N2/O2/H2 Dual-Pump Cars: Validation Experiments

NASA Technical Reports Server (NTRS)

OByrne, S.; Danehy, P. M.; Cutler, A. D.

2003-01-01

The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method is used to measure temperature and the relative species densities of N2, O2 and H2 in two experiments. Average values and root-mean-square (RMS) deviations are determined. Mean temperature measurements in a furnace containing air between 300 and 1800 K agreed with thermocouple measurements within 26 K on average, while mean mole fractions agree to within 1.6 % of the expected value. The temperature measurement standard deviation averaged 64 K while the standard deviation of the species mole fractions averaged 7.8% for O2 and 3.8% for N2, based on 200 single-shot measurements. Preliminary measurements have also been performed in a flat-flame burner for fuel-lean and fuel-rich flames. Temperature standard deviations of 77 K were measured, and the ratios of H2 to N2 and O2 to N2 respectively had standard deviations from the mean value of 12.3% and 10% of the measured ratio.

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

Production of N2O/+/ by reaction of metastable O2/+/ ions with N2

NASA Technical Reports Server (NTRS)

Ajello, J. M.; Rayermann, P.

1975-01-01

Photoionization mass spectrometry examination of the production of N2O(+) was undertaken to determine whether N2(+) or O2(+) ions are responsible for onset of N2O(+). It appears that the N2(+) ion does not contribute significantly to the production of N2O(+) in this experiment. Therefore, it is clear that excited O2(+) is responsible for the formation of N2O(+) near the appearance potential of these ions.

Stratospheric N2O5, CH4, and N2O profiles from IR solar occultation spectra

NASA Technical Reports Server (NTRS)

Camy-Peyret, C.; Flaud, J.-M.; Perrin, A.; Rinsland, C. P.; Goldman, A.; Murcray, F. J.

1993-01-01

Stratospheric volume mixing ratio profiles of N2O5, CH4, and N2O have been retrieved from a set of 0.052/cm resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur l'Adour, France (44 N latitude) on 12 October 1990. The N2O5 results have been derived from measurements of the integrated absorption by the 1246/cm band. Assuming a total intensity of 4.32 x 10 exp -17 cm/molecule/sq cm independent of temperature, the retrieved N2O5 volume mixing ratios in ppbv, interpolated to 2 km height spacings, are 1.64 +/- 0.49 at 37.5 km, 1.92 +/- 0.56 at 35.5 km, 2.06 +/- 0.47 at 33.5 km, 1.95 +/- 0.42 at 31.5 km, 1.60 +/- 0.33 at 29.5 km, 1.26 +/- 0.28 at 27.5 km, and 0.85 +/- 0.20 at 25.5 km. Error bars indicate the estimated 1-sigma uncertainty including the error in the total band intensity. The retrieved profiles are compared with previous measurements and photochemical model results.

Troposphere-to-Stratosphere Transport in the Lowermost Stratosphere from Measurements of H2O, CO2, N2O and O3

NASA Technical Reports Server (NTRS)

Hintsa, E. J.; Boering, K. A.; Weinstock, E. M.; Anderson, J. G.; Gary, B. L.; Pfister, L.; Daube, B. C.; Wofsy, S. C.; Loewenstein, M.; Podolske, J.R.;

Troposphere-to-Stratosphere Transport in the Lowermost Stratosphere from Measurements of H2O, CO2, N2O and O3

NASA Technical Reports Server (NTRS)

Hintsa, E. J.; Boering, K. A.; Weinstock, E. M.; Anderson, J. G.; Gary, B. L.; Pfister, L.; Daube, B. C.; Wofsy, S. C.; Loewenstein, M.; Podolske, J. R.

1998-01-01

The origin of air in the lowermost stratosphere is investigated with measurements from the NASA ER-2 aircraft. Air with high water vapor mixing ratios was observed in the stratosphere at theta = 330-380 K near 40 N in May 1995, indicating the influence of intrusions of tropospheric air. Assuming that observed tracer-tracer relationships reflect mixing lines between tropospheric and stratospheric air masses, we calculate mixing ratios of H2O (12-24 ppmv) and CO2 for the admixed tropospheric air at theta = 352-364 K. Temperatures on the 355 K surface at 20-40 N were low enough to dehydrate air to these values. While most ER-2 CO2 data in both hemispheres are consistent with tropical or subtropical air entering the lowermost stratosphere, measurements from May 1995 for theta < 362 K suggest that entry of air from the midlatitude upper troposphere can occur in conjunction with mixing processes near the tropopause.

Troposphere-to-Stratosphere Transport in the Lowermost Stratosphere from Measurements of H2O, CO2, N2O, and O3

NASA Technical Reports Server (NTRS)

Hintsa, E. J.; Boering, K. A.; Weinstock, E. M.; Anderson, J. G.; Gary, B. L.; Pfister, L.; Daube, B. C.; Wofsy, S. C.; Loewenstein, M.; Podolske, J. R.;

Troposphere-to-Stratosphere Transport in the Lowermost Stratosphere from Measurements of H2O, CO2, N2O and O3

NASA Technical Reports Server (NTRS)

Hintsa, E. J.; Boering, K. A.; Weinstock, E. M.; Anderson, J. G.; Gary, B. L.; Pfister, L.; Daube, B. C.; Wofsy, S. C.; Loewenstein, M.; Podolske, J. R.;

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.

O2 Herzberg State Reaction with N2: A Possible Source of Stratospheric N2O

NASA Technical Reports Server (NTRS)

Slanger, Tom G.; Copeland, Richard A.

1997-01-01

The goal of this one-year investigation was to determine whether N2O is formed in atmospherically significant quantities by the reaction of vibrationally excited levels of the O2((A3 Sigma(sub u)(sup +)) state with nitrogen. O2(A3 Sigma(sub u)(sup +)) is made throughout the upper stratosphere in considerable amounts by solar photoabsorption, and only a very small reactive yield is necessary for this mechanism to be a major N2O source. By long-term 245-252 nm irradiation of O2/N2 mixtures on- and off-resonance with absorption lines in the O2(A3 Sigma(sub u)(sup +) - X3 Sigma(sub g)(sup -)) transition, followed by N2O analysis by frequency-modulated diode laser absorption spectroscopy, we determined an upper limit for the N2O yield of the candidate reaction. This limit, 3 x 10(exp -5), eliminates O2(A3 Sigma(sub u)(sup +)) + N2 as a significant channel for the generation of stratospheric N2O. In further measurements, we established that N2O is stable under our photolysis conditions, showing that the small amounts of ozone generated from the reaction of O2(A) and O2 do not indirectly lead to destruction of N2O.

Influence of Ar/O2/H2O Feed Gas and N2/O2/H2O Environment on the Interaction of Time Modulated MHz Atmospheric Pressure Plasma Jet (APPJ) with Model Polymers

NASA Astrophysics Data System (ADS)

Oehrlein, Gottlieb; Luan, Pingshan; Knoll, Andrew; Kondeti, Santosh; Bruggeman, Peter

2016-09-01

An Ar/O2/H2O fed time modulated MHz atmospheric pressure plasma jet (APPJ) in a sealed chamber was used to study plasma interaction with model polymers (polystyrene, poly-methyl methacrylate, etc.). The amount of H2O in the feed gas and/or present in the N2, O2, or N2/O2 environment was controlled. Short lived species such as O atoms and OH radicals play a crucial role in polymer etching and surface modifications (obtained from X-ray photoelectron spectroscopy of treated polymers without additional atmospheric exposure). Polymer etching depth for Ar/air fed APPJ mirrors the decay of gas phase O atoms with distance from the APPJ nozzle in air and is consistent with the estimated O atom flux at the polymer surface. Furthermore, whereas separate O2 or H2O admixture to Ar enhances polymer etching, simultaneous addition of O2 and H2O to Ar quenches polymer etching. This can be explained by the mutual quenching of O with OH, H and HO2 in the gas phase. Results where O2 and/or H2O in the environment were varied are consistent with these mechanisms. All results will be compared with measured and simulated species densities reported in the literature. We gratefully acknowledge funding from US Department of Energy (DE-SC0001939) and National Science Foundation (PHY-1415353).

Stratospheric N2O5, CH4, and N2O Profiles from IR Solar Occultation Spectra

NASA Technical Reports Server (NTRS)

Peyeret, C. Camy; Flaud, J.-M.; Perrin, A.; Rinsland, C. P.; Goldman, A.; Murcray, F. J.

1993-01-01

Stratospheric volume mixing ratio profiles of N2O5, CH4, and N2O have been retrieved from a set of 0.052/ cm resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur I'Adour, France (44 deg N latitude) on 12 October 1990. The N2O5 results have been derived from measurements of the integrated absorption by the 1246/ cm band. Assuming a total intensity of 4.32 x 10(exp 17)cm(exp -1) molecule sq cm(exp -2) independent of temperature, the retrieved N2O5 volume mixing ratios in ppbv (parts per billion by volume, 10(exp -9)), interpolated to 2 km height spacings, are 1.64 +/- 0.49 at 37.5 km, 1.92 +/- 0.56 at 35.5 km, 2.06 +/- 0.47 at 33.5 km, 1.95 +/- 0.42 at 31.5 km, 1.60 +/- 0.33 at 29.5 km, 1.26 +/- 0.28 at 27.5 km, and 0.85 +/- 0.20 at 25.5 km. Error bars indicate the estimated I-sigma uncertainty including the error in the total band intensity (+/- 20% has been assumed). The retrieved profiles are compared with previous measurements and photochemical model results.

Selective Encaging of N2O in N2O-N2 Binary Gas Hydrates via Hydrate-Based Gas Separation.

PubMed

Yang, Youjeong; Shin, Donghoon; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Kim, Dongseon; Shin, Hee-Young; Cha, Minjun; Yoon, Ji-Ho

2017-03-21

The crystal structure and guest inclusion behaviors of nitrous oxide-nitrogen (N 2 O-N 2 ) binary gas hydrates formed from N 2 O/N 2 gas mixtures are determined through spectroscopic analysis. Powder X-ray diffraction results indicate that the crystal structure of all the N 2 O-N 2 binary gas hydrates is identified as the structure I (sI) hydrate. Raman spectra for the N 2 O-N 2 binary gas hydrate formed from N 2 O/N 2 (80/20, 60/40, 40/60 mol %) gas mixtures reveal that N 2 O molecules occupy both large and small cages of the sI hydrate. In contrast, there is a single Raman band of N 2 O molecules for the N 2 O-N 2 binary gas hydrate formed from the N 2 O/N 2 (20/80 mol %) gas mixture, indicating that N 2 O molecules are trapped in only large cages of the sI hydrate. From temperature-dependent Raman spectra and the Predictive Soave-Redlich-Kwong (PSRK) model calculation, we confirm the self-preservation of N 2 O-N 2 binary gas hydrates in the temperature range of 210-270 K. Both the experimental measurements and the PSRK model calculations demonstrate the preferential occupation of N 2 O molecules rather than N 2 molecules in the hydrate cages, leading to a possible process for separating N 2 O from gas mixtures via hydrate formation. The phase equilibrium conditions, pseudo-pressure-composition (P-x) diagram, and gas storage capacity of N 2 O-N 2 binary gas hydrates are discussed in detail.

The vibration-rotation-tunneling levels of N2-H2O and N2-D2O.

PubMed

Wang, Xiao-Gang; Carrington, Tucker

2015-07-14

In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

The vibration-rotation-tunneling levels of N2-H2O and N2-D2O

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Carrington, Tucker

2015-07-01

In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

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

The series Bi2Sr2Ca(n-1) Cu(n)O(2n+4) (1 less than or equal to n less than or equal to 5): Phase stability and superconducting properties

NASA Technical Reports Server (NTRS)

Deguire, Mark R.; Bansal, Narottam P.; Farrell, David E.; Finan, Valerie; Kim, Cheol J.; Hills, Bethanie J.; Allen, Christopher J.

1989-01-01

Phase relations at 850 and 870 C, melting transitions in air, oxygen, and helium were studied for Bi(2.1)Sr(1.9) CuO6 and for the Bi2Sr2Ca(n-1) Cu(n)O(2n+4) for n = 1, 2, 3, 4, 5, and infinity (CaCuO2). Up to 870 C, the n = 2 composition resides in the compatibility tetrahedron bounded by Bi(2+x)(Sr,Ca)(3-y) Cu2O8, (Sr,Ca)14 Cu24O41, Ca2CuO3, and a Bi-Sr-Ca-O phase. The n is greater than or equal to 3 compositions reside in the compatibility tetrahedron Bi(2+x)(Sr,Ca)(3-y) Cu2O8 - (Sr,Ca)14 Cu24O41 - Ca2CuO3 - CuO up to 850 C. However, Bi(2+x)Sr(4-y) Cu3O10 forms for n is greater than or equal to 3 after extended heating at 870 C. Bi(2+x)Sr(2-y) CuO6 and Bi(2+x)(Sr,Ca)(3-y) Cu2O8 melt in air at 914 C and 895 C respectively. During melting, all of the compositions studied lose 1 to 2 percent by weight of oxygen from the reduction of copper. Bi(2+x)Sr(2-y) CuO6, Bi(2+n)(Sr,Ca)(3-y) Cu2O8, and Bi(2+x)(Sr,Ca)(4-y) Cu3O10 exhibit crystallographic alignment in a magnetic field, with the c-axes orienting parallel to the field.

Quenching of I(2P1/2) by NO2, N2O4, and N2O.

PubMed

Kabir, Md Humayun; Azyazov, Valeriy N; Heaven, Michael C

2007-10-11

Quenching of excited iodine atoms (I(5p5, 2P1/2)) by nitrogen oxides are processes of relevance to discharge-driven oxygen iodine lasers. Rate constants at ambient and elevated temperatures (293-380 K) for quenching of I(2P1/2) atoms by NO2, N2O4, and N2O have been measured using time-resolved I(2P1/2) --> I(2P3/2) 1315 nm emission. The excited atoms were generated by pulsed laser photodissociation of CF3I at 248 nm. The rate constants for I(2P1/2) quenching by NO2 and N2O were found to be independent of temperature over the range examined with average values of (2.9 +/- 0.3) x 10(-15) and (1.4 +/- 0.1) x 10(-15) cm3 s(-1), respectively. The rate constant for quenching of I(2P1/2) by N2O4 was found to be (3.5 +/- 0.5) x 10(-13) cm3 s(-1) at ambient temperature.

Characterization of the N2O isotopic composition (15N, 18O and N2O isotopomers) emitted from incubated Amazon forest soils. Implications for the global N2O isotope budget

NASA Astrophysics Data System (ADS)

Pérez, T.; García, D.; Trumbore, S.; Tyler, S.; de Camargo, P.; Moreira, M.; Piccolo, M.; Park, S.; Boering, K.; Cerri, C.

2003-04-01

Tropical rain forest soils are the largest natural source of N2O to the atmosphere. Uncertainty in the signature of this source limits the utility of isotopes in constraining the global N2O budget. Differentiating the relative contribution of nitrification and denitrification to the emitted N2O using stable isotopes has been difficult due to the lack of enrichment factors values for each process measured in situ. We have devised a method for measuring enrichment factors using soil incubation experiments. We selected three Amazon rain forest soils: (1) Clay and (2) Sandy from Santarem, Pará State, and (3) Sandy from Nova Vida Farm, Rondonia State, Brazil. The enrichment factor values for nitrification and denitrification are: -97.8±4.2 and -9.9±3.8 per mil for clay Santarem soil, -86.8±4.3 and -45.2±4.5 per mil for sandy Santarem soil and-112.6±3.8 and -10.4±3.5 per mil for Nova Vida Farm soils, respectively. Our results show that enrichment factors for both processes differ with soil texture and location. The enrichment factors for nitrification are significantly smaller than the range reported in the literature (-66 to -42 per mil). Also, the enrichment factors for the Santarem soils (clay and sandy) differ significantly implying that soil texture (which will affect the soil air filled pore space at a given water content) is influencing the bacteria isotopic discrimination. However, the enrichment factors for the Santarem clay sand Nova Vida sandy soils do not differ by much. This suggests that the enrichment factors not only can be affected by texture but also by the microbial fauna present in these soils. We also determined the measurement of the N2O positional dependence. N2O is a linear molecule with two nitrogen atoms. The 15N isotope can be located in either the central nitrogen (alpha position) or in the terminal nitrogen (beta position). The isotopomer site preference (15N alpha - 15N beta) can be used to differentiate processes of production and

Fiber-Optic Determination of N2, O2, and Fuel Vapor in the Ullage of Liquid-Fuel Tanks

NASA Technical Reports Server (NTRS)

Nguyen, Quang-Viet

2008-01-01

A fiber-optic sensor system has been developed that can remotely measure the concentration of molecular oxygen (O2), nitrogen (N2), hydrocarbon vapor, and other gases (CO2, CO, H2O, chlorofluorocarbons, etc.) in the ullage of a liquid-fuel tank. The system provides an accurate and quantitative identification of the above gases with an accuracy of better than 1 percent by volume (for O2 or N2) in real-time (5 seconds). In an effort to prevent aircraft fuel tank fires or explosions similar to the tragic TWA Flight 800 explosion in 1996, OBIGGS are currently being developed for large commercial aircraft to prevent dangerous conditions from forming inside fuel tanks by providing an inerting gas blanket that is low in oxygen, thus preventing the ignition of the fuel/air mixture in the ullage. OBIGGS have been used in military aircraft for many years and are now standard equipment on some newer large commercial aircraft (such as the Boeing 787). Currently, OBIGGS are being developed for retrofitting to existing commercial aircraft fleets in response to pending mandates from the FAA. Most OBIGGS use an air separation module (ASM) that separates O2 from N2 to make nitrogen-enriched air from compressed air flow diverted from the engine (bleed air). Current OBIGGS systems do not have a closed-loop feedback control, in part, due to the lack of suitable process sensors that can reliably measure N2 or O2 and at the same time, do not constitute an inherent source of ignition. Thus, current OBIGGS operate with a high factor-of-safety dictated by process protocol to ensure adequate fuel-tank inerting. This approach is inherently inefficient as it consumes more engine bleed air than is necessary compared to a closed-loop controlled approach. The reduction of bleed air usage is important as it reduces fuel consumption, which translates to both increased flight range and lower operational costs. Numerous approaches to developing OBIGGS feedback-control sensors have been under

N-type Cu2O doped activated carbon as catalyst for improving power generation of air cathode microbial fuel cells.

PubMed

Zhang, Xi; Li, Kexun; Yan, Pengyu; Liu, Ziqi; Pu, Liangtao

2015-01-01

A novel n-type Cu2O doped activated carbon (AC) air cathode (Cu/AC) was developed as an alternative to Pt electrode for oxygen reduction in microbial fuel cells (MFCs). The maximum power density of MFCs using this novel air cathode was as high as 1390±76mWm(-2), almost 59% higher than the bare AC air cathode. Specifically, the resistance including total resistance and charge transfer resistance significantly decreased comparing to the control. Tafel curve also showed the faster electro-transfer kinetics of Cu/AC with exchange current density of 1.03×10(-3)Acm(-2), which was 69% higher than the control. Ribbon-like Cu2O was deposited on the surface of AC with the mesopore surface area increasing. Cubic Cu2O crystals exclusively expose (111) planes with the interplanar crystal spacing of 2.48Å, which was the dominate active sites for oxygen reduction reaction (ORR). N-type Cu2O with oxygen vacancies played crucial roles in electrochemical catalytic activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Uncertainties in United States agricultural N2O emissions: comparing forward model simulations to atmospheric N2O data.

NASA Astrophysics Data System (ADS)

Nevison, C. D.; Saikawa, E.; Dlugokencky, E. J.; Andrews, A. E.; Sweeney, C.

2014-12-01

Atmospheric N2O concentrations have increased from 275 ppb in the preindustrial to about 325 ppb in recent years, a ~20% increase with important implications for both anthropogenic greenhouse forcing and stratospheric ozone recovery. This increase has been driven largely by synthetic fertilizer production and other perturbations to the global nitrogen cycle associated with human agriculture. Several recent regional atmospheric inversion studies have quantified North American agricultural N2O emissions using top-down constraints based on atmospheric N2O data from the National Oceanic and Atmospheric Administration (NOAA) Global Greenhouse Gas Reference Network, including surface, aircraft and tall tower platforms. These studies have concluded that global N2O inventories such as EDGAR may be underestimating the true U.S. anthropogenic N2O source by a factor of 3 or more. However, simple back-of-the-envelope calculations show that emissions of this magnitude are difficult to reconcile with the basic constraints of the global N2O budget. Here, we explore some possible reasons why regional atmospheric inversions might overestimate the U.S. agricultural N2O source. First, the seasonality of N2O agricultural sources is not well known, but can have an important influence on inversion results, particularly when the inversions are based on data that are concentrated in the spring/summer growing season. Second, boundary conditions can strongly influence regional inversions but the boundary conditions used may not adequately account for remote influences on surface data such as the seasonal stratospheric influx of N2O-depleted air. We will present a set of forward model simulations, using the Community Land Model (CLM) and two atmospheric chemistry tracer transport models, MOZART and the Whole Atmosphere Community Climate Model (WACCM), that examine the influence of terrestrial emissions and atmospheric chemistry and dynamics on atmospheric variability in N2O at U.S. and

Infrared spectra of N2O-(ortho-D2)N and N2O-(HD)N clusters trapped in bulk solid parahydrogen.

PubMed

Lorenz, Britney D; Anderson, David T

2007-05-14

High-resolution infrared spectra of the clusters N2O-(ortho-D2)N and N2O-(HD)N, N=1-4, isolated in bulk solid parahydrogen at liquid helium temperatures are studied in the 2225 cm-1 region of the nu3 antisymmetric stretch of N2O. The clusters form during vapor deposition of separate gas streams of a precooled hydrogen mixture (ortho-D2para-H2 or HDpara-H2) and N2O onto a BaF2 optical substrate held at approximately 2.5 K in a sample-in-vacuum liquid helium cryostat. The cluster spectra reveal the N2O nu3 vibrational frequency shifts to higher energy as a function of N, and the shifts are larger for ortho-D2 compared to HD. These vibrational shifts result from the reduced translational zero-point energy for N2O solvated by the heavier hydrogen isotopomers. These spectra allow the N=0 peak at 2221.634 cm-1, corresponding to the nu3 vibrational frequency of N2O isolated in pure solid parahydrogen, to be assigned. The intensity of the N=0 absorption feature displays a strong temperature dependence, suggesting that significant structural changes occur in the parahydrogen solvation environment of N2O in the 1.8-4.9 K temperature range studied.

Conversion of nitrogen oxides in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures subjected to a dc corona discharge

NASA Astrophysics Data System (ADS)

Dors, Mirosław; Mizeraczyk, Jerzy

1996-10-01

This paper concerns the influence of a direct current (dc) corona discharge on production and reduction of NO, NO2 and N2O in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures. The corona discharge was generated in a needle-to-plate reactor. The positively polarized electrode consisted of 7 needles. The grounded electrode was a stainless steel plate. The gas flow rate through the reactor was varied from 28 to 110 cm3/s. The time-averaged discharge current ranged from 0 to 6 mA. It was found that in the N2:O2:CO2 mixture the corona discharge produced NO, NO2 and N2O. In the N2:O2:CO2:NO2 mixture the reduction of NO2 was between 6-56%, depending on the concentration of O2, gas flow rate and corona discharge current. The NO2 reduction was accompanied by production of NO and N2O. The results show that efficient reduction of nitrogen oxides by a corona discharge cannot be expected in the mixtures containing N2 and O2 if reducing additives are not employed.

