Comparison of nitrous oxide (N2O) analyzers for high-precision measurements of atmospheric mole fractions

NASA Astrophysics Data System (ADS)

Lebegue, B.; Schmidt, M.; Ramonet, M.; Wastine, B.; Yver Kwok, C.; Laurent, O.; Belviso, S.; Guemri, A.; Philippon, C.; Smith, J.; Conil, S.; Jost, H. J.; Crosson, E. R.

2015-10-01

Over the last few decades, in-situ measurements of atmospheric N2O mole fractions have been performed using gas chromatographs (GCs) equipped with electron capture detectors (ECDs). When trying to meet the World Meteorological Organization's (WMO) quality goal, this technique becomes very challenging as the detectors are highly non-linear and the GCs at remote stations require a considerable amount of maintenance by qualified technicians to maintain good short-term and long-term repeatability. With more robust optical spectrometers being now available for N2O measurements, we aim to identify a robust and stable analyzer that can be integrated into atmospheric monitoring networks, such as the Integrated Carbon Observation System (ICOS). In this study, we tested seven analyzers that were developed and commercialized from five different companies and compared the results with established techniques. Each instrument was characterized during a time period of approximately eight weeks. The test protocols included the characterization of the short-term and long-term repeatability, drift, temperature dependence, linearity and sensitivity to water vapor. During the test period, ambient air measurements were compared under field conditions at the Gif-sur-Yvette station. All of the analyzers showed a standard deviation better than 0.1 ppb for the 10 min averages. Some analyzers would benefit from improvements in temperature stability to reduce the instrument drift, which could then help in reducing the frequency of calibrations. For most instruments, the water vapor correction algorithms applied by companies are not sufficient for high-precision atmospheric measurements, which results in the need to dry the ambient air prior to analysis.

Ignition and Combustion of Pulverized Coal and Biomass under Different Oxy-fuel O2/N2 and O2/CO2 Environments

NASA Astrophysics Data System (ADS)

Khatami Firoozabadi, Seyed Reza

This work studied the ignition and combustion of burning pulverized coals and biomasses particles under either conventional combustion in air or oxy-fuel combustion conditions. Oxy-fuel combustion is a 'clean-coal' process that takes place in O2/CO2 environments, which are achieved by removing nitrogen from the intake gases and recirculating large amounts of flue gases to the boiler. Removal of nitrogen from the combustion gases generates a high CO2-content, sequestration-ready gas at the boiler effluent. Flue gas recirculation moderates the high temperatures caused by the elevated oxygen partial pressure in the boiler. In this study, combustion of the fuels took place in a laboratory laminar-flow drop-tube furnace (DTF), electrically-heated to 1400 K, in environments containing various mole fractions of oxygen in either nitrogen or carbon-dioxide background gases. The experiments were conducted at two different gas conditions inside the furnace: (a) quiescent gas condition (i.e., no flow or inactive flow) and, (b) an active gas flow condition in both the injector and furnace. Eight coals from different ranks (anthracite, semi-snthracite, three bituminous, subbituminous and two lignites) and four biomasses from different sources were utilized in this work to study the ignition and combustion characteristics of solid fuels in O2/N2 or O2/CO2 environments. The main objective is to study the effect of replacing background N2 with CO2, increasing O2 mole fraction and fuel type and rank on a number of qualitative and quantitative parameters such as ignition/combustion mode, ignition temperature, ignition delay time, combustion temperatures, burnout times and envelope flame soot volume fractions. Regarding ignition, in the quiescent gas condition, bituminous and sub-bituminous coal particles experienced homogeneous ignition in both O2/N 2 and O2/CO2 atmospheres, while in the active gas flow condition, heterogeneous ignition was evident in O2/CO 2. Anthracite, semi

Mass-independent fractionation of oxygen isotopes during H2O2 formation by gas-phase discharge from water vapour

NASA Astrophysics Data System (ADS)

Velivetskaya, Tatiana A.; Ignatiev, Alexander V.; Budnitskiy, Sergey Y.; Yakovenko, Victoria V.; Vysotskiy, Sergey V.

2016-11-01

Hydrogen peroxide is an important atmospheric component involved in various gas-phase and aqueous-phase transformation processes in the Earth's atmosphere. A study of mass-independent 17O anomalies in H2O2 can provide additional insights into the chemistry of the modern atmosphere and, possibly, of the ancient atmosphere. Here, we report the results of laboratory experiments to study the fractionation of three oxygen isotopes (16O, 17O, and 18O) during H2O2 formation from products of water vapour dissociation. The experiments were carried out by passing an electrical discharge through a gaseous mixture of helium and water at atmospheric pressure. The effect of the presence of O2 in the gas mixture on the isotopic composition of H2O2 was also investigated. All of the experiments showed that H2O2 produced under two different conditions (with or without O2 added in the gas mixtures) was mass-independently fractionated (MIF). We found a positive MIF signal (∼1.4‰) in the no-O2 added experiments, and this signal increased to ∼2.5‰ once O2 was added (1.6% mixing ratio). We suggest that if O2 concentrations are very low, the hydroxyl radical recombination reaction is the dominant pathway for H2O2 formation and is the source of MIF in H2O2. Although H2O2 formation via a hydroxyl radical recombination process is limited in the modern atmosphere, it would be possible in the Archean atmosphere when O2 was a trace constituent, and H2O2 would be mass-independently fractionated. The anomalous 17O excess, which was observed in H2O2 produced by spark discharge experiments, may provide useful information about the radical chemistry of the ancient atmosphere and the role of H2O2 in maintaining and controlling the atmospheric composition.

Interpreting activity in H(2)O-H(2)SO(4) binary nucleation.

PubMed

Bein, Keith J; Wexler, Anthony S

2007-09-28

Sulfuric acid-water nucleation is thought to be a key atmospheric mechanism for forming new condensation nuclei. In earlier literature, measurements of sulfuric acid activity were interpreted as the total (monomer plus hydrate) concentration above solution. Due to recent reinterpretations, most literature values for H(2)SO(4) activity are thought to represent the number density of monomers. Based on this reinterpretation, the current work uses the most recent models of H(2)O-H(2)SO(4) binary nucleation along with perturbation analyses to predict a decrease in critical cluster mole fraction, increase in critical cluster diameter, and orders of magnitude decrease in nucleation rate. Nucleation rate parameterizations available in the literature, however, give opposite trends. To resolve these discrepancies, nucleation rates were calculated for both interpretations of H(2)SO(4) activity and directly compared to the available parameterizations as well as the perturbation analysis. Results were in excellent agreement with older parameterizations that assumed H(2)SO(4) activity represents the total concentration and duplicated the predicted trends from the perturbation analysis, but differed by orders of magnitude from more recent parameterizations that assume H(2)SO(4) activity represents only the monomer. Comparison with experimental measurements available in the literature revealed that the calculations of the current work assuming a(a) represents the total concentration are most frequently in agreement with observations.

Herschel Survey of Galactic OH+, H2O+, and H3O+: Probing the Molecular Hydrogen Fraction and Cosmic-Ray Ionization Rate

NASA Astrophysics Data System (ADS)

Indriolo, Nick; Neufeld, D. A.; Gerin, M.; Schilke, P.; Benz, A. O.; Winkel, B.; Menten, K. M.; Chambers, E. T.; Black, John H.; Bruderer, S.; Falgarone, E.; Godard, B.; Goicoechea, J. R.; Gupta, H.; Lis, D. C.; Ossenkopf, V.; Persson, C. M.; Sonnentrucker, P.; van der Tak, F. F. S.; van Dishoeck, E. F.; Wolfire, Mark G.; Wyrowski, F.

2015-02-01

In diffuse interstellar clouds the chemistry that leads to the formation of the oxygen-bearing ions OH+, H2O+, and H3O+ begins with the ionization of atomic hydrogen by cosmic rays, and continues through subsequent hydrogen abstraction reactions involving H2. Given these reaction pathways, the observed abundances of these molecules are useful in constraining both the total cosmic-ray ionization rate of atomic hydrogen (ζH) and molecular hydrogen fraction (f_H_2). We present observations targeting transitions of OH+, H2O+, and H3O+ made with the Herschel Space Observatory along 20 Galactic sight lines toward bright submillimeter continuum sources. Both OH+ and H2O+ are detected in absorption in multiple velocity components along every sight line, but H3O+ is only detected along 7 sight lines. From the molecular abundances we compute f_H_2 in multiple distinct components along each line of sight, and find a Gaussian distribution with mean and standard deviation 0.042 ± 0.018. This confirms previous findings that OH+ and H2O+ primarily reside in gas with low H2 fractions. We also infer ζH throughout our sample, and find a lognormal distribution with mean log (ζH) = -15.75 (ζH = 1.78 × 10-16 s-1) and standard deviation 0.29 for gas within the Galactic disk, but outside of the Galactic center. This is in good agreement with the mean and distribution of cosmic-ray ionization rates previously inferred from H_3^+ observations. Ionization rates in the Galactic center tend to be 10-100 times larger than found in the Galactic disk, also in accord with prior studies. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Mid-infrared laser-absorption diagnostic for vapor-phase fuel mole fraction and liquid fuel film thickness

NASA Astrophysics Data System (ADS)

Porter, J. M.; Jeffries, J. B.; Hanson, R. K.

2011-02-01

A novel two-wavelength mid-infrared laser-absorption diagnostic has been developed for simultaneous measurements of vapor-phase fuel mole fraction and liquid fuel film thickness. The diagnostic was demonstrated for time-resolved measurements of n-dodecane liquid films in the absence and presence of n-decane vapor at 25°C and 1 atm. Laser wavelengths were selected from FTIR measurements of the C-H stretching band of vapor n-decane and liquid n-dodecane near 3.4 μm (3000 cm-1). n-Dodecane film thicknesses <20 μm were accurately measured in the absence of vapor, and simultaneous measurements of n-dodecane liquid film thickness and n-decane vapor mole fraction (300 ppm) were measured with <10% uncertainty for film thicknesses <10 μm. A potential application of the measurement technique is to provide accurate values of vapor mole fraction in combustion environments where strong absorption by liquid fuel or oil films on windows make conventional direct absorption measurements of the gas problematic.

The Link between low H2O Activity and Chloride Brines in High-Grade Metamorphism - A Status Report

NASA Astrophysics Data System (ADS)

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

2006-12-01

High-grade metamorphic mineral assemblages typically record low activity of H2O (aH2O) at peak conditions. Substantial debate has centered on whether low aH2O requires the presence of a hydrous melt or of a fluid phase. Lowering aH2O in a fluid phase by CO2 is problematic because (1) at requisite compositions and observed fO2, graphite should be stable but is not observed; and (2) H2O-CO2 fluids are poor solvents for many of the components observed to be mobile at the amphibolite-granulite transition. In contrast, chloride brines are more likely to be responsible for reduced aH2O where a fluid phase is present (e.g., Newton et al., 1998, Precambrian Res., 91, 41). However, the properties of such brines are poorly understood at high P and T. We are addressing this problem through a program of experimental measurement of mineral solubilities in NaCl-H2O solutions at high P and T. Results indicate that, at 800°C and 10 kbar, solubilities of volatile-bearing, congruently soluble Ca minerals increase strongly with NaCl to halite saturation. At XNaCl = 0.3 (assuming full dissociation), Ca mole fractions in solutions increase as follows: 0.0012 (apatite), 0.0075 (fluorite), 0.0107 (calcite), 0.0513 (anhydrite). Because solubilities of F, CO2, and SO4 will increase correspondingly, H2O-NaCl brines will promote significant volatile transfer. By contrast, oxides exhibit variable behavior. At the same P and T, quartz solubility decreases monotonically with increasing NaCl, whereas corundum, hematite, wollastonite, diopside, and grossular mole fractions all increase to maxima at low to moderate XNaCl, and then decline to halite saturation. These results indicate that SiO2 does not ineract with NaCl, whereas the dissolution of the other minerals involves consumption of NaCl by solutes to a greater extent than H2O. Notably, solubility of Al is strongly enhanced in NaCl-H2O with SiO2 ± CaO. It is unlikely that all instances of low aH2O in high-grade metamorphic rocks are

Prediction of absolute infrared intensities for the fundamental vibrations of H2O2

NASA Technical Reports Server (NTRS)

Rogers, J. D.; Hillman, J. J.

1981-01-01

Absolute infrared intensities are predicted for the vibrational bands of gas-phase H2O2 by the use of a hydrogen atomic polar tensor transferred from the hydroxyl hydrogen atom of CH3OH. These predicted intensities are compared with intensities predicted by the use of a hydrogen atomic polar tensor transferred from H2O. The predicted relative intensities agree well with published spectra of gas-phase H2O2, and the predicted absolute intensities are expected to be accurate to within at least a factor of two. Among the vibrational degrees of freedom, the antisymmetric O-H bending mode nu(6) is found to be the strongest with a calculated intensity of 60.5 km/mole. The torsional band, a consequence of hindered rotation, is found to be the most intense fundamental with a predicted intensity of 120 km/mole. These results are compared with the recent absolute intensity determinations for the nu(6) band.

Oxygen isotope fractionation in the CaCO3-DIC-H2O system

NASA Astrophysics Data System (ADS)

Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

2017-10-01

The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading

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).

Gibbs energies of transferring triglycine from water into H2O-DMSO solvent

NASA Astrophysics Data System (ADS)

Usacheva, T. R.; Kuz'mina, K. I.; Lan, Pham Thi; Kuz'mina, I. A.; Sharnin, V. A.

2014-08-01

The Gibbs energies of transferring triglycine (3Gly, glycyl-glycyl-glycine) from water into mixtures of water with dimethyl sulfoxide (χDMSO = 0.05, 0.10, and 0.15 mole fractions) at 298.15 K are determined from the interphase distribution. An increased dimethyl sulfoxide (DMSO) concentration in the solvent slightly raises the positive values of Δtr G ○(3Gly), possibly indicating the formation of more stable 3Gly-H2O solvated complexes than ones of 3Gly-DMSO. It is shown that the change in the Gibbs energy of transfer of 3Gly is determined by the enthalpy component. The relationship of 3Gly and 18-crown-6 ether (18C6) solvation's contributions to the change in the Gibbs energy of [3Gly18C6] molecular complex formation in H2O-DMSO solvents is analyzed, and the key role of 3Gly solvation's contribution to the change in the stability of [3Gly18C6] upon moving from H2O to mixtures with DMSO is revealed.

H2O2 treatment or serum deprivation induces autophagy and apoptosis in naked mole-rat skin fibroblasts by inhibiting the PI3K/Akt signaling pathway.

PubMed

Zhao, Shanmin; Li, Li; Wang, Shiyong; Yu, Chenlin; Xiao, Bang; Lin, Lifang; Cong, Wei; Cheng, Jishuai; Yang, Wenjing; Sun, Wei; Cui, Shufang

2016-12-20

Naked mole-rats (NMR; Heterocephalus glaber) display extreme longevity and resistance to cancer. Here, we examined whether autophagy contributes to the longevity of NMRs by assessing the effects of the PI3K/Akt pathway inhibitor LY294002 and the autophagy inhibitor chloroquine (CQ) on autophagy and apoptosis in NMR skin fibroblasts. Serum starvation, H2O2 treatment, and LY294002 treatment all increased the LC3-II/LC3-I ratio and numbers of double-membraned autophagosomes and autophagic vacuoles, and decreased levels of p70S6K, p-AktSer473, and p-AktThr308. By contrast, CQ treatment decreased p70S6K, AktSer473, and AktThr308 levels. The Bax/Bcl-2 ratio increased after 12 h of exposure to LY294002 or CQ. These data show that inhibiting the Akt pathway promotes autophagy and apoptosis in NMR skin fibroblasts. Furthermore, LY294002 or CQ treatment decreased caspase-3, p53, and HIF1-α levels, suggesting that serum starvation or H2O2 treatment increase autophagy and apoptosis in NMR skin fibroblasts by inhibiting the PI3K/Akt pathway. CQ-induced inhibition of late autophagy stages also prevented Akt activation and induced apoptosis. Finally, the HIF-1α and p53 pathways were involved in serum starvation- or H2O2-induced autophagy in NMR skin fibroblasts.

[Mechanism and performance of styrene oxidation by O3/H2O2].

PubMed

He, Jue-Cong; Huang, Qian-Ru; Ye, Qi-Hong; Luo, Yu-Wei; Zhang, Zai-Li; Fan, Qing-Juan; Wei, Zai-Shan

2013-10-01

It can produce a large number of free radicals in O3/H2O2, system, ozone and free radical coupling oxidation can improve the styrene removal efficiency. Styrene oxidation by O3/H2O2 was investigated. Ozone dosage, residence time, H2o2 volume fraction, spray density and molar ratio of O3/C8H8 on styrene removal were evaluated. The experimental results showed that styrene removal efficiency achieved 85.7%. The optimal residence time, H2O2, volume fraction, spray density and O3/C8H8 molar ratio were 20. 6 s, 10% , 1.72 m3.(m2.h)-1 and 0.46, respectively. The gas-phase degradation intermediate products were benzaldehyde(C6H5CHO) and benzoic acid (C6H5 COOH) , which were identified by means of gas chromatography-mass spectrometry(GC-MS). The degradation mechanism of styrene is presented.

Low-Temperature Thermal Reactions Between SO2 and H2O2 and Their Relevance to the Jovian Icy Satellites

NASA Technical Reports Server (NTRS)

Loeffler, Mark J.; Hudson, Reggie L.

2013-01-01

Here we present first results on a non-radiolytic, thermally-driven reaction sequence in solid H2O +SO2 + H2O2 mixtures at 50-130 K, which produces sulfate (SO(-2)/(4)), and has an activation energy of 53 kJ/mole. We suspect that these results 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.

D/H isotopic fractionation effects in the H2-H2O system: An in-situ experimental study at supercritical water conditions

NASA Astrophysics Data System (ADS)

Foustoukos, D.; Mysen, B. O.

2011-12-01

Understanding the effect of temperature on the relative distribution of volatiles in supercritical aqueous solutions is important to constrain elemental and isotopic partitioning/fractionation effects in systems applicable to planetary interiors where the temperature-pressure conditions are often beyond existing experimental or theoretical datasets. For example, very little exists for the fundamental equilibria between H2, D2 and HD (H2 + D2 = 2HD), which, in turn, constrains the internal D/H isotope exchange and the evolution of HD in H2-containing systems such as H2-CH4 and H2-H2O. Theoretical calculations considering the partition functions of the molecules predict that with temperature increase, the equilibrium constant of this reaction approximates values that correspond to the stochastic distribution of species. These calculations consider pure harmonic vibrational frequencies, which, however, do not apply to the diatomic molecule of hydrogen, especially because anharmonic oscillations are anticipated to become stronger at high temperatures. Published experimental data have been limited to conditions lower than 468°C with large uncertainties at elevated temperatures. To address the lack of experimental data, a series of hydrothermal diamond anvil experiments has been conducted utilizing vibrational spectroscopy as a novel quantitative method to explore the relative distribution of H- and D-bearing volatiles in the H2-D2-D2O-H2O-Ti-TiO2 system. The fundamentals of this methodology are based on the distinct Raman frequency shift resulting from deuterium substitution in the H-H and O-H bonds. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (for 3-9hrs) at 600-800°C and pressures of 0.5-1 GPa, leading to formation of H2, D2, HD and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in-situ and in the quenched gas phase, indicate a significant deviation from the theoretical estimate of the equilibrium

Rate coefficient for H + O2 + M = HO2 + M evaluated from shock tube measurements of induction times

NASA Technical Reports Server (NTRS)

Slack, M. W.

1977-01-01

Shock tube experiments measured hydrogen-air induction times near the second explosion limit. By matching these experimental results with numerically predicted induction times, the rate coefficient for the reaction H + O2 + M = HO2 + M was evaluated as k-sub 4,N2 = 3.3 (plus or minus .6) x 10 to the 15 cm to the 6th/sq mole/s.

Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)

NASA Astrophysics Data System (ADS)

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

This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)' providing data from direct measurement of pressure and mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.

The solubility of gold in H 2 O-H 2 S vapour at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Zezin, Denis Yu.; Migdisov, Artashes A.; Williams-Jones, Anthony E.

2011-09-01

This experimental study sheds light on the complexation of gold in reduced sulphur-bearing vapour, specifically, in H 2O-H 2S gas mixtures. The solubility of gold was determined in experiments at temperatures of 300, 350 and 365 °C and reached 2.2, 6.6 and 6.3 μg/kg, respectively. The density of the vapour varied from 0.02 to 0.22 g/cm 3, the mole fraction of H 2S varied from 0.03 to 0.96, and the pressure in the cell reached 263 bar. Statistically significant correlations of the amount of gold dissolved in the fluid with the fugacity of H 2O and H 2S permit the experimental data to be fitted to a solvation/hydration model. According to this model, the solubility of gold in H 2O-H 2S gas mixtures is controlled by the formation of sulphide or bisulphide species solvated by H 2S or H 2O molecules. Formation of gold sulphide species is favoured statistically over gold bisulphide species and thus the gold is interpreted to dissolve according to reactions of the form: Au(s)+(n+1)HS(g)=AuS·(HS)n(g)+H(g) Au(s)+HS(g)+mHO(g)=AuS·(HO)m(g)+H(g) Equilibrium constants for Reaction (A1) and the corresponding solvation numbers ( K A1 and n) were evaluated from the study of Zezin et al. (2007). The equilibrium constants as well as the hydration numbers for Reaction (A2) ( K A2 and m) were adjusted simultaneously by a custom-designed optimization algorithm and were tested statistically. The resulting values of log K A2 and m are -15.3 and 2.3 at 300 and 350 °C and -15.1 and 2.2 at 365 °C, respectively. Using the calculated stoichiometry and stability of Reactions (A1) and (A2), it is now possible to quantitatively evaluate the contribution of reduced sulphur species to the transport of gold in aqueous vapour at temperatures up to 365 °C. This information will find application in modelling gold ore-forming processes in vapour-bearing magmatic hydrothermal systems, notably those of epithermal environments.

Current transport mechanism in graphene/AlGaN/GaN heterostructures with various Al mole fractions

NASA Astrophysics Data System (ADS)

Pandit, Bhishma; Seo, Tae Hoon; Ryu, Beo Deul; Cho, Jaehee

2016-06-01

The current transport mechanism of graphene formed on AlxGa1-xN/GaN heterostructures with various Al mole fractions (x = 0.15, 0.20, 0.30, and 0.40) is investigated. The current-voltage measurement from graphene to AlGaN/GaN shows an excellent rectifying property. The extracted Schottky barrier height of the graphene/AlGaN/GaN contacts increases with the Al mole fraction in AlGaN. However, the current transport mechanism deviates from the Schottky-Mott theory owing to the deterioration of AlGaN crystal quality at high Al mole fractions confirmed by reverse leakage current measurement.

H2O activity in concentrated NaCl solutions at high pressures and temperatures measured by the brucite-periclase equilibrium

NASA Astrophysics Data System (ADS)

Aranovich, L. Y.; Newton, R. C.

1996-10-01

H2O activities in concentrated NaCl solutions were measured in the ranges 600° 900° C and 2 15 kbar and at NaCl concentrations up to halite saturation by depression of the brucite (Mg(OH)2) periclase (MgO) dehydration equilibrium. Experiments were made in internally heated Ar pressure apparatus at 2 and 4.2 kbar and in 1.91-cm-diameter piston-cylinder apparatus with NaCl pressure medium at 4.2, 7, 10 and 15 kbar. Fluid compositions in equilibrium with brucite and periclase were reversed to closures of less than 2 mol% by measuring weight changes after drying of punctured Pt capsules. Brucite-periclase equilibrium in the binary system was redetermined using coarsely crystalline synthetic brucite and periclase to inhibit back-reaction in quenching. These data lead to a linear expression for the standard Gibbs free energy of the brucite dehydration reaction in the experimental temperature range: ΔG° (±120J)=73418 134.95 T(K). Using this function as a baseline, the experimental dehydration points in the system MgO-H2O-NaCl lead to a simple systematic relationship of high-temperature H2O activity in NaCl solution. At low pressure and low fluid densities near 2 kbar the H2O activity is closely approximated by its mole fraction. At pressures of 10 kbar and greater, with fluid densities approaching those of condensed H2O, the H2O activity becomes nearly equal to the square of its mole fraction. Isobaric halite saturation points terminating the univariant brucite-periclase curves were determined at each experimental pressure. The five temperature-composition points in the system NaCl-H2O are in close agreement with the halite saturation curves (liquidus curves) given by existing data from differential thermal analysis to 6 kbar. Solubility of MgO in the vapor phase near halite saturation is much less than one mole percent and could not have influenced our determinations. Activity concentration relations in the experimental P-T range may be retrieved for the binary

Defining the chemical role of H2O in mantle melts: Effect of melt composition and H2O content on the activity of SiO2

NASA Astrophysics Data System (ADS)

Moore, G.; Roggensack, K.

2007-12-01

then used, along with the mole fraction of SiO2 that is measured in the glass, to calculate an activity coefficient for SiO2 in that particular melt. The results show that for two starting compositions, H2O clearly has a strong negative effect on the activity coefficient of SiO2, consistent with some earlier intepretations. Further work is being conducted on differing starting compositions, as well as increasing the range of volatile contents, in order to better quantify their influence on this important chemical parameter of mantle melts. Ultimately, these experiments will help determine whether hydrous arc lavas, including high-Mg andesites, can be attributed to a primitive mantle origin, or whether other magmatic processes are necessary to generate their observed bulk compositions. It will also quantify the amount of H2O necessary to generate such magmas, giving insight into the potential H2O content present in the sub-arc mantle source regions, and allowing a more precise estimate of volatile fluxes in volcanic arc settings.

Hydrogen isotope fractionation between C-H-O species in magmatic fluids

NASA Astrophysics Data System (ADS)

Foustoukos, D. I.; Mysen, B. O.

