100 nm as seen by atomic force microscopy. The VACNF was grown as individual, vertically, and freestanding structures using plasma-enhanced chemical vapor deposition. The electrochemical sensor, for the hydrogen peroxide measurement in solution, showed stability and reproducibility in five consecutive calibration curves with different hydrogen peroxide concentrations over a period of 3 days. The detection limit was 66 μM. The sensitivity for hydrogen peroxide electrochemical detection was 0.0906 mA cm-2 mM-1, respectively. The sensor was also used for the measurement of hydrogen peroxide as the by-product of the reaction of cholesterol with cholesterol oxidase as a biosensor application. The sensor exhibits linear behavior in the range of 50 μM-1 mM in cholesterol concentrations. The surface analysis and electrochemistry characterization is presented.

  12. Aircraft Measurements of BrO, IO, Glyoxal, NO2, H2O, O2-O2 and Aerosol Extinction Profiles in the Tropics: Comparison with Aircraft-/Ship-Based in Situ and Lidar Measurements

    NASA Technical Reports Server (NTRS)

    Volkamer, R.; Baidar, S.; Campos, T. L.; Coburn, S.; DiGangi, J. P.; Dix, B.; Eloranta, E. W.; Koenig, T. K.; Morley, B.; Ortega, I.; Pierce, B. R.; Reeves, M.; Sinreich, R.; Wang, S.; Zondlo, M. A.; Romashkin, P. A.

    2015-01-01

    Tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2-O2 collision complexes (O4/ were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAXDOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/ National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity

  13. Aircraft measurements of BrO, IO, glyoxal, NO2, H2O, O2-O2 and aerosol extinction profiles in the tropics: comparison with aircraft-/ship-based in situ and lidar measurements

    NASA Astrophysics Data System (ADS)

    Volkamer, R.; Baidar, S.; Campos, T. L.; Coburn, S.; DiGangi, J. P.; Dix, B.; Eloranta, E. W.; Koenig, T. K.; Morley, B.; Ortega, I.; Pierce, B. R.; Reeves, M.; Sinreich, R.; Wang, S.; Zondlo, M. A.; Romashkin, P. A.

    2015-05-01

    Tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2-O2 collision complexes (O4) were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAX-DOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity

  14. In situ growth and performance of spherical Fe2F5·H2O nanoparticles in multi-walled carbon nanotube network matrix as cathode material for sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Jiang, Miaoling; Wang, Xianyou; Hu, Hai; Wei, Shuangying; Fu, Yanqing; Shen, Yongqiang

    2016-06-01

    The multi-wall carbon nanotubes wired spherical Fe2F5·H2O particles (MWCNTs-wired Fe2F5·H2O) are synthesized via an ionic liquid (IL) based precipitation route as the cathode material for sodium ion batteries (SIBs), in which the IL 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMimBF4) is used as environmentally friendly fluorine source, appropriate solvent and binder. The structure, morphology and electrochemical performance of the as-prepared samples have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), charge/discharge tests, cyclic voltammetric measurements (CV). The results show that the MWCNTs-wired spherical Fe2F5·H2O particles present the cubic crystal structure with the cell volume of 1.12821 nm3. Moreover, the SEM and TEM images show that the spherical Fe2F5·H2O particles and disentangled MWCNTs are intertwined together to form a chestnut-like micrometer-sized aggregates. Furthermore, the MWCNTs-wired spherical Fe2F5·H2O particles show a high initial discharge capacity of 251.2 mAh g-1 at 20 mA g-1 in the voltage of 1.0-4.0 V, and the corresponding reversible discharge capacity is 197.4 mAh g-1. Comparing with bare Fe2F5·H2O, the discharge capacity of the MWCNTs-wired spherical Fe2F5·H2O particles still can maintain about 115.0 mAh g-1 after 50 cycles when the current density increased to 100 mA g-1, and the corresponding capacity retention reaches 90.2%.

  15. Impact of salinity on organic matter and nitrogen removal from a municipal wastewater RO concentrate using biologically activated carbon coupled with UV/H2O2.

    PubMed

    Pradhan, Shovana; Fan, Linhua; Roddick, Felicity A; Shahsavari, Esmaeil; Ball, Andrew S

    2016-05-01

    The concentrate streams generated from reverse osmosis (RO)-based municipal wastewater reclamation processes contain organic substances and nutrients at elevated concentrations, posing environmental and health risks on their disposal to confined receiving environments such as bays. The impact of salinity (TDS at 7, 10 and 16 g/L) of a RO concentrate (ROC) on the treatment efficiency of a biological activated carbon (BAC) system after pre-oxidation with UV/H2O2 was characterised in terms of removal of organic matter and nitrogen species, and the bacterial communities. Organic matter removal was comparable for the ROC over the tested salinity range, with 45-49% of DOC and 70-74% of UVA254 removed by the combined treatment. However, removal in total nitrogen (TN) was considerably higher for the ROC at the high salinity (TDS ∼ 16 mg/L) compared with the low (∼7 g/L) and medium salinity (∼10 g/L). Effective nitrification with high ammonium removal (>90%) was achieved at all salinity levels, whereas greater denitrification (39%) was obtained at high salinity than low (23%) and medium salinity (27%) which might suggest that the bacterial communities contributing to the greater denitrification were more halotolerant. Microbiological characterisation using polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) and culture based techniques showed that diversified bacterial communities were present in the BAC system as evident from different 16S rDNA. The major bacterial groups residing on the BAC media belonged to Bacillus (Firmicutes), Pseudomonas (γ-Proteobacteria), and Rhodococcus (Actinobacteria) for all salinity levels, confirming that these microbial communities could be responsible for carbon and nitrogen removal at the different salinity levels. This has implications in understanding the effectiveness and robustness of the BAC system over the salinity range of the ROC and so would be useful for optimising the treatment efficiency of

  16. A Thermodynamic Model for Predicting Mineral Reactivity in Supercritical Carbon Dioxide: I. Phase Behavior of Carbon Dioxide - Water - Chloride Salt Systems Across the H2O-Rich to the CO2-Rich Regions

    SciTech Connect

    Springer, Ronald D.; Wang, Zheming; Anderko, Andre; Wang, Peiming; Felmy, Andrew R.

    2012-09-05

    Phase equilibria in mixtures containing carbon dioxide, water, and chloride salts have been investigated using a combination of solubility measurements and thermodynamic modeling. The solubility of water in the CO2-rich phase of ternary mixtures of CO2, H2O and NaCl or CaCl2 was determined, using near infrared spectroscopy, at 90 atm and 40 to 100 °C. These measurements fill a gap in the experimental database for CO2 water salt systems, for which phase composition data have been available only for the H2O-rich phases. A thermodynamic model for CO2 water salt systems has been constructed on the basis of the previously developed Mixed-Solvent Electrolyte (MSE) framework, which is capable of modeling aqueous solutions over broad ranges of temperature and pressure, is valid to high electrolyte concentrations, treats mixed-phase systems (with both scCO2 and water present) and can predict the thermodynamic properties of dry and partially water-saturated supercritical CO2 over broad ranges of temperature and pressure. Within the MSE framework the standard-state properties are calculated from the Helgeson-Kirkham-Flowers equation of state whereas the excess Gibbs energy includes a long-range electrostatic interaction term expressed by a Pitzer-Debye-Hückel equation, a virial coefficient-type term for interactions between ions and a short-range term for interactions involving neutral molecules. The parameters of the MSE model have been evaluated using literature data for both the H2O-rich and CO2-rich phases in the CO2 - H2O binary and for the H2O-rich phase in the CO2 - H2O - NaCl / KCl / CaCl2 / MgCl2 ternary and multicompontent systems. The model accurately represents the properties of these systems at temperatures from 0°C to 300 °C and pressures up to ~4000 atm. Further, the solubilities of H2O in CO2-rich phases that are predicted by the model are in agreement with the new measurements for the CO2 - H2O - NaCl and CO2 - H2O - CaCl2 systems. Thus, the model can be

  17. In Situ Study of CO2 and H2O Partitioning Between Na-Montmorillonite and Variably Wet Supercritical Carbon Dioxide

    SciTech Connect

    Loring, John S.; Ilton, Eugene S.; Chen, Jeffrey; Thompson, Christopher J.; Martin, Paul F.; Benezeth, Pascale; Rosso, Kevin M.; Felmy, Andrew R.; Schaef, Herbert T.

    2014-06-03

    Shale formations play fundamental roles in large-scale geologic carbon sequestration (GCS) aimed primarily to mitigate climate change, and in smaller-scale GCS targeted mainly for CO2-enhanced gas recovery operations. In both technologies, CO2 is injected underground as a supercritical fluid (scCO2), where interactions with shale minerals could influence successful GCS implementation. Reactive components of shales include expandable clays, such as montmorillonites and mixed-layer illite/smectite clays. In this work, we used in situ X-ray diffraction (XRD) and in situ infrared (IR) spectroscopy to investigate the swelling/shrinkage and water/CO2 sorption of a pure montmorillonite, Na-SWy-2, when the clay is exposed to variably hydrated scCO2 at 50 °C and 90 bar. Measured interlayer spacings and sorbed water concentrations at varying levels of scCO2 hydration are similar to previously reported values measured in air at ambient pressure over a range of relative humidities. IR spectra show evidence of both water and CO2 intercalation, and variations in peak shapes and positions suggest multiple sorbed types with distinct chemical environments. Based on the intensity of the asymmetric CO stretching band of the CO2 associated with the Na-SWy-2, we observed a significant increase in sorbed CO2 as the clay expands from a 0W to a 1W state, suggesting that water props open the interlayer so that CO2 can enter. However, as the clay transitions from a 1W to a 2W state, CO2 desorbs sharply. These observations were placed in the context of two conceptual models concerning hydration mechanisms for expandable clays and were also discussed in light of recent theoretical studies on CO2-H2O-clay interactions. The swelling/shrinkage of expandable clays could affect solid volume, porosity, and permeability of shales. Consequently, the results from this work could aid predictions of shale caprock integrity in large-scale GCS, as well as methane transmissivity in enhanced gas recovery

  18. Sunphotometric Measurement of Columnar H2O and Aerosol Optical Depth During the 3rd Water Vapor IOP in Fall 2000 at the SGP ARM Site

    NASA Technical Reports Server (NTRS)

    Schmid, B; Eilers, J. A.; McIntosh, D. M.; Longo, K.; Livingston, J. M.; Redemann, J.; Russell, P. B.; Braun, J.; Rocken, C.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    We conducted ground-based measurements with the Ames Airborne Tracking 6-channel Sunphotometer (AATS-6) during the 3rd Water Vapor IOP (WVIOP3), September 18 - October 8, 2000 at the SGP ARM site. For this deployment our primary result was columnar water vapor (CWV) obtained from continuous solar transmittance measurements in the 0.94-micron band. In addition, we simultaneously measured aerosol optical depth (AOD) at 380, 450, 525, 864 and 1020 nm. During the IOP, preliminary results of CWV and AOD were displayed in real-time. The result files were made available to other investigators by noon of the next day. During WVIOP3 those data were shown on the daily intercomparison plots on the IOP web-site. Our preliminary results for CWV fell within the spread of values obtained from other techniques. After conclusion of WVIOP3, AATS-6 was shipped directly to Mauna Loa, Hawaii for post-mission calibration. The updated calibration, a cloud screening technique for AOD, along with other mostly cosmetic changes were applied to the WVIOP3 data set and released as version 0.1. The resulting changes in CWV are small, the changes in AOD and Angstrom parameter are more noticeable. Data version 0.1 was successfully submitted to the ARM External Data Center. In the poster we will show data examples for both CWV and AOD. We will also compare our CWV results with those obtained from a GPS (Global Positioning System) slant path method.

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

    NASA Astrophysics Data System (ADS)

    Houtkooper, Joop M.; Schulze-Makuch, Dirk

    2007-08-01

    evolved into employing H2O2 as an antifreeze, which would also have the function as a water collector. If we would find life on Mars based on an intracellular H2O2-H2O mixture, this would not necessarily imply an independent origin of terrestrial and martian life. For that, a detailed study of the biochemistry and genetics is needed. The transfer of terrestrial organisms to Mars or vice versa is a possibility given favorable conditions for the origin and persistance of life on both planets early in solar system history (Schulze-Makuch and Houtkooper, 2007). The transfer of terrestrial organisms by early spacecrafts to Mars that either landed or crashed is a possibility, but it is not plausible that these organisms evolved in a few years. We suggest that we already have evidence of their existence from the Viking landers in two widely distant locations. The H2O2-H2O hypothesis does explain the Viking observations remarkably well, especially (1) the lack of organics detected by GC-MS, (2) the lack of detected oxidant(s) to support a chemical explanation, (3) evolution of O2 upon wetting (GEx experiment), (4) limited organic synthesis reactions (PR experiment), and (5) the gas release observations made (LR experiment)(Houtkooper and Schulze-Makuch, 2007). From the amounts of evolved CO2, O2 and N2 in the GEx experiment it can be concluded that the organisms have an excess oxidative content. This is a problem since in any destructive test, even by laser desorption-mass spectrometry (LDMS), the organisms may decompose completely into H2O, CO2, O2, and N2. The same will occur if the organisms are exposed to excess water, as they will perish due to hyperhydration. The consequence for future biology experiments is that the most fruitful approach may be the detection of metabolism under close to local environmental conditions, especially avoiding the addition of too much water. Of the Viking experiments, the PR experiment which aimed at carbon assimilation was the closest to

  20. Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O3, NO2, H2O, OH and NO3

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Garland, R. M.; Pöschl, U.

    2009-12-01

    We present a kinetic double-layer surface model (K2-SURF) that describes the degradation of polycyclic aromatic hydrocarbons (PAHs) on aerosol particles exposed to ozone, nitrogen dioxide, water vapor, hydroxyl and nitrate radicals. The model is based on multiple experimental studies of PAH degradation and on the PRA framework (Pöschl-Rudich-Ammann, 2007) for aerosol and cloud surface chemistry and gas-particle interactions. For a wide range of substrates, including solid and liquid organic and inorganic substances (soot, silica, sodium chloride, octanol/decanol, organic acids, etc.), the concentration- and time-dependence of the heterogeneous reaction between PAHs and O3 can be efficiently described with a Langmuir-Hinshelwood-type mechanism. Depending on the substrate material, the Langmuir adsorption constants for O3 vary over three orders of magnitude (Kads,O3 ≍ 10-15-10-13 cm3), and the second-order rate coefficients for the surface layer reaction of O3 with different PAH vary over two orders of magnitude (kSLR,PAH,O3 ≍ 10-18-10-17 cm2 s-1). The available data indicate that the Langmuir adsorption constants for NO2 are similar to those of O3, while those of H2O are several orders of magnitude smaller (Kads,H2O ≍ 10-18-10-17 cm3). The desorption lifetimes and adsorption enthalpies inferred from the Langmuir adsorption constants suggest chemisorption of NO2 and O3 and physisorption of H2O. Note, however, that the exact reaction mechanisms, rate limiting steps and possible intermediates still remain to be resolved (e.g., surface diffusion and formation of O atoms or O3- ions at the surface). The K2-SURF model enables the calculation of ozone uptake coefficients, γO3, and of PAH concentrations in the quasi-static particle surface layer. Competitive adsorption and chemical transformation of the surface (aging) lead to a strong non-linear dependence of γO3 on time and gas phase composition, with different characteristics under dilute atmospheric and

  1. Infrared and Raman spectroscopic characterization of the silicate-carbonate mineral carletonite - KNa4Ca4Si8O18(CO3)4(OH,F)·H2O

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Xi, Yunfei; Scholz, Ricardo; López, Andrés; Belotti, Fernanda Maria

    2013-06-01

    An assessment of the molecular structure of carletonite a rare phyllosilicate mineral with general chemical formula given as KNa4Ca4Si8O18(CO3)4(OH,F)·H2O has been undertaken using vibrational spectroscopy. Carletonite has a complex layered structure. Within one period of c, it contains a silicate layer of composition NaKSi8O18·H2O, a carbonate layer of composition NaCO3·0.5H2O and two carbonate layers of composition NaCa2CO3(F,OH)0.5. Raman bands are observed at 1066, 1075 and 1086 cm-1. Whether these bands are due to the CO32- ν1 symmetric stretching mode or to an SiO stretching vibration is open to question. Multiple bands are observed in the 300-800 cm-1 spectral region, making the attribution of these bands difficult. Multiple water stretching and bending modes are observed showing that there is much variation in hydrogen bonding between water and the silicate and carbonate surfaces.

  2. Application of a High-Throughput Analyzer in Evaluating Solid Adsorbents for Post-Combustion Carbon Capture via Multicomponent Adsorption of CO2, N-2, and H2O

    SciTech Connect

    Mason, JA; McDonald, TM; Bae, TH; Bachman, JE; Sumida, K; Dutton, JJ; Kaye, SS; Long, JR

    2015-04-15

    Despite the large number of metal-organic frameworks that have been studied in the context of post-combustion carbon capture, adsorption equilibria of gas mixtures including CO2, N-2, and H2O, which are the three biggest components of the flue gas emanating from a coal- or natural gas-fired power plant, have never been reported. Here, we disclose the design and validation of a high-throughput multicomponent adsorption instrument that can measure equilibrium adsorption isotherms for mixtures of gases at conditions that are representative of an actual flue gas from a power plant. This instrument is used to study 15 different metal-organic frameworks, zeolites, mesoporous silicas, and activated carbons representative of the broad range of solid adsorbents that have received attention for CO2 capture. While the multicomponent results presented in this work provide many interesting fundamental insights, only adsorbents functionalized with alkylamines are shown to have any significant CO2 capacity in the presence of N-2 and H2O at equilibrium partial pressures similar to those expected in a carbon capture process. Most significantly, the amine-appended metal organic framework mmen-Mg-2(dobpdc) (mmen = N,N'-dimethylethylenediamine, dobpdc (4-) = 4,4'-dioxido-3,3'-biphenyldicarboxylate) exhibits a record CO2 capacity of 4.2 +/- 0.2 mmol/g (16 wt %) at 0.1 bar and 40 degrees C in the presence of a high partial pressure of H2O.

  3. A novel and facile synthesis of carbon quantum dots via salep hydrothermal treatment as the silver nanoparticles support: Application to electroanalytical determination of H2O2 in fetal bovine serum.

    PubMed

    Jahanbakhshi, Mojtaba; Habibi, Biuck

    2016-07-15

    A simple, low-cost, and green process was used for the synthesis of carbon quantum dots (CQDs) through the hydrothermal treatment of salep as a novel bio-polymeric carbon source in presence of only pure water. The silver nanoparticles (AgNPs) were embedded on the surface of CQDs by ultra-violate (UV) irradiation to the CQDs and silver nitrate mixture solution. The as-synthesized CQDs and AgNPs decorated CQDs nanohybrid (AgNPs/CQDs) were characterized by UV-vis and photoluminescence spectroscopy, Fourier transform-infrared spectroscopy, transmission electron microscopy, atomic force microcopy, X-ray diffraction, and field emission scanning electron microscopy. Then, the AgNPs/CQDs nanohybrid was casted on the glassy carbon electrode in order to prepare an amperometric hydrogen peroxide (H2O2) sensor. The electrochemical investigations show that the AgNPs/CQDs nanohybrid possesses an excellent performance toward the H2O2 reduction. In the optimum condition, the linear range of H2O2 determination was achieved from 0.2 to 27.0μM with high sensitivity (1.5μA/µM) and the limit of detection was obtained about 80nM (S/N=3). Finally, the prepared nanohybrid modified electrode was effectively applied to the H2O2 detection in the disinfected fetal bovine serum samples, and the recovery was obtained about 98%. The achieved results indicate that the AgNPs/CQDs nanohybrid with high reproducibility, repeatability, and stability has a favorable capability in electrochemical sensors improvement.

  4. Flow-injection analysis for the determination of total inorganic carbon and total organic carbon in water using the H2O2-luminol-uranine chemiluminescent reaction.

    PubMed

    Fan, Shun-Li; Qu, Fang; Zhao, Lixia; Lin, Jin-Ming

    2006-12-01

    In the presence of carbonate and uranine, the chemiluminescent intensity from the reaction of luminol with hydrogen peroxide was dramatically enhanced in a basic medium. Based on this fact and coupled with the technique of flow-injection analysis, a highly sensitive method was developed for the determination of carbonate with a wide linear range. The method provided the determination of carbonate with a wide linear range of 1.0 x 10(-10)-5.0 x 10(-6) mol L(-1) and a low detection limit (S/N = 3) of carbonate of 1.2 x 10(-11) mol L(-1). The average relative standard deviation for 1.0 x 10(-9)-9.0 x 10(-7) mol L(-1) of carbonate was 3.7% (n = 11). Combined with the wet oxidation of potassium persulfate, the method was applied to the simultaneous determination of total inorganic carbon (TIC) and total organic carbon (TOC) in water. The linear ranges for TIC and TOC were 1.2 x 10(-6)-6.0 x 10(-2) mg L(-1) and 0.08-30 mg L(-1) carbon, respectively. Recoveries of 97.4-106.4% for TIC and 96.0-98.5% for TOC were obtained by adding 5 or 50 mg L(-1) of carbon to the water samples. The relative standard deviations (RSDs) were 2.6-4.8% for TIC and 4.6-6.6% for TOC (n = 5). The mechanism of the chemiluminescent reaction was also explored and a reasonable explanation about chemical energy transfer from luminol to uranine was proposed.

  5. A simple strategy for the immobilization of catalase on multi-walled carbon nanotube/poly (L-lysine) biocomposite for the detection of H2O2 and iodate.

    PubMed

    Ezhil Vilian, A T; Chen, Shen-Ming; Lou, Bih-Show

    2014-11-15

    Herein, we report a novel third-generation H2O2 and IO3- biosensor, which was fabricated by loading catalase (CAT) onto l-lysine/multiwalled carbon nanotube (PLL/f-MWCNT) film modified glassy carbon electrode (GCE). The UV-visible (UV-vis) and Fourier-transform infrared (FTIR) spectra show that the catalase encapsulated in the PLL/f-MWCNT film can effectively retain its bioactivity. The immobilized CAT retained its bioactivity with a high protein loading of 4.072 × 10(-10) mol cm(-2), thus exhibiting a surface-controlled reversible redox reaction, with a fast heterogeneous electron transfer rate of 5.48 s(-1). The immobilized CAT shows a couple of reversible and well-defined cyclic voltammetry peaks with a formal potential (E(0)) of -0.471 V (vs. Ag/AgCl) in a pH 6.5 phosphate buffer solution (PBS). Moreover, the modified film exhibited high electrocatalytic activity for the reduction of hydrogen peroxide (H2O2). It exhibited a wide linear response to H2O2 in the concentration range of 1 × 10(-6) - 3.6 × 10(-3), with higher sensitivity (392 mA cm(-2) M(-1)) and a lower Michaelis-Menten constant (0.224 mM). It provided high-catalytic activity towards H2O2 in a shorter time (5s), with a detection limit of 8 nM. These results indicate great improvement in the electrochemical and electrocatalytic properties of the CAT/PLL/f-MWCNT biosensor, offering a new idea for the design of third-generation electrochemical biosensors.

  6. Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): degradation of polycyclic aromatic hydrocarbons exposed to O3, NO2, H2O, OH and NO3

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Garland, R. M.; Pöschl, U.