O2-O2 and O2-N2 collision-induced absorption mechanisms unravelled

NASA Astrophysics Data System (ADS)

Karman, Tijs; Koenis, Mark A. J.; Banerjee, Agniva; Parker, David H.; Gordon, Iouli E.; van der Avoird, Ad; van der Zande, Wim J.; Groenenboom, Gerrit C.

2018-05-01

Collision-induced absorption is the phenomenon in which interactions between colliding molecules lead to absorption of light, even for transitions that are forbidden for the isolated molecules. Collision-induced absorption contributes to the atmospheric heat balance and is important for the electronic excitations of O2 that are used for remote sensing. Here, we present a theoretical study of five vibronic transitions in O2-O2 and O2-N2, using analytical models and numerical quantum scattering calculations. We unambiguously identify the underlying absorption mechanism, which is shown to depend explicitly on the collision partner—contrary to textbook knowledge. This explains experimentally observed qualitative differences between O2-O2 and O2-N2 collisions in the overall intensity, line shape and vibrational dependence of the absorption spectrum. It is shown that these results can be used to discriminate between conflicting experimental data and even to identify unphysical results, thus impacting future experimental studies and atmospheric applications.

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.

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

Method for measuring changes in the atmospheric O2/N2 ratio by a gas chromatograph equipped with a thermal conductivity detector

NASA Astrophysics Data System (ADS)

Tohjima, Yasunori

2000-06-01

We present a method for measuring changes in the atmospheric O2/N2 ratio based on data from a gas chromatograph (GC) equipped with a thermal conductivity detector (TCD). In this method, O2 and N2 in an air sample are separated on a column filled with molecular sieve 5A with H2 carrier gas. Since the separated O2 includes Ar, which has a retention time similar to that of O2, the (O2+Ar)/N2 ratio is actually measured. The change in the measured (O2+Ar)/N2 ratio can be easily converted to that in the O2/N2 ratio with a very small error based on the fact that the atmospheric Ar/N2 ratio is almost constant. The improvements to achieve the high-precision measurement include stabilization of the pressure at the GC column head and at the outlets of the TCD and the sample loop. Additionally, the precision is improved statistically by repeating alternate analyses of sample and a reference gas. The standard deviation of the replicate cycles of reference and sample analyses is about 18 per meg (corresponding to 3.8 parts per million (ppm) O2 in air). This means that the standard error is about 7 per meg (1.5 ppm O2 in air) for seven cycles of alternate analyses, which takes about 70 min. The response of this method is likely to have a 2% nonlinearity. Ambient air samples are collected under pressure in glass flasks equipped with two stopcocks sealed by Viton O-rings at both ends. Pressure depletion in the flask during the O2/N2 measurement does not cause any detectable change in the O2/N2 ratio, but the O2/N2 ratio in the flask was found to gradually decrease during the storage period. We also present preliminary results from air samples collected at Hateruma Island (latitude 24°03'N, longitude 123°49') from July 1997 through March 1999. The observed O2/N2 ratios clearly show a seasonal variation, increasing in spring and summer and decreasing in autumn and winter.

Method for generating O.sub.2-rich gas from air using water

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

Nakano, Anna; Nakano, Jinichiro; Bennett, James P.

The present disclosure is directed to a method for enriching an inlet air stream utilizing a number of enrichment sub-units connected in series, where each enrichment sub-unit conducts both a dissolution and degasification cycle. Each enrichment sub-unit comprises a compressor, an aeration unit, a deaeration unit, and a pump for the recirculation of water between the aeration and deaeration units. The methodology provides a manner in which the relationship between the respective Henry's coefficients of the oxygen and nitrogen in water may be exploited to enrich the O.sub.2 volume percent and diminish the N.sub.2 volume percent over repeated dissolution andmore » degasification cycles. By utilizing a number of enrichment sub-units connected in series, the water contained in each enrichment sub-unit acts to progressively increase the O.sub.2 volume percent. Additional enrichment sub-units may be added and utilized until the O.sub.2 volume percent equals or exceeds a target O.sub.2 volume percent. In a particular embodiment, air having a general composition of about 78 vol. % N.sub.2 and 21 vol. % O.sub.2 is progressively enriched to provide a final mixture of about 92% vol. % O.sub.2 and 8% vol. % N.sub.2.« less

Production of NO2/-/ and N2O by nitrifying bacteria at reduced concentrations of oxygen

NASA Technical Reports Server (NTRS)

Goreau, T. J.; Kaplan, W. A.; Wofsy, S. C.; Mcelroy, M. B.; Valois, F. W.; Watson, S. W.

1980-01-01

The influence of oxygen concentration on the production of NO2(-) and N2O by nitrifying marine bacteria of the genus Nitrosomonas is investigated. Pure cultures of the ammonium-oxiding bacteria isolated from the Western Tropical Atlantic Ocean were grown at oxygen partial pressures from 0.005 to 0.2 atm, and concentrations of N2O in the air above the growth medium and dissolved NO2(-) were determined. Decreasing oxygen concentrations are observed to induce a marked decrease in NO2(-) production rates and increase in N2O evolution, leading to an increase of the relative yield of N2O with respect to NO2(-) from 0.3% to nearly 10%. Similar yields of N2O at atmospheric oxygen levels are found for nitrifying bacteria of the genera Nitrosomonas, Nitrosolobus, Nitrosospira and Nitrosococcus, while nitrite-oxydizing bacteria and a dinoflagellate did not produce detectable quantities of N2O. Results support the view that nitrification is a major source of N2O in the environment.

The structure, stability, and infrared spectrum of B 2N, B 2N +, B 2N -, BO, B 2O and B 2N 2.

NASA Astrophysics Data System (ADS)

Martin, J. M. L.; François, J. P.; Gijbels, R.

1992-05-01

The structure, infrared spectrum, and heat of formation of B 2N, B 2N -, BO, and B 2O have been studied ab initio. B 2N is very stable; B 2O even more so. B 2N, B 2N -, B 2O, and probably B 2N + have symmetric linear ground-state structures; for B 2O, an asymmetric linear structure lies about 12 kcal/mol above the ground state. B 2N +, B 2N - and B 2O have intense asymmetric stretching frequencies, predicted near 870, 1590 and 1400 cm -1, respectively. Our predicted harmonic frequencies and isotopic shifts for B 2O confirm the recent experimental identification by Andrews and Burkholder. Absorptions at 1889.5 and 1998.5 cm -1 in noble-gas trapped boron nitride vapor belong the BNB and BNBN ( 3Π), respectively; a tentative assignment of 882.5 cm -1 to BNB + is proposed. Total atomization energies Σ De (Σ D0) are computed (accuracy ±2 kcal/mol) as: BO 193.1 (190.4), B 2O 292.5 (288.7), B 2N 225.0 (250.3) kcal/mol. The ionization potential and electron affinity of B 2N are predicted to be 8.62±0.1 and 3.34±0.1 eV. The MP4-level additivity approximations involved in G1 theory results in errors on the order of 1 kcal/mol in the Σ De values.

Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

PubMed

De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

2014-03-28

New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed.

Mixed Matrix Membranes for O2/N2 Separation: The Influence of Temperature

PubMed Central

Fernández-Barquín, Ana; Casado-Coterillo, Clara; Valencia, Susana; Irabien, Angel

2016-01-01

In this work, mixed matrix membranes (MMMs) composed of small-pore zeolites with various topologies (CHA (Si/Al = 5), LTA (Si/Al = 1 and 5), and Rho (Si/Al = 5)) as dispersed phase, and the hugely permeable poly(1-trimethylsilyl-1-propyne) (PTMSP) as continuous phase, have been synthesized via solution casting, in order to obtain membranes that could be attractive for oxygen-enriched air production. The O2/N2 gas separation performance of the MMMs has been analyzed in terms of permeability, diffusivity, and solubility in the temperature range of 298–333 K. The higher the temperature of the oxygen-enriched stream, the lower the energy required for the combustion process. The effect of temperature on the gas permeability, diffusivity, and solubility of these MMMs is described in terms of the Arrhenius and Van’t Hoff relationships with acceptable accuracy. Moreover, the O2/N2 permselectivity of the MMMs increases with temperature, the O2/N2 selectivities being considerably higher than those of the pure PTMSP. In consequence, most of the MMMs prepared in this work exceeded the Robeson’s upper bound for the O2/N2 gas pair in the temperature range under study, with not much decrease in the O2 permeabilities, reaching O2/N2 selectivities of up to 8.43 and O2 permeabilities up to 4,800 Barrer at 333 K. PMID:27196937

Quantifying N2O reduction to N2 based on N2O isotopocules - validation with independent methods (helium incubation and 15N gas flux method)

NASA Astrophysics Data System (ADS)

Lewicka-Szczebak, Dominika; Augustin, Jürgen; Giesemann, Anette; Well, Reinhard

2017-02-01

Stable isotopic analyses of soil-emitted N2O (δ15Nbulk, δ18O and δ15Nsp = 15N site preference within the linear N2O molecule) may help to quantify N2O reduction to N2, an important but rarely quantified process in the soil nitrogen cycle. The N2O residual fraction (remaining unreduced N2O, rN2O) can be theoretically calculated from the measured isotopic enrichment of the residual N2O. However, various N2O-producing pathways may also influence the N2O isotopic signatures, and hence complicate the application of this isotopic fractionation approach. Here this approach was tested based on laboratory soil incubations with two different soil types, applying two reference methods for quantification of rN2O: helium incubation with direct measurement of N2 flux and the 15N gas flux method. This allowed a comparison of the measured rN2O values with the ones calculated based on isotopic enrichment of residual N2O. The results indicate that the performance of the N2O isotopic fractionation approach is related to the accompanying N2O and N2 source processes and the most critical is the determination of the initial isotopic signature of N2O before reduction (δ0). We show that δ0 can be well determined experimentally if stable in time and then successfully applied for determination of rN2O based on δ15Nsp values. Much more problematic to deal with are temporal changes of δ0 values leading to failure of the approach based on δ15Nsp values only. For this case, we propose here a dual N2O isotopocule mapping approach, where calculations are based on the relation between δ18O and δ15Nsp values. This allows for the simultaneous estimation of the N2O-producing pathways' contribution and the rN2O value.

Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy-ethyl)methylamino]ethanolato-2:1κ(4) O (1),N,O (2):O (1)}[μ-2,2'-(methylimino)diethanolato-1:2κ(4) O,N,O':O]dithiocyanato-1κN,2κN-chromium(III)copper(II).

PubMed

Rusanova, Julia A; Semenaka, Valentina V; Dyakonenko, Viktoriya V; Shishkin, Oleg V

2015-09-01

The title compound, [CrCu(C5H11NO2)(C5H12NO2)(NCS)2(H2O)] or [Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methylethanolamine, C5H13NO2) is formed as a neutral heterometal Cu(II)/Cr(III) complex. The mol-ecular structure of the complex is based on a binuclear {CuCr(μ-O)2} core. The coordination environment of each metal atom involves the N,O,O atoms of the tridentate ligand, one bridging O atom of the ligand and the N atom of the thio-cyanato ligands. The Cu(II) ion adopts a distorted square-pyramidal coordination while the Cr(III) ion has a distorted octa-hedral coordination geometry completed by the aqua ligand. In the crystal, the binuclear complexes are linked via two pairs of O-H⋯O hydrogen bonds to form inversion dimers, which are arranged in columns parallel to the a axis. In the μ-mdea ligand two -CH2 groups and the methyl group were refined as disordered over two sets of sites with equal occupancies. The structure was refined as a two-component twin with a twin scale factor of 0.242 (1).

Infrared spectra of seeded hydrogen clusters: (para-H2)N-N2O and (ortho-H2)N-N2O, N = 2-13.

PubMed

Tang, Jian; McKellar, A R W

2005-09-15

High-resolution infrared spectra of clusters containing para-H2 and/or ortho-H2 and a single nitrous oxide molecule are studied in the 2225-cm(-1) region of the upsilon1 fundamental band of N2O. The clusters are formed in pulsed supersonic jet expansions from a cooled nozzle and probed using a tunable infrared diode laser spectrometer. The simple symmetric rotor-type spectra generally show no resolved K structure, with prominent Q-branch features for ortho-H2 but not para-H2 clusters. The observed vibrational shifts and rotational constants are reported. There is no obvious indication of superfluid effects for para-H2 clusters up to N=13. Sharp transitions due to even larger clusters are observed, but no definite assignments are possible. Mixed (para-H2)N-(ortho-H2)M-N2O cluster line positions can be well predicted by linear interpolation between the corresponding transitions of the pure clusters.

Catalytic performance of V2O5-MoO3/γ-Al2O3 catalysts for partial oxidation of n-hexane1

NASA Astrophysics Data System (ADS)

Mahmoudian, R.; Khodadadi, Z.; Mahdavi, Vahid; Salehi, Mohammed

2016-01-01

In the current study, a series of V2O5-MoO3 catalyst supported on γ-Al2O3 with various V2O5 and MoO3 loadings was prepared by wet impregnation technique. The characterization of prepared catalysts includes BET surface area, powder X-ray diffraction (XRD), and oxygen chemisorptions. The partial oxidation of n-hexane by air over V2O5-MoO3/γ-Al2O3 catalysts was carried out under flow condition in a fixed bed glass reactor. The effect of V2O5 loading, temperature, MoO3 loading, and n-hexane LHSV on the n-hexane conversion and the product selectivity were investigated. The partial oxygenated products of n-hexane oxidation were ethanol, acetic anhydride, acetic acid, and acetaldehyde. The 10% V2O5-1%MoO3/γ-Al2O3 was found in most active and selective catalyst during partial oxidation of n-hexane. The results indicated that by increasing the temperature, the n-hexane conversion increases as well, although the selectivity of the products passes through a maximum by increasing the temperature.

{μ-2-[(3-Amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1:2κ(5)O(1),O(6):N,N',O(1)}{2-[(3-amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1κ(3)N,N',O(1)}-μ-azido-1:2κ(2)N:N-azido-2κN-methanol-2κO-dinickel(II).

PubMed

Ghaemi, Akbar; Rayati, Saeed; Fayyazi, Kazem; Ng, Seik Weng; Tiekink, Edward R T

2012-08-01

Two distinct coordination geometries are found in the binuclear title complex, [Ni(2)(C(13)H(19)N(2)O(2))(2)(N(3))(2)(CH(3)OH)], as one Schiff base ligand is penta-dentate, coordinating via the anti-cipated oxide O, imine N and amine N atoms (as for the second, tridentate, ligand) but the oxide O is bridging and coordination also occurs through the meth-oxy O atom. The Ni(II) atoms are linked by a μ(2)-oxide atom and one end of a μ(2)-azide ligand, forming an Ni(2)ON core. The coordination geometry for the Ni(II) atom coordinated by the tridentate ligand is completed by the meth-oxy O atom derived from the penta-dentate ligand, with the resulting N(3)O(3) donor set defining a fac octa-hedron. The second Ni(II) atom has its cis-octa-hedral N(4)O(2) coordination geometry completed by the imine N and amine N atoms of the penta-dentate Schiff base ligand, a terminally coordinated azide N and a methanol O atom. The arrangement is stabilized by an intra-molecular hydrogen bond between the methanol H and the oxide O atom. Linear supra-molecular chains along the a axis are formed in the crystal packing whereby two amine H atoms from different amine atoms hydrogen bond to the terminal N atom of the monodentate azide ligand.

Air Plasma-Sprayed La2Zr2O7-SrZrO3 Composite Thermal Barrier Coating Subjected to CaO-MgO-Al2O3-SiO2 (CMAS)

NASA Astrophysics Data System (ADS)

Cai, Lili; Ma, Wen; Ma, Bole; Guo, Feng; Chen, Weidong; Dong, Hongying; Shuang, Yingchai

2017-08-01

La2Zr2O7-SrZrO3 composite thermal barrier coatings (TBCs) were prepared by air plasma spray (APS). The La2Zr2O7-SrZrO3 composite TBCs covered with calcium-magnesium-aluminum-silicate (CMAS) powder, as well as the powder mixture of CMAS and spray-dried La2Zr2O7-SrZrO3 composite powder, were heat-treated at 1250 °C in air for 1, 4, 8, and 12 h. The phase constituents and microstructures of the reaction products were characterized by x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. Experimental results showed that the La2Zr2O7-SrZrO3 composite TBCs had higher CMAS resistance than 8YSZ coating. A dense new layer developed between CMAS and La2Zr2O7-SrZrO3 composite TBCs during interaction, and this new layer consisted mostly of apatite (Ca2La8(SiO4)6O2) and c-ZrO2. The newly developed layer effectively protected the La2Zr2O7-SrZrO3 composite TBCs from further CMAS attack.

The Nitrous Oxide (N2O) Budget: Constraints from Atmospheric Observations and Models

NASA Astrophysics Data System (ADS)

Tian, H.; Thompson, R.; Canadell, J.; Winiwarter, W.; Tian, H.; Thompson, R.; Prather, M. J.

2017-12-01

The increasing global abundance of N2O poses a threat to human health and society over this coming century through both climate change and ozone depletion. In the sense of greenhouse gases, N2O ranks third behind CO2 and CH4. In the sense of ozone depletion, N2O stands alone. In order to identify the cause of these increases and hopefully reverse them, we need to have a thorough understanding of the sources and sinks (a.k.a. the budget) of N2O and how they can be altered. A bottom-up approach to the budget evaluates individual biogeochemical sources of N2O from the land and ocean; whereas, a top-down approach uses atmospheric observations of the variability, combined with modeling of the atmospheric chemistry and transport, to infer the magnitude of sources and sinks throughout the Earth system. This paper reviews top-down approaches using atmospheric data; a similar top-down approach can be taken with oceanic measurements of N2O, but is not covered here. Stratospheric chemistry is the predominant loss of N2O, and here we review how a merging of new measurements with stratospheric chemistry models is able to provide a constrained budget for the global N2O sink. N2O surface sources are transported and mixed throughout the atmosphere, providing positive anomalies in the N2O abundance (mole fraction of N2O with respect to dry air); while N2O-depleted air from the stratosphere provides negative anomalies. With accurate atmospheric transport models, including for stratosphere-troposphere exchange, the observed tropospheric variability in N2O is effectively a fingerprint of the location and magnitude of sources. This inverse modeling of sources is part of the top-down constraints and is reviewed here.

The denitrification paradox: The role of O2 in sediment N2O production

NASA Astrophysics Data System (ADS)

Barnes, Jonathan; Upstill-Goddard, Robert C.

2018-01-01

We designed a novel laboratory sediment flux chamber in which we maintained the headspace O2 partial pressure at preselected values, allowing us to experimentally regulate "in-situ" O2 to evaluate its role in net N2O production by an intertidal estuarine sediment (Tyne, UK). In short-term (30 h) incubations with 10 L of overlying estuarine water (∼3 cm depth) and headspace O2 regulation (headspace: sediment/water ratio ∼9:1), net N2O production was highest at 1.2% O2 (sub-oxic; 32.3 nmol N2O m-2 d-1), an order of magnitude higher than at either 0.0% (anoxic; 2.5 N2O nmol m-2 d-1) or 20.85% (ambient; 2.3 nmol N2O m-2 d-1) O2. In a longer-term sealed incubation (∼490 h) without O2 control, time-dependent behaviour of N2O in the tank headspace was highly non-linear with time, showing distinct phases: (i) an initial period of no or little change in O2 or N2O up to ∼ 100 h; (ii) a quasi-linear, inverse correlation between O2 and N2O to ∼360 h, in which O2 declined to ∼2.1% and N2O rose to ∼7800 natm; (iii) over the following 50 h a slower O2 decline, to ∼1.1%, and a more rapid N2O increase, to ∼12000 natm; (iv) over the next 24 h a slowed O2 decline towards undetectable levels and a sharp fall in N2O to ∼4600 natm; (iv) a continued N2O decrease at zero O2, to ∼3000 natm by ∼ 490 h. These results show clearly that rapid N2O consumption (∼115 nmol m-2 d-1), presumably via heterotrophic denitrification (HD), occurs under fully anoxic conditions and therefore that N2O production, which was optimal for sub-oxic O2, results from other nitrogen transformation processes. In experiments in which we amended sediment overlying water to either 1 mM NH4+ or 1 mM NO3-, N2O production rates were 2-134 nmol N2O m-2 d-1 (NH4+ addition) and 0.4-2.2 nmol N2O m-2 d-1 (NO3- addition). We conclude that processes involving NH4+ oxidation (nitrifier nitrification; nitrifier denitrification; nitrification-coupled denitrification) are principally responsible for N2O

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.

On the production of N2O from the reaction of O/1D/with N2.

NASA Technical Reports Server (NTRS)

Simonaitis, R.; Lissi, E.; Heicklen, J.

1972-01-01

Ozone was photolyzed at 2537 A and at 25 C in the presence of 42-115 torr of O2 and about 880 torr of N2 to test the relative importance of the two reactions O(1D) + N2 + M leading to N2O + M and O(1D) + N2 leading to O(3P) + N2. In this study N2O was not found as a product. Thus from our detectability limit for N2O an upper limit to the efficiency of the first reaction relative to the second of 2.5 times 10 to the -6 power at 1000-torr total pressure was computed.

On the production of N2O from the reaction of O(1 D) with N2

NASA Technical Reports Server (NTRS)

Simonaitis, R.; Lissi, E.; Heicklen, J.

1972-01-01

Ozone was photolyzed at 2537 A and 25 C in the presence of 42-115 torr of O2 and about 880 torr of N2 to test the relative importance of the two reactions: (1) O(1D) + N2 + M yields N2O + M, and (2) O(1D) + N2 yields O(3P) + N2. N2O was not found as a product. Thus from our detectability limit for N2O (0.3 micron), an upper limit to the efficiency of the first reaction relative to the second of 0.0000025 at 1000 torr total pressure was computed. This corresponds to k1/k2 smaller than 0.8 x 10 to the minus 25 power cu cm/particle.

Investigation on the charging process of Li 2O 2-based air electrodes in Li-O 2 batteries with organic carbonate electrolytes

NASA Astrophysics Data System (ADS)

Xu, Wu; Viswanathan, Vilayanur V.; Wang, Deyu; Towne, Silas A.; Xiao, Jie; Nie, Zimin; Hu, Dehong; Zhang, Ji-Guang

The charging process of Li 2O 2-based air electrodes in Li-O 2 batteries with organic carbonate electrolytes was investigated using in situ gas chromatography/mass spectroscopy (GC/MS) to analyze gas evolution. A mixture of Li 2O 2/Fe 3O 4/Super P carbon/polyvinylidene fluoride (PVDF) was used as the starting air electrode material, and 1-M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in carbonate-based solvents was used as the electrolyte. We found that Li 2O 2 was actively reactive to 1-methyl-2-pyrrolidinone and PVDF that were used to prepare the electrode. During the first charging (up to 4.6 V), O 2 was the main component in the gases released. The amount of O 2 measured by GC/MS was consistent with the amount of Li 2O 2 that decomposed during the electrochemical process as measured by the charge capacity, which is indicative of the good chargeability of Li 2O 2. However, after the cell was discharged to 2.0 V in an O 2 atmosphere and then recharged to ∼4.6 V, CO 2 was dominant in the released gases. Further analysis of the discharged air electrodes by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy indicated that lithium-containing carbonate species (lithium alkyl carbonates and/or Li 2CO 3) were the main discharge products. Therefore, compatible electrolytes and electrodes, as well as the electrode-preparation procedures, need to be developed for rechargeable Li-air batteries for long term operation.