2012-12-01

Constraining the hydrogen isotope fractionation between H-bearing volatiles (e.g. H2, CH4, hydrocarbons, H2O) as function of temperature and pressure helps to promote our understanding of the isotopic composition of evolved magmatic fluids and the overall mantle-cycling of water and reduced C-O-H volatiles. To describe the thermodynamics of the exchange reactions between the different H/D isotopologues of H2 and CH4 under supercritical water conditions, a novel experimental technique has been developed by combining vibrational Raman spectroscopy with hydrothermal diamond anvil cell designs (HDAC), which offers a method to monitor the in-situ evolution of H/D containing species. To this end, the equilibrium relationship between H2-D2-HD in supercritical fluid was investigated at temperatures ranging from 300 - 800 oC and pressures ~ 0.3 - 1.3 GPa [1]. Experimental results obtained in-situ and ex-situ show a significant deviation from the theoretical values of the equilibrium constant predicted for ideal-gas reference state, and with an apparent negative temperature effect triggered by the enthalpy contributions due to mixing in supercritical water. Here, we present a series of HDAC experiments conducted to evaluate the role of supercritical water on the isotopic equilibrium between H/D methane isotopologues at 600 - 800 oC and 409 - 1622 MPa. In detail, tetrakis-silane (Si5C12H36) was reacted with H2O-D2O aqueous solution in the presence of either Ni or Pt metal catalyst, resulting to the formation of deuterated methane species such as CH3D, CHD3, CH2D2 and CD4. Two distinctly different set of experiments ("gas phase"; "liquid phase") were performed by adjusting the silane/water proportions. By measuring the relative intensities of Raman vibrational modes of species, experimental results demonstrate distinctly different thermodynamic properties for the CH4-CH3D-CHD3-CH2D2 equilibrium in gas and liquid-water-bearing systems. In addition, the D/H molar ratio of

A high level Ab initio study of the anionic hydrogen-bonded complexes FH-CN-, FH-NC-, H2O-CN- and H2O-NC-

NASA Technical Reports Server (NTRS)

Lee, Timothy J.

1989-01-01

HF, H2O, CN- and their hydrogen-bonded complexes were studied using state-of-the-art ab initio quantum mechanical methods. A large Gaussian one particle basis set consisting of triple zeta plus double polarization plus diffuse s and p functions (TZ2P + diffuse) was used. The theoretical methods employed include self consistent field, second order Moller-Plesset perturbation theory, singles and doubles configuration interaction theory and the singles and doubles coupled cluster approach. The FH-CN- and FH-NC- and H2O-CN-, H2O-NC- pairs of complexes are found to be essentially isoenergetic. The first pair of complexes are predicted to be bound by approx. 24 kcal/mole and the latter pair bound by approximately 15 kcal/mole. The ab initio binding energies are in good agreement with the experimental values. The two being shorter than the analogous C-N hydrogen bond. The infrared (IR) spectra of the two pairs of complexes are also very similar, though a severe perturbation of the potential energy surface by proton exchange means that the accurate prediction of the band center of the most intense IR mode requires a high level of electronic structure theory as well as a complete treatment of anharmonic effects. The bonding of anionic hydrogen-bonded complexes is discussed and contrasted with that of neutral hydrogen-bonded complexes.

Oxygen Isotopic Fractionation During Evaporation of SiO2 in Vacuum and in H Gas

NASA Astrophysics Data System (ADS)

Nagahara, H.; Young, E. D.; Hoering, T. C.; Mysen, B. O.

1993-07-01

isotope measurements, including ^17O and silicon isotope measurements, are now in progress, and some of the results are shown in this paper. Oxygen isotopic compositions of residues in vacuum and in hydrogen gas of total pressure of 2.6 x 10^-5 bar, which approximates the pressure of the solar nebula at the midplane at 2-3 AU, are shown in comparison with evaporation rate (Figs. 1 and 2). Oxygen isotopic fractionation is remarkable in a constant evacuation, but is negligible in hydrogen gas of 2.6 x 10^-5 bar total pressure. In vacuum, delta ^18O of solid residue increases with increasing degree of evaporation. The curve is best fit to delta ^18O = 0.00094x^2 + 0.00173x + 19.606 (r = 0.997), where x is the degree of evaporation in weight percent. The curve is fit to the Rayleigh fractionation curve with a constant fractionation factor (alpha(sub)vap-sol) of 0.9970. Figures 1 and 2 show that evaporation is significant but oxygen isotopic fractionation is insignificant in hydrogen gas in the approximate solar nebular condition. The high evaporation rate in hydrogen gas is due to the fact that evaporation is a decomposition reaction of an oxide, which should be accelerated in reducing condition. The rate, however, can be explained by an unknown diffusion process that is possible when hydrogen is reactive with silica [2]. In a fairly high hydrogen pressure, isotopic fractionation is suppressed. On the other hand, in vacuum, the evaporation rate is small but the degree of isotopic fractionation is significant. The results suggest that chondrules and CAIs without isotopic mass fractionation could have been formed in the solar nebula, but that mass loss during heating should have been significant. The CAIs with significant mass fractionation such as HAL could have been formed in vacuum. References: [1] Davis A. et al. (1990) Nature, 347, 655-658. [2] Nagahara H. (1993) LPS XXIV, 1045-1046. Fig. 1, which appears here in the hard copy, shows the evaporation rate of SiO2 heated at

OH-LIF measurement of H2/O2/N2 flames in a micro flow reactor with a controlled temperature profile

NASA Astrophysics Data System (ADS)

Shimizu, T.; Nakamura, H.; Tezuka, T.; Hasegawa, S.; Maruta, K.

2014-11-01

This paper presents combustion and ignition characteristic of H2/O2/N2 flames in a micro flow reactor with a controlled temperature profile. OH-LIF measurement was conducted to capture flame images. Flame responses were investigated for variable inlet flow velocity, U, and equivalence ratio, phi. Three kinds of flame responses were experimentally observed for the inlet flow velocities: stable flat flames (normal flames) in the high inlet flow velocity regime; unstable flames called Flames with Repetitive Extinction and Ignition (FREI) in the intermediate flow velocity regime; and stable weak flames in the low flow velocity regime, at phi = 0.6, 1.0 and 1.2. On the other hand, weak flame was not observed at phi = 3.0 by OH-LIF measurement. Computational OH mole fractions showed lower level at the rich conditions than those at stoichiometric and lean conditions. To examine this response of OH signal to equivalence ratio, rate of production analysis was conducted and four kinds of major contributed reaction for OH production: R3(O + H2 <=> H + OH); R38(H + O2 <=> O + OH); R46(H + HO2 <=> 2OH); and R86(2OH <=> O + H2O), were found. Three reactions among them, R3, R38 and R46, did not showed significant difference in rate of OH production for different equivalence ratios. On the other hand, rate of OH production from R86 at phi = 3.0 was extremely lower than those at phi = 0.6 and 1.0. Therefore, R86 was considered to be a key reaction for the reduction of the OH production at phi = 3.0.

Study of atmospheric CH4 mole fractions at three WMO/GAW stations in China

NASA Astrophysics Data System (ADS)

Fang, Shuang-Xi; Zhou, Ling-Xi; Masarie, Kenneth A.; Xu, Lin; Rella, Chris W.

2013-05-01

CH4 mole fractions were continuously measured from 2009 to 2011 at three WMO/GAW stations in China (Lin'an, LAN; Longfengshan, LFS; and Waliguan, WLG) using three Cavity Ring Down Spectroscopy instruments. LAN and LFS are GAW regional measurement stations. LAN is located in China's most economically developed region, and LFS is in a rice production area (planting area > 40,000 km2). WLG is a global measurement station in remote northwest China. At LAN, high methane mole fractions are observed in all seasons. Surface winds from the northeast enhance CH4 values, with a maximum increase of 32 ± 15 ppb in summer. The peak to peak amplitude of the seasonal cycle is 77 ± 35 ppb. At LFS, the diurnal cycle amplitude is approximately constant throughout the year except summer, when a value of 196 ± 65 ppb is observed. CH4 values at LFS reach their peak in July, which is different from seasonal variations typically observed in the northern hemisphere. CH4 mole fractions at WLG show both the smallest values and the lowest variability. Maximum values occur during summer, which is different from other northern hemisphere WMO/GAW global stations. The seasonal cycle amplitude is 17 ± 11 ppb. The linear growth rates at LAN, LFS, and WLG are 8.0 ± 1.2, 7.9 ± 0.9, and 9.4 ± 0.2 ppb yr-1, respectively, which are all larger than the global mean over the same 3 year period. Results from this study attempt to improve our basic understanding of observed atmospheric CH4 in China.

Single-coal-particle combustion in O{sub 2}/N{sub 2} and O{sub 2}/CO{sub 2} environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bejarano, Paula A.; Levendis, Yiannis A.

A fundamental investigation has been conducted on the combustion of single particles of a bituminous coal (45-53, 75-90, and 150-180 {mu}m), of a lignite coal (45-53 and 75-90 {mu}m), and of spherical and monodisperse synthetic chars (43 {mu}m) at increasing O{sub 2} mole fractions in either N{sub 2} or CO{sub 2} balance gases. The synthetic particles were used to facilitate the observation of combustion phenomena with minimum distractions from particle-to-particle variabilities. The laboratory setup consisted of a drop-tube furnace operated at temperatures of 1400 and 1600 K. A calibrated three-color pyrometer, interfaced with the furnace, recorded luminous particle temperature-time profiles.more » Experimental results revealed that coal particles burned at higher mean temperatures and shorter combustion times in O{sub 2}/N{sub 2} than in O{sub 2}/CO{sub 2} environments at analogous oxygen mole fractions. In the case of the bituminous coal used herein and for the experimental combustion conditions tested, measured volatile and char temperatures as in air (21% O{sub 2}) were attained with an oxygen content in the CO{sub 2} mixtures in the neighborhood of 30%. Bituminous coal volatile and char burnout times comparable to those in air (21% O{sub 2}) were attained with oxygen content in the CO{sub 2} mixtures in the range of 30-35%. In the case of the lignite coal burned, the corresponding differences in oxygen mole fractions, which result in similar particle temperatures and burnout times in the two different gas mixtures, were less pronounced. (author)« less

Background Mole Fractions of Hydrocarbons in North America Determined from NOAA Global Reference Network Data

NASA Astrophysics Data System (ADS)

Mielke-Maday, I.

2015-12-01

The National Oceanic and Atmospheric Administration (NOAA) Global Monitoring Division (GMD) maintains a global reference network for over 50 trace gas species and analyzes discrete air samples collected by this network throughout the world at the Earth System Research Laboratory in Boulder, Colorado. In particular, flask samples are analyzed for a number of hydrocarbons with policy and health relevance such as ozone precursors, greenhouse gases, and hazardous air pollutants. Because this global network's sites are remote and therefore minimally influenced by local anthropogenic emissions, these data yield information about background ambient mole fractions and can provide a context for observations collected in intensive field campaigns, such as the Front Range Air Pollution and Photochemistry Experiment (FRAPPE), the Southeast Nexus (SENEX) study, and the DISCOVER-AQ deployments. Information about background mole fractions during field campaigns is critical for calculating hydrocarbon enhancements in the region of study and for assessing the extent to which a particular region's local emissions sources contribute to these enhancements. Understanding the geographic variability of the background and its contribution to regional ambient mole fractions is also crucial for the development of realistic regulations. We present background hydrocarbon mole fractions and their ratios in North America using data from air samples collected in the planetary boundary layer at tall towers and aboard aircraft from 2008 to 2014. We discuss the spatial and seasonal variability in these data. We present trends over the time period of measurements and propose possible explanations for these trends.

OH+ and H2O+: Probes of the Molecular Hydrogen Fraction and Cosmic-Ray Ionization Rate

NASA Astrophysics Data System (ADS)

Indriolo, Nick; Neufeld, D. A.; Gerin, M.; PRISMAS; WISH

2014-01-01

The fast ion-molecule chemistry that occurs in the interstellar medium (ISM) is initiated by cosmic-ray ionization of both atomic and molecular hydrogen. Species that are near the beginning of the network of interstellar chemistry such as the oxygen-bearing ions OH+ and H2O+ can be useful probes of the cosmic-ray ionization rate. This parameter is of particular interest as, to some extent, it controls the abundances of several molecules. Using observations of OH+ and H2O+ made with HIFI on board Herschel, we have inferred the cosmic-ray ionization rate of atomic hydrogen in multiple distinct clouds along 12 Galactic sight lines. These two molecules also allow us to determine the molecular hydrogen fraction (amount of hydrogen nuclei in H2 versus H) as OH+ and H2O+ abundances are dependent on the competition between dissociative recombination with electrons and hydrogen abstraction reactions involving H2. Our observations of OH+ and H2O+ indicate environments where H2 accounts for less than 10% of the available hydrogen nuclei, suggesting that these species primarily reside in the diffuse, atomic ISM. Average ionization rates in this gas are on the order of a few times 10-16 s-1, with most values in specific clouds above or below this average by a factor of 3 or so. This result is in good agreement with the most up-to-date determination of the distribution of cosmic-ray ionization rates in diffuse molecular clouds as inferred from observations of H3+.

Neuroprotective property of low molecular weight fraction from B. jararaca snake venom in H2O2-induced cytotoxicity in cultured hippocampal cells.

PubMed

Querobino, Samyr Machado; Carrettiero, Daniel Carneiro; Costa, Maricilia Silva; Alberto-Silva, Carlos

2017-04-01

In central nervous system cells, low molecular weight fractions (LMWF) from snake venoms can inhibit changes in mitochondrial membrane permeability, preventing the diffusion of cytochrome c to the cytoplasm, inhibiting the activation of pro-apoptotic factors. Here, we evaluated the neuroprotective activity of LMWF from Bothrops jararaca (Bj) snake venom in H 2 O 2 -induced cytotoxicity in cultured hippocampal cells. SDS-PAGE, FT-IR and MALDI-TOF analysis of LMWF (<14 kDa) confirmed the absence of high-molecular-weight proteins in the fraction. LMWF did not present cytotoxicity in all concentrations and time tested by MTT assay. Neuroprotection was evaluated in cells pretreated with LMWF for 4 h prior to the addition of 50 μM H 2 O 2 for 20 h. We demonstrated that LMWF reduced the argininosuccinate synthase (AsS) and superoxide dismutase (SOD1) expressions, suggesting that this fraction as an effective neuroprotective compound that could increase the hippocampal cells viability by attenuation of oxidative stress. In addition, LMWF protects against apoptosis induced by H 2 O 2 , reducing the expression of caspase-3 and caspase-8. Overall, this study opens new perspectives for the identification of new molecules for the development of drugs applied to the treatment of neurodegenerative diseases. Copyright © 2017 Elsevier Ltd. All rights reserved.

Liquidus Diagram of the Ba-Y-Cu-O System in the Vicinity of the Ba2YCu3O6+x Phase Field

PubMed Central

Wong-Ng, Winnie; Cook, Lawrence P.

1998-01-01

This paper describes the melting equilibria in the vicinity of the high Tc phase Ba2YCu3O6+x, including evidence for two Ba-Y-Cu-O immiscible liquids. Melting equilibria have been investigated in purified air using a combination of differential thermal analysis (DTA), thermogravimetric analysis (TGA), powder x-ray diffraction (XRD), MgO wick entrapment of liquid for analysis, scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis (EDS), and hydrogen reduction for determination of copper oxidation state. For relatively barium-rich compositions, it was necessary to prepare the starting materials under controlled atmosphere conditions using BaO. A liquidus diagram was derived from quantitative data for the melts involved in various melting reactions. In general the 1/2(Y2O3) contents of the melts participating in these equilibria were low (mole fraction <4 %). The primary phase field of Ba2YCu3O6+x occurs at a mole fraction of <2.0 % 1/2Y2O3 and lies very close along the BaO-CuOx edge, extending from a mole fraction of ≈43 % CuO to a mole fraction of ≈76 % CuO. It is divided by a liquid miscibility gap and extends on either side about this gap. The topological sequence of melting reactions associated with the liquidus is presented as a function of temperature. Implications for the growth of Ba2YCu3O6+x crystals are discussed. PMID:28009382

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.

Experimental study and detailed modeling of toluene degradation in a low-pressure stoichiometric premixed CH4/O2/N2 flame.

PubMed

Bakali, A El; Dupont, L; Lefort, B; Lamoureux, N; Pauwels, J F; Montero, M

2007-05-17

Temperature and mole fraction profiles have been measured in laminar stoichiometric premixed CH4/O2/N2 and CH4/1.5%C6H5CH3/O2/N2 flames at low pressure (0.0519 bar) by using thermocouple, molecular beam/mass spectrometry (MB/MS), and gas chromatography/mass spectrometry (GC/MS) techniques. The present study completes our previous work performed on the thermal degradation of benzene in CH4/O2/N2 operating at similar conditions. Mole fraction profiles of reactants, final products, and reactive and stable intermediate species have been analyzed. The main intermediate aromatic species analyzed in the methane-toluene flame were benzene, phenol, ethylbenzene, benzylalcohol, styrene, and benzaldehyde. These new experimental results have been modeled with our previous model including submechanisms for aromatics (benzene up to p-xylene) and aliphatic (C1 up to C7) oxidation. Good agreement has been observed for the main species analyzed. The main reaction paths governing the degradation of toluene in the methane flame were identified, and it occurs mainly via the formation of benzene (C6H5CH3 + H = C6H6 + CH3) and benzyl radical (C6H5CH3 + H = C6H5CH2 + H2). Due to the abundance of methyl radicals, it was observed that recombination of benzyl and methyl is responsible for main monosubstitute aromatic species analyzed in the methane-toluene flame. The oxidation of these substitute species led to cyclopentadienyl radical as observed in a methane-benzene flame.

CO Diffusion into Amorphous H2O Ices

NASA Astrophysics Data System (ADS)

Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

2015-03-01

The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

Phase Equilibria and Transport Properties in the Systems AgNO3/RCN/H2O. R = CH3, C2H5, C3H7, C4H,, C6H5, and C6H5CH2

NASA Astrophysics Data System (ADS)

Das, Surjya P.; Wittekopf, Burghard; Weil, Konrad G.

1988-11-01

Silver nitrate can form homogeneous liquid phases with some organic nitriles and water, even when there is no miscibility between the pure liquid components. We determined the shapes of the single phase regions in the ternary phase diagram for the following systems: silver nitrate /RCN /H2O with R =CH3, C3H7, C6H5, and C6H5CH2 at room temperature and for R =C6H5 also at 60 °C and O °C. Furthermore we studied kinematic viscosities, electrical conductivities, and densities of mixtures containing silver nitrate, RCN, and water with the mole ratios X /4 /1 (0.2≦ X ≦S 3.4). In these cases also R = C2H5 and C4H9 were studied. The organic nitriles show different dependences of viscosity and conductivity on the silver nitrate content from the aliphatic ones.

Wavelength-modulation spectroscopy near 1.4 µm for measurements of H2O and temperature in high-pressure and -temperature gases

NASA Astrophysics Data System (ADS)

Goldenstein, C. S.; Spearrin, R. M.; Schultz, I. A.; Jeffries, J. B.; Hanson, R. K.

2014-05-01

The development, validation and demonstration of a two-color tunable diode laser (TDL) absorption sensor for measurements of temperature and H2O in high-pressure and high-temperature gases are presented. This sensor uses first-harmonic-normalized wavelength-modulation spectroscopy with second-harmonic detection (WMS-2f/1f) to account for non-absorbing transmission losses and emission encountered in harsh, high-pressure environments. Two telecommunications-grade TDLs were used to probe H2O absorption transitions near 1391.7 and 1469.3 nm. The lasers were frequency-multiplexed and modulated at 160 and 200 kHz to enable a measurement bandwidth up to 30 kHz along a single line-of-sight. In addition, accurate measurements are enabled at extreme conditions via an experimentally derived spectroscopic database. This sensor was validated under low-absorbance (<0.05) conditions in shock-heated H2O-N2 mixtures at temperatures and pressures from 700 to 2400 K and 2 to 25 atm. There, this sensor recovered the known temperature and H2O mole fraction with a nominal accuracy of 2.8% and 4.7% RMS, respectively. Lastly, this sensor resolved expected transients with high bandwidth and high precision in a reactive shock tube experiment and a pulse detonation combustor.

Low temperature synthesis of monolithic transparent Ta2O5 gels from hydrolysis of metal alkoxide

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.

1993-01-01

Tantalum oxide gels in the form of transparent monoliths and powder were prepared from hydrolysis of tantalum pentaethoxide under controlled conditions using different mole ratios of Ta(OC2H5)5:C2H50H:H20:HCl. Alcohol acts as the mutual solvent and HCl as the deflocculating agent. For a fixed alkoxide:water:HCl ratio, time of gel formation increased with the alcohol to alkoxide mole ratio. Thermal evolution of the physical and structural changes in the gel was monitored by differential thermal analysis, thermogravimetric analysis, x-ray diffraction, and infrared spectroscopy. On heating to approximately 400 C, the amorphous gel crystallized into the low temperature orthorhombic phase Beta-Ta2O5, which transformed into the high temperature tetragonal phase Alpha-Ta2O5 when further heated to approximately 1450 C. The volume fraction of the crystalline phase increased with the firing temperature. The Alpha-Ta205 converted back into the low temperature phase, Beta-Ta2O5, on slow cooling through the transformation temperature of 1360 C indicating a slow but reversible transformation.

Kinetics and Efficiency of H2O2 Activation by Iron-Containing Minerals and Aquifer Materials

PubMed Central

Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

2014-01-01

To gain insight into factors that control H2O2 persistence and ˙OH yield in H2O2-based in situ chemical oxidation systems, the decomposition of H2O2 and transformation of phenol were investigated in the presence of iron-containing minerals and aquifer materials. Under conditions expected during remediation of soil and groundwater, the stoichiometric efficiency, defined as the amount of phenol transformed per mole of H2O2 decomposed, varied from 0.005 to 0.28%. Among the iron-containing minerals, iron oxides were 2 to 10 times less efficient in transforming phenol than iron-containing clays and synthetic iron-containing catalysts. In both iron-containing mineral and aquifer materials systems, the stoichiometric efficiency was inversely correlated with the rate of H2O2 decomposition. In aquifer materials systems, the stoichiometric efficiency was also inversely correlated with the Mn content, consistent with the fact that the decomposition of H2O2 on manganese oxides does not produce ˙OH. Removal of iron and manganese oxide coatings from the surface of aquifer materials by extraction with citrate-bicarbonate-dithionite slowed the rate of H2O2 decomposition on aquifer materials and increased the stoichiometric efficiency. In addition, the presence of 2 mM of dissolved SiO2 slowed the rate of H2O2 decomposition on aquifer materials by over 80% without affecting the stoichiometric efficiency. PMID:23047055

Kinetics and efficiency of H2O2 activation by iron-containing minerals and aquifer materials.

PubMed

Pham, Anh Le-Tuan; Doyle, Fiona M; Sedlak, David L

2012-12-01

To gain insight into factors that control H(2)O(2) persistence and ·OH yield in H(2)O(2)-based in situ chemical oxidation systems, the decomposition of H(2)O(2) and transformation of phenol were investigated in the presence of iron-containing minerals and aquifer materials. Under conditions expected during remediation of soil and groundwater, the stoichiometric efficiency, defined as the amount of phenol transformed per mole of H(2)O(2) decomposed, varied from 0.005 to 0.28%. Among the iron-containing minerals, iron oxides were 2-10 times less efficient in transforming phenol than iron-containing clays and synthetic iron-containing catalysts. In both iron-containing mineral and aquifer materials systems, the stoichiometric efficiency was inversely correlated with the rate of H(2)O(2) decomposition. In aquifer materials systems, the stoichiometric efficiency was also inversely correlated with the Mn content, consistent with the fact that the decomposition of H(2)O(2) on manganese oxides does not produce ·OH. Removal of iron and manganese oxide coatings from the surface of aquifer materials by extraction with citrate-bicarbonate-dithionite slowed the rate of H(2)O(2) decomposition on aquifer materials and increased the stoichiometric efficiency. In addition, the presence of 2 mM of dissolved SiO(2) slowed the rate of H(2)O(2) decomposition on aquifer materials by over 80% without affecting the stoichiometric efficiency. Copyright © 2012 Elsevier Ltd. All rights reserved.

Geochemical mole-balance modeling with uncertain data

USGS Publications Warehouse

Parkhurst, David L.

1997-01-01

Geochemical mole-balance models are sets of chemical reactions that quantitatively account for changes in the chemical and isotopic composition of water along a flow path. A revised mole-balance formulation that includes an uncertainty term for each chemical and isotopic datum is derived. The revised formulation is comprised of mole-balance equations for each element or element redox state, alkalinity, electrons, solvent water, and each isotope; a charge-balance equation and an equation that relates the uncertainty terms for pH, alkalinity, and total dissolved inorganic carbon for each aqueous solution; inequality constraints on the size of the uncertainty terms; and inequality constraints on the sign of the mole transfer of reactants. The equations and inequality constraints are solved by a modification of the simplex algorithm combined with an exhaustive search for unique combinations of aqueous solutions and reactants for which the equations and inequality constraints can be solved and the uncertainty terms minimized. Additional algorithms find only the simplest mole-balance models and determine the ranges of mixing fractions for each solution and mole transfers for each reactant that are consistent with specified limits on the uncertainty terms. The revised formulation produces simpler and more robust mole-balance models and allows the significance of mixing fractions and mole transfers to be evaluated. In an example from the central Oklahoma aquifer, inclusion of up to 5% uncertainty in the chemical data can reduce the number of reactants in mole-balance models from seven or more to as few as three, these being cation exchange, dolomite dissolution, and silica precipitation. In another example from the Madison aquifer, inclusion of the charge-balance constraint requires significant increases in the mole transfers of calcite, dolomite, and organic matter, which reduce the estimated maximum carbon 14 age of the sample by about 10,000 years, from 22,700 years to

Effects of H2O, CO2, and N2 Air Contaminants on Critical Airside Strain Rates for Extinction of Hydrogen-Air Counterflow Diffusion Flames

NASA Technical Reports Server (NTRS)

Pellett, G. L.; Wilson, L. G.; Northam, G. B.; Guerra, Rosemary

1989-01-01

Coaxial tubular opposed jet burners (OJB) were used to form dish shaped counterflow diffusion flames (CFDF), centered by opposing laminar jets of H2, N2 and both clean and contaminated air (O2/N2 mixtures) in an argon bath at 1 atm. Jet velocities for flame extinction and restoration limits are shown versus wide ranges of contaminant and O2 concentrations in the air jet, and also input H2 concentration. Blowoff, a sudden breaking of CFDF to a stable ring shape, occurs in highly stretched stagnation flows and is generally believed to measure kinetically limited flame reactivity. Restore, a sudden restoration of central flame, is a relatively new phenomenon which exhibits a H2 dependent hysteresis from Blowoff. For 25 percent O2 air mixtures, mole for mole replacement of 25 percent N2 contaminant by steam increased U(air) or flame strength at Blowoff by about 5 percent. This result is consistent with laminar burning velocity results from analogous substitution of steam for N2 in a premixed stoichiometric H2-O2-N2 (or steam) flame, shown by Koroll and Mulpuru to promote a 10 percent increase in experimental and calculated laminar burning velocity, due to enhanced third body efficiency of water in: H + O2 + M yields HO2 + M. When the OJB results were compared with Liu and MacFarlane's experimental laminar burning velocity of premixed stoichiometric H2 + air + steam, a crossover occurred, i.e., steam enhanced OJB flame strength at extinction relative to laminar burning velocity.