    2009-09-01

    We present a kinetic double-layer surface model (K2-SURF) that describes the degradation of polycyclic aromatic hydrocarbons (PAHs) on aerosol particles exposed to ozone, nitrogen dioxide, water vapor, hydroxyl and nitrate radicals. The model is based on multiple experimental studies of PAH degradation and on the PRA framework (Pöschl et al., 2007) for aerosol and cloud surface chemistry and gas-particle interactions. For a wide range of substrates, including solid and liquid organic and inorganic substances (soot, silica, sodium chloride, octanol/decanol, organic acids, etc.), the concentration- and time-dependence of the heterogeneous reaction between PAHs and O3 can be efficiently described with a Langmuir-Hinshelwood-type mechanism. Depending on the substrate material, the Langmuir adsorption constants for O3 vary over three orders of magnitude (Kads,O3≍10-15-10-13 cm3), and the second-order rate coefficients for the surface layer reaction of O3 with different PAH vary over two orders of magnitude (kSLR,PAH,O3≍10-18-10-17 cm2 s-1). The available data indicate that the Langmuir adsorption constants for NO2 are similar to those of O3, while those of H2O are several orders of magnitude smaller (Kads,H2O≍10-18-10-17 cm3). The desorption lifetimes and adsorption enthalpies inferred from the Langmuir adsorption constants suggest chemisorption of NO2 and O3 - possibly in the form of O atoms - and physisorption of H2O. The K2-SURF model enables the calculation of ozone uptake coefficients, γO3, and of PAH concentrations in the quasi-static particle surface layer. Competitive adsorption and chemical transformation of the surface (aging) lead to a strong non-linear dependence of γO3 on time and gas phase composition, with different characteristics under dilute atmospheric and concentrated laboratory conditions. Under typical ambient conditions, γO3 of PAH-coated aerosol particles are expected to be in the range of 10-6-10-5. At ambient temperatures, NO2 alone

  7. Synthesis of Ru(0.58)In(0.42)O(y)⋅nH(2)O nanoparticles dispersed onto poly(sodium-4-styrene sulfonate)-functionalized multi-walled carbon nanotubes and their application for electrochemical capacitors.

    PubMed

    Yuan, Changzhou; Hou, Linrui; Yang, Long; Li, Diankai; Tan, Jie; Shen, Laifa; Zhang, Fang; Zhang, Xiaogang

    2011-02-15

    In this work, poly(sodium-4-styrene sulfonate) (PSS)-functionalized multi-walled carbon nanotubes (FMWCNTs) were first synthesized via a polymer-assisted technique. Then, Ru(0.58)In(0.42)O(y)⋅nH(2)O nanoparticles (NPs) were mono-dispersed onto the FMWCNTs surfaces under mild hydrothermal condition. Here, PSS with negative charge serves as a bifunctional molecule both for solubilizing and dispersing MWCNTs into aqueous solution and for tethering Ru(3+) and In(3+) to facilitate the good dispersion of Ru(1-)(x)In(x)O(y)⋅nH(2)O NPs onto their surfaces. The good dispersion of Ru(0.58)In(0.42)O(y)⋅nH(2)O NPs onto FMWCNTs makes OH(-) ions and electrons easily contact these NPs with abundant electroactive sites, which results in a large specific capacitance (SC) of 319Fg(-1) for the naocomposites. Moreover, a symmetric electrochemical capacitor (EC) is constructed by using the nanocomposites as electrodes and delivers large specific energy density of 18.1Whkg(-1), desirable power property of 1302Wkg(-1), high electrochemical reversibility and good SC retention of 84.7%.

  8. 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.

  9. 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

  10. Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O3, NO2, H2O, OH and NO3

    NASA Astrophysics Data System (ADS)

    Shiraiwa, Manabu; Garland, Rebecca M.; Pöschl, Ulrich

    2010-05-01

    We present a kinetic double-layer surface model (K2-SURF) that describes the degradation of polycyclic aromatic hydrocarbons (PAHs) on aerosol particles exposed to ozone, nitrogen dioxide, water vapor, hydroxyl and nitrate radicals [1]. The model is based on multiple experimental studies of PAH degradation and on the Pöschl-Rudich-Ammann (PRA) framework [2] for aerosol and cloud surface chemistry and gas-particle interactions. For a wide range of substrates, including solid and liquid organic and inorganic substances (soot, silica, sodium chloride, octanol/decanol, organic acids, etc.), the concentration- and time-dependence of the heterogeneous reaction between PAHs and O3 can be efficiently described with a Langmuir-Hinshelwood-type mechanism. Depending on the substrate material, the Langmuir adsorption constants for O3 vary over three orders of magnitude, and the second-order rate coefficients for the surface layer reaction of O3 with different PAH vary over two orders of magnitude. The available data indicate that the Langmuir adsorption constants for NO2 are similar to those of O3, while those of H2O are several orders of magnitude smaller. The desorption lifetimes and adsorption enthalpies suggest chemisorption of NO2 and O3 and physisorption of H2O. Note, however, that the exact reaction mechanisms, rate limiting steps and possible intermediates still remain to be resolved (e.g., surface diffusion and formation of O atoms or O3- ions at the surface). The K2-SURF model enables the calculation of ozone uptake coefficients, γO3, and of PAH concentrations in the quasi-static particle surface layer. Competitive adsorption and chemical transformation of the surface (aging) lead to a strong non-linear dependence of γO3 on time and gas phase composition, with different characteristics under dilute atmospheric and concentrated laboratory conditions. Under typical ambient conditions, γO3 of PAH-coated aerosol particles are expected to be in the range of 10-6 - 10

  11. 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.

  12. Infrared and Raman spectroscopic characterization of the carbonate mineral weloganite - Sr3Na2Zr(CO3)6·3H2O and in comparison with selected carbonates

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Xi, Yunfei; Scholz, Ricardo; Belotti, Fernanda Maria; Filho, Mauro Cândido

    2013-05-01

    The mineral weloganite Na2Sr3Zr(CO3)6·3H2O has been studied by using vibrational spectroscopy and a comparison is made with the spectra of weloganite with other carbonate minerals. Weloganite is member of the mckelveyite group that includes donnayite-(Y) and mckelveyite-(Y). The Raman spectrum of weloganite is characterized by an intense band at 1082 cm-1 with shoulder bands at 1061 and 1073 cm-1, attributed to the CO32- symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of CO32- symmetric stretching vibration varies with mineral composition. The Raman bands at 1350, 1371, 1385, 1417, 1526, 1546, and 1563 cm-1 are assigned to the ν3 (CO3)2- antisymmetric stretching mode. The observation of additional Raman bands for the ν3 modes for weloganite is significant in that it shows distortion of the carbonate anion in the mineral structure. The Raman band observed at 870 cm-1 is assigned to the (CO3)2- ν2 bending mode. Raman bands observed for weloganite at 679, 682, 696, 728, 736, 749, and 762 cm-1 are assigned to the (CO3)2- ν4 bending modes. A comparison of the vibrational spectra is made with that of the rare earth carbonates decrespignyite, bastnasite, hydroxybastnasite, parisite, and northupite.

  13. CO2 and H2O: Understanding Different Stakeholder Perspectives on the Use of Carbon Credits to Finance Household Water Treatment Projects

    PubMed Central

    Summers, Sarah K.; Rainey, Rochelle; Kaur, Maneet; Graham, Jay P.

    2015-01-01

    Background Carbon credits are an increasingly prevalent market-based mechanism used to subsidize household water treatment technologies (HWT). This involves generating credits through the reduction of carbon emissions from boiling water by providing a technology that reduces greenhouse gas emissions linked to climate change. Proponents claim this process delivers health and environmental benefits by providing clean drinking water and reducing greenhouse gases. Selling carbon credits associated with HWT projects requires rigorous monitoring to ensure households are using the HWT and achieving the desired benefits of the device. Critics have suggested that the technologies provide neither the benefits of clean water nor reduced emissions. This study explores the perspectives of carbon credit and water, sanitation and hygiene (WASH) experts on HWT carbon credit projects. Methods Thirteen semi-structured, in-depth interviews were conducted with key informants from the WASH and carbon credit development sectors. The interviews explored perceptions of the two groups with respect to the procedures applied in the Gold Standard methodology for trading Voluntary Emission Reduction (VER) credits. Results Agreement among the WASH and carbon credit experts existed for the concept of suppressed demand and parameters in the baseline water boiling test. Key differences, however, existed. WASH experts’ responses highlighted a focus on objectively verifiable data for monitoring carbon projects while carbon credit experts called for contextualizing observed data with the need for flexibility and balancing financial viability with quality assurance. Conclusions Carbon credit projects have the potential to become an important financing mechanism for clean energy in low- and middle-income countries. Based on this research we recommend that more effort be placed on building consensus on the underlying assumptions for obtaining carbon credits from HWT projects, as well as the approved

  14. 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.

  15. 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.

  16. Highly dispersed encapsulated AuPd nanoparticles on ordered mesoporous carbons for the direct synthesis of H2O2 from molecular oxygen and hydrogen.

    PubMed

    García, Tomás; Murillo, Ramón; Agouram, Said; Dejoz, Ana; Lázaro, María J; Torrente-Murciano, Laura; Solsona, Benjamín

    2012-05-28

    AuPd nanoparticles (<3 nm) have been encapsulated on the pores of a nanostructured CMK-3 carbon prepared by a nanocasting procedure. This material has been shown to be an excellent catalyst for the direct synthesis of hydrogen peroxide from molecular hydrogen and oxygen.

  17. 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.

  18. 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.

  19. Destruction and Sequestration of H2O on Mars

    NASA Astrophysics Data System (ADS)

    Clark, Benton

    2016-07-01

    minerals which are candidates for oxidation by reaction with H2O. The FeO in mafic minerals (e.g., olivines and pyroxenes) can cause net destruction of H2O by weathering to magnetite or various ferric oxides. Each atom of Fe2+ will destroy 0.5 molecules of H2O when oxidized to the Fe3+ state. Although this ratio is relatively small, ferrous minerals are widespread. Some alteration forms are oxyhydroxides, such as goethite, which destroy H2O to extract -OH. The most potent destroyer of H2O would be forms of igneous FeSx (e.g., pyrite and pyrrhotite), which when fully oxidized and hydrated not only consume large quantities of H2O but also lower the pH so drastically that only acidophiles could survive. Mars is close to the asteroid belt. Accretion of asteroidal material brings quantities of metallic Fe, FeS (troilite), and also significant amount of carbonaceous material, the bulk of which is macromolecular in forms, as ~ CH0.5. The martian soil should contain several percent of meteoritic material but today has only ppm levels of any organics, indicating conversion to CO2 (in the atmosphere, or carbonates) via destruction of H2O. This work will quantitatively evaluate these powerful processes which adversely affect the availability of H2O to support biological activity on Mars.

  20. Silicate Carbonation in Supercritical CO2 Containing Dissolved H2O: An in situ High Pressure X-Ray Diffraction Study

    SciTech Connect

    Schaef, Herbert T.; Miller, Quin RS; Thompson, Christopher J.; Loring, John S.; Bowden, Mark E.; Arey, Bruce W.; McGrail, B. Peter; Rosso, Kevin M.

    2013-06-30

    Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring between supercritical CO2 containing water and the silicate minerals forsterite (Mg2SiO4), wollastonite (CaSiO3), and enstatite (MgSiO3). This study utilizes newly developed in situ high pressure x-ray diffraction (HXRD) and in situ infra red (IR) to examine mineral transformation reactions. Forsterite and enstatite were selected as they are important minerals present in igneous and mafic rocks and have been the subject of a large number of aqueous dissolution studies that can be compared with non-aqueous fluid tests in this study. Wollastonite, classified as a pyroxenoid (similar to a pyroxene), was chosen as a suitably fast reacting proxy for examining silicate carbonation processes associated with a wet scCO2 fluid as related to geologic carbon sequestration. The experiments were conducted under modest pressures (90 to 160 bar), temperatures between 35° to 70° C, and varying concentrations of dissolved water. Under these conditions scCO2 contains up to 3,500 ppm dissolved water.

  1. Fundamental study of CO2-H2O-mineral interactions for carbon sequestration, with emphasis on the nature of the supercritical fluid-mineral interface.

    SciTech Connect

    Bryan, Charles R.; Dewers, Thomas A.; Heath, Jason E.; Wang, Yifeng; Matteo, Edward N.; Meserole, Stephen P.; Tallant, David Robert

    2013-09-01

    In the supercritical CO2-water-mineral systems relevant to subsurface CO2 sequestration, interfacial processes at the supercritical fluid-mineral interface will strongly affect core- and reservoir-scale hydrologic properties. Experimental and theoretical studies have shown that water films will form on mineral surfaces in supercritical CO2, but will be thinner than those that form in vadose zone environments at any given matric potential. The theoretical model presented here allows assessment of water saturation as a function of matric potential, a critical step for evaluating relative permeabilities the CO2 sequestration environment. The experimental water adsorption studies, using Quartz Crystal Microbalance and Fourier Transform Infrared Spectroscopy methods, confirm the major conclusions of the adsorption/condensation model. Additional data provided by the FTIR study is that CO2 intercalation into clays, if it occurs, does not involve carbonate or bicarbonate formation, or significant restriction of CO2 mobility. We have shown that the water film that forms in supercritical CO2 is reactive with common rock-forming minerals, including albite, orthoclase, labradorite, and muscovite. The experimental data indicate that reactivity is a function of water film thickness; at an activity of water of 0.9, the greatest extent of reaction in scCO2 occurred in areas (step edges, surface pits) where capillary condensation thickened the water films. This suggests that dissolution/precipitation reactions may occur preferentially in small pores and pore throats, where it may have a disproportionately large effect on rock hydrologic properties. Finally, a theoretical model is presented here that describes the formation and movement of CO2 ganglia in porous media, allowing assessment of the effect of pore size and structural heterogeneity on capillary trapping efficiency. The model results also suggest possible engineering approaches for optimizing trapping capacity and for

  2. FTIR study of CO2 and H2O/CO2 nanoparticles and their temporal evolution at 80 K.

    PubMed

    Taraschewski, M; Cammenga, H K; Tuckermann, R; Bauerecker, S

    2005-04-21

    Fourier transform infrared (FTIR) spectroscopy combined with a long-path collisional cooling cell was used to investigate the temporal evolution of CO2 nanoparticles and binary H2O/CO2 nanocomposites in the aerosol phase at 80 K. The experimental conditions for the formation of different CO2 particle shapes as slab, shell, sphere, cube, and needle have been studied by comparison with calculated data from the literature. The H2O/CO2 nanoparticles were generated with a newly developed multiple-pulse injection technique and with the simpler flow-in technique. The carbon dioxide nu3-vibration band at 2360 cm(-1) and the water ice OH-dangling band at 3700 cm(-1) were used to study the evolution of structure, shape, and contact area of the nanocomposites over 150 s. Different stages of binary nanocomposites with primary water ice cores were identified dependent on the injected CO2 portion: (a) disordered (amorphous) CO2 slabs on water particle surfaces, (b) globular crystalline CO2 humps sticking on the water cores, and (c) water cores being completely enclosed in bigger predominantly crystalline CO2 nanoparticles. However, regular CO2 shell structures on primary water particles showing both longitudinal (LO) and transverse (TO) optical mode features of the nu3-vibration band could not be observed. Experiments with reversed nucleation order indicate that H2O/CO2 composite particles with different initial structures evolve toward similar molecular nanocomposites with separated CO2 and H2O regions.

  3. 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.

  4. 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.

  5. 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...

  6. 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...

  7. 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.

  8. Jörgkellerite, Na3Mn3+ 3(PO4)2(CO3)O2·5H2O, a new layered phosphate-carbonate mineral from the Oldoinyo Lengai volcano, Gregory rift, northern Tanzania

    NASA Astrophysics Data System (ADS)

    Zaitsev, Anatoly N.; Britvin, Sergey N.; Kearsley, Anton; Wenzel, Thomas; Kirk, Caroline

    2016-12-01

    Jörgkellerite, ideally Na3Mn3+ 3(PO4)2(CO3)O2·5H2O, is a new layered phosphate-carbonate from the Oldoinyo Lengai volcano in the Gregory Rift (northern Tanzania). The mineral occurs as spherulites, up to 200 μm in diameter, consisting of plates up to 10 μm in thickness in shortite-calcite and calcite carbonatites. Jörgkellerite is brown with a vitreous lustre and has a perfect micaceous cleavage on {001}, Mohs hardness is 3. The calculated density is 2.56 g/cm3. Jörgkellerite is uniaxial (-), ω = 1.700(2), ɛ = 1.625(2) (Na light, 589 nm) with distinct pleochroism: O = dark brown, E = light brown. The empirical formula of the mineral (average of 10 electron microprobe analyses) is (Na2.46K0.28Ca0.08Sr0.04Ba0.02)Σ2.88(Mn3+ 2.39Fe3+ 0.56)Σ2.95((PO4)1.95(SiO4)0.05))Σ2.00(CO3)(O1.84(OH)0.16)Σ2.00·5H2O. The oxidation state of Mn has been determined by XANES. Jörgkellerite is trigonal, space group P-3, a = 11.201(2) Å, c = 10.969(2) Å, V = 1191.9(7) Å3 and Z = 3. The five strongest powder-diffraction lines [d in Å, (I/I o), (hkl)] are: 10.970 (100) (001), 5.597 (15) (002), 4.993 (8) (111), 2.796 (14) (220) and 2.724 (20) (004). The crystal structure is built up of the layers composed of disordered edge-sharing [MnO6] octahedra. Each fourth Mn site in octahedral layer is vacant that results in appearance of ordered system of hexagonal "holes" occupied by (CO3) groups. The overall composition of the layer can be expressed as [Mn3O8(CO3)]. These manganese-carbonate layers are linked in the third dimension by (PO4) tetrahedra and Na-polyhedra. The origin of jörgkellerite is related to low-temperature oxidative alteration of gregoryite-nyerereite carbonatites.

  9. Magnetic coupling through the carbon skeleton of malonate in two polymorphs of ([Cu(bpy)(H2O)][Cu(bpy)(mal)(H2O)])(ClO4)2 (H2mal = malonic acid; bpy = 2,2'-bipyridine).

    PubMed

    Ruiz-Pérez, C; Hernández-Molina, M; Lorenzo-Luis, P; Lloret, F; Cano, J; Julve, M

    2000-08-21

    Two polymorphic malonato-bridged copper(II) complexes of formula ([Cu(bpy)(H2O)][Cu(bpy)(mal)(H2O)])-(ClO4)2 (1 and 2) (bpy = 2,2'-bipyridine and mal = malonate dianion) have been prepared and their structures solved by X-ray diffraction methods. Compound 1 crystallizes in the monoclinic space group P2(1)/a, with a = 23.743(3) A, b = 9.7522(5) A, c = 27.731(2) A, beta = 114.580(10) degrees, and Z = 4. Compound 2 crystallizes in the orthorhombic space group Pbcn, with a = 23.700(5) A, b = 25.162(5) A, c = 9.693(5) A, and Z = 4. The structures of 1 and 2 are made up of uncoordinated perchlorate anions and malonate-bridged zigzag copper(II) chains grouped in an isosceles triangle running parallel to the b (1) and c (2) axes. These chains are built by a [Cu(bpy)(mal)(H2O)] unit acting as bis-monodentate ligand toward two [Cu(bpy)(H2O)] adjacent units through its OCCCO skeleton in an anti-anti conformation, whereas the OCO carboxylate bridges exhibit the anti-syn conformation. Compounds 1 and 2 contain four crystallographically independent copper(II) atoms, but the environment of all of them is distorted square pyramidal: the axial position is occupied by a water molecule, whereas the equatorial plane is formed by a chelating bpy and either a bidentate malonate or two carboxylate oxygens from two malonate groups. The equatorial Cu-O(mal) (1.911(4)-1.978(4) (1) and 1.897(5)-1.991(4) A (2)) and Cu-N(bpy) (1.983(4)-2.008(5) (1) and 1.971(6)-2.007(6) A (2)) bonds are somewhat shorter than the axial Cu-O(w) one (2.257(5)-2.524(5) (1) and 2.236(5)-2.505(6) A (2)). The angles subtended at the copper atom by the chelating bpy vary in the ranges 80.9(2)-81.8(2) degrees (1) and 80.4(2)-82.1(2) degrees (2), values which are somewhat smaller than those of the chelating malonate (80.4(2)-82.1(2) degrees (1) and 93.0(2)-93.6(2) degrees (2)). The intrachain copper-copper separations through the OCCCO fragment are 8.227(1) (1) and 8.206(2) A (2), whereas those through the OCO bridging

  10. 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.

  11. 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.

  12. 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%.

  13. [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.

  14. 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

  15. Dissolution kinetics of calcium carbonate minerals in H 2OCO 2 solutions in turbulent flow: The role of the diffusion boundary layer and the slow reaction H 2O + CO 2 → H + + HCO 3-

    NASA Astrophysics Data System (ADS)

    Liu, Zaihua; Dreybrod, Wolfgang

    1997-07-01

    Dissolution and precipitation of calcium carbonate minerals in aqueous solutions with turbulent flow are controlled by a diffusion boundary layer (DBL) adjacent to the surface of the mineral, across which mass transfer is effected by molecular diffusion. A rotating disk technique was used to investigate the effect of the DBL on the dissolution rates of CaCO 3. This technique allows an exact adjustment of the thickness of the DBL by controlling the rotation speed of a circular sample of CaCO 3. Measurements of the dissolution rates in H 2OCO 2Ca 2+-solutions in equilibrium with various partial pressures of CO 2 from 1·10 -3 up to 1 atm showed a dependence of the rates R on the rotation frequency ω, given by R ∝ ωn. The exponent n varies from 0.25 at low Pco 2 to about 0.01 at a Pco 2 of 1 atm. This reveals that the rates are not controlled by mass transport only, which would require n = 0.5. The experimental data can be explained employing a theoretical model, which also takes into account the slow reaction CO 2 + H 2O → H + + HCO 3- and the chemical reactions at the surface (Dreybrodt and Buhmann, 1991). Interpretation of the experimental data in view of this model reveals that conversion of CO 2 plays an important role in the control of the rates. At high PCO 2 and large DBL thickness (ε > 0.001 cm), conversion of CO 2 occurs mainly in the DBL and, therefore, becomes rate limiting. This is corroborated by the observation that upon addition of the enzyme carbonic anhydrase, which catalyzes CO 2-conversion, the dissolution rates are enhanced by 1 order of magnitude. From our experimental observations we conclude that the theoretical model above enables one to predict dissolution rates with satisfactory precision. Since the precipitation rates from supersaturated solutions are determined by the same mechanisms as dissolution, we infer that this model is also valid to predict precipitation rates. The predicted rates for both dissolution and precipitation

  16. 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.

  17. Two New Families of Lanthanide Mixed-Ligand Complexes, Oxalate-Carbonate and Oxalate-Formate: Synthesis and Structure of [Ce(H 2O)] 2(C 2O 4) 2(CO 3)·2.5 H 2O and Ce(C 2O 4)(HCO 2)

    NASA Astrophysics Data System (ADS)

    Romero, S.; Mosset, A.; Trombe, J. C.

    1996-12-01

    Two new families of lanthanide complexes associating the ligands oxalate and carbonate or oxalate and formate have been prepared under autogenous pressure at 200°C using a pseudo-hydrothermal method. The two families have been extended to some lanthanides ( Ln): oxalate-carbonate Ln= Ce, Pr, Nd, and Eu; oxalate-formate Ln= La, Ce, and Sm. The starting suspension contains either oxalate or a mixture of oxalate and oxalic acid. The structures have been solved for the element cerium. In both cases, the structure is built up from cerium atoms sharing all their oxygen atoms with oxalate and carbonate or oxalate and formate ligands, thus forming a three-dimensional network. The cerium polyhedra share either faces or edges or corners. The coordination scheme of the oxalate ligands is variable: bischelating, bischelating and monodentate, or bischelating and bismonodentate. The carbonate group acts as a bischelating and bismonodentate ligand while the formate group is chelating and monodentate. The characterization of these two original families by infrared spectra and thermal behavior is presented for some pure phases. A tentative explanation of the synthesis of these two phases will be emphasized.

  18. 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.