Partial nitrogen loss in SrTaO2N and LaTiO2N oxynitride perovskites

NASA Astrophysics Data System (ADS)

Chen, Daixi; Habu, Daiki; Masubuchi, Yuji; Torii, Shuki; Kamiyama, Takashi; Kikkawa, Shinichi

2016-04-01

SrTaO2N heated in a helium atmosphere began to release nitrogen of approximately 30 at% at 950 °C while maintaining the perovskite structure and its color changed from orange to dark green. Then it decomposed above 1200 °C to a black mixture of Sr1.4Ta0.6O2.73, Ta2N, and Sr5Ta4O15. The second decomposition was not clearly observed when SrTaO2N was heated in a nitrogen atmosphere below 1550 °C. After heating at 1500 °C for 3 h under a 0.2 MPa nitrogen atmosphere, the perovskite product became dark green and conductive. Structure refinement results suggested that the product was a mixture of tetragonal and cubic perovskites with a decreased ordering of N3-/O2-. The sintered body was changed to an n-type semiconductor after a partial loss of nitrogen to be reduced from the originally insulating SrTaO2N perovskite lattice. LaTiO2N was confirmed to have a similar cis-configuration of the TiO4N2 octahedron as that of TaO4N2 in SrTaO2N. It also released some of its nitrogen at 800 °C changing its color from brown to black and then decomposed to a mixture of LaTiO3, La2O3, and TiN at 1100 °C. These temperatures are lower than those in SrTaO2N.

Microwave dielectric properties of BaO-2CeO{sub 2}-nTiO{sub 2} ceramics

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

Sreemoolanadhan, H.; Sebastian, M.T.; Ratheesh, R.

2004-11-01

The BaO-2CeO{sub 2}-nTiO{sub 2} ceramics with n=3, 4 and 5 have been prepared with CeO{sub 2} as starting material. The ceramics have been characterized using scanning electron microscopy, X-ray diffraction, Raman and X-ray photoelectron spectroscopy techniques. The microwave dielectric properties have been measured using standard dielectric resonator techniques. BaO-2CeO{sub 2}-3TiO{sub 2} (123), BaO-2CeO{sub 2}-4TiO{sub 2} (124) and BaO-2CeO{sub 2}-5TiO{sub 2} (125) ceramics showed dielectric constants of 38, 27 and 32, respectively. All the ceramics showed fairly good unloaded Q-factors. 124 and 125 compounds exhibited low {tau}f values, while 123 showed a high {tau}f value.

Binder-free NiFe2O4/C nanofibers as air cathodes for Li-O2 batteries

NASA Astrophysics Data System (ADS)

Zhang, Xin; Wang, Chengyi; Chen, Ya-Nan; Wang, Xin-Gai; Xie, Zhaojun; Zhou, Zhen

2018-02-01

Rechargeable Li-O2 batteries have aroused much attention for their high energy density. However, the poor rechargeability and low efficiency hinder their practical applications. To solve these issues, free-standing carbon films combined with high-activity NiFe2O4 catalysts are prepared by electrospinning method, and directly used as air cathodes for Li-O2 batteries. The obtained films have 3D networks formed by stacking and interlacing massive nanofibers with uniformly dispersed NiFe2O4 nanoparticles on them. The Li-O2 batteries with such binder-free air cathodes show low charging overpotential even comparable to precious metal cathodes, and can sustain excellent discharge/charge cyclic stability. The unique structure and binder-free superiority greatly facilitates the Li+ and O2 diffusion, accelerates the decomposition of Li2O2, and avoid the disturbance of polymer binders.

Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy­ethyl)methylamino]ethanolato-2:1κ4 O 1,N,O 2:O 1}[μ-2,2′-(methylimino)diethanolato-1:2κ4 O,N,O′:O]dithiocyanato-1κN,2κN-chromium(III)copper(II)

PubMed Central

Rusanova, Julia A.; Semenaka, Valentina V.; Dyakonenko, Viktoriya V.; Shishkin, Oleg V.

2015-01-01

The title compound, [CrCu(C5H11NO2)(C5H12NO2)(NCS)2(H2O)] or [Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methylethanolamine, C5H13NO2) is formed as a neutral heterometal CuII/CrIII complex. The mol­ecular structure of the complex is based on a binuclear {CuCr(μ-O)2} core. The coordination environment of each metal atom involves the N,O,O atoms of the tridentate ligand, one bridging O atom of the ligand and the N atom of the thio­cyanato ligands. The CuII ion adopts a distorted square-pyramidal coordination while the CrIII ion has a distorted octa­hedral coordination geometry completed by the aqua ligand. In the crystal, the binuclear complexes are linked via two pairs of O—H⋯O hydrogen bonds to form inversion dimers, which are arranged in columns parallel to the a axis. In the μ-mdea ligand two –CH2 groups and the methyl group were refined as disordered over two sets of sites with equal occupancies. The structure was refined as a two-component twin with a twin scale factor of 0.242 (1). PMID:26396853

Potassium (2,2'-bipyridine-κN,N')bis-(carbonato-κO,O')cobaltate(III) dihydrate.

PubMed

Wang, Jian-Fei; Lin, Jian-Li

2010-09-30

In the title compound, K[Co(CO(3))(2)(C(10)H(8)N(2))]·2H(2)O, the Co(III) atom is coordinated by two bipyridine N atoms and four O atoms from two bidentate chelating carbonate anions, and thus adopts a distorted octa-hedral N(2)O(4) environment. The [Co(bipy)(CO(3))(2)](-) (bipy is 2,2'-bipyridine) -units are stacked along [100] via π-π stacking inter-actions, with inter-planar distances between the bipyridine rings of 3.36 (4) and 3.44 (6) Å, forming chains. Classical O-H⋯O hydrogen-bonding inter-actions link the chains, forming channels along (100) in which the K(+) ions reside and leading to a three-dimensional supra-molecular architecture.

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

Characterization of Water Coordination to Ferrous Nitrosyl Complexes with fac-N2O, cis-N2O2, and N2O3 Donor Ligands.

PubMed

McCracken, John; Cappillino, Patrick J; McNally, Joshua S; Krzyaniak, Matthew D; Howart, Michael; Tarves, Paul C; Caradonna, John P

2015-07-06

Electron paramagnetic resonance (EPR) experiments were done on a series of S = (3)/2 ferrous nitrosyl model complexes prepared with chelating ligands that mimic the 2-His-1-carboxylate facial triad iron binding motif of the mononuclear nonheme iron oxidases. These complexes formed a comparative family, {FeNO}(7)(N2Ox)(H2O)3-x with x = 1-3, where the labile coordination sites for the binding of NO and solvent water were fac for x = 1 and cis for x = 2. The continuous-wave EPR spectra of these three complexes were typical of high-spin S = (3)/2 transition-metal ions with resonances near g = 4 and 2. Orientation-selective hyperfine sublevel correlation (HYSCORE) spectra revealed cross peaks arising from the protons of coordinated water in a clean spectral window from g = 3.0 to 2.3. These cross peaks were absent for the {FeNO}(7)(N2O3) complex. HYSCORE spectra were analyzed using a straightforward model for defining the spin Hamiltonian parameters of bound water and showed that, for the {FeNO}(7)(N2O2)(H2O) complex, a single water conformer with an isotropic hyperfine coupling, Aiso = 0.0 ± 0.3 MHz, and a dipolar coupling of T = 4.8 ± 0.2 MHz could account for the data. For the {FeNO}(7)(N2O)(H2O)2 complex, the HYSCORE cross peaks assigned to coordinated water showed more frequency dispersion and were analyzed with discrete orientations and hyperfine couplings for the two water molecules that accounted for the observed orientation-selective contour shapes. The use of three-pulse electron spin echo envelope modulation (ESEEM) data to quantify the number of water ligands coordinated to the {FeNO}(7) centers was explored. For this aspect of the study, HYSCORE spectra were important for defining a spectral window where empirical integration of ESEEM spectra would be the most accurate.

Theoretical characterization of stable eta1-N2O-, eta2-N2O-, eta1-N2-, and eta2-N2-bound species: intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion.

PubMed

Olabe, José A; Estiú, Guillermina L

2003-08-11

The addition of nitrogen hydrides (hydrazine, hydroxylamine, ammonia, azide) to the pentacyanonitrosylferrate(II) ion has been analyzed by means of density functional calculations, focusing on the identification of stable intermediates along the reaction paths. Initial reversible adduct formation and further decomposition lead to the eta(1)- and eta(2)-linkage isomers of N(2)O and N(2), depending on the nucleophile. The intermediates (adducts and gas-releasing precursors) have been characterized at the B3LYP/6-31G level of theory through the calculation of their structural and spectroscopic properties, modeling the solvent by means of a continuous approach. The eta(2)-N(2)O isomer is formed at an initial stage of adduct decompositions with the hydrazine and azide adducts. Further conversion to the eta(1)-N(2)O isomer is followed by Fe-N(2)O dissociation. Only the eta(1)-N(2)O isomer is predicted for the reaction with hydroxylamine, revealing a kinetically controlled N(2)O formation. eta(1)-N(2) and eta(2)-N(2) isomers are also predicted as stable species.

OH and O radicals production in atmospheric pressure air/Ar/H2O gliding arc discharge plasma jet

NASA Astrophysics Data System (ADS)

N, C. ROY; M, R. TALUKDER; A, N. CHOWDHURY

2017-12-01

Atmospheric pressure air/Ar/H2O gliding arc discharge plasma is produced by a pulsed dc power supply. An optical emission spectroscopic (OES) diagnostic technique is used for the characterization of plasmas and for identifications of {{OH}} and {{O}} radicals along with other species in the plasmas. The OES diagnostic technique reveals the excitation T x ≈ 5550-9000 K, rotational T r ≈ 1350-2700 K and gas T g ≈ 850-1600 K temperatures, and electron density {n}{{e}}≈ ({1.1-1.9})× {10}14 {{{cm}}}-3 under different experimental conditions. The production and destruction of {{OH}} and {{O}} radicals are investigated as functions of applied voltage and air flow rate. Relative intensities of {{OH}} and {{O}} radicals indicate that their production rates are increased with increasing {{Ar}} content in the gas mixture and applied voltage. {n}{{e}} reveals that the higher densities of {{OH}} and {{O}} radicals are produced in the discharge due to more effective electron impact dissociation of {{{H}}}2{{O}} and {{{O}}}2 molecules caused by higher kinetic energies as gained by electrons from the enhanced electric field as well as by enhanced {n}{{e}}. The productions of {{OH}} and {{O}} are decreasing with increasing air flow rate due to removal of Joule heat from the discharge region but enhanced air flow rate significantly modifies discharge maintenance properties. Besides, {T}{{g}} significantly reduces with the enhanced air flow rate. This investigation reveals that {{Ar}} plays a significant role in the production of {{OH}} and {{O}} radicals.

Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

PubMed

Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

2012-04-19

The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

(Carbonato-κ(2)O,O')bis-(5,5'-dimethyl-2,2'-bipyridyl-κ(2)N,N')cobalt(III) bromide trihydrate.

PubMed

Arun Kumar, Kannan; Meera, Parthsarathi; Amutha Selvi, Madhavan; Dayalan, Arunachalam

2012-04-01

In the title complex, [Co(CO(3))(C(12)H(12)N(2))(2)]Br·3H(2)O, the Co(III) cation has a distorted octa-hedral coordination environment. It is chelated by four N atoms of two different 5,5'-dimethyl-2,2'-bipyridyl (dmbpy) ligands in axial and equatorial positions, and by two O atoms of a carbonate anion completing the equatorial positions. Although the water mol-ecules are disordered and their H atoms were not located, there are typical O⋯O distances between 2.8 and 3.0 Å, indicating O-H⋯O hydrogen bonding. The crystal packing is consolidated by C-H⋯O and C-H⋯Br hydrogen bonds, as well as π-π stacking inter-actions between adjacent pyridine rings of the dmbpy ligands, with centroid-centroid distances of 3.694 (3) and 3.7053 (3) Å.

Estimating N2O processes during grassland renewal and grassland conversion to maize cropping using N2O isotopocules

NASA Astrophysics Data System (ADS)

Buchen, Caroline; Well, Reinhard; Flessa, Heinz; Fuß, Roland; Helfrich, Mirjam; Lewicka-Szczebak, Dominika

2017-04-01

Grassland break-up due to grassland renewal and grassland conversion to cropland can lead to a flush of mineral nitrogen from decomposition of the old grass sward and the decomposition of soil organic matter. Moreover, increased carbon and nitrogen mineralisation can result in enhanced nitrous oxide (N2O) emissions. As N2O is known to be an important greenhouse gas and a major precursor for ozone depletion, its emissions need to be mitigated by adjusting agricultural management practices. Therefore, it is necessary to understand the N2O processes involved, as well as the contribution of N2O reduction to N2. Apart from the widely used 15N gas flux method, natural abundance isotopic analysis of the four most abundant isotopocules of N2O species is a promising alternative to assess N2O production pathways. We used stable isotope analyses of soil-emitted N2O (δ18ON2O, δ15NN2Obulk and δ15NN2OSP= intramolecular distribution of 15N within the linear N2O molecule) with an isotopocule mapping approach to simultaneously estimate the magnitude of N2O reduction to N2 and the fraction of N2O originating from the bacterial denitrification pathway or fungal denitrification and/or nitrification. This approach is based on endmember areas of isotopic values for the N2O produced from different sources reported in the literature. For this purpose, we calculated two main scenarios with different assumptions for N2O produced: N2O is reduced to N2 before residual N2O is mixed with N2O of various sources (Scenario a) and vice versa (Scenario b). Based on this, we applied seven different scenario variations, where we evaluated the range of possible values for the potential N2O production pathways (heterotrophic bacterial denitrification and/or nitrifier denitrification and fungal denitrification and/or nitrification). This was done by using a range of isotopic endmember values and assuming different fractionation factors of N2O reduction in order to find the most reliable scenario

Photocatalytic decomposition of N2O over TiO2/g-C3N4 photocatalysts heterojunction

NASA Astrophysics Data System (ADS)

Kočí, K.; Reli, M.; Troppová, I.; Šihor, M.; Kupková, J.; Kustrowski, P.; Praus, P.

2017-02-01

TiO2/g-C3N4 photocatalysts with the various TiO2/g-C3N4 weight ratios from 1:2 to 1:6 were fabricated by mechanical mixing in water suspension followed by calcination. Pure TiO2 was prepared by thermal hydrolysis and pure g-C3N4 was prepared from commercial melamine by thermal annealing at 620 °C. All the nanocomposites were characterized by X-ray powder diffraction, UV-vis diffuse reflectance spectroscopy, Raman spectroscopy, infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, photoelectrochemical measurements and nitrogen physisorption. The prepared mixtures along with pure TiO2 and g-C3N4 were tested for the photocatalytic decomposition of nitrous oxide under UVC (λ = 254 nm), UVA (λ = 365 nm) and Vis (λ > 400 nm) irradiation. The TiO2/g-C3N4 nanocomposites showed moderate improvement compared to pure g-C3N4 but pure TiO2 proved to be a better photocatalyst under UVC irradiation. However, under UVA irradiation conditions, the photocatalytic activity of TiO2/g-C3N4 (1:2) nanocomposite exhibited an increase compared to pure TiO2. Nevertheless, further increase of g-C3N4 amount leads/led to a decrease in reactivity. These results are suggesting the nanocomposite with the optimal weight ratio of TiO2 and g-C3N4 have shifted absorption edge energy towards longer wavelengths and decreased the recombination rate of charge carriers compared to pure g-C3N4. This is probably due to the generation of heterojunction on the TiO2/g-C3N4 interface.

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).

Life on N2O: deciphering the ecophysiology of N2O respiring bacterial communities in a continuous culture.

PubMed

Conthe, Monica; Wittorf, Lea; Kuenen, J Gijs; Kleerebezem, Robbert; van Loosdrecht, Mark C M; Hallin, Sara

2018-04-01

Reduction of the greenhouse gas N 2 O to N 2 is a trait among denitrifying and non-denitrifying microorganisms having an N 2 O reductase, encoded by nosZ. The nosZ phylogeny has two major clades, I and II, and physiological differences among organisms within the clades may affect N 2 O emissions from ecosystems. To increase our understanding of the ecophysiology of N 2 O reducers, we determined the thermodynamic growth efficiency of N 2 O reduction and the selection of N 2 O reducers under N 2 O- or acetate-limiting conditions in a continuous culture enriched from a natural community with N 2 O as electron acceptor and acetate as electron donor. The biomass yields were higher during N 2 O limitation, irrespective of dilution rate and community composition. The former was corroborated in a continuous culture of Pseudomonas stutzeri and was potentially due to cytotoxic effects of surplus N 2 O. Denitrifiers were favored over non-denitrifying N 2 O reducers under all conditions and Proteobacteria harboring clade I nosZ dominated. The abundance of nosZ clade II increased when allowing for lower growth rates, but bacteria with nosZ clade I had a higher affinity for N 2 O, as defined by μ max /K s . Thus, the specific growth rate is likely a key factor determining the composition of communities living on N 2 O respiration under growth-limited conditions.

Uptake properties of Ni2+ by nCaO.Al2O3.2SiO2 (n=1-4) prepared from solid-state reaction of kaolinite and calcite.

PubMed

Jha, Vinay Kumar; Kameshima, Yoshikazu; Nakajima, Akira; Okada, Kiyoshi; MacKenzie, Kenneth J D

2005-08-31

A series of nCaO.Al2O3.2SiO2 samples (n=1-4) were prepared by solid-state reaction of mechanochemically treated mixtures of kaolinite and calcite fired at 600-1000 degrees C for 24 h. All the samples were X-ray amorphous after firing at 600-800 degrees C but had crystallized by 900 degrees C. The main crystalline phases were anorthite (n=1), gehlenite (n=2 and 3) and larnite (n=4). The uptake of Ni2+ by nCaO.Al2O3.2SiO2 samples fired at 800 and 900 degrees C was investigated at room temperature using solutions with initial Ni2+ concentrations of 0.1-50 mmol/l. Amorphous samples (fired at 800 degrees C) showed a higher Ni2+ uptake capacity than crystalline samples (fired at 900 degrees C). Ni2+ uptake was found to increase with increasing of CaO content. Amorphous 4CaO.Al2O3.2SiO2 showed the highest Ni2+ uptake capacity (about 9 mmol/g). The Ni2+ uptake abilities of the present samples are higher than those of other materials reported in the literature. Since the sorbed Ni2+/released Ca2+ ratios of these samples are close to unity, ion replacement of Ni2+ for Ca2+ is thought to be the principal mechanism of Ni2+ uptake by the present samples.

A field robot for autonomous laser-based N2O flux measurements

NASA Astrophysics Data System (ADS)

Molstad, Lars; Reent Köster, Jan; Bakken, Lars; Dörsch, Peter; Lien, Torgrim; Overskeid, Øyvind; Utstumo, Trygve; Løvås, Daniel; Brevik, Anders

2014-05-01

N2O measurements in multi-plot field trials are usually carried out by chamber-based manual gas sampling and subsequent laboratory-based gas chromatographic N2O determination. Spatial and temporal resolution of these measurements are commonly limited by available manpower. However, high spatial and temporal variability of N2O fluxes within individual field plots can add large uncertainties to time- and area-integrated flux estimates. Detailed mapping of this variability would improve these estimates, as well as help our understanding of the factors causing N2O emissions. An autonomous field robot was developed to increase the sampling frequency and to operate outside normal working hours. The base of this system was designed as an open platform able to carry versatile instrumentation. It consists of an electrically motorized platform powered by a lithium-ion battery pack, which is capable of autonomous navigation by means of a combined high precision real-time kinematic (RTK) GPS and an inertial measurement unit (IMU) system. On this platform an elevator is mounted, carrying a lateral boom with a static chamber on each side of the robot. Each chamber is equipped with a frame of plastic foam to seal the chamber when lowered onto the ground by the elevator. N2O flux from the soil covered by the two chambers is sequentially determined by circulating air between each chamber and a laser spectrometer (DLT-100, Los Gatos Research, Mountain View, CA, USA), which monitors the increase in N2O concentration. The target enclosure time is 1 - 2 minutes, but may be longer when emissions are low. CO2 concentrations are determined by a CO2/H2O gas analyzer (LI-840A, LI-COR Inc., Lincoln, NE, USA). Air temperature and air pressure inside both chambers are continuously monitored and logged. Wind speed and direction are monitored by a 3D sonic anemometer on top of the elevator boom. This autonomous field robot can operate during day and night time, and its working hours are only

Effect of COD/N ratio on N2O production during nitrogen removal by aerobic granular sludge.

PubMed

Velho, V F; Magnus, B S; Daudt, G C; Xavier, J A; Guimarães, L B; Costa, R H R

2017-12-01

N 2 O-production was investigated during nitrogen removal using aerobic granular sludge (AGS) technology. A pilot sequencing batch reactor (SBR) with AGS achieved an effluent in accordance with national discharge limits, although presented a nitrite accumulation rate of 95.79% with no simultaneous nitrification-denitrification. N 2 O production was 2.06 mg L -1 during the anoxic phase, with N 2 O emission during air pulses and the aeration phase of 1.6% of the nitrogen loading rate. Batch tests with AGS from the pilot reactor verified that at the greatest COD/N ratio (1.55), the N 2 O production (1.08 mgN 2 O-N L -1 ) and consumption (up to 0.05 mgN 2 O-N L -1 ), resulted in the lowest remaining dissolved N 2 O (0.03 mgN 2 O-N L -1 ), stripping the minimum N 2 O gas (0.018 mgN 2 O-N L -1 ). Conversely, the carbon supply shortage, under low C/N ratios, increased N 2 O emission (0.040 mgN 2 O-N L -1 ), due to incomplete denitrification. High abundance of ammonia-oxidizing and low abundance of nitrite-oxidizing bacteria were found, corroborating the fact of partial nitrification. A denitrifying heterotrophic community, represented mainly by Pseudoxanthomonas, was predominant in the AGS. Overall, the AGS showed stable partial nitrification ability representing capital and operating cost savings. The SBR operation flexibility could be advantageous for controlling N 2 O emissions, and extending the anoxic phase would benefit complete denitrification in cases of low C/N influents.

Octa-akis(4-amino-pyridine)-1κN,2κN-aqua-2κO-μ-carbonato-1:2κO,O':O''-dinickel(II) dichloride penta-hydrate.

PubMed

Fun, Hoong-Kun; Sinthiya, A; Jebas, Samuel Robinson; Ravindran Durai Nayagam, B; Alfred Cecil Raj, S

2008-10-18

In the title compound, [Ni(2)(CO(3))(C(5)H(6)N(2))(8)(H(2)O)]Cl(2)·5H(2)O, one of the the Ni(II) ions is six-coordinated in a distorted octa-hedral geometry, with the equatorial plane defined by four pyridine N atoms from four amino-pyridine ligands, the axial positions being occupied by one water O and a carbonate O atom. The other Ni(II) ion is also six-coordinated, by four other pyridine N atoms from four other amino-pyridine ligands and two carbonate O atoms to complete a distorted octa-hedral geometry. In the crystal structure, mol-ecules are linked into an infinite three-dimensional network by O-H⋯O, N-H⋯Cl, N-H⋯O, O-H⋯N, C-H⋯O, C-H⋯N and C/N-H⋯π inter-actions involving the pyridine rings.

Bis(2,2'-bipyridyl-κN,N')(carbonato-κO,O')cobalt(III) bromide trihydrate.