1-Propanol probing methodology: two-dimensional characterization of the effect of solute on H2O.

PubMed

Koga, Yoshikata

2013-09-21

The wording "hydrophobicity/hydrophilicity" has been used in a loose manner based on human experiences. We have devised a more quantitative way to redefine "hydrophobes" and "hydrophiles" in terms of the mole fraction dependence pattern of one of the third derivative quantities, the enthalpic interaction between solute molecules. We then devised a thermodynamic methodology to characterize the effect of a solute on H2O in terms of its hydrophobicity and/or hydrophilicity. We use a thermodynamic signature, the enthalpic interaction of 1-propanol, H, to monitor how the test solute modifies H2O. By this method, characterization is facilitated by two indices; one pertaining to its hydrophobicity and the other its hydrophilicity. Hence differences among amphiphiles are quantified in a two-dimensional manner. Furthermore, an individual ion can be characterized independent of a counter ion. By using this methodology, we have studied the effects on H2O of a number of solutes, and gained some important new insights. For example, such commonly used examples of hydrophobes in the literature as tetramethyl urea, trimethylamine-N-oxide, and tetramethylammonium salts are in fact surprisingly hydrophilic. Hence the conclusions about "hydrophobes" using these samples ought to be interpreted with caution. The effects of anions on H2O found by this methodology are in the same sequence of the Hofmeister ranking, which will no doubt aid a further investigation into this enigma in biochemistry. Thus, it is likely that this methodology could play an important role in the characterization of the effects of solutes in H2O, and a perspective view may be useful. Here, we describe the basis on which the methodology is developed and the methodology itself in m.ore detail than given in individual papers. We then summarize the results in two dimensional hydrophobicity/hydrophilicity maps.

Influence of H2O on Liquidus Temperatures of Primitive Basalts and Olivine-Liquid Thermometry.

NASA Astrophysics Data System (ADS)

Medard, E.; Grove, T. L.

2005-12-01

We have undertaken a systematic experimental study aimed at understanding the effect of water on olivine liquidus temperatures of primitive basalts. Experiments have been performed on a primitive tholeiitic basalt from Medicine Lake Volcano, California (sample 82-72f, Bartels et al. 1991). The dry liquidus has been characterized from 0.1 MPa to 1.2 GPa. The wet liquidus has been constrained to within 15 °C using water-saturated experiments performed in a MHC externally heated pressure vessel. Preliminary results show that the olivine-liquidus depression (i.e., the difference between dry and water-bearing liquidus) is essentially a linear function of the water content of the melt: ΔT = 560  X(HO0.5), where X(HO0.5) is the mole fraction of water, calculated on a single-cation oxide basis. For 82-72f, this roughly translates into a 30 °C / wt% H2O depression. Simple systems (e.g., diopside/H2O, albite/H2O) suggest that melt structure / composition may have an influence on H2O liquidus depression, and this potential influence is currently under investigation. Experimental phase equilibria and thermobarometry of primitive basalts provide the primary evidence for estimating melting conditions and thermal structures in the Earth's mantle. Assessing the influence of H2O is critical, because it is the dominant volatile component involved in igneous processes, and it has been shown to cause a significant reduction in liquidus temperatures. However, recent model parameterizations vary from very large effects at low H2O contents (about 75 °C at 1 wt% H2O, Falloon and Danyushevsky 2000) to linear effect of H2O vs liquidus temperature (about 25 °C at 1 wt% H2O, Sugawara 2000). Our experimental determination more closely approximates the latter model. A key consequence is that the presence of small amounts of water in MORB magmas (< 1wt%) will only have a very small effect (< 30 °C) on liquidus temperature determination for mid-ocean-ridges. For magmas that are more

Glass transition temperature and conductivity in Li2O and Na2O doped borophosphate glasses

NASA Astrophysics Data System (ADS)

Ashwajeet, J. S.; Sankarappa, T.; Ramanna, R.; Sujatha, T.; Awasthi, A. M.

2015-08-01

Two alkali doped Borophosphate glasses in the composition, (B2O3)0.2. (P2O5)0.3. (Na2O)(0.5-x). (Li2O)x, where x = 0.05 to 0.50 were prepared by standard melt quenching method at 1200K. Non-crystalline nature was confirmed by XRD studies. Room temperature density was measured by Archimedes principle. DC conductivity in the temperature range from 300K to 575K has been measured. Samples were DSC studied in the temperature range from 423K to 673K and glass transition temperature was determined. Glass transition temperature passed through minima for Li2O con.2centration between 0.25 and 0.30 mole fractions. Activation energy of conduction has been determined by analyzing temperature variation of conductivity determining Arrhenius law. Conductivity passed through minimum and activation passed through maximum for Li2O content from 0.25 to 0.30 mole fractions. Glass transition temperature passed through minimum for the same range of Li2O content. These results revealed mixed alkali effect taking place in these glasses. It is for the first time borophosphate glasses doped with Li2O and Na2O have been studied for density and dc conductivity and, the mixed alkali effect (MAE) has been observed.

Cavity Enhanced Spectrometer performance assessment for greenhouse gas dry mole fraction measurement in humid air.

NASA Astrophysics Data System (ADS)

Laurent, Olivier; Yver Kwok, Camille; Guemri, Ali; Philippon, Carole; Rivier, Leonard; Ramonet, Michel

2017-04-01

Due to the high variability of the water vapor content in the atmosphere, the mole fraction of trace gas such as greenhouse gas (GHG) in the atmosphere is usually presented as mole fraction in dry air. In consequence, the first technology used for GHG measurement, gas chromatography or non-dispersive infra-red spectroscopy, required to dry the air sample prior to analysis at a dew point lower than -50°C. The emergence of new GHG analyzers using infrared Enhanced Cavity Spectroscopy which measure the water vapor content in the air sample, allows providing the dry mole fraction of GHG without any drying system upstream by applying appropriate correction of the water vapor effects (dilution, pressure broadening…). In the framework of ICOS, a European research infrastructure aiming to provide harmonized high precision data for advanced research on carbon cycle and GHG budgets over Europe, the Metrology Lab of the Atmosphere Thematic Centre (ATC), located at LSCE in France, is mainly dedicated to elaborating measurement protocols and evaluating performance of GHG analyzers. Among the different tests conducted to characterize the metrological performance, the Metrology Lab focuses on the water vapor correction to apply on the GHG measurement. Most of the analyzers tested at the Metrology Lab are based on Cavity Enhanced Spectroscopy measuring the ICOS mandatory species, CO2, CH4 and CO. This presentation presents the results of the performance assessment of the manufacturer built-in water vapor correction and the possible improvement. Thanks to the large number of instrument tested, the presentation provides a performance overview of the GHG analyzers deployed in the ICOS atmospheric station network. Finally the performance of the water vapor correction will be discussed in regard of the performance obtained by using a drying system.

Exploring the plasma chemistry in microwave chemical vapor deposition of diamond from C/H/O gas mixtures.

PubMed

Kelly, Mark W; Richley, James C; Western, Colin M; Ashfold, Michael N R; Mankelevich, Yuri A

2012-09-27

Microwave (MW)-activated CH(4)/CO(2)/H(2) gas mixtures operating under conditions relevant to diamond chemical vapor deposition (i.e., X(C/Σ) = X(elem)(C)/(X(elem)(C) + X(elem)(O)) ≈ 0.5, H(2) mole fraction = 0.3, pressure, p = 150 Torr, and input power, P = 1 kW) have been explored in detail by a combination of spatially resolved absorption measurements (of CH, C(2)(a), and OH radicals and H(n = 2) atoms) within the hot plasma region and companion 2-dimensional modeling of the plasma. CO and H(2) are identified as the dominant species in the plasma core. The lower thermal conductivity of such a mixture (cf. the H(2)-rich plasmas used in most diamond chemical vapor deposition) accounts for the finding that CH(4)/CO(2)/H(2) plasmas can yield similar maximal gas temperatures and diamond growth rates at lower input powers than traditional CH(4)/H(2) plasmas. The plasma chemistry and composition is seen to switch upon changing from oxygen-rich (X(C/Σ) < 0.5) to carbon-rich (X(C/Σ) > 0.5) source gas mixtures and, by comparing CH(4)/CO(2)/H(2) (X(C/Σ) = 0.5) and CO/H(2) plasmas, to be sensitive to the choice of source gas (by virtue of the different prevailing gas activation mechanisms), in contrast to C/H process gas mixtures. CH(3) radicals are identified as the most abundant C(1)H(x) [x = 0-3] species near the growing diamond surface within the process window for successful diamond growth (X(C/Σ) ≈ 0.5-0.54) identified by Bachmann et al. (Diamond Relat. Mater.1991, 1, 1). This, and the findings of similar maximal gas temperatures (T(gas) ~2800-3000 K) and H atom mole fractions (X(H)~5-10%) to those found in MW-activated C/H plasmas, points to the prevalence of similar CH(3) radical based diamond growth mechanisms in both C/H and C/H/O plasmas.

High-bandwidth scanned-wavelength-modulation spectroscopy sensors for temperature and H2O in a rotating detonation engine

NASA Astrophysics Data System (ADS)

Goldenstein, Christopher S.; Almodóvar, Christopher A.; Jeffries, Jay B.; Hanson, Ronald K.; Brophy, Christopher M.

2014-10-01

The design and use of two-color tunable diode laser (TDL) absorption sensors for measurements of temperature and H2O in a rotating detonation engine (RDE) are presented. Both sensors used first-harmonic-normalized scanned-wavelength-modulation spectroscopy with second-harmonic detection (scanned-WMS-2f/1f) to account for non-absorbing transmission losses and emission encountered in the harsh combustion environment. One sensor used two near-infrared (NIR) TDLs near 1391.7 nm and 1469.3 nm that were modulated at 225 kHz and 285 kHz, respectively, and sinusoidally scanned across the peak of their respective H2O absorption transitions to provide a measurement rate of 50 kHz and a detection limit in the RDE of 0.2% H2O by mole. The other sensor used two mid-infrared (MIR) TDLs near 2551 nm and 2482 nm that were modulated at 90 kHz and 112 kHz, respectively, and sinusoidally scanned across the peak of their respective H2O transitions to provide a measurement rate of 10 kHz and a detection limit in the RDE of 0.02% H2O by mole. Four H2O absorption transitions with different lower-state energies were used to assess the homogeneity of temperature in the measurement plane. Experimentally derived spectroscopic parameters that enable temperature and H2O sensing to within 1.5-3.5% of known values are reported. The sensor design enabling the high-bandwidth scanned-WMS-2f/1f measurements is presented. The two sensors were deployed across two orthogonal and coplanar lines-of-sight (LOS) located in the throat of a converging-diverging nozzle at the RDE combustor exit. Measurements in the non-premixed H2-fueled RDE indicate that the temperature and H2O oscillate at the detonation frequency (≈3.25 kHz) and that production of H2O is a weak function of global equivalence ratio.

Rhus verniciflua Stokes Extract and Its Flavonoids Protect PC-12 Cells against H2O2-Induced Cytotoxicity.

PubMed

Nam, Tae Gyu; Lee, Bong Han; Choi, Hyo-Kyoung; Mansur, Ahmad Rois; Lee, Sang Gil; Kim, Dae-Ok

2017-06-28

Rhus verniciflua Stokes (RVS), an herbal medicine found in East Asia, was extracted and further fractionated to investigate its antioxidant capacity and neuroprotective effects. The RVS ethyl acetate (EtOAc) fraction had the highest level of total phenolics and antioxidant capacity among all solvent fractions tested. Pretreatment of PC-12 cells with the EtOAc fraction effectively attenuated H 2 O 2 -induced oxidative damage. Furthermore, the EtOAc fraction significantly attenuated caspase-3 activity, resulting in inhibition of H 2 O 2 -induced apoptosis. We identified and quantified fustin, sulfuretin, and butein in the EtOAc fraction using accurate mass quadrupole time-of-flight mass spectrometry and reversed-phase high-performance liquid chromatography. The intracellular antioxidant capacity and superoxide dismutase (SOD) activity were significantly increased in PC-12 cells treated with the EtOAc fraction and with individual flavonoids. When cells were pretreated with the EtOAc fraction or individual flavonoids and then co-incubated with diethyldithiocarbamic acid (an inhibitor of SOD activity), cell viability against H 2 O 2 -induced oxidative stress was attenuated. These results suggest that the RVS EtOAc fraction and its flavonoid constituents protect PC-12 cells against H 2 O 2 -induced neurotoxicity through their antioxidant properties.

Ionization of the group 3 metals La, Y and Sc in H2---O2---Ar flames

NASA Astrophysics Data System (ADS)

Patterson, Patricia M.; Goodings, John M.

1995-09-01

Four pairs of premixed, fuel-rich/fuel-lean (FR/FL; equivalence ratio [Phi] = 1.5/0.75). H2---O2---Ar flames at four temperatures in the range 1900-2425 K, all at atmospheric pressure, were doped with about 10-6 mole fraction of the group 3 metals La, Y and Sc using atomizer techniques. The metals produce solid particles in the flames and gaseous metallic species. The latter include free metallic atoms, A, near the flame reaction zone, but only the monoxide AO and the oxide-hydroxide OAOH further downstream at equilibrium; the [OAOH]/[AO] ratio varies in FR/FL flames. Metallic ions (<1% of the total metal) were observed by sampling a given flame along its axis through a nozzle into a mass spectrometer. All of the observed ions can be represented by an oxide ion series AO+·nH2O (n = 0-3 or more) although their actual structures may be different; e.g. A(OH)2+ for n = 1, interpreted as protonated OAOH. A major objective was to ascertain the ionization mechanism, principally that of La. The ionization appears to receive an initial boost from the exothermic chemi-ionization reaction of A with atomic O to produce AO+; further downstream, the ionization level is sustained by the thermal (collisional) ionization of AO to produce AO+ and/or the chemi-ionization of OAOH with H to produce A(OH)2+. The ions AO+, A(OH)2+ and higher hydrates are all rapidly equilibrated by three-body association reactions with water. Ions are lost by dissociative electron-ion recombination of A(OH)2+ and possibly higher hydrates. The chemical ionization of the metallic species by H3O+ was investigated by adding a small quantity of CH4 to the flames. The ion chemistry is discussed in detail. An estimate of the bond dissociation energy D0°(OLa---OH) = 408 ± 40 kJ mol-1 (4.23 ± 0.41 eV) was obtained.

Magnesite Solubility at 800 ºC, 10 kbar, in H2O-CO2± NaCl solutions: implications for carbon transport in the mantle

NASA Astrophysics Data System (ADS)

Fineman, D.; Manning, C. E.

2017-12-01

Magnesite (MgCO3) is an important carbon reservoir in the upper mantle. It can be a product of interaction with mantle fluids, but its solubility has not been determined at high P and T. We measured magnesite solubility at 800 ºC, 10 kbar, in H2O-CO2± NaCl solutions. The NaCl mole fraction (XNaCl) ranged from 0 to 0.4. XCO2 = 0.05 was fixed by addition of hydrous oxalic acid and low fH2 generated by hematite or Mn oxide sealed in inner Pt capsules, added along with a crimped Pt capsule containing pure natural magnesite crystals to a larger Pt capsule containing H2O-CO2± NaCl fluid. Solubility was determined after quenching by the weight loss of the capsule containing magnesite. Magnesite solubility in pure water is 0.02 molal, nearly the same as calcite, 0.025 molal. Solubility rises to 0.37 molal with addition of NaCl to XNaCl =0.3. This value is 1/3 that of calcite at the same XNaCl. Graphite precipitated in experiments at XNaCl > 0.3 and resulted in inconsistent solubility measurements. There are two probable causes: (1) reduction of H2O activity and increase in CO2 activity via NaCl addition, or (2) exhaustion of the fO2 buffer. The experiments demonstrate that transport of Mg+2 and carbonate are substantially increased by saline solutions in the mantle.

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.

Roles of K2O on the CaO-ZnO Catalyst and Its Influence on Catalyst Basicity for Biodiesel Production

NASA Astrophysics Data System (ADS)

Buchori, Luqman; Istadi, I.; Purwanto; Marpaung, Louis Claudia; Safitri, Rahmatika Luthfiani

2018-02-01

This research aimed to study the effect of K2O impregnation on the basicity of the CaO-ZnO catalyst and its effect on biodiesel production. The effect of mole ratio of CaO to ZnO catalyst and %wt K2O were also studied. The mole ratio of CaO to ZnO catalyst was varied at 1:1, 1:1.5, 1:2, 1:3, and 3:1, while the %wt K2O was varied at 1, 3, and 5 %. The catalyst basicity was determined by titration method. The basicity of the catalyst increased after the CaO-ZnO catalyst was impregnated with K2O in all mole ratios of CaO-ZnO catalyst. The addition of K2O as a promoter also increase the basicity. The highest basicity was obtained at the CaO-ZnO mole ratio of 3:1 and 5%wt K2O. The tranesterification process was carried out in a batch reactor at a methanol to oil mole ratio of 15:1, a reaction temperature of 60°C, a reaction time of 4 h, and a catalyst loading of 5%wt oil. The FAME yields obtained were 41.33%. These results proved that K2O plays a role in enhancing the catalyst basicity. In addition, K2O also serves as a binding agent to improve the mechanical properties of the catalyst.

Preparation, Characterization and Photocatalytic Activity of Ag/TiO2 Nanoparticle Semiconductor Catalysts

NASA Astrophysics Data System (ADS)

Zhang, Yaoyao; Li, Mengyao; Guo, Yinli

2018-01-01

A series of Ag-doped TiO2 powder photocatalysts were prepared by the sol-gel method. The phase structure and morphology of the samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The persistent organic pollutant sodium pentachlorophenol ate (PCP-Na) was selected as the target pollutant, and the photocatalytic property of the material Ag/TiO2 was evaluated by PCP-Na degradation rate. It was found that the calcination at 450 °C was conducive to form the anatase structure with high catalytic activity, and the catalytic activity was higher when the silver mole fraction of Ag/TiO2 was 0.50%. The influence of Ag/TiO2 dosage, hydrogen peroxide volume, silver mole fraction and PCP-Na initial concentration was investigated by the single factor experiment.

Direct numerical simulation of turbulent H2-O2 combustion using reduced chemistry

NASA Technical Reports Server (NTRS)

Montgomery, Christopher J.; Kosaly, George; Riley, James J.

1993-01-01

Results of direct numerical simulations of hydrogen-oxygen combustion using a partial-equilibrium chemistry scheme in constant density, decaying, isotropic turbulence are reported. The simulations qualitatively reproduce many features of experimental results, such as superequilibrium radical species mole fractions, with temperature and major species mole fractions closer to chemical equilibrium. It was also observed that the peak reaction rates occur in narrow zones where the stoichiometric surface intersects regions of high scalar dissipation, as might be expected for combustion conditions close to chemical equilibrium. Another finding was that high OH mole fraction correspond more closely to the stoichiometric surface than to areas of high reaction rate for conditions of the simulations. Simulation results were compared to predictions of the Conditional Moment Closure model. This model was found to give good results for all quantities of interest when the conditionally averaged scalar dissipation was used in the prediction. When the nonconditioned average dissipation was used, the predictions compared well to the simulations for most of the species and temperature, but not for the reaction rate. The comparison would be expected to improve for higher Reynolds number flows, however.

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

New experimental constraints on liquidi, critical mixing, and the second critical end point in the system albite-H2O

NASA Astrophysics Data System (ADS)

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

2013-12-01

Supercritical fluids in rock-H2O systems have been proposed to be important agents of mass transfer in high-pressure environments such as subduction zones. We conducted new experimental studies of the important model system H2O-albite (NaAlSi3O8). Equilibrium phase relations were determined in isobaric T-XH2O binaries at 10.0, 12.5, 14.0, 16.0, and 17.0 kbar, at 600-1060 °C and H2O mole fractions (XH2O) of 0.35 to 0.99. All experiments were conducted in a piston-cylinder apparatus. Stabilities of hydrous albite liquid (L) and H2O-rich vapor (V) were determined from textural analysis of run products by binocular, petrographic and scanning electron microscopy. At each pressure, the experiments bracketed the liquidus curve, the topology of the L+V miscibility gap, and the temperature of critical mixing (TC). The bulk composition at critical mixing of L+V is ~50 wt% H2O at all pressures investigated. The P-T trace of the critical curve is described by the equation TC = -59.9P + 1650 (R2=0.998) where T is in °C and P is in kbar, and the equation is valid over the investigated P and T. The results indicate a critical endpoint on the hydrous melting curve at 16.3 kbar and 667 °C. Our results agree reasonably well with the work of Burnham and Jahns (1962, Am. Journal of Sci., 260, 721) and Shen and Keppler (1997, Nature, 385, 710). The constraints on the phase equilibria allow derivation of a thermodynamic model using a modified version of the Redlich-Kister method (1948, Indus. and Eng. Chem., 40b, 345) which allows quantification of the NaAlSi3O8 activity, aAb, and H2O activity, aH2O, over the entire composition range at each of the above listed pressures, between the solidus temperatures and critical temperatures. The results provide fundamental constraints on the physical chemical controls on the generation and solution properties of supercritical and subcritical fluids in the albite-H2O system.

New metal-organic frameworks of [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La, Ce) and [Ce2(C2O4)(C6H6O7)2] . 4H2O

NASA Astrophysics Data System (ADS)

Weng, Sheng-Feng; Wang, Yun-Hsin; Lee, Chi-Shen

2012-04-01

Two novel materials, [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La(1a), Ce(1b)) and [Ce2(C2O4)(C6H6O7)2] . 4H2O (2), with a metal-organic framework (MOF) were prepared with hydrothermal reactions and characterized with photoluminescence, magnetic susceptibility, thermogravimetric analysis and X-ray powder diffraction in situ. The crystal structures were determined by single-crystal X-ray diffraction. Compound 1 crystallized in triclinic space group P1¯ (No. 2); compound 2 crystallized in monoclinic space group P21/c (No. 14). The structure of 1 is built from a 1D MOF, composed of deprotonated citric ligands of three kinds. Compound 2 contains a 2D MOF structure consisting of citrate and oxalate ligands; the oxalate ligand arose from the decomposition in situ of citric acid in the presence of CuII ions. Photoluminescence spectra of compounds 1b and 2 revealed transitions between the 5d1 excited state and two levels of the 4f1 ground state (2F5/2 and 2F7/2). Compounds 1b and 2 containing CeIII ion exhibit a paramagnetic property with weak antiferromagnetic interactions between the two adjacent magnetic centers.

Arsenite oxidation by H 2O 2 in aqueous solutions

NASA Astrophysics Data System (ADS)

Pettine, Maurizio; Campanella, Luigi; Millero, Frank J.

1999-09-01

The rates of the oxidation of As( III) with H 2O 2 were measured in NaCl solutions as a function of pH (7.5-10.3), temperature (10-50C) and ionic strength ( I = 0.01-4). The rate of the oxidation of As( III) with H 2O 2 can be described by the general expression: d[As( III)]/ dt = k[As( III)] [H 2O 2] where k (mol/L -1 min -1) can be determined from (σ = ±0.12) log k=5.29+1.41 pH-0.57 I+1.40 I0.5-4898/ T. The effect of pH on the rates indicates that the reaction is due to AsO( OH) 2-+ H2O2k 1→productsAsO2( OH) 2-+ H2O2k 2→products, AsO33-+ H2O2k 3→products where k = k1 α AsO(OH) 2- + k2 α AsO 2(OH) 2- + k3 α AsO 3 3- and α i are the molar fraction of species i. The values of k1 = 42 ± 20, k2 = (8 ± 1) × 10 4, and k3 = (72 ± 18) × 10 6 mol/L -1 min -1 were found at 25C and I = 0.01 mol/L. The undissociated As(OH) 3 does not react with H 2O 2. The effect of ionic strength on the rate constants has been attributed to the effect of ionic strength on the speciation of As( III). The rate expression has been shown to be valid for NaClO 4 solutions, northern Adriatic sea waters, and Tiber River waters. The cations Fe 2+ and Cu 2+ were found to exert a catalytic effect on the rates. Cu 2+ plays a role at concentration levels (>0.1 μmol/L) which are typical of polluted aquatic systems, while Fe 2+ is important at levels which may be found in lacustrine environments (>5-10 μmol/L). The reaction of As( III) with H 2O 2 may play a role in marine and lacustrine surface waters limiting the accumulation of As( III) resulting from biologically mediated reduction processes of As( V).

Tracking the energy flow in the hydrogen exchange reaction OH + H2O → H2O + OH.

PubMed

Zhu, Yongfa; Ping, Leilei; Bai, Mengna; Liu, Yang; Song, Hongwei; Li, Jun; Yang, Minghui

2018-05-09

The prototypical hydrogen exchange reaction OH + H2O → H2O + OH has attracted considerable interest due to its importance in a wide range of chemically active environments. In this work, an accurate global potential energy surface (PES) for the ground electronic state was developed based on ∼44 000 ab initio points at the level of UCCSD(T)-F12a/aug-cc-pVTZ. The PES was fitted using the fundamental invariant-neural network method with a root mean squared error of 4.37 meV. The mode specific dynamics was then studied by the quasi-classical trajectory method on the PES. Furthermore, the normal mode analysis approach was employed to calculate the final vibrational state distribution of the product H2O, in which a new scheme to acquire the Cartesian coordinates and momenta of each atom in the product molecule from the trajectories was proposed. It was found that, on one hand, excitation of either the symmetric stretching mode or the asymmetric stretching mode of the reactant H2O promotes the reaction more than the translational energy, which can be rationalized by the sudden vector projection model. On the other hand, the relatively higher efficacy of exciting the symmetric stretching mode than that of the asymmetric stretching mode is caused by the prevalence of the indirect mechanism at low collision energies and the stripping mechanism at high collision energies. In addition, the initial collision energy turns ineffectively into the vibrational energy of the products H2O and OH while a fraction of the energy transforms into the rotational energy of the product H2O. Fundamental excitation of the stretching modes of H2O results in the product H2O having the highest population in the fundamental state of the asymmetric stretching mode, followed by the ground state and the fundamental state of the symmetric stretching mode.

Combining two complementary micrometeorological methods to measure CH4 and N2O fluxes over pasture

NASA Astrophysics Data System (ADS)

Laubach, J.; Barthel, M.; Fraser, A.; Hunt, J. E.; Griffith, D. W. T.