  19. High atmospheric carbon dioxide-dependent alleviation of salt stress is linked to RESPIRATORY BURST OXIDASE 1 (RBOH1)-dependent H2O2 production in tomato (Solanum lycopersicum)

    PubMed Central

    Yi, Changyu; Yao, Kaiqian; Cai, Shuyu; Li, Huizi; Zhou, Jie; Xia, Xiaojian; Shi, Kai; Yu, Jingquan; Foyer, Christine Helen; Zhou, Yanhong

    2015-01-01

    Plants acclimate rapidly to stressful environmental conditions. Increasing atmospheric CO2 levels are predicted to influence tolerance to stresses such as soil salinity but the mechanisms are poorly understood. To resolve this issue, tomato (Solanum lycopersicum) plants were grown under ambient (380 μmol mol–1) or high (760 μmol mol–1) CO2 in the absence or presence of sodium chloride (100mM). The higher atmospheric CO2 level induced the expression of RESPIRATORY BURST OXIDASE 1 (SlRBOH1) and enhanced H2O2 accumulation in the vascular cells of roots, stems, leaf petioles, and the leaf apoplast. Plants grown with higher CO2 levels showed improved salt tolerance, together with decreased leaf transpiration rates and lower sodium concentrations in the xylem sap, vascular tissues, and leaves. Silencing SlRBOH1 abolished high CO2 -induced salt tolerance and increased leaf transpiration rates, as well as enhancing Na+ accumulation in the plants. The higher atmospheric CO2 level increased the abundance of a subset of transcripts involved in Na+ homeostasis in the controls but not in the SlRBOH1-silenced plants. It is concluded that high atmospheric CO2 concentrations increase salt stress tolerance in an apoplastic H2O2 dependent manner, by suppressing transpiration and hence Na+ delivery from the roots to the shoots, leading to decreased leaf Na+ accumulation. PMID:26417022

  20. High atmospheric carbon dioxide-dependent alleviation of salt stress is linked to RESPIRATORY BURST OXIDASE 1 (RBOH1)-dependent H2O2 production in tomato (Solanum lycopersicum).

    PubMed

    Yi, Changyu; Yao, Kaiqian; Cai, Shuyu; Li, Huizi; Zhou, Jie; Xia, Xiaojian; Shi, Kai; Yu, Jingquan; Foyer, Christine Helen; Zhou, Yanhong

    2015-12-01

    Plants acclimate rapidly to stressful environmental conditions. Increasing atmospheric CO2 levels are predicted to influence tolerance to stresses such as soil salinity but the mechanisms are poorly understood. To resolve this issue, tomato (Solanum lycopersicum) plants were grown under ambient (380 μmol mol(-1)) or high (760 μmol mol(-1)) CO2 in the absence or presence of sodium chloride (100mM). The higher atmospheric CO2 level induced the expression of RESPIRATORY BURST OXIDASE 1 (SlRBOH1) and enhanced H2O2 accumulation in the vascular cells of roots, stems, leaf petioles, and the leaf apoplast. Plants grown with higher CO2 levels showed improved salt tolerance, together with decreased leaf transpiration rates and lower sodium concentrations in the xylem sap, vascular tissues, and leaves. Silencing SlRBOH1 abolished high CO2 -induced salt tolerance and increased leaf transpiration rates, as well as enhancing Na(+) accumulation in the plants. The higher atmospheric CO2 level increased the abundance of a subset of transcripts involved in Na(+) homeostasis in the controls but not in the SlRBOH1-silenced plants. It is concluded that high atmospheric CO2 concentrations increase salt stress tolerance in an apoplastic H2O2 dependent manner, by suppressing transpiration and hence Na(+) delivery from the roots to the shoots, leading to decreased leaf Na(+) accumulation.

  1. 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.

  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. 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.

  4. 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.

  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

    's, however, requires higher Sr/Nd than that predicted by most published estimates of slab fluid compositions, consistent with the high Sr/Nd carbonate- rich sediments subducting at the Central American trench. Therefore cpx phenocrysts not only track magmatic history during ascent, but also may record conditions of the mantle source. Reference: Hauri, E.H., Gaetani, G.A., Green, T.H. (2006) Partitioning of water during melting of Earth's upper mantle at H2O-undersaturated conditions. EPSL 248(3-4) p. 715-734.

  6. 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

  7. Contribution of methane to aerosol carbon mass

    NASA Astrophysics Data System (ADS)

    Bianchi, F.; Barmet, P.; Stirnweis, L.; El Haddad, I.; Platt, S. M.; Saurer, M.; Lötscher, C.; Siegwolf, R.; Bigi, A.; Hoyle, C. R.; DeCarlo, P. F.; Slowik, J. G.; Prévôt, A. S. H.; Baltensperger, U.; Dommen, J.

    2016-09-01

    Small volatile organic compounds (VOC) such as methane (CH4) have long been considered non-relevant to aerosol formation due to the high volatility of their oxidation products. However, even low aerosol yields from CH4, the most abundant VOC in the atmosphere, would contribute significantly to the total particulate carbon budget. In this study, organic aerosol (OA) mass yields from CH4 oxidation were evaluated at the Paul Scherrer Institute (PSI) smog chamber in the presence of inorganic and organic seed aerosols. Using labeled 13C methane, we could detect its oxidation products in the aerosol phase, with yields up to 0.09

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. A Novel Triple-Pulsed 2-micrometer Lidar for Simultaneous and Independent CO2 and H2O Column Measurement

    NASA Technical Reports Server (NTRS)

    Yu, Jirong; Singh, Upendra; Petros, Mulugeta; Refaat, Tamer

    2015-01-01

    The study of global warming needs precisely and accurately measuring greenhouse gases concentrations in the atmosphere. CO2 and H2O are important greenhouse gases that significantly contribute to the carbon cycle and global radiation budget on Earth. NRC Decadal Survey recommends a mission for Active Sensing of Carbon Dioxide (CO2) over Nights, Days and Seasons (ASCENDS). 2 micron laser is a viable IPDA transmitter to measure CO2 and H2O column density from space. The objective is to demonstrate a first airborne direct detection 2 micron IPDA lidar for CO2 and H2O measurements.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Ultrasensitive Analyzer for Realtime, In-Situ Airborne and Terrestrial Measurements of OCS, CO2, CO, and H2O

    NASA Astrophysics Data System (ADS)

    Provencal, R. A.; Gupta, M.; Baer, D. S.; Genty, B.

    2012-12-01

    mid-infrared Off-Axis ICOS system operating near 4.86 microns for the simultaneous quantification of OCS, CO2, CO, and H2O in ambient air. The sensor was thoroughly tested on diluted, certified samples and found to be precise (OCS, CO2, CO, and H2O to better than ±4 ppt, ±0.2 ppm, ±0.31 ppb, and ±3.7 ppm respectively, 1-sigma at 1 Hz) and linear (R-squared > 0.9997 for all gases) over a wide dynamic range (OCS, CO2, CO, and H2O ranging from 0.2 - 70 ppb, 500 - 3000 ppm, 150 - 480 ppb, and 7000 - 21000 ppm respectively). The instrument's time response (1/e) was limited by the gas flow rate through the measurement cell and can readily exceed 10 Hz for eddy flux studies. Cross-interference measurements showed that there was no appreciable change in measured OCS concentration with variations in CO2 (500 - 3500 ppm), CO, or H2O.

  1. 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.

  2. 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

  3. Synthesis and formation mechanism of micro/nano flower-like MgCO3·5H2O

    NASA Astrophysics Data System (ADS)

    Yin, Wan-zhong; Wang, Yu-lian; Ji, Qiang-dong; Yao, Jin; Hou, Ying; Wang, Lei; Zhong, Wen-xing

    2014-03-01

    Micro/nano magnesium carbonate pentahydrate (MgCO3·5H2O) with flower-like morphology was synthesized using magnesite as a substrate and potassium dihydrogen phosphate as an additive. The synthesized samples were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry and differential scanning calorimetry. The influence of pyrolysis time on crystal morphology was explored. The formation mechanism was investigated on the basis of the characterized results and the crystal structure of MgCO3·5H2O. The results showed that the flower-like MgCO3·5H2O was 1.5-3.0 μm in length and 100-500 nm in diameter and was successfully obtained with a pyrolysis time of 30 min. The formation mechanism of flower-like MgCO3·5H2O is suggested to be the selective adsorption of potassium dihydrogen phosphate on the surface. The process of flower-like crystal growth is as follows: amorphous nanoparticles formation, acicular and rod monocrystal formation, flower-like monocrystal formation, and flower-like polymers (MgCO3·5H2O) crystallization. In the MgCO3·5H2O crystal, the magnesium ion presents two different octahedral coordinations corresponding to Mg(H2O){6/2-} and [Mg(H2O) (CO{3/2-})2]2-, and the chemical formula of the crystal is Mg(H2O)6 · Mg(H2O)4 (CO{3/2-})2.

  4. Black carbon in aerosol during BIBLE B

    NASA Astrophysics Data System (ADS)

    Liley, J. Ben; Baumgardner, D.; Kondo, Y.; Kita, K.; Blake, D. R.; Koike, M.; Machida, T.; Takegawa, N.; Kawakami, S.; Shirai, T.; Ogawa, T.

    2003-02-01

    The Biomass Burning and Lightning Experiment (BIBLE) A and B campaigns over the tropical western Pacific during springtime deployed a Gulfstream-II aircraft with systems to measure ozone and numerous precursor species. Aerosol measuring systems included a MASP optical particle counter, a condensation nucleus (CN) counter, and an absorption spectrometer for black carbon. Aerosol volume was very low in the middle and upper troposphere during both campaigns, and during BIBLE A, there was little aerosol enhancement in the boundary layer away from urban areas. In BIBLE B, there was marked aerosol enhancement in the lowest 3 km of the atmosphere. Mixing ratios of CN in cloud-free conditions in the upper troposphere were in general higher than in the boundary layer, indicating new particle formation from gaseous precursors. High concentrations of black carbon were observed during BIBLE B, with mass loadings up to 40 μg m-3 representing as much as one quarter of total aerosol mass. Strong correlations with hydrocarbon enhancement allow the determination of a black carbon emission ratio for the fires at that time. Expressed as elemental carbon, it is about 0.5% of carbon dioxide and 6% of carbon monoxide emissions from the same fires, comparable to methane production, and greater than that of other hydrocarbons.

  5. Black carbon in aerosol during BIBLE B

    NASA Astrophysics Data System (ADS)

    Liley, J. Ben; Baumgardner, D.; Kondo, Y.; Kita, K.; Blake, D. R.; Koike, M.; Machida, T.; Takegawa, N.; Kawakami, S.; Shirai, T.; Ogawa, T.

    2002-02-01

    The Biomass Burning and Lightning Experiment (BIBLE) A and B campaigns over the tropical western Pacific during springtime deployed a Gulfstream-II aircraft with systems to measure ozone and numerous precursor species. Aerosol measuring systems included a MASP optical particle counter, a condensation nucleus (CN) counter, and an absorption spectrometer for black carbon. Aerosol volume was very low in the middle and upper troposphere during both campaigns, and during BIBLE A, there was little aerosol enhancement in the boundary layer away from urban areas. In BIBLE B, there was marked aerosol enhancement in the lowest 3 km of the atmosphere. Mixing ratios of CN in cloud-free conditions in the upper troposphere were in general higher than in the boundary layer, indicating new particle formation from gaseous precursors. High concentrations of black carbon were observed during BIBLE B, with mass loadings up to 40 μg m-3 representing as much as one quarter of total aerosol mass. Strong correlations with hydrocarbon enhancement allow the determination of a black carbon emission ratio for the fires at that time. Expressed as elemental carbon, it is about 0.5% of carbon dioxide and 6% of carbon monoxide emissions from the same fires, comparable to methane production, and greater than that of other hydrocarbons.

  6. 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.

  7. 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

  8. O2 and H2O2 transformation steps for the oxygen reduction reaction catalyzed by graphitic nitrogen-doped carbon nanotubes in acidic electrolyte from first principles calculations.

    PubMed

    Li, Yuhang; Zhong, Guoyu; Yu, Hao; Wang, Hongjuan; Peng, Feng

    2015-09-14

    It is highly challenging but extremely desirable to develop carbon catalysts with high oxygen reduction reaction (ORR) activity and stability in acidic medium for commercial application. In this paper, based on density functional theory (DFT) calculations with long range interaction correction and solvation effects, the elementary transformations of all the probable intermediates in the ORR and the hydrogen peroxide reduction reaction (HPRR) over graphitic nitrogen-doped carbon nanotubes (NCNTs) in acidic medium were evaluated, and it was found that all the rate determining steps are related to the bonding hydroxyl group because of the strong interaction between the hydroxyl group and carbon. Thus, it is hard for the direct four-electron ORR and the two-electron HPRR to proceed. Together with hydrogen peroxide disproportionation (HPD), a mixed mechanism for the ORR in acidic electrolyte was proposed, where the two-electron and three-electron ORRs and HPD dominate the electrode reaction. The experimental result for the ORR catalyzed by NCNTs in acidic electrolyte also well illustrated the rationality of the theoretical calculations. This study not only gives new insights into the effect of graphitic nitrogen doping on the ORR catalyzed by carbon, but also provides a guide to design carbon catalysts with high ORR activity in acidic electrolyte.

  9. 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.

  10. 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.

  11. 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).

  12. 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.

  13. 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)(-).

  14. 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.

  15. 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

  16. 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

  17. 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).

  18. Towards a consistent mantle carbon flux estimate: Insights from volatile systematics (H 2O/Ce, δD, CO 2/Nb) in the North Atlantic mantle (14° N and 34° N)

    NASA Astrophysics Data System (ADS)

    Cartigny, Pierre; Pineau, Françoise; Aubaud, Cyril; Javoy, Marc

    2008-01-01

    In order to better characterise mantle CO 2/Nb-variability, we obtained and compiled major and trace elements, content and isotope composition of both CO 2 and water on two series of mid-ocean ridge basalt (MORB) samples dredged at ˜ 14° N ( n = 6) and 34° N ( n = 11) on the mid-Atlantic ridge. All samples are carbon-saturated. One, the so-called popping rock 2ΠD43 kept its vesicles, the initial (pre-degassing) C-contents of the 16 other samples being reconstructed from their assumed degassing history. For water, the samples show large variations, from 1300 to 6900 ppm and from 1900 to 7900 ppm with associated δD-values ranging from - 55 to - 79‰ and from - 55 to - 88‰ for samples at 14° N and 34° N respectively. For carbon, the inferred initial predegassing contents vary greatly, from 660 to 14,700 ppmCO 2 and from 1400 to 57,600 ppmCO 2 for samples at 14° N and 34° N respectively. Measured Nb-contents range from 4.5 to 29.6 ppm show both good agreement with previously published data and positive correlations with reconstructed initial CO 2-contents. The mean CO 2/Nb range from ˜ 570 to ˜ 730 at 14° N and 34° N respectively. CO 2 and Nb data for the two undegassed samples available so far (i.e. the popping rock of the present study and the basaltic glasses from the Siqueiros transform fault from the study of Saal et al., 2002) show significant variations in CO 2/Nb over a factor of 2 and thus questions the constant CO 2/Nb previously emphasised for these two samples, this view being supported by CO 2/Nb-ratios of samples whose initial C-contents were reconstructed. For incompatible elements such as Ce, K and including water, a comparison of the geochemical characteristics of transform fault basaltic magmatism with other MORB systems shows magma transform fault magmatism to be unrepresentative of mantle compositions. Assuming a more appropriate average MORB CO 2/Nb-ratio of ˜ 530 and a mean MORB Nb-content of 3.31-1.8+3.99, we computed a mantle

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. Characterization of Ambient Black Carbon Aerosols

    NASA Astrophysics Data System (ADS)

    Zhang, R.; Levy, M. E.; Zheng, J.; Molina, L. T.

    2013-12-01

    Because of the strong absorption over a broad range of the electromagnetic spectra, black carbon (BC) is a key short-lived climate forcer, which contributes significantly to climate change by direct radiative forcing and is the second most important component causing global warming after carbon dioxide. The impact of BC on the radiative forcing of the Earth-Atmosphere system is highly dependent of the particle properties. In this presentation, emphasis will be placed on characterizing BC containing aerosols in at the California-Mexico border to obtain a greater understanding of the atmospheric aging and properties of ambient BC aerosols. A comprehensive set of directly measured aerosol properties, including the particle size distribution, effective density, hygroscopicity, volatility, and several optical properties, will be discussed to quantify the mixing state and composition of ambient particles. In Tijuana, Mexico, submicron aerosols are strongly influenced by vehicle emissions; subsequently, the BC concentration in Tijuana is considerably higher than most US cities with an average BC concentration of 2.71 × 2.65 g cm-3. BC accounts for 24.75 % × 9.44 of the total submicron concentration on average, but periodically accounts for over 50%. This high concentration of BC strongly influences many observed aerosol properties such as single scattering albedo, hygroscopicity, effective density, and volatility.

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. Improved quasi-unary nucleation model for binary H2SO4-H2O homogeneous nucleation

    NASA Astrophysics Data System (ADS)

    Yu, Fangqun

    2007-08-01

    Aerosol nucleation events have been observed at a variety of locations worldwide, and may have significant climatic and health implications. Binary homogeneous nucleation (BHN) of H2SO4 and H2O is the foundation of recently proposed nucleation mechanisms involving additional species such as ammonia, ions, and organic compounds, and it may dominate atmospheric nucleation under certain conditions. We have shown in previous work that H2SO4-H2O BHN can be treated as a quasi-unary nucleation (QUN) process involving H2SO4 in equilibrium with H2O vapor, and we have developed a self-consistent kinetic model for H2SO4-H2O nucleation. Here, the QUN approach is improved, and an analytical expression yielding H2SO4-H2O QUN rates is derived. Two independent measurements related to monomer hydration are used to constrain the equilibrium constants for this process, which reduces a major source of uncertainty. It is also shown that the capillarity approximation may lead to a large error in the calculated Gibbs free energy change for the evaporation of H2SO4 molecules from small H2SO4-H2O clusters, which affects the accuracy of predicted BHN nucleation rates. The improved QUN model—taking into account the recently measured energetics of small clusters—is thermodynamically more robust. Moreover, predicted QUN nucleation rates are in better agreement with available experimental data than rates calculated using classical H2SO4-H2O BHN theory.

  13. Differential absorption lidar measurements of H2O and O2 using a coherent white light continuum

    NASA Astrophysics Data System (ADS)

    Somekawa, T.; Manago, N.; Kuze, H.; Fujita, M.

    2016-10-01

    We applied a broadband and coherent white light continuum to differential absorption lidar (DIAL) detection of H2O and O2 profiles in the troposphere. The white light continuum can be generated by focusing high intensity femtosecond laser pulses at 800 nm into a Kr gas cell covering a broad spectral range from UV to mid-IR. Thus, the use of white light continuum potentially enables the DIAL measurement of several greenhouse and/or pollutant gases simultaneously while minimizing the lead time for developing a tunable light source. In order to demonstrate such capability, here we report the lidar measurements of H2O and O2. These molecular species exhibit absorption lines in the near IR region where relatively high intensity of the white light continuum is available. The white light continuum was transmitted through the atmosphere collinearly to the axis of a receiver telescope. Backscattered light was passed through bandpass filters (H2O On: 725 and 730 nm, H2O Off: 750 nm, O2 On: 760 nm, O2 Off: 780 nm), and was detected by a photomultiplier tube. The detection wavelengths were selected consecutively by rotating the filter wheels that contain five bandpass filters with an interval of 1 minute. In addition, we propose a method for retrieving vertical profiles of H2O by considering wavelength dependence of the aerosol extinction coefficient α and backscatter coefficient β. These results show that for achieving precise retrieval of H2O distribution, one needs to reduce the effect of aerosol temporal variations by means of long-time accumulation or simultaneous detection of the On- and Off-wavelength signals.

  14. Aerosol and graphitic carbon content of snow

    SciTech Connect

    Chy-acute-accentlek, P.; Srivastava, V.; Cahenzli, L.; Pinnick, R.G.; Dod, R.L.; Novakov, T.; Cook, T.L.; Hinds, B.D.

    1987-08-20

    Snow samples from southern New Mexico, west Texas, Antarctica, and Greenland were analyzed for aerosol and graphitic carbon. Graphitic carbon contents were found to be between 2.2 and 25 ..mu..g L/sup -1/ of snow meltwater; water-insoluble aerosol content varied between 0.62 and 8.5 mg L/sup -1/. For comparison, two samples of Camp Century, Greenland, ice core, having approximate ages of 4,000 and 6,000 years, were also analyzed. Ice core graphitic carbon contents were found to be 2.5 and 1.1 ..mu..g L/sup -1/. copyrightAmerican Geophysical Union 1987

  15. 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.

  16. Laboratory Infrared Spectra of Polycyclic Aromatic Nitrogen Heterocycles: Quinoline, and Phenanthridine in Solid Argon and H2O

    NASA Technical Reports Server (NTRS)

    Bernstein, M. P.; Mattioda, A. L.; Sandford, S. A.; Hudgins, D. M.

    2004-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe. Their detection and identification are based on telescopic infrared (IR) spectra compared with laboratory data. Polycyclic Aromatic Nitrogen Heterocycles (PANHs) are heterocyclic aromatics i.e., PAHs with carbon atoms replaced by a nitrogen atom. These molecules should be present in the interstellar medium, but have received relatively little attention. We present mid-IR spectra of two PANHs, quinoline (C9H7N), and phenanthridine (C13H9N) isolated in solid argon and frozen in solid H2O at 12 K, conditions yielding data directly comparable to astronomical observations. In contrast to simple PAHs, that do not interact strongly with solid H2O, the nitrogen atoms in PANHs are potentially capable of hydrogen bonding with H2O. Whereas the IR spectrum of phenanthridine in H2O is similar to that of the same compound isolated in an argon matrix, quinoline absorptions shift up to 16 cm(sup -1) (0.072 mm) between argon and H2O. Thus, astronomers will not always be able to rely on IR band positions of matrix isolated PANHs to correctly interpret the absorptions of PANHs frozen in H2O ice grains. Furthermore, our data suggest that relative band areas also vary, so determining column densities to better than a factor of 3 will require knowledge of the matrix in which the PANH is embedded and laboratory studies of relevant samples.

  17. Efficiency of the UV/H2O2 process for the disinfection of humic surface waters.

    PubMed

    Alkan, Ufuk; Teksoy, Arzu; Atesli, Ahu; Baskaya, Huseyin S

    2007-03-01

    The efficiency of the UV/H2O2 process for the disinfection of total coliforms and the prevention of bacterial regrowth in humic surface waters were investigated. Inactivation of total coliforms was determined in water samples containing various concentrations ranging from 0-10 mg/L dissolved organic carbon (DOC) of fulvic acid, which were exposed to various doses (68-681 mWs/cm2) of UV radiation in the presence of 0.125 mg/L and 3.000 mg/L of hydrogen peroxide. Disinfection efficiencies of the UV radiation and the UV/H2O2 processes were compared. The results of bacterial inactivation experiments showed that the performances of the UV and the UV/H2O2 (0.125) were comparable whereas the UV/H2O2 (3.000) process showed significant improvement in performance, especially, in highly humic waters. Inactivation coefficient appeared to be almost doubled by the addition of 3.000 mg/L hydrogen peroxide during the treatment of highly humic waters. In contradiction to significant regrowth which occurred in the single UV radiation treatment, residual bacteria following the UV/H2O2 (0.125) and the UV/H2O2 (3.000) treatments were completely inactivated during dark incubation indicating the elimination of possible bacterial regrowth.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. [Catalyzed oxidation of catechol by the heterogeneous Fenton-like reaction of nano-Fe3O4-H2O2 system].

    PubMed

    He, Jie; Yang, Xiao-fang; Zhang, Wei-jun; Wang, Dong-sheng

    2013-05-01

    A Fenton-like system, consisting of magnetite (Fe3O4) and hydrogen peroxide (H2O2), was utilized to remove refractory organic pollutants using the hydroxyl radicals generated from the decomposition of H2O2. The characteristic of the catalyzed oxidation of catechol in a nano-Fe3O4-H2O2 Fenton-like system was studied. The catalytic activity of the synthesized nano-Fe3O4 was compared to that of the purchased micro-Fe3O4. The effect of initial H2O2 concentration on the oxidation of catechol was also studied. Results showed that the removal of catechol and total organic carbon and the decomposition of H2O2 were faster in the nano-Fe3O4-H2O2 system than in the purchased-Fe3O4-H2O2 system. The removal of catechol achieved nearly 100% in the former system. The catalyzed oxidation of catechol in nano-Fe3O4-H2O2 system followed pseudo-first-order kinetics. The decomposition of H2O2 could be fitted by third-order kinetics. The release of total iron was below 0.3 mg x L(-1), implying that the homogeneous Fenton reaction was not dominant. Therefore, surface reaction controlled heterogeneous Fenton-like reaction mechanism was deduced.