PubMed

Ma, Peng-Tao; Wang, Yu-Xia; Zhang, Guo-Qian; Li, Ming-Xue

2007-12-06

The title complex, [Co(CO(3))(C(10)H(8)N(2))(2)]Br·3H(2)O, is isostructural with the chloride analogue. The six-coordinated octahedral [Co(2,2'-bipy)(2)CO(3)](+) cation (2,2'-bipy is 2,2'-bipyrid-yl), bromide ion and water mol-ecules are linked together via O-H⋯Br and O-H⋯O hydrogen bonds, generating a one-dimensional chain.

Decreased N2O reduction by low soil pH causes high N2O emissions in a riparian ecosystem.

PubMed

Van den Heuvel, R N; Bakker, S E; Jetten, M S M; Hefting, M M

2011-05-01

Quantification of harmful nitrous oxide (N(2)O) emissions from soils is essential for mitigation measures. An important N(2)O producing and reducing process in soils is denitrification, which shows deceased rates at low pH. No clear relationship between N(2)O emissions and soil pH has yet been established because also the relative contribution of N(2)O as the denitrification end product decreases with pH. Our aim was to show the net effect of soil pH on N(2)O production and emission. Therefore, experiments were designed to investigate the effects of pH on NO(3)(-) reduction, N(2)O production and reduction and N(2) production in incubations with pH values set between 4 and 7. Furthermore, field measurements of soil pH and N(2)O emissions were carried out. In incubations, NO(3)(-) reduction and N(2) production rates increased with pH and net N(2)O production rate was highest at pH 5. N(2)O reduction to N(2) was halted until NO(3)(-) was depleted at low pH values, resulting in a built up of N(2)O. As a consequence, N(2)O:N(2) production ratio decreased exponentially with pH. N(2)O reduction appeared therefore more important than N(2)O production in explaining net N(2)O production rates. In the field, a negative exponential relationship for soil pH against N(2)O emissions was observed. Soil pH could therefore be used as a predictive tool for average N(2)O emissions in the studied ecosystem. The occurrence of low pH spots may explain N(2)O emission hotspot occurrence. Future studies should focus on the mechanism behind small scale soil pH variability and the effect of manipulating the pH of soils. © 2011 Blackwell Publishing Ltd.

Collisional Removal of OH (X (sup 2)Pi, nu=7) by O2, N2, CO2, and N2O

NASA Technical Reports Server (NTRS)

Knutsen, Karen; Dyer, Mark J.; Copeland, Richard A.

1996-01-01

Collisional removal rate constants for the OH (X 2PI, nu = 7) radical are measured for the colliders O2, CO2, and N2O, and an upper limit is established for N2. OH(nu = 4) molecules, generated in a microwave discharge flow cell by the reaction of hydrogen atoms with ozone, are excited to v = 7 by the output of a pulsed infrared laser via direct vibrational overtone excitation. The temporal evolution of the P = 7 population is probed as a function of the collider gas partial pressure by a time-delayed pulsed ultraviolet laser. Fluorescence from the B 21 + state is detected in the visible spectral region.

Theoretical study of the interaction of N/sub 2/ with water molecules. (H/sub 2/O)/sub n/:N/sub 2/, n = 1--8

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

Curtiss, L.A.; Eisgruber, C.L.

1984-03-01

Ab initio molecular orbital calculations including correlation energy have been carried out on the interaction of a single H/sub 2/O molecule with N/sub 2/. The potential energy surface for H/sub 2/O:N/sub 2/ is found to have a minimum corresponding to a HOH xxx N/sub 2/ structure with a weak (<2 kcal mol/sup -1/) hydrogen bond. A second, less stable, configuration corresponding to a H/sub 2/O xxx N/sub 2/ structure with N/sub 2/ bonded side on to the oxygen of H/sub 2/O was found to be either a minimum or a saddle point in the potential energy surface depending on themore » level of calculation. The minimal STO-3G basis set was used to investigate the interaction of up to eight H/sub 2/O molecules with N/sub 2/. Two types of clusters, one containing only HOH xxx N/sub 2/ interactions and the other containing both HOH xxxN/sub 2/ and H/sub 2/O xxx N/sub 2/ interactions, were investigated for (N/sub 2/:(H/sub 2/O)/sub n/, n = 2--8).« less

α-MnO2 nanorods supported on porous graphitic carbon nitride as efficient electrocatalysts for lithium-air batteries

NASA Astrophysics Data System (ADS)

Hang, Yang; Zhang, Chaofeng; Luo, Xiaoman; Xie, Yingshen; Xin, Sen; Li, Yutao; Zhang, Dawei; Goodenough, John B.

2018-07-01

Synthesis of α-MnO2 nanorods grown on porous graphitic carbon nitride (g-C3N4) sheets via a facile hydrothermal treatment gives a porous composite exhibiting higher activity for an air cathode than the individual component of α-MnO2 or porous g-C3N4 for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The porous g-C3N4/α-MnO2 composite also exhibits better performance in a Li-air battery than pure α-MnO2 or XC-72 carbon catalysts, which includes superior discharge capacity, low voltage gap and high cycle stability. The α-MnO2 nanorods catalyze the OER and the porous g-C3N4 sheets catalyze the ORR.

Spatial variability in groundwater N2 and N2O in the San Joaquin River

NASA Astrophysics Data System (ADS)

Hinshaw, S.; Dahlgren, R. A.

2010-12-01

The San Joaquin River is surrounded by nearly 2 million acres of irrigated agricultural land. Groundwater inputs from agricultural areas can have severe negative effects on water quality with high nitrate concentrations being a major concern. Riparian zones are important ecological habitats that mitigate nitrogen loading from groundwater discharging into rivers primarily by denitrification. Denitrification is a permanent removal of nitrate by anaerobic microbial communities via the reduction to NO, N2O and N2. However, previous studies have shown that these areas can be source of N2O emissions. Although removal of nitrate through denitrification is advantageous from a water quality perspective, N2O is a harmful greenhouse gas. This study aimed to investigate nitrogen dynamics and dissolved N gases in surface and groundwater of the riparian zones of the San Joaquin River. Excess N2 and N2O concentrations were measured in surface and groundwater at 4 locations along a 33 km reach of the river. Samples were collected within bank sediments and 5 transect points across the river at depth intervals between 2-3 cm and 150 cm. Dissolved N2 and Ar were measured by membrane inlet mass spectrometry and used to estimate excess dissolved N2 concentrations. Dissolved N2O concentrations were measured using the headspace equilibrium technique and analyzed with a gas chromatograph. Both N2 uptake and excess N2 were present, ranging from -3.40 to 8.65 N2 mg/L with a median concentration of 1.20 N2 mg/L. Significantly lower concentrations of N2O were present ranging from 0.0 to 0.12 N2O mg/L. Deeper groundwater sites had significantly higher N2 and N2O concentrations coinciding with decreased O2. The presence of excess N2 and low N2O concentrations documents the importance of denitrification in removing nitrate from groundwater. Further investigation will examine N2O emissions from riparian soils and benthic sediments using static chambers and focus on nitrogen pathways that

Synthesis and characterization of different MnO2 morphologies for lithium-air batteries

NASA Astrophysics Data System (ADS)

Choi, Hyun-A.; Jang, Hyuk; Hwang, Hyein; Choi, Mincheol; Lim, Dongwook; Shim, Sang Eun; Baeck, Sung-Hyeon

2014-09-01

Manganese dioxide (MnO2) was synthesized in the forms of nanorods, nanoparticles, and mesoporous structures and the characteristics of these materials were investigated. Crystallinities were studied by x-ray diffraction and morphologies by scanning and transmission electron microscopy. Average pore sizes and specific surface areas were analyzed using the Barret-Joyner-Halenda and Brunauer-Emmett-Teller methods, respectively. Samples were also studied by cyclic voltammetry using 1M aqueous KOH solution saturated with either O2 or N2 as electrolytes to investigate their ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) activities. Of the samples produced, mesoporous MnO2 exhibited the highest ORR and OER catalytic activities. Mesoporous MnO2 supported on a gas diffusion layer was also used as a catalyst on the air electrode (cathode) of a lithium-air battery in organic electrolyte. The charge-discharge behavior of mesoporous MnO2 was investigated at a current density 0.2 mAcm-2 in a pure oxygen environment. Mesoporous MnO2 electrodes showed stable cycleability up to 65 cycles at a cell capacity of 700 mAhg-1.

Influence of velocity effects on the shape of N2 (and air) broadened H2O lines revisited with classical molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Ngo, N. H.; Tran, H.; Gamache, R. R.; Bermejo, D.; Domenech, J.-L.

2012-08-01

The modeling of the shape of H2O lines perturbed by N2 (and air) using the Keilson-Storer (KS) kernel for collision-induced velocity changes is revisited with classical molecular dynamics simulations (CMDS). The latter have been performed for a large number of molecules starting from intermolecular-potential surfaces. Contrary to the assumption made in a previous study [H. Tran, D. Bermejo, J.-L. Domenech, P. Joubert, R. R. Gamache, and J.-M. Hartmann, J. Quant. Spectrosc. Radiat. Transf. 108, 126 (2007)], 10.1016/j.jqsrt.2007.03.009, the results of these CMDS show that the velocity-orientation and -modulus changes statistically occur at the same time scale. This validates the use of a single memory parameter in the Keilson-Storer kernel to describe both the velocity-orientation and -modulus changes. The CMDS results also show that velocity- and rotational state-changing collisions are statistically partially correlated. A partially correlated speed-dependent Keilson-Storer model has thus been used to describe the line-shape. For this, the velocity changes KS kernel parameters have been directly determined from CMDS, while the speed-dependent broadening and shifting coefficients have been calculated with a semi-classical approach. Comparisons between calculated spectra and measurements of several lines of H2O broadened by N2 (and air) in the ν3 and 2ν1 + ν2 + ν3 bands for a wide range of pressure show very satisfactory agreement. The evolution of non-Voigt effects from Doppler to collisional regimes is also presented and discussed.

KCd2[N(CN)2]5(H2O)4: an enmeshed honeycomb grid.

PubMed

Schlueter, John A; Geiser, Urs; Funk, Kylee A

2008-02-01

The title compound, poly[potassium [diaquapenta-micro(2)-dicyanamido-dicadmium(II)] dihydrate], {K[Cd(2)(C(2)N(3))(5)(H(2)O)(2)].2H(2)O}(n), contains two-dimensional anionic sheets of {[Cd(2){N(CN)(2)}(H(2)O)(2)](-)}(n) with a modified (6,3)-net (layer group cm2m, No. 35). Two sets of equivalent sheets interpenetrate orthogonally to form a tetragonal enmeshed grid.

Atmospheric chemistry of C 2F 5CHO: reaction with Cl atoms and OH radicals, IR spectrum of C 2F 5C(O)O 2NO 2

NASA Astrophysics Data System (ADS)

Sulbaek Andersen, M. P.; Hurley, M. D.; Wallington, T. J.; Ball, J. C.; Martin, J. W.; Ellis, D. A.; Mabury, S. A.; Nielsen, O. J.

2003-09-01

Smog chamber/FTIR techniques were used to measure k(Cl + C 2F 5CHO)=(1.96 ± 0.28) × 10 -12 and k(OH + C 2F 5CHO)=(5.26 ± 0.80) × 10 -13 cm 3 molecule -1 s -1 in 700 Torr of N 2 or air at 296 ± 2 K. The Cl initiated oxidation of C 2F 5CHO in the presence of NO in air diluent gave COF 2, CF 3ONO 2, and C 2F 5C(O)O 2NO 2 in molar yields of 180 ± 19%, 6.1 ± 0.6%, and 1.0 ± 0.3%, respectively. The IR spectrum for C 2F 5C(O)O 2NO 2 is reported. Results are discussed with respect to the potential for the atmospheric degradation of fluorinated aldehydes, C nF 2 n+1 CHO, to contribute to the observed environmental burden of fluorinated carboxylic acids, C nF 2 n+1 C(O)OH.

Statistical modeling of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2.

PubMed

Ushakov, Vladimir G; Troe, Jürgen; Johnson, Ryan S; Guo, Hua; Ard, Shaun G; Melko, Joshua J; Shuman, Nicholas S; Viggiano, Albert A

2015-08-14

The rates of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2 are modeled by statistical rate theory accounting for energy- and angular momentum-specific rate constants for formation of the primary and secondary cationic adducts and their backward and forward reactions. The reactions are both suggested to proceed on sextet and quartet potential energy surfaces with efficient, but probably not complete, equilibration by spin-inversion of the populations of the sextet and quartet adducts. The influence of spin-inversion on the overall reaction rate is investigated. The differences of the two reaction rates mostly are due to different numbers of entrance states (atom + linear rotor or linear rotor + linear rotor, respectively). The reaction Fe(+) + N2O was studied either with (6)Fe(+) or with (4)Fe(+) reactants. Differences in the rate constants of (6)Fe(+) and (4)Fe(+) reacting with N2O are attributed to different contributions from electronically excited potential energy surfaces, such as they originate from the open-electronic shell reactants.

Tracer-tracer relationships and lower stratospheric dynamics: CO2 and N2O correlations during SPADE

NASA Technical Reports Server (NTRS)

Boering, Kristie A.; Daube, Bruce C.; Wofsy, Steven C.; Loewenstein, Max; Podolske, James R.; Keim, Eric R.

1994-01-01

Simultaneous measurements of CO2 and N2O from the NASA ER-2 aircraft during SPADE deployments in November 1992, April/May 1993, and October 1993 provide new information on transport rates in the lower stratosphere. The tropospheric seasonal cycle in CO2, superimposed on the long-term trend, is observed to propagate into the statosphere. The compact correlations observed between CO2 and N2O indicate that meridional transport is sufficiently rapid to create a uniform set of relationships over the northern hemisphere up to at least 21 km even though CO2 changes significantly on a time scale of 8 to 12 weeks. the observed seasonal dependence of the correlations indicates that vertical transport above 20 km is slower in northern summer than in winter and slow throughout the year between 19 km and the tropopause. The inferred amplitude of the seasonal CO2 oscillation in the statopshere, viewed relative to N2O, places constraints on the mean latitude for air entering the statosphere.

N and O isotope (δ15 Nα , δ15 Nβ , δ18 O, δ17 O) analyses of dissolved NO3- and NO2- by the Cd-azide reduction method and N2 O laser spectrometry.

PubMed

Wassenaar, Leonard I; Douence, Cedric; Altabet, Mark A; Aggarwal, Pradeep K

2018-02-15

The nitrogen and oxygen (δ 15 N, δ 18 O, δ 17 O) isotopic compositions of NO 3 - and NO 2 - are important tracers of nutrient dynamics in soil, rain, groundwater and oceans. The Cd-azide method was used to convert NO 3 - or NO 2 - to N 2 O for N and triple-O isotopic analyses by N 2 O laser spectrometry. A protocol for laser-based headspace isotope analyses was compared with isotope ratio mass spectrometry. Lasers provide the ability to directly measure 17 O anomalies which can help discern atmospheric N sources. δ 15 N, δ 18 O and δ 17 O values were measured on N/O stable isotopic reference materials (IAEA, USGS) by conversion to N 2 O using the Cd-azide method and headspace N 2 O laser spectrometry. A 15 N tracer test assessed the position-specific routing of N to the α or β positions in the N 2 O molecule. A data processing algorithm was used to correct for isotopic dependencies on N 2 O concentration, cavity pressure and water content. NO 3 - /NO 2 - nitrogen is routed to the 15 N α position of N 2 O in the azide reaction; hence the δ 15 N α value should be used for N 2 O laser spectrometry results. With corrections for cavity pressure, N 2 O concentration and water content, the δ 15 N α AIR , δ 18 O VSMOW and δ 17 O VSMOW values (‰) of international reference materials were +4.8 ± 0.1, +25.9 ± 0.3, +12.7 ± 0.2 (IAEA NO 3 ), -1.7 ± 0.1, -26.8 ± 0.8, -14.4 ± 1.1 (USGS34) and +2.6 ± 0.1, +57.6 ± 1.2, +51.2 ± 2.0 (USGS35), in agreement with their values and with the isotope ratio mass spectrometry results. The 17 O excess for USGS35 was +21.2 ± 9‰, in good agreement with previous results. The Cd-azide method yielded excellent results for routine determination of δ 15 N, δ 18 O and δ 17 O values (and the 17 O excess) of nitrate or nitrite by laser spectrometry. Disadvantages are the toxicity of Cd-azide chemicals and the lack of automated sampling devices for N 2 O laser spectrometers. The 15 N-enriched tracer test revealed potential

Excessive use of nitrogen in Chinese agriculture results in high N2O/(N2O+N2) product ratio of denitrification, primarily due to acidification of the soils

PubMed Central

Qu, Zhi; Wang, Jingguo; Almøy, Trygve; Bakken, Lars R

2014-01-01

China is the world's largest producer and consumer of fertilizer N, and decades of overuse has caused nitrate leaching and possibly soil acidification. We hypothesized that this would enhance the soils' propensity to emit N2O from denitrification by reducing the expression of the enzyme N2O reductase. We investigated this by standardized oxic/anoxic incubations of soils from five long-term fertilization experiments in different regions of China. After adjusting the nitrate concentration to 2 mM, we measured oxic respiration (R), potential denitrification (D), substrate-induced denitrification, and the denitrification product stoichiometry (NO, N2O, N2). Soils with a history of high fertilizer N levels had high N2O/(N2O+N2) ratios, but only in those field experiments where soil pH had been lowered by N fertilization. By comparing all soils, we found a strong negative correlation between pH and the N2O/(N2O+N2) product ratio (r2 = 0.759, P < 0.001). In contrast, the potential denitrification (D) was found to be a linear function of oxic respiration (R), and the ratio D/R was largely unaffected by soil pH. The immediate effect of liming acidified soils was lowered N2O/(N2O+N2) ratios. The results provide evidence that soil pH has a marginal direct effect on potential denitrification, but that it is the master variable controlling the percentage of denitrified N emitted as N2O. It has been known for long that low pH may result in high N2O/(N2O+N2) product ratios of denitrification, but our documentation of a pervasive pH-control of this ratio across soil types and management practices is new. The results are in good agreement with new understanding of how pH may interfere with the expression of N2O reductase. We argue that the management of soil pH should be high on the agenda for mitigating N2O emissions in the future, particularly for countries where ongoing intensification of plant production is likely to acidify the soils. PMID:24249526

Development of AlN and TiB2 Composites with Nb2O5, Y2O3 and ZrO2 as Sintering Aids

PubMed Central

González, José C.; Rodríguez, Miguel Á.; Figueroa, Ignacio A.; Villafuerte-Castrejón, María-Elena; Díaz, Gerardo C.

2017-01-01

The synthesis of AlN and TiB2 by spark plasma sintering (SPS) and the effect of Nb2O5, Y2O3 and ZrO2 additions on the mechanical properties and densification of the produced composites is reported and discussed. After the SPS process, dense AlN and TiB2 composites with Nb2O5, Y2O3 and ZrO2 were successfully prepared. X-ray diffraction analysis showed that in the AlN composites, the addition of Nb2O5 gives rise to Nb4N3 during sintering. The compound Y3Al5O12 (YAG) was observed as precipitate in the sample with Y2O3. X-ray diffraction analysis of the TiB2 composites showed TiB2 as a single phase in these materials. The maximum Vickers and toughness values were 14.19 ± 1.43 GPa and 27.52 ± 1.75 GPa for the AlN and TiB2 composites, respectively. PMID:28772681

Fate of the CHBrsub2O radical in air

NASA Technical Reports Server (NTRS)

Bayes, K. D.; Friedl, R. F.

2003-01-01

Trace amounts of bromoform in air have been photolyzed at 266 and 303 nm to form Br atoms and CHBr2 radicals. The Br concentration as a funtion of time is followed by resonance fluorescence. The CHBr2 radicals react with O2 in the air to form peroxy radicals.

Reaction of N2O5 with H2O on carbonaceous surfaces

NASA Technical Reports Server (NTRS)

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

1986-01-01

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

Isotopic Monitoring of N2O Emissions from Wastewater Treatment: Evidence for N2O Production Associated with Anammox Metabolism?

NASA Astrophysics Data System (ADS)

Harris, E. J.; Wunderlin, P.; Joss, A.; Emmenegger, L.; Kipf, M.; Wolf, B.; Mohn, J.

2015-12-01

Microbial production is the major source of N2O, the strongest greenhouse gas produced within the nitrogen cycle, and the most important stratospheric ozone destructant released in the 21st century. Wastewater treatment is an important and growing source of N2O, with best estimates predicting N2O emissions from this sector will have increased by >25% by 2020. Novel treatment employing partial nitritation-anammox, rather than traditional nitrification-denitrification, has the potential to achieve a neutral carbon footprint due to increased biogas production - if N2O production accounts for <0.5-1% of total nitrogen turnover. As a further motivation for this research, microbial pathways identified from wastewater treatment can be applied to our understanding of N cycling in the natural environment. This study presents the first online isotopic measurements of offgas N2O from a partial-nitritation anammox reactor 1. The measured N2O isotopic composition - in particular the N2O isotopic site preference (SP = δ15Nα - δ15Nβ) - was used to understand N2O production pathways in the reactor. When N2O emissions peaked due to high dissolved oxygen concentrations, low SP showed that N2O was produced primarily via nitrifier denitrification by ammonia oxidizing bacteria (AOBs). N2O production by AOBs via NH2OH oxidation, in contrast, did not appear to be important under any conditions. Over the majority of the one-month measurement period, the measured SP was much higher than expected following our current understanding of N2O production pathways 2. SP reached 41‰ during normal operating conditions and achieved a maximum of 45‰ when nitrite was added under anoxic conditions. These results could be explained by unexpectedly strong heterotrophic N2O reduction despite low dissolved organic matter concentrations, or by an incomplete understanding of isotopic fractionation during N2O production from NH2OH oxidation by AOBs - however the explanation most consistent with all

O2(b1Σg+) Quenching by O2, CO2, H2O, and N2 at Temperatures of 300-800 K.

PubMed

Zagidullin, M V; Khvatov, N A; Medvedkov, I A; Tolstov, G I; Mebel, A M; Heaven, M C; Azyazov, V N

2017-10-05

Rate constants for the removal of O 2 (b 1 Σ g + ) by collisions with O 2 , N 2 , CO 2 , and H 2 O have been determined over the temperature range from 297 to 800 K. O 2 (b 1 Σ g + ) was excited by pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the b 1 Σ g + -X 3 Σ g - fluorescence. The removal rate constants for CO 2 , N 2 , and H 2 O were not strongly dependent on temperature and could be represented by the expressions k CO2 = (1.18 ± 0.05) × 10 -17 × T 1.5 × exp[Formula: see text], k N2 = (8 ± 0.3) × 10 -20 × T 1.5 × exp[Formula: see text], and k H2O = (1.27 ± 0.08) × 10 -16 × T 1.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . Rate constants for O 2 (b 1 Σ g + ) removal by O 2 (X), being orders of magnitude lower, demonstrated a sharp increase with temperature, represented by the fitted expression k O2 = (7.4 ± 0.8) × 10 -17 × T 0.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . All of the rate constants measured at room temperature were found to be in good agreement with previously reported values.

Ionic complexation of N 2O 4 by 18-crown-6

NASA Astrophysics Data System (ADS)

Ricard, S.; Audet, P.; Savoie, R.

1988-08-01

An ionic complex has been obtained from N 2O 4 in the presence of the macrocyclic ether 18-crown-6. This crystalline compound has been shown from its Raman spectrum to have the formula NO +·crown·H(NO 3) 2-, with the nitrosonium ion closely associated with the crown ether rather than with the hydrogen dinitrate accompanying ion. This adduct decomposes readily in moist air to give the known complex (HNO 3·H 2O) 2·crown.