2015-09-01

New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier-transform infrared spectrometer (FTIR), measuring the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently-emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 60 % of days at one site and 77 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for one year at the unfertilised, winter-grazed site were 8.2 (± 0.91) nmol CH4 m-2 s-1 and 0.40 (± 0.018) nmol N2O m-2 s-1. During the same year, mean emission rates at the irrigated, fertilised and rotationally-grazed site were 7.0 (± 0.89) nmol CH4 m-2 s-1 and 0.57 (± 0.019) nmol N2O m-2 s-1. At this site, the N2O emissions amounted to 1.19 (± 0.15) % of the

Combining two complementary micrometeorological methods to measure CH4 and N2O fluxes over pasture

NASA Astrophysics Data System (ADS)

Laubach, Johannes; Barthel, Matti; Fraser, Anitra; Hunt, John E.; Griffith, David W. T.

2016-03-01

New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier transform infrared (FTIR) spectrometer, which measured the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 56 % of days at one site and 73 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for 1 year at the unfertilised, winter-grazed site were 8.9 (±0.79) nmol CH4 m-2 s-1 and 0.38 (±0.018) nmol N2O m-2 s-1. During the same year, mean emission rates at the irrigated, fertilised and rotationally grazed site were 8.9 (±0.79) nmol CH4 m-2 s-1 and 0.58 (±0.020) nmol N2O m-2 s-1. At this site, the N2O emissions amounted to 1.21 (±0.15) % of the nitrogen

Energetics of CO2 and H2O adsorption on zinc oxide.

PubMed

Gouvêa, Douglas; Ushakov, Sergey V; Navrotsky, Alexandra

2014-08-05

Adsorption of H2O and CO2 on zinc oxide surfaces was studied by gas adsorption calorimetry on nanocrystalline samples prepared by laser evaporation in oxygen to minimize surface impurities and degassed at 450 °C. Differential enthalpies of H2O and CO2 chemisorption are in the range -150 ±10 kJ/mol and -110 ±10 kJ/mol up to a coverage of 2 molecules per nm(2). Integral enthalpy of chemisorption for H2O is -96.8 ±2.5 kJ/mol at 5.6 H2O/nm(2) when enthalpy of water condensation is reached, and for CO2 is -96.6 ±2.5 kJ/mol at 2.6 CO2/nm(2) when adsorption ceases. These values are consistent with those reported for ZnO prepared by other methods after similar degas conditions. The similar energetics suggests possible competition of CO2 and H2O for binding to ZnO surfaces. Exposure of bulk and nanocrystalline ZnO with preadsorbed CO2 to water vapor results in partial displacement of CO2 by H2O. In contrast, temperature-programmed desorption (TPD) indicates that a small fraction of CO2 is retained on ZnO surfaces up to 800 °C, under conditions where all H2O is desorbed, with adsorption energies near -200 kJ/mol. Although molecular mechanisms of adsorption were not studied, the thermodynamic data are consistent with dissociative adsorption of H2O at low coverage and with several different modes of CO2 binding.

In situ quantitative analysis of individual H2O-CO2 fluid inclusions by laser Raman spectroscopy

USGS Publications Warehouse

Azbej, T.; Severs, M.J.; Rusk, B.G.; Bodnar, R.J.

2007-01-01

Raman spectral parameters for the Raman ??1 (1285??cm- 1) and 2??2 (1388??cm- 1) bands for CO2 and for the O-H stretching vibration band of H2O (3600??cm- 1) were determined in H2O-CO2 fluid inclusions. Synthetic fluid inclusions containing 2.5 to 50??mol% CO2 were analyzed at temperatures equal to or greater than the homogenization temperature. The results were used to develop an empirical relationship between composition and Raman spectral parameters. The linear peak intensity ratio (IR = ICO2/(ICO2 + IH2O)) is related to the CO2 concentration in the inclusion according to the relation:Mole % C O2 = e- 3.959 IR2 + 8.0734 IRwhere ICO2 is the intensity of the 1388 cm- 1 peak and IH2O is the intensity of the 3600 cm- 1 peak. The relationship between linear peak intensity and composition was established at 350????C for compositions ranging from 2.5 to 50??mol% CO2. The CO2-H2O linear peak intensity ratio (IR) varies with temperature and the relationship between composition and IR is strictly valid only if the inclusions are analyzed at 350????C. The peak area ratio is defined as AR = ACO2/(ACO2 + AH2O), where ACO2 is the integrated area under the 1388??cm- 1 peak and AH2O is the integrated area under the 3600??cm- 1 peak. The relationship between peak area ratio (AR) and the CO2 concentration in the inclusions is given as:Mole % C O2 = 312.5 AR. The equation relating peak area ratio and composition is valid up to 25??mol% CO2 and from 300 to 450????C. The relationship between linear peak intensity ratio and composition should be used for inclusions containing ??? 50??mol% CO2 and which can be analyzed at 350????C. The relationship between composition and peak area ratios should be used when analyzing inclusions at temperatures less than or greater than 350????C (300-450) but can only be used for compositions ??? 25??mol% CO2. Note that this latter relationship has a somewhat larger standard deviation compared to the intensity ratio relationship. Calibration

H2 Ortho-to-para Conversion on Grains: A Route to Fast Deuterium Fractionation in Dense Cloud Cores?

NASA Astrophysics Data System (ADS)

Bovino, S.; Grassi, T.; Schleicher, D. R. G.; Caselli, P.

2017-11-01

Deuterium fractionation, I.e., the enhancement of deuterated species with respect to non-deuterated ones, is considered to be a reliable chemical clock of star-forming regions. This process is strongly affected by the ortho-to-para H2 ratio. In this Letter we explore the effect of the ortho-para (o-p) H2 conversion on grains on the deuteration timescale in fully-depleted dense cores, including the most relevant uncertainties that affect this complex process. We show that (I) the o-p H2 conversion on grains is not strongly influenced by the uncertainties on the conversion time and the sticking coefficient, and (II) that the process is controlled by the temperature and the residence time of ortho-H2 on the surface, I.e., by the binding energy. We find that for binding energies between 330 and 550 K, depending on the temperature, the o-p H2 conversion on grains can shorten the deuterium fractionation timescale by orders of magnitude, opening a new route for explaining the large observed deuteration fraction D frac in dense molecular cloud cores. Our results suggest that the star formation timescale, when estimated through the timescale to reach the observed deuteration fractions, might be shorter than previously proposed. However, more accurate measurements of the binding energy are needed in order to better assess the overall role of this process.

Constraining N2O emissions since 1940 using firn air isotope measurements in both hemispheres

NASA Astrophysics Data System (ADS)

Prokopiou, Markella; Martinerie, Patricia; Sapart, Célia J.; Witrant, Emmanuel; Monteil, Guillaume; Ishijima, Kentaro; Bernard, Sophie; Kaiser, Jan; Levin, Ingeborg; Blunier, Thomas; Etheridge, David; Dlugokencky, Ed; van de Wal, Roderik S. W.; Röckmann, Thomas

2017-04-01

N2O is currently the third most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes over the past decades, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using new and previously published firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290 ± 1) nmol mol-1 in 1940 to (322 ± 1) nmol mol-1 in 2008, the isotopic composition of atmospheric N2O decreased by (-2.2 ± 0.2) ‰ for δ15Nav, (-1.0 ± 0.3) ‰ for δ18O, (-1.3 ± 0.6) ‰ for δ15Nα, and (-2.8 ± 0.6) ‰ for δ15Nβ over the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric box and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to fix at 123 years. The average isotopic composition over the investigated period is δ15Nav = (-7.6 ± 0.8) ‰ (vs. air-N2), δ18O = (32.2 ± 0.2) ‰ (vs. Vienna Standard Mean Ocean Water - VSMOW) for δ18O, δ15Nα = (-3.0 ± 1.9) ‰ and δ15Nβ = (-11.7 ± 2.3) ‰. δ15Nav, and δ15Nβ show some temporal variability, while for the other signatures the error bars of the reconstruction are too large to retrieve reliable temporal changes. Possible processes that may explain trends in 15N are discussed. The 15N site preference ( = δ15Nα - δ15Nβ) provides evidence of a shift in emissions from denitrification to nitrification, although the uncertainty envelopes are large.

Vibrations and reorientations of H2O molecules in [Sr(H2O)6]Cl2 studied by Raman light scattering, incoherent inelastic neutron scattering and proton magnetic resonance.

PubMed

Hetmańczyk, Joanna; Hetmańczyk, Lukasz; Migdał-Mikuli, Anna; Mikuli, Edward; Florek-Wojciechowska, Małgorzata; Harańczyk, Hubert

2014-04-24

Vibrational-reorientational dynamics of H2O ligands in the high- and low-temperature phases of [Sr(H2O)6]Cl2 was investigated by Raman Spectroscopy (RS), proton magnetic resonance ((1)H NMR), quasielastic and inelastic incoherent Neutron Scattering (QENS and IINS) methods. Neutron powder diffraction (NPD) measurements, performed simultaneously with QENS, did not indicated a change of the crystal structure at the phase transition (detected earlier by differential scanning calorimetry (DSC) at TC(h)=252.9 K (on heating) and at TC(c)=226.5K (on cooling)). Temperature dependence of the full-width at half-maximum (FWHM) of νs(OH) band at ca. 3248 cm(-1) in the RS spectra indicated small discontinuity in the vicinity of phase transition temperature, what suggests that the observed phase transition may be associated with a change of the H2O reorientational dynamics. However, an activation energy value (Ea) for the reorientational motions of H2O ligands in both phases is nearly the same and equals to ca. 8 kJ mol(-1). The QENS peaks, registered for low temperature phase do not show any broadening. However, in the high temperature phase a small QENS broadening is clearly visible, what implies that the reorientational dynamics of H2O ligands undergoes a change at the phase transition. (1)H NMR line is a superposition of two powder Pake doublets, differentiated by a dipolar broadening, suggesting that there are two types of the water molecules in the crystal lattice of [Sr(H2O)6]Cl2 which are structurally not equivalent average distances between the interacting protons are: 1.39 and 1.18 Å. However, their reorientational dynamics is very similar (τc=3.3⋅10(-10) s). Activation energies for the reorientational motion of these both kinds of H2O ligands have nearly the same values in an experimental error limit: and equal to ca. 40 kJ mole(-1). The phase transition is not seen in the (1)H NMR spectra temperature dependencies. Infrared (IR), Raman (RS) and inelastic

Effect of Genetic Database Comprehensiveness on Fractional Proteomics of Escherichia coli O157:H7

DTIC Science & Technology

2014-01-01

proteins would be observed in the extracellular fraction. 15. SUBJECT TERMS Escherichia coli O157:H7 Liquid chromatography Mass spectrometry...Preparation ...............1 2.2 Liquid Chromatography /Mass Spectrometry Sample Preparation ....................2 2.3 Liquid Chromatography /Mass... Chromatography /Mass Spectrometry Sample Preparation. Samples were prepared for liquid chromatography tandem mass spectrometry (LC-MS/MS) in a similar

Estimating regional methane surface fluxes: the relative importance of surface and GOSAT mole fraction measurements

NASA Astrophysics Data System (ADS)

Fraser, A.; Palmer, P. I.; Feng, L.; Boesch, H.; Cogan, A.; Parker, R.; Dlugokencky, E. J.; Fraser, P. J.; Krummel, P. B.; Langenfelds, R. L.; O'Doherty, S.; Prinn, R. G.; Steele, L. P.; van der Schoot, M.; Weiss, R. F.

2013-06-01

We use an ensemble Kalman filter (EnKF), together with the GEOS-Chem chemistry transport model, to estimate regional monthly methane (CH4) fluxes for the period June 2009-December 2010 using proxy dry-air column-averaged mole fractions of methane (XCH4) from GOSAT (Greenhouse gases Observing SATellite) and/or NOAA ESRL (Earth System Research Laboratory) and CSIRO GASLAB (Global Atmospheric Sampling Laboratory) CH4 surface mole fraction measurements. Global posterior estimates using GOSAT and/or surface measurements are between 510-516 Tg yr-1, which is less than, though within the uncertainty of, the prior global flux of 529 ± 25 Tg yr-1. We find larger differences between regional prior and posterior fluxes, with the largest changes in monthly emissions (75 Tg yr-1) occurring in Temperate Eurasia. In non-boreal regions the error reductions for inversions using the GOSAT data are at least three times larger (up to 45%) than if only surface data are assimilated, a reflection of the greater spatial coverage of GOSAT, with the two exceptions of latitudes >60° associated with a data filter and over Europe where the surface network adequately describes fluxes on our model spatial and temporal grid. We use CarbonTracker and GEOS-Chem XCO2 model output to investigate model error on quantifying proxy GOSAT XCH4 (involving model XCO2) and inferring methane flux estimates from surface mole fraction data and show similar resulting fluxes, with differences reflecting initial differences in the proxy value. Using a series of observing system simulation experiments (OSSEs) we characterize the posterior flux error introduced by non-uniform atmospheric sampling by GOSAT. We show that clear-sky measurements can theoretically reproduce fluxes within 10% of true values, with the exception of tropical regions where, due to a large seasonal cycle in the number of measurements because of clouds and aerosols, fluxes are within 15% of true fluxes. We evaluate our posterior methane

Estimating regional methane surface fluxes: the relative importance of surface and GOSAT mole fraction measurements

NASA Astrophysics Data System (ADS)

Fraser, A.; Palmer, P. I.; Feng, L.; Boesch, H.; Cogan, A.; Parker, R.; Dlugokencky, E. J.; Fraser, P. J.; Krummel, P. B.; Langenfelds, R. L.; O'Doherty, S.; Prinn, R. G.; Steele, L. P.; van der Schoot, M.; Weiss, R. F.

2012-12-01

We use an ensemble Kalman filter (EnKF), together with the GEOS-Chem chemistry transport model, to estimate regional monthly methane (CH4) fluxes for the period June 2009-December 2010 using proxy dry-air column-averaged mole fractions of methane (XCH4) from GOSAT (Greenhouse gases Observing SATellite) and/or NOAA ESRL (Earth System Research Laboratory) and CSIRO GASLAB (Global Atmospheric Sampling Laboratory) CH4 surface mole fraction measurements. Global posterior estimates using GOSAT and/or surface measurements are between 510-516 Tg yr-1, which is less than, though within the uncertainty of, the prior global flux of 529 ± 25 Tg yr-1. We find larger differences between regional prior and posterior fluxes, with the largest changes (75 Tg yr-1) occurring in Temperate Eurasia. In non-boreal regions the error reductions for inversions using the GOSAT data are at least three times larger (up to 45%) than if only surface data are assimilated, a reflection of the greater spatial coverage of GOSAT, with the two exceptions of latitudes > 60° associated with a data filter and over Europe where the surface network adequately describes fluxes on our model spatial and temporal grid. We use CarbonTracker and GEOS-Chem XCO2 model output to investigate model error on quantifying proxy GOSAT XCH4 (involving model XCO2) and inferring methane flux estimates from surface mole fraction data and show similar resulting fluxes, with differences reflecting initial differences in the proxy value. Using a series of observing system simulation experiments (OSSEs) we characterize the posterior flux error introduced by non-uniform atmospheric sampling by GOSAT. We show that clear-sky measurements can theoretically reproduce fluxes within 5% of true values, with the exception of South Africa and Tropical South America where, due to a large seasonal cycle in the number of measurements because of clouds and aerosols, fluxes are within 17% and 19% of true fluxes, respectively. We evaluate our

Application of time-division-multiplexed lasers for measurements of gas temperature and CH4 and H2O concentrations at 30 kHz in a high-pressure combustor.

PubMed

Caswell, Andrew W; Kraetschmer, Thilo; Rein, Keith; Sanders, Scott T; Roy, Sukesh; Shouse, Dale T; Gord, James R

2010-09-10

Two time-division-multiplexed (TDM) sources based on fiber Bragg gratings were applied to monitor gas temperature, H(2)O mole fraction, and CH(4) mole fraction using line-of-sight absorption spectroscopy in a practical high-pressure gas turbine combustor test article. Collectively, the two sources cycle through 14 wavelengths in the 1329-1667 nm range every 33 μs. Although it is based on absorption spectroscopy, this sensing technology is fundamentally different from typical diode-laser-based absorption sensors and has many advantages. Specifically, the TDM lasers allow efficient, flexible acquisition of discrete-wavelength information over a wide spectral range at very high speeds (typically 30 kHz) and thereby provide a multiplicity of precise data at high speeds. For the present gas turbine application, the TDM source wavelengths were chosen using simulated temperature-difference spectra. This approach is used to select TDM wavelengths that are near the optimum values for precise temperature and species-concentration measurements. The application of TDM lasers for other measurements in high-pressure, turbulent reacting flows and for two-dimensional tomographic reconstruction of the temperature and species-concentration fields is also forecast.

Injectant mole-fraction imaging in compressible mixing flows using planar laser-induced iodine fluorescence

NASA Technical Reports Server (NTRS)

Hartfield, Roy J., Jr.; Abbitt, John D., III; Mcdaniel, James C.

1989-01-01

A technique is described for imaging the injectant mole-fraction distribution in nonreacting compressible mixing flow fields. Planar fluorescence from iodine, seeded into air, is induced by a broadband argon-ion laser and collected using an intensified charge-injection-device array camera. The technique eliminates the thermodynamic dependence of the iodine fluorescence in the compressible flow field by taking the ratio of two images collected with identical thermodynamic flow conditions but different iodine seeding conditions.

H2O Paradox and its Implications on H2O in Moon

NASA Astrophysics Data System (ADS)

Zhang, Youxue

2017-04-01

The concentration of H2O in the mantle of a planetary body plays a significant role in the viscosity and partial melting and hence the convection and evolution of the planetary body. Even though the composition of the primitive terrestrial mantle (PTM) is thought to be well known [1-2], the concentration of H2O in PTM remains paradoxial because different methods of estimation give different results [3]: Using H2O/Ce ratio in MORB and OIB and Ce concentration in PTM, the H2O concentration in PTM would be (300÷×1.5) ppm; using mass balance by adding surface water to the mantle [3-4], H2O concentration in PTM would be (900÷×1.3) ppm [2-3]. The inconsistency based on these two seemingly reliable methods is referred to as the H2O paradox [3]. For Moon, H2O contents in the primitive lunar mantle (PLM) estimated from H2O in plagioclase in lunar anorthosite and that from H2O/Ce ratio in melt inclusions are roughly consistent at ˜110 ppm [5-6] even though there is still debate about the volatile depletion trend [7]. One possible solution to the H2O paradox in PTM is to assume that early Earth experienced whole mantle degassing, which lowered the H2O/Ce ratio in the whole mantle but without depleting Ce in the mantle. The second possible solution is that some deep Earth reservoirs with high H2O/Ce ratios have not been sampled by MORB and OIB. Candidates include the transition zone [8] and the D" layer. The third possible solution is that ocean water only partially originated from mantle degassing, but partially from extraterrestrial sources such as comets [9-10]. At present, there is not enough information to determine which scenario is the answer to the H2O paradox. On the other hand, each scenario would have its own implications to H2O in PLM. If the first scenario applies to Moon, because degassed H2O or H2 would have escaped from the lunar surface, the very early lunar mantle could have much higher H2O [11] than that obtained using the H2O/Ce ratio method. The

Automated calibration of laser spectrometer measurements of δ18 O and δ2 H values in water vapour using a Dew Point Generator.

PubMed

Munksgaard, Niels C; Cheesman, Alexander W; Gray-Spence, Andrew; Cernusak, Lucas A; Bird, Michael I

2018-06-30

Continuous measurement of stable O and H isotope compositions in water vapour requires automated calibration for remote field deployments. We developed a new low-cost device for calibration of both water vapour mole fraction and isotope composition. We coupled a commercially available dew point generator (DPG) to a laser spectrometer and developed hardware for water and air handling along with software for automated operation and data processing. We characterised isotopic fractionation in the DPG, conducted a field test and assessed the influence of critical parameters on the performance of the device. An analysis time of 1 hour was sufficient to achieve memory-free analysis of two water vapour standards and the δ 18 O and δ 2 H values were found to be independent of water vapour concentration over a range of ≈20,000-33,000 ppm. The reproducibility of the standard vapours over a 10-day period was better than 0.14 ‰ and 0.75 ‰ for δ 18 O and δ 2 H values, respectively (1 σ, n = 11) prior to drift correction and calibration. The analytical accuracy was confirmed by the analysis of a third independent vapour standard. The DPG distillation process requires that isotope calibration takes account of DPG temperature, analysis time, injected water volume and air flow rate. The automated calibration system provides high accuracy and precision and is a robust, cost-effective option for long-term field measurements of water vapour isotopes. The necessary modifications to the DPG are minor and easily reversible. Copyright © 2018 John Wiley & Sons, Ltd.

Exploration of H2O-CO2 Solubility in Alkali Basalt at low-H2O

NASA Astrophysics Data System (ADS)

Roggensack, K.; Allison, C. M.; Clarke, A. B.

2017-12-01

A number of recent experimental studies have found conflicting evidence for and against the influence of H2O on CO2 solubility in basalt and alkali-rich mafic magma (e.g. Behrens et al., 2009; Shishkina et al., 2010;2014; Iacono-Marziano et al., 2012). Some of the uncertainty is due to the error with spectroscopic determination (FTIR) of carbon and the challenge of controlling H2O abundance in experiments. It's been widely observed that even experimental capsules without added H2O may produce hydrous glasses containing several wt.% H2O. We conducted fluid-saturated, mixed-fluid (H2O-CO2) experiments to determine the solubility in alkali basalt with particular emphasis on conditions at low-H2O. To limit possible H2O contamination, materials were dried prior to loading and experimental capsules were sealed under vacuum. Experiments were run using a piston-cylinder, in Pt (pre-soaked in Fe) or AuPd capsules and operating at pressures from 400 to 600 MPa. Post-run the capsules were punctured under vacuum and fluids were condensed, separated, and measured by mercury manometry. A comparison between two experiments run at the same temperature and pressure conditions but with different fluid compositions illustrates the correlation between carbonate and H2O solubility. Uncertainties associated with using concentrations calculated from FTIR data can be reduced by directly comparing analyses on wafers of similar thickness. We observe that the experiment with greater H2O absorbance also has a higher carbonate absorbance than the experiment with lower H2O absorbance. Since the experiments were run at the same pressure, the experiment with more water-rich fluid, and higher dissolved H2O, has lower CO2 fugacity, but surprisingly has higher dissolved CO2 content. Overall, the results show two distinct trends. Experiments conducted at low-H2O (0.5 to 0.8 wt.%) show lower dissolved CO2 than those conducted at moderate-H2O (2 to 3 wt.%) at similar CO2 fugacity. These data show that

Lateral variation of H2O/K2O ratios in Quaternary Magma of the Northeastern Japan arc

NASA Astrophysics Data System (ADS)

Miyagi, I.

2012-12-01

Water plays a fundamental role in the magma genesis beneath subduction zones. In order to estimate a spatial distribution of the density of water flux in the wedge mantle of the Northeastern Japan arc, this study examines a lateral variation of pre-eruptive bulk rock H2O/K2O contents among volcanoes located both in the frontal and in back arc settings. The analytical targets are the frontal volcanoes Nigorikawa (N42.12 E140.45), Zenikame (N41.74 E140.85), Adachi (N38.22 E140.65), and Nanashigure (N40.07 E141.11), and the back arc ones Hijiori (N38.61 E140.17) and Kanpu (N39.93 E139.88). The bulk magmatic H2O content (TH2O) is calculated from a mass balance of hydrogen isotopic ratios among three phases in a batch of magma; dissolved water in melt, excess H2O vapor, and hydrous phenocrysts such as amphiboles (Miyagi and Matsubaya, 2003). Since the amount of H2O in hydrous phenocryst is negligible, the bulk magmatic H2O content can be written as TH2O = (30 XD CD) / (15 - dT + dMW), where dMW is the measured hydrogen isotopic ratio of hydrous phenocrysts, XD is a melt fraction of magma, CD is a water concentration of the melt, and dT is hydrogen isotopic ratios of a bulk magma (assumed to be -50 per-mil). Both XD and CD are estimated from bulk rock chemistry of the sample using the MELTS program (Ghiorso and Sack, 1995). Hydrogen isotopic fractionation factors are assumed to be -15 and -30 per-mil for vapor and hydrous mineral, and vapor and silicate melt, respectively. There observed a clear difference among the H2O/K2O ratios of bulk magmas from the frontal and back arc volcanoes. For instance higher H2O/K2O wt ratios was observed in the frontal volcanoes (Nigorikawa 5.3, Zenikame 11-12, Adachi 8-10, and Nanashigure 4-18), while lower H2O/K2O wt ratios was observed in the back arc ones (Kanpu 0-2.5 and Hijiori 1.4). The lateral variation of H2O/K2O ratios infer the higher water flux through the frontal side of wedge mantle, which can be a potential cause of the

Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2H 4) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2O

NASA Astrophysics Data System (ADS)

Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon

1996-11-01

The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= 18.425(4) Å,c= 8.954(2) Å, β = 93.69(2)0,V= 1221.1(4) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = 10.090(2) Å, α = 104.50(2)0, β = 100.39(2)0, δ = 92.13(2)0,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.

Preparation of ZrO II/nano-TiO II composite powder by sol-gel method

NASA Astrophysics Data System (ADS)

Baharvandi, H. R.; Mohammadi, E.; Abdizadeh, H.; Hadian, A. M.; Ehsani, N.

2007-07-01

The effects of concentration of TTIP, amount of distilled water, and calcination temperature on morphology and particle size distribution of ZrO II/nano-TiO II catalysts were investigated. Mixed ZrO II/nano-TiO II powders were prepared by a modified sol-gel method by varying the mole fraction of TTIP from 0.002 to 0.01, H IIO/TTIP fraction from 2 to 8, and various stirring time (2, 4, and 10 h). The prepared ZrO II/nano-TiO II powders have been characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and TG/DTA. Each oxide was calcined at the temperature between 110 and 1000°C. The results showed that the calcinations temperature has a pronounced effect on the phase formation and particle size of the calcined zirconium titanate (ZT) powders.