  11. 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.

  12. Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

    SciTech Connect

    Ali, Hashim M.; Iedema, Martin J.; Yu, Xiao-Ying; Cowin, James P.

    2014-06-20

    The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium particles was studied by utilizing a crossflow-mini reactor. The reaction kinetics was followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely SEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry’s law solubility of H2O2 to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to eventually a mixed NaHSO4 plus H2SO4 brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted rates using previously established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the Henry’s law constant of H2O2 dependence on ionic strength.

  13. Absorbing Aerosols: Field and Laboratory Studies of Black Carbon and Dust

    NASA Astrophysics Data System (ADS)

    Aiken, A. C.; Flowers, B. A.; Dubey, M. K.

    2011-12-01

    Currently, absorbing aerosols are thought to be the most uncertain factor in atmospheric climate models (~0.4-1.2 W/m2), and the 2nd most important factor after CO2 in global warming (1.6 W/m2; Ramanathan and Carmichael, Nature Geoscience, 2008; Myhre, Science, 2009). While most well-recognized atmospheric aerosols, e.g., sulfate from power-plants, have a cooling effect on the atmosphere by scattering solar radiation, black carbon (BC or soot) absorbs sunlight strongly which results in a warming of the atmosphere. Dust particles are also present globally and can absorb radiation, contributing to a warmer and drier atmosphere. Direct on-line measurements of BC and hematite, an absorbing dust aerosol, can be made with the Single Particle Soot Photometer (SP2), which measures the mass of the particles by incandescence on an individual particle basis. Measurements from the SP2 are combined with absorption measurements from the three-wavelength photoacoustic soot spectrometer (PASS-3) at 405, 532, and 781 nm and the ultraviolet photoacoustic soot spectrometer (PASS-UV) at 375 nm to determine wavelength-dependent mass absorption coefficients (MACs). Laboratory aerosol samples include flame-generated soot, fullerene soot, Aquadag, hematite, and hematite-containing dusts. Measured BC MAC's compare well with published values, and hematite MAC's are an order of magnitude less than BC. Absorbing aerosols measured in the laboratory are compared with those from ambient aerosols measured during the Las Conchas fire and BEACHON-RoMBAS. The Las Conchas fire was a wildfire in the Jemez Mountains of New Mexico that burned over 100,000 acres during the Summer of 2011, and BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study) is a field campaign focusing on biogenic aerosols at the Manitou Forest Observatory near Colorado Springs, CO in Summer 2011. Optical properties and size

  14. [{(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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Radical loss in the atmosphere from Cu-Fe redox coupling in aerosols

    NASA Astrophysics Data System (ADS)

    Mao, J.; Fan, S.; Jacob, D. J.; Travis, K. R.

    2013-01-01

    The hydroperoxyl radical (HO2) is a major precursor of OH and tropospheric ozone. OH is the main atmospheric oxidant, while tropospheric ozone is an important surface pollutant and greenhouse gas. Standard gas-phase models for atmospheric chemistry tend to overestimate observed HO2 concentrations, and this has been tentatively attributed to heterogeneous uptake by aerosol particles. It is generally assumed that HO2 uptake by aerosol involves conversion to H2O2, but this is of limited efficacy as an HO2 sink because H2O2 can photolyze to regenerate OH and from there HO2. Joint atmospheric observations of HO2 and H2O2 suggest that HO2 uptake by aerosols may in fact not produce H2O2. Here we propose a catalytic mechanism involving coupling of the transition metal ions Cu(I)/Cu(II) and Fe(II)/Fe(III) to rapidly convert HO2 to H2O in aqueous aerosols. The implied HO2 uptake and conversion to H2O significantly affects global model predictions of tropospheric OH, ozone, carbon monoxide (CO) and other species, improving comparisons to observations in the GEOS-Chem model. It represents a previously unrecognized positive radiative forcing of aerosols through the effects on the chemical budgets of major greenhouse gases including methane and hydrofluorocarbons (HFCs).

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Black carbon aerosol size in snow.

    PubMed

    Schwarz, J P; Gao, R S; Perring, A E; Spackman, J R; Fahey, D W

    2013-01-01

    The effect of anthropogenic black carbon (BC) aerosol on snow is of enduring interest due to its consequences for climate forcing. Until now, too little attention has been focused on BC's size in snow, an important parameter affecting BC light absorption in snow. Here we present first observations of this parameter, revealing that BC can be shifted to larger sizes in snow than are typically seen in the atmosphere, in part due to the processes associated with BC removal from the atmosphere. Mie theory analysis indicates a corresponding reduction in BC absorption in snow of 40%, making BC size in snow the dominant source of uncertainty in BC's absorption properties for calculations of BC's snow albedo climate forcing. The shift reduces estimated BC global mean snow forcing by 30%, and has scientific implications for our understanding of snow albedo and the processing of atmospheric BC aerosol in snowfall.

  7. HDO and H2O total column retrievals from TROPOMI shortwave infrared measurements

    NASA Astrophysics Data System (ADS)

    Scheepmaker, Remco A.; aan de Brugh, Joost; Hu, Haili; Borsdorff, Tobias; Frankenberg, Christian; Risi, Camille; Hasekamp, Otto; Aben, Ilse; Landgraf, Jochen

    2016-08-01

    The TROPOspheric Monitoring Instrument (TROPOMI) on board the European Space Agency Sentinel-5 Precursor mission is scheduled for launch in the last quarter of 2016. As part of its operational processing the mission will provide CH4 and CO total columns using backscattered sunlight in the shortwave infrared band (2.3 µm). By adapting the CO retrieval algorithm, we have developed a non-scattering algorithm to retrieve total column HDO and H2O from the same measurements under clear-sky conditions. The isotopologue ratio HDO / H2O is a powerful diagnostic in the efforts to improve our understanding of the hydrological cycle and its role in climate change, as it provides an insight into the source and transport history of water vapour, nature's strongest greenhouse gas. Due to the weak reflectivity over water surfaces, we need to restrict the retrieval to cloud-free scenes over land. We exploit a novel 2-band filter technique, using strong vs. weak water or methane absorption bands, to prefilter scenes with medium-to-high-level clouds, cirrus or aerosol and to significantly reduce processing time. Scenes with cloud top heights ≲1 km, very low fractions of high-level clouds or an aerosol layer above a high surface albedo are not filtered out. We use an ensemble of realistic measurement simulations for various conditions to show the efficiency of the cloud filter and to quantify the performance of the retrieval. The single-measurement precision in terms of δD is better than 15-25 ‰ for even the lowest surface albedo (2-4 ‰ for high albedos), while a small bias remains possible of up to ˜ 20 ‰ due to remaining aerosol or up to ˜ 70 ‰ due to remaining cloud contamination. We also present an analysis of the sensitivity towards prior assumptions, which shows that the retrieval has a small but significant sensitivity to the a priori assumption of the atmospheric trace gas profiles. Averaging multiple measurements over time and space, however, will reduce these

  8. 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.

  9. Sorption of diclofenac and naproxen onto MWCNT in model wastewater treated by H2O2 and/or UV.

    PubMed

    Czech, Bożena; Oleszczuk, Patryk

    2016-04-01

    The application of oxidation processes such as UV and/or H2O2 will change the physicochemical properties of carbon nanotubes (CNT). It may affect the sorption affinity of CNT to different contaminants and then affect their fate in the environment. In the present study the adsorption of two very common used pharmaceuticals (diclofenac and naproxen) onto CNT treated by UV, H2O2 or UV/H2O2 was investigated. Four different adsorption models (Freundlich, Langmuir, Temkin, Dubinin-Radushkevich) were tested. The best fitting of experimental data was observed for Freundlich or Langmuir model. The significant relationships between Q calculated from Langmuir model with O% and dispersity were observed. Kinetics of diclofenac and naproxen followed mainly pseudo-second order indicating for chemisorption limiting step of adsorption. The data showed that the mechanism of sorption was physical or chemical depending on the type of CNT modification.

  10. 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.

  11. SPADE H2O measurements and the seasonal cycle of statospheric water vapor

    NASA Technical Reports Server (NTRS)

    Hintsa, Eric J.; Weinstock, Elliot M.; Dessler, Andrew E.; Anderson, James G.; Loewenstein, Max; Podolske, James R.

    1994-01-01

    We present measurements of lower statospheric water vapor obtained during the Stratospheric Phototchemistry, Aerosols and Dynamics Expedition (SPADE) mission with a new high precision, fast response, Lyman-alpha hygrometer. The H2O data show a distinct seasonal cycle. For air that recently entered the statosphere, data collected during the fall show much more water vapor than data from the spring. Fast quasi-horizontal mixing causes compact relationships between water and N2O to be established on relatively short time scales. The measurements are consistent with horizontal mixing times of a few months or less. Vertical mixing appears to cause the seasonal variations in water vapor to propagate up to levels corresponding to air that has been in the stratosphere approximately one year.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. The Role of H2O in Brucite-Supercritical CO2 Reaction: Relevance to CO2 Sequestration

    NASA Astrophysics Data System (ADS)

    Dong, S.; Zhao, L.; Chen, Z.; Teng, H.

    2013-12-01

    It is widely recognized that the presence of water is vital for brucite carbonation in supercritical CO2 (scCO2) based upon the observation that nesquehonite (MgCO3`3H2O) precipitated instantly in brucite-water-scCO2 system while no carbonate was detected in brucite-scCO2 medium. The importance of water is further emphasized by the result that shows higher water concentrations led to greater carbonation rates. However, the mechanism of water effect is not fully understood as two possible pathways exist for the carbonation reaction: 1) the dissociation of H2O provides a) H+ to release Mg2+ through associating with OH- in brucite, and b) OH- to combine with CO2 to form HCO3-, leading to the interaction of magnesium cations with carbonate anions; 2) H2O molecules polarizes CO2 through hydrogen bonding to promote direct interactions between carbon dioxide and brucite followed by water release from Mg(OH)2. The present study attempts to determine whether proton-effect or polarity-effect is the governing force for brucite carbonation in scCO2 - H2O system. Experiments were carried out in water-saturated scCO2 (experimental H2O mole fraction in CO2 is 4.1×10-2, solubility of H2O in CO2 at experimental condition is 3.5×10-3), and formamide (FM, HCONH2)-saturated scCO2 (experimental FM mole fraction in CO2 is 1.8×10-2), at 50 oC temperature and 8MPa pressure. Formamide was selected because of its similar permittivity to water (ɛH2O,20oC=80.1, ɛHCONH2,20oC=84.0) but the lack of proton-donating ability. In situ Raman spectroscopy data revealed that nesquehonite and hydromagnesite (Mg5(CO3)4(OH)2`4H2O, minor quantity) formed in both brucite-water-scCO2 and brucite-FM-scCO2 systems but at a different rate, with the former within 5h and the latter 45h to reach similar carbonation extent. While this result cannot completely rule out the role of water as brucite may dehydrate in FM, it shows that liquid water may not be needed for mineral-scCO2 interaction as long as the

  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. Formation of Submicron Magnesite during Reaction of Natural Forsterite in H2O-Saturated Supercritical CO2

    SciTech Connect

    Qafoku, Odeta; Hu, Jian Z.; Hess, Nancy J.; Hu, Mary Y.; Ilton, Eugene S.; Feng, Ju; Arey, Bruce W.; Felmy, Andrew R.

    2014-06-01

    Natural forsterite was reacted in a) liquid water saturated with supercritical CO2 (scCO2) and in b) H2O-saturated scCO2 at 35-80 °C and 90 atm. The solid reaction products were analyzed with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and confocal Raman spectroscopy. Two carbonate phases, nesquehonite (MgCO3.3H2O) and magnesite (MgCO3), were identified with the proportions of the two phases depending on experimental conditions. In water saturated with scCO2, nesquehonite was the dominant carbonate phase at 35-80 °C with only a limited number of large, micron size magnesite particles forming at the highest temperature, 80 °C. In contrast, in H2O-saturated scCO2 magnesite formation was identified at all three temperatures: 35 °, 50 °, and 80 °C. Magnesite was the dominant carbonation reaction product at 50 ° and 80 °C; but nesquehonite was dominant at 35 °C. The magnesite particles formed under H2O-saturated scCO2 conditions exhibited an extremely uniform submicron grain-size and nearly identical rhombohedral morphologies at all temperatures. The distribution and form of the particles were not consistent with epitaxial nucleation and growth on the forsterite surface.

  3. Photodegradation of the antineoplastic cyclophosphamide: a comparative study of the efficiencies of UV/H2O2, UV/Fe2+/H2O2 and UV/TiO2 processes.

    PubMed

    Lutterbeck, Carlos Alexandre; Machado, Ênio Leandro; Kümmerer, Klaus

    2015-02-01

    Anticancer drugs are harmful substances that can have carcinogenic, mutagenic, teratogenic, genotoxic, and cytotoxic effects even at low concentrations. More than 50 years after its introduction, the alkylating agent cyclophosphamide (CP) is still one of the most consumed anticancer drug worldwide. CP has been detected in water bodies in several studies and is known as being persistent in the aquatic environment. As the traditional water and wastewater treatment technologies are not able to remove CP from the water, different treatment options such as advanced oxidation processes (AOPs) are under discussion to eliminate these compounds. The present study investigated the degradation of CP by three different AOPs: UV/H2O2, UV/Fe(2+)/H2O2 and UV/TiO2. The light source was a Hg medium-pressure lamp. Prescreening tests were carried out and afterwards experiments based on the optimized conditions were performed. The primary elimination of the parent compounds and the detection of transformation products (TPs) were monitored with LC-UV-MS/MS analysis, whereas the degree of mineralization was monitored by measuring the dissolved organic carbon (DOC). Ecotoxicological assays were carried out with the luminescent bacteria Vibrio fischeri. CP was completely degraded in all treatments and UV/Fe(2+)/H2O2 was the fastest process, followed by UV/H2O2 and UV/TiO2. All the reactions obeyed pseudo-first order kinetics. Considering the mineralization UV/Fe(2+)/H2O2 and UV/TiO2 were the most efficient process with mineralization degrees higher than 85%, whereas UV/H2O2 achieved 72.5% of DOC removal. Five transformation products were formed during the reactions and identified. None of them showed significant toxicity against V. fischeri.

  4. 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.

  5. Near-infrared spectroscopy of M dwarfs. II. H2O molecule as an abundance indicator of oxygen†

    NASA Astrophysics Data System (ADS)

    Tsuji, Takashi; Nakajima, Tadashi; Takeda, Yoichi

    2015-04-01

    Based on the near-infrared spectra (R ≈ 20000) of M dwarfs, oxygen abundances are determined from the rovibrational lines of H2O. Although H2O lines in M dwarfs are badly blended with each other and the continuum levels are depressed appreciably by the collective effect of the numerous H2O lines themselves, quantitative analysis of H2O lines has been carried out by referring to the pseudo-continua, consistently defined on the observed and theoretical spectra. For this purpose, the pseudo-continuum on the theoretical spectrum has been evaluated accurately by the use of the recent high-precision H2O line-list. Then, we propose a simple and flexible method of analyzing the equivalent widths (EWs) of blended features (i.e., not necessarily limited to single lines) by the use of a mini-curve-of-growth (CG), which is a small portion of the usual CG around the observed EW. The mini-CG is generated by using the theoretical EWs evaluated from the synthetic spectrum in exactly the same way as the EWs are measured from the observed spectrum. The observed EW is converted to the abundance by the use of the mini-CG, and the process is repeated for all the observed EWs line-by-line or blend-by-blend. In cool M dwarfs, almost all the oxygen atoms left after CO formation are in stable H2O molecules, which suffer little change for the uncertainties due to imperfect modelling of the photospheres. Thus the numerous H2O lines are excellent abundance indicators of oxygen. The oxygen abundances are determined to be log AO (AO = NO/NH) between -3.5 and -3.0 in 38 M dwarfs, but cannot be determined in four early M dwarfs in which H2O lines are detected only marginally. The resulting log AO/AC values plotted against log AC appear to be systematically smaller in the carbon-rich M dwarfs, showing the different formation histories of oxygen and carbon in the chemical evolution of the Galactic disk. Also, AO/AFe ratios in most M dwarfs are closer to the solar AO/AFe ratio, based on the

  6. Precipitation of ALn(CO3),xH2O and Dy2(CO3),xH2O compounds from aqueous solutions for A=Li,Na,K,Cs,NH4+ and =La,Nd,Eu,Dy

    NASA Astrophysics Data System (ADS)

    Philippini, Violaine; Vercouter, Thomas; Chaussé, Annie; Vitorge, Pierre

    2008-09-01

    Double carbonates of lanthanide ( Ln) and alkaline or ammonium ( A) ions, noted ALn(CO3)2,xH2O, were precipitated from concentrated A2CO3 aqueous solutions at room temperature and atmospheric pressure. Twelve hydrated compounds out of the twenty targeted ones have been obtained: Li(Nd or Eu)(CO3)2, NaLa(CO3)2, KNd(CO3)2,xH2O, Cs(La or Nd)(CO3)2, NH4(Nd, Eu or Dy)(CO3)2, Dy2(CO3)3 from concentrated A2CO3 solutions and Na(Nd, Eu or Dy)(CO3)2 from concentrated AHCO3 solutions. Although the trivalent lanthanide ions are often considered as analogs in solution, differences in their precipitation behaviour was observed, which is believed to have a kinetic origin in relation to the small differences in their ionic radii. The solid compounds were characterised by elemental analyses, thermogravimetry (TG), X-ray diffraction (XRD) and scanning electron microscope-energy dispersive spectroscopy (SEM-EDS). The powder diffraction patterns of nine solids were fitted using the tetragonal P4/mmm Laüe class: LiNd(CO3)2,xH2O: a=(12.16±0.02) A˚, c=(9.21±0.02) A˚, LiEu(CO3)2,3H2O: a=(12.201±0.007) A˚, c=(9.23±0.01) A˚, KNd(CO3)2,xH2O: a=(13.28±0.04) A˚, c=(10.00±0.04) A˚, CsLa(CO3)2,xH2O: a=(10.82±0.02) A˚, c=(8.18±0.02) A˚, CsNd(CO3)2,xH2O: a=(10.81±0.07) A˚, c=(8.16±0.07) A˚ for NaLn(CO3)2,xH2O: a=(11.10+1.75r) A˚ and c=(8.60+1.13r) A˚, where r is the ionic radius of for a coordination number of 8 ( r=1.16 A˚, r=1.12 A˚, r=1.07 A˚ and r=1.03 A˚). It is proposed that all the NaLn(CO3)2,xH2O compounds are of very similar structure, as evidenced by their XRD patterns and by the linear variations of the lattice parameters with r. The small differences in the lattice parameters can induce large modification of the precipitation pathways. Conversely, structural changes were evidenced within the A+ series for ANd(CO3)2,xH2O. Dy2(CO3)3,xH2O was also obtained as a by-product. Its lattice parameters are in good agreement with Eu2(CO3)3,3H2O ones.

  7. Aerosol generation and measurement of multi-wall carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Myojo, Toshihiko; Oyabu, Takako; Nishi, Kenichiro; Kadoya, Chikara; Tanaka, Isamu; Ono-Ogasawara, Mariko; Sakae, Hirokazu; Shirai, Tadashi

    2009-01-01

    Mass production of some kinds of carbon nanotubes (CNT) is now imminent, but little is known about the risk associated with their exposure. It is important to assess the propensity of the CNT to release particles into air for its risk assessment. In this study, we conducted aerosolization of a multi-walled CNT (MWCNT) to assess several aerosol measuring instruments. A Palas RBG-1000 aerosol generator applied mechanical stress to the MWCNT by a rotating brush at feed rates ranging from 2 to 20 mm/h, which the MWCNT was fed to a two-component fluidized bed. The fluidized bed aerosol generator was used to disperse the MWCNT aerosol once more. We monitored the generated MWCNT aerosol concentrations based on number, area, and mass using a condensation particle counter and nanoparticle surface area monitor. Also we quantified carbon mass in MWCNT aerosol samples by a carbon monitor. The shape of aerosolized MWCNT fibers was observed by a scanning electron microscope (SEM). The MWCNT was well dispersed by our system. We found isolated MWCNT fibers in the aerosols by SEM and the count median lengths of MWCNT fibers were 4-6 μm. The MWCNT was quantified by the carbon monitor with a modified condition based on the NIOSH analytical manual. The MWCNT aerosol concentration (EC mass base) was 4 mg/m3 at 2 mm/h in this study.

  8. ALA Inhibits ABA-induced Stomatal Closure via Reducing H2O2 and Ca2+ Levels in Guard Cells

    PubMed Central

    An, Yuyan; Liu, Longbo; Chen, Linghui; Wang, Liangju

    2016-01-01

    5-Aminolevulinic acid (ALA), a newly proved natural plant growth regulator, is well known to improve plant photosynthesis under both normal and stressful conditions. However, its underlying mechanism remains largely unknown. Stomatal closure is one of the major limiting factors for photosynthesis and abscisic acid (ABA) is the most important hormone in provoking stomatal closing. Here, we showed that ALA significantly inhibited ABA-induced stomatal closure using wild-type and ALA-overproducing transgenic Arabidopsis (YHem1). We found that ALA decreased ABA-induced H2O2 and cytosolic Ca2+ accumulation in guard cells with stomatal bioassay, laser-scanning confocal microscopy and pharmacological methods. The inhibitory effect of ALA on ABA-induced stomatal closure was similar to that of AsA (an important reducing substrate for H2O2 removal), CAT (a H2O2-scavenging enzyme), DPI (an inhibitor of the H2O2-generating NADPH oxidase), EGTA (a Ca-chelating agent), and AlCl3 (an inhibitor of calcium channel). Furthermore, ALA inhibited exogenous H2O2- or Ca2+-induced stomatal closure. Taken together, we conclude that ALA inhibits ABA-induced stomatal closure via reducing H2O2, probably by scavenging, and Ca2+ levels in guard cells. Moreover, the inhibitive effect of ALA on ABA-induced stomatal closure was further confirmed in the whole plant. Finally, we demonstrated that ALA inhibits stomatal closing, but significantly improves plant drought tolerance. Our results provide valuable information for the promotion of plant production and development of a sustainable low-carbon society. PMID:27148309

  9. 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.

  10. 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.

  11. [Fly ash-catalyzed oxidation of p-nitro phenol with H2O2].

    PubMed

    Zhang, Ai-Li; Deng, Fang-Fang; Zhou, Ji-Ti; Jin, Ruo-Fei; Liang, Li-Li; Zhang, Guo-Liang

    2009-07-15

    Fly ash was investigated as a catalyst in the oxidation of p-nitro phenol (PNP) with H2O2 at ambient temperature and pressure. The physical and chemical properties of fly ash were analyzed. The effects of fly ash composition, pretreatment methods and other parameters (such as dosage, pH, reaction time and oxidant concentration) on PNP removal rate were studied. It was found that fly ash with larger specific surface area and higher carbon content demonstrated higher catalytic activity. Heat treatment (350 degrees C) on fly ash could effectively improve the PNP removal rate. With an initial H2O2 concentration of 200 mg/L, 60 g/L heat-treated fly ash could remove 62.38% PNP at 25 degrees C, pH = 2. Specific surface area, carbon and metal oxide contents of fly ash play an important role in the catalysis process. The adsorption control experiment showed that adsorption was the main effect (65.97%) in the catalysis process. The activity of the catalyst gradually increased during its reuse. The PNP removal rate could reach 82.47% and 98.72% in the second and third rounds of reuse, respectively. The removal rate remained at about 99% in the rest 9 rounds of reuse. And the catalytic properties decreased after 12 times uses.