The diversity of the N2O reducers matters for the N2O:N2 denitrification end-product ratio across an annual and a perennial cropping system.

PubMed

Domeignoz-Horta, Luiz A; Spor, Aymé; Bru, David; Breuil, Marie-Christine; Bizouard, Florian; Léonard, Joël; Philippot, Laurent

2015-01-01

Agriculture is the main source of terrestrial emissions of N2O, a potent greenhouse gas and the main cause of ozone layer depletion. The reduction of N2O into N2 by microorganisms carrying the nitrous oxide reductase gene (nosZ) is the only biological process known to eliminate this greenhouse gas. Recent studies showed that a previously unknown clade of N2O-reducers was related to the capacity of the soil to act as an N2O sink, opening the way for new strategies to mitigate emissions. Here, we investigated whether the agricultural practices could differently influence the two N2O reducer clades with consequences for denitrification end-products. The abundance of N2O-reducers and producers was quantified by real-time PCR, and the diversity of both nosZ clades was determined by 454 pyrosequencing. Potential N2O production and potential denitrification activity were used to calculate the denitrification gaseous end-product ratio. Overall, the results showed limited differences between management practices but there were significant differences between cropping systems in both the abundance and structure of the nosZII community, as well as in the [rN2O/r(N2O+N2)] ratio. More limited differences were observed in the nosZI community, suggesting that the newly identified nosZII clade is more sensitive than nosZI to environmental changes. Potential denitrification activity and potential N2O production were explained mainly by the soil properties while the diversity of the nosZII clade on its own explained 26% of the denitrification end-product ratio, which highlights the importance of understanding the ecology of this newly identified clade of N2O reducers for mitigation strategies.

Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

PubMed

Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

2016-02-01

This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

Infrared spectra and tunneling dynamics of the N2-D2O and OC-D2O complexes in the v2 bend region of D2O.

PubMed

Zhu, Yu; Zheng, Rui; Li, Song; Yang, Yu; Duan, Chuanxi

2013-12-07

The rovibrational spectra of the N2-D2O and OC-D2O complexes in the v2 bend region of D2O have been measured in a supersonic slit jet expansion using a rapid-scan tunable diode laser spectrometer. Both a-type and b-type transitions were observed for these two complexes. All transitions are doubled, due to the heavy water tunneling within the complexes. Assuming the tunneling splittings are the same in K(a) = 0 and K(a) = 1, the band origins, all three rotational and several distortion constants of each tunneling state were determined for N2-D2O in the ground and excited vibrational states, and for OC-D2O in the excited vibrational state, respectively. The averaged band origin of OC-D2O is blueshifted by 2.241 cm(-1) from that of the v2 band of the D2O monomer, compared with 1.247 cm(-1) for N2-D2O. The tunneling splitting of N2-D2O in the ground state is 0.16359(28) cm(-1), which is about five times that of OC-D2O. The tunneling splittings decrease by about 26% for N2-D2O and 23% for OC-D2O, respectively, upon excitation of the D2O bending vibration, indicating an increase of the tunneling barrier in the excited vibrational state. The tunneling splittings are found to have a strong dependence on intramolecular vibrational excitation as well as a weak dependence on quantum number K(a).

Triaqua-1κO,2κ2 O-bis­(2,2′-bipyridine)-1κ2 N,N′;2κ2 N,N′-chlorido-1κCl-μ-terephthalato-1:2κ2 O 1:O 4-dicopper(II) nitrate monohydrate

PubMed Central

Liu, Yang; Feng, Yong-Lan; Kuang, Dai-Zhi

2012-01-01

In the binuclear title compound, [Cu2(C8H4O4)Cl(C10H8N2)2(H2O)3]NO3·H2O, the two crystallographically independent CuII ions have similar coordination environments. One of the CuII ions has a square-pyramidal arrangement, which is defined by a water mol­ecule occupying the apical position, with the equatorial ligators consisting of two N atoms from a 2,2′-bipyridine mol­ecule, one carboxyl­ate O atom from a terephthalate ligand and one O atom from a water mol­ecule. The other CuII ion has a similar coordination environment, except that the apical position is occupied by a chloride ligand instead of a water mol­ecule. An O—H⋯O and O—H⋯Cl hydrogen-bonded three-dimensional network is formed between the components. PMID:22719307

Crystal structure and optical property of complex perovskite oxynitrides ALi0.2Nb0.8O2.8N0.2, ANa0.2Nb0.8O2.8N0.2, and AMg0.2Nb0.8O2.6N0.4 (A = Sr, Ba)

NASA Astrophysics Data System (ADS)

Moon, Keon Ho; Avdeev, Maxim; Kim, Young-Il

2017-10-01

Oxynitride type complex perovskites AM0.2Nb0.8O3-xNx (A = Sr, Ba; M = Li, Na, Mg) were newly synthesized by the solid state diffusion of Li+, Na+, or Mg2+ into the layered oxide, A5Nb4O15, with concurrent O/N substitution. Neutron and synchrotron X-ray Rietveld refinement showed that SrLi0.2Nb0.8O2.8N0.2, SrNa0.2Nb0.8O2.8N0.2, and SrMg0.2Nb0.8O2.6N0.4 had body-centered tetragonal symmetry (I4/mcm), while those with A = Ba had simple cubic symmetry (Pm 3 ̅ m). In the tetragonal Sr-compounds, the nitrogen atoms were localized on the c-axial 4a site. However, the octahedral cations, M/Nb (M = Li, Na, Mg) were distributed randomly in all six compounds. The lattice volume of AM0.2Nb0.8O3-xNx was dependent on various factors including the type of A and the electronegativity of M. Compared to the simple perovskites, ANbO2N (A = Sr, Ba), AM0.2Nb0.8O3-xNx had wider band gaps (1.76-2.15 eV for A = Sr and 1.65-2.10 eV for A = Ba), but significantly lower sub-gap absorption.

Gas entrapment and microbial N2O reduction reduce N2O emissions from a biochar-amended sandy clay loam soil

PubMed Central

Harter, Johannes; Guzman-Bustamante, Ivan; Kuehfuss, Stefanie; Ruser, Reiner; Well, Reinhard; Spott, Oliver; Kappler, Andreas; Behrens, Sebastian

2016-01-01

Nitrous oxide (N2O) is a potent greenhouse gas that is produced during microbial nitrogen transformation processes such as nitrification and denitrification. Soils represent the largest sources of N2O emissions with nitrogen fertilizer application being the main driver of rising atmospheric N2O concentrations. Soil biochar amendment has been proposed as a promising tool to mitigate N2O emissions from soils. However, the underlying processes that cause N2O emission suppression in biochar-amended soils are still poorly understood. We set up microcosm experiments with fertilized, wet soil in which we used 15N tracing techniques and quantitative polymerase chain reaction (qPCR) to investigate the impact of biochar on mineral and gaseous nitrogen dynamics and denitrification-specific functional marker gene abundance and expression. In accordance with previous studies our results showed that biochar addition can lead to a significant decrease in N2O emissions. Furthermore, we determined significantly higher quantities of soil-entrapped N2O and N2 in biochar microcosms and a biochar-induced increase in typical and atypical nosZ transcript copy numbers. Our findings suggest that biochar-induced N2O emission mitigation is based on the entrapment of N2O in water-saturated pores of the soil matrix and concurrent stimulation of microbial N2O reduction resulting in an overall decrease of the N2O/(N2O + N2) ratio. PMID:28008997

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

Global and regional emissions estimates for N2O

NASA Astrophysics Data System (ADS)

Saikawa, E.; Prinn, R. G.; Dlugokencky, E.; Ishijima, K.; Dutton, G. S.; Hall, B. D.; Langenfelds, R.; Tohjima, Y.; Machida, T.; Manizza, M.; Rigby, M.; O'Doherty, S.; Patra, P. K.; Harth, C. M.; Weiss, R. F.; Krummel, P. B.; van der Schoot, M.; Fraser, P. J.; Steele, L. P.; Aoki, S.; Nakazawa, T.; Elkins, J. W.

2014-05-01

We present a comprehensive estimate of nitrous oxide (N2O) emissions using observations and models from 1995 to 2008. High-frequency records of tropospheric N2O are available from measurements at Cape Grim, Tasmania; Cape Matatula, American Samoa; Ragged Point, Barbados; Mace Head, Ireland; and at Trinidad Head, California using the Advanced Global Atmospheric Gases Experiment (AGAGE) instrumentation and calibrations. The Global Monitoring Division of the National Oceanic and Atmospheric Administration/Earth System Research Laboratory (NOAA/ESRL) has also collected discrete air samples in flasks and in situ measurements from remote sites across the globe and analyzed them for a suite of species including N2O. In addition to these major networks, we include in situ and aircraft measurements from the National Institute of Environmental Studies (NIES) and flask measurements from the Tohoku University and Commonwealth Scientific and Industrial Research Organization (CSIRO) networks. All measurements show increasing atmospheric mole fractions of N2O, with a varying growth rate of 0.1-0.7% per year, resulting in a 7.4% increase in the background atmospheric mole fraction between 1979 and 2011. Using existing emission inventories as well as bottom-up process modeling results, we first create globally gridded a priori N2O emissions over the 37 years since 1975. We then use the three-dimensional chemical transport model, Model for Ozone and Related Chemical Tracers version 4 (MOZART v4), and a Bayesian inverse method to estimate global as well as regional annual emissions for five source sectors from 13 regions in the world. This is the first time that all of these measurements from multiple networks have been combined to determine emissions. Our inversion indicates that global and regional N2O emissions have an increasing trend between 1995 and 2008. Despite large uncertainties, a significant increase is seen from the Asian agricultural sector in recent years, most likely

Structural and spectral analyses of N,N'-(2,2'-dithiodi-o-phenylene)bis-(furan-2-carboxamide)

NASA Astrophysics Data System (ADS)

Yıldırım, Sema Öztürk; Büyükmumcu, Zeki; Pekdur, Özlem Savaş; Butcher, Ray J.; Doǧan, Şengül Dilem

2018-02-01

In this study we report structure determination of N,N'-(2,2'-dithiodi-o-phenylene)bis-(furan-2-carboxamide). 2,2'-Dithiobis(benzamide) derivatives have been reported to possess important biological properties such as antibacterial, antifungal activities and inhibition of blood platelet aggregation and redeterrmined at 100(2)K from the data published by Raftery, Lallbeeharry, Bhowon, Laulloo & Joulea [Acta Cryst. 2009, E65, o16]. 2,2'-Dithiobis(N-butyl-benzamide) has been reported to be useful as an antiseptic for cosmetics. The structural properties of the compound have been characterized by using 1H NMR and the structure were determined by single-crystal X-ray diffraction. Molecular structure crystallizes in triclinic form, space group with a = 9.6396(7) Å, b = 9.9115(7) Å, c = 12.0026(8) Å, α = 109.743(6)°, β = 103.653(6)°, γ = 104.633(6)° and V = 977.15(13) Å3. In the solid state of the molecular structure N-H…S, N-H…O and C-H…O, type interactions provide for stabilization. The geometries of the title compound have been optimized using density functional theory (DFT) method. The calculated values were found to be in agreement with the experimental data.

Measurements of N2O and SF6 mole fraction between 1977 and 1998 in archived air samples from Cape Meares, Oregon

NASA Astrophysics Data System (ADS)

Rolfe, T.; Rice, A. L.; Radda, J.

2015-12-01

The quantification of greenhouse gas concentrations in the atmosphere is important for monitoring imbalances in their global budgets between sources and sinks and their changes in time. Nitrous oxide (N2O) is a strong radiative trace gas with a GWP of ~300 times CO2 over a 100 year period and an atmospheric lifetime of ~100 years. The preindustrial revolution background concentration of N2O was ~270 ppb. Today, the concentration is ~330 ppb. Sulfur hexafluoride (SF6) is another potent greenhouse gas with a long lifetime (800 to 3200 years) and very large GWP (~23000 times CO2 over a 100 year period). Its current atmospheric concentration is low (~8 ppt today). Direct measurements of N2O and SF6 in air prior to the mid-1990s are few. Over 200 archived atmospheric gas samples collected at Cape Meares, Oregon between 1977 and 1998 were analyzed for their N2O and SF6 concentrations using an Agilent (model 6890 N) gas chromatograph fitted with an electron capture detector using a two column "heart-cut" technique. Precision of measurement of N2O and SF6 is calculated at 0.13% (1σ) and 1.35% (1σ) respectively. N2O concentrations in the late 1970s and early 1980s average around 303 ppb, rising to 309 ppb in the early 1990s. Between 1980 and 1990, the increase in N2O concentrations is found to be ~0.5 ppb/yr. SF6 concentrations during the late 1970s and early 1980s average around 0.9 ppt and rise slowly, reaching 1.6 ppt in the 1990s. We find that the increase in SF6 between 1980 and 1990 to be ~0.07 ppt/yr. We also discuss sample integrity in storage and observed temporal trends of N2O and SF6.

Formation mechanisms of Si3N4 and Si2N2O in silicon powder nitridation

NASA Astrophysics Data System (ADS)

Yao, Guisheng; Li, Yong; Jiang, Peng; Jin, Xiuming; Long, Menglong; Qin, Haixia; Kumar, R. Vasant

2017-04-01

Commercial silicon powders are nitrided at constant temperatures (1453 K; 1513 K; 1633 K; 1693 K). The X-ray diffraction results show that small amounts of Si3N4 and Si2N2O are formed as the nitridation products in the samples. Fibroid and short columnar Si3N4 are detected in the samples. The formation mechanisms of Si3N4 and Si2N2O are analyzed. During the initial stage of silicon powder nitridation, Si on the outside of sample captures slight amount of O2 in N2 atmosphere, forming a thin film of SiO2 on the surface which seals the residual silicon inside. And the oxygen partial pressure between the SiO2 film and free silicon is decreasing gradually, so passive oxidation transforms to active oxidation and metastable SiO(g) is produced. When the SiO(g) partial pressure is high enough, the SiO2 film will crack, and N2 is infiltrated into the central section of the sample through cracks, generating Si2N2O and short columnar Si3N4 in situ. At the same time, metastable SiO(g) reacts with N2 and form fibroid Si3N4. In the regions where the oxygen partial pressure is high, Si3N4 is oxidized into Si2N2O.

trans-Bis(azido-kappaN)bis(pyridine-2-carboxamide-kappa2N1,O2)nickel(II).

PubMed

Daković, Marijana; Popović, Zora

2007-11-01

In the title compound, [Ni(N(3))(2)(C(6)H(6)N(2)O)(2)], the Ni(II) atom lies on an inversion centre. The distorted octahedral nickel(II) coordination environment contains two planar trans-related N,O-chelating picolinamide ligands in one plane and two monodentate azide ligands perpendicular to this plane. Molecules are linked into a three-dimensional framework by N-H...N hydrogen bonds.

Ocean N2O Emissions : Recent Global Estimates and Anthropogenically Influenced Changes

NASA Astrophysics Data System (ADS)

Suntharalingam, P.; Buithenuis, E.; Andrews, O.; Le Quere, C.

2016-12-01

models, and (iii) air-sea flux calculations which combine surface ocean N2O measurements with gas-exchange relationships. We will also present results from ongoing ocean biogeochemistry model analyses evaluating the separate influences of climate variation and anthropogenic nutrient inputs on ocean N2O emissions for recent decades.

A novel amido-pyrophosphate Mn(II) chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O.

PubMed

Tarahhomi, Atekeh; Pourayoubi, Mehrdad; Fejfarová, Karla; Dušek, Michal

2013-03-01

The title complex, trans-bis(dimethylformamide-κO)bis{N,N'-N'',N'''-tetra-tert-butyl[oxybis(phosphonic diamide-κO)]}manganese(II) dichloride dihydrate, [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis-chelate amido-pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn(II) atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six-membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2. This analysis shows that the six-membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N-H...O and N-H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O-H...Cl hydrogen bonds.

Removal of NO in NO/N2, NO/N2/O2, NO/CH4/N2, and NO/CH4/O2/N2 systems by flowing microwave discharges.

PubMed

Hueso, José L; Gonzalez-Elipe, Agustín R; Cotrino, José; Caballero, Alfonso

2007-02-15

In this paper, continuing previous work, we report on experiments carried out to investigate the removal of NO from simulated flue gas in nonthermal plasmas. The plasma-induced decomposition of small concentrations of NO in N2 used as the carrier gas and O2 and CH4 as minority components has been studied in a surface wave discharge induced with a surfatron launcher. The reaction products and efficiency have been monitored by mass spectrometry as a function of the composition of the mixture. NO is effectively decomposed into N2 and O2 even in the presence of O2, provided always that enough CH4 is also present in the mixture. Other majority products of the plasma reactions under these conditions are NH3, CO, and H2. In the absence of O2, decomposition of NO also occurs, although in that case HCN accompanies the other reaction products as a majority component. The plasma for the different reaction mixtures has been characterized by optical emission spectroscopy. Intermediate excited species of NO*, C*, CN*, NH*, and CH* have been monitored depending on the gas mixture. The type of species detected and their evolution with the gas composition are in agreement with the reaction products detected in each case. The observations by mass spectrometry and optical emission spectroscopy are in agreement with the kinetic reaction models available in literature for simple plasma reactions in simple reaction mixtures.

Reactions of hydrated electrons (H2O)n- with carbon dioxide and molecular oxygen: hydration of the CO2- and O2- ions.

PubMed

Balaj, O Petru; Siu, Chi-Kit; Balteanu, Iulia; Beyer, Martin K; Bondybey, Vladimir E

2004-10-04

The gas-phase reactions of hydrated electrons with carbon dioxide and molecular oxygen were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Both CO2 and O2 react efficiently with (H2O)n- because they possess low-lying empty pi* orbitals. The molecular CO2- and O2- anions are concurrently solvated and stabilized by the water ligands to form CO2(-)(H2O)n and O2(-)(H2O)n. Core exchange reactions are also observed, in which CO2(-)(H2O)n is transformed into O2(-)(H2O)n upon collision with O2. This is in agreement with the prediction based on density functional theory calculations that O2(-)(H2O)n clusters are thermodynamically favored with respect to CO2(-)(H2O)n. Electron detachment from the product species is only observed for CO2(-)(H2O)2, in agreement with the calculated electron affinities and solvation energies.

Interfacial RhO{sub x}/CeO{sub 2} sites as locations for low temperature N{sub 2}O dissociation

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

Cunningham, J.; Hickey, J.N.; Soria, J.

Temperatures required for extensive N{sub 2}O dissociation to N{sub 2}, or to N{sub 2} plus O{sub 2}, over 0.5% RhO{sub x}/CeO{sub 2} materials, and over polycrystalline Rh{sub 2}O{sub 3} or CeO{sub 2}, are compared for preoxidised and for prereduced samples on the basis of conversions achieved in pulsed-reactant, continuous-flow and recirculatory microcatalytic reactors. Influences of sample prereduction or preoxidation upon those measurements and upon results from parallel ESR and FTIR studies of N{sub 2}O interactions with such materials are presented and compared. Over partially reduced 0.5% RhO{sub x}/CeO{sub 2} materials complete dissociation of N{sub 2}O pulses to N{sub 2} plusmore » O{sub 2} is obtained at temperatures 50-100{degrees} lower than those required for extensive dissociation over prereduced Rh{sub 2}O{sub 3}. Furthermore, N{sub 2} was the sole product from the latter. Higher ongoing N{sub 2}O conversions to N{sub 2} plus O{sub 2} at 623 K over 0.5% Rh/CeO{sub 2} in pulsed-reactant than in continuous-flow mode point to regeneration of active sites under helium flushing between pulses. The TPD profile for dioxygen release from Rhodia containing samples at temperatures 350-550 K is presented. ESR measurements reveal complementary effects of outgassings at temperatures, T{sub v}, {ge} 573 K upon the availability at RhO{sub x}/CeO{sub 2} surfaces of electron-excess sites reactive towards N{sub 2}O. Differences from observations over Rh{sub 2}O{sub 3} and CeO{sub 2} can be understood by attributing the low-temperature activity of RhO{sub x}/CeO{sub 2} to electron excess sites at microinterfaces between the dispersed Rhodia component and the Ceria support.« less

Site-specific 15N isotopic signatures of abiotically produced N2O

NASA Astrophysics Data System (ADS)

Heil, Jannis; Wolf, Benjamin; Brüggemann, Nicolas; Emmenegger, Lukas; Tuzson, Béla; Vereecken, Harry; Mohn, Joachim

2014-08-01

Efficient nitrous oxide (N2O) mitigation strategies require the identification of the main source and sink processes and their contribution to total soil N2O production. Several abiotic reactions of nitrification intermediates leading to N2O production are known, but their contribution to total N2O production in soils is uncertain. As the site preference (SP) of 15N in N2O is a promising tool to give more insight into N2O production processes, we investigated the SP of N2O produced by different abiotic reactions in a laboratory study. All reactions involved the nitrification intermediate hydroxylamine (NH2OH) in combination with nitrite (NO2-), Fe3+, Fe2+ and Cu2+, reactants commonly or potentially found in soils, at different concentrations and pH values. N2O production and its four main isotopic species (14N14N16O, 15N14N16O, 14N15N16O, and 14N14N18O) were quantified simultaneously and online at high temporal resolution using quantum cascade laser absorption spectroscopy. Thereby, our study presents the first continuous analysis of δ18O in N2O. The experiments revealed the possibility of purely abiotic reactions over a wide range of acidity (pH 3-8) by different mechanisms. All studied abiotic pathways produced N2O with a characteristic SP in the range of 34-35‰, unaffected by process conditions and remaining constant over the course of the experiments. These findings reflect the benefit of continuous N2O isotopic analysis by laser spectroscopy, contribute new information to the challenging source partitioning of N2O emissions from soils, and emphasize the potentially significant role of coupled biotic-abiotic reactions in soils.

Structure of (Ga2O3)2(ZnO)13 and a unified description of the homologous series (Ga2O3)2(ZnO)(2n + 1).

PubMed

Michiue, Yuichi; Kimizuka, Noboru; Kanke, Yasushi; Mori, Takao

2012-06-01

The structure of (Ga(2)O(3))(2)(ZnO)(13) has been determined by a single-crystal X-ray diffraction technique. In the monoclinic structure of the space group C2/m with cell parameters a = 19.66 (4), b = 3.2487 (5), c = 27.31 (2) Å, and β = 105.9 (1)°, a unit cell is constructed by combining the halves of the unit cell of Ga(2)O(3)(ZnO)(6) and Ga(2)O(3)(ZnO)(7) in the homologous series Ga(2)O(3)(ZnO)(m). The homologous series (Ga(2)O(3))(2)(ZnO)(2n + 1) is derived and a unified description for structures in the series is presented using the (3+1)-dimensional superspace formalism. The phases are treated as compositely modulated structures consisting of two subsystems. One is constructed by metal ions and another is by O ions. In the (3 + 1)-dimensional model, displacive modulations of ions are described by the asymmetric zigzag function with large amplitudes, which was replaced by a combination of the sawtooth function in refinements. Similarities and differences between the two homologous series (Ga(2)O(3))(2)(ZnO)(2n + 1) and Ga(2)O(3)(ZnO)(m) are clarified in (3 + 1)-dimensional superspace. The validity of the (3 + 1)-dimensional model is confirmed by the refinements of (Ga(2)O(3))(2)(ZnO)(13), while a few complex phenomena in the real structure are taken into account by modifying the model.