Kinetic stable Cr isotopic fractionation between aqueous Cr(III)-Cl-H2O complexes at 25 °C: Implications for Cr(III) mobility and isotopic variations in modern and ancient natural systems

NASA Astrophysics Data System (ADS)

Babechuk, Michael G.; Kleinhanns, Ilka C.; Reitter, Elmar; Schoenberg, Ronny

2018-02-01

The stable Cr isotope fractionation preserved in natural substances has been attributed predominantly to Cr(III)-Cr(VI) redox transformations. However, non-redox reaction pathways (e.g., ligand-promoted dissolution, ligand exchange, adsorption of Cr(III)) are liable to contribute to isotopic fractionation in natural systems given that soluble Cr(III)-ligands have been directly documented or modeled in several marine, continental, and hydrothermal environments. This study isolates the stable Cr isotope fractionation accompanying Cl-H2O ligand exchange during the transformation of three aqueous species in the Cr(III)-Cl-H2O system, [CrCl2(H2O)4]+aq (abr. CrCl2+ or S1), [CrCl(H2O)5]2+aq (abr. CrCl2+ or S2), and [Cr(H2O)6]3+aq (abr. Cr3+ or S3), at low pH (≤2). In dilute HCl (0.01 to 1 M), Cr3+ is the kinetically favoured species and transformation of CrCl2+ to CrCl2+ to Cr3+ via 2 steps of dechlorination/hydrolyzation begins immediately upon dissolution of a Cr(III)-Cl solid. Individual species are separated with cation exchange chromatography at different stages of transformation and inter- and intra-species (across an elution peak of one species) isotopic fractionation of up to 1 and 2‰ (δ53/52Cr), respectively, is documented. Comparison of peak elution characteristics with Cr-Cl-H-O isotopologue mass abundances suggests mass-dependent sorting of isotopologues alone cannot explain intra-species fractionation, supporting a previously published proposal that preferential adsorption of light Cr isotopes on the resin is driven by vibrational energy effects. The transformation of CrCl2+ to CrCl2+ is faster than CrCl2+ to Cr3+ and the rates of both transformations increase with solution pH. Preferential reaction of light Cr(III) isotopes into product species occurs during each transformation, consistent with closed-system, kinetic fractionation during Cl-H2O ligand exchange. Inter-species fractionation is assessed using time-series experiments beginning from the

Development of a field-deployable method for simultaneous, real-time measurements of the four most abundant N2O isotopocules.

PubMed

Ibraim, Erkan; Harris, Eliza; Eyer, Simon; Tuzson, Béla; Emmenegger, Lukas; Six, Johan; Mohn, Joachim

2018-03-01

Understanding and quantifying the biogeochemical cycle of N 2 O is essential to develop effective N 2 O emission mitigation strategies. This study presents a novel, fully automated measurement technique that allows simultaneous, high-precision quantification of the four main N 2 O isotopocules ( 14 N 14 N 16 O, 14 N 15 N 16 O, 15 N 14 N 16 O and 14 N 14 N 18 O) in ambient air. The instrumentation consists of a trace gas extractor (TREX) coupled to a quantum cascade laser absorption spectrometer, designed for autonomous operation at remote measurement sites. The main advantages this system has over its predecessors are a compact spectrometer design with improved temperature control and a more compact and powerful TREX device. The adopted TREX device enhances the flexibility of the preconcentration technique for higher adsorption volumes to target rare isotope species and lower adsorption temperatures for highly volatile substances. All system components have been integrated into a standardized instrument rack to improve portability and accessibility for maintenance. With an average sampling frequency of approximately 1 h -1 , this instrumentation achieves a repeatability of 0.09, 0.13, 0.17 and 0.12 ‰ for δ 15 N α , δ 15 N β , δ 18 O and site preference of N 2 O, respectively, for pressurized ambient air. The repeatability for N 2 O mole fraction measurements is better than 1 ppb (parts per billion, 10 -9 moles per mole of dry air).

Constraining N2O emissions since 1940 by firn air isotope measurements in both hemispheres

NASA Astrophysics Data System (ADS)

Prokopiou, Markella; Martinerie, Patricia; Sapart, Celia; Witrant, Emmanuel; Monteil, Guillaume; Ishijima, Kentaro; Kaiser, Jan; Levin, Ingeborg; Sowers, Todd; Blunier, Thomas; Etheridge, David; Dlugokencky, Ed; van de Wal, Roderik; Röckmann, Thomas

2017-04-01

N2O is currently the 3rd most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290±1) nmol mol-1 in 1940 to (322±1) nmol mol-1 in 2008 the isotopic δ values of atmospheric N2O decreased by (- 2.2±0.2) ‰ for δ15Nav, (- 1.0±0.3) ‰ for δ18O, (- 1.3±0.6) ‰ for δ15Nα, and (- 2.8±0.6) ‰ for δ15Nβover the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to be 123 a. Adopting this lifetime results in total average source isotopic signatures of (- 7.6±0.8) ‰ (vs. Air-N2) for δ15Nav, (32.2±0.2) ‰ (vs. VSMOW) for δ18O, (- 3.0±1.9) ‰ (vs. Air-N2) for δ15Nα, and (- 11.7±2.3) ‰ (vs. Air-N2) for δ15Nβ over the investigated period. δ15Navand δ15Nβ show some temporal variability while the other source isotopic signatures remain unchanged. The 15N site-preference (= δ15Nα - δ15Nβ) can be used to reveal further information on the source emission origins. Based on the changes in the isotopes we conclude that the main contribution to N2O changes in the atmosphere since 1940 is from soils, with agricultural soils being the principal anthropogenic component, which is in line with previous studies.

Impact of underlap and mole-fraction on RF performance of strained-Si/Si1-xGex/strained-Si DG MOSFETs

NASA Astrophysics Data System (ADS)

Dutta, Arka; Koley, Kalyan; Sarkar, Chandan K.

2014-11-01

In this paper, a systematic RF performance analysis of double-gate strained silicon (DGSS) nMOSFETs is presented. The analysis is focused upon impact of Germanium mole-fraction variation on RF performance of underlap engineered DGSS nMOSFET. The RF performance of the device is analysed as a function of intrinsic RF figure of merits (FOMs) including non-quasi static effects (NQS). The RF FOMs are represented by the intrinsic gate to source/drain capacitance (Cgs and Cgd) and resistance (Rgs and Rgd), the transport delay (τm), the intrinsic inductance (Lsd), the cut-off frequency (fT), and the maximum oscillation frequency (fMAX). The results of the study suggested a significant improvement in the device performance, up to 40% increase in Germanium mole fraction (χ).

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

PubMed

Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

2012-02-20

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

State-to-State integral cross section for the H+H2O-->H2+OH abstraction reaction.

PubMed

Zhang, Dong H; Xie, Daiqian; Yang, Minghui; Lee, Soo-Y

2002-12-31

The initial state selected time-dependent wave-packet method was extended to calculate the state-to-state integral cross section for the title reaction with H2O in the ground rovibrational state on the potential energy surface of Yang, Zhang, Collins, and Lee. One OH bond length was fixed in the study, which is justifiable for the abstraction reaction, but the remaining 5 degrees of freedom were treated exactly. It was found that the H2 molecule is produced vibrationally cold for collision energy up to 1.6 eV. The OH rotation takes away about 4% of total available energy in the products, while the fraction of energy going to H2 rotation increases with collision energy to about 20% at 1.6 eV.

Vibrational spectroscopy of NO + (H2O)n: Evidence for the intracluster reaction NO + (H2O)n --> H3O + (H2O)n - 2 (HONO) at n => 4

NASA Astrophysics Data System (ADS)

Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

1994-05-01

Infrared spectra of mass-selected clusters NO+(H2O)n for n=1 to 5 were recorded from 2700 to 3800 cm-1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

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

DOEpatents

Smith, Brian; Menchaca, Leticia

1999-01-01

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

Synthesis of Nanoscale CaO-Al2O3-SiO2-H2O and Na2O-Al2O3-SiO2-H2O Using the Hydrothermal Method and Their Characterization

PubMed Central

Yang, Jingbin; Li, Dongxu; Fang, Yuan

2017-01-01

C-A-S-H (CaO-Al2O3-SiO2-H2O) and N-A-S-H (Na2O-Al2O3-SiO2-H2O) have a wide range of chemical compositions and structures and are difficult to separate from alkali-activated materials. Therefore, it is difficult to analyze their microscopic properties directly. This paper reports research on the synthesis of C-A-S-H and N-A-S-H particles with an average particle size smaller than 300 nm by applying the hydrothermal method. The composition and microstructure of the products with different CaO(Na2O)/SiO2 ratios and curing conditions were characterized using XRD, the RIR method, FTIR, SEM, TEM, and laser particle size analysis. The results showed that the C-A-S-H system products with a low CaO/SiO2 ratio were mainly amorphous C-A-S-H gels. With an increase in the CaO/SiO2 ratio, an excess of Ca(OH)2 was observed at room temperature, while in a high-temperature reaction system, katoite, C4AcH11, and other crystallized products were observed. The katoite content was related to the curing temperature and the content of Ca(OH)2 and it tended to form at a high-temperature and high-calcium environment, and an increase in the temperature renders the C-A-S-H gels more compact. The main products of the N-A-S-H system at room temperature were amorphous N-A-S-H gels and a small amount of sodalite. An increase in the curing temperature promoted the formation of the crystalline products faujasite and zeolite-P. The crystallization products consisted of only zeolite-P in the high-temperature N-A-S-H system and its content were stable above 70%. An increase in the Na2O/SiO2 ratio resulted in more non-bridging oxygen and the TO4 was more isolated in the N-A-S-H structure. The composition and microstructure of the C-A-S-H and N-A-S-H system products synthesized by the hydrothermal method were closely related to the ratio of the raw materials and the curing conditions. The results of this study increase our understanding of the hydration products of alkali-activated materials. PMID

High accuracy measurements of dry mole fractions of carbon dioxide and methane in humid air

NASA Astrophysics Data System (ADS)

Rella, C. W.; Chen, H.; Andrews, A. E.; Filges, A.; Gerbig, C.; Hatakka, J.; Karion, A.; Miles, N. L.; Richardson, S. J.; Steinbacher, M.; Sweeney, C.; Wastine, B.; Zellweger, C.

2013-03-01

Traditional techniques for measuring the mole fractions of greenhouse gases in the well-mixed atmosphere have required dry sample gas streams (dew point < -25 °C) to achieve the inter-laboratory compatibility goals set forth by the Global Atmosphere Watch programme of the World Meteorological Organisation (WMO/GAW) for carbon dioxide (±0.1 ppm in the Northern Hemisphere and ±0.05 ppm in the Southern Hemisphere) and methane (±2 ppb). Drying the sample gas to low levels of water vapour can be expensive, time-consuming, and/or problematic, especially at remote sites where access is difficult. Recent advances in optical measurement techniques, in particular cavity ring down spectroscopy, have led to the development of greenhouse gas analysers capable of simultaneous measurements of carbon dioxide, methane and water vapour. Unlike many older technologies, which can suffer from significant uncorrected interference from water vapour, these instruments permit accurate and precise greenhouse gas measurements that can meet the WMO/GAW inter-laboratory compatibility goals (WMO, 2011a) without drying the sample gas. In this paper, we present laboratory methodology for empirically deriving the water vapour correction factors, and we summarise a series of in-situ validation experiments comparing the measurements in humid gas streams to well-characterised dry-gas measurements. By using the manufacturer-supplied correction factors, the dry-mole fraction measurements have been demonstrated to be well within the GAW compatibility goals up to a water vapour concentration of at least 1%. By determining the correction factors for individual instruments once at the start of life, this water vapour concentration range can be extended to at least 2% over the life of the instrument, and if the correction factors are determined periodically over time, the evidence suggests that this range can be extended up to and even above 4% water vapour concentrations.

High accuracy measurements of dry mole fractions of carbon dioxide and methane in humid air

NASA Astrophysics Data System (ADS)

Rella, C. W.; Chen, H.; Andrews, A. E.; Filges, A.; Gerbig, C.; Hatakka, J.; Karion, A.; Miles, N. L.; Richardson, S. J.; Steinbacher, M.; Sweeney, C.; Wastine, B.; Zellweger, C.

2012-08-01

Traditional techniques for measuring the mole fractions of greenhouse gas in the well-mixed atmosphere have required extremely dry sample gas streams (dew point < -25 °C) to achieve the inter-laboratory compatibility goals set forth by the Global Atmospheric Watch program of the World Meteorological Organization (WMO/GAW) for carbon dioxide (±0.1 ppm) and methane (±2 ppb). Drying the sample gas to low levels of water vapor can be expensive, time-consuming, and/or problematic, especially at remote sites where access is difficult. Recent advances in optical measurement techniques, in particular Cavity Ring Down Spectroscopy (CRDS), have led to the development of highly stable and precise greenhouse gas analyzers capable of highly accurate measurements of carbon dioxide, methane, and water vapor. Unlike many older technologies, which can suffer from significant uncorrected interference from water vapor, these instruments permit for the first time accurate and precise greenhouse gas measurements that can meet the WMO/GAW inter-laboratory compatibility goals without drying the sample gas. In this paper, we present laboratory methodology for empirically deriving the water vapor correction factors, and we summarize a series of in-situ validation experiments comparing the measurements in humid gas streams to well-characterized dry-gas measurements. By using the manufacturer-supplied correction factors, the dry-mole fraction measurements have been demonstrated to be well within the GAW compatibility goals up to at least 1% water vapor. By determining the correction factors for individual instruments once at the start of life, this range can be extended to at least 2% over the life of the instrument, and if the correction factors are determined periodically over time, the evidence suggests that this range can be extended above 4%.

Effect of air composition (N2, O2, Ar, and H2O) on CO2 and CH4 measurement by wavelength-scanned cavity ring-down spectroscopy: calibration and measurement strategy

NASA Astrophysics Data System (ADS)

Nara, H.; Tanimoto, H.; Tohjima, Y.; Mukai, H.; Nojiri, Y.; Katsumata, K.; Rella, C. W.

2012-11-01

We examined potential interferences from water vapor and atmospheric background gases (N2, O2, and Ar), and biases by isotopologues of target species, on accurate measurement of atmospheric CO2 and CH4 by means of wavelength-scanned cavity ring-down spectroscopy (WS-CRDS). Changes of the background gas mole fractions in the sample air substantially impacted the CO2 and CH4 measurements: variation of CO2 and CH4 due to relative increase of each background gas increased as Ar < O2 < N2, suggesting similar relation for the pressure-broadening effects (PBEs) among the background gas. The pressure-broadening coefficients due to variations in O2 and Ar for CO2 and CH4 are empirically determined from these experimental results. Calculated PBEs using the pressure-broadening coefficients are linearly correlated with the differences between the mole fractions of O2 and Ar and their ambient abundances. Although the PBEs calculation showed that impact of natural variation of O2 is negligible on the CO2 and CH4 measurements, significant bias was inferred for the measurement of synthetic standard gases. For gas standards balanced with purified air, the PBEs were estimated to be marginal (up to 0.05 ppm for CO2 and 0.01 ppb for CH4) although the PBEs were substantial (up to 0.87 ppm for CO2 and 1.4 ppb for CH4) for standards balanced with synthetic air. For isotopic biases on CO2 measurements, we compared experimental results and theoretical calculations, which showed excellent agreement within their uncertainty. We derived instrument-specific water correction functions empirically for three WS-CRDS instruments (Picarro EnviroSense 3000i, G-1301, and G-2301), and evaluated the transferability of the water correction function from G-1301 among these instruments. Although the transferability was not proven, no significant difference was found in the water vapor correction function for the investigated WS-CRDS instruments as well as the instruments reported in the past studies

Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase, and Fe2(SO4)3(H2O)5

USGS Publications Warehouse

Majzlan, J.; Navrotsky, A.; McCleskey, R. Blaine; Alpers, Charles N.

2006-01-01

Enthalpies of formation of ferricopiapite [nominally Fe4.67(SO4)6(OH)2 (H2O)20]. coquimbite [Fe2(SO4)3(H2O)9], rhomboclase [(H3O)Fe(SO4)2 (H2O)3], and Fe2(SO4)3(H2O)5 were measured by acid (5 N HCl) solution calorimetry. The samples were characterized by wet chemical analyses and synchrotron powder X-ray diffraction (XRD). The refinement of XRD patterns gave lattice parameters, atomic positions, thermal factors, and occupancies of the sites. The calculated formulae differ slightly from the nominal compositions: Fe4.78(SO4)6 (OH)2.34(H2O)20.71 (ferricopiapite), (Fe1.47Al0.53)(SO4)3 (H2O)9.65 (coquimbite), (H3O)1.34Fe(SO4)2.17 (H2O)3.06 (rhomboclase), and Fe2(SO4)3 (H2O)5.03. All thermodynamic data are given per mole of these formulae. The measured standard enthalpies (in kJ/mol) of formation from the elements (crystalline Fe, Al, S, and ideal gases O2 and H2) at T = 298.15 K are -4115.8??4.1 [Fe2(SO4)3 (H2O)5.03], -12045.1??9.2 (ferricopiapite), -5738.4??3.3 (coquimbite), and -3201.1??2.6 (rhomboclase). Standard entropy (S??) was estimated as a sum of entropies of oxide, hydroxide, and sulfate components. The estimated S?? (in J/mol.K) values for the iron sulfates are 488.2 [Fe2(SO4)3 (H2O)5.03], 1449.2 (ferricopiapite), 638.3 (coquimbite), and 380.1 (rhomboclase). The calculated Gibbs free energies of formation (in kJ/mol) are -3499.7??4.2 [Fe2(SO4)3 (H2O)5.03], -10089.8??9.3 (ferricopiapite), -4845.6??3.3 (coquimbite), and -2688.0??2.7 (rhomboclase). These results combined with other available thermodynamic data allow construction of mineral stability diagrams in the FeIII2(SO4)3-FeII SO4-H2O system. One such diagram is provided, indicating that the order of stability of ferric sulfate minerals with decreasing pH in the range of 1.5 to -0.5 is: hydronium jarosite, ferricopiapite, and rhomboclase. ?? 2006 E. Schweizerbart'sche Verlagsbuchhandlung.

Simulated retrievals for the remote sensing of CO2, CH4, CO, and H2O from geostationary orbit

NASA Astrophysics Data System (ADS)

Xi, X.; Natraj, V.; Shia, R. L.; Luo, M.; Zhang, Q.; Newman, S.; Sander, S. P.; Yung, Y. L.

2015-11-01

The Geostationary Fourier Transform Spectrometer (GeoFTS) is designed to measure high-resolution spectra of reflected sunlight in three near-infrared bands centered around 0.76, 1.6, and 2.3 μm and to deliver simultaneous retrievals of column-averaged dry air mole fractions of CO2, CH4, CO, and H2O (denoted XCO2, XCH4, XCO, and XH2O, respectively) at different times of day over North America. In this study, we perform radiative transfer simulations over both clear-sky and all-sky scenes expected to be observed by GeoFTS and estimate the prospective performance of retrievals based on results from Bayesian error analysis and characterization. We find that, for simulated clear-sky retrievals, the average retrieval biases and single-measurement precisions are < 0.2 % for XCO2, XCH4, and XH2O, and < 2 % for XCO, when the a priori values have a bias of 3 % and an uncertainty of 3 %. In addition, an increase in the amount of aerosols and ice clouds leads to a notable increase in the retrieval biases and slight worsening of the retrieval precisions. Furthermore, retrieval precision is a strong function of signal-to-noise ratio and spectral resolution. This simulation study can help guide decisions on the design of the GeoFTS observing system, which can result in cost-effective measurement strategies while achieving satisfactory levels of retrieval precisions and biases. The simultaneous retrievals at different times of day will be important for more accurate estimation of carbon sources and sinks on fine spatiotemporal scales and for studies related to the atmospheric component of the water cycle.

2Q NMR of 2H2O ordering at solid interfaces

NASA Astrophysics Data System (ADS)

Krivokhizhina, Tatiana V.; Wittebort, R. J.

2014-06-01

Solvent ordering at an interface can be studied by multiple-quantum NMR. Quantitative studies of 2H2O ordering require clean double-quantum (2Q) filtration and an analysis of 2Q buildup curves that accounts for relaxation and, if randomly oriented samples are used, the distribution of residual couplings. A pulse sequence with absorption mode detection is extended for separating coherences by order and measuring relaxation times such as the 2Q filtered T2. Coherence separation is used to verify 2Q filtration and the 2Q filtered T2 is required to extract the coupling from the 2Q buildup curve when it is unresolved. With our analysis, the coupling extracted from the buildup curve in 2H2O hydrated collagen was equivalent to the resolved coupling measured in the usual 1D experiment and the 2Q to 1Q signal ratio was in accord with theory. Application to buildup curves from 2H2O hydrated elastin, which has an unresolved coupling, revealed a large increase in the 2Q signal upon mechanical stretch that is due to an increase in the ordered water fraction while changes in the residual coupling and T2 are small.

The relationship between reorientational molecular motions and phase transitions in [Mg(H{sub 2}O){sub 6}](BF{sub 4}){sub 2}, studied with the use of {sup 1}H and {sup 19}F NMR and FT-MIR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mikuli, Edward, E-mail: mikuli@chemia.uj.edu.pl; Hetmańczyk, Joanna; Grad, Bartłomiej

2015-02-14

A {sup 1}H and {sup 19}F nuclear magnetic resonance study of [Mg(H{sub 2}O){sub 6}](BF{sub 4}){sub 2} has confirmed the existence of two phase transitions at T{sub c1} ≈ 257 K and T{sub c2} ≈ 142 K, detected earlier by the DSC method. These transitions were reflected by changes in the temperature dependences of both proton and fluorine of second moments M{sub 2}{sup H} and M{sub 2}{sup F} and of spin-lattice relaxation times T{sub 1}{sup H} and T{sub 1}{sup F}. The study revealed anisotropic reorientations of whole [Mg(H{sub 2}O){sub 6}]{sup 2+} cations, reorientations by 180° jumps of H{sub 2}O ligands, andmore » aniso- and isotropic reorientations of BF{sub 4}{sup −} anions. The activation parameters for these motions were obtained. It was found that the phase transition at T{sub c1} is associated with the reorientation of the cation as a whole unit around the C{sub 3} axis and that at T{sub c2} with isotropic reorientation of the BF{sub 4}{sup −} anions. The temperature dependence of the full width at half maximum value of the infrared band of ρ{sub t}(H{sub 2}O) mode (at ∼596 cm{sup −1}) indicated that in phases I and II, all H{sub 2}O ligands in [Mg(H{sub 2}O){sub 6}]{sup 2+} perform fast reorientational motions (180° jumps) with a mean value of activation energy equal to ca 10 kJ mole{sup −1}, what is fully consistent with NMR results. The phase transition at T{sub c1} is associated with a sudden change of speed of fast (τ{sub R} ≈ 10{sup −12} s) reorientational motions of H{sub 2}O ligands. Below T{sub c2} (in phase III), the reorientations of certain part of the H{sub 2}O ligands significantly slow down, while others continue their fast reorientation with an activation energy of ca 2 kJ mole{sup −1}. This fast reorientation cannot be evidenced in NMR relaxation experiments. Splitting of certain IR bands connected with H{sub 2}O ligands at the observed phase transitions suggests a reduction of the symmetry of the octahedral [Mg(H

Cross section data sets for electron collisions with H2, O2, CO, CO2, N2O and H2O

NASA Astrophysics Data System (ADS)

Anzai, K.; Kato, H.; Hoshino, M.; Tanaka, H.; Itikawa, Y.; Campbell, L.; Brunger, M. J.; Buckman, S. J.; Cho, H.; Blanco, F.; Garcia, G.; Limão-Vieira, P.; Ingólfsson, O.

2012-02-01

We review earlier cross section data sets for electron-collisions with H2, O2, CO, CO2, H2O and N2O, updated here by experimental results for their electronic states. Based on our recent measurements of differential cross sections for the electronic states of those molecules, integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis and then assessed against theory (BE f-scaling [Y.-K. Kim, J. Chem. Phys. 126, 064305 (2007)]). As they now represent benchmark electronic state cross sections, those ICSs for the above molecules are added into the original cross section sets taken from the data reviews for H2, O2, CO2 and H2O (the Itikawa group), and for CO and N2O (the Zecca group).

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

2012-08-08

Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

Experimental approach to form anorthositic melts: phase relations in the system CaAl2Si2O8 - CaMgSi2O6 - Mg2SiO4 at 6 wt.% H2O

NASA Astrophysics Data System (ADS)

Zirner, Aurelia Lucretia Katharina; Ballhaus, Chris; Fonseca, Raúl; Müncker, Carsten

2014-05-01

Massive anorthosite dykes are documented for the first time from the Limassol Forest Complex (LFC) of Cyprus, the LFC being a deformed equivalent of the Troodos ultramafic massif. Both the Troodos and LFC complexes are part of the Tethyan realm consisting of Cretaceous oceanic crust that formed within a backarc basin 90 Ma ago and was obduced during late Miocene. From crosscutting relations with the sheeted dyke complex, it follows that the anorthosites belong to one of the latest magmatic events on Cyprus. In hand specimen, the rocks appear massive and unaltered, although in thin section magmatic plagioclase (An93) is partially replaced by albite and thomsonite (zeolite). Where magmatic textures are preserved, plagioclase forms cm-sized, acicular, radially arranged crystal aggregates that remind of spinifex textures. Six major types of anorthosite occurrences have previously been described, none of them matching with the above described anorthosite dykes [1]. The origin of these anorthosite dykes remains poorly understood. Even though they occur as intrusive dykes, it is evident that they cannot represent liquidus compositions, at least under dry conditions. Whole-sale melting of pure An93 would require temperatures in excess of 1450 °C, which is a quite unrealistic temperature of the modern Earth's crust. The working hypothesis is that boninitic melts with approximately 4 wt.% H2O, as found in the cyprian upper pillow lavas (UPL), could produce such rocks by olivine-pyroxene fractionation. Indeed, experiments indicate that such lithologies can be generated by medium-pressure fractional crystallization of hydrous basaltic melts followed by decompression-degassing. High pH2O stabilizes olivine but tends to suppress plagioclase as the highest polymerized phase. Hence the An component is accumulated in the (late-stage) melt. When such a system experiences sudden decompression, the aqueous phase will exsolve and will trigger massive precipitation of anorthite

Physical and chemical effects on crystalline H2O2 induced by 20 keV protons.

PubMed

Loeffler, M J; Baragiola, R A

2009-03-21

We present laboratory studies on radiation chemistry, sputtering, and amorphization of crystalline H(2)O(2) induced by 20 keV protons at 80 K. We used infrared spectroscopy to identify H(2)O, O(3), and possibly HO(3), measure the fluence dependence of the fraction of crystalline and amorphous H(2)O(2) and of the production of H(2)O and destruction of H(2)O(2). Furthermore, using complementary techniques, we observe that the sputtering yield depends on fluence due to the buildup of O(2) radiation products in the sample. In addition, we find that the effective cross sections for the destruction of hydrogen peroxide and the production of water are very high compared to radiation chemical processes in water even though the fluence dependence of amorphization is nearly the same for the two materials. This result is consistent with a model of fast cooling of a liquid track produced by each projectile ion rather than with the disorder produced by the formation of radiolytic products.

Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

PubMed

Srithep, Sirinthip; Phattarapattamawong, Songkeart

2017-06-01

The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H 2 O 2 , UV/O 3 , and UV/H 2 O 2 /O 3 ) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H 2 O 2 /O 3 was the most effective process for removing HAN precursors, followed by UV/H 2 O 2 , and UV/O 3 , respectively. For 20min contact time, the UV/H 2 O 2 /O 3 , UV/H 2 O 2 , and UV/O 3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL -1 in UV/O 3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H 2 O 2 , and UV/H 2 O 2 /O 3 ), except for the UV/O 3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k' DCANFP ) by the UV/H 2 O 2 /O 3 , UV/H 2 O 2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O 3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k' DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Using H2O2 treatments for the degradation of cyanobacteria and microcystins in a shallow hypertrophic reservoir.

PubMed

Papadimitriou, Theodoti; Kormas, Konstantinos; Dionysiou, Dionysios D; Laspidou, Chrysi

2016-11-01

Toxins produced by cyanobacteria in freshwater ecosystems constitute a serious health risk worldwide for humans that may use the affected water bodies for recreation, drinking water, and/or irrigation. Cyanotoxins have also been deemed responsible for loss of animal life in many places around the world. This paper explores the effect of H 2 O 2 treatments on cyanobacteria and microcystins in natural samples from a hypertrophic reservoir in microcosm experiments. According to the results, cyanobacteria were more easily affected by H 2 O 2 than by other phytoplanktonic groups. This was shown by the increase in the fractions of chlorophyll-a (a proxy for phytoplankton) and chlorophyll-b (a proxy for green algae) over total phytoplankton pigments and the decrease in the fraction of phycocyanin (a proxy for cyanobacteria) over total phytoplankton pigments. Thus, while an overall increase in phytoplankton occurred, a preferential decrease in cyanobacteria was observed with H 2 O 2 treatments over a few hours. Moreover, significant degradation of total microcystins was observed under H 2 O 2 treatments, while more microcystins were degraded when UV radiation was used in combination with H 2 O 2 . The combination of H 2 O 2 and ultraviolet (UV) treatment in natural samples resulted in total microcystin concentrations that were below the World Health Organization limit for safe consumption of drinking water of 1 μg/L. Although further investigation into the effects of H 2 O 2 addition on ecosystem function must be performed, our results show that the application of H 2 O 2 could be a promising method for the degradation of microcystins in reservoirs and the reduction of public health risks related to the occurrence of harmful algal blooms.

MOLE 2.0: advanced approach for analysis of biomacromolecular channels

PubMed Central

2013-01-01

Background Channels and pores in biomacromolecules (proteins, nucleic acids and their complexes) play significant biological roles, e.g., in molecular recognition and enzyme substrate specificity. Results We present an advanced software tool entitled MOLE 2.0, which has been designed to analyze molecular channels and pores. Benchmark tests against other available software tools showed that MOLE 2.0 is by comparison quicker, more robust and more versatile. As a new feature, MOLE 2.0 estimates physicochemical properties of the identified channels, i.e., hydropathy, hydrophobicity, polarity, charge, and mutability. We also assessed the variability in physicochemical properties of eighty X-ray structures of two members of the cytochrome P450 superfamily. Conclusion Estimated physicochemical properties of the identified channels in the selected biomacromolecules corresponded well with the known functions of the respective channels. Thus, the predicted physicochemical properties may provide useful information about the potential functions of identified channels. The MOLE 2.0 software is available at http://mole.chemi.muni.cz. PMID:23953065

Ab Initio Reaction Kinetics of CH 3 O$$\\dot{C}$$(=O) and $$\\dot{C}$$H 2 OC(=O)H Radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tan, Ting; Yang, Xueliang; Ju, Yiguang

The dissociation and isomerization kinetics of the methyl ester combustion intermediates methoxycarbonyl radical (CH3Omore » $$\\dot{C}$$(=O)) and (formyloxy)methyl radical ($$\\dot{C}$$H2OC(=O)H) are investigated theoretically using high-level ab initio methods and Rice–Ramsperger–Kassel–Marcus (RRKM)/master equation (ME) theory. Geometries obtained at the hybrid density functional theory (DFT) and coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) levels of theory are found to be similar. We employ high-level ab initio wave function methods to refine the potential energy surface: CCSD(T), multireference singles and doubles configuration interaction (MRSDCI) with the Davidson–Silver (DS) correction, and multireference averaged coupled-pair functional (MRACPF2) theory. MRSDCI+DS and MRACPF2 capture the multiconfigurational character of transition states (TSs) and predict lower barrier heights than CCSD(T). The temperature- and pressure-dependent rate coefficients are computed using RRKM/ME theory in the temperature range 300–2500 K and a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. Dissociation of CH3O$$\\dot{C}$$(=O) to $$\\dot{C}$$H3 and CO2 is predicted to be much faster than dissociating to CH3$$\\dot{O}$$ and CO, consistent with its greater exothermicity. Isomerization between CH3O$$\\dot{C}$$(=O) and $$\\dot{C}$$H2OC(=O)H is predicted to be the slowest among the studied reactions and rarely happens even at high temperature and high pressure, suggesting the decomposition pathways of the two radicals are not strongly coupled. The predicted rate coefficients and branching fractions at finite pressures differ significantly from the corresponding high-pressure-limit results, especially at relatively high temperatures. Finally, because it is one of the most important CH3$$\\dot{O}$$ removal mechanisms under atmospheric conditions, the reaction kinetics of

H2CO3(s): a new candidate for CO2 capture and sequestration.

PubMed

Tossell, J A

2009-04-01

To reduce the magnitude of anthropogenic global warming it is necessary to remove CO2(g) from the effluent streams of coal-fired power plants and to sequester the CO2 either as a liquid or by reaction with other compounds. A major difficulty in achieving this goal arises from the very weak acidity of CO2(g), causing it to react only incompletely with weak bases, although this weak interaction does provide a means for "stripping" the CO2 from the acid-base complex at high temperatures. Reaction with strong bases like Na0H yields more stable complexes, but massive amounts of chemical reactants would need to be purchased and chemical products like NaHCO3 then stored. However, when gas-phase CO2 reacts with the weak base water (or when bicarbonate reacts with strong acid) the unstable product monomeric "H2CO3" can be formed. The free energy required is about 16 kcal/mol in the gas phase and about 10 kcal/mol in aqueous solution. This energy can be supplied by particle or photon excitation and is only a small fraction ofthe energy released when a mole of CH4 is converted to a mole of CO2. Although this monomeric compound is highly unstable, its oligomers are considerably more stable, due to internal H-bonding, with free energies for the larger oligomers in the gas phase which are about 4 kcal/(mol of H2CO3) lower, only about 6 kcal/mol H2CO3 higher than the gas-phase combination of CO2 and H2O at room temperature. Also, at lower temperature the entropic penalty for the oligomer is less and oligomeric H2CO3 becomes stable around the sublimation temperature of dry ice. This indicates that it may be possible to capture gas-phase CO2 directly, using only cheap and abundant H2O as a reactant, and to store the resulting (H2CO3)n as a oligomeric solid at only moderately cold temperatures. These conclusions are based on quantum computations that accurately reproduce the structures, spectra, and stabilities of H2CO3 oligomers. Methods for producing and characterizing the H2CO3

Crystal structures of Sr(ClO4)2·3H2O, Sr(ClO4)2·4H2O and Sr(ClO4)2·9H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, strontium perchlorate trihydrate {di-μ-aqua-aquadi-μ-perchlorato-strontium, [Sr(ClO4)2(H2O)3]n}, strontium perchlorate tetra­hydrate {di-μ-aqua-bis­(tri­aqua­diperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona­hydrate {hepta­aqua­diperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]·2H2O}, were crystallized at low temperatures according to the solid–liquid phase diagram. The structures of the tri- and tetra­hydrate consist of Sr2+ cations coordinated by five water mol­ecules and four O atoms of four perchlorate tetra­hedra in a distorted tricapped trigonal–prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol­ecules and thus forming chains parallel to [100]. In the tetra­hydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol­ecules are formed. The structure of the nona­hydrate contains one Sr2+ cation coordinated by seven water mol­ecules and by two O atoms of two perchlorate tetra­hedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol­ecules, which are located on twofold rotation axes. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures. PMID:25552979

Studies of CW lasing action in CO2-CO, N2O-CO, CO2-H2O, and N2O-H2O mixtures pumped by blackbody radiation

NASA Technical Reports Server (NTRS)

Abel, Robert W.; Christiansen, Walter H.; Li, Jian-Guo

1988-01-01

A proof of principle experiment to evaluate the efficacy of CO and H2O in increasing the power output for N2O and CO2 lasing mixtures has been conducted and theoretically analyzed for a blackbody radiation-pumped laser. The results for N2O-CO, CO2-CO, N2O-H2O and CO2-H2O mixtures are presented. Additions of CO to the N2O lasant increased power up to 28 percent for N2O laser mixtures, whereas additions of CO to the CO2 lasant, and the addition of H2O to both the CO2 and N2O lasants, resulted in decreased output power.

Time course of fractional gluconeogenesis after meat ingestion in healthy adults: a D2O study.

PubMed

Gaudichon, Claire; Ta, Hai-Yen; Khodorova, Nadezda V; Oberli, Marion; Breton, Isabelle; Benamouzig, Robert; Tomé, Daniel; Godin, Jean-Philippe

2018-06-19

In the postprandial state, glucose homeostasis is challenged by macronutrient intake, including proteins that trigger insulin secretion and provide glucose precursors. However, little is known about the postprandial response of gluconeogenesis to a protein meal. We aimed to quantify the evolution of fractional gluconeogenesis after a meat meal. Thirteen healthy subjects received oral doses of D 2 O. After fasting overnight, they ingested a steak (120 g). Glycemia, insulinemia and 2 H enrichments in glucose and plasma water were measured for 8 h after the meal. Fractional gluconeogenesis was assessed using the average method. Glucose was stable for 5 h and then decreased. There was a slight increase of insulin 1 h after the meal. 2 H enrichment in C5 increased after 2 h, whereas it decreased in plasma water. Consequently, fractional gluconeogenesis increased from 68.2 {plus minus} 7.2% before the meal to 75.5 {plus minus} 5.8% 8 h after the meal, the latter corresponding to 22 h without a glucose supply. These values are consistent with the exhaustion of glycogen stores after 24 h, but represents the highest among values in the literature. The impact of methodological conditions is discussed.

Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl2·4.5H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetra­hedral coordination with Cl− and in an octa­hedral environment defined by five water mol­ecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O)5] (penta­aqua-μ-chlorido-tri­chlorido­di­zinc). The trihydrate {hexa­aqua­zinc tetra­chlorido­zinc, [Zn(H2O)6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetra­hedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octa­hedrally surrounded by water mol­ecules. The [ZnCl4] tetra­hedra and [Zn(H2O)6] octa­hedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexa­aqua­zinc tetra­chlorido­zinc trihydrate, [Zn(H2O)6][ZnCl4]·3H2O}, consists of isolated octa­hedral [Zn(H2O)6] and tetra­hedral [ZnCl4] units, as well as additional lattice water mol­ecules. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ZnCl4 tetra­hedra and water mol­ecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures. PMID:25552980

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.

Crystal and molecular structure of Sr{sub 2}(Edta) . 5H{sub 2}O, Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O, and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O strontium ethylenediaminetetraacetates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Poznyak, A. L.; Sergienko, V. S.

2009-03-15

Three Sr{sup 2+} compounds with the Edta{sup 4-} and H{sub 2}Edta{sup 2-} ligands-Sr{sub 2}(Edta) . 5H{sub 2}O (I), Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O (II), and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O (III)-are synthesized, and their crystal structures are studied. In I, the Sr(1) atom is coordinated by the hexadentate Edta{sup 4-} ligand following the 2N + 4O pattern and by two O atoms of the neighboring ligands, which affords the formation of zigzag chains. The Sr(2) atom forms bonds with O atoms of five water molecules and attaches itself to a chain via bonds with threemore » O atoms of the Edta{sup 4-} ligands. The Sr(1)-O and Sr(2)-O bond lengths fall in the ranges 2.520(2)-2.656(3) and 2.527(3)-2.683(2) A, respectively. The Sr(1)-N bonds are 2.702(3) and 2.743(3) A long. In II and III, the H{sub 2}Edta{sup 2-} anions have a centrosymmetric structure with the trans configuration of the planar ethylenediamine fragment. The N atoms are blocked by acid protons. In II, the environment of the Sr atom is formed by six O atoms of three H{sub 2}Edta ligands, two O atoms of water molecules, and an O atom of the bicarbonate ion, which is disordered over two positions. In III, the environment of the Sr atom includes six O atoms of four H{sub 2}Edta{sup 2-} ligands and three O atoms of water molecules. The coordination number of the Sr atoms is equal to 8 + 1. In II and III, the main bonds fall in the ranges 2.534(3)-2.732(2) and 2.482(2)-2.746(3) A, whereas the ninth bond is elongated to 2.937(3) and 3.055(3) A, respectively. In II, all the structural elements are linked into wavy layers. The O-H-O interactions contribute to the stabilization of the layer and link neighboring layers. In III, hydrated Sr{sup 2+} cations and H{sub 2}Edta{sup -} anions form a three-dimensional [Sr{sub 2}(H{sub 2}Edta)(H{sub 2}O){sub 3}]{sub n}{sup 2n+} framework. The Cl{sup -} anions are fixed in channels of the framework by hydrogen bonds with four water

Microwave Plasma-Activated Chemical Vapor Deposition of Nitrogen-Doped Diamond. II: CH4/N2/H2 Plasmas

PubMed Central

2016-01-01

We report a combined experimental and modeling study of microwave-activated dilute CH4/N2/H2 plasmas, as used for chemical vapor deposition (CVD) of diamond, under very similar conditions to previous studies of CH4/H2, CH4/H2/Ar, and N2/H2 gas mixtures. Using cavity ring-down spectroscopy, absolute column densities of CH(X, v = 0), CN(X, v = 0), and NH(X, v = 0) radicals in the hot plasma have been determined as functions of height, z, source gas mixing ratio, total gas pressure, p, and input power, P. Optical emission spectroscopy has been used to investigate, with respect to the same variables, the relative number densities of electronically excited species, namely, H atoms, CH, C2, CN, and NH radicals and triplet N2 molecules. The measurements have been reproduced and rationalized from first-principles by 2-D (r, z) coupled kinetic and transport modeling, and comparison between experiment and simulation has afforded a detailed understanding of C/N/H plasma-chemical reactivity and variations with process conditions and with location within the reactor. The experimentally validated simulations have been extended to much lower N2 input fractions and higher microwave powers than were probed experimentally, providing predictions for the gas-phase chemistry adjacent to the diamond surface and its variation across a wide range of conditions employed in practical diamond-growing CVD processes. The strongly bound N2 molecule is very resistant to dissociation at the input MW powers and pressures prevailing in typical diamond CVD reactors, but its chemical reactivity is boosted through energy pooling in its lowest-lying (metastable) triplet state and subsequent reactions with H atoms. For a CH4 input mole fraction of 4%, with N2 present at 1–6000 ppm, at pressure p = 150 Torr, and with applied microwave power P = 1.5 kW, the near-substrate gas-phase N atom concentration, [N]ns, scales linearly with the N2 input mole fraction and exceeds the concentrations [NH]ns, [NH2]ns

Improving plant water isotope models with precise estimates of source water δ2H and δ18O values for trees from precipitation δ2H and δ18O values

NASA Astrophysics Data System (ADS)

Kahmen, A.; Brinkmann, N.; Seeger, S.; Buchmann, N. C.; Eugster, W.; Weiler, M.

2016-12-01

δ2H and δ18O values in plant water and plant organic compounds have established as powerful tools in ecology, biogeochemistry and paleoclimatology. In general, the δ2H and δ18O values in plants are driven by (i) the isotope composition of the plants' source water, (ii) the evaporative 2H or 18O enrichment of foliar water, and (iii) fractionations during the biosynthesis of organic compounds. While we have a robust understanding of what determines the evaporative 2H or 18O enrichment in plant water and biosynthetic fractionation factors have also been reasonably well constrained, our understanding how a plant's source water δ2H and δ18O values are linked to seasonal variation in precipitation δ2H and δ18O values is surprisingly poor. Precise estimates of a plant's source water δ2H and δ18O values, e.g. from the GNIP database are thus not possible and limit the application of plant water isotope models for the interpretation of δ2H and δ18O in plants. Here we present a four-year dataset of precipitation, soil water (0 - 80 cm) and plant source water δ2H and δ18O values from a mixed temperate forest. We employed this dataset to (i) estimate the link between precipitation and soil water δ2H and δ18O values at different soil depths, (ii) apply a hydrological model to estimate the mean residence time of precipitation water in different soil depths and (iii) estimate the integration time of seasonal precipitation for the source water δ2H and δ18O values of four tree species. Our data show a seasonal amplitude in δ2H and δ18O of precipitation of xx and xx, respectively. This seasonal variability in precipitation is transferred into the soil, where it declines with soil depth. Mean residence time of precipitation is xx days in the upper soil layers (5 cm) and increases to xx days in the lower soil layers (80 cm). The trees' source water originated from soil depths between 20 and 70 cm. The δ2H and δ18O values of the trees source water resemble mean

Composition of steam in the system NaCl-KCl-H2O-quartz at 600°C

USGS Publications Warehouse

Fournier, Robert O.; Thompson, J. Michael

1993-01-01

In the system NaCl-KCl-H2O, with and without ??-quartz present, steam was equilibrated in a large-volume reaction vessel with brine and/or precipitated salt at 600??C and pressures ranging from about 100 to 0.4 MPa. Episodically, steam was extracted for chemical analysis, accompanied by a decrease in pressure within the reaction vessel. In the absence of precipitated salt, within the analytical uncertainty stoichiometric quantities of Cl and total alkali, metals (Na + K) dissolve in steam coexisting with chloriderich brine. In contrast, in the presence of precipitated salt (in our experiments halite with some KCl in solid solution), significant excess chloride as associated hydrogen chloride (HCl0??) dissolves in steam. The HCl0 is generated by the reaction of steam with solid NaCl(s), producing solid NaOH(s) that diffuses into halite, forming a solid solution. In our quasistatic experiments, compared to dynamic flow-through experiments of others, higher initial ratios of H2O/NaCl have apparently resulted in higher model fractions of NaOH(s) in solid solution in halite. This, in turn, resulted in incrementally higher concentrations of associated NaOHo dissolved in steam. Addition of quartz to the system NaCl + KC1 + H2O resulted in an order of magnitude increase in the concentration of HCl0 dissolved in steam, apparently as a consequence of the formation of sodium disilicate by reaction of silica with NaOH(s). The measured dissolved silica in steam saturated with alkali halides at 600??C in the pressure range 7-70 MPa agrees nicely with calculated values of the solubility of ??-quartz obtained using the equation of Fournier and Potter (1982), corrected for dissolved salt by the method of fournier (1983). Na K ratios in steam at 600??C tend to be slightly greater than in coexisting brine. When precipitated halite is present, larger mole fractions of NaOH(s) in solid solution in that halite apparently result in even larger Na K ratios in coexisting steam

CdS nanoparticles/CeO2 nanorods composite with high-efficiency visible-light-driven photocatalytic activity

NASA Astrophysics Data System (ADS)

You, Daotong; Pan, Bao; Jiang, Fan; Zhou, Yangen; Su, Wenyue

2016-02-01

Different mole ratios of CdS nanoparticles (NPs)/CeO2 nanorods (NRs) composites with effective contacts were synthesized through a two-step hydrothermal method. The crystal phase, microstructure, optical absorption properties, electrochemical properties and photocatalytic H2 production activity of these composites were investigated. It was concluded that the photogenerated charge carriers in the CdS NPs/CeO2 NRs composite with a proper mole ratio (1:1) exhibited the longest lifetime and highest separation efficiency, which was responsible for the highest H2-production rate of 8.4 mmol h-1 g-1 under visible-light irradiation (λ > 420 nm). The superior photocatalytic H2 evolution properties are attributed to the transfer of visible-excited electrons of CdS NPs to CeO2 NRs, which can effectively extend the light absorption range of wide-band gap CeO2 NRs. This work provides feasible routes to develop visible-light responsive CeO2-based nanomaterial for efficient solar utilization.

Experimental Determination of Carbon Isotope Fractionation in C-O-H-Fluids and the Carbonate-melt - Graphite System at High Temperatures

NASA Astrophysics Data System (ADS)

Kueter, N.; Schmidt, M. W.; Lilley, M. D.; Bernasconi, S. M.

2017-12-01

The understanding of deep-earth carbon fluxes depends greatly on the investigation of carbon isotope systematics in C-O-H-fluids and carbon minerals, such as graphite and diamond (C0). The isotope fractionation factors between the different C-phases and species (in e.g. a fluid) thus govern the observed isotope fractionation patterns. C-isotope fractionation factors relevant for high temperatures are mainly derived from theoretical calculations [e.g. 1,2,3] and, with few exceptions, lack experimental determinations [e.g. 4]. Hundreds of own experiments aimed at equilibrating elemental carbon (C0, graphite/diamond) with C-O-H-fluids demonstrate that kinetics reigns as no system would be closed for H on time scales and temperatures allowing for graphite to equilibrate. To overcome this problem, we performed two studies to determine the C-isotope fractionation in 1) the CO2-CO-CH4 system and 2) the carbonate-melt - graphite system. Equilibrium C-isotope fractionation factors were obtained for CO2 - CO and CH4 - CO pairs (600 - 1200°C) and graphite - Na2CO3/CaCO3melt (900 - 1500°C). Combined with the already available fractionation data for the CaCO3-CO2 pair (400-950°C) from Chacko et al. [4], we determined experimentally based C-isotope fractionation factors for C0 - CH4 and CO2 - C0 pairs by 1) Δ13CCO2-graphite = Δ13CCO2-carbonate + Δ13CCarbonate-graphite and 2) Δ13Cgraphite-CH4 = Δ13CCO2-CH4 - Δ13CCO2-graphite . Current calculated fractionation factors relevant for mantle temperatures (1100 - 1500°C) suggest C-isotope partitioning in the CO2 - C0 pair on the order of 4.2 to 2.4‰, about 2‰ less than predicted by theoretically derived factors [3]. In contrast, our calculations suggest fractionation of about 1.4 to 1.1‰ for the C0 - CH4 pair, about 1‰ higher than expected by theory [3]. [1] Richet et al. (1977) Ann. Rev. Earth Planet. Sci.; [2] Polyakov & Kharlashina (1995) GCA; [3] Bottinga (1969) GCA; [4] Chacko et al. (2001) Rev Mineral Geochem

Full-dimensional, high-level ab initio potential energy surfaces for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2} with application to hydrogen clathrate hydrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Homayoon, Zahra; Conte, Riccardo; Qu, Chen

2015-08-28

New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H{sub 2}(H{sub 2}O) two-body and H{sub 2}(H{sub 2}O){sub 2} three-body potentials. The database for H{sub 2}(H{sub 2}O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are comparedmore » to computationally faster ones obtained via “purified” symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H{sub 2}, H{sub 2}O, and (H{sub 2}O){sub 2}, to obtain full PESs for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2}. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H{sub 2}(H{sub 2}O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H{sub 2}@(H{sub 2}O){sub 20}. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H{sub 2} from the calculated equilibrium structure.« less

Photo-induced CO2 reduction by CH4/H2O to fuels over Cu-modified g-C3N4 nanorods under simulated solar energy

NASA Astrophysics Data System (ADS)

Tahir, Beenish; Tahir, Muhammad; Amin, Nor Aishah Saidina

2017-10-01

Copper modified polymeric graphitic carbon nitride (Cu/g-C3N4) nanorods for photo-induced CO2 conversion with methane (CH4) and water (H2O) as reducing system under simulated solar energy has been investigated. The nanocatalysts, synthesized by pyrolysis and sonication, were characterized by XRD, FTIR, Raman analysis, XPS, SEM, N2 adsorption-desorption and PL spectroscopy. The presence of Cu2+ ions over the g-C3N4 structure inhibited charge carriers recombination process. The results indicated that photo-activity and selectivity of Cu/g-C3N4 photo-catalyst for CO2 reduction greatly dependent on the type of CO2-reduction system. CO2 was efficiently converted to CH4 and CH3OH with traces of C2H4 and C2H6 hydrocarbons in the CO2-water system. The yield of the main product, CH4 over 3 wt.% Cu/g-C3N4 was 109 μmole g-cata.-1 h-1 under visible light irradiation, significantly higher than the pure g-C3N4 catalyst (60 μmole/g.cat). In photo-induced CO2-CH4 reaction, CO and H2 were detected as the main products with smaller amount of hydrocarbons. The highest efficiency was detected over 3 wt.%Cu-loading of g-C3N4 and at optimal CH4/CO2 feed ratio of 1.0. The maximum yield of CO and H2 detected were 142 and 76 μmole g-catal.-1 h-1, respectively at selectivity 66.6% and 32.5%, respectively. Significantly enhanced CO2/CH4 reduction over Cu/g-C3N4 was attributed to its polymeric structure with efficient charge transfer property and inhibited charges recombination rate. A proposed photo-induced reaction mechanism, corroborated with the experimental data, was also deliberated.

Candidate Water Vapor Lines to Locate the H2O Snowline through High-dispersion Spectroscopic Observations. III. Submillimeter H2 16O and H2 18O Lines

NASA Astrophysics Data System (ADS)

Notsu, Shota; Nomura, Hideko; Walsh, Catherine; Honda, Mitsuhiko; Hirota, Tomoya; Akiyama, Eiji; Millar, T. J.

2018-03-01

In this paper, we extend the results presented in our former papers on using ortho-{{{H}}}2{}16{{O}} line profiles to constrain the location of the H2O snowline in T Tauri and Herbig Ae disks, to include submillimeter para-{{{H}}}2{}16{{O}} and ortho- and para-{{{H}}}2{}18{{O}} lines. Since the number densities of the ortho- and para-{{{H}}}2{}18{{O}} molecules are about 560 times smaller than their 16O analogs, they trace deeper into the disk than the ortho-{{{H}}}2{}16{{O}} lines (down to z = 0, i.e., the midplane). Thus these {{{H}}}2{}18{{O}} lines are potentially better probes of the position of the H2O snowline at the disk midplane, depending on the dust optical depth. The values of the Einstein A coefficients of submillimeter candidate water lines tend to be lower (typically <10‑4 s‑1) than infrared candidate water lines. Thus in the submillimeter candidate water line cases, the local intensity from the outer optically thin region in the disk is around 104 times smaller than that in the infrared candidate water line cases. Therefore, in the submillimeter lines, especially {{{H}}}2{}18{{O}} and para-{{{H}}}2{}16{{O}} lines with relatively lower upper state energies (∼a few 100 K) can also locate the position of the H2O snowline. We also investigate the possibility of future observations with ALMA to identify the position of the water snowline. There are several candidate water lines that trace the hot water gas inside the H2O snowline in ALMA Bands 5–10.

Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1).

PubMed

Li, Xiang; Wang, Haopeng; Bowen, Kit H

2010-10-14

The hydrated nucleoside anions, uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1), have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine(-)(H(2)O)(1) and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1

NASA Astrophysics Data System (ADS)

Li, Xiang; Wang, Haopeng; Bowen, Kit H.

2010-10-01

The hydrated nucleoside anions, uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1, have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine-(H2O)1 and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

Structural and optical properties of Bi2O3-B2O3-CdO-Na2O glass system for gamma ray shielding applications

NASA Astrophysics Data System (ADS)

Dogra, Mridula; Singh, K. J.; Kaur, Kulwinder

2018-05-01

Quaternary system of the composition (0.15+x) Bi2O3-(0.55-x) B2O3-0.15CdO-0.15Na2O (where x=0, 0.1, 0.3 and 0.5 mole fraction) has been synthesized using melt-quenching technique. Gamma ray shielding properties are measured in terms of mass attenuation coefficient and half value layer at photon energies 662, 1173 and 1332 keV. These parameters are compared with standard nuclear radiation shielding `barite and ferrite' concretes. The results reflect better radiation shielding properties as compared to barite and ferrite concretes. Effective atomic number is calculated at photon energies 662 and 1173 keV. Density, molar volume and XRD studies are analyzed to know physical and structural properties of the glass system. Optical band gap, refractive index and molar refraction are calculated from UV-Visible measurements. Decrease in optical band gap and increase in molar refraction have been observed indicating the increase of non-bridging oxygens in the structure.

Accurate measurements of carbon monoxide in humid air using the cavity ring-down spectroscopy (CRDS) technique

NASA Astrophysics Data System (ADS)

Chen, H.; Karion, A.; Rella, C. W.; Winderlich, J.; Gerbig, C.; Filges, A.; Newberger, T.; Sweeney, C.; Tans, P. P.

2013-04-01

Accurate measurements of carbon monoxide (CO) in humid air have been made using the cavity ring-down spectroscopy (CRDS) technique. The measurements of CO mole fractions are determined from the strength of its spectral absorption in the near-infrared region (~1.57 μm) after removing interferences from adjacent carbon dioxide (CO2) and water vapor (H2O) absorption lines. Water correction functions that account for the dilution and pressure-broadening effects as well as absorption line interferences from adjacent CO2 and H2O lines have been derived for CO2 mole fractions between 360-390 ppm and for reported H2O mole fractions between 0-4%. The line interference corrections are independent of CO mole fractions. The dependence of the line interference correction on CO2 abundance is estimated to be approximately -0.3 ppb/100 ppm CO2 for dry mole fractions of CO. Comparisons of water correction functions from different analyzers of the same type show significant differences, making it necessary to perform instrument-specific water tests for each individual analyzer. The CRDS analyzer was flown on an aircraft in Alaska from April to November in 2011, and the accuracy of the CO measurements by the CRDS analyzer has been validated against discrete NOAA/ESRL flask sample measurements made on board the same aircraft, with a mean difference between integrated in situ and flask measurements of -0.6 ppb and a standard deviation of 2.8 ppb. Preliminary testing of CRDS instrumentation that employs improved spectroscopic model functions for CO2, H2O, and CO to fit the raw spectral data (available since the beginning of 2012) indicates a smaller water vapor dependence than the models discussed here, but more work is necessary to fully validate the performance. The CRDS technique provides an accurate and low-maintenance method of monitoring the atmospheric dry mole fractions of CO in humid air streams.

Equilibrium 2H/1H fractionation in organic molecules: III. Cyclic ketones and hydrocarbons

NASA Astrophysics Data System (ADS)

Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A.

2013-04-01

Quantitative interpretation of stable hydrogen isotope ratios (2H/1H) in organic compounds is greatly aided by knowledge of the relevant equilibrium fractionation factors (ɛeq). Previous efforts have combined experimental measurements and hybrid Density Functional Theory (DFT) calculations to accurately predict equilibrium fractionations in linear (acyclic) organic molecules (Wang et al., 2009a,b), but the calibration produced by that study is not applicable to cyclic compounds. Here we report experimental measurements of equilibrium 2H/1H fractionation in six cyclic ketones, and use those data to evaluate DFT calculations of fractionation in diverse monocyclic and polycyclic compounds commonly found in sedimentary organic matter and petroleum. At 25, 50, and 75 °C, the experimentally measured ɛeq values for secondary and tertiary Hα in isotopic equilibrium with water are in the ranges of -130‰ to -150‰ and +10‰ to -40‰ respectively. Measured data are similar to DFT calculations of ɛeq for axial Hα but not equatorial Hα. In tertiary Cα positions with methyl substituents, this can be understood as a result of the methyl group forcing Hα atoms into a dominantly axial position. For secondary Cα positions containing both axial and equatorial Hα atoms, we propose that axial Hα exchanges with water significantly faster than the equatorial Hα does, due to the hyperconjugation-stabilized transition state. Interconversion of axial and equatorial positions via ring flipping is much faster than isotopic exchange at either position, and as a result the steady-state isotopic composition of both H's is strongly weighted toward that of axial Hα. Based on comparison with measured ɛeq values, a total uncertainty of 10-30‰ remains for theoretical ɛeq values. Using DFT, we systematically estimated the ɛeq values for individual H positions in various cyclic structures. By summing over all individual H positions, the molecular equilibrium fractionation was

Structural Investigation of Phosphorus in CaO-SiO2-P2O5 Ternary Glass

NASA Astrophysics Data System (ADS)

Wang, Zhanjun; Cai, Shengjia; Zhang, Mei; Guo, Min; Zhang, Zuotai

2017-04-01

The system of CaO-SiO2-P2O5 ternary glass is not only among the major constituents of steelmaking slags in iron and steel industry, but also play a significant role in other industrial process, such as chemical engineering and glass industry. In the present study, the structure of CaO-SiO2-P2O5 ternary glass with varying P2O5 content from 0 to 15 wt pct at a fixed CaO/SiO2 = 1.4 was investigated using molecular dynamics (MD) simulation combined with X-ray photoelectron spectroscopy and Raman spectra techniques. The results indicated that P5+ ions have a higher affinity to Ca2+ ions which are then stripped away from the silicate network with the addition of P2O5, resulting in the formation of Ca-O-P and Si-O-Si linkages. In addition, almost all P5+ ions displayed as {{Q}}_{{P}}0 ( {{Q}}_{{P}}n , n is the number of bridging oxygen in one [PO4]-tetrahedra units) and a small fraction of P5+ ions behave as {{Q}}_{{P}}1 (P-O-P) and P-O-Si. The enhanced degree of polymerization can be detected from the increase of {{X}}_{{Si}}3 and X_{{P}}1 /X_{{P}}0 (mole fraction of {{Q}}_{{Si}}i or {{Q}}_{{P}}i ). Furthermore, the ratio of Raman scattering coefficients for Q_{{Si}}i /Q_{{Si}}1 and Q_{{P}}i /Q_{{P}}1 were determined by combining MD simulated result with Raman spectra, which were considered to be suitable to the present study.

Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets

NASA Technical Reports Server (NTRS)

Boering, Kristie A.; Connell, Peter; Rotman, Douglas

2004-01-01

We investigated the isotopic fractionation of CH4 and hydrogen (H2) in the stratosphere by incorporating isotope-specific rate coefficients into the Lawrence Livermore National Laboratory (LLNL) 2D model and comparing the model results with new observations from the NASA ER-2 aircraft (funded through a separate task under the Upper Atmosphere Research Program). The model results reveal that fractionation which occurs in the stratosphere has a significant influence on isotope compositions in the free troposphere, an important point which had previously been ignored, unrecognized or unquantified for many long-lived trace gases, including CH4 and H2 which we have focused our efforts on to date. Our analyses of the model results and new isotope observations have also been used to test how well the kinetic isotope effects are known, at least to within the uncertainties in model chemistry and transport. Overall, these results represent an important step forward in our understanding of isotope fractionation in the atmosphere and demonstrate that stratospheric isotope fractionation cannot be ignored in modeling studies which use isotope observations in the troposphere to infer the global budgets of CH4 (an important greenhouse gas) and of H2 (a gas whose atmospheric budget must be better quantified, particularly before a large human perturbation from fuel cell use is realized). Our analyses of model results and observations from the NASA ER-2 aircraft are briefly summarized separately below for CH4, H2, and H2O and for the contribution of these modeling studies to date to our understanding of isotope fractionation for N2O, CO2, and O3 as well.

Synthesis and characterization of Cu2O/TiO2 photocatalysts for H2 evolution from aqueous solution with different scavengers

NASA Astrophysics Data System (ADS)

Li, Yanping; Wang, Baowei; Liu, Sihan; Duan, Xiaofei; Hu, Zongyuan

2015-01-01

A series of Cu2O/TiO2 photocatalysts with different molar fraction of Cu2O were prepared by a facile modified ethanol-induced approach followed by a calcination process. The chemical state of copper compound was proved to be cuprous oxide by the characterization of X-ray photoelectron spectra (XPS). Furthermore, these composite oxides were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption desorption and UV-vis techniques to study the morphologies, structures, and optical properties of the as-prepared samples. The results indicated that the photocatalytic activity of n-type TiO2 was significantly enhanced by combined with p-type Cu2O, due to the efficient p-n heterojunction. The p-n heterojunction between Cu2O and TiO2 can enhance visible-light adsorption, efficiently suppress charge recombination, improve interfacial charge transfer, and especially provide plentiful reaction active sites on the surface of photocatalyst. As a consequence, the prepared 2.5-Cu2O/TiO2 photocatalyst exhibited the highest photocatalytic activity for H2 evolution rate and reached 2048.25 μmol/(g h), which is 14.48 times larger than that of pure P25. The apparent quantum yield (AQY) of the 2.5-Cu2O/TiO2 sample at 365 nm was estimated to be 4.32%. In addition, the influence of different scavengers, namely methanol, anhydrous ethanol, ethylene glycol and glycerol, on the photocatalytic activity for H2 evolution rate was discussed.

Moles

MedlinePlus

... noticeable, or they may contain dark hairs. Having hairs in a mole doesn't make it more dangerous. Moles can ... steroid drugs. There is little risk of melanoma cancer developing in these moles. Atypical moles (dysplastic nevi or Clarks nevi) An ...

Infrared photodissociation spectroscopy of H(+)(H2O)6·M(m) (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O(+) and H5O2(+) core isomers.

PubMed

Mizuse, Kenta; Fujii, Asuka

2011-04-21

Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.

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. Copyright © 2014 Elsevier B.V. All rights reserved.

On the role of the termolecular reactions 2O2 + H2 → 2HO2 and 2O2 + H2 → H + HO2 + O2 in formation of the first radicals in hydrogen combustion: ab initio predictions of energy barriers.

PubMed

Monge-Palacios, M; Rafatijo, Homayoon

2017-01-18

We have investigated the role of termolecular reactions in the early chemistry of hydrogen combustion. We performed molecular chemical dynamics simulations using ReaxFF in LAMMPS to identify potential initial reactions for a 1 : 4 mixture of H 2  : O 2 in the NVT ensemble at density 276.3 kg m -3 and ∼3000 K (∼4000 atm) and ∼4000 K (∼5000 atm), and then characterized the saddle points for those reactions using ab initio methods: CCSD(T) = FC/cc-pVTZ//MP2/6-31G, CCSD(T) = FULL/aug-cc-pVTZ//CCSD = FC/cc-pVTZ and CASSCF MP2/6-31G//MP2/6-31G. The main initial reaction is H 2 + O 2 → H + HO 2 , frequently occurring in the presence of a second O 2 as a third body; that is, 2O 2 + H 2 → H + HO 2 + O 2 . The second most frequent reaction is 2O 2 + H 2 → 2HO 2 . We found three saddle points on the triplet PES of these termolecular reactions: one for 2O 2 + H 2 → H + HO 2 + O 2 and two for 2O 2 + H 2 → 2HO 2 . In the latter case, one has a symmetric structure consistent with simultaneous formation of two HO 2 and the other corresponds to a bimolecular reaction between O 2 and H 2 that is "interrupted" by a second O 2 before going to completion. The classical barrier height of the symmetric saddle point for 2O 2 + H 2 → 2HO 2 is 49.8 kcal mol -1 . The barrier to H 2 + O 2 → H + HO 2 is 58.9 kcal mol -1 . The termolecular reaction will be competitive with H 2 + O 2 → H + HO 2 only at sufficiently high pressures.

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

NASA Astrophysics Data System (ADS)

Ertl, G.; Alefeld, G.; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

2011-03-01

"H2O H2O everywhere; ne'er a drop to drink"[Coleridge(1798)]; now: "H2 H2 everywhere; STILL ne'er a drop to drink": ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): {O/H2O}=[16]/[18] 90 % ; O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [{3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9/2007)] crucial geomorph-ology which ONLY maximal-buoyancy H2 can exploit, to again make "Mountains into Fountains", ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': "terraforming"(and ocean-rebasificaton!!!) Siegel proprietary magnetic-hydrogen-valve (MHV) permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/famine) Hydrogen-economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!!!

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

Simultaneous 183 GHz H2O maser and SiO observations towards evolved stars using APEX SEPIA Band 5

NASA Astrophysics Data System (ADS)

Humphreys, E. M. L.; Immer, K.; Gray, M. D.; De Beck, E.; Vlemmings, W. H. T.; Baudry, A.; Richards, A. M. S.; Wittkowski, M.; Torstensson, K.; De Breuck, C.; Møller, P.; Etoka, S.; Olberg, M.

2017-07-01

Aims: The aim is to investigate the use of 183 GHz H2O masers for characterization of the physical conditions and mass loss process in the circumstellar envelopes of evolved stars. Methods: We used APEX SEPIA Band 5 (an ALMA Band 5 receiver on the APEX telescope) to observe the 183 GHz H2O line towards two red supergiant (RSG) and three asymptotic giant branch (AGB) stars. Simultaneously, we observed the J = 4-3 line for 28SiO v = 0, 1, 2 and 3, and for 29SiO v = 0 and 1. We compared the results with simulations and radiative transfer models for H2O and SiO, and examined data for the individual linear orthogonal polarizations. Results: We detected the 183 GHz H2O line towards all the stars with peak flux densities >100 Jy, including a new detection from VY CMa. Towards all five targets, the water line had indications of being caused by maser emission and had higher peak flux densities than for the SiO lines. The SiO lines appear to originate from both thermal and maser processes. Comparison with simulations and models indicate that 183 GHz maser emission is likely to extend to greater radii in the circumstellar envelopes than SiO maser emission and to similar or greater radii than water masers at 22, 321 and 325 GHz. We speculate that a prominent blue-shifted feature in the W Hya 183 GHz spectrum is amplifying the stellar continuum, and is located at a similar distance from the star as mainline OH maser emission. We note that the coupling of an SiO maser model to a hydrodynamical pulsating model of an AGB star yields qualitatively similar simulated results to the observations. From a comparison of the individual polarizations, we find that the SiO maser linear polarization fraction of several features exceeds the maximum fraction allowed under standard maser assumptions and requires strong anisotropic pumping of the maser transition and strongly saturated maser emission. The low polarization fraction of the H2O maser however, fits with the expectation for a non

Diffusion Monte Carlo studies of MB-pol (H2O)2-6 and (D2O)2-6 clusters: Structures and binding energies

NASA Astrophysics Data System (ADS)

Mallory, Joel D.; Mandelshtam, Vladimir A.

2016-08-01

We employ the diffusion Monte Carlo (DMC) method in conjunction with the recently developed, ab initio-based MB-pol potential energy surface to characterize the ground states of small (H2O)2-6 clusters and their deuterated isotopomers. Observables, other than the ground state energies, are computed using the descendant weighting approach. Among those are various spatial correlation functions and relative isomer fractions. Interestingly, the ground states of all clusters considered in this study, except for the dimer, are delocalized over at least two conformations that differ by the orientation of one or more water monomers with the relative isomer populations being sensitive to the isotope substitution. Most remarkably, the ground state of the (H2O)6 hexamer is represented by four distinct cage structures, while that of (D2O)6 is dominated by the prism, i.e., the global minimum geometry, with a very small contribution from a prism-book geometry. In addition, for (H2O)6 and (D2O)6, we performed DMC calculations to compute the ground states constrained to the cage and prism geometries. These calculations compared results for three different potentials, MB-pol, TTM3/F, and q-TIP4P/F.

Fluid inclusion volatile analysis by gas chromatography with photoionization micro-thermal conductivity detectors: Applications to magmatic MoS 2 and other H 2O-CO 2 and H 2O-CH 4 fluids

NASA Astrophysics Data System (ADS)

Bray, C. J.; Spooner, E. T. C.

1992-01-01

Eighteen fluid inclusion volatile peaks have been detected and identified from 1-2 g samples (quartz) by gas chromatography using heated (~105°C) on-line crushing, helium carrier gas, a single porous polymer column (HayeSep R; 10' × 1/8″: 100/120#; Ni alloy tubing), two temperature programme conditions for separate sample aliquots, micro-thermal conductivity (TCD) and photoionization detectors (PID; 11.7 eV lamp), and off-line digital peak processing. In order of retention time these volatile peaks are: N 2, Ar, CO, CH 4, CO 2, C 2H 4, C 2H 6, C 2H 2, COS, C 3H 6, C 3H 8, C 3H 4 (propyne), H 2O (22.7 min at 80°C), SO 2, ± iso- C4H10 ± C4H8 (1-butene) ± CH3SH, C 4H 8 (iso-butylene), (?) C 4H 6 (1,3 butadiene) and ± n- C4H10 ± C4H8 (trans-2-butene) (80 and -70°C temperature programme conditions combined). H 2O is analysed directly. O 2 can be analysed cryogenically between N 2 and Ar, but has not been detected in natural samples to date in this study. H 2S, SO 2, NH 3, HCl, HCN, and H 2 ca nnot be analysed at present. Blanks determined by crushing heat-treated Brazilian quartz (800-900°C/4 h) are zero for 80°C temperature programme conditions, except for a large, unidentified peak at ~64 min, but contain H 2O, CO 2, and some low molecular weight hydrocarbons at -70°C temperature conditions due to cryogenic accumulation from the carrier gas and subsequent elution. TCD detection limits are ~30 ppm molar in inclusions; PID detection limits are ~ 1 ppm molar in inclusions and lower for unsaturated hydrocarbons (e.g., ~0.2 ppm for C 2H 4; ~ 1 ppb for C 2H 2; ~0.3 ppb for C 3H 6). Precisions (1σ) are ~ ±1-2% and ~ ± 13% for H 2O in terms of total moles detected; the latter value is equivalent to ±0.6 mol% at the 95 mol% H 2O level. Major fluid inclusion volatile species have been successfully analysed on a ~50 mg fluid inclusion section chip (~7 mm × ~10 mm × ~100 μm). Initial inclusion volatile analyses of fluids of interpreted magmatic origin from

Ab initio studies on Al(+)(H(2)O)(n), HAlOH(+)(H(2)O)(n-1), and the size-dependent H(2) elimination reaction.

PubMed

Siu, Chi-Kit; Liu, Zhi-Feng; Tse, John S

2002-09-11

We report computational studies on Al(+)(H(2)O)(n), and HAlOH(+)(H(2)O)(n-1), n = 6-14, by the density functional theory based ab initio molecular dynamics method, employing a planewave basis set with pseudopotentials, and also by conventional methods with Gaussian basis sets. The mechanism for the intracluster H(2) elimination reaction is explored. First, a new size-dependent insertion reaction for the transformation of Al(+)(H(2)O)(n), into HAlOH(+)(H(2)O)(n-1) is discovered for n > or = 8. This is because of the presence of a fairly stable six-water-ring structure in Al(+)(H(2)O)(n) with 12 members, including the Al(+). This structure promotes acidic dissociation and, for n > or = 8, leads to the insertion reaction. Gaussian based BPW91 and MP2 calculations with 6-31G* and 6-31G** basis sets confirmed the existence of such structures and located the transition structures for the insertion reaction. The calculated transition barrier is 10.0 kcal/mol for n = 9 and 7.1 kcal/mol for n = 8 at the MP2/6-31G** level, with zero-point energy corrections. Second, the experimentally observed size-dependent H(2) elimination reaction is related to the conformation of HAlOH(+)(H(2)O)(n-1), instead of Al(+)(H(2)O)(n). As n increases from 6 to 14, the structure of the HAlOH(+)(H(2)O)(n-1) cluster changes into a caged structure, with the Al-H bond buried inside, and protons produced in acidic dissociation could then travel through the H(2)O network to the vicinity of the Al-H bond and react with the hydride H to produce H(2). The structural transformation is completed at n = 13, coincident approximately with the onset of the H(2) elimination reaction. From constrained ab initio MD simulations, we estimated the free energy barrier for the H(2) elimination reaction to be 0.7 eV (16 kcal/mol) at n = 13, 1.5 eV (35 kcal/mol) at n = 12, and 4.5 eV (100 kcal/mol) at n = 8. The existence of transition structures for the H(2) elimination has also been verified by ab initio calculations

Detection of interstellar ethylene oxide (c-C2H4O).

PubMed

Dickens, J E; Irvine, W M; Ohishi, M; Ikeda, M; Ishikawa, S; Nummelin, A; Hjalmarson, A

1997-11-10

We report the identification of 10 transitions that support the detection of the small cyclic molecule ethylene oxide (c-C2H4O) in Sgr B2N. Although one of these transitions is severely blended, so that an accurate intensity and line width could not be determined, and two other lines are only marginally detected, we have done Gaussian fits to the remaining seven lines and have performed a rotation diagram analysis. Our results indicate a rotation temperature T(rot) = 18 K and a molecular column density N(c-C2H4O) = 3.3 x 10(14) cm-2, corresponding to a fractional abundance relative to molecular hydrogen of order 6 x 10(-11). This is a factor of more than 200 higher than the abundance for this molecule suggested by the "new standard" chemistry model of Lee, Bettens, & Herbst. This result suggests that grain chemistry might play an effective role in the production of c-C2H4O. No transitions of this molecule were detected in either Sgr B2M or Sgr B2NW.

Feature Modeling of HfO2 Atomic Layer Deposition Using HfCl4/H2O

NASA Astrophysics Data System (ADS)

Stout, Phillip J.; Adams, Vance; Ventzek, Peter L. G.

2003-03-01

A Monte Carlo based feature scale model (Papaya) has been applied to atomic layer deposition (ALD) of HfO2 using HfCl_4/H_20. The model includes physical effects of transport to surface, specular and diffusive reflection within feature, adsorption, surface diffusion, deposition and etching. Discussed will be the 3D feature modeling of HfO2 deposition in assorted features (vias and trenches). The effect of feature aspect ratios, pulse times, cycle number, and temperature on film thickness, feature coverage, and film Cl fraction (surface/bulk) will be discussed. Differences between HfO2 ALD on blanket wafers and in features will be highlighted. For instance, the minimum pulse times sufficient for surface reaction saturation on blanket wafers needs to be increased when depositing on features. Also, HCl products created during the HfCl4 and H_20 pulses are more likely to react within a feature than at the field, reducing OH coverage within the feature (vs blanket wafer) thus limiting the maximum coverage attainable for a pulse over a feature.

New Optical Constants for Amorphous and Crystalline H2O-ice

NASA Technical Reports Server (NTRS)

Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

2006-01-01

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

Experimental, in-situ carbon solution mechanisms and isotope fractionation in and between (C-O-H)-saturated silicate melt and silicate-saturated (C-O-H) fluid to upper mantle temperatures and pressures

NASA Astrophysics Data System (ADS)

Mysen, Bjorn

2017-02-01

Our understanding of materials transport processes in the Earth relies on characterizing the behavior of fluid and melt in silicate-(C-O-H) systems at high temperature and pressure. Here, Raman spectroscopy was employed to determine structure of and carbon isotope partitioning between melts and fluids in alkali aluminosilicate-C-O-H systems. The experimental data were recorded in-situ while the samples were at equilibrium in a hydrothermal diamond anvil cell at temperatures and pressures to 825 °C and >1300 MPa, respectively. The carbon solution equilibrium in both (C-O-H)-saturated melt and coexisting, silicate-saturated (C-O-H) fluid is 2CO3 + H2O + 2Qn + 1 = 2HCO3 + 2Qn. In the Qn-notation, the superscript, n, is the number of bridging oxygen in silicate structural units. At least one oxygen in CO3 and HCO3 groups likely is shared with silicate tetrahedra. The structural behavior of volatile components described with this equilibrium governs carbon isotope fractionation factors between melt and fluid. For example, the ΔH equals 3.2 ± 0.7 kJ/mol for the bulk 13C/12C exchange equilibrium between fluid and melt. From these experimental data, it is suggested that at deep crustal and upper mantle temperatures and pressures, the δ13C-differences between coexisting silicate-saturated (C-O-H) fluid and (C-O-H)-saturated silicate melts may change by more than 100‰ as a function of temperature in the range of magmatic processes. Absent information on temperature and pressure, the use of carbon isotopes of mantle-derived magma to derive isotopic composition of magma source regions in the Earth's interior, therefore, should be exercised with care.

Organic Contaminant Abatement in Reclaimed Water by UV/H2O2 and a Combined Process Consisting of O3/H2O2 Followed by UV/H2O2: Prediction of Abatement Efficiency, Energy Consumption, and Byproduct Formation.

PubMed

Lee, Yunho; Gerrity, Daniel; Lee, Minju; Gamage, Sujanie; Pisarenko, Aleksey; Trenholm, Rebecca A; Canonica, Silvio; Snyder, Shane A; von Gunten, Urs

2016-04-05

UV/H2O2 processes can be applied to improve the quality of effluents from municipal wastewater treatment plants by attenuating trace organic contaminants (micropollutants). This study presents a kinetic model based on UV photolysis parameters, including UV absorption rate and quantum yield, and hydroxyl radical (·OH) oxidation parameters, including second-order rate constants for ·OH reactions and steady-state ·OH concentrations, that can be used to predict micropollutant abatement in wastewater. The UV/H2O2 kinetic model successfully predicted the abatement efficiencies of 16 target micropollutants in bench-scale UV and UV/H2O2 experiments in 10 secondary wastewater effluents. The model was then used to calculate the electric energies required to achieve specific levels of micropollutant abatement in several advanced wastewater treatment scenarios using various combinations of ozone, UV, and H2O2. UV/H2O2 is more energy-intensive than ozonation for abatement of most micropollutants. Nevertheless, UV/H2O2 is not limited by the formation of N-nitrosodimethylamine (NDMA) and bromate whereas ozonation may produce significant concentrations of these oxidation byproducts, as observed in some of the tested wastewater effluents. The combined process of O3/H2O2 followed by UV/H2O2, which may be warranted in some potable reuse applications, can achieve superior micropollutant abatement with reduced energy consumption compared to UV/H2O2 and reduced oxidation byproduct formation (i.e., NDMA and/or bromate) compared to conventional ozonation.