  12. In-situ non-disruptive cleaning of Ge(100) using H2O2(g) and atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Kaufman-Osborn, Tobin; Kiantaj, Kiarash; Chang, Chorng-Ping; Kummel, Andrew C.

    2014-12-01

    In-situ gas phase cleaning of the Ge(100) surface was studied at the atomic level using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) while chemical analysis of the surface was performed using X-ray photoelectron spectroscopy (XPS). High purity H2O2(g) dosing removed carbon contamination from an air exposed Ge(100) sample. The oxide formed via H2O2(g) dosing was subsequently removed via either atomic hydrogen exposure at 300 °C or 550-700 °C annealing. STM imaging showed an air exposed Ge(100) surface after H2O2(g) dosing and 600-700 °C annealing produced a flat and ordered surface while STS verified the density of states (DOS) is equal to that of a Ge(100) surface which has been cleaned via sputter (500 °C) and annealing (700 °C). Combining H2O2(g) with atomic hydrogen dosing or annealing removed carbon via oxidation and oxygen via thermal desorption or reduction from an air exposed Ge(100) surface.

  13. Atomic imaging of nucleation of trimethylaluminum on clean and H2O functionalized Ge(100) surfaces

    NASA Astrophysics Data System (ADS)

    Lee, Joon Sung; Kaufman-Osborn, Tobin; Melitz, Wilhelm; Lee, Sangyeob; Delabie, Annelies; Sioncke, Sonja; Caymax, Matty; Pourtois, Geoffrey; Kummel, Andrew C.

    2011-08-01

    The direct reaction of trimethylaluminum (TMA) on a Ge(100) surface and the effects of monolayer H2O pre-dosing were investigated using ultrahigh vacuum techniques, such as scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). At room temperature (RT), a saturation TMA dose produced 0.8 monolayers (ML) of semi-ordered species on a Ge(100) surface due to the dissociative chemisorption of TMA. STS confirmed the chemisorption of TMA passivated the bandgap states due to dangling bonds. By annealing the TMA-dosed Ge surface, the STM observed coverage of TMA sites decreased to 0.4 ML at 250 °C, and to 0.15 ML at 450 °C. XPS analysis showed that only carbon content was reduced during annealing, while the Al coverage was maintained at 0.15 ML, consistent with the desorption of methyl (-CH3) groups from the TMA adsorbates. Conversely, saturation TMA dosing at RT on the monolayer H2O pre-dosed Ge(100) surface followed by annealing at 200 °C formed a layer of Ge-O-Al bonds with an Al coverage a factor of two greater than the TMA only dosed Ge(100), consistent with Ge-OH activation of TMA chemisorption and Ge-H blocking of CH3 chemisorption. The DFT shows that the reaction of TMA has lower activation energy and is more exothermic on Ge-OH than Ge-H sites. It is proposed that the H2O pre-dosing enhances the concentration of adsorbed Al and forms thermally stable Ge-O-Al bonds along the Ge dimer row which could serve as a nearly ideal atomic layer deposition nucleation layer on Ge(100) surface.

  14. 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.

  15. 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.

  16. 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).

  17. 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

  18. 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.

  19. Volumetric Properties and Fluid Phase Equilibria of CO2 + H2O

    SciTech Connect

    Capobianco, Ryan; Gruszkiewicz, Miroslaw {Mirek} S; Wesolowski, David J; Cole, David R; Bodnar, Robert

    2013-01-01

    The need for accurate modeling of fluid-mineral processes over wide ranges of temperature, pressure and composition highlighted considerable uncertainties of available property data and equations of state, even for the CO2 + H2O binary system. In particular, the solubility, activity, and ionic dissociation equilibrium data for the CO2-rich phase, which are essential for understanding dissolution/precipitation, fluid-matrix reactions, and solute transport, are uncertain or missing. In this paper we report the results of a new experimental study of volumetric and phase equilibrium properties of CO2 + H2O, to be followed by measurements for bulk and confined multicomponent fluid mixtures. Mixture densities were measured by vibrating tube densimetry (VTD) over the entire composition range at T = 200 and 250 C and P = 20, 40, 60, and 80 MPa. Initial analysis of the mutual solubilities, determined from volumetric data, shows good agreement with earlier results for the aqueous phase, but finds that the data of Takenouchi and Kennedy (1964) significantly overestimated the solubility of water in supercritical CO2 (by a factor of more than two at 200 C). Resolving this well-known discrepancy will have a direct impact on the accuracy of predictive modeling of CO2 injection in geothermal reservoirs and geological carbon sequestration through improved equations of state, needed for calibration of predictive molecular-scale models and large-scale reactive transport simulations.

  20. 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.

  1. Formation and removal of genotoxic activity during UV/H(2)O(2)-GAC treatment of drinking water.

    PubMed

    Heringa, M B; Harmsen, D J H; Beerendonk, E F; Reus, A A; Krul, C A M; Metz, D H; Ijpelaar, G F

    2011-01-01

    The objective of this study was to determine the genotoxic activity of water after UV/H(2)O(2) oxidation and GAC filtration. Pre-treated surface water from three locations was treated with UV/H(2)O(2) with medium pressure (MP) lamps and passed through granulated activated carbon (GAC). Samples taken before and after each treatment step were extracted and concentrated by solid phase extraction (SPE) and analyzed for genotoxicity using the Comet assay with HepG2 cells and the Ames II assay. The Comet assay showed no genotoxic response in any of the samples. In the Ames II, no genotoxic response was obtained with the TAMix (a mix of six strains), but the TA98 strain showed an increase in genotoxic activity after MP-UV/H(2)O(2) for all three locations. GAC post treatment effectively reduced the activities to control levels at two of the three locations and to below the level of the pre-treated water at one site. The results indicate that UV/H(2)O(2) treatment may lead to the formation of genotoxic by-products, which can be removed by subsequent GAC filtration.

  2. 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.

  3. 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.

  4. Degradation of dyehouse effluent containing C.I. Direct Blue 199 by processes of ozonation, UV/H2O2 and in sequence of ozonation with UV/H2O2.

    PubMed

    Shu, Hung-Yee

    2006-05-20

    The decolorization and mineralization of cotton dyeing effluent containing C.I. Direct Blue 199 (DB 199) by advanced oxidation processes (AOPs) such as ozonation, UV/H(2)O(2), and in sequence of ozonation with UV/H(2)O(2) processes were evaluated in this study. By ozonation alone, the color removal was almost 100% for DB 199 and greater than 80% for dye bath effluent rapidly within 5 and 15 min, respectively. Meanwhile, the reduction of total organic carbon (TOC) was about 60% for DB 199 and almost no change for dye bath effluent, respectively due to incomplete mineralization. On the other hand, by UV/H(2)O(2) alone, the color removing not only took longer time but obtained lower removal efficiencies for DB 199 and dye bath effluent about 80% and 95% in 30 and 120 min, respectively. Nevertheless, it was more effective than ozonation for TOC removal while about 75% and 80% in 30 and 120 min, respectively. As a result, this study conducted the combination with the above two processes in order to shorten time demand as well as the higher removal efficiencies of both color and TOC simultaneously. Thus, the sequence process was designed to begin with ozonation to rapidly remove color proficiently, following by UV/H(2)O(2) in order to promptly remove remaining TOC efficiently. The successful process design by sequence of ozonation with UV/H(2)O(2) has proved the significant improvement for the removal of both color and TOC in dye bath effluent shortly. Besides, the lab prepared dye solution was substantially much easier to be decolorized than field dye bath effluent so that the lab results were utilized to design the further applications of pilot or full scale.

  5. Black Carbon, Aerosols, and the Tooth Fairy

    NASA Astrophysics Data System (ADS)

    Buseck, P. R.; Adachi, K.; Posfai, M.

    2012-12-01

    Black carbon (BC) is widely cited in the atmospheric literature as a major aerosol particle type with significant effects on climate warming. Several analytical techniques are used for its determination, primarily through optical absorption measurements. A recently developed and widely used method is single particle soot photometry (SP2). During attempts to obtain reliable BC samples for study using transmission electron microscopy (TEM), it became apparent that no such samples exist. Instead, surrogate materials such as graphite, fullerene, Aquadag, and perhaps other things are used as calibration standards. It became rapidly evident that BC is an inferred rather than actual, identifiable substance with distinct material properties other than its absorption spectrum and refractory character (accounting for the subset of refractory black carbon, or rBC). Since climate effects depend on optical properties, and these are estimated for BC, it may not be critical at this time whether or not it is a discrete material. However, the same term is also used by other environmental communities for things that are distinctly different. Such imprecision in terms can lead to unnecessary confusion. The situation is summarized in the Table. We propose that 1) the term BC should be restricted to light-absorbing refractory carbonaceous matter of uncertain character and 2) the uncertainty be stated explicitly. We also propose a more precise definition for soot as a specific material, which we call ns-soot, where "ns" refers to carbon nanospheres. We define ns-soot as particles that consist of nanospheres, typically with diameters <100 nm, that possess distinct structures of concentrically wrapped, graphene-like layers of carbon and with grape-like (acinoform) morphologies.;

  6. Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

    1993-01-01

    Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

  7. The effect of UV/H2O2 treatment on biofilm formation potential.

    PubMed

    Metz, D H; Reynolds, K; Meyer, M; Dionysiou, D D

    2011-01-01

    Greater Cincinnati Water Works (GCWW) evaluated the efficacy of ultraviolet light/hydrogen peroxide advanced oxidation (UV/H(2)O(2)) for reducing trace organic contaminants in natural water with varying water qualities. A year-long UV/H(2)O(2) pilot study was conducted to examine a variety of seasonal and granular activated carbon (GAC) breakthrough conditions. The UV pilot-scale reactors were set to consistently achieve 80% atrazine degradation, allowing comparison of low pressure (LP) and medium pressure (MP) lamp technologies for by-product formation. Because hydroxyl radicals react non-selectively with organic compounds, unintended by-product formation occurred. Total assimilable organic carbon (AOC) concentration increased through the reactors from 14 to 33% on average, depending on water quality. Natural organic matter (NOM) contains the precursors for AOC production, so when post-GAC water (versus conventionally treated water) served as reactor influent, less AOC was produced. No appreciable difference in AOC concentration was observed between LP and MP UV reactors. The Spirillum strain NOX fraction of the AOC increased from 50 to 65% on average, depending on the quality of the water. The increase in this fraction of AOC occurred because oxidation of NOM yielded smaller more assimilable organic compounds such as organic acids that are necessary for NOX growth. The Pseudomonas fluorescens strain P17 AOC concentration increased only when conventionally treated plant water was used as pilot influent. This organism thrives in waters of differing organic energy sources, but does not thrive well in carboxylic acids alone. The CONV water had more overall TOC that could contribute to higher P17 AOC counts. Biofilm coupon studies indicated that biofilms with greater heterotrophic plate counts were observed in the granular activated carbon (GAC) effluent streams receiving UV/H(2)O(2) pre-treatment. Biofilm coupon studies additionally indicated that the effluent stream

  8. 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.

  9. Variations of the HDO/H2O ratio in the martian atmosphere and loss of water from Mars

    NASA Astrophysics Data System (ADS)

    Krasnopolsky, Vladimir A.

    2015-09-01

    Ground-based spatially-resolved high-resolution spectroscopy is currently the only means to observe variations of the HDO/H2O ratio in the martian atmosphere. These observations are difficult because telluric water exceeds the martian water by two orders of magnitude even at the excellent conditions of NASA IRTF. Our observations of HDO and H2O at the close wavenumbers of 2722 and 2994 cm-1, respectively, cover six martian seasons in the period from 2007 to 2014. Infrared properties of water ice and dust are rather similar at these wavenumbers, and the HDO and H2O line equivalent widths are comparable; therefore effects of aerosol absorption and scattering significantly cancel out in the HDO/H2O ratios. These ratios are rather constant in wide latitude ranges at four observing sessions, in accord with the GCM model by Montmessin et al. (Montmessin, F., Fouchet, T., Forget, F. [2005]. J. Geophys. Res. 110, E03006). Results of two other sessions demonstrate significant deviations from the model predictions and strong correlation between HDO/H2O and temperature at ∼7 km above the surface with correlation coefficients of 0.9. The observed global-mean HDO/H2O ratio is 4.6 ± 0.7 times the terrestrial ratio, the ratio in vapor released by the north polar cap is 6.2 ± 1.4, and the ratio in the north polar cap ice is 7.1 ± 1.6. Updating the model of isotope fractionation in hydrogen escape by Krasnopolsky and Feldman (Krasnopolsky, V.A., Feldman, P.D. [2001]. Science 294, 1914-1917), 60 m of the global water layer was lost in the last 4 Byr and more than 1200 m could be lost by hydrodynamic escape of H2 released in the reaction between water and iron. Variations of telluric D/H above Mauna Kea (Hawaii, elevation 4.2 km) are by-products of our observations; D/H varies from 0.4 to 0.9 in nine observations with a mean D/H = 0.67.

  10. Kinetics and thermodynamics of H2O dissociation and CO oxidation on the Pt/WC (0001) surface: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Liang, Yuanyuan; Chen, Litao; Ma, Chun'an

    2017-02-01

    Adsorptions of H2O and CO on the Pt/WC(0001) [pseudomorphic platinum monolayer on WC(0001)] surface have been studied with periodical slab model by PW91 approach of GGA within the framework of density functional theory (DFT). The reaction pathways and mechanisms of H2O dissociation and CO oxidation are also investigated. For a comparison, similar calculation scheme are performed on the Pt (111) surface as well. The adsorption energies of H2O and CO on both concerned surfaces suggest that H2O binds preferentially on the Pt/WC (0001) surface, while CO prefers the metal surface Pt (111), agreeing well with the experimental observation that the tungsten carbides based material is less susceptible to CO poisoning than platinum. The activation energies for the stepwise H2O dehydrogenation reaction show that the progress of H2O dissociation is similar on the two surfaces; and coincidentally the oxidation of CO by surface hydroxyl is much more likely to occur than that by surface oxygen which comes up with the H2O dissociation. Although the activation barrier of H2O dissociation on the Pt/WC (0001) is similar to that on Pt (111), the key oxidant OH specials which play a key role in turning over surface carbon monoxide to carbon dioxide prefer the Pt/WC(0001) surface, and the improved CO oxidation reaction progress confirms that the Pt/WC surface is more CO-tolerant than the pure Pt. According to the electronic structure analysis we find that the increased CO tolerance is ascribed to the downshift of Pt d-band center because of the charge transfer from WC support to the coating surface.

  11. Graphene-amplified electrogenerated chemiluminescence of CdTe quantum dots for H2O2 sensing.

    PubMed

    Wang, Zhonghui; Song, Hongjie; Zhao, Huihui; Lv, Yi

    2013-01-01

    Electrogenerated chemiluminescence (ECL) of thiol-capped CdTe quantum dots (QDs) in aqueous solution was greatly enhanced by PDDA-protected graphene (P-GR) film that were used for the sensitive detection of H2 O2 . When the potential was cycled between 0 and -2.3 V, two ECL peaks were observed at -1.1 (ECL-1) and -1.4 V (ECL-2) in pH 11.0, 0.1 M phosphate buffer solution (PBS), respectively. The electron-transfer reaction between individual electrochemically-reduced CdTe nanocrystal species and oxidant coreactants (H2 O2 or reduced dissolved oxygen) led to the production of ECL-1. While mass nanocrystals packed densely in the film were reduced electrochemically, assembly of reduced nanocrystal species reacted with coreactants to produce an ECL-2 signal. ECL-1 showed higher sensitivity for the detection of H2 O2 concentrations than that of ECL-2. Further, P-GR film not only enhanced ECL intensity of CdTe QDs but also decreased its onset potential. Thus, a novel CdTe QDs ECL sensor was developed for sensing H2O2. Light intensity was linearly proportional to the concentration of H2 O2 between 1.0 × 10(-5) and 2.0 x 10(-7) mol L(-1) with a detection limit of 9.8 x 10(-8) mol L(-1). The P-GR thin-film modified glassy carbon electrode (GCE) displayed acceptable reproducibility and long-term stability.

  12. Volatile (H2O, CO2, Cl, S) budget of the Central American subduction zone

    NASA Astrophysics Data System (ADS)

    Freundt, A.; Grevemeyer, I.; Rabbel, W.; Hansteen, T. H.; Hensen, C.; Wehrmann, H.; Kutterolf, S.; Halama, R.; Frische, M.

    2014-02-01

    After more than a decade of multidisciplinary studies of the Central American subduction zone mainly in the framework of two large research programmes, the US MARGINS program and the German Collaborative Research Center SFB 574, we here review and interpret the data pertinent to quantify the cycling of mineral-bound volatiles (H2O, CO2, Cl, S) through this subduction system. For input-flux calculations, we divide the Middle America Trench into four segments differing in convergence rate and slab lithological profiles, use the latest evidence for mantle serpentinization of the Cocos slab approaching the trench, and for the first time explicitly include subduction erosion of forearc basement. Resulting input fluxes are 40-62 (53) Tg/Ma/m H2O, 7.8-11.4 (9.3) Tg/Ma/m CO2, 1.3-1.9 (1.6) Tg/Ma/m Cl, and 1.3-2.1 (1.6) Tg/Ma/m S (bracketed are mean values for entire trench length). Output by cold seeps on the forearc amounts to 0.625-1.25 Tg/Ma/m H2O partly derived from the slab sediments as determined by geochemical analyses of fluids and carbonates. The major volatile output occurs at the Central American volcanic arc that is divided into ten arc segments by dextral strike-slip tectonics. Based on volcanic edifice and widespread tephra volumes as well as calculated parental magma masses needed to form observed evolved compositions, we determine long-term (105 years) average magma and K2O fluxes for each of the ten segments as 32-242 (106) Tg/Ma/m magma and 0.28-2.91 (1.38) Tg/Ma/m K2O (bracketed are mean values for entire Central American volcanic arc length). Volatile/K2O concentration ratios derived from melt inclusion analyses and petrologic modelling then allow to calculate volatile fluxes as 1.02-14.3 (6.2) Tg/Ma/m H2O, 0.02-0.45 (0.17) Tg/Ma/m CO2, and 0.07-0.34 (0.22) Tg/Ma/m Cl. The same approach yields long-term sulfur fluxes of 0.12-1.08 (0.54) Tg/Ma/m while present-day open-vent SO2-flux monitoring yields 0.06-2.37 (0.83) Tg/Ma/m S. Input-output comparisons

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. X-Ray Irradiation of H2O + CO Ice Mixtures with Synchrotron Light

    NASA Astrophysics Data System (ADS)

    Jiménez-Escobar, A.; Chen, Y.-J.; Ciaravella, A.; Huang, C.-H.; Micela, G.; Cecchi-Pestellini, C.

    2016-03-01

    We irradiated a (4:1) mixture of water and carbon monoxide with soft X-rays of energies up to 1.2 keV. The experiments were performed using the spherical grating monochromator beamline at National Synchrotron Radiation Research Center in Taiwan. Both monochromatic (300 and 900 eV) and broader energy fluxes (250-1200 eV) were employed. During the irradiation, the H2O + CO mixture was ionized, excited, and fragmented, producing a number of reactive species. The composition of the ice has been monitored throughout both the irradiation and warm-up phases. We identified several products, which can be related through a plausible chemical reaction scheme. Such chemistry is initiated by the injection of energetic photoelectrons that produce multiple ionization events generating a secondary electron cascade. The results have been discussed in light of a model for protoplanetary disks around young solar-type stars.

  18. On the significant enhancement of the continuum-collision induced absorption in H2O+CO2 mixtures

    NASA Astrophysics Data System (ADS)

    Baranov, Yu. I.

    2016-05-01

    The IR spectra of water vapor-carbon dioxide mixtures as well as the spectra of pure gas samples have been recorded using a Fourier-transform infrared spectrometer at a resolution of 0.1 cm-1 in order to explore the effect of colliding CO2 and H2O molecules on their continuum absorptions. The sample temperatures were 294, 311, 325 and 339 K. Measurements have been conducted at several different water vapor partial pressures depending on the cell temperature. Carbon dioxide pressures were kept close to the three values of 103, 207 and 311 kPa (1.02, 2.04 and 3.07 atm). The path length used in the study was 100 m. It was established that, in the region around 1100 cm-1, the continuum absorption coefficient C H2 O + CO2 is about 20 times stronger than the water-nitrogen continuum absorption coefficient CH2O+N2. On the other hand, in the far wing region (2500 cm-1) of the ν3 CO2 fundamental band, the binary absorption coefficient CCO2+H2O appears to be about one order of magnitude stronger than the absorption coefficient CCO2+CO2 in pure carbon dioxide. The continuum interpretation and the main problem of molecular band shape formation are discussed in light of these experimental facts.

  19. Formation of submicron magnesite during reaction of natural forsterite in H2O-saturated supercritical CO2

    NASA Astrophysics Data System (ADS)

    Qafoku, Odeta; Hu, Jianzhi; Hess, Nancy J.; Hu, Mary Y.; Ilton, Eugene S.; Feng, Ju; Arey, Bruce W.; Felmy, Andrew R.

    2014-06-01

    Natural forsterite was reacted in bulk liquid water saturated with supercritical CO2 (scCO2) and scCO2 saturated with water at 35-80 °C and 90 atm. The solid reaction products were analyzed with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and confocal Raman spectroscopy. Two carbonate phases, nesquehonite (MgCO3·3H2O) and magnesite (MgCO3), were identified with the proportions of the two phases depending on experimental conditions. In liquid water saturated with scCO2, nesquehonite was the dominant carbonate phase at 35-80 °C with only a limited number of large, micron size magnesite particles forming at the highest temperature, 80 °C. In contrast, in scCO2 saturated with H2O magnesite formation was identified at all three temperatures: 35, 50, and 80 °C. Magnesite was the dominant carbonation reaction product at 50 and 80 °C, but nesquehonite was dominant at 35 °C. The magnesite particles formed under scCO2 saturated with H2O conditions exhibited an extremely uniform submicron grain-size and nearly identical rhombohedral morphologies at all temperatures. The distribution and form of the particles were not consistent with nucleation and growth on the forsterite surface.

  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. 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.

  5. 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.

  6. Microwave-enhanced UV/H2O2 degradation of an azo dye (tartrazine): optimization, colour removal, mineralization and ecotoxicity.

    PubMed

    Parolin, Fernanda; Nascimento, Ulisses Magalhães; Azevedo, Eduardo Bessa

    2013-01-01

    This study optimizes two factors, pH and initial [H2O2], in the ultraviolet (UV)/H2O2/microwave (MW) process through experimental design and assesses the effect of MWs on the colour removal of an azo-dye (tartrazine) solution that was favoured by an acidic pH. The estimated optimal conditions were: initial [H2O2] = 2.0 mmol L(-1) and pH = 2.6, at 30 +/- 2 degrees C. We obtained colour removals of approximately 92% in 24 min of irradiation (EDL, 244.2 W), following zero order kinetics: k = (3.9 +/- 0.52) x 10(-2) a.u. min(-1) and R2 = 0.989. Chemical and biological oxygen demand were significantly removed. On the other hand, the carbon content, biodegradability and ecotoxicity (Lactuca sativa) remained approximately the same. The UV/H2O2/MW process was shown to be eight times faster than other tested processes (MW, H2O2, H2O2/MW, and UV/MW).

  7. Impact of UV-H2O2 Advanced Oxidation and Aging Processes on GAC Capacity for the Removal of Cyanobacterial Taste and Odor Compounds.

    PubMed

    Zamyadi, Arash; Sawade, Emma; Ho, Lionel; Newcombe, Gayle; Hofmann, Ron

    2015-01-01

    Cyanobacteria and their taste and odor (T&O) compounds are a growing concern in water sources globally. Geosmin and 2-methylisoborneol (MIB) are the most commonly detected T&O compounds associated with cyanobacterial presence in drinking water sources. The use of ultraviolet and hydrogen peroxide (H2O2) as an advanced oxidation treatment for T&O control is an emerging technology. However, residual H2O2 (>80% of the initial dose) has to be removed from water prior final disinfection. Recently, granular activated carbon (GAC) is used to remove H2O2 residual. The objective of this study is to assess the impact of H2O2 quenching and aging processes on GAC capacity for the removal of geosmin and MIB. Pilot columns with different types of GAC and presence/absence of H2O2 have been used for this study. H2O2 removal for the operational period of 6 months has no significant impact on GAC capacity to remove the geosmin and MIB from water.