First on-line isotopic characterization of N2O above intensively managed grassland

NASA Astrophysics Data System (ADS)

Wolf, B.; Merbold, L.; Decock, C.; Tuzson, B.; Harris, E.; Six, J.; Emmenegger, L.; Mohn, J.

2015-04-01

The analysis of the four main isotopic N2O species (14N14N16O, 14N15N16O, 15N14N16O, 14N14N18O) and especially the intramolecular distribution of 15N ("site preference", SP) has been suggested as a tool to distinguish source processes and to help constrain the global N2O budget. However, current studies suffer from limited spatial and temporal resolution capabilities due to the combination of discrete flask sampling with subsequent laboratory-based mass-spectrometric analysis. Quantum cascade laser absorption spectroscopy (QCLAS) allows the selective high-precision analysis of N2O isotopic species at trace levels and is suitable for in situ measurements. Here, we present results from the first field campaign, conducted on an intensively managed grassland site in central Switzerland. N2O mole fractions and isotopic composition were determined in the atmospheric surface layer (at 2.2 m height) at a high temporal resolution with a modified state-of-the-art laser spectrometer connected to an automated N2O preconcentration unit. The analytical performance was determined from repeated measurements of a compressed air tank and resulted in measurement repeatability of 0.20, 0.12 and 0.11‰ for δ15Nα, δ15Nβ and δ18O, respectively. Simultaneous eddy-covariance N2O flux measurements were used to determine the flux-averaged isotopic signature of soil-emitted N2O. Our measurements indicate that, in general, nitrifier-denitrification and denitrification were the prevalent sources of N2O during the campaign and that variations in isotopic composition were due to alterations in the extent to which N2O was reduced to N2 rather than to other pathways, such as hydroxylamine oxidation. Management and rewetting events were characterized by low values of the intramolecular 15N site preference (SP), δ15Nbulk and δ18O, suggesting that nitrifier-denitrification and incomplete heterotrophic bacterial denitrification responded most strongly to the induced disturbances. The flux

N2O emissions from a nitrogen-enriched river

USGS Publications Warehouse

McMahon, P.B.; Dennehy, K.F.

1999-01-01

Nitrous oxide (N2O) emissions from the South Platte River in Colorado were measured using closed chambers in the fall, winter, and summer of 1994- 1995. The South Platte River was enriched in inorganic N (9-800 ??M) derived from municipal wastewater effluent and groundwater return flows from irrigated agricultural fields. River water was as much as 2500% supersaturated with N2O, and median N2O emission rates from the river surface ranged from less than 90 to 32 600 ??g-N m-2 d-1. Seventy-nine percent of the variance in N2O emission rates was explained by concentrations of total inorganic N in river water and by water temperature. The estimated total annual N2O emissions from the South Platte River were 2 x 1013-6 x 1013 ??g-N yr-1. This amount of annual N2O emissions was similar to the estimated annual N2O emissions from all primary municipal wastewater treatment processes in the United States (1). Results from this study indicate that N-enriched rivers could be important anthropogenic sources of N2O to the atmosphere. However, N2O emission measurements from other N-enriched rivers are needed to better quantify this source.Nitrous oxide (N2O) emissions from the South Platte River in Colorado were measured using closed chambers in the fall, winter, and summer of 1994-1995. The South Platte River was enriched in inorganic N (9-800 ??M) derived from municipal wastewater effluent and groundwater return flows from irrigated agricultural fields. River water was as much as 2500% supersaturated with N2O, and median N2O emission rates from the river surface ranged from less than 90 to 32 600 ??g-N m-2 d-1. Seventy-nine percent of the variance in N2O emission rates was explained by concentrations of total inorganic N in river water and by water temperature. The estimated total annual N2O emissions from the South Platte River were 2??1013-6??1013 ??g-N yr-1. This amount of annual N2O emissions was similar to the estimated annual N2O emissions from all primary municipal

Oxidation mechanisms of CF2Br2 and CH2Br2 induced by air nonthermal plasma.

PubMed

Schiorlin, Milko; Marotta, Ester; Dal Molin, Marta; Paradisi, Cristina

2013-01-02

Oxidation mechanisms in air nonthermal plasma (NTP) at room temperature and atmospheric pressure were investigated in a corona reactor energized by +dc, -dc, or +pulsed high voltage.. The two bromomethanes CF(2)Br(2) and CH(2)Br(2) were chosen as model organic pollutants because of their very different reactivities with OH radicals. Thus, they served as useful mechanistic probes: they respond differently to the presence of humidity in the air and give different products. By FT-IR analysis of the postdischarge gas the following products were detected and quantified: CO(2) and CO in the case of CH(2)Br(2), CO(2) and F(2)C ═ O in the case of CF(2)Br(2). F(2)C ═ O is a long-lived oxidation intermediate due to its low reactivity with atmospheric radicals. It is however removed from the NTP processed gas by passage through a water scrubber resulting in hydrolysis to CO(2) and HF. Other noncarbon containing products of the discharge were also monitored by FT-IR analysis, including HNO(3) and N(2)O. Ozone, an important product of air NTP, was never detected in experiments with CF(2)Br(2) and CH(2)Br(2) because of the highly efficient ozone depleting cycles catalyzed by BrOx species formed from the bromomethanes. It is concluded that, regardless of the type of corona applied, CF(2)Br(2) reacts in air NTP via a common intermediate, the CF(2)Br radical. The possible reactions leading to this radical are discussed, including, for -dc activation, charge exchange with O(2)(-), a species detected by APCI mass spectrometry.

Effects of N2O narcosis on the contraction and repayment of an oxygen debt

NASA Technical Reports Server (NTRS)

Schatte, C. L.; Hall, P.; Fitch, J. W.; Loader, J. E.

1974-01-01

The oxygen deficit, oxygen debt, and the difference between them were measured in five male and three female subjects during and after exercise while breathing either air or a normoxic mixture containing 33% N2O and nitrogen. With the exception of a higher respiratory quotient at rest in N2O, there were no statistically significant differences for oxygen consumption, carbon dioxide production, expired gas volume, heart rate or blood lactate while breathing N2O during rest, exercise, or recovery. An appreciably, but not statistically, greater mean oxygen deficit was found in N2O along with a significantly greater mean oxygen debt; deficit-debt difference was unaffected by N2O. It was speculated that N2O narcosis did not affect the ability to utilize oxygen but that the response to the greater oxygen need of exercise may have been slowed with perhaps a concomitant greater depletion of stored high energy compounds.

Are dual isotope and isotopomer ratios of N2O useful indicators for N2O turnover during denitrification in nitrate-contaminated aquifers?

NASA Astrophysics Data System (ADS)

Well, Reinhard; Eschenbach, Wolfram; Flessa, Heinz; von der Heide, Carolin; Weymann, Daniel

2012-08-01

Denitrifying aquifers are sources of the greenhouse gas N2O. Isotopic signatures reflect processes of production and reduction of N2O, but it is not clear to which extent these can be used to quantify those processes. We investigated the spatial distribution of isotopologue values of N2O (δ18O, average δ15N, and 15N site preference, SP) in two denitrifying sandy aquifers to study N2O production and reduction and associated isotope effects in groundwater. For the first time, we combined this approach with direct estimation of N2O reduction from excess-N2 analysis. Groundwater samples were collected from 15 monitoring wells and four multilevel sampling wells and analysed for NO3-, dissolved N2O, dissolved O2, excess N2 from denitrification and isotopic signatures of NO3- and N2O. Both aquifers exhibited high NO3- concentrations with average concentrations of 22 and 15 mg N L-1, respectively. Evidence of intense denitrification with associated N2O formation was obtained from mean excess-N2 of 3.5 and 4.3 mg N L-1, respectively. Isotopic signatures of N2O were highly variable with ranges of 17.6-113.2‰ (δ18O), -55.4 to 89.4‰ (δ15Nbulk) and 1.8-97.9‰ (SP). δ15N and δ18O of NO3- ranged from -2.1‰ to 65.5‰ and from -5‰ to 33.5‰, respectively. The relationships between δ15N of NO3-, δ15Nbulk and SP were not in good agreement with the distribution predicted by a Rayleigh-model of isotope fractionation. The large ranges of δ18O and SP of N2O as well as the close correlation between these values could be explained by the fact that N2O reduction to N2 was strongly progressed but variable. We confirm and explain that a large range in SP and δ18O is typical for N2O from denitrifying aquifers, showing that this source signature can be distinguished from the isotopic fingerprint of N2O emitted from soils without water-logging. We conclude that isotopologue values of N2O in our sites were not suitable to quantify production or reduction of N2O or the

Overlap corrections for emissivity calculations of H2O-CO2-CO-N2 mixtures

NASA Astrophysics Data System (ADS)

Alberti, Michael; Weber, Roman; Mancini, Marco

2018-01-01

Calculations of total gas emissivities of gas mixtures containing several radiatively active species require corrections for band overlapping. In this paper, we generate such overlap correction charts for H2O-CO2-N2, H2O-CO-N2, and CO2-CO-N2 mixtures. These charts are applicable in the 0.1-40 bar total pressure range and in the 500 K-2500 K temperature range. For H2O-CO2-N2 mixtures, differences between our charts and Hottel's graphs as well as models of Leckner and Modak are highlighted and analyzed.

Heterojunction p-Cu2O/n-Ga2O3 diode with high breakdown voltage

NASA Astrophysics Data System (ADS)

Watahiki, Tatsuro; Yuda, Yohei; Furukawa, Akihiko; Yamamuka, Mikio; Takiguchi, Yuki; Miyajima, Shinsuke

2017-11-01

Heterojunction p-Cu2O/n-β-Ga2O3 diodes were fabricated on an epitaxially grown β-Ga2O3(001) layer. The reverse breakdown voltage of these p-n diodes reached 1.49 kV with a specific on-resistance of 8.2 mΩ cm2. The leakage current of the p-n diodes was lower than that of the Schottky barrier diode due to the higher barrier height against the electron. The ideality factor of the p-n diode was 1.31. It indicated that some portion of the recombination current at the interface contributed to the forward current, but the diffusion current was the dominant. The forward current more than 100 A/cm2 indicated the lower conduction band offset at the hetero-interface between Cu2O and Ga2O3 layers than that predicted from the bulk properties, resulting in such a high forward current without limitation. These results open the possibility of advanced device structures for wide bandgap Ga2O3 to achieve higher breakdown voltage and lower on-resistance.

N2O fluxes at the soil-atmosphere interface in various ecosystems and the global N2O budget

NASA Technical Reports Server (NTRS)

Banin, Amos

1987-01-01

The overall purpose of this research task is to study the effects of soil properties and ecosystem variables on N2O exchanges at the soil-atmosphere interface, and to assess their effects on the globle N2O budget. Experimental procedures are implemented in various sites to measure the source/sink relations of N2O at the soil-atmosphere interface over prolonged periods of time as part of the research of biogeochemical cycling in terrestrial ecosystems. A data-base for establishing quantitative correlations between N2O fluxes and soil and environmental parameters that are of potential use for remote sensing, is being developed.

Detection of interstellar N2O: A new molecule containing an N-O bond

NASA Technical Reports Server (NTRS)

Ziurys, L. M.; Apponi, A. J.; Hollis, J. M.; Snyder, L. E.

1994-01-01

A new interstellar molecule, N2O, known as nitrous oxide or 'laughing gas,' has been detected using the NRAO 12 m telescope. The J = 3 - 2, 4 - 3, 5 - 4, and 6 - 5 rotational transitions of this species at 75, 100, 125, and 150 GHz, respectively, were observed toward Sgr B2(M). The column density derived for N2O in this source is N(sub tot) approx. 10(exp 15)/sq. cm, which corresponds to a fractional abundance of approx. 10(exp -9), relative to H2. This value implies abundance ratios of N2O/NO approx. 0.1 and N2O/HNO approx. 3 in the Galactic center. Such ratios are in excellent agreement with predictions of ion-molecule models of interstellar chemistry using early-time calculations and primarily neutral-neutral reactions. N2O is the third interstellar molecule detected thus far containing an N-O bond. Such bonds cannot be so rare as previously thought.

2'-O-[2-[2-(N,N-Dimethylamino)ethoxy]ethyl] Modified Antisense Oligonucleotides: Symbiosis of Charge Interaction Factors and Stereoelectronic Effects

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

Prhavc, M.; Prakash, T.P.; Minasov, G.

Oligonucleotides with a novel, 2'-O-[2-[2-(N,N-dimethylamino)ethoxy]ethyl] (2'-O-DMAEOE) modification have been synthesized. This modification, a cationic analogue of the 2'-O-(2-methoxyethyl) (2'-O-MOE) modification, exhibits high binding affinity to target RNA (but not to DNA) and exceptional resistance to nuclease degradation. Analysis of the crystal structure of a self-complementary oligonucleotide containing a single 2'-O-DMAEOE modification explains the importance of charge factors and gauche effects on the observed antisense properties. 2'-O-DMAEOE modified oligonucleotides are ideal candidates for antisense drugs.

Desflurane usage during anesthesia with and without N2O using FLOW-i Automatic Gas Control with three different wash-in speeds.

PubMed

De Medts, Robrecht; Carette, Rik; De Wolf, Andre M; Hendrickx, Jan F A

2017-06-09

AGC ® (Automatic Gas Control) is the FLOW-i's automated low flow tool (Maquet, Solna, Sweden) that target controls the inspired O 2 (F I O 2 ) and end-expired desflurane concentration (F A des) while (by design) exponentially decreasing fresh gas flow (FGF) during wash-in to a maintenance default FGF of 300 mL min -1 . It also offers a choice of wash-in speeds for the inhaled agents. We examined AGC performance and hypothesized that the use of lower wash-in speeds and N 2 O both reduce desflurane usage (Vdes). After obtaining IRB approval and patient consent, 78 ASA I-II patients undergoing abdominal surgery were randomly assigned to 1 of 6 groups (n = 13 each), depending on carrier gas (O 2 /air or O 2 /N 2 O) and wash-in speed (AGC speed 2, 4, or 6) of desflurane, resulting in groups air/2, air/4, air/6, N 2 O/2, N 2 O/4, and N 2 O/6. The target for F I O 2 was set at 35%, while the F A des target was selected so that the AGC displayed 1.3 MAC (corrected for the additive affect of N 2 O if used). AGC was activated upon starting mechanical ventilation. Varvel's criteria were used to describe performance of achieving the targets. Patient demographics, end-expired N 2 O concentration, MAC, FGF, and Vdes were compared using ANOVA. Data are presented as mean ± standard deviation, except for Varvel's criteria (median ± quartiles). Patient demographics did not differ among the groups. Median performance error was -2-0% for F I O 2 and -3-1% for F A des; median absolute performance error was 1-2% for F I O 2 and 0-3% for F A des. MAC increased faster in N 2 O groups, but total MAC decreased 0.1-0.25 MAC below that in the O 2 /air groups after 60 min. The effect of wash-in speed on Vdes faded over time. N 2 O decreased Vdes by 62%. AGC performance for O 2 and desflurane targeting is excellent. After 1 h, the wash-in speeds tested are unlikely to affect desflurane usage. N 2 O usage decreases Vdes proportionally with its reduction in F A tdes.

First on-line isotopic characterization of N2O emitted from intensively managed grassland

NASA Astrophysics Data System (ADS)

Wolf, B.; Merbold, L.; Decock, C.; Tuzson, B.; Harris, E.; Six, J.; Emmenegger, L.; Mohn, J.

2015-01-01

The analysis of the four main isotopic N2O species (14N14N16O, 14N15N16O, 15N14N16O, 14N14N18O) and especially the intramolecular distribution of 15N (site preference, SP) has been suggested as a tool to distinguish source processes and to help constrain the global N2O budget. However, current studies suffer from limited spatial and temporal resolution capabilities due to the combination of discrete flask sampling with subsequent laboratory-based mass spectrometric analysis. Quantum cascade laser absorption spectroscopy (QCLAS) allows selective high-precision analysis of N2O isotopic species at trace levels and is suitable for in situ measurements. Here, we present results from the first field campaign, conducted on an intensively managed grassland in central Switzerland. N2O mole fractions and isotopic composition were determined in the atmospheric surface layer (2 m height) at high temporal resolution with a modified state-of-the-art laser spectrometer connected to an automated N2O preconcentration unit. The analytical performance was determined from repeated measurements of a compressed air tank and resulted in measurement repeatability of 0.20, 0.12 and 0.11‰ for δ15Nα, δ15Nβ and δ18O, respectively. Simultaneous eddy-covariance N2O flux measurements were used to determine the flux-averaged isotopic signature of soil-emitted N2O. Our measurements indicate that in general, nitrifier-denitrification and denitrification were the prevalent sources of N2O during the campaign, and that variations in isotopic composition were rather due to alterations in the extent to which N2O was reduced to N2, than other pathways such as hydroxylamine oxidation. Management and rewetting events were characterized by low values of the intra-molecular 15N site preference (SP), δ15Nbulk and δ18O, suggesting nitrifier denitrification and incomplete heterotrophic bacterial denitrification responded most strongly to the induced disturbances. Flux-averaged isotopic composition of N

Development of a High Precision and Stability Ambient N2O and CO Analyzer

NASA Astrophysics Data System (ADS)

Zhou, Jingang; Hoffnagle, John; Tan, Sze; Dong, Feng; Fleck, Derek; Yiu, John; Huang, Kuan; Leggett, Graham; He, Yonggang

2016-04-01

With a global warming potential of nearly 300, N2O is a critically important greenhouse gas, contributing about 5 % of the US total GHG emissions. Agriculture soil management practices are the dominant source of anthropogenic N2O emissions, contributing nearly 75 % of US N2O emissions. In urban areas, vehicle tailpipe emissions and waste water treatment plants are significant sources of N2O. We report here a new mid-infrared laser-based cavity ring-down spectrometer (Picarro G5310) that was recently developed to simultaneously measure sub-ppb ambient concentrations of two key greenhouse gas species, N2O and CO, while measuring H2O as well. It combines a quantum cascade laser with a proprietary 3-mirror optical cavity. The ambient N2O and CO measurement precisions are 0.1ppb (10sec), 0.014ppb (600sec), and 0.006ppb (3000sec); and the measurements could even be averaged down over 3 hours, giving measurement precisions of 0.003ppb. The measurable N2O and CO ranges have been tested up to 2.5ppm. With the high precision and unparalleled stability, G5310 is believed a promising tool for long-term monitoring in atmospheric sciences. The new optical analyzer was set up to monitor N2O and CO (G5310), along with CO2 and CH4(G4301), in ambient air obtained from a 10 meter tower in Santa Clara, California. Evidence of contributions from traffic and a nearby sewage treatment facility were expected in the measurement data.

Detection of interstellar N2O: A new molecule containing an N-O bond

NASA Astrophysics Data System (ADS)

Ziurys, L. M.; Apponi, A. J.; Hollis, J. M.; Snyder, L. E.

1994-12-01

A new interstellar molecule, N2O, known as nitrous oxide or 'laughing gas,' has been detected using the NRAO 12 m telescope. The J = 3 - 2, 4 - 3, 5 - 4, and 6 - 5 rotational transitions of this species at 75, 100, 125, and 150 GHz, respectively, were observed toward Sgr B2(M). The column density derived for N2O in this source is Ntot approx. 1015/sq. cm, which corresponds to a fractional abundance of approx. 10-9, relative to H2. This value implies abundance ratios of N2O/NO approx. 0.1 and N2O/HNO approx. 3 in the Galactic center. Such ratios are in excellent agreement with predictions of ion-molecule models of interstellar chemistry using early-time calculations and primarily neutral-neutral reactions. N2O is the third interstellar molecule detected thus far containing an N-O bond. Such bonds cannot be so rare as previously thought.

Implications of the formation of small polarons in Li2O2 for Li-air batteries

NASA Astrophysics Data System (ADS)

Kang, Joongoo; Jung, Yoon Seok; Wei, Su-Huai; Dillon, Anne C.

2012-01-01

Lithium-air batteries (LABs) are an intriguing next-generation technology due to their high theoretical energy density of ˜11 kWh/kg. However, LABs are hindered by both poor rate capability and significant polarization in cell voltage, primarily due to the formation of Li2O2 in the air cathode. Here, by employing hybrid density functional theory, we show that the formation of small polarons in Li2O2 limits electron transport. Consequently, the low electron mobility μ = 10-10-10-9 cm2/V s contributes to both the poor rate capability and the polarization that limit the LAB power and energy densities. The self-trapping of electrons in the small polarons arises from the molecular nature of the conduction band states of Li2O2 and the strong spin polarization of the O 2p state. Our understanding of the polaronic electron transport in Li2O2 suggests that designing alternative carrier conduction paths for the cathode reaction could significantly improve the performance of LABs at high current densities.

CW EC-QCL-based sensor for simultaneous detection of H 2O, HDO, N 2O and CH 4 using multi-pass absorption spectroscopy

DOE PAGES

Yu, Yajun; Sanchez, Nancy P.; Griffin, Robert J.; ...

2016-05-03

A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H 2O, HDO, N 2O and CH 4 using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm -1 operating at similar to 7.8 mu m was scanned covering four neighboring absorption lines, for H 2O at 1281.161 cm -1, HDO at 1281.455 cm -1, N 2O at 1281.53 cm -1 and CH 4 at 1281.61 cm -1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonicmore » detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviation analysis indicated that minimum detection limits of 1.77 ppmv for H 2O, 3.92 ppbv for HDO, 1.43 ppbv for N 2O, and 2.2 ppbv for CH 4 were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. In conclusion, experimental measurements of ambient air are also reported.« less

Effects of Carbon and Cover Crop Residues on N2O and N2 Emissions

NASA Astrophysics Data System (ADS)

Burger, M.; Cooperman, Y.; Horwath, W. R.

2016-12-01

In Mediterranean climate, nitrous oxide emissions occurring with the first rainfall after the dry summer season can contribute up to 50% of agricultural systems' total annual emissions, but the drivers of these emissions have not been clearly identified, and there are only few measurements of atmospheric nitrogen (N2) production (denitrification) during these events. In lab incubations, we investigated N2O and N2 production, gross ammonification and nitrification, and microbial N immobilization with wet-up in soil from a vineyard that was previously fallow or where cover crop residue had been incorporated the previous spring. Before the first rainfall, we measured 120 mg dissolved organic carbon (DOC-C) kg-1 soil in the 0-5 cm layer of this vineyard, and after the rain 10 mg DOC-C kg-1, while nitrate levels before the rain were <5 mg N kg-1 in fallow and <10 mg N kg-1 in previously cover cropped soil. The N2O/N2 production was 2, 7, 9, and 86% in fallow, legume-grass mixture, rye, and legume cover cropped soil. The N2O/N2 ratio tended to increase with lower DOC (post-rain) levels in the soil. The results suggest that accumulated carbon in dry surface soil is the main driving factor of N2O and N2 emissions through denitrification with the first rainfall after prolonged dry periods.

N2O and CO production by electric discharge - Atmospheric implications. [Venus atmosphere simulation

NASA Technical Reports Server (NTRS)

Levine, J. S.; Howell, W. E.; Hughes, R. E.; Chameides, W. L.