Near-infrared kinetic spectroscopy of the HO2 and C2H5O2 self-reactions and cross reactions.

PubMed

Noell, A C; Alconcel, L S; Robichaud, D J; Okumura, M; Sander, S P

2010-07-08

The self-reactions and cross reactions of the peroxy radicals C2H5O2 and HO2 were monitored using simultaneous independent spectroscopic probes to observe each radical species. Wavelength modulation (WM) near-infrared (NIR) spectroscopy was used to detect HO2, and UV absorption monitored C2H5O2. The temperature dependences of these reactions were investigated over a range of interest to tropospheric chemistry, 221-296 K. The Arrhenius expression determined for the cross reaction, k2(T) = (6.01(-1.47)(+1.95)) x 10(-13) exp((638 +/- 73)/T) cm3 molecules(-1) s(-1) is in agreement with other work from the literature. The measurements of the HO2 self-reaction agreed with previous work from this lab and were not further refined. The C2H5O2 self-reaction is complicated by secondary production of HO2. This experiment performed the first direct measurement of the self-reaction rate constant, as well as the branching fraction to the radical channel, in part by measurement of the secondary HO2. The Arrhenius expression for the self-reaction rate constant is k3(T) = (1.29(-0.27)(+0.34)) x 10(-13)exp((-23 +/- 61)/T) cm3 molecules(-1) s(-1), and the branching fraction value is alpha = 0.28 +/- 0.06, independent of temperature. These values are in disagreement with previous measurements based on end product studies of the branching fraction. The results suggest that better characterization of the products from RO2 self-reactions are required.

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

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

Evaluation of soil water stable isotope analysis by H2O(liquid)-H2O(vapor) equilibration method

NASA Astrophysics Data System (ADS)

Gralher, Benjamin; Stumpp, Christine

2014-05-01

Environmental tracers like stable isotopes of water (δ18O, δ2H) have proven to be valuable tools to study water flow and transport processes in soils. Recently, a new technique for soil water isotope analysis has been developed that employs a vapor phase being in isothermal equilibrium with the liquid phase of interest. This has increased the potential application of water stable isotopes in unsaturated zone studies as it supersedes laborious extraction of soil water. However, uncertainties of analysis and influencing factors need to be considered. Therefore, the objective of this study was to evaluate different methodologies of analysing stable isotopes in soil water in order to reduce measurement uncertainty. The methodologies included different preparation procedures of soil cores for equilibration of vapor and soil water as well as raw data correction. Two different inflatable sample containers (freezer bags, bags containing a metal layer) and equilibration atmospheres (N2, dry air) were tested. The results showed that uncertainties for δ18O were higher compared to δ2H that cannot be attributed to any specific detail of the processing routine. Particularly, soil samples with high contents of organic matter showed an apparent isotope enrichment which is indicative for fractionation due to evaporation. However, comparison of water samples obtained from suction cups with the local meteoric water line indicated negligible fractionation processes in the investigated soils. Therefore, a method was developed to correct the raw data reducing the uncertainties of the analysis.. We conclude that the evaluated method is advantageous over traditional methods regarding simplicity, resource requirements and sample throughput but careful consideration needs to be made regarding sample handling and data processing. Thus, stable isotopes of water are still a good tool to determine water flow and transport processes in the unsaturated zone.

Comparative study of the degradation of real textile effluents by photocatalytic reactions involving UV/TiO2/H2O2 and UV/Fe2+/H2O2 systems.

PubMed

Garcia, J C; Oliveira, J L; Silva, A E C; Oliveira, C C; Nozaki, J; de Souza, N E

2007-08-17

This work investigated the treatability of real textile effluents using several systems involving advanced oxidation processes (AOPs) such as UV/H2O2, UV/TiO2, UV/TiO2/H2O2, and UV/Fe2+/H2O2. The efficiency of each technique was evaluated according to the reduction levels observed in the UV absorbance of the effluents, COD, and organic nitrogen reduction, as well as mineralization as indicated by the formation of ammonium, nitrate, and sulfate ions. The results indicate the association of TiO2 and H2O2 as the most efficient treatment for removing organic pollutants from textile effluents. In spite of their efficiency, Fenton reactions based treatment proved to be slower and exhibited more complicated kinetics than the ones using TiO2, which are pseudo-first-order reactions. Decolorization was fast and effective in all the experiments despite the fact that only H2O2 was used.

LiOH - H2O2 - H2O trinary system study for the selection of optimal conditions of lithium peroxide synthesis

NASA Astrophysics Data System (ADS)

Nefedov, R. A.; Ferapontov, Yu A.; Kozlova, N. P.

2016-01-01

Using solubility method the decay kinetics of peroxide products contained in liquid phase of LiOH - H2O2 - H2O trinary system with 2 to 6% by wt hydrogen peroxide content in liquid phase in 21 to 33 °C temperature range has been studied. Conducted studies have allowed to determine temperature and concentration limits of solid phase existence of Li2O2·H2O content, distinctness of which has been confirmed using chemical and qualitative X- ray phase analysis. Stabilizing effect of solid phase of Li2O2·H2O content on hydrogen peroxide decay contained in liquid phase of LiOH - H2O2 - H2O trinary system under conditions of experiments conducted has been shown.

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

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

Studies of proton irradiated H2O + CO2 and H2O + CO ices and analysis of synthesized molecules

NASA Technical Reports Server (NTRS)

Moore, M. H.; Khanna, R.; Donn, B.

1991-01-01

Infrared spectra of H2O + CO2 and H2O + CO ices before and after proton irradiation showed that a major reaction in both mixtures was the interconversion of CO2 yields CO. Radiation synthesized organic compounds such as carbonic acid were identified in the H2O + CO2 ice. Different chemical pathways dominate in the H2O + CO ice in which formaldehyde, methanol, ethanol, and methane were identified. Sublimed material was also analyzed using a mass spectrometer. Implications of these results are discussed in reference to comets.

Selective photocatalytic reduction of CO2 by H2O/H2 to CH4 and CH3OH over Cu-promoted In2O3/TiO2 nanocatalyst

NASA Astrophysics Data System (ADS)

Tahir, Muhammad; Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar

2016-12-01

Photocatalytic CO2 reduction by H2O and/or H2 reductant to selective fuels over Cu-promoted In2O3/TiO2 photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N2 adsorption-desorption, UV-vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO2, oxidized as Cu2+ and In3+, promoted efficient separation of photo-generated electron/hole pairs (e-/h+). The results indicate that the reduction rate of CO2 by H2O to CH4 approached to 181 μmol g-1 h-1 using 0.5% Cu-3% In2O3/TiO2 catalyst, a 1.53 fold higher than the production rate over the 3% In2O3/TiO2 and 5 times the amount produced over the pure TiO2. In addition, Cu was found to promote efficient production of CH3OH and yield rate reached to 68 μmol g-1 h-1 over 1% Cu-3% In2O3/TiO2 catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H2 reductant was less favorable for CH4 production, yet a significant amount of CH4 and CH3OH were obtained using a mixture of H2O/H2 reductant. Therefore, Cu-loaded In2O3/TiO2 catalyst has shown to be capable for methanol production, whereas product selectivity was greatly depending on the amount of Cu-loading and the type of reductant. A photocatalytic reaction mechanism was proposed to understand the experimental results over the Cu-loaded In2O3/TiO2 catalyst.

Two mixed-ligand lanthanide–hydrazone complexes: [Pr(NCS)3(pbh)2]·H2O and [Nd(NCS)(NO3)(pbh)2(H2O)]NO3·2.33H2O [pbh is N′-(pyridin-2-ylmethylidene)benzo­hydrazide, C13H11N3O

PubMed Central

Paschalidis, Damianos G.; Harrison, William T. A.

2016-01-01

The gel-mediated syntheses and crystal structures of [N′-(pyridin-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O]tris(thiocyanato-κN)praseodymium(III) mono­hydrate, [Pr(NCS)3(C13H11N3O)2]·H2O, (I), and aqua(nitrato-κ2 O,O′)[N′-(pyri­din-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O](thiocyanato-κN)neo­dym­ium(III) nitrate 2.33-hydrate, [Nd(NCS)(NO3)(C13H11N3O)2(H2O)]NO3·2.33H2O, (II), are reported. The Pr3+ ion in (I) is coordinated by two N,N,O-tridentate N′-(pyridin-2-ylmethylidene)benzohydrazide (pbh) ligands and three N-bonded thio­cyanate ions to generate an irregular PrN7O2 coordination polyhedron. The Nd3+ ion in (II) is coordinated by two N,N,O-tridentate pbh ligands, an N-bonded thio­cyanate ion, a bidentate nitrate ion and a water mol­ecule to generate a distorted NdN5O5 bicapped square anti­prism. The crystal structures of (I) and (II) feature numerous hydrogen bonds, which lead to the formation of three-dimensional networks in each case. PMID:26958385

High-Level ab initio electronic structure calculations of Water Clusters (H2O)16 and (H2O)17: a new global minimum for (H2O)16

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoo, Soohaeng; Apra, Edoardo; Zeng, Xiao Cheng

The lowest-energy structures of water clusters (H2O)16 and (H2O)17 were revisited at the MP2 and CCSD(T) levels of theory. A new global minimum structure for (H2O)16 was found at the MP2 and CCSD(T) levels of theory and the effect of zero-point energy corrections on the relative stability of the low-lying minimum energy structures was assessed. For (H2O)17 the CCSD(T) calculations confirm the previously found at the MP2 level of theory "interior" arrangement (fully coordinated water molecule inside a spherical cluster) as the global minimum.

High-Level ab-initio Electronic Structure Calculations of Water Clusters (H2O)16 and (H2O)17 : a New Global Minimum for (H2O)16

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoo, Soohaeng; Apra, Edoardo; Zeng, X.C.

The lowest-energy structures of water clusters (H2O)16 and (H2O)17 were revisited at the MP2 and CCSD(T) levels of theory. A new global minimum structure for (H2O)16 was found at both the MP2 and CCSD(T) levels of theory, and the effect of zero-point energy corrections on the relative stability of the low-lying minimum energy structures was assessed. For (H2O)17, the CCSD(T) calculations confirm the previously found at the MP2 level of theory interior arrangement (fully coordinated water molecule inside a spherical cluster) as the global minimum

The catalytic effects of H2CO3, CH3COOH, HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

NASA Astrophysics Data System (ADS)

Zhang, Tianlei; Lan, Xinguang; Wang, Rui; Roy, Soumendra; Qiao, Zhangyu; Lu, Yousong; Wang, Zhuqing

2018-07-01

The addition reaction of CH2OO + H2O → CH2(OH)OOH without and with X (X = H2CO3, CH3COOH and HCOOH) and H2O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH2OO + H2O → CH2(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH2OO...H2O is favourable one. Water-assisted CH2OO + H2O → CH2(OH)OOH can occur by H2O moiety of (H2O)2 or the whole (H2O)2 forming cyclic structure with CH2OO, where the latter form is more favourable. Because the concentration of H2CO3 is unknown, the influence of CH3COOH, HCOOH and H2O were calculated within 0-30 km altitude of the Earth's atmosphere. The results calculated within 0-5 km altitude show that H2O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%-77.26% and 0.04%-1.76%. Within 5-30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%-98.28%. However, compared with the reaction of CH2OO + HCOOH, the rate of CH2OO...H2O + HCOOH is much slower.

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

NASA Astrophysics Data System (ADS)

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

2013-03-01

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

Isotope mass fractionation during evaporation of Mg2SiO4

NASA Technical Reports Server (NTRS)

Davis, Andrew M.; Clayton, Robert N.; Mayeda, Toshiko K.; Hashimoto, Akihiko

1990-01-01

Synthetic forsterite (Mg2SiO4) was partially evaporated in vacuum for various durations and at different temperatures. The residual charges obtained when molten Mg2SiO4 was evaporated to 12 percent of its initial mass were enriched in heavy isotopes by about 20, 30, and 15 per mil/amu for O, Mg, and Si, respectively, whereas solid forsterite evaporated to a similar residual mass fraction showed negligible fractionations. These results imply that calcium and aluminum-rich refractory inclusions in carbonaceous chondrites must have been at least partially molten in the primordial solar nebula if the observed large mass fractionation effects were caused by evaporation processes in the nebula.

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.

Synthesis and characterization of polymer eight-coordinate (enH 2)[Y III(pdta)(H 2O)] 2·10H 2O as well as the interaction of [Y III(pdta)(H 2O)] 22- with BSA

NASA Astrophysics Data System (ADS)

Liu, Bin; Wang, Jun; Wang, Xin; Liu, Bing-Mi; He, Ling-Ling; Xu, Shu-Kun

2010-12-01

The eight-coordinate (enH 2)[Y III(pdta)(H 2O)] 2·10H 2O (en = ethylenediamine and H 4pdta = 1,3-propylenediamine- N, N, N', N'-tetraacetic acid) was synthesized, meanwhile its molecular and crystal structures were determined by single-crystal X-ray diffraction technology. The interaction between [Y III(pdta)(H 2O)] 22- and bovine serum albumin (BSA) was investigated by UV-vis and fluorescence spectra. The results indicate that [Y III(pdta)(H 2O)] 22- quenched effectively the intrinsic fluorescence of BSA via a static quenching process with the binding constant ( Ka) of the order of 10 4. Meanwhile, the binding and damaging sites to BSA molecules were also estimated by synchronous fluorescence. Results indicate that the hydrophobic environments around Trp and Tyr residues were all slightly changed. The thermodynamic parameters (Δ G = -25.20 kJ mol -1, Δ H = -26.57 kJ mol -1 and Δ S = -4.58 J mol -1 K -1) showed that the reaction was spontaneous and exothermic. What is more, both Δ H and Δ S were negative values indicated that hydrogen bond and Van der Waals forces were the predominant intermolecular forces between [Y III(pdta)(H 2O)] 22- and BSA.

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

NASA Astrophysics Data System (ADS)

Lyons, M.; Siegel, E.

2010-03-01

``Water water everywhere; ne'er a drop to drink''[Coleridg(1798)]; now:``Hydrogen hydrogen everywhere;STILL ne'er a drop to drink'': ONLY H2 can be ``FLYING-WATER''/``chemical-rain-in-pipelines''/ ``Hindenberg-effect (H2-UP;H2O-DOWN): atomic-weights ratio: O/H2O=[16]/[18]˜90%; O already in air uphill; NO H2O pumping need! In water-starved glacial-melting world, rescue ONLY by Siegel[3rd Intl.Conf.Alt.Energy,Hemisphere/Springer(1980)- vol.5/ p.459]Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating- system. Rosenfeld[Sci.315,1396(3/9/2007)]-Biello[Sci.Am.(3/9/ 2007)]crucial geomorphology which ONLY maximal-buoyancy light- est-element H2 can exploit, to again make ``Mountains into Fount- ains": Siegel ``terra-forming''(and ocean-rebasificaton!!!) long pre-``Holdren''-``Ciccerine" ``geo-enginering'', only via Siegel proprietary magnetic-hydrogen-valve permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Sci.300,1740(03)]global-pandemics (cancers/blindness/famine)dire-warning about H2-(ALONE)economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!

The Influence of Growth Rate on 2H/1H Fractionation in Continuous Cultures of the Coccolithophorid Emiliania huxleyi and the Diatom Thalassiosira pseudonana

PubMed Central

Sachs, Julian P.; Kawka, Orest E.

2015-01-01

The hydrogen isotope (2H/1H) ratio of lipids from phytoplankton is a powerful new tool for reconstructing hydroclimate variations in the geologic past from marine and lacustrine sediments. Water 2H/1H changes are reflected in lipid 2H/1H changes with R2 > 0.99, and salinity variations have been shown to cause about a 1‰ change in lipid δ2H values per unit (ppt) change in salinity. Less understood are the effects of growth rate, nutrient limitation and light on 2H/1H fractionation in phytoplankton. Here we present the first published study of growth rate effects on 2H/1H fractionation in the lipids of coccolithophorids grown in continuous cultures. Emiliania huxleyi was cultivated in steady state at four growth rates and the δ2H value of individual alkenones (C37:2, C37:3, C38:2, C38:3), fatty acids (C14:0, C16:0, C18:0), and 24-methyl cholest-5,22-dien-3β-ol (brassicasterol) were measured. 2H/1H fractionation increased in all lipids as growth rate increased by 24‰ to 79‰ (div d-1)-1. We attribute this response to a proportional increase in the fraction of NADPH from Photosystem I (PS1) of photosynthesis relative to NADPH from the cytosolic oxidative pentose phosphate (OPP) pathway in the synthesis of lipids as growth rate increases. A 3-endmember model is presented in which lipid hydrogen comes from NADPH produced in PS1, NADPH produced by OPP, and intracellular water. With published values or best estimates of the fractionation factors for these sources (αPS1 = 0.4, αOPP = 0.75, and αH2O = 0) and half of the hydrogen in a lipid derived from water the model indicates αlipid = 0.79. This value is within the range measured for alkenones (αalkenone = 0.77 to 0.81) and fatty acids (αFA = 0.75 to 0.82) in the chemostat cultures, but is greater than the range for brassicasterol (αbrassicasterol = 0.68 to 0.72). The latter is attributed to a greater proportion of hydrogen from NADPH relative to water in isoprenoid lipids. The model successfully explains

The Influence of Growth Rate on 2H/1H Fractionation in Continuous Cultures of the Coccolithophorid Emiliania huxleyi and the Diatom Thalassiosira pseudonana.

PubMed

Sachs, Julian P; Kawka, Orest E

2015-01-01

The hydrogen isotope (2H/1H) ratio of lipids from phytoplankton is a powerful new tool for reconstructing hydroclimate variations in the geologic past from marine and lacustrine sediments. Water 2H/1H changes are reflected in lipid 2H/1H changes with R2 > 0.99, and salinity variations have been shown to cause about a 1‰ change in lipid δ2H values per unit (ppt) change in salinity. Less understood are the effects of growth rate, nutrient limitation and light on 2H/1H fractionation in phytoplankton. Here we present the first published study of growth rate effects on 2H/1H fractionation in the lipids of coccolithophorids grown in continuous cultures. Emiliania huxleyi was cultivated in steady state at four growth rates and the δ2H value of individual alkenones (C37:2, C37:3, C38:2, C38:3), fatty acids (C14:0, C16:0, C18:0), and 24-methyl cholest-5,22-dien-3β-ol (brassicasterol) were measured. 2H/1H fractionation increased in all lipids as growth rate increased by 24‰ to 79‰ (div d-1)-1. We attribute this response to a proportional increase in the fraction of NADPH from Photosystem I (PS1) of photosynthesis relative to NADPH from the cytosolic oxidative pentose phosphate (OPP) pathway in the synthesis of lipids as growth rate increases. A 3-endmember model is presented in which lipid hydrogen comes from NADPH produced in PS1, NADPH produced by OPP, and intracellular water. With published values or best estimates of the fractionation factors for these sources (αPS1 = 0.4, αOPP = 0.75, and αH2O = 0) and half of the hydrogen in a lipid derived from water the model indicates αlipid = 0.79. This value is within the range measured for alkenones (αalkenone = 0.77 to 0.81) and fatty acids (αFA = 0.75 to 0.82) in the chemostat cultures, but is greater than the range for brassicasterol (αbrassicasterol = 0.68 to 0.72). The latter is attributed to a greater proportion of hydrogen from NADPH relative to water in isoprenoid lipids. The model successfully explains

Solid state reactions of CeO 2, PuO 2, (U,Ce)O 2 and (U,Pu)O 2 with K 2S 2O 8

NASA Astrophysics Data System (ADS)

Keskar, Meera; Kasar, U. M.; Mudher, K. D. Singh; Venugopal, V.

2004-09-01

Solid state reactions of CeO 2, PuO 2 and mixed oxides (U,Ce)O 2 and (U,Pu)O 2 containing different mol.% of Ce and Pu, were carried out with K 2S 2O 8 at different temperatures to identify the formation of various products and to investigate their dissolution behaviour. X-ray, chemical and thermal analysis methods were used to characterise the products formed at various temperatures. The products obtained by heating two moles of K 2S 2O 8 with one mole each of CeO 2, PuO 2, (U,Ce)O 2 and (U,Pu)O 2 at 400 °C were identified as K 4Ce(SO 4) 4, K 4Pu(SO 4) 4, K 4(U,Ce)(SO 4) 4 and K 4(U,Pu)(SO 4) 4, respectively. K 4Ce(SO 4) 4 further decomposed to form K 4Ce(SO 4) 3.5 at 600 °C and mixture of K 2SO 4 and CeO 2 at 950 °C. Thus the products formed during the reaction of 2K 2S 2O 8 + CeO 2 show that cerium undergoes changes in oxidation state from +4 to +3 and again to +4. XRD data of K 4Ce(SO 4) 4 and K 4Ce(SO 4) 3.5 were indexed on triclinic and monoclinic system, respectively. PuO 2 + 2K 2S 2O 8 reacts at 400 °C to form K 4Pu(SO 4) 4 which was stable upto 750 °C and further decomposes to form K 2SO 4 + PuO 2 at 1000 °C. The products formed at 400 °C during the reactions of the oxides and mixed oxides were found to be readily soluble in 1-2 M HNO 3.

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.

Catalase activity is stimulated by H2O2 in rich culture medium and is required for H2O2 resistance and adaptation in yeast☆

PubMed Central

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. PMID:24563848

X-ray-induced dissociation of H.sub.2O and formation of an O.sub.2-H.sub.2 alloy at high pressure

DOEpatents

Mao, Ho-kwang [Washington, DC; Mao, Wendy L [Washington, DC

2011-11-29

A novel molecular alloy of O.sub.2 and H.sub.2 and a method of producing such a molecular alloy are provided. When subjected to high pressure and extensive x-radiation, H.sub.2O molecules cleaved, forming O--O and H--H bonds. In the method of the present invention, the O and H framework in ice VII was converted into a molecular alloy of O.sub.2 and H.sub.2. X-ray diffraction, x-ray Raman scattering, and optical Raman spectroscopy demonstrate that this crystalline solid differs from previously known phases.

Ground and excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters: Insight into the electronic structure of the [Fe(H2O)6]2+ – [Fe(H2O)6]3+ complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miliordos, Evangelos; Xantheas, Sotiris S.

We report the ground and low lying electronically excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters using multi-configuration electronic structure theory. In particular, we have constructed the Potential Energy Curves (PECs) with respect to the iron-oxygen distance when removing all water ligands at the same time from the cluster minima and established their correlation to the long range dissociation channels. Due to the fact that both the second and third ionization potentials of iron are larger than the one for water, the ground state products asymptotically correlate with dissociation channels that are repulsive in nature at large separations as theymore » contain at least one H2O+ fragment and a positive metal center. The most stable equilibrium structures emanate – via intersections and/or avoided crossings – from the channels consisting of the lowest electronic states of Fe2+(5D; 3d6) or Fe3+(6S; 3d5) and six neutral water molecules. Upon hydration, the ground state of Fe2+(H2O)6 is a triply (5Tg) degenerate one with the doubly (5Eg) degenerate state lying slightly higher in energy. Similarly, Fe3+(H2O)6 has a ground state of 6Ag symmetry under Th symmetry. We furthermore examine a multitude of electronically excited states of many possible spin multiplicities, and report the optimized geometries for several selected states. The PECs for those cases are characterized by a high density of states. Focusing on the ground and the first few excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters, we studied their mutual interaction in the gas phase. We obtained the optimal geometries of the Fe2+(H2O)6 – Fe3+(H2O)6 gas phase complex for different Fe–Fe distances. For distances shorter than 6.0 Å, the water molecules in the respective first solvation shells located between the two metal centers were found to interact via weak hydrogen bonds. We examined a total of ten electronic states for this complex, including those corresponding to the

The effect of ZnO addition on H2O activation over Co/ZrO2 catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davidson, Stephen D.; Sun, Junming; Wang, Yong

The effect of ZnO addition on the dissociation of H2O and subsequent effects on cobalt oxidation state and ethanol reaction pathway were investigated over Co/ZrO2 catalyst during ethanol steam reforming (ESR). Catalyst physical properties were characterized by BET, XRD, and TEM. To characterize the catalysts ability to dissociate H2O, Raman spectroscopy, H2O-TPO, and pulsed H2O oxidation coupled with H2-TPR were used. It was found that the addition of ZnO to cobalt supported on ZrO2 decreased the activity for H2O dissociation, leading to a lower degree of cobalt oxidation. The decreased H2O dissociation was also found to affect the reaction pathway,more » evidenced by a shift in liquid product selectivity away from acetone and towards acetaldehyde.« less

Coherent Anti-Stokes Raman Scattering (CARS) as a Probe for Supersonic Hydrogen-Fuel/Air Mixing

NASA Technical Reports Server (NTRS)

Danehy, P. M.; O'Byrne, S.; Cutler, A. D.; Rodriguez, C. G.

2003-01-01

The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method was used to measure temperature and the absolute mole fractions of N2, O2 and H2 in a supersonic non-reacting fuel-air mixing experiment. Experiments were conducted in NASA Langley Research Center s Direct Connect Supersonic Combustion Test Facility. Under normal operation of this facility, hydrogen and air burn to increase the enthalpy of the test gas and O2 is added to simulate air. This gas is expanded through a Mach 2 nozzle and into a combustor model where fuel is then injected, mixes and burns. In the present experiment the O2 of the test gas is replaced by N2. The lack of oxidizer inhibited combustion of the injected H2 fuel jet allowing the fuel/air mixing process to be studied. CARS measurements were performed 427 mm downstream of the nozzle exit and 260 mm downstream of the fuel injector. Maps were obtained of the mean temperature, as well as the N2, O2 and H2 mean mole fraction fields. A map of mean H2O vapor mole fraction was also inferred from these measurements. Correlations between different measured parameters and their fluctuations are presented. The CARS measurements are compared with a preliminary computational prediction of the flow.

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.