  8. Determination of H2O and CO2 concentrations in fluid inclusions in minerals using laser decrepitation and capacitance manometer analysis

    NASA Technical Reports Server (NTRS)

    Yonover, R. N.; Bourcier, W. L.; Gibson, E. K.

    1985-01-01

    Water and carbon dioxide concentrations within individual and selected groups of fluid inclusions in quartz were analyzed by using laser decrepitation and quantitative capacitance manometer determination. The useful limit of detection (calculated as ten times the typical background level) is about 5 x 10(-10) mol of H2O and 5 x 10(-11) mol of CO2; this H2O content translates into an aqueous fluid inclusion approximately 25 micrometers in diameter. CO2/H2O determinations for 38 samples (100 separate measurements) have a range of H2O amounts of 5.119 x 10(-9) to 1.261 x 10(-7) mol; CO2 amounts of 7.216 x 10(-10) to 1.488 x 10(-8) mol, and CO2/H2O mole ratios of 0.011 to 1.241. Replicate mole ratio determinations of CO2/H2O for three identical (?) clusters of inclusions in quartz have average mole ratios of 0.0305 +/- 0.0041 1 sigma. Our method offers much promise for analysis of individual fluid inclusions, is sensitive, is selective when the laser energy is not so great as to melt the mineral (laser pits approximately 50 micrometers in diameter), and permits rapid analysis (approximately 1 h per sample analysis).

  9. Electrocatalytic reduction of O 2 and H 2O 2 by adsorbed cobalt tetramethoxyphenyl porphyrin and its application for fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Liu, Hansan; Zhang, Lei; Zhang, Jiujun; Ghosh, Dave; Jung, Joey; Downing, Bruce W.; Whittemore, Earl

    In this paper, the mechanism and kinetics of oxygen and hydrogen peroxide electrochemical reduction that is catalyzed by an adsorbed cobalt tetramethoxyphenyl porphyrin (CoTMPP) on a graphite electrode were investigated using cyclic voltammetry (CV) and the rotating disk electrode (RDE) technique. The temperature and anion effects on O 2 and H 2O 2 electroreduction processes were also studied. The pH dependencies of cobalt redox centers, and oxygen and hydrogen peroxide reductions were measured for the purpose of exploring the reaction mechanism. In neutral solutions, the oxygen reduction reaction was observed to be a two-electron process, producing H 2O 2 in the low potential polarization range. In the high potential polarization range, an overall four-electron reduction of O 2 to H 2O was found to be the dominating process. The kinetic parameters obtained from the RDE experiments indicate that in a neutral solution, the reduction rate at the step from H 2O 2 to H 2O is faster than that seen from O 2 to H 2O 2. Carbon particle-based air cathodes catalyzed by CoTMPP were fabricated for metal-air fuel cell application. The obtained non-noble catalyst content cathodes show considerably improved performance and stability.

  10. Impact of UV–H2O2 Advanced Oxidation and Aging Processes on GAC Capacity for the Removal of Cyanobacterial Taste and Odor Compounds

    PubMed Central

    Zamyadi, Arash; Sawade, Emma; Ho, Lionel; Newcombe, Gayle; Hofmann, Ron

    2015-01-01

    Cyanobacteria and their taste and odor (T&O) compounds are a growing concern in water sources globally. Geosmin and 2-methylisoborneol (MIB) are the most commonly detected T&O compounds associated with cyanobacterial presence in drinking water sources. The use of ultraviolet and hydrogen peroxide (H2O2) as an advanced oxidation treatment for T&O control is an emerging technology. However, residual H2O2 (>80% of the initial dose) has to be removed from water prior final disinfection. Recently, granular activated carbon (GAC) is used to remove H2O2 residual. The objective of this study is to assess the impact of H2O2 quenching and aging processes on GAC capacity for the removal of geosmin and MIB. Pilot columns with different types of GAC and presence/absence of H2O2 have been used for this study. H2O2 removal for the operational period of 6 months has no significant impact on GAC capacity to remove the geosmin and MIB from water. PMID:26462247

  11. Comparative study of diethyl phthalate degradation by UV/H2O2 and UV/TiO2: kinetics, mechanism, and effects of operational parameters.

    PubMed

    Song, Chengjie; Wang, Liping; Ren, Jie; Lv, Bo; Sun, Zhonghao; Yan, Jing; Li, Xinying; Liu, Jingjing

    2016-02-01

    The photodegradation of diethyl phthalate (DEP) by UV/H2O2 and UV/TiO2 is studied. The DEP degradation kinetics and multiple crucial factors effecting the clearance of DEP are investigated, including initial DEP concentration ([DEP]0), initial pH values (pH0), UV light intensity, anions (Cl(-), NO(3-), SO4 (2-), HCO3 (-), and CO3 (2-)), cations (Mg(2+), Ca(2+), Mn(2+), and Fe(3+)), and humic acid (HA). Total organic carbon (TOC) removal is tested by two treatments. And, cytotoxicity evolution of DEP degradation intermediates is detected. The relationship between molar ratio ([H2O2]/[DEP] or [TiO2]/[DEP]) and degradation kinetic constant (K) is also studied. And, the cytotoxicity tests of DEP and its degradation intermediates in UV/H2O2 and UV/TiO2 treatments are researched. The DEP removal efficiency of UV/H2O2 treatment is higher than UV/TiO2 treatment. The DEP degradation fitted a pseudo-first-order kinetic pattern under experimental conditions. The K linearly related with molar ratio in UV/H2O2 treatment while nature exponential relationship is observed in the case of UV/TiO2. However, K fitted corresponding trends better in H2O2 treatment than in TiO2 treatment. The Cl(-) is in favor of the DEP degradation in UV/H2O2 treatment; in contrast, it is disadvantageous to the DEP degradation in UV/TiO2 treatment. Other anions are all disadvantageous to the DEP degradation in two treatments. Fe(3+) promotes the degradation rates significantly. And, all other cations in question inhibit the degradation of DEP. HA hinders DEP degradation in two treatments. The intermediates of DEP degradation in UV/TiO2 treatment are less toxic to biological cell than that in UV/H2O2 treatment.

  12. 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

  13. Carbonaceous aerosols influencing atmospheric radiation: Black and organic carbon

    SciTech Connect

    Penner, J.E.

    1994-09-01

    Carbonaceous particles in the atmosphere may both scatter and absorb solar radiation. The fraction associated with the absorbing component is generally referred to as black carbon (BC) and is mainly produced from incomplete combustion processes. The fraction associated with condensed organic compounds is generally referred to as organic carbon (OC) or organic matter and is mainly scattering. Absorption of solar radiation by carbonaceous aerosols may heat the atmosphere, thereby altering the vertical temperature profile, while scattering of solar radiation may lead to a net cooling of the atmosphere/ocean system. Carbonaceous aerosols may also enhance the concentrations of cloud condensation nuclei. This paper summarizes observed concentrations of aerosols in remote continental and marine locations and provides estimates for the fine particle (D < 2.5 {mu}m) source rates of both OC and BC. The source rates for anthropogenic organic aerosols may be as large as the source rates for anthropogenic sulfate aerosols, suggesting a similar magnitude of direct forcing of climate. The role of BC in decreasing the amount of reflected solar radiation by OC and sulfates is discussed. The total estimated forcing depends on the source estimates for organic and black carbon aerosols which are highly uncertain. The role of organic aerosols acting as cloud condensation nuclei (CCN) is also described.

  14. The effect of CNTs on structures and catalytic properties of AuPd clusters for H2O2 synthesis.

    PubMed

    Yang, Hua-feng; Xie, Peng-yang; Yu, Hui-you; Li, Xiao-nian; Wang, Jian-guo

    2012-12-28

    The structures and catalytic properties of AuPd clusters supported on carbon nanotubes (CNTs) for H(2)O(2) synthesis have been investigated by means of density functional theory calculations. Firstly, the structures of AuPd clusters are strongly influenced by CNTs, in which the bottom layers are mainly composed of Pd and the top layers are a mix of Au and Pd due to the stronger binding of Pd than Au on CNTs. Especially, it is found that O(2) adsorption on the Pd/CNTs interfacial sites is much weaker than that on the only Pd sites, which is in contrast to transition metal oxide (for example TiO(2), Al(2)O(3), CeO(2)) supported metal clusters. Furthermore, Pd ensembles on the interfacial sites have far superior catalytic properties for H(2)O(2) formation than those away from CNT supports due to the changes in electronic structures caused by the CNTs. Therefore, our study provides a physical insight into the enhanced role of carbon supports in H(2)O(2) synthesis over supported AuPd catalysts.

  15. Change in haloacetic acid formation potential during UV and UV/H2O2 treatment of model organic compounds.

    PubMed

    Sakai, Hiroshi; Autin, Olivier; Parsons, Simon

    2013-07-01

    Haloacetic acids (HAAs) are disinfection by-products produced by the chlorination of organic matter, including amino acids. Advanced oxidation processes are expected to be effective for the destruction of HAA precursors; however, recent studies have reported the possible failure of these processes to reduce HAA formation potential. This study examined HAA formation potential during the course of UV or UV/H2O2 treatment of three organic compounds: leucine, serine, and resorcinol. HAA formation potential decreased in the treatment of resorcinol, while the potential increased slightly in the treatment of serine and greatly increased for leucine. The chemical structure required for HAA formation was assumed to be produced during the course of UV/H2O2 treatment of leucine and serine. Also, H abstraction from the δ carbon was assumed to result from the initial degradation of leucine by the hydroxyl radical during the UV/H2O2 treatment. The hydroxyl radical may have further reacted with leucine moiety to shorten its carbon chain. This would have produced a chemical structure capable of forming HAA, thus increasing HAA formation potential.

  16. 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.

  17. 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.

  18. 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+).

  19. Monte Carlo simulations of high-pressure phase equilibria of CO2-H2O mixtures.

    PubMed

    Liu, Yang; Panagiotopoulos, Athanassios Z; Debenedetti, Pablo G

    2011-05-26

    Histogram-reweighting grand canonical Monte Carlo simulations were used to obtain the phase behavior of CO(2)-H(2)O mixtures over a broad temperature and pressure range (50 °C ≤ T ≤ 350 °C, 0 ≤ P ≤ 1000 bar). We performed a comprehensive test of several existing water (SPC, TIP4P, TIP4P2005, and exponential-6) and carbon dioxide (EPM2, TraPPE, and exponential-6) models using conventional Lorentz-Berthelot combining rules for the unlike-pair parameters. None of the models we studied reproduce adequately experimental data over the entire temperature and pressure range, but critical assessments were made on the range of T and P where particular model pairs perform better. Away from the critical region (T ≤ 250 °C), the exponential-6 model combination yields the best predictions for the CO(2)-rich phase, whereas the TraPPE/TIP4P2005 model combination provides the most accurate coexistence composition and pressure for the H(2)O-rich phase. Near the critical region (250 °C < T ≤ 350 °C), the critical points are not accurately estimated by any of the models studied, but the exponential-6 models are able to qualitatively capture the critical loci and the shape of the phase envelopes. Local improvements can be achieved at specific temperatures by introducing modification factors to the Lorentz-Berthelot combining rules, but the modified combining rule is still not able to achieve global improvements over the entire temperature and pressure range. Our work points to the challenge and importance of improving current atomistic models so as to accurately predict the phase behavior of this important binary mixture.

  20. 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

  1. 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 ...

  2. 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.

  3. 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...

  4. 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...

  5. 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.

  6. 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.

  7. 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.

  8. Ice - not just H2O (Louis Agassiz Medal Lecture)

    NASA Astrophysics Data System (ADS)

    Wolff, E. W.

    2009-04-01

    Many of the important properties and uses of ice that fascinate cryospheric scientists actually depend on impurities that are present: isotopic variants of water molecules, small amounts of soluble and insoluble material derived from the aerosol and gas phase, and the trace constituents of the air bubbles that make up around 10% of the volume of ice at atmospheric pressure. In this lecture, I will first discuss how these impurities, and their location within the ice structure, affect local properties of the ice such as the electrical conductivity and mechanical strength, which scale up to give ice sheets their geophysical properties. I will then consider how the concentrations of different impurities are used to give unique records of palaeoclimate and palaeoenvironmental properties, extending so far 800,000 years back in time. This will be illustrated particularly with data from the EPICA Dome C ice core. Bringing the presentation full circle (and towards Agassiz!), I will discuss how the data from ice cores and other palaeoclimatic archives are starting to lead us towards understanding of the causes of the most prominent feature of late Quaternary climate: the huge glacial/interglacial swings in temperature, that are accompanied by the waxing and waning, roughly every 100,000 years, of great northern hemisphere ice sheets.

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Hydrothermal phase equilibria in Ln 2O 3-H 2O-CO 2 systems . I. The lighter lanthanides

    NASA Astrophysics Data System (ADS)

    Tareen, J. A. K.; Kutty, T. R. N.

    1980-10-01

    Phase diagrams for Nd 2O 3-H 2O-CO 2 and Gd 2O 3-H 2O-CO 2 systems at 1500 atm are given along with the results of selected runs in La, Sm and Eu systems. The stable phases in systems of La and Nd, are Ln(OH)CO 3-B, Ln 2O 2CO 3-II and LnOOH, in addition to the Ln(OH) 3 phase at extremely low partial pressures of CO 2 in the system. The systems become more and more complex with decreasing ionic radi and the number of stable carbonate phases increases. Ln 2(CO 3) 3 · 3H 2O orthorhombic (tengerate-like phase) is stable from Sm to Gd in addition to the other phases. The Gd(OH)CO 3-A (ancylite-like phase) is hydrothermally stable at XCO 2 ⩾ 0.5 while its hexagonal polymorph, Gd(OH)CO 3-B is stable at low partial pressures of CO 2 in the system.

  1. Cobalt ferrite nanoparticles decorated on exfoliated graphene oxide, application for amperometric determination of NADH and H2O2.

    PubMed

    Ensafi, Ali A; Alinajafi, Hossein A; Jafari-Asl, M; Rezaei, B; Ghazaei, F

    2016-03-01

    Here, cobalt ferrite nanohybrid decorated on exfoliated graphene oxide (CoFe2O4/EGO) was synthesized. The nanohybrid was characterized by different methods such as X-ray diffraction spectroscopy, scanning electron microscopy, energy dispersive X-ray diffraction microanalysis, transmission electron microscopy, FT-IR, Raman spectroscopy and electrochemical methods. The CoFe2O4/EGO nanohybrid was used to modify glassy carbon electrode (GCE). The voltammetric investigations showed that CoFe2O4/EGO nanohybrid has synergetic effect towards the electro-reduction of H2O2 and electro-oxidation of nicotinamide adenine dinucleotide (NADH). Rotating disk chronoamperometry was used for their quantitative analysis. The calibration curves were observed in the range of 0.50 to 100.0 μmol L(-1) NADH and 0.9 to 900.0 μmol L(-1) H2O2 with detections limit of 0.38 and 0.54 μmol L(-1), respectively. The repeatability, reproducibility and selectivity of the electrochemical sensor for analysis of the analytes were studied. The new electrochemical sensor was successfully applied for the determination of NADH and H2O2 in real samples with satisfactory results.

  2. In situ Immobilization of Copper Nanoparticles on Polydopamine Coated Graphene Oxide for H2O2 Determination

    PubMed Central

    Liu, Yingzhu; Han, Yanwei; Chen, Rongsheng; Zhang, Haijun; Liu, Simin; Liang, Feng

    2016-01-01

    Nanostructured electrochemical sensors often suffer from irreversible aggregation and poor adhesion to the supporting materials, resulting in reduced sensitivity and selectivity over time. We describe a versatile method for fabrication of a H2O2 sensor by immobilizing copper nanoparticles (Cu NPs; 20 nm) on graphene oxide (GO) sheets via in-situ reduction of copper(II) on a polydopamine (PDA) coating on a glassy carbon electrode. The PDA film with its amino groups and catechol groups acts as both a reductant and an adhesive that warrants tight bonding between the Cu NPs and the support. The modified electrode, best operated at a working voltage of −0.4 V (vs. Ag/AgCl), has a linear response to H2O2 in the 5 μM to 12 mM concentration range, a sensitivity of 141.54 μA∙mM‾1∙cm‾2, a response time of 4 s, and a 1.4 μM detection limit (at an S/N ratio of 3). The sensor is highly reproducible and selective (with minimal interference to ascorbic acid and uric acid). The method was applied to the determination of H2O2 in sterilant by the standard addition method and gave recoveries between 97% and 99%. PMID:27380524

  3. The correlation between HCN/H2O flux ratios and disk mass: evidence for protoplanet formation

    NASA Astrophysics Data System (ADS)

    Rose, Caitlin; Salyk, Colette

    2017-01-01

    We analyze hydrogen cyanide (HCN) and water vapor flux ratios in protoplanetary disks as a way to trace planet formation. Analyzing only disks in the Taurus molecular cloud, Najita et al. (2013) found a tentative correlation between protoplanetary disk mass and the HCN/H2O line flux ratio in Spitzer-IRS emission spectra. They interpret this correlation to be a consequence of more massive disks forming planetesimals more efficiently than smaller disks, as the formation of large planetesimals may lock up water ice in the cool outer disk region and prevent it from migrating, drying out the inner disk. The sequestering of water (and therefore oxygen) in the outer disk may also increase the carbon-to- oxygen ratio in the inner disk, leading to enhanced organic molecule (e.g. HCN) emission. To confirm this trend, we expand the Najita et al. sample by calculating HCN/H2O line flux ratios for 8 more sources with known disk masses from clusters besides Taurus. We find agreement with the Najita et al. trend, suggesting that this is a widespread phenomenon. In addition, we find HCN/H2O line flux ratios for 17 more sources that await disk mass measurements, which should become commonplace in the ALMA era. Finally, we investigate linear fits and outliers to this trend, and discuss possible causes.

  4. Rapid synthesis of ethyl cellulose supported platinum nanoparticles for the non-enzymatic determination of H2O2.

    PubMed

    Karthik, Raj; Karikalan, Natarajan; Chen, Shen-Ming

    2017-05-15

    Cellulose derivatives are one of the carbohydrate polymers which received a great interest in the construction of nanostructured materials. Particularly, the ethyl cellulose provides an enormous support to the metal nanoparticles. To the best of our knowledge, this is the first time report for the simple and rapid synthesis of ethyl cellulose (EC) supported platinum nanoparticles (PtNPs) for the determination of non-enzymatic hydrogen peroxide (H2O2). The PtNPs/EC composite was confirmed by various characterizations such as fourier transform infra-red spectra, energy dispersive X-ray spectra, field emission scanning electron microscope and cyclic voltammetry. Further, the PtNPs/EC composite modified glassy carbon electrode (GCE) was successfully determined the H2O2 with the linear concentration range from 0.05μM to 2.22mM and the lowest detection limit of 0.01μM. Moreover, the PtNPs/EC/GCE sensor electrode manifested an acceptable sensitivity, selectivity and reproducibility. In addition, we have determined the H2O2 in contact lens solution and human blood serum samples.

  5. A robust one-compartment fuel cell with a polynuclear cyanide complex as a cathode for utilizing H2O2 as a sustainable fuel at ambient conditions.

    PubMed

    Yamada, Yusuke; Yoneda, Masaki; Fukuzumi, Shunichi

    2013-08-26

    A robust one-compartment H2O2 fuel cell, which operates without membranes at room temperature, has been constructed by using a series of polynuclear cyanide complexes that contain Fe, Co, Mn, and Cr as cathodes, in sharp contrast to conventional H2 and MeOH fuel cells, which require membranes and high temperatures. A high open-circuit potential of 0.68 V was achieved by using Fe3[{Co(III)(CN)6}2] on a carbon cloth as the cathode and a Ni mesh as the anode of a H2O2 fuel cell by using an aqueous solution of H2O2 (0.30  M, pH 3) with a maximum power density of 0.45 mW cm(-2). The open-circuit potential and maximum power density of the H2O2 fuel cell were further increased to 0.78 V and 1.2 mW cm(-2), respectively, by operation under these conditions at pH 1. No catalytic activity of Co3[{Co(III)(CN)6}2] and Co3[{Fe(III)(CN)6}2] towards H2O2 reduction suggests that the N-bound Fe ions are active species for H2O2 reduction. H2O2 fuel cells that used Fe3[{Mn(III)(CN)6}2] and Fe3[{Cr(III)(CN)6}2] as the cathode exhibited lower performance compared with that using Fe3[{Co(III)(CN)6}2] as a cathode, because ligand isomerization of Fe3[{M(III)(CN)6}2] into (FeM2)[{Fe(II)(CN)6}2] (M = Cr or Mn) occurred to form inactive Fe-C bonds under ambient conditions, whereas no ligand isomerization of Fe3[{Co(III)(CN)6}2] occurred under the same reaction conditions. The importance of stable Fe(2+)-N bonds was further indicated by the high performance of the H2O2 fuel cells with Fe3[{Ir(III)(CN)6}2] and Fe3[{Rh(III)(CN)6}2], which also contained stable Fe(2+)-N bonds. The stable Fe(2+)-N bonds in Fe3[{Co(III)(CN)6}2], which lead to high activity for the electrocatalytic reduction of H2O2, allow Fe3[{Co(III)(CN)6}2] to act as a superior cathode in one-compartment H2O2 fuel cells.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Comparison of H2O2/UV and heterogeneous photocatalytic processes for the degradation of dichloroacetic acid in water.

    PubMed

    Zalazar, C S; Satuf, M L; Alfano, O M; Cassano, A E

    2008-08-15

    A comparative study between two advanced oxidation technologies for pollutant degradation has been made. With the use of dichloroacetic acid (DCA) as the model pollutant, the reactions with hydrogen peroxide and UV radiation (H2O2/UV, 253.7 nm) and photocatalysis with titanium dioxide (TiO2/UV, 300-400 nm) are analyzed. Three criteria have been selected to compare the performances of both processes: (i) the percentage conversion of DCA and TOC (total organic carbon) at a fixed reaction time; (ii) the quantum efficiency, employing the true radiation absorption rates for both activated species (H2O2 and TiO2); (iii) the specific energy consumption to degrade 50% of the initial TOC. The optimal molar concentration ratio of H2O2/DCA and the optimal catalyst concentration have been employed in the experiments. The results indicate that, under the optimal operating conditions, the H2O2/UV process exhibits, by a large difference, the best performance taking into account the above-mentioned criteria. Nevertheless, both systems show similar values of specific energy consumption when a thinner reactor is employed. These results cannot be safely extrapolated to other contexts if (i) other compounds of different structure are degraded and (ii) a different catalyst is used. Moreover, they were obtained under optimized conditions, and typical, real-life situations may render quite different results due to the robustness of the titanium dioxide operation. They should serve as an indication that, under the studied conditions, a much-improved catalyst performance must be achieved to parallel, with a heterogeneous process, a yield similar to the one obtained with the homogeneous system.

  11. Structure and dynamics of forsterite-scCO2/H2O interfaces as a function of water content

    NASA Astrophysics Data System (ADS)

    Kerisit, Sebastien; Weare, John H.; Felmy, Andrew R.