1979-01-01

Enhanced levels of N2O and CO were measured in tropospheric air samples exposed to a 17,500-J laboratory discharge. These enhanced levels correspond to an N2O production rate of about 4 trillion molecules/J and a CO production rate of about 10 to the 14th molecules/J. The CO measurements suggest that the primary region of chemical production in the discharge is the shocked air surrounding the lightning channel, as opposed to the slower-cooling inner core. Additional experiments in a simulated Venus atmosphere (CO2 - 95%, N2 - 5%, at one atmosphere) indicate an enhancement of CO from less than 0.1 ppm prior to the laboratory discharge to more than 2000 ppm after the discharge. Comparison with theoretical calculations appears to confirm the ability of a shock-wave/thermochemical model to predict the rate of production of trace species by an electrical discharge.

Responses of CH(4), CO(2) and N(2)O fluxes to increasing nitrogen deposition in alpine grassland of the Tianshan Mountains.

PubMed

Li, Kaihui; Gong, Yanming; Song, Wei; He, Guixiang; Hu, Yukun; Tian, Changyan; Liu, Xuejun

2012-06-01

To assess the effects of nitrogen (N) deposition on greenhouse gas (GHG) fluxes in alpine grassland of the Tianshan Mountains in central Asia, CH(4), CO(2) and N(2)O fluxes were measured from June 2010 to May 2011. Nitrogen deposition tended to significantly increase CH(4) uptake, CO(2) and N(2)O emissions at sites receiving N addition compared with those at site without N addition during the growing season, but no significant differences were found for all sites outside the growing season. Air temperature, soil temperature and water content were the important factors that influence CO(2) and N(2)O emissions at year-round scale, indicating that increased temperature and precipitation in the future will exert greater impacts on CO(2) and N(2)O emissions in the alpine grassland. In addition, plant coverage in July was also positively correlated with CO(2) and N(2)O emissions under elevated N deposition rates. The present study will deepen our understanding of N deposition impacts on GHG balance in the alpine grassland ecosystem, and help us assess the global N effects, parameterize Earth System models and inform decision makers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Equation of state for Eu-doped SrSi2O2N2

NASA Astrophysics Data System (ADS)

Ermakova, Olga; Paszkowicz, Wojciech; Kaminska, Agata; Barzowska, Justyna; Szczodrowski, Karol; Grinberg, Marek; Minikayev, Roman; Nowakowska, Małgorzata; Carlson, Stefan; Li, Guogang; Liu, Ru-Shi; Suchocki, Andrzej

2014-07-01

α-SrSi2O2N2 is one of the recently studied oxonitridosilicates applicable in optoelectronics, in particular in white LEDs. Its elastic properties remain unknown. A survey of literature shows that, up to now, nine oxonitridosilicate materials have been identified. For most of these compounds, doped with rare earths and manganese, a luminescence has been reported at a wavelength characteristic for the given material; all together cover a broad spectral range. The present study focuses on the elastic properties of one of these oxonitridosilicates, the Eu-doped triclinic α-SrSi2O2N2. High-pressure powder diffraction experiments are used in order to experimentally determine, for the first time, the equation of state of this compound. The in situ experiment was performed for pressures ranging up to 9.65 GPa, for Eu-doped α-SrSi2O2N2 sample mounted in a diamond anvil cell ascertaining the hydrostatic compression conditions. The obtained experimental variation of volume of the triclinic unit cell of α-SrSi2O2N2:Eu with rising pressure served for determination of the Birch-Murnaghan equation of state. The determined above quoted bulk modulus is 103(5) GPa, its first derivative is 4.5(1.1). The above quoted bulk modulus value is found to be comparable to that of earlier reported oxynitrides of different composition.

Oxygen vibrations in the series Bi2Sr2Ca{_{n-1}}Cu{n}O{_{4+2 n+y}}

NASA Astrophysics Data System (ADS)

Faulques, E.; Dupouy, P.; Lefrant, S.

1991-06-01

We present a discussion of the oxygen vibrations in the Bi{2}Sr{2}Ca{n-1}Cu{n}O{4+2 n+y} high T_c superconductors with the aim of interpreting Raman spectra in the case of the non-symmorphic Amaa structure. Group theory shows that the oxygen atoms belonging to the central CuO{2} plane generate a Raman activity for the n=1,3 phases. Consequently, we propose a novel assignment for the lines of weak intensity at 297, 316 and 333 cm^{-1}. It is shown that the two components of the 460 cm^{-1} band may be consistent with the Amma structure. Spectra recorded in crossed polarization exhibit weak lines which could be assigned to B {1g} modes expected for the three phases. Nous présentons une discussion sur les vibrations des atomes d'oxygène dans la série des supraconducteurs Bi{2}Sr{2}Ca{n-1}Cu{n}O{4+2 n+y} dans le but d'interpréter les spectres Raman. L'analyse des modes normaux de vibration de la structure Amaa pour les phases n=1 ou 3 montre que les atomes d'oxygène du plan CuO{2} contenant les centres d'inversion donnent lieu à une activité Raman. En conséquence, nous proposons une nouvelle attribution pour les raies de faible intensité à 297, 316 et 333 cm^{-1}. Nous montrons que le dédoublement de la bande à 460 cm^{-1} pourrait être dû à la structure Amaa. Les spectres enregistrés en polarization croisée montrent de faibles bandes qui peuvent être attribuées aux modes B {1g} attendus pour les trois phases.

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).

Crystallization and characterization of Y2O3-SiO2 glasses

NASA Technical Reports Server (NTRS)

Drummond, C. H., III; Lee, W. E.; Sanders, W. A.; Kiser, J. D.

1988-01-01

Glasses in the yttria-silica system with 20-40 mol pct Y2O3 have been subjected to recrystallization studies after melting at 1900-2100 C in W crucibles in 1 and 50 atm N2. The TEM and XRD results obtained indicate the presence of the delta, gamma, gamma-prime, and beta-Y2Si2O7 crystalline phases, depending on melting and quenching conditions. Heat-treatment in air at 1100-1600 C increased the amount of crystallization, and led to the formation of Y2SiO5, cristobalite, and polymorphs of Y2Si2O7. Also investigated were the effects of 5 and 10 wt pct zirconia additions.

Crystallization and characterization of Y2O3-SiO2 glasses

NASA Technical Reports Server (NTRS)

Drummond, Charles H., III; Lee, William E.; Sanders, W. A.; Kiser, J. D.

1991-01-01

Glasses in the yttria-silica system with 20 to 40 mol pct Y2O3 were subjected to recrystallization studies after melting at 1900 to 2100 C in W crucibles in 1 and 50 atm N2. The TEM and XRD results obtained indicate the presence of the delta, gamma, gamma prime, and beta-Y2Si2O7 crystalline phases, depending on melting and quenching conditions. Heat treatment in air at 1100 to 1600 C increased the amount of crystallization, and led to the formation of Y2SiO5, cristabalite, and polymorphs of Y2Si2O7. Also investigated were the effects of 5 and 10 wt pct zirconia additions.

Tidal and spatial variability of nitrous oxide (N2O) in Sado estuary (Portugal)

NASA Astrophysics Data System (ADS)

Gonçalves, Célia; Brogueira, Maria José; Nogueira, Marta

2015-12-01

The estimate of the nitrous oxide (N2O) fluxes is fundamental to assess its impact on global warming. The tidal and spatial variability of N2O and the air-sea fluxes in the Sado estuary in July/August 2007 are examined. Measurements of N2O and other relevant environmental parameters (temperature, salinity, dissolved oxygen and dissolved inorganic nitrogen - nitrate plus nitrite and ammonium) were recorded during two diurnal tidal cycles performed in the Bay and Marateca region and along the estuary during ebb, at spring tide. N2O presented tidal and spatial variability and varied spatially from 5.0 nmol L-1 in Marateca region to 12.5 nmol L-1 in Sado river input. Although the Sado river may constitute a considerable N2O source to the estuary, the respective chemical signal discharge was rapidly lost in the main body of the estuary due to the low river flow during the sampling period. N2O varied with tide similarly between 5.2 nmol L-1 (Marateca) and 10.0 nmol L-1 (Sado Bay), with the maximum value reached two hours after flooding period. The influence of N2O enriched upwelled seawater (˜10.0 nmol L-1) was well visible in the estuary mouth and apparently represented an important contribution of N2O in the main body of Sado estuary. Despite the high water column oxygen saturation in most of Sado estuary, nitrification did not seem a relevant process for N2O production, probably as the concentration of the substrate, NH4+, was not adequate for this process to occur. Most of the estuary functioned as a N2O source, and only Marateca zone has acted as N2O sink. The N2O emission from Sado estuary was estimated to be 3.7 Mg N-N2O yr-1 (FC96) (4.4 Mg N-N2O yr-1, FRC01). These results have implications for future sampling and scaling strategies for estimating greenhouse gases (GHGs) fluxes in tidal ecosystems.

Technical Note: Simultaneous measurement of sedimentary N2 and N2O production and a modified 15N isotope pairing technique

NASA Astrophysics Data System (ADS)

Hsu, T.-C.; Kao, S.-J.

2013-12-01

Dinitrogen (N2) and/or nitrous oxide (N2O) are produced through denitrification, anaerobic ammonium oxidation (anammox) or nitrification in sediments, of which entangled processes complicate the absolute rate estimations of gaseous nitrogen production from individual pathways. The classical isotope pairing technique (IPT), the most common 15N nitrate enrichment method to quantify denitrification, has recently been modified by different researchers to (1) discriminate between the N2 produced by denitrification and anammox or to (2) provide a more accurate denitrification rate under considering production of both N2O and N2. In case 1, the revised IPT focused on N2 production being suitable for the environments of a low N2O-to-N2 production ratio, while in case 2, anammox was neglected. This paper develops a modified method to refine previous versions of IPT. Cryogenic traps were installed to separately preconcentrate N2 and N2O, thus allowing for subsequent measurement of the two gases generated in one sample vial. The precision is better than 2% for N2 (m/z 28, m/z 29 and m/z 30), and 1.5% for N2O (m/z 44, m/z 45 and m/z 46). Based on the six m/z peaks of the two gases, the 15N nitrate traceable processes including N2 and N2O from denitrification and N2 from anammox were estimated. Meanwhile, N2O produced by nitrification was estimated via the production rate of unlabeled 44N2O. To validate the applicability of our modified method, incubation experiments were conducted using sediment cores taken from the Danshuei Estuary in Taiwan. Rates of the aforementioned nitrogen removal processes were successfully determined. Moreover, N2O yield was as high as 66%, which would significantly bias previous IPT approaches if N2O was not considered. Our modified method not only complements previous versions of IPT but also provides more comprehensive information to advance our understanding of nitrogen dynamics of the water-sediment interface.

Characterization of remote O2-plasma-enhanced CVD SiO2/GaN(0001) structure using photoemission measurements

NASA Astrophysics Data System (ADS)

Truyen, Nguyen Xuan; Ohta, Akio; Makihara, Katsunori; Ikeda, Mitsuhisa; Miyazaki, Seiichi

2018-01-01

The control of chemical composition and bonding features at a SiO2/GaN interface is a key to realizing high-performance GaN power devices. In this study, an ∼5.2-nm-thick SiO2 film has been deposited on an epitaxial GaN(0001) surface by remote O2-plasma-enhanced chemical vapor deposition (O2-RPCVD) using SiH4 and Ar/O2 mixture gases at a substrate temperature of 500 °C. The depth profile of chemical structures and electronic defects of the O2-RPCVD SiO2/GaN structures has been evaluated from a combination of SiO2 thinning examined by X-ray photoelectron spectroscopy (XPS) and the total photoelectron yield spectroscopy (PYS) measurements. As a highlight, we found that O2-RPCVD is effective for fabricating an abrupt SiO2/GaN interface.

The influence of ionic strength and organic compounds on nanoparticle TiO2 (n-TiO2) aggregation.

PubMed

Lee, Jaewoong; Bartelt-Hunt, Shannon L; Li, Yusong; Gilrein, Erica Jeanne

2016-07-01

This study investigated the aggregation of n-TiO2 in the presence of humic acid (HA) and/or 17β-estradiol (E2) under high ionic strength conditions simulating levels detected in landfill leachate. Aggregation of n-TiO2 was strongly influenced by ionic strength as well as ionic valence in that divalent cations (Ca(2+)) were more effective than monovalent (Na(+)) at the surface modification. HA or E2 enhanced aggregation of n-TiO2 in 20 mM CaCl2, however little aggregation was observed in 100 mM NaCl. Similarly, we observed only the increased aggregation of n-TiO2 in the presence of HA/E2. These results showed the critical role of particles' surface charges on the aggregation behaviors of n-TiO2 that HA plays more significantly than E2. However, the slightly increased zeta potential and aggregation of n-TiO2 in the combination of HA and E2 at both 20 mM CaCl2 and 100 mM NaCl means that E2 has influenced on the surface modification of n-TiO2 by adsorption. Based on the aggregation of n-TiO2 under high ionic strength with HA and/or E2, we simulated the mobility of aggregated n-TiO2 in porous media. As a result, we observed that the mobility distance of aggregated n-TiO2 was dramatically influenced by the surface modification with both HA and/or E2 between particles and media. Furthermore, larger mobility distance was observed with larger aggregation of n-TiO2 particles that can be explained by clean bed filtration (CFT) theory. Copyright © 2016 Elsevier Ltd. All rights reserved.

Global terrestrial N2O budget for present and future

NASA Astrophysics Data System (ADS)

Olin, Stefan; Xing, Xu-Ri; Wårlind, David; Eliasson, Peter; Smith, Ben; Arneth, Almut

2017-04-01

Nitrogen (N) plays an important role in plant productivity and physiology and is the main limiting nutrient in a majority of the terrestrial ecosystems. The enhanced input of anthropogenic reactive nitrogen (Nr) in agriculture have enhanced global food production, but with adverse effects on biodiversity and water quality, and substantially increased emissions of N trace gases that affect air quality and climate. Emissions of N gases affects the climate, either through cloud forming nitrogen oxides (NOx) gases or as greenhouse gases, where nitrous oxide (N2O) is the most important being approximately 300 times more potent than carbon dioxide (CO2). In this study we use the process-based global vegetation model Lund-Potsdam-Jena General Ecosystem Simulator (LPJ-GUESS) (Olin et al. 2015) that recently have incorporated a new soil N transformation scheme, adopted from Xu-Ri and Prentice (2008), which makes it possible to study the N2O emission respond to changes in climate and CO2 concentration as well as anthropogenic N enhancements on a global scale. We present here results from the validation of the new model against site-scale N2O measurements from agricultural and non-agricultural ecosystems. We will also present results from a study to examine how land use, land use change and anthropogenic N fertilisation influence historical and future global N2O emissions. This new development represents a key component within future projects in CMIP6 (LUMIP) and in EC-Earth for the EU Horizon 2020 project CRESCENDO. Olin, S., Lindeskog, M., Pugh, T., Schurgers, G., Mischurow, M., Wårlind, D., Zaehle, S., Stocker, B., Smith, B. and Arneth, A. 2015. Soil carbon management in large-scale Earth system modelling: implications for crop yields and nitrogen leaching. Earth System Dynamics, 6, 745-768. Xu-Ri and Prentice IC. 2008. Terrestrial nitrogen cycle simulation with a dynamic global vegetation model. Global Change Biology, 14, 1745-1764.

The natural greenhouse effect of atmospheric oxygen (O2) and nitrogen (N2)

NASA Astrophysics Data System (ADS)

Höpfner, M.; Milz, M.; Buehler, S.; Orphal, J.; Stiller, G.

2012-05-01

The effect of collision-induced absorption by molecular oxygen (O2) and nitrogen (N2) on the outgoing longwave radiation (OLR) of the Earth's atmosphere has been quantified. We have found that on global average under clear-sky conditions the OLR is reduced due to O2 by 0.11 Wm-2 and due to N2 by 0.17 Wm-2. Together this amounts to 15% of the OLR-reduction caused by CH4 at present atmospheric concentrations. Over Antarctica the combined effect of O2 and N2 increases on average to about 38% of CH4 with single values reaching up to 80%. This is explained by less interference of H2O spectral bands on the absorption features of O2 and N2 for dry atmospheric conditions.

Syntheses and structures of [UO2( L)5](ClO4)2 and [U( L')4(H2O)4](ClO4)4 ( L is dimethylformamide, L' is N,N-dimethylcarbamide)

NASA Astrophysics Data System (ADS)

Serezhkin, V. N.; Vologzhanina, A. V.; Pushkin, D. V.; Astashkina, D. A.; Savchenkov, A. V.; Serezhkina, L. B.

2017-09-01

The reaction of aqueous solutions of uranyl perchlorate with selected organic amides was studied in the dark and under the sunlight. The complexes [UVIO2(C3H7NO)5](ClO4)2 ( I) and [UIV(C3H8N2O)4(H2O)4](ClO4)4 ( II), where C3H7NO is N,N-dimethylformamide ( Dmfa) and C3H8N2O is N,N-dimethylcarbamide ( a-Dmur), were studied by X-ray diffraction. Complex II and the complex UIV( s-Dmur)4(H2O)4(ClO4)4 ( III), where s-Dmur is N,N'-dimethylcarbamide, were studied by IR spectroscopy. Crystals I and II are composed of mononuclear [UO2( Dmfa)5]2+ and [U( Dmur)4(H2O)4]4+ groups as uranium-containing structural units belonging to the crystal-chemical groups AM 7 1 ( A = UVI, M 1 = O2- and Dmfa) and AM 8 1 ( A = UIV, M 1 = Dmur and H2O) of uranium complexes, respectively. The mononuclear uranium- containing complexes in the crystals of U(IV) and U(VI) perchlorates were found to obey the 14 neighbors rule.

Morphological modification of alpha-MnO2 catalyst for use in Li/air batteries.

PubMed

Park, Min-Sik; Kim, Jae-Hun; Kim, Ki Jae; Jeong, Goojin; Kim, Young-Jun

2013-05-01

Single crystal alpha-MnO2 nanowires and nanopowders have been successfully synthesized in order to facilitate a comparison of their catalytic activity for use in Li-air batteries. The importance of the morphological modification of the alpha-MnO2 catalyst for facilitating electrochemical reactions between Li and O2 is addressed. Distinctive catalytic activity of alpha-MnO2 is observed, which is in line with its different morphologies. The catalytic activity significantly affects the reversible capacity of Li-air batteries. A high aspect ratio, large surface area and good dispersibility of alpha-MnO2 in the nanowire form are advantageous providing larger active surfaces for promoting the fundamental reactions in Li-air batteries. We also introduce a robustly designed air-electrode composed of highly porous carbon and nanostructured alpha-MnO2 catalysts, with employs a metal foam current collector to ensure sufficient air-permeability and to maximize electronic conduction during cycles. Our suggestions should prove helpful in forming a basis for further investigations in developing advanced Li-air batteries.

Surveying N2O-producing pathways in bacteria.

PubMed

Stein, Lisa Y

2011-01-01

Nitrous oxide (N(2)O) is produced by bacteria as an intermediate of both dissimilatory and detoxification pathways under a range of oxygen levels, although the majority of N(2)O is released in suboxic to anoxic environments. N(2)O production under physiologically relevant conditions appears to require the reduction of nitric oxide (NO) produced from the oxidation of hydroxylamine (nitrification), reduction of nitrite (denitrification), or by host cells of pathogenic bacteria. In a single bacterial isolate, N(2)O-producing pathways can be complex, overlapping, involve multiple enzymes with the same function, and require multiple layers of regulatory machinery. This overview discusses how to identify known N(2)O-producing inventory and regulatory sequences within bacterial genome sequences and basic physiological approaches for investigating the function of that inventory. A multitude of review articles have been published on individual enzymes, pathways, regulation, and environmental significance of N(2)O-production encompassing a large diversity of bacterial isolates. The combination of next-generation deep sequencing platforms, emerging proteomics technologies, and basic microbial physiology can be used to expand what is known about N(2)O-producing pathways in individual bacterial species to discover novel inventory and unifying features of pathways. A combination of approaches is required to understand and generalize the function and control of N(2)O production across a range of temporal and spatial scales within natural and host environments. Copyright © 2011 Elsevier Inc. All rights reserved.

Effect of Si3N4 powder reactivity on the preparation of the Si2N2O-Al2O3 silicon aluminum oxynitride solid solution

NASA Technical Reports Server (NTRS)

Sekercioglu, I.; Wills, R. R.

1979-01-01

Dense high-purity silicon aluminum oxynitride was prepared by reactive hot-pressing of an Si3N4-Al2O3-SiO2 mixture. The formation of a single-phase material was found to be critically dependent on the Si3N4 powder in the starting mixture. It is suggested that evolution of a chlorine- and nitrogen-containing species may enhance the reactivity of Si3N4 in this reaction. Densities of O prime sialons are very similar to that of Si2N2O, the widely quoted value in the ceramics literature of 3.1 g/cu cm for the density of Si2N2O being incorrect.

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

Diet effects on urine composition of cattle and N2O emissions.

PubMed

Dijkstra, J; Oenema, O; van Groenigen, J W; Spek, J W; van Vuuren, A M; Bannink, A

2013-06-01

Ruminant production contributes to emissions of nitrogen (N) to the environment, principally ammonia (NH3), nitrous oxide (N2O) and di-nitrogen (N2) to air, nitrate (NO3 -) to groundwater and particulate N to surface waters. Variation in dietary N intake will particularly affect excretion of urinary N, which is much more vulnerable to losses than is faecal N. Our objective is to review dietary effects on the level and form of N excreted in cattle urine, as well as its consequences for emissions of N2O. The quantity of N excreted in urine varies widely. Urinary N excretion, in particular that of urea N, is decreased upon reduction of dietary N intake or an increase in the supply of energy to the rumen microorganisms and to the host animal itself. Most of the N in urine (from 50% to well over 90%) is present in the form of urea. Other nitrogenous components include purine derivatives (PD), hippuric acid, creatine and creatinine. Excretion of PD is related to rumen microbial protein synthesis, and that of hippuric acid to dietary concentration of degradable phenolic acids. The N concentration of cattle urine ranges from 3 to 20 g/l. High-dietary mineral levels increase urine volume and lead to reduced urinary N concentration as well as reduced urea concentration in plasma and milk. In lactating dairy cattle, variation in urine volume affects the relationship between milk urea and urinary N excretion, which hampers the use of milk urea as an accurate indicator of urinary N excretion. Following its deposition in pastures or in animal houses, ubiquitous microorganisms in soil and waters transform urinary N components into ammonium (NH4 +), and thereafter into NO3 - and ultimately in N2 accompanied with the release of N2O. Urinary hippuric acid, creatine and creatinine decompose more slowly than urea. Hippuric acid may act as a natural inhibitor of N2O emissions, but inhibition conditions have not been defined properly yet. Environmental and soil conditions at the site of

N(2)O emissions and source processes in snow-covered soils in the Swiss Alps.

PubMed

Mohn, Joachim; Steinlin, Christine; Merbold, Lutz; Emmenegger, Lukas; Hagedorn, Frank

2013-01-01

Nitrous oxide (N2O) emissions from snow-covered soils represent a significant fraction of the annual flux from alpine, subalpine or cold-temperate regions. In winter 2010-2011, we investigated the temporal variability of N2O emissions and source processes from a subalpine valley in the Swiss Alps. The study included regular measurements of N2O snow profiles at a fixed location and an intensive sampling campaign along a transversal cut through the valley with grassland at the bottom and coniferous forest at the slopes. During the intensive campaign, recently developed laser spectroscopy was employed for high-precision N2O isotopomer analysis. Maximum N2O fluxes (0.77±0.64 nmol m(-2) h(-1)) were found for periods with elevated air temperature and, in contrast to our expectations, were higher from forest than from grassland in mid-February. At maximum snow height (63 cm) the main N2O source processes were heterotrophic denitrification and nitrifier denitrification. The reduction of N2O by heterotrophic denitrifiers was much more pronounced for the grassland compared with the forest soil, as indicated by the (15)N site preferences of 16.4±11.5 ‰ (grassland) and-1.6±2.1 ‰ (forest). This illustrates the potential of laser spectroscopic N2O isotopomer analysis for the identification of source processes even at low emission rates in nutrient poor ecosystems.

A novel 15N tracer approach for the quantification of N2 and N2O emissions from soil incubations in a completely automated laboratory set up

NASA Astrophysics Data System (ADS)

Scheer, Clemens; Dannenmann, Michael; Meier, Rudolf

2015-04-01

The microbial mediated production of nitrous oxide (N2O) and its reduction to dinitrogen (N2) via denitrification represents a loss of nitrogen (N) from fertilised agro-ecosystems to the atmosphere. Although denitrification has received great interest by biogeochemists in the last decades, the magnitude of N2lossesand related N2:N2O ratios from soils still are largely unknown due to methodical constraints. We present a novel 15N tracer approach, based on a previous developed tracer method to study denitrification in pure bacterial cultures which was modified for the use on soil incubations in a completely automated laboratory set up. The method uses a background air in the incubation vessels that is replaced with a helium-oxygen gas mixture with a 50-fold reduced N2 background (2 % v/v). This method allows for a direct and sensitive quantification of the N2 and N2O emissions from the soil with isotope-ratio mass spectrometry after 15N labelling of denitrification N substrates and minimises the sensitivity to the intrusion of atmospheric N2 at the same time. The incubation set up was used to determine the influence of different soil moisture levels on N2 and N2O emissions from a sub-tropical pasture soil in Queensland/Australia. The soil was labelled with an equivalent of 50 μg-N per gram dry soil by broadcast application of KNO3solution (4 at.% 15N) and incubated for 3 days at 80% and 100% water filled pore space (WFPS), respectively. The headspace of the incubation vessel was sampled automatically over 12hrs each day and 3 samples (0, 6, and 12 hrs after incubation start) of headspace gas analysed for N2 and N2O with an isotope-ratio mass spectrometer (DELTA V Plus, Thermo Fisher Scientific, Bremen, Germany(. In addition, the soil was analysed for 15N NO3- and NH4+ using the 15N diffusion method, which enabled us to obtain a complete N balance. The method proved to be highly sensitive for N2 and N2O emissions detecting N2O emissions ranging from 20 to 627 μN kg

N2O production, a widespread trait in fungi

NASA Astrophysics Data System (ADS)

Maeda, Koki; Spor, Aymé; Edel-Hermann, Véronique; Heraud, Cécile; Breuil, Marie-Christine; Bizouard, Florian; Toyoda, Sakae; Yoshida, Naohiro; Steinberg, Christian; Philippot, Laurent

2015-04-01

N2O is a powerful greenhouse gas contributing both to global warming and ozone depletion. While fungi have been identified as a putative source of N2O, little is known about their production of this greenhouse gas. Here we investigated the N2O-producing ability of a collection of 207 fungal isolates. Seventy strains producing N2O in pure culture were identified. They were mostly species from the order Hypocreales order--particularly Fusarium oxysporum and Trichoderma spp.--and to a lesser extent species from the orders Eurotiales, Sordariales, and Chaetosphaeriales. The N2O 15N site preference (SP) values of the fungal strains ranged from 15.8‰ to 36.7‰, and we observed a significant taxa effect, with Penicillium strains displaying lower SP values than the other fungal genera. Inoculation of 15 N2O-producing strains into pre-sterilized arable, forest and grassland soils confirmed the ability of the strains to produce N2O in soil with a significant strain-by-soil effect. The copper-containing nitrite reductase gene (nirK) was amplified from 45 N2O-producing strains, and its genetic variability showed a strong congruence with the ITS phylogeny, indicating vertical inheritance of this trait. Taken together, this comprehensive set of findings should enhance our knowledge of fungi as a source of N2O in the environment.

N2O production, a widespread trait in fungi.

PubMed

Maeda, Koki; Spor, Aymé; Edel-Hermann, Véronique; Heraud, Cécile; Breuil, Marie-Christine; Bizouard, Florian; Toyoda, Sakae; Yoshida, Naohiro; Steinberg, Christian; Philippot, Laurent

2015-04-20

N2O is a powerful greenhouse gas contributing both to global warming and ozone depletion. While fungi have been identified as a putative source of N2O, little is known about their production of this greenhouse gas. Here we investigated the N2O-producing ability of a collection of 207 fungal isolates. Seventy strains producing N2O in pure culture were identified. They were mostly species from the order Hypocreales order-particularly Fusarium oxysporum and Trichoderma spp.-and to a lesser extent species from the orders Eurotiales, Sordariales, and Chaetosphaeriales. The N2O (15)N site preference (SP) values of the fungal strains ranged from 15.8‰ to 36.7‰, and we observed a significant taxa effect, with Penicillium strains displaying lower SP values than the other fungal genera. Inoculation of 15 N2O-producing strains into pre-sterilized arable, forest and grassland soils confirmed the ability of the strains to produce N2O in soil with a significant strain-by-soil effect. The copper-containing nitrite reductase gene (nirK) was amplified from 45 N2O-producing strains, and its genetic variability showed a strong congruence with the ITS phylogeny, indicating vertical inheritance of this trait. Taken together, this comprehensive set of findings should enhance our knowledge of fungi as a source of N2O in the environment.

NO(y) Correlation with N2O and CH4 in the Midlatitude Stratosphere

NASA Technical Reports Server (NTRS)

Kondo, Y.; Schmidt, U.; Sugita, T.; Engel, A.; Koike, M.; Aimedieu, P.; Gunson, M. R.; Rodriguez, J.

1996-01-01

Total reactive nitrogen (NO(y)), nitrous oxide (NO2), methane (CH4), and ozone (03) were measured on board a balloon launched from Aire sur l'Adour (44 deg N, 0 deg W), France on October 12, 1994. Generally, NO(y) was highly anti-correlated with N2O and CH4 at altitudes between 15 and 32 km. The linear NO(y) - N2O and NO(y) - CH4 relationships obtained by the present observations are very similar to those obtained on board ER-2 and DC-8 aircraft previously at altitude below 20 km in the northern hemisphere. They also agree well with the data obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument at 41 deg N in November 1994. Slight departures from linear correlations occurred around 29 km, where N2O and CH4 mixing ratios were larger than typical midlatitude values, suggesting horizontal transport of tropical airmasses to northern midlatitudes in a confined altitude region.

Optimization of photoelectrochemical performance in Pt-modified p-Cu2O/n-Cu2O nanocomposite

NASA Astrophysics Data System (ADS)

Wang, Yichen; Lou, Zirui; Niu, Wenzhe; Ye, Zhizhen; Zhu, Liping

2018-04-01

As it is expected to be one of the most promising materials for utilizing solar energy, Cu2O has attracted considerable attention with respect to the achievement of solar energy conversion. Until now, the photocurrent densities of all planar structure of the Cu2O photocathode have not even come close to the theoretical value of -14.7 mA cm-2 due to the incompatible light absorption and charge carrier diffusion lengths. Here, we have fabricated p-n Cu2O homojunction nanocomposite by multiple steps of electrochemical deposition processing with the optimization of deposition periods. The p-Cu2O/n-Cu2O nanocomposite fabricated by optimized pH (4.9) and deposition time (4 min) exhibited double the photocurrent density of that of the bare p-Cu2O photocathode. And the highest photocurrent density of nanostructured p-n Cu2O nanorod homojunction photocathode with a p-Cu2O blocking layer reached -10.0 mA cm-2 at 0 V versus the reversible hydrogen electrode under simulated AM 1.5G illumination (100 mW cm-2).

The Effects of Flame Structure on Extinction of CH4-O2-N2 Diffusion Flames

NASA Technical Reports Server (NTRS)

Du, J.; Axelbaum, R. L.; Gokoglu, S. (Technical Monitor)

1996-01-01

The effects of flame structure on the extinction limits of CH4-O2-N2 counterflow diffusion flames were investigated experimentally and numerically by varying the stoichiometric mixture fraction Z(sub st), Z(sub st) was varied by varying free-stream concentrations, while the adiabatic flame temperature T(sub ad) was held fixed by maintaining a fixed amount of nitrogen at the flame. Z(sub st) was varied between 0.055 (methane-air flame) and 0.78 (diluted- methane-oxygen flame). The experimental results yielded an extinction strain rate K(sub ext) of 375/s for the methane-air flame, increasing monotonically to 1042/s for the diluted-methane-oxygen flame. Numerical results with a 58-step Cl mechanism yielded 494/s and 1488/s, respectively. The increase in K(sub ext) with Z(sub st) for a fixed T(sub ad) is explained by the shift in the O2 profile toward the region of maximum temperature and the subsequent increase in rates for chain-branching reactions. The flame temperature at extinction reached a minimum at Z(sub st) = 0.65, where it was 200 C lower than that of the methane-air flame. This significant increase in resistance to extinction is seen to correspond to the condition in which the OH and O production zones are centered on the location of maximum temperature.

A comparison of CH4, N2O and CO2 emissions from three different cover types in a municipal solid waste landfill.

PubMed

Wang, Xiaojun; Jia, Mingsheng; Lin, Xiangyu; Xu, Ying; Ye, Xin; Kao, Chih Ming; Chen, Shaohua

2017-04-01

High-density polyethylene (HDPE) membranes are commonly used as a cover component in sanitary landfills, although only limited evaluations of its effect on greenhouse gas (GHG) emissions have been completed. In this study, field GHG emission were investigated at the Dongbu landfill, using three different cover systems: HDPE covering; no covering, on the working face; and a novel material-Oreezyme Waste Cover (OWC) material as a trial material. Results showed that the HDPE membrane achieved a high CH 4 retention, 99.8% (CH 4 mean flux of 12 mg C m -2 h -1 ) compared with the air-permeable OWC surface (CH4 mean flux of 5933 mg C m -2 h -1 ) of the same landfill age. Fresh waste at the working face emitted a large fraction of N 2 O, with average fluxes of 10 mg N m -2 h -2 , while N 2 O emissions were small at both the HDPE and the OWC sections. At the OWC section, CH 4 emissions were elevated under high air temperatures but decreased as landfill age increased. N 2 O emissions from the working face had a significant negative correlation with air temperature, with peak values in winter. A massive presence of CO 2 was observed at both the working face and the OWC sections. Most importantly, the annual GHG emissions were 4.9 Gg yr -1 in CO 2 equivalents for the landfill site, of which the OWC-covered section contributed the most CH 4 (41.9%), while the working face contributed the most N 2 O (97.2%). HDPE membrane is therefore, a recommended cover material for GHG control. Monitoring of GHG emissions at three different cover types in a municipal solid waste landfill during a 1-year period showed that the working face was a hotspot of N 2 O, which should draw attention. High CH 4 fluxes occurred on the permeable surface covering a 1- to 2-year-old landfill. In contrast, the high-density polyethylene (HDPE) membrane achieved high CH 4 retention, and therefore is a recommended cover material for GHG control.

Thermally Oxidized C, N Co-Doped ANATASE-TiO2 Coatings on Stainless Steel for Tribological Properties

NASA Astrophysics Data System (ADS)

Wang, Hefeng; Shu, Xuefeng; Li, Xiuyan; Tang, Bin; Lin, Naiming

2013-07-01

Ti(C, N) coatings were prepared on stainless steel (SS) substrates by plasma surface alloying technique. Carbon-nitrogen co-doped titanium dioxide (C-N-TiO2) coatings were fabricated by oxidative of the Ti(C, N) coatings in air. The prepared C-N-TiO2 coatings were characterized by SEM, XPS and XRD. Results reveal that the SS substrates were entirely shielded by the C-N-TiO2 coatings. The C-N-TiO2 coatings are anatase in structure as characterized by X-ray diffraction. The tribological behavior of the coatings was tested with ball-on-disc sliding wear and compared with substrate. Such a C-N-TiO2 coatings showed good adhesion with the substrate and tribological properties of the SS in terms of much reduced friction coefficient and increased wear resistance.

Selective Adsorption Resonances in the Scattering of n-H2 p-H2 n-D2 and o-D2 from Ag(111)

NASA Astrophysics Data System (ADS)

Yu, Chien-Fan; Whaley, K. Birgitta; Hogg, Charles S.; Sibener, Steven J.

1983-12-01

Diffractive and rotationally mediated selective adsorption scattering resonances are reported for n-H2 p-H2 n-D2 and o-D2 on Ag(111). Small resonance shifts and line-width differences are observed between n-H2 and p-H2 indicating a weak orientation dependence of the laterally averaged H2/Ag(111) potential. The p-H2 and o-D2 levels were used to determine the isotropic component of this potential, yielding a well depth of ~ 32 meV.

Wavelength-dependent UV photodesorption of pure N2 and O2 ices

NASA Astrophysics Data System (ADS)

Fayolle, E. C.; Bertin, M.; Romanzin, C.; Poderoso, H. A. M.; Philippe, L.; Michaut, X.; Jeseck, P.; Linnartz, H.; Öberg, K. I.; Fillion, J.-H.

2013-08-01

Context. Ultraviolet photodesorption of molecules from icy interstellar grains can explain observations of cold gas in regions where thermal desorption is negligible. This non-thermal desorption mechanism should be especially important where UV fluxes are high. Aims: N2 and O2 are expected to play key roles in astrochemical reaction networks, both in the solid state and in the gas phase. Measurements of the wavelength-dependent photodesorption rates of these two infrared-inactive molecules provide astronomical and physical-chemical insights into the conditions required for their photodesorption. Methods: Tunable radiation from the DESIRS beamline at the SOLEIL synchrotron in the astrophysically relevant 7 to 13.6 eV range is used to irradiate pure N2 and O2 thin ice films. Photodesorption of molecules is monitored through quadrupole mass spectrometry. Absolute rates are calculated by using the well-calibrated CO photodesorption rates. Strategic N2 and O2 isotopolog mixtures are used to investigate the importance of dissociation upon irradiation. Results: N2 photodesorption mainly occurs through excitation of the b1Πu state and subsequent desorption of surface molecules. The observed vibronic structure in the N2 photodesorption spectrum, together with the absence of N3 formation, supports that the photodesorption mechanism of N2 is similar to CO, i.e., an indirect DIET (Desorption Induced by Electronic Transition) process without dissociation of the desorbing molecule. In contrast, O2 photodesorption in the 7-13.6 eV range occurs through dissociation and presents no vibrational structure. Conclusions: Photodesorption rates of N2 and O2 integrated over the far-UV field from various star-forming environments are lower than for CO. Rates vary between 10-3 and 10-2 photodesorbed molecules per incoming photon.

Hierarchically Designed 3D Holey C2N Aerogels as Bifunctional Oxygen Electrodes for Flexible and Rechargeable Zn-Air Batteries.

PubMed

Shinde, Sambhaji S; Lee, Chi Ho; Yu, Jin-Young; Kim, Dong-Hyung; Lee, Sang Uck; Lee, Jung-Ho

2018-01-23

The future of electrochemical energy storage spotlights on the designed formation of highly efficient and robust bifunctional oxygen electrocatalysts that facilitate advanced rechargeable metal-air batteries. We introduce a scalable facile strategy for the construction of a hierarchical three-dimensional sulfur-modulated holey C 2 N aerogels (S-C 2 NA) as bifunctional catalysts for Zn-air and Li-O 2 batteries. The S-C 2 NA exhibited ultrahigh surface area (∼1943 m 2 g -1 ) and superb electrocatalytic activities with lowest reversible oxygen electrode index ∼0.65 V, outperforms the highly active bifunctional and commercial (Pt/C and RuO 2 ) catalysts. Density functional theory and experimental results reveal that the favorable electronic structure and atomic coordination of holey C-N skeleton enable the reversible oxygen reactions. The resulting Zn-air batteries with liquid electrolytes and the solid-state batteries with S-C 2 NA air cathodes exhibit superb energy densities (958 and 862 Wh kg -1 ), low charge-discharge polarizations, excellent reversibility, and ultralong cycling lives (750 and 460 h) than the commercial Pt/C+RuO 2 catalysts, respectively. Notably, Li-O 2 batteries with S-C 2 NA demonstrated an outstanding specific capacity of ∼648.7 mA h g -1 and reversible charge-discharge potentials over 200 cycles, illustrating great potential for commercial next-generation rechargeable power sources of flexible electronics.

Aqua­(dicyanamido-κN 1)(nitrato-κ2 O,O′)(2,3,5,6-tetra-2-pyridylpyrazine-κ3 N 2,N 1,N 6)manganese(II)

PubMed Central

Callejo, Lorena; De la Pinta, Noelia; Vitoria, Pablo; Cortés, Roberto

2009-01-01

In the title compound, [Mn(C2N3)(NO3)(C24H16N6)(H2O)], the central manganese(II) ion is hepta­coordinated to a tridentate 2,3,5,6-tetra-2-pyridylpyrazine ligand (tppz), a bidentate nitrate ligand, a terminal monodentate dicyanamide ligand (dca) and a water mol­ecule. The structure contains isolated neutral complexes, which are linked by O(water)—H⋯N hydrogen bonds generating chains along [010]. PMID:21581535

Infrared spectroscopic and theoretical study of the HC2n+1O+ (n = 2-5) cations

NASA Astrophysics Data System (ADS)

Jin, Jiaye; Li, Wei; Liu, Yuhong; Wang, Guanjun; Zhou, Mingfei

2017-06-01

The carbon chain cations, HC2n+1O+ (n = 2-5), are produced via pulsed laser vaporization of a graphite target in supersonic expansions containing carbon monoxide and hydrogen. The infrared spectra are measured via mass-selected infrared photodissociation spectroscopy of the CO "tagged" [HC2n+1O.CO]+ cation complexes in the 1600-3500 cm-1 region. The geometries and electronic ground states of these cation complexes are determined by their infrared spectra compared to the predications of theoretical calculations. All of the HC2n+1O+ (n = 2-5) core cations are characterized to be linear carbon chain derivatives terminated by hydrogen and oxygen, which have the closed-shell singlet ground states with polyyne-like carbon chain structures.

Aqua[bis(pyrimidin-2-yl-kappa N)amine](carbonato-kappa 2O,O')copper(II) dihydrate.

PubMed

van Albada, Gerard A; Mutikainen, Ilpo; Turpeinen, Urho; Reedijk, Jan

2002-03-01

The title mononuclear complex, [Cu(CO(3))(C(8)H(7)N(5))(H(2)O)] x 2H(2)O, was obtained by fixation of CO(2) by a mixture of copper(II) tetrafluoroborate and the ligand bis(pyrimidin-2-yl)amine in ethanol/water. The Cu(II) ion of the complex has a distorted square-pyramidal environment, with a basal plane formed by two N atoms of the ligand and two chelating O atoms of the carbonate group, while the apical position is occupied by the O atom of the coordinating water molecule. In the solid state, hydrogen-bonding interactions are dominant, the most unusual being the Watson-Crick-type coplanar ligand pairing through two N--H...N bonds. Lattice water molecules also participate in hydrogen bonding.

Soil invertebrate fauna affect N2 O emissions from soil.

PubMed

Kuiper, Imke; de Deyn, Gerlinde B; Thakur, Madhav P; van Groenigen, Jan Willem

2013-09-01

Nitrous oxide (N2 O) emissions from soils contribute significantly to global warming. Mitigation of N2 O emissions is severely hampered by a lack of understanding of its main controls. Fluxes can only partly be predicted from soil abiotic factors and microbial analyses - a possible role for soil fauna has until now largely been overlooked. We studied the effect of six groups of soil invertebrate fauna and tested the hypothesis that all of them increase N2 O emissions, although to different extents. We conducted three microcosm experiments with sandy soil and hay residue. Faunal groups included in our experiments were as follows: fungal-feeding nematodes, mites, springtails, potworms, earthworms and isopods. In experiment I, involving all six faunal groups, N2 O emissions declined with earthworms and potworms from 78.4 (control) to 37.0 (earthworms) or 53.5 (potworms) mg N2 O-N m(-2) . In experiment II, with a higher soil-to-hay ratio and mites, springtails and potworms as faunal treatments, N2 O emissions increased with potworms from 51.9 (control) to 123.5 mg N2 O-N m(-2) . Experiment III studied the effect of potworm density; we found that higher densities of potworms accelerated the peak of the N2 O emissions by 5 days (P < 0.001), but the cumulative N2 O emissions remained unaffected. We propose that increased soil aeration by the soil fauna reduced N2 O emissions in experiment I, whereas in experiment II N2 O emissions were driven by increased nitrogen and carbon availability. In experiment III, higher densities of potworms accelerated nitrogen and carbon availability and N2 O emissions, but did not increase them. Overall, our data show that soil fauna can suppress, increase, delay or accelerate N2 O emissions from soil and should therefore be an integral part of future N2 O studies. © 2013 John Wiley & Sons Ltd.

Nitrous oxide (N2O) emission from aquaculture: a review.

PubMed

Hu, Zhen; Lee, Jae Woo; Chandran, Kartik; Kim, Sungpyo; Khanal, Samir Kumar

2012-06-19

Nitrous oxide (N(2)O) is an important greenhouse gas (GHG) which has a global warming potential 310 times that of carbon dioxide (CO(2)) over a hundred year lifespan. N(2)O is generated during microbial nitrification and denitrification, which are common in aquaculture systems. To date, few studies have been conducted to quantify N(2)O emission from aquaculture. Additionally, very little is known with respect to the microbial pathways through which N(2)O is formed in aquaculture systems. This review suggests that aquaculture can be an important anthropogenic source of N(2)O emission. The global N(2)O-N emission from aquaculture in 2009 is estimated to be 9.30 × 10(10) g, and will increase to 3.83 × 10(11)g which could account for 5.72% of anthropogenic N(2)O-N emission by 2030 if the aquaculture industry continues to increase at the present annual growth rate (about 7.10%). The possible mechanisms and various factors affecting N(2)O production are summarized, and two possible methods to minimize N(2)O emission, namely aquaponic and biofloc technology aquaculture, are also discussed. The paper concludes with future research directions.

Experimental and modeling study on effects of N2 and CO2 on ignition characteristics of methane/air mixture

PubMed Central

Zeng, Wen; Ma, Hongan; Liang, Yuntao; Hu, Erjiang

2014-01-01

The ignition delay times of methane/air mixture diluted by N2 and CO2 were experimentally measured in a chemical shock tube. The experiments were performed over the temperature range of 1300–2100 K, pressure range of 0.1–1.0 MPa, equivalence ratio range of 0.5–2.0 and for the dilution coefficients of 0%, 20% and 50%. The results suggest that a linear relationship exists between the reciprocal of temperature and the logarithm of the ignition delay times. Meanwhile, with ignition temperature and pressure increasing, the measured ignition delay times of methane/air mixture are decreasing. Furthermore, an increase in the dilution coefficient of N2 or CO2 results in increasing ignition delays and the inhibition effect of CO2 on methane/air mixture ignition is stronger than that of N2. Simulated ignition delays of methane/air mixture using three kinetic models were compared to the experimental data. Results show that GRI_3.0 mechanism gives the best prediction on ignition delays of methane/air mixture and it was selected to identify the effects of N2 and CO2 on ignition delays and the key elementary reactions in the ignition chemistry of methane/air mixture. Comparisons of the calculated ignition delays with the experimental data of methane/air mixture diluted by N2 and CO2 show excellent agreement, and sensitivity coefficients of chain branching reactions which promote mixture ignition decrease with increasing dilution coefficient of N2 or CO2. PMID:25750753