    2012-05-01

    Molecular dynamics (MD) simulations of forsterite surfaces in contact with supercritical carbon dioxide (scCO2) fluids of varying water content were performed to determine the partition of water between the scCO2 fluid and the mineral surface, the nature of CO2 and H2O bonding at the interface, and the regions of the interface that may be conducive to HCO3(2-x)- formation. Calculations of the free energy of the associative adsorption of water onto the (0 1 0) forsterite surface from the scCO2 phase indicated that the formation of a water film up to three-monolayer thick can be exothermic even for water contents below the water saturation concentration of the scCO2 fluid. In MD simulations of scCO2/H2O mixtures in contact with the (0 1 0) forsterite surface, H2O was found to readily displace CO2 at the surface and, therefore, CO2 directly contacted the surface only for water coverages below two monolayers. For thicker water films, a two-monolayer hydration layer formed that CO2 could not penetrate. The MD simulations thus suggest that, in the presence of sufficient water, HCO3(2-x)- formation occurs in the water films and not via direct reaction of CO2 with the forsterite surface. Simulations of the hydroxylated (0 1 0) surface and of the (0 1 1) surface suggested that this conclusion can be extended to forsterite surfaces with different surface structures and/or compositions. The density, diffusion, and degree of hydration of CO2 as well as the extent of CO2/H2O mixing at the interface were all predicted to depend strongly on the thickness of the water-rich film, i.e., on the water content of the scCO2 fluid.

  12. Structure and Dynamics of Forsterite-scCO2/H2O Interfaces as a Function of Water Content

    SciTech Connect

    Kerisit, Sebastien N.; Weare, John H.; Felmy, Andrew R.

    2012-05-01

    Molecular dynamics (MD) simulations of forsterite surfaces in contact with supercritical carbon dioxide (scCO2) fluids of varying water content were performed to determine the partition of water between the scCO2 fluid and the mineral surface, the nature of CO2 and H2O bonding at the interface, and the regions of the interface that may be conducive to HxCO3(2-x)- formation. Calculations of the free energy of the associative adsorption of water onto the (010) forsterite surface from the scCO2 phase indicated that the formation of a water film up to three-monolayer thick can be exothermic even for water contents below the water saturation concentration of the scCO2 fluid. In MD simulations of scCO2/H2O mixtures in contact with the (010) forsterite surface, H2O was found to readily displace CO2 at the surface and, therefore, CO2 directly contacted the surface only for water coverages below two monolayers. For thicker water films, a two-monolayer hydration layer formed that CO2 could not penetrate. Simulations of the hydroxylated (010) surface and of the (011) surface suggested that this conclusion can be extended to forsterite surfaces with different surface structures and/or compositions. The density, diffusion, and degree of hydration of CO2 as well as the extent of CO2/H2O mixing at the interface were all predicted to depend strongly on the thickness of the water-rich film, i.e., on the water content of the scCO2 fluid.

  13. 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.

  14. Martian Gullies: H2O or CO2 snow?

    NASA Astrophysics Data System (ADS)

    Yolanda, C.; Durand-Manterola, H. J.

    2007-05-01

    The theories proposed to try to explain the origin of the Martian gullies involve either liquid water, liquid carbon dioxide or flows of dry granular material. We propose another processes that can be favorable for the origin of the Martian gullies, with our model by gaseous fluidification of CO2. We propose that on the Martian slopes, CO2 snow and dust transported by winds, are accumulate. During the Martian spring, sublimation of carbonic snow starts because of heat and weigth of the frezze layer, causing that the material mixed its fluidifized and slide downslope by gravity. By experimental work with dry granular material, we simulated the development of the Martian gullies injecting air inside the granular material. We also present the characteristics of some terrestrial gullies forms at cold environment, sited at Nevado de Toluca Volcano near Toluca City, México. We compared them with some Martian gullies, to identify possible processes evolved in its formation. We measured the lengths of those Martian gullies and the range was from 24 meters to 1775 meters. Finally, we present results of our experimental work at laboratory with dry granular material and our field trip to Nevado de Toluca Volcano.

  15. Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol.

    PubMed

    Hicks, Raea K; Day, Douglas A; Jimenez, Jose L; Tolbert, Margaret A

    2016-11-01

    Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres. Key Words: Atmosphere-Early Earth-Planetary atmospheres-Carbon dioxide-Methane. Astrobiology 16, 822-830.

  16. Decolouration of H2SO4 leachate from phosphorus-saturated alum sludge using H2O2 and advanced oxidation processes in phosphorus recovery strategy.

    PubMed

    Zhao, X H; Zhao, Y Q

    2009-12-01

    As a part of attempt for phosphorus (P) recovery from P-saturated alum sludge, which was used as a low-cost P-adsorbent in treatment reed bed for wastewater treatment, decolouration of H(2)SO(4) leachate obtained from previous experiment, possessing a great deal of P, aluminum and red-brown coloured materials (RBCMs), by using H(2)O(2) and advanced oxidation processes (AOPs) was investigated. The use of H(2)O(2) and AOPs in the forms of Fenton (H(2)O(2)/Fe(2 +)) and photo-Fenton (UV/H(2)O(2)/Fe(2 +)) were tested. The changes in colour and total organic carbon (TOC) were taken place as a result of mineralization of RBCMs. The results revealed that all of these three processes examined were efficient. It was found that about 98% colour and 47% TOC can be removed under photo-Fenton treatment after 8 hours of UV irradiation.Correspondingly, the reaction rates of H(2)O(2) and Fenton systems were slow, but 100% colour and 59% TOC removal of H(2)O(2) process and 100% colour and 67% TOC reductions of Fenton process can be achieved after 72 hours of reaction. The changes of structure and molecular weight/size of RBCMs were also evaluated by HPLC and UV-vis spectroscopic analysis. From the results, some chromophores of RBCMs such as aromatic groups were appeared to be easily degraded to the smaller refractory components. Hence, based on the experimental results and considering the investment and expediency of operation, H(2)O(2) and Fenton oxidation could be suitable technologies for the treatment of the RBCMs derived from P-extraction stage by using H(2)SO(4) leaching.

  17. 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

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. Effect of CO2 on the Second Critical Endpoint in the System Peridotite-CO2-H2O (Invited)

    NASA Astrophysics Data System (ADS)

    Mibe, K.; Kawamoto, T.; Ono, S.

    2009-12-01

    Under high pressure and temperature conditions, it is known that aqueous fluid and hydrous silicate melt become completely miscible and form supercritical fluid in the system peridotite-H2O [Mibe et al., 2007 JGR]. Because some amounts of CO2 are thought to be present in the Earth’s interior, it is important to clarify the effect of CO2 on the second critical endpoint in the system peridotite-CO2-H2O in order to understand the magmatism and mass transport in the Earth’s mantle. Experiments were conducted using X-ray radiography technique together with Kawai-type double-stage multi-anvil high pressure apparatus (SPEED-1500) installed at SPring-8, Japan. Direct X-ray beam, which passes through the anvil gaps of SPEED-1500 and sample under high pressure, is observed with an X-ray camera. We used a sample container which is composed of a AuPd tube and a pair of single crystal diamond lids put on both ends of AuPd tube. The sample was prepared by mixing hydroxides, carbonates, silicate glass, and water. The molar ratio of H2O (XH2O = H2O/(H2O + CO2)) in the starting material is about 0.92 to 0.94. The experimental conditions are at pressures from 2.0 to 4.0 GPa and at temperatures up to about 1400 deg. C. Pressure is applied first, and then temperature is increased. In the experiments up to 3.5 GPa, both aqueous fluid and silicate melt were observed. Above 3.5 GPa, however, we could not distinguish two phases in the radiographic images, indicating that aqueous fluid and silicate melt can coexist up to 3.5 GPa and there is no difference between these two phases above 3.5 GPa. From these observations, it can be concluded that the second critical endpoint in the system peridotite-CO2-H2O occurs at around 3.5 GPa. Our previous results [Mibe et al., 2007 JGR] in the system peridotite-H2O (i.e., CO2-free system) showed that the second critical endpoint occurred at around 3.8 GPa. Therefore, it is revealed that the addition of CO2 to the system causes the reduction of

  8. 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.

  9. 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.

  10. 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.

  11. Post-treatment of biologically treated wastewater containing organic contaminants using a sequence of H2O2 based advanced oxidation processes: photolysis and catalytic wet oxidation.

    PubMed

    Rueda-Márquez, J J; Sillanpää, M; Pocostales, P; Acevedo, A; Manzano, M A

    2015-03-15

    In this paper the feasibility of a multi-barrier treatment (MBT) for the regeneration of synthetic industrial wastewater (SIWW) was evaluated. Industrial pollutants (orange II, phenol, 4-chlorophenol and phenanthrene) were added to the effluent of municipal wastewater treatment plant. The proposed MBT begins with a microfiltration membrane pretreatment (MF), followed by hydrogen peroxide photolysis (H2O2/UVC) and finishing, as a polishing step, with catalytic wet peroxide oxidation (CWPO) using granular activated carbon (GAC) at ambient conditions. During the microfiltration step (0.7 μm) the decrease of suspended solids concentration, turbidity and Escherichia coli in treated water were 88, 94 and 99%, respectively. Also, the effluent's transmittance (254 nm) was increased by 14.7%. Removal of more than 99.9% of all added pollutants, mineralization of 63% of organic compounds and complete disinfection of total coliforms were reached during the H2O2/UVC treatment step (H2O2:TOC w/w ratio = 5 and an UVC average dose accumulated by wastewater 8.80 WUVC s cm(-2)). The power and efficiency of the lamp, the water transmittance and photoreactor geometry are taken into account and a new equation to estimate the accumulated dose in water is suggested. Remaining organic pollutants with a higher oxidation state of carbon atoms (+0.47) and toxic concentration of residual H2O2 were present in the effluent of the H2O2/UVC process. After 2.3 min of contact time with GAC at CWPO step, 90 and 100% of total organic carbon and residual H2O2 were removed, respectively. Also, the wastewater toxicity was studied using Vibrio fischeri and Sparus aurata larvae. The MBT operational and maintenance costs (O&M) was estimated to be 0.59 € m(-3).

  12. 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.

  13. 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.

  14. Eddy Covariance measurements of stable CO2 and H2O isotopologues

    NASA Astrophysics Data System (ADS)

    Braden-Behrens, Jelka; Knohl, Alexander

    2015-04-01

    The analysis of the stable isotope composition of CO2 and H2O fluxes (such as 13C, 18O and 2H in H2O and CO2) has provided valuable insights into ecosystem gas exchange. The approach builds on differences in the isotope signature of different ecosystem components that are primarily caused by the preference for or the discrimination against respective isotope species by important processes within the ecosystem (e.g. photosynthesis or leaf water diffusion). With the ongoing development of laser spectrometric methods, fast and precise measurements of isotopologue mixing ratios became possible, hence also enabling Eddy Covariance (EC) based approaches to directly measure the isotopic composition of CO2 and H2Ov net fluxes on ecosystem scale. During an eight month long measurement campaign in 2015, we plan to simultaneously measure CO2 and H2Ov isotopologue fluxes using an EC approach in a managed beech forest in Thuringia, Germany. For this purpose, we will use two different laser spectrometers for high frequency measurements of isotopic compositions: For H2Ov measurements, we will use an off axis cavity output water vapour isotope analyser (WVIA, Los Gatos Research Inc.) with 5 Hz response; and for CO2 measurements, we will use a quantum cascade laser-based system (QCLAS, Aerodyne Research Inc.) with thermoelectrically cooled detectors and up to 10 Hz measurement capability. The resulting continuous isotopologue flux measurements will be accompanied by intensive sampling campaigns on the leaf scale: Water from leaf, twig, soil and precipitation samples will be analysed in the lab using isotope ratio mass spectrometry. During data analysis we will put a focus on (i) the influence of carbon and oxygen discrimination on the isotopic signature of respective net ecosystem exchange, (ii) on the relationship between evapotranspiration and leaf water enrichment, and (iii) on the 18O exchange between carbon dioxide and water. At present, we already carried out extensive

  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. 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.

  17. 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.

  18. Modeling of the solubility of a one-component H2O or CO2 fluid in silicate liquids

    NASA Astrophysics Data System (ADS)

    Papale, Paolo

    The modeling of the solubility of water and carbon dioxide in silicate liquids (flash problem) is performed by assuming mechanical, thermal, and chemical equilibrium between the liquid magma and the gas phase. The liquid phase is treated as a mixture of ten silicate components+H2O or CO2, and the gas phase as a pure H2O or CO2. A general model for the solubility of a volatile component in a liquid is adopted. This requires the definition of a mixing equation for the excess Gibbs free energy of the liquid phase and an appropriate reference state for the dissolved volatile. To constrain the model parameters and identify the most appropriate form of the solubility equations for each dissolved volatile, a large number of experimental solubility determinations (640 for H2O and 263 for CO2) have been used. These determinations cover a large region of the P-T-composition space of interest. The resultant water and carbon dioxide solubility models differ in that the water model is regular and isometric, and the carbon dioxide model is regular and non-isometric. This difference is consistent with the different speciation modalities of the two volatiles in the silicate liquids, producing a composition-independent partial molar volume of dissolved water and a composition-dependent partial molar volume of dissolved carbon dioxide. The H2O solubility model may be applied to natural magmas of virtually any composition in the P-T range 0.1 MPa-1 GPa and > 1000 K, whereas the CO2 solubility model may be applied to several GPa pressures. The general consistency of the water solubility data and their relatively large number as compared to the calibrated model parameters (11) contrast with the large inconsistencies of the carbon dioxide solubility determinations and their low number with respect to the CO2 model parameters (22). As a result, most of the solubility data in the database are reproduced within 10% of approximation in the case of water, and 30% in the case of carbon

  19. Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol

    NASA Astrophysics Data System (ADS)

    Hicks, Raea K.; Day, Douglas A.; Jimenez, Jose L.; Tolbert, Margaret A.

    2016-11-01

    Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres.

  20. Facile preparation of hexagonal WO3·0.33H2O/C nanostructures and its electrochemical properties for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Liu, Zhiwei; Li, Ping; Dong, Yuan; Wan, Qi; Zhai, Fuqiang; Volinsky, Alex A.; Qu, Xuanhui

    2017-02-01

    Nano-sized hexagonal WO3·0.33H2O/C is prepared by the solution combustion synthesis & hydrothermal method. This material has been used as the anode for high performance lithium-ion batteries for the first time. Carbon layer is uniformly coated on hexagonal WO3·0.33H2O nanoparticles. The samples are characterized by X-ray diffraction (XRD), thermal analysis (TG-DSC), Raman spectra, scanning and transmission electron microscopy (FESEM and TEM). Electrochemical properties are studied by cyclic voltammetry and galvanostatic charge/discharge cycling. Prepared WO3·0.33H2O/C electrode shows high and reversible capacity of 768 mAh g-1 after 200 cycles at 100 mA g-1, which is higher than the reported orthorhombic WO3·0.33H2O. The specific structure can provide efficient channels for transporting Li+ swiftly. Therefore, hexagonal WO3·0.33H2O/C shows a great potential as the anode material for lithium-ion batteries.

  1. 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

  2. Calculating CO2 and H2O eddy covariance fluxes from an enclosed gas analyzer using an instantaneous mixing ratio 2159

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Eddy covariance flux research has relied on open- or closed-path gas analyzers for producing estimates of net ecosystem exchange of carbon dioxide (CO2) and water vapor (H2O). The two instruments have had different challenges that have led to development of an enclosed design that is intended to max...

  3. 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.

  4. Updated H2SO4-H2O binary homogeneous nucleation look-up tables

    NASA Astrophysics Data System (ADS)

    Yu, Fangqun

    2008-12-01

    The calculated rates of H2SO4-H2O binary homogeneous nucleation (BHN), which is the only nucleation mechanism currently widely used in global aerosol models, are well known to have large uncertainties. Recently, we have reduced the uncertainties in the BHN rates on the basis of a kinetic quasi-unary nucleation (KQUN) model, by taking into account the measured bonding energetics of H2SO4 monomers with hydrated sulfuric acid dimers and trimers. The uncertainties were further reduced by using two independent measurements to constrain the equilibrium constants for monomer hydration. In this paper, we present updated BHN rate look-up tables derived from the improved KQUN model which can be used by anyone to obtain the BHN rates under given conditions. The look-up tables cover a wide range of key parameters that can be found in the atmosphere and laboratory studies, and their usage significantly reduces the computational costs of the BHN rate calculations, which is critical for multidimensional modeling. The look-up tables can also be used by those involved in experiments and field measurements to quickly assess the likeliness of BHN. For quick application, one can obtain the BHN rates and properties of critical clusters by browsing through the tables. A comparison of results based on the look-up tables with those from widely used classical BHN model indicates that, in addition to several orders of magnitude difference in nucleation rates, there also exists substantial difference in the predicted numbers of sulfuric acid molecules in the critical clusters and their dependence on key parameters.

  5. Study of H2O and CO in Martian atmosphere with PFS/MEX data

    NASA Astrophysics Data System (ADS)

    Sindoni, Giuseppe; Formisano, Vittorio

    2010-05-01

    In the history of the Mars exploration its atmosphere and planetary climatology has from time aroused particular interest. In the study of the minor gas abundance in the Martian CO2 atmosphere, the water vapour assumes particular importance, both because it is the most variable trace gas, and because it is involved in several processes characterizing the planetary atmosphere. The water vapour photolysis regulates the Martian atmosphere photochemistry, and so it is strictly bounded to the carbon monoxide. The CO study is very important for the so called "atmosphere stability problem" (the whole CO2 atmosphere should be destroyed in 6000 years by photolysis), solved by the theoretical modelling involving photochemical reactions in which the H2O and the CO gases are main characters. The Planetary Fourier Spectrometer (PFS) on board of ESA Mars Express (MEX) mission can probe the Mars atmosphere in the infrared spectral range between 200 and 2000 cm-1 (5-50 μm) with the Long wavelength channel (LWC) and between 1700 and 8000 cm-1 (1.2-5.8 μm) with the Short wavelength channel (SWC). Although there are several H2O and CO absorption bands in the spectral range covered by PFS, we chose to use the 3845 cm-1 (2.6 μm) band for the water vapour and the 4235 cm-1 (2.36 μm) band for the CO analysis, because these ranges are less affected by instrumental problems respect to other ones. The gaseous abundances are retrieved by using a particular algorithm developed for this purpose. The analysis procedure is based on the best fit between the measured averaged spectrum and a synthetic one appositely generated in each step of the fitting loop. The averaged water vapour mixing ratio results to be about 130 ppm, while the averaged carbon monoxide mixing ratio results to be about 1000 ppm, but with strong seasonal variations at high latitudes. The seasonal water vapour map reproduces very well the known seasonal water cycle. In the northern summer the water vapour and CO show a

  6. Optimization of an enclosed gas analyzer sampling system for measuring eddy covariance fluxes of H2O and CO2

    NASA Astrophysics Data System (ADS)

    Metzger, Stefan; Burba, George; Burns, Sean P.; Blanken, Peter D.; Li, Jiahong; Luo, Hongyan; Zulueta, Rommel C.

    2016-03-01

    Several initiatives are currently emerging to observe the exchange of energy and matter between the earth's surface and atmosphere standardized over larger space and time domains. For example, the National Ecological Observatory Network (NEON) and the Integrated Carbon Observing System (ICOS) are set to provide the ability of unbiased ecological inference across ecoclimatic zones and decades by deploying highly scalable and robust instruments and data processing. In the construction of these observatories, enclosed infrared gas analyzers are widely employed for eddy covariance applications. While these sensors represent a substantial improvement compared to their open- and closed-path predecessors, remaining high-frequency attenuation varies with site properties and gas sampling systems, and requires correction. Here, we show that components of the gas sampling system can substantially contribute to such high-frequency attenuation, but their effects can be significantly reduced by careful system design. From laboratory tests we determine the frequency at which signal attenuation reaches 50 % for individual parts of the gas sampling system. For different models of rain caps and particulate filters, this frequency falls into ranges of 2.5-16.5 Hz for CO2, 2.4-14.3 Hz for H2O, and 8.3-21.8 Hz for CO2, 1.4-19.9 Hz for H2O, respectively. A short and thin stainless steel intake tube was found to not limit frequency response, with 50 % attenuation occurring at frequencies well above 10 Hz for both H2O and CO2. From field tests we found that heating the intake tube and particulate filter continuously with 4 W was effective, and reduced the occurrence of problematic relative humidity levels (RH > 60 %) by 50 % in the infrared gas analyzer cell. No further improvement of H2O frequency response was found for heating in excess of 4 W. These laboratory and field tests were reconciled using resistor-capacitor theory, and NEON's final gas sampling system was developed on this

  7. Optimization of a gas sampling system for measuring eddy-covariance fluxes of H2O and CO2

    NASA Astrophysics Data System (ADS)

    Metzger, S.; Burba, G.; Burns, S. P.; Blanken, P. D.; Li, J.; Luo, H.; Zulueta, R. C.

    2015-10-01

    Several initiatives are currently emerging to observe the exchange of energy and matter between the earth's surface and atmosphere standardized over larger space and time domains. For example, the National Ecological Observatory Network (NEON) and the Integrated Carbon Observing System (ICOS) will provide the ability of unbiased ecological inference across eco-climatic zones and decades by deploying highly scalable and robust instruments and data processing. In the construction of these observatories, enclosed infrared gas analysers are widely employed for eddy-covariance applications. While these sensors represent a substantial improvement compared to their open- and closed-path predecessors, remaining high-frequency attenuation varies with site properties, and requires correction. Here, we show that the gas sampling system substantially contributes to high-frequency attenuation, which can be minimized by careful design. From laboratory tests we determine the frequency at which signal attenuation reaches 50 % for individual parts of the gas sampling system. For different models of rain caps and particulate filters, this frequency falls into ranges of 2.5-16.5 Hz for CO2, 2.4-14.3 Hz for H2O, and 8.3-21.8 Hz for CO2, 1.4-19.9 Hz for H2O, respectively. A short and thin stainless steel intake tube was found to not limit frequency response, with 50 % attenuation occurring at frequencies well above 10 Hz for both H2O and CO2. From field tests we found that heating the intake tube and particulate filter continuously with 4 W was effective, and reduced the occurrence of problematic relative humidity levels (RH > 60 %) by 50 % in the infrared gas analyser cell. No further improvement of H2O frequency response was found for heating in excess of 4 W. These laboratory and field tests were reconciled using resistor-capacitor theory, and NEON's final gas sampling system was developed on this basis. The design consists of the stainless steel intake tube, a pleated mesh

  8. 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....

  9. 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.

  10. 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).

  11. 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.

  12. 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 ...

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. 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).

  8. 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.

  9. 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

  10. 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.

  11. Impact of climate anomalies on CO2 and H2O fluxes of a temperate Scots pine forest.

    NASA Astrophysics Data System (ADS)

    Gielen, Bert; Neirynck, Johan; Janssens, Ivan

    2010-05-01

    Climate anomalies can have a severe impact on the exchange of CO2 and H2O of forest ecosystems with the atmosphere. Previous studies have revealed that drought events and heat waves can significantly reduce carbon uptake and water use of forests and even lower leaf area if the drought period is persistent. Consequently, these effects can be a cause of the year to year variation in the carbon and water balance of forest ecosystems. This study focuses on the effect of climate anomalies on total stand scale evapotranspiration, gross primary productivity, ecosystem respiration, soil respiration and net ecosystem exchange of a Scots pine (Pinus sylvestris L.) forest. The study site is located 20 km NE of Antwerp, near Brasschaat (Belgium) and consists of an 80-year-old even aged Scots pine stand, which belongs to a larger mixed coniferous/deciduous forest and is part of the ICP-II and Fluxnet/CarboEurope-IP networks since 1997. This analysis is based on a 13 year long eddy covariance dataset of ecosystem H2O and CO2 fluxes together with half hourly recorded temperature, VPD, precipitation and global radiation. Water stress is indentified by using continuous measurements of soil water content. In addition to climate anomalies we also looked at the effect of high ozone events which can significantly reduce carbon uptake of forest ecosystems.

  12. Assessment of the Aerosol Generation and Toxicity of Carbon Nanotubes

    PubMed Central

    O’Shaughnessy, Patrick T.; Adamcakova-Dodd, Andrea; Altmaier, Ralph; Thorne, Peter S.

    2014-01-01

    Current interest in the pulmonary toxicity of carbon nanotubes (CNTs) has resulted in a need for an aerosol generation system that is capable of consistently producing a CNT aerosol at a desired concentration level. This two-part study was designed to: (1) assess the properties of a commercially-available aerosol generator when producing an aerosol from a purchased powder supply of double-walled carbon nanotubes (DWCNTs); and (2) assess the pulmonary sub-acute toxicity of DWCNTs in a murine model during a 5-day (4 h/day) whole-body exposure. The aerosol generator, consisting of a novel dustfeed mechanism and venturi ejector was determined to be capable of producing a DWCNT consistently over a 4 h exposure period at an average level of 10.8 mg/m3. The count median diameter was 121 nm with a geometric standard deviation of 2.04. The estimated deposited dose was 32 µg/mouse. The total number of cells in bronchoalveolar lavage (BAL) fluid was significantly (p < 0.01) increased in exposed mice compared to controls. Similarly, macrophages in BAL fluid were significantly elevated in exposed mice, but not neutrophils. All animals exposed to CNT and euthanized immediately after exposure had changes in the lung tissues showing acute inflammation and injury; however these pathological changes resolved two weeks after the exposure.

  13. 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.

  14. 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

  15. 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

  16. 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

  17. Direct radiative forcing from black carbon aerosols over urban environment

    NASA Astrophysics Data System (ADS)

    Badarinath, K. V. S.; Madhavi Latha, K.

    There is growing evidence that the earth’s climate is changing and will likely continue to change in the future. It is still debated whether these changes are due to natural variability of the climate system or a result of increases in the concentration of greenhouse gases in the atmosphere. Black carbon (BC) has become the subject of interest for a variety of reasons. BC aerosol may cause environmental as well as harmful health effects in densely inhabited regions. BC is a strong absorber of radiation in the visible and near-infrared part of the spectrum, where most of the solar energy is distributed. Black carbon is emitted into the atmosphere as a byproduct of all combustion processes, viz., vegetation burning, industrial effluents and motor vehicle exhausts, etc. In this paper, we present results from our measurements on black carbon aerosols, total aerosol mass concentration and aerosol optical depth over an urban environment namely Hyderabad during January to May, 2003. Diurnal variations of BC indicate high BC concentrations during 6:00 9:00 and 19:00 23:00 h. Weekday variations of BC concentrations increase gradually from Monday to Wednesday and gradually decrease from Thursday to Sunday. Analysis of traffic density along with meteorological parameters suggests that the primary determinant for BC concentration levels and patterns is traffic density. Seasonal variations of BC suggest that the BC concentrations are high during dry season compared to rainy season due to the scavenging by air. The fraction of BC to total mass concentration has been observed to be 7% during January to May. BC showed positive correlation with total mass concentration and aerosol optical depth at 500 nm. Radiative transfer calculations suggests that during January to May, diurnal averaged aerosol forcing at the surface is -33 Wm2 and at the top of the atmosphere (TOA) above 100 km it is observed to be +9 Wm-2. The results have been discussed in detail in the paper.

  18. Climate Impacts of Atmospheric Sulfate and Black Carbon Aerosols

    SciTech Connect

    Qian, Yun; Song, Qingyuan; Menon, Surabi; Yu, Shaocai; Liu, Shaw C.; Shi, Guangyu; Leung, Lai R.; Luo, Yunfeng

    2008-09-19

    Although the global average surface temperature has increased by about 0.6°C during the last century (IPCC, 2001), some regions such as East Asia, Eastern North America, and Western Europe have cooled rather than warmed during the past decades (Jones, 1988; Qian and Giorgi, 2000). Coherent changes at the regional scale may reflect responses to different climate forcings that need to be understood in order to predict the future net climate response at the global and regional scales under different emission scenarios. Atmospheric aerosols play an important role in global climate change (IPCC 2001). They perturb the earth’s radiative budget directly by scattering and absorbing solar and long wave radiation, and indirectly by changing cloud reflectivity, lifetime, and precipitation efficiency via their role as cloud condensation nuclei. Because aerosols have much shorter lifetime (days to weeks) compared to most greenhouse gases, they tend to concentrate near their emission sources and distribute very unevenly both in time and space. This non-uniform distribution of aerosols, in conjunction with the greenhouse effect, may lead to differential net heating in some areas and net cooling in others (Penner et al. 1994). Sulfate aerosols come mainly from the oxidation of sulfur dioxide (SO2) emitted from fossil fuel burning. Black carbon aerosols are directly emitted during incomplete combustion of biomass, coal, and diesel derived sources. Due to the different optical properties, sulfate and black carbon affect climate in different ways. Because of the massive emissions of sulfur and black carbon that accompany the rapid economic expansions in East Asia, understanding the effects of aerosols on climate is particularly important scientifically and politically in order to develop adaptation and mitigation strategies.

  19. 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

  20. Gas and aerosol fluxes. [emphasizing sulfur, nitrogen, and carbon

    NASA Technical Reports Server (NTRS)

    Martens, C. S.

    1980-01-01

    The development of remote sensing techniques to address the global need for accurate distribution and flux determinations of both man made and natural materials which affect the chemical composition of the atmosphere, the heat budget of the Earth, and the depletion, of stratospheric ozone is considered. Specifically, trace gas fluxes, sea salt aerosol production, and the effect of sea surface microlayer on gas and aerosol fluxes are examined. Volatile sulfur, carbon, nitrogen, and halocarbon compounds are discussed including a statement of the problem associated with each compound or group of compounds, a brief summary of current understanding, and suggestions for needed research.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Evaluation of Cloud and Aerosol Screening of Early Orbiting Carbon Observatory-2 (OCO-2) Observations with Collocated MODIS Cloud Mask

    NASA Astrophysics Data System (ADS)

    Nelson, R. R.; Taylor, T.; O'Dell, C.; Cronk, H. Q.; Partain, P.; Frankenberg, C.; Eldering, A.; Crisp, D.; Gunson, M. R.; Chang, A.; Fisher, B.; Osterman, G. B.; Pollock, H. R.; Savtchenko, A.; Rosenthal, E. J.

    2015-12-01

    Effective cloud and aerosol screening is critically important to the Orbiting Carbon Observatory-2 (OCO-2), which can accurately determine column averaged dry air mole fraction of carbon dioxide (XCO2) only when scenes are sufficiently clear of scattering material. It is crucial to avoid sampling biases, in order to maintain a globally unbiased XCO2 record for inversion modeling to determine sources and sinks of carbon dioxide. This work presents analysis from the current operational B7 data set, which is identifying as clear approximately 20% of the order one million daily soundings. Of those soundings that are passed to the L2 retrieval algorithm, we find that almost 80% are yielding XCO2 estimates that converge. Two primary preprocessor algorithms are used to cloud screen the OCO-2 soundings. The A-Band Preprocessor (ABP) uses measurements in the Oxygen-A band near 0.76 microns (mm) to determine scenes with large photon path length modifications due to scattering by aerosol and clouds. The Iterative Maximum A-Posteriori (IMAP) Differential Optical Absorption Spectroscopy (DOAS) algorithm (IDP) computes ratios of retrieved CO2 (and H2O) in the 1.6mm (weak CO2) and 2.0mm (strong CO2) spectral bands to determine scenes with spectral differences, indicating contamination by scattering materials. We demonstrate that applying these two algorithms in tandem provides robust cloud screening of the OCO-2 data set. We compare the OCO-2 cloud screening results to collocated Moderate Resolution Imaging Spectroradiometer (MODIS) cloud mask data and show that agreement between the two sensors is approximately 85-90%. A detailed statistical analysis is performed on a winter and spring 16-day repeat cycle for the nadir-land, glint-land and glint-water viewing geometries. No strong seasonal, spatial or footprint dependencies are found, although the agreement tends to be worse at high solar zenith angles and for snow and ice covered surfaces.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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...

  15. Multivariate analysis of anionic, cationic and nonionic textile surfactant degradation with the H(2)O(2)/UV-C process by using the capabilities of response surface methodology.

    PubMed

    Olmez-Hanci, Tugba; Arslan-Alaton, Idil; Basar, Gulcan

    2011-01-15

    Anionic, cationic and nonionic surfactants being frequently employed in the textile preparation process were subjected to H(2)O(2)/UV-C treatment. As a consequence of the considerable number of parameters affecting the H(2)O(2)/UV-C process, an experimental design methodology was used to mathematically describe and optimize the single and combined influences of the critical process variables treatment time, initial H(2)O(2)concentration and chemical oxygen demand (COD) on parent pollutant (surfactant) as well as organic carbon (COD and total organic carbon (TOC)) removal efficiencies. Multivariate analysis was based on two different photochemical treatment targets; (i) full oxidation/complete treatment of the surfactants or, alternatively, (ii) partial oxidation/pretreatment of the surfactants to comply with the legislative discharge requirements. According to the established polynomial regression models, the process independent variables "treatment time" (exerting a positive effect) and "initial COD content" (exerting a negative effect) played more significant roles in surfactant photodegradation than the process variable "initial H(2)O(2) concentration" under the studied experimental conditions.

  16. 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.

  17. Fe and H 2O 2 distributions in the upper water column in the Indian sector of the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Sarthou, G´raldine; Jeandel, Catherine; Brisset, Laurence; Amouroux, David; Besson, Thierry; Donard, Olivier F. X.

    1997-03-01

    Total dissolvable iron (TDFe), particulate iron (PFe) and hydrogen peroxide (H 2O 2 measurements were performed along a N-S transect in the upper 250 m in the Southern Ocean (62°00E/66°42S-49°00S, ANTARES II cruise, February 1994). TDFe was organically extracted (APDC/DDDC-chloroform) and analysed by Graphite Furnace Atomic Absorption Spectrometry (GFAAS), PFe was analysed by GFAAS following a strong mixed-acid leach, and H 2O 2 was analysed on board by fluorometry. The respective detection limits are equal to 0.13 nmol/kg, 0.02 nmol/kg, and 3.0 nmol/kg. TDFe concentrations vary from 0.4 to 6.2 nmol/kg and profiles are not completely depleted in the surface. PFe concentrations vary from 0.02 to 0.2 nmol/kg. Iron/carbon (Fe/C) uptake ratios for phytoplankton were calculated either from seawater or particle measurements. They are variable along the transect but are consistent when they could be compared. All the observed ratios are within the range of values proposed for the Fe/C uptake ratios by phytoplankton. Using our uptake ratio calculated in the Permanent Open Ocean Zone (4 · 10 -6 mol/mol), we estimate that the primary production which can be supported by the iron input flux into the surface waters is two times higher than the measured primary production in the same area. In the surface waters, H 2O 2 concentrations vary from 5.0 to 19.7 nmol/kg. Such low concentrations are due to strong vertical mixing, low dissolved organic matter concentrations and the latitude of the site.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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;

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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

  12. Hygroscopicity of Black-Carbon-Containing Aerosol in Wildfire Plumes

    NASA Astrophysics Data System (ADS)

    Perring, A. E.; Schwarz, J. P.; Markovic, M. Z.; Fahey, D. W.; Yokelson, R. J.; Jimenez, J. L.; Campuzano Jost, P.; Day, D. A.; Palm, B. B.; Wisthaler, A.; Ziemba, L. D.; Anderson, B. E.; Diskin, G. S.; Huey, L. G.; Gao, R. S.

    2015-12-01

    Water uptake by black carbon (BC) containing aerosol has been quantified in wildfire plumes of varying age (from 1 to ~40 hr old) sampled in North America during the NASA SEAC4RS mission of 2013. Measurements were made in flight using parallel single-particle soot photometers (SP2) that simultaneously detected the BC component of the ambient aerosol ensemble under contrasting humidity conditions. The hygroscopicity parameter, κ, of material internally mixed with BC derived from this data set is consistent with previous estimates of bulk aerosol hygroscopicity from biomass burning sources. We explore the temporal evolution of κ during aging of the Yosemite Rim Fire plume to constrain the rate of conversion of BC-containing aerosol from hydrophobic to hydrophilic modes in these emissions. We also investigate the relationship between κ values for BC-containing particles and the oxidation state and hygroscopicity of the bulk aerosol. These observations have implications for BC transport and removal in biomass burning plumes and provide important constraints on model treatment of BC optical and microphysical properties from wildfire sources in ambient conditions.

  13. Observation of hydration of single, modified carbon aerosols

    NASA Technical Reports Server (NTRS)

    Wyslouzil, B. E.; Carleton, K. L.; Sonnenfroh, D. M.; Rawlins, W. T.; Arnold, S.

    1994-01-01

    We have compared the hydration behavior of single carbon particles that have been treated by exposure to gaseous H2SO4 with that of untreated particles. Untreated carbon particles did not hydrate as the relative humidity varied from 0 to 80% at 23 C. In contrast, treated particles hydrated under subsaturation conditions; mass increases of up to 30% were observed. The mass increase is consistent with sulfuric acid equilibration with the ambient relative humidity in the presence of inert carbon. For the samples studied, the average amount of absorbed acid was 14% +/- 6% by weight, which corresponds to a surface coverage of approximately 0.1 monolayer. The mass fraction of surface-absorbed acid is comparable to the soluble mass fraction observed by Whitefield et al. (1993) in jet aircraft engine aerosols. Estimates indicate this mass fraction corresponds to 0.1% of the available SO2 exiting an aircraft engine ending up as H2SO4 on the carbon aerosol. If this heterogeneous process occurs early enough in the exhaust plume, it may compete with homogeneous nucleation as a mechanism for producing sulfuric acid rich aerosols.

  14. Atmospheric Carbon Dioxide and Aerosols: Effects of Large Increases on Global Climate

    ERIC Educational Resources Information Center

    Science, 1971

    1971-01-01

    Mathematical models indicate increasing atmospheric carbon dioxide causes an increase in surface temperature at a decreasing rate, and the rate of temperature decrease caused by increasing aerosols increases with aerosol concentration. (AL)

  15. The Cheshire-cat-like Behavior of 2nu(sub 3) Overtone of Co2 near 2.134 micron: NIR Lab Spectra of Solid CO2 in H2O and CH3OH

    NASA Technical Reports Server (NTRS)

    Bernstein, Max; Sandford, Scott; Cruikshank, Dale

    2005-01-01

    Infrared (IR) spectra have demonstrated that solid H2O is very common in the outer Solar System, and solid carbon dioxide (CO2) has been detected on icy satellites, comets, and planetismals throughout the outer Solar System. In such environments, CO2 and H2O must sometimes be mixed at a molecular level, changing their IR absorption features. In fact, the IR spectra of CO2-H2O mixtures are not equivalent to a linear combination of the spectra of the pure materials. Laboratory IR spectra of pure CO2 and H2O have been published but a lack of near-IR spectra of CO2-H2O mixtures has made the interpretation of outer Solar System spectra more difficult. We present near infrared (IR) spectra of CO2 in H2O and in CH3OH compared to that of pure solid CO2 and find significant differences. Peaks not present in either pure H2O or pure CO2 spectra become evident. First, the CO2 (2nu(sub 3)) overtone near 2.134 micron (4685/ cm) that is not seen in pure solid CO2 is prominent in the spectrum of a CO2/H2O = 25 mixture. Second, a 2.74 micron (3650/ cm) dangling OH feature of water (and a potentially related peak at 1.89 micron) appear in the spectra of CO2-H2O ice mixtures, but may not be specific to the presence of CO2. Other CO2 peaks display shifts in position and increased width because of intermolecular interactions with water. Changes in CO2 peak positions and profiles on warming of a CO2/H2O = 5 mixture are consistent with 'segregation' of the ice into nearly pure separate components. Absolute strengths for absorptions of CO2 in solid H2O are estimated. Similar results are observed for CO2 in solid CH3OH. Since the CO2 ( 2nu(sub 3)) overtone near 2.134 micron (4685/ cm) is not present in pure CO2 but prominent in mixtures it may be a good observational indicator of whether solid CO2 is a pure material or intimately mixed with other molecules. Significant changes in the near IR spectrum of solid CO2 in the presence of H2O and CH3OH means that the abundance of solid CO2 in the

  16. Hydrogen peroxide in the marine atmospheric boundary layer during the Atlantic Stratocumulus Transition Experiment/Marine Aerosol and Gas Exchange experiment in the eastern subtropical North Atlantic

    NASA Astrophysics Data System (ADS)

    Martin, Daniel; Tsivou, Maria; Bonsang, Bernard; Abonnel, Christian; Carsey, Thomas; Springer-Young, Margie; Pszenny, Alex; Suhre, Karsten

    1997-03-01

    Gas phase H2O2 was measured in surface air on the NOAA ship Malcolm Baldrige from June 8 to 27, 1992 (Julian days 160-179), during the Atlantic Stratocumulus Transition Experiment/Marine Aerosol and Gas Exchange experiment in the eastern subtropical North Atlantic region. Average H2O2 mixing ratios observed were 0.63±0.28 ppbv, ranging between detection limit and 1.5 ppbv. For the entire experiment, only weak or no correlation was found between H2O2 mixing ratio and meteorological parameters (pressure, temperature, humidity, or UV radiation flux) as well as with tracers of continental air masses (CO, black carbon, radon). The average daily H2O2 cycle for the entire period exhibits a maximum of 0.8±0.3 ppbv near sunset and a minimum of 0.4±0.2 ppbv 4-5 hours after sunrise. Several clear H2O2 diurnal variations have been observed, from which a first-order removal rate of about 1×10-5 s-1 for H2O2 can be inferred from nighttime measurements. This rate compares well with those deduced from measurements taken at Cape Grim (Tasmania, 41°S) and during the Soviet-American Gas and Aerosol III experiment (equatorial Pacific Ocean).

  17. Ozonation and combined ozone/H2O2, UV/ozone and UV/H2O2 for treatment of fuel oxygenates MTBE, ETBE, TAME, and DIPE from water--a comparison of removal efficiencies.

    PubMed

    Baus, C; Sona, M; Brauch, H J

    2007-01-01

    Methyl tert-butylether (MTBE) used as fuel oxygenate poses problems for water suppliers since it is persistent in the aquatic environment and the removal efficiency by conventional water treatment methods (aeration or activated carbon filtration) is rather low. Substitution by other ether compounds such as ethyl tert-butylether (ETBE), tert-amylmethylether (TAME) or di-isopropylether (DIPE) is discussed, however, their environmental behaviour is similar to that of MTBE. Experiments investigating the elimination efficiency of AOP were carried out in tap water and water from Lake Constance. The elimination efficiency for all treatment processes was found to follow the order: MTBE < TAME approximately equal ETBE < DIPE For all compounds under investigation, neither pure ozonation nor UV irradiation yield a considerable concentration decline. Only the formation of highly reactive OH radicals shows a potential for removing the ethers from water. Therefore the addition of H2O2 in equimolar ratio prior to ozone admixing proved to be quite efficient. The application of combined UV/H2O2 showed good results in all cases; the best concentration decline was achieved with UV/ozone. The rate of elimination of the three substitutes for MTBE (ETBE, TAME and DIPE) is higher in all processes; nevertheless, no complete removal could be achieved. Therefore, from the point of view of water suppliers, the use of other ethers as substitute for MTBE is posing the same problems as MTBE.

  18. 3D CFD Model of High Temperature H2O/CO2 Co-electrolysis

    SciTech Connect

    Grant Hawkes; James O'Brien; Carl Stoots; Stephen Herring; Joe Hartvigsen

    2007-06-01

    3D CFD Model of High Temperature H2O/CO2 Co-Electrolysis Grant Hawkes1, James O’Brien1, Carl Stoots1, Stephen Herring1 Joe Hartvigsen2 1 Idaho National Laboratory, Idaho Falls, Idaho, grant.hawkes@inl.gov 2 Ceramatec Inc, Salt Lake City, Utah INTRODUCTION A three-dimensional computational fluid dynamics (CFD) model has been created to model high temperature co-electrolysis of steam and carbon dioxide in a planar solid oxide electrolyzer (SOE) using solid oxide fuel cell technology. A research program is under way at the Idaho National Laboratory (INL) to simultaneously address the research and scale-up issues associated with the implementation of planar solid-oxide electrolysis cell technology for syn-gas production from CO2 and steam. Various runs have been performed under different run conditions to help assess the performance of the SOE. This paper presents CFD results of this model compared with experimental results. The Idaho National Laboratory (INL), in conjunction with Ceramatec Inc. (Salt Lake City, USA) has been researching for several years the use of solid-oxide fuel cell technology to electrolyze steam for large-scale nuclear-powered hydrogen production. Now, an experimental research project is underway at the INL to produce syngas by simultaneously electrolyzing at high-temperature steam and carbon dioxide (CO2) using solid oxide fuel cell technology. A strong interest exists in the large-scale production of syn-gas from CO2 and steam to be reformed into a usable transportation fuel. If biomass is used as the carbon source, the overall process is climate neutral. Consequently, there is a high level of interest in production of syn-gas from CO2 and steam electrolysis. With the price of oil currently around $60 / barrel, synthetically-derived hydrocarbon fuels (synfuels) have become economical. Synfuels are typically produced from syngas – hydrogen (H2) and carbon monoxide (CO) -- using the Fischer-Tropsch process, discovered by Germany before World

  19. 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.

  20. 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.

  1. 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.

  2. 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).

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. [Fe(bipy)(CN)(4)](-) as a versatile building block for the design of heterometallic systems: synthesis, crystal structure, and magnetic properties of PPh(4)[Fe(III)(bipy)(CN)(4)] x H(2)O, [[Fe(III)(bipy)(CN)(4)](2)M(II)(H(2)O)(4)] x 4H(2)O, and [[Fe(III)(bipy)(CN)(4)](2)Zn(II)] x 2H(2)O [bipy = 2,2'-Bipyridine; M = Mn and Zn].

    PubMed

    Lescouëzec, Rodrigue; Lloret, Francesc; Julve, Miguel; Vaissermann, Jacqueline; Verdaguer, Michel

    2002-02-25

    The new cyano complexes of formulas PPh(4)[Fe(III)(bipy)(CN)(4)] x H(2)O (1), [[Fe(III)(bipy)(CN)(4)](2)M(II)(H(2)O)(4)] x 4H(2)O with M = Mn (2) and Zn (3), and [[Fe(III)(bipy)(CN)(4)](2)Zn(II)] x 2H(2)O (4) [bipy = 2,2'-bipyridine and PPh(4) = tetraphenylphosphonium cation] have been synthesized and structurally characterized. The structure of complex 1 is made up of mononuclear [Fe(bipy)(CN)(4)](-) anions, tetraphenyphosphonium cations, and water molecules of crystallization. The iron(III) is hexacoordinated with two nitrogen atoms of a chelating bipy and four carbon atoms of four terminal cyanide groups, building a distorted octahedron around the metal atom. The structure of complexes 2 and 3 consists of neutral centrosymmetric [[Fe(III)(bipy)(CN)(4)](2)M(II)(H(2)O)(4)] heterotrinuclear units and crystallization water molecules. The [Fe(bipy)(CN)(4)](-) entity of 1 is present in 2 and 3 acting as a monodentate ligand toward M(H(2)O)(4) units [M = Mn(II) (2) and Zn(II) (3)] through one cyanide group, the other three cyanides remaining terminal. Four water molecules and two cyanide nitrogen atoms from two [Fe(bipy)(CN)(4)](-) units in trans positions build a distorted octahedron surrounding Mn(II) (2) and Zn(II) (3). The structure of the [Fe(phen)(CN)(4)](-) complex ligand in 2 and 3 is close to that of the one in 1. The intramolecular Fe-M distances are 5.126(1) and 5.018(1) A in 2 and 3, respectively. 4 exhibits a neutral one-dimensional polymeric structure containing two types of [Fe(bipy)(CN)(4)](-) units acting as bismonodentate (Fe(1)) and trismonodentate (Fe(2)) ligands versus the divalent zinc cations through two cis-cyanide (Fe(1)) and three fac-cyanide (Fe(2)) groups. The environment of the iron atoms in 4 is distorted octahedral as in 1-3, whereas the zinc atom is pentacoordinated with five cyanide nitrogen atoms, describing a very distorted square pyramid. The iron-zinc separations across the single bridging cyanides are 5.013(1) and 5.142(1) A at Fe

  11. 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

  12. [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 